AU602010B2 - Method for common development processing of two kinds of light-sensitive silver halide photographic material - Google Patents

Description

I U 6020 S F Ref: 39639 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: Published: Priority: IThi- d unent contains lhc e al ciCdi icd'lt mlade lndler beCtit' 49 and is correct for priinting. Related Art: Name and Address of Applicant: Address for Service: Konishiroku Photo Industry Co., Ltd.

26-2, Nishi-shinjuku l-choma Shinjuku-ku Tokyo

JAPAN

Spruson Fo"guson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia r Complete Specification for the invention entitled: Method for Common Development Processing of Two Kinds of Light-Sensitive Silver Halide Photographic Material The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 FP-1613 lI- Method for common development processing of two kinds of light-sensitive silver halide photographic material BACKGROUND OF THE INVENTION This invention relates to a method for development processing which processes an internal latent image positive silver halide photographic material (hereinafter called internal latent direct positive sensitive material) and a negativetype light sensitive silver halide photographic material (hereinafter called negative-type sensitive material) with a common developing solution.

The method used for preparation of a positive-image by use of an internal latent type direct positive sesnsitive material may be classified primarily into the two types, excluding special ones.

One type is to use a previously fogged silver halide eimulsion and obtain a positive-image after development by destroying the fogged nuclei (latent image) at the exposed portion by 20 utilizing solarization or Herschel effect, etc.

The other embodiment is to use an internal latent image type silver halide emulsion which is not fogged and obtain a positive-image by performing after image exposure surface 2 development after application of fogging treatment or while applying fogging treatment.

The above internal latent image type silver halide emulsion refers to a silver halide photographic emulsion, having light-sensitive nuclei primarily internally of the silver halide grains, which can form latent images internally of the grains by exposure.

The method of the latter type has generally higher sensitivity as compared with the method of the former type, and is suitable for image formation requiring high sensitivity, and the present invention concerns the latter type.

In this technical field, various techniques have been hitherto known. For example, the principal techniques are disclosed in U.S. Patents No. 2,592,250, No. 2,466,957, No.

2,497,875, No. 2,588,982, No. 3,761,266, No. 3,761,276 and No. 3,796,577 and GB Patent No. 1,151,363, and by use of o o. 20 these methods, as the direct positive type, light-sensitive 0 photographic materials with relatively higher sensitivity can s be prepared.

00 Although it is difficult to say that clear explanation has S been given about details of the mechanism of forming direct 0 .o positive images, the process of forming positive-image can be 0 0 o0j o"o understood to some extent by the "sensitivity reduction action by internal latent images" as discussed in Mieth and James, "The Theory of the Photographic Process", Third Edi- °o 30 tion, page 161.

0 Q0

O

Shortly speaking, it seems likely that, due to the surface sensitivity reduction action caused by the so-called internal latent image produced internally of the silver halide grains by the internal image exposure, fogged nuclei are formed selectively only on the surfaces of the unexposed silver I- 3 -3halide grains, and then photographic images are formed at the unexposed portion by conventional development.

As the means for forming selectively fogged nuclei as mentioned above, there have been known the method called "chemical fogging'' in which fogging is effected by use of a fogging agent, and the method called "light fogging" in which fogging is effected by g-ving whole surface exposure.

Whereas, for processing an internal latent type direct positive sensitive material in a photographic developing station, it is a generall practice to perform processing by providing a processing line for exclusive use for the internal latent type direct positive sensitive material separately from the processing line for the negative-type sensitive material of the prior art.

The processing line for the negative-type sensitive material has, for example, the three kinds of instruments of an automatic developing machine for negative-film, an automatic developing machine for negative-paper and an automatic printing device arranged separately, while the processing line for the inner latent type direct positive sensitive material comprises two kinds of an automatic printing device for exclusive use and an automatic developing machine for exclusive use. Generally speaking, these respective instruments S require working spaces of predetermined broadness therearound, and further spaces necessaary for supplemental cock adjustment, vaporization correction, tank liquid exchange and supplement working must be ensured around these instruments.

Accordingly, when the above instruments are irranged separately, care must be taken so that the working spaces around the respective instruments may not overlap each other, whereby there is a fear that troubles may be brought about ina narrow place in a small scale color photographic developing 4 station. Thus, simplification of the processing method and miniaturization of the automatic developing machine are now becoming important tasks.

In view of the state of the art as described above, the present inventors have continued to study about processing of an internal latent type direct positive sensitive material and a negative-type sensitive material with a common developing solution, and first attempted to process an internal latent type direct positive sensitive material and a negative-type sensitive material with a developing solution of the same composition according to the chemical fogging method, but fogging occurred remarkable in the negative-type sensitive material. The developing solution for processing commonly an internal latent type direct positive sensitive material and a negative-type sensitive material is rquired to be maintained and managed more highly in activity than is required for other processing solutions, and furhter required to be set at a higher solution temperature than other processing solutions. Thus, it has been found not easy to inhibit generation fogging for the above negative-type sensitive material.

Accordingly, the present inventors have investigated about the light fogging method. More specifically, it has been attempted to turn the light source for giving the whole S surface exposure ON during the development processing of an internal latert type direct positive sensitive material, while to turn the above light source OFF during development processing of a negative-type sensitive material. However, this light cogging method was found to involuve the following problem.

That is, by employment of the above light fogging method, although it has been rendered possible to process both an internal latent type direct positive sensitive material and a Ily--- ^II_-l -I-IILiilllll-I-- ~-LI..-ili~~~^iil negative-type sensitive material with a common developing solution, even if developing solution may be supplemented corresponding to the respective light-sensitive materials, it has been found that coloration of the solution occurred, whereby the color formed dye density changed due to the filter effect of the secondary exposure.

j Further, there ensured that problem that the exposure dose of light fogging for the internal latent type positive sensitive 10 materia was fluctuated and fluctuation in light fogging I exposure dose was too great between the newly prepared solution and the fatigued solution after use for prolonged time, ji whereby no stable photographic performance could be obtained.

;i 15 As the result of extensive studies by the present inventors, ;i it has been found that the causes for giving rise to colora- Stion of solution may be firstly, oxidized colored product having absorption at specific wavelength, which may result in j .yellow coloration to cause lowering in color formed density i 20 of yellow dyes or stain, and secondly, coloration of an anti-irradiation dye (hereinafter called AI dye) used for the Spurpose of improving sharpness of the light-sensitive material, whereby lowering in color formed density and generation of stain may be caused. These problems have particularly greater Influencce when using an internal latent type direct positive sensitive material, but also generation of stain will occur even in a negative-type sensitive material.

For this reason, it may be considered possible to solve the problem by reducing the amount of the AI dye added or using no such dye, but since it is one of the important elements for improvement of sharpness or control of sensitivity, it is impossible to employ such solution method.

And, this problem is an important problem to be solved, when an internal latent type direct positive sensitive material -6and a negative-type sensitive material are to be processed with a common developing solution.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing of a light-sensitive silver halide photographic material, which performs development processing of an Internal latent type direct positive light-sensitive material with a common developer to give stable photographic performance.

According to a broad form of the present invention, there is provided a method for common development processing of two kinds of light-sensitive silver halide photographic material which comprises the step of development processing an internal latent type direct positive light-sensitive silver halide photographic material and a negative-type light-sensitive silver halide photographic material in the same development processing bath, and the step of applying whole surface exposure on said internal latent type direct positive light-sensitive silver halide photographic material during development processing of said internal latent type direct positive light-sensitive silver halide photographic material, characterized in that said developing processing solution contains a hydroxylamine compound o o.0 represented by the formula shown below: o a 00 0 N-OH (A) 09 0 a

R/

a 0 wherein RI and R 2 each represent hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent or may be combined with each other to form a heterocyclic ring, Preferably, the hydroxylamine compound is hydroxylamine.

30 Alternatively, R 1 and R 2 cannot be hydrogen at the same time.

04 4 0 0 4 0 4 L i _1 7 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic illustration showing an example of the automatic developing machine whieh can be used for processing of the present invention, in which 7 is a development processing tank, 8 is a bleach-fixing processing tank, 9 and 9' are stabilizing tanks and 11 is an exposure device.

DESCRIPTION OF THE PREFERRED EMBODIMENTS By use of the compound represented by the formula not only production of the component having absorption at a specific wavelength can be prevented, but also solution coloration with the Al dye dissolved out from the light-sensitive material can be prevented, to give the result that coolor fluctuation and stain by the secondary reversal exposure can be rduced, In the prior art, the At dye has been said to form generally reduced leuco with sulfite ion, and recently Al dyes without reducing decoloration have been frequently used for improvement of sharpness. The present inventors have found in the same processing of an inernal latent type direct positive light-sensitive material and a negative-type light-sensitive material that the AT of the present invention effots decolorj 1. ation very effectively in the presence of hydroxylamire in an amo Int of the present invention and dose not obstruct the light fogging effect of the internal latent type direct i positive light-seositive material, to accomplish the present invention.

The present invention performs development processing of an internal .atent type direct positive light-sensitivo material and a negative-type light-sensitive material with a common development processtng solution, and also can use an automatic developing machine which enables control of the whole L i

I

8 surface exposure may be given when the internal latent type direct positive light-sensitive material is conveyed in for the development processing layer, while no whole surface exposure may be given when the negative-type light-sensitive material is conveyed in for the development processing layer.

In the present invention, the negative-type light-sensitive material means color printing paper, color negative film, color reversal film and color reversal paper.

The processing step to be used in the present invention should be preferably a color developing step as the development processing.

Particularly, as the color development processing, it is preferable to practice a color development processing step, a bleaching processing step, a fixing processing step, a stabilizing processing step substituting for water washing, but in place of the processing step by use of a bleaching solution and the processing step by use of a fixing solution, a bleachfixing processing step can be also practiced, These processing Btep may be also combined with pre-filmhardening step, its neutralization stop, stop fixing processing step, post-film-hardening step, etc. In these processings, in place of the color development processing step, the activator processing step may be also practiced, in which a color developing agent or its precursor is incorporated in the light-sensitive material and the development processing is performed with an activator solution.

S Representative examples of these processings are shown below.

in these processings, as the final stop (the final bath), either the water washing processing step, the stabiiallng processing step substituting for water washing or (3) the water washing processing step and the stabilizing pro- -9cessing step.

The proc'-ssing method of the present invention employs a developing tank which is made substantial. common, and can also use the processing tanks made into a unit, which may be also linked together, if desired, The processing tanks in the processing method Qf the present invention may have ai constitution, employing the processing tanks according to the known processing steps, Preferable representative examples in the p ,7"Pssinq steso the invention (Bleaching->(ing(nl (Colov bath develop iog (S'leach ig (iing Fi~alh() bat Fia (Color (B Wch n -M-(inslng (2)devlopng><Blachng (Linsing -(Fixing *~(Final bath (A) *~(Final bath ()(color _',.v(leach-f ixing (Final bath deVeloping)N"'> (Bleach-Pixing )--(Final bath

A)~

dovoopinYN~Neuta~iiny(~loahin !Xinfg *.(Final bath (A) (FinalI bath ($)uraizn doioi~)

(W)

(Fixing bath (A) S(Fixing,() >FiL bath (83)) ~I 10 (Neutralizing (Bleach-fixing (Final ((Color -bath developing)", (Neutralizing (Bleach-fixing (Final bath Color (Bleaching) (Fixing(Final developing) (Blehing -(Fixing) bath) (Color (Final (Bleach-fixing) e developing) bath) (Color (Neutra- (Bleach- (Final developing) lzing) ing) (Fixing)-- bath) (1 (Color (Newtra- (Bleach- (Final developing) lizing) fixing) bath) (11) (Pre-hard- (Neutra- (Color (Neutraening) lizing) developing) lizing) (washing)-- (Bleaching)- (Fixing) (Washing) (Post-hard- (Final ening) bath) (Black and white (Neutraliz- (Water developing ing washing (color (Final oping->- (Bleaching) (Fixing)--- a developing) (Bleachin9) (Lixin9) bath) In the above processing steps to (12) the step enclosed with great parenthesis represents the common step, while the step enclosed with small paronthesis individual processing step, A representing use for the internal latent type direct positive light-sensitive and 8 use for the negative--type S light-sensitive material.

In the present invention, "substantiall common processing tank" means generally one tank, but it is also inclusive of a 1O counarcurront system (cascade system) partitioned into 2 to 3 tanks. As the ccountercurrent system, there may be included the cocurrent system of the countercurrent system when the Clows are n parallel in the plan view in the direction in which the light-sensitive material to be treated is moved, and the parallel overflow system in which the flows are perpendicular to each other. Also, a processing tank com- 11 prising two tanks communicated by provision of a pipeline or a hole is also included. Details of these are in Japanese Provisional Patent publication No. 139548/1987, Next, the compound represented by the formula is to be described.

R 1and R 2 may be either the same or different and, when R and/or R 2 represents an alkyl group, said alkyl group is inclusive of those havin9 substituents, As said substituent, a sulfonic acid group, a hydroxy group, an alkoxy group (a methoxy group, an ethoxy group, a propyloxy qroup and the like), a carboxyl group, an amino group, etc., may be included, Preferred exemplary compounds represened by the formula (A) are enumerated below.

(2) c (3) (4) (6 25 (7) a a0

NEI

2 -014 C 3 -NH-O11 3 7

C

2 t14-NH-O( io-CH 2 7 -N-EI1 HClNE1-QH

CU

3 -C l -NH-OH 24

CFCII

H3-0-C2 ti4- M1-01 3\ ,N-011

C

3 113' 25N-Oft l~~C 3 1 7 iso-0 3 17 (13) (9)l (1) (11) (12) (1) (17) (19) 10-C C 2 114 NUt-O11 HQOC-2-4-[ 1 ftQOC C 2 N 3 -Nl-0l1 4

H

2 N *C l4-NE-OtI EIQ-CE1 11 -0 2l-C 1 E1 t'f 3 a a (16) CL3, jIl Ih117 1H7 7 I i C La) 12 (22) (24) (26) (28) (32) (34)

CH

3 0 2

H

4

C

2

H

HO SC H 32iN-OH 3 O 3SC H HO H6N-OH

HO

3

SC

3 6

NH

2 C3H 6

N-OH

H-N N-OH1

H

3 C- NN-OH (23) CH3C2

H

4 OH-o CH3/ (25)

C

2

H

5 0 2

H

4

?N-OH

C

2

H

5 0 2

H

4 (27) HOOCC 2

H

4 OOCC2 H

/NOH

2 4 (29) H 3

SC

5

H

10

\-OF

02 (31) (33) 0 N-QFI HQ-N N-OH1 These compounds may be generally used in the form of salts such as hbdrochiloridesf sulfates, p-toluenesulfonate.,- oxalates, phosphates, acetates, et-.

These compounds can be easily synthesized according to the methods as described in U.S. Patents No. 3,287,125, No.

3,293,034, No. 3,287,124, The color devreLoping solution may contain the compound opresented by the above formula at a concentration generaLly of, for example, preferably 0.05 9/liter to 50 g/liter, more preferably 0.3 9/liter to 30 g/liter, particularly prcEtrably g/liter to 20 g/liter.

13 The above ccompounds may be used either individually or as a combination of two or more compounds.

The color developing solution contains a poly(alkyleneimine) or an alkanolamine. The poly(alkyleneimine) comprises a substituted or unsubstituted recurring alkylene chain units bonded mutually through nitrogen atom. These are also commercially available. Representative poly(alkyleneimine) may include the compound represented by the following formula (P

I):

I (P I) Rp pl n wherein Rp1 represents an alkylene group having 1 to 6 carbon atoms; Rp2 represents an alkyl group; and n is an integer of 500 to 20,000.

The alkylene group having 1 to 6 carbon atoms represented by the above Rp l may be either straight or branched, preferabl, an alkylene group having 2 to 4 carbon atoms such as an ethylene group, a propylene group, a butene group, an isobutene group, a dimethylethylene group, an ethylethylene group, and the like. The alkyl group represented by Rp2 may be preferable an alkyl group ;,avit.g 1 to 4 carbon atoms such i us a methyl group, an ethyl group, a propyl group and the a, like, and is also inclusive of those having substituents a hydroxyl group, etc.) n represents the number of reccurring units in the polymer chain, representing an integet of 500 to 20,000, preferably 500 to 2,000. A poly(ethyleneimine) in which Rp is an ethylene group is the most preferable for the objecot of the present invention.

Specific examples of the poly(alkyleneimine) to be used in the color developing solution are shown below, but they are not limitative of the present invention.

14 [Exemplary compounds] PAI 1 Poly(ethyleneimine) PAI 2 Poly(propyleneimine) PAI 3 Poly(buteneimine) PAI 4 Poly(isobuteneimine) PAI 5 Poly(N-methylethyleneimine) PAI 6 Poly(N-f-hydroxyethylethyleneimine) PAI 7 Poly(2,2-dimethylethyleneimine) PAI 8 Poly(2-ethylethyleneimine) PAI 9 Poly(2-methylethyleneimine) The poly(alkyleneimine) can be used inthe color developing solution in any desired amount which can accomplish the object of the present invention, but is generally preferred o°o 15 to be 0,1 to 500 g, more preferably 0.5 to 300 g, per one liter of the color developing solution.

Japanese Provisional Patent Publication No. 94349/1981 's- S closes that the poly(alkyleneimine) of the present invention can be used together with hydroxylamine in the color developing solution to improve storage stability of the color developing solution and also lower the sulfite salt concentration.

However, the above Patent Publication is entirely silent on the fact that the poly(alkyleneimine) can effectively solve the problem of coloration of the solution which occurs during processing of an internal latent image type positive lightsensitive material and the negative type light-sensitive material with a common developer. Thus, it has been entirely unexpected that the poly(alkyleneimine) can effectively solve coloration of such solution.

The color developing solution of the present invention can also accomplish the above objects by incorporating an alkanolamine in place of or in combination with poly(alkyleneimine).

Said alkanolamine may be preferably a compound represented by the following formula (P II): 15 R NI(P IT) p3\ R p wherein R p 3 represents a hydroxyalkyl group having 2 to 6 carbon atoms, R p4and R p5each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl x group or a formula: -Cn H 2-N n in the above formula being an integer of 1 to 6, X and Z each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.

Of -the compounds represented by the above formula (P II), particularly those in which R 3represents a hydroxyalkyl group having 2 to 4 carbon atoms, and R p 4 and R p 5 each represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms are prefecred.

Preferred specific examples of the compounds represented by the above formula (P II) are as follows: ethanolamine, diethanolamine, triethanolamine, dilsopropartolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-dimethylaminoe thao'L, 2-diethvlaminoethano1, l-diethylamino-2propanol, 3-diethylamino-l-propanol, 3-dimethylamino-l--propanol, isopropylaminoethaniol, 3-amino--i-propanol, 2-'amino-2methyl-1,3-propanediol, ethylenediaminetetraisopropanol, benzylethanolamine, 2-amiino-2-(hydroxymethyl)-l,3-propanedi ol.

Among them, ethanolamine and diethanolarnine ars, preferred, and particularly ethanolamine is the most pre~erred.

The above Compound may be added either singly or as a combi- 16 nation of two or more kinds in the color developing solution.

The amount added may be preferably 0.1 g to 200 g, more preferauly 0.3 g to 50 g, per one liter of the developing solution.

In the present invention, the development processing solution should preferably contain the compound represented by the above formula as the prepresentative.

In the present invention, it is particularly preferred to use a sulfite or sulfite ion releasing compound together with the compound represented by the formula That is, the effect of preventing the solution coloration as described above will ao0OD15 become further conspicuous in the presence of a sulfite or a 0 4 sulfite ion releasing compound, o o a o Specific examples of sulfite or sulfite ion releasing com- Le pounds may include potassium sulfite, sodium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite, sulfurous acid adduct of formaldehyde, sulfurous acid adduct of acetaldehyde, sulfurous acid adduct of glutaraldehyde, 01, The concentration of the above compound may be in the range o from 1.0 x 10 to 1.0 x 10 mole/liter of the color devela oping solution, but when a sulfite or sulfite ion releasing compound exists in a large amount, lowering in color formed S density of the dye in the light-sensitive material is liable to occur, and therefore, it should preferably be 5.0 x 10 -2 to 5.0 x 10 2 mole per liter.

The color developing solution to be used in the prosent invention means a surface developing solution containing substantially no silver halide solvent, and the color developing agent contained in the color developing solution is an -17 aromatic primary amine type color developing agent, including aminophenol type and p-phenylenediamine type derivatives.

These color developing agents can be used as the salts of organic acids and inorganic acids, for example, hydrochlorides, sulfates, p-toluenesulfonates, sulfites, oxalates, benzenesulfonates, etc.

These compounds aru used generally at concentrations of about 0.1 g to about 200 g, more preferably about 1 g to 50 g, per one liter of the color developir-3 solution.

The proce-,.'ng temperature of these color developing solution may preferaoly be 10 00 to 65 00, more preferably 25 00 to 00.

These above amino phenol type developing agent may include, for example, o-amincophenol, p-amiinophenol, 5-amino-2-oxytoluenr,, 2-amino-3-oxy-toltuene, 2-oxy-3-amino-l,4-dimethylbenzene, etc, Particularly useful aromatic primary amine type color developing agents are N,NI-cialkyl-p-"phenyleniediamine type cornpounds, of which alkyl group and phenyl group may be either substituted or not, Among them, particularly useful compound examples may include N,N'-dimethyL-p-phnytflediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'diethyl-p-phenylenediamirte hydrochloride, 2-amino-5- (N-ethyl- N-dodecylamino) toluen~e, N-e thyl-N-f-me thanes If onamidoe thylI- 3-methyl-4-aminoaniline sulfate, N-ethyl-N-f-hydroxyethylam~noaniline, 4-amino-3-rethyl-NN'-diethylaniline, 4-amino- N- 0-me thoxye thy1) -N-e thyl-3 -methy lan ilI n-p- tOlUenesUlIC~oat and the like, Also, the above color developing ager be used either 3$ singly or as a combination of two or more kinds. Further, the above color developing agent may bfn internally Included 18 within the color photographic material. For example, there may be employed the method in which the color developing agent is included as a metal salt as in U.S. Patent No.

3,719,492 :h mh in 'hich the color developing agentiincluded as a Schiff salt; inRP rrh nin leu 5l? (c96) the method in which it is included as a dye precursor as discloser in Japanese Provisional Patent Publications No. 65429/1983 and No. 24137/1983; or the method in which it is included as the color developing agent precursor as disclosed in U.S. Patent No. 3,342,597. In this case, the light-sensitive silver halide color photographic material can be also processed with an alkaline solution (activator solution) in place of the color developing solution, and subjected to bleach-fixing processing immediately after the alkaline solution processing.

ooQa The color devleoping solution to be used in the present invention can contain alkali agents conventionally used in a developing solutions, such a sodium hydroxide, potassium 20 hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborates or borax, and further additives can be contained therein, such as benzyl S4 alcohol, alkali metal halides, for example, potassium bromide 0 oo or potassium chloride, etc. Also, as the development controller, for example, citradinic acid, etc. may be contained.

Further, various defoaming agents, surfactants, or ocganic solvents such as methanol, dimethylformamide or dimethyl suL'foxide may be suitably contained.

Also, the color developing solution to be used in the present invention can optionally contain antioxidants succh as tetronic acid, tetronimide, 2-anilinoethanoL, dihydroxyacetone, aromatic secondary alcohols, hydroxamic acid, pentose or hexose, pyrogallol-l,3-dimethyl ether, etc.

In the color developing solution to be used in the present

LIC-V-

19 invention, various chelating agents can be used in combination as the sequestering agent. For example, as said chelating agent, there may be included aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethlenetriaminopentaacetic acid, etc.; organic phosphonic acids such as 1-hydroxyethylidene-l,l-diphosphonic acid, etc.; aminopolyphosphonic acids such as aminotri(methylenephosphcnic acid) or ethylenediaminetetraphosphoric acid, etc.; oxycarboxylic acids such as citric acid or gluconic acid; phosphonocarboxylic acids such as 2-phosphonobutane-l,2,3-tricarboxylic acid, etc.; polyphosphoric acids such as tripolyphosphoric acid or hexamethanoic acid.; polyhydroxy compounds; and the like.

The whole surface exposure to oe used in the present invention is effected in the initial stage of development, which is preferable in the sense of shortening the development time, and in that case, it is advantageous to initiate exposure after the developing solution has been sufficiently penetrated into the emulsion layer.

In the present invention, as the means for controlling lighting of the whole surface exposure, it is possible to utilize the exposure devices as disclosed in Japanese Utility Model Publication No. 22351/1985, Japanese Provisional Utility S Model Publications No. 145049/1981, No. 87051/1984 and No.

87052/1984, and Japanese Provisional Patent Publication No.

114237/1986.

In the present invention, for controlling lighting of the whole surface exposure, Eor example, the operator of an automatic developing machine can judge previousLy which one of the above light-sensitive materials is to be processed and, when the light-sensitive material to be processed is the internal latent image type, truns on manually the switch of the exposure device before the light-sensitive material to be processed enters the development processing solution, or alternatively, when the light-sensitive material to be processed is a negative-type, can turn off manually the switch before the light-sensitive material enters the developing solution. Also, in place of the manual change-over of the switch of the reversal exposure device by the operator, with the use of notch or bar code in the light-sensitive material as the detection mark, the light-sensitive material can be automatically judged whether it is the internal latent image type or the negative-type to control automatically lighting of the whole surface exposure. Further, discrimination judgement may be automatic, and said judgement result may be informed to the operator by sound or mark display and lighting change-over for tho whole surface exposure may be performed manually by the operator.

As the light source for light fogging to be used in the present invention, at least one light source within the sensitive wavelength for the light-sensitive photographic material may be empl.oyed, but it is desired to use at least one light source having a broad spectral distribution over the range from 400 to 700 nm in the visible light region as the light source for the light-sensitive color photographic S material, for example, a fluorescent lamp with high color rendering. Also, tow or more kinds of light sources with different emission distribution or color temperatures may be -ised in combination, or various filters such as color temperature conversion filter, etc. may be used.

The illuminance of the whole surface exposure, namely light fogging to be used in the present invention may be preferably an illuminance which does not cause illuminance irregularity during light fogging, which may differ depending on the light-sensitive material, but generally 0.01 to 2000 lux, preferably 0.05 to 30 lux, further preferably 0.1 to 5 lux, The light fogging illuminance may be adjusted by varying the 21 luminosity of the light source, or can be done by utilizing light reduction with various filters, the distance between the light-sensitive material and the light source or the angle between the light-sensitive material and the light source, etc. Also, for shortening the light fogging exposure time, there may be employed the method in which fogging is effected with weak light at the initiation of exposure of light fogging, and then fogging is effected with stronger light than that. Also, it is possible to practive advantageously the method in which the whole surface exposure is effected while increasing the illuminance as described in Japanese Patent Publication No, 117286/1983.

As the exposure device to be used for the whole surface 15 exposure, there may be advantageously used the devices as S described in Japanese Utility Model Publication No. 22351/- 1985, Japanese Provisional Utility Model Publications No, 145049/1981, No, 87051/1984 and No, 87052/1984, and Japanese Provisional Patent Publication No. 114237/1986.

o The bleaching processing step as mentioned in the present invention refers to the step of bleaching the silver image developed after the color development processing step with an oxidizing agent (bleaching agent) As the bleaching agent, a metal complex of an organic acid i t may be preferably used, for example, metal ions such as of iron, cobalt, copper, etc. coordinated with organic acid such as polycaboxylic acid, aminopolycarboxylic acid, or oxalic acid, citric acid, etc. Among the above organic acids, the most preferred organic acid may include polycarboxylic acid or aminopolycarbo<xyic acid. Those polycarboxyl.z acids may be alkali metal salts, ammonium salts or water-insoluble amine salts. Specific oxamples of these may include the following compounds, namely ethylenediamirentetraacetic acid, diothylenetriaminepontaacetic acid, pentasodium 22 diethylenetriaminepentaacetate and the like. These bleaching agents are used in amounts of 5 to 450 g/liter, more preferably 20 to 250 g/liter.

In the bleaching solution, other than the bleacing agent as mentioned above, a halide such as ammonium bormide may be preferably addedt As the above halide, other than ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, I0 potassium iodide, ammonium iodide and the like can be also used.

In the present invention, the fixing processing step refers to the step of fixing by desilverization with a fixing solu- 15 tion containing a silver halide fixing agent. As the silver halide fixing agent to be used in said fixing solution, there may be included compounds forming water-soluble complexes throuah the reaction with silver halie as used in conventional fixing processing, of which representative examples are thiosu:fates such as potassium thiosulfate, sodium thiosulfate; thiocyanates such as ammonium thiocyanate; thiourea; thioether; etc. These fixing agents are used in amounts of g/liter or more in the range which can be dissolved, generally from 70 g/liter to 250 g/litero In the present invention, it is preferred to perform the bleaching processing step and the fixing processing step in one processing step with a bleach-fixing solution, and the metal complex of an organic acid as the bleaching agent to be used in said bleach-fixing solution comprises metal ions such as iron, cobalt, copper, etc. coordinated with organic acids such as aminopolycarboxyltc acid or oxalic acid, citric aid, etc. As the organic acid to be usod for formation of such metal complex of organic acid, the same acids as mentioned for the bleaching solution can be used.

-L1-uu-- ~F---lrrrcrrrc~~~r 23 As the silver halide fixing agent to be contained in the bleach-fixing solution, compounds forming water-soluble complexes through the reaction with silver halide as used in conventional fixing processing may be used.

After'processing with a processing solution having a fixing ability, conventional water washing processing may be performed, but it is particularly preferred in the present invention to apply stabilizing processing substantially without including water washing step, The stabilizing processing substantially without including water washing step refers to performing stabilizing processing substituting for water washing according to a single tank or a multiple tank countercurrent system, etc. immidiately after processing with a processing solution having a fixing ability, but processing steps other than water washing in general suCh as rinsing, auxiliary water washing and known water washing promoting bath, etc. may be also included, In the stabilizing processing step in the present invention, the method of bringing a stabilizing solution into contact with a light-sensitive silver halide material may be preferably to dip the light-sensitive silver halide photographic material in a bath similarly as in the case of processing solutions in general, but it may be coated on the emulsion surface of the light-sensitive silver halide photographic material and both surfaces of the conveying leader, the Sconveying belt, with sponge, synthetic Fiber cloth, etc., or sprayed by means of a spray, etc. In the following, descriptlon Is made primarily about the case of using a stabilizing bath according to the dipping method.

The above stabilizing solution should preferably contain a chelating aget wich a chelate stabilizing constant of 6 or more relative to iron ion.

24 As the chelating agent having a chelate stabilizing constant of 6 or more relative to iron ion may include organic carboxylic chelating agents, organic phosphoric chelating agents, inorganic phosphoric chelating agents, polyhydroxy compounds 3+ may be employed. The above iron ion means ferric ion (Fe Specific compound examples of chelating agents having a chelate stabilizing constant of 6 or more relative to ferric ion may include deithelenetriaminepentaacetic acid, nitrilotriacetic acid, l-hydroxyethylidene-l,l-diphosphonic acid, etc.

The amount of the -oove chelating agent employed may be in the range from 0.01 to 50 g, preferably from 0.05 to 20 g.

Further, preferable compounds to be added in the stabilizing solution may include antifugal agents, water-soluble metal salts, ammonium compounds, etc. Examples of the above antifugal agent may include hydroxybenzoic acid type compounds, phenolic compounds, isothiazole type compounds, pyridine type compounds, guanidine type compounds, carbamate type compounds, morpholine type compounds, quaternary phosphonium type compounds, ammonium type compounds, urea type compounds, isoxazole type compounds, propanolamine type compounds, sulfamide type compounds, amino acid type compounds and benztirazolo type compounds.

Furthor, as the metal salts, there may be included metal salts of Ba, Ca, Ce, Co, In, La, Mn, Ni, Pb, Sn, Zn, Ti, Mg, Al and Sr, which can be supplied as halides, hydroxides, inorganic salts such as sulfates, carbonates, phosphates, acetates, etc, or water-soluble cholating agents, The metal salt may be added in an amount ranging from I x 10 to t x mole, preferable Erom 4 x 10 to 2 x 10 2 mole, further preferably from 8 x 10 4 to I x 102 mole, per liter of the Stabilizing solution.

In the stablizing solution, in addition to the above compounds, various additives for amelioration and expansion of the processing effect may be addedd as desired, including fluorescent brighteners; organic sulfur compounds; onium salts; film harceners; droplet irregularity preventives such as quaternary salts, polyethyleneoxide derivatives, siloxane derivatives, etc.; pH controllers such as boric acid, citric acid, phosphotic acid, acetic acid, or sodium hydroxide, sodium acetaLe, potassium citrate, etc,; organic solvents such as methanol, ethanol, dimethyl sulfoxide, etc. dispersing agents such as ethylene glycol, polyethylene glycol, etc.; and other tone controllers; etc.

As the method for adding the above compound or other additive, the above compound or other additives may be added as a concentrated solution into the stabilizing tank or into the stabilizing solution to be supplied into the stabilizing tank to provide a feeding solution into the stabilizing solution, or alternatively they can be added into the previous bath before the stabilizing processing step to be contained in the light-sensitive silver halide photWgraphic material and exist in the stabilizing bath. Any additional method may be available.

4 4 The method for feeding the stabilizing solution in the stabilizing processing stop in the case of the multi-Lank countercurrent system should proferably be one in which the solution Is fed to the later bath and overflowed from the eariler bath.

The p1l value of the processLng solution in Lthe stabilizing bath should be preforably in the range of ptH 4 to 8.

Control of pH can be done with the use of the p1H controlLer as mentioned above.

26 The processing temperature during the stabilizing processing may be, for example, 20 oC to 50 oC, preferably in the range from 25 OC to 40 oC, The processing time shouild be preferably as short as possible fro the standpoint of rapid processing, but generally seconds to 5 minutes, most preferably 30 seconds to 2 minutes, =nd in the multi-tank countercurrent system, processing time should be shorter for earlier step and longer for later scep.

In the present invention, no water washing processing is requiced before and after the stabilizing processing, but there may be optionally provided a processing tank for rinsing with a small amount of water within a short time, surface cleaning with sponge, and stabilizing the image or control- Ying the surface characteristics of the light-sensitive silver halide photographic material.

As the material for stabilizing the image or controlling the surface characteristics of the light-sensitive silver halide photographic material as mentioned above, there may be employed activators such as formalin and derivatives thereof, siloxane derivatives, polyethylene oxide compounds, quesernary salts, etc.

In the present invention, other than the processing steps as described above, additional processing steps may be provided above, additional processing steps may be provided as desired, F-om the above stabilizing solution as a matter of course, and also from the processing solutions containing soluble silver co:nplexs such as the fixing solution, the bleach-fixing solution, etc., silver may be recovered according to a known method.

Also, by practitcing the stabilizing processing as described 40 27 above, substantially no water washing step is required, and therefore no pipeline equipment for water washing processing is required, whereby ther is the advantage that the apparatus itself can be set handily at any desired place.

Other than these processings, processing may be performed by use of the developing method for increasing the dye amount produced such as the method, in which the developing solution produced by color developing is subjected to halogenation bleaching and then again applied with color developing, or various augumentation methods (amplification processing), etc. as disclosed in Japanese Provisional Patent Publication No, 154839/1983, Each processing step is performed generally by dipping the light-sensitive material into the processing solution, but it may be also possible to use other methods such as the spray system in which the processing solution is fed in atomized state, the web system in which processing is effected by contact with a carrier impregnated with the processing solution or the method in which viscous evelopment processing is effected.

The internal latent image type silver halide emulsion is an emulsion which forms latent image' primarily internally of silver halide grains, thus having most of light-sensitive nuclei internally of the grains, and may include any silver halide, such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chlo )iodobromide, etc. Particularly, with respect to grains with great developing rate, silver chloride, silver chlorobromide, silver chloroiodobromide, silver iodochloride are preferred.

The internal latent image type silver halide grains to be used in the present invention should preferably be not chemically sensitized, if any, to slight extent.

28 Specifically, there may be included, for example, the conversion type silver halide emulsion disclosed in U.S. Patent No. 2,592,250; the core/shell type silver halide emulsion doped with internally chemically sensitized neclei or polyvalent metal ions disclosed in U.S. Patents No. 3,761,266 and i No. 3,761,276; the lamination type silver halide emulsion disclosed in Japanese Provisional Patent Publications No.

8524/1975, No. 38525/1975 and 2408/1978; and otherwise those emulsions as disclosed in Japanese Provisional patent Publication No. 156614/1977 and Japanese Patent No. 1,377,173.

Hereinafter, the silver halide emulsion of the present invention refers comprehensively to the internal latent type dire.t positive silver halide emulsion and the negative-type silver halide meulsion, unless otherwise specifically noted.

The silver halide grains to be used in the silver halide emulsion of the present invention may be one notained according to any of the acidic method, the neutral method and the ammoniacal method, Said grains may be grown at one time, or grown after preparation of seed grains, The method for preparing the seed grains and the method for growing the seed grains may be either the same or different, The silver halide emulsion of the present invention may be prepared either by simultaneous mixing of the halide ions and silver ions or by mixing of the other with a solution in which one exists, Also, it may be formed by adding successively the halide ions and the silver ions while controlling pt and pAg in the mixing kettle in view of the critical growth rate of silver halide crystals. By this method, silver halide grains with regular crystal forms and grain sizes approximate to uniform can be obtainedd. After the growth, the halide composition of the grains may be varied by use of the conversion method.

29 The silver halide emulsion of the present invention can be controlled in grain size of silver halide grains, shape of grains, grain size distribution and growth rate of grains by using optionally a silver halide solvent during its preparation.

The silver halide grains to be used in the silver halide emulsion of the present invention can be added with metal ions by use of at least one selected from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (compleses containing the same) and iron salts (complexes containing the same) in the process of forming grains and/or the process of growing the same, thereby incorporating these metal elements internally of the grains and/or on the surfaces of the grains, or can be placed in an appropriate reducing atmosphere to impart reducing sensitizing neclei to the inner portions and/or the surfaces of the grains.

The silver halide emulsion of the present invention may have unnecessary soluble salts removed or contained as such after completion of growth of silver halide grains. When said salts are to be removed, it can be practiced on the basis of the method as disclosed in Research Disclosure No. 17643.

I e The silver halide grains to be used in the present invention o, may have a uniform silver halide composition distribution within the grain or core/shell grains with different silver halide compositions betweer the inner portions and the sur- Sface layers of the grains.

The silver halide grains to be used in the silver halide emulsion of the present invention may have regular crstal forms such as cubic, octahedral, tetradecahedral forms, or irregular shapes such as spheres or plates. In these grains, any desired ratio of the (100} plane to the (111) plane can be used. Also, these crystal forms may have a composite l L 30 form, and grains with various crystal forms may be mixed therein.

The silver halide grains of the present invention may have an average grain size (grain size: as defined below) preferably of 5 pm or less, particularly preferably 3 pm or less.

The silver halide emulsion to be used in the present invention may have any desired grain size distribution. An emulsion with a broad size distribution (called polydispersed emulsion) or an emulsion with a narrow grain size distribution (called monodispersed emulsion. The monodispersed emulsion as herein mentioned refers to one with the value of the standard deviation of the grain size distribution divided by the average grain size of 0.20 or less, preferably 0.15 or less. Here, the grain size refers to the diameter in the case of spherical silver shape.) either alone or as a mixture of several kinds. Also, the polydispersed emulsion and the monodispersed emulsion can be used as a mixture.

The silver halide emulsion of the present invention may be also prepared by mixing two or more kinds of silver halide emulsions separately formed.

25 The silver halide emulsion can be chemically sensitized in conventional manner. More specifically, the sulfur sensi- S tizing method, the selenium sensitizing method, the reducing sensitizing method, the noble metal sensiti.ing method by use of gold and other noble metal compounds, etc. may be used either singly or in combination.

The silver halide emulsion of the present invention can be optically sensitized to desired wavelength region by use of a dye known as the sensitizing dye in the field of photography.

The sensitizing dye may be used alone, but a combination of two or more kinds may be employed. Together with a sensi- 31 tizing dye, a potentiating sensitizer which is a compound having itself no spectral sensitizing dye or absorbing substantially no visible light, but potentiating the sensitizing action of the sensitizing dye, may be also contained in the emulsion.

In the light-sensitive silver halide photographic material of the present invention, for improving sharpness, it is preferable to use an AI dye, particularly an AI dye represented by the formula (AI (AI (AI II), (AI III) or (AI IV) for the purpose of decoloration.

(Rf 4 )q 0(10S)m 0 (AI I) OL (Rf)p (S0 SCH CH 3 wherein X represents a chalcogen atom, C group, Rf group, LI, L2, L3, L4, L 5 and L 5 each represent a methine group; Rf£ represents an alkyl group or an aryl group; Rf I represents a substitutable group; Rf 2 represents an aryl group, a heretocyclic group, an amino group, an acylamino group, an imide group, a ureido group, a carboxyl group, an alkoxycarbonyl group, a (ICC carbamoyl group, an alkoxy group, an aryloxy group, a hydroxy group, an alkyl group or a cyano group; RfC 3 represents an alkyl group; Rf, represents a substitutable group; M represents a hydrogen atom or a cation; I represents 0.1 or 2; m represents 0, 1 or 2; n 2 and n 3 each represent 0 or L; p represents an integer of 0 to 5; and g represents an integer of 0 to 4; provided that I m 0.

32- (Rf' )q L iL L2 =n<L L4 n g Le R fr (Al -I' (M0S) n LfL 0 Rf 3 w wherein W represents a hydrogen atom, an alkyl group or a heterocyclic group; Rf 2 represents an alkyl group, an aryl group, a heretocyclic group, an amino group, an acylamino group, an imide group, a ureido group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an aryloxy group, an alkoxy group, a hydroxy group or a cyano group; Rf 3 represents an alkyl group; Rf 4 represents a substitutable group; X represent CH C Rf chalcgen aom, CH 3 C 3 a chlcogen atom, C group, group, 1

L

2 L 3 L 4, 1 5 and LS each represent a methine group; Rf 5 represents an alkyl group or an aryl group; M represents a hydrogen atom or a cation m represents 0, 1 or 2; n, n 2 and n 3 each represent 0 or 1; and g represents an integer of 0 to 4.

Rf7~IiiRf; dp/n 0 HO N (A II)

(CH

2 )m (CHg)M 3 11 1 Rf RfC wherein R"6 and RE' each represent a hydrogen atom, an alkyl group, an aryl group or a hoterocylic group; RE and Rf 7 each represent a hydroxy group, an alkoxy group, a substituted alkoxy group, a cyano group, a 33 trifluoromethyl group, -COORf -CONHRf8, -NHCORf 8 an amino group, a substituted amino group, substituted with a alkyl group having 1 to 4 carbon atoms or a cyclic (CH 2 amino group represented by: -N X" (CH 2)q (where 2 and each represent 1 or 2, and X represents an oxygen atom, a sulfur atom or -CH 2 group); Rf 8 represents a hydrogen atom, an alkyl group or an aryl group; L represents a methine group; n represents 0, 1, 2; and m represents 0 or 1.

Rf 3 0 0 Rf I I !I N 0. 0 -C C LEL Wc (Al 1I1) C ii RTc O 09 RG, Rf 31 0 OH Rfa2 wherein r represents an integer of 1 to 3; W r.presents an oxygen atom or a sulfur atom; b represents a methine group; RE 31 to Rfe 34 each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a heterocylic group, of which at least one is a substituont other than the hydrogen atom, R f IL R fc i" (Al IV) 0 Rf 44 463 wherein I ropresents an integor of I or 2- L represents a methine group; Rf,4 1 represents an alkyl group, an aryl group or a heterooacyclic group; Rf 42 represents a hydroxy group, an alkyl group, an alkoxy group, a substituted alkoxy group, a oyano group, a trifluoromethyl group,

-COORE

8 -C0NRf8, -NHCORr 8 an amino group, a substi- 34tuted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or a cyclic amino group represented

(CH

2

P\

I by: -N H) X (H2)q (where p and each represent 1 or 2, and X represents an oxygen atom, a sulfur atom or -CH 2 group); Rf 8 represents a hydrogen atom, an alkyl group or an aryl group; Rf 43 represents -OZ. group or a group:

Z

2 group; Z, Z 2 and Z3 each represent a hydrogen z 3 atom or an alkyl group, Z 2 and Z 3 may be either the same or different, or can be bonded together to form a ring;

RP

44 represents a hydrogen atom, an alkyl group, a chlorine atom or an alkoxy group.

First, the formula (AI I) is to be described in more detail.

RfE represents a group which can be substituted on a phenyl group, and example of substituents may include an alkyl group a methyl group, an ethyl group, a butyl group, etc,), which may be further substituted with, for example, a halogen atom, a cyano group, a sulfo group (which can be further substituted); an alkoxy group a methoxy group, an ethoxy group, a butoxy group, etc.); a hydroxy group; a cyano group; a halogen atom a chlorine atom, a bromine atom, a Cluorine atom, etc.), a carbamoyl group; a sulfamoyl group; an acyloxy group an acetyloxy group, etc.); aln akoxycarbonyl group a methoxycarbonyl group, an othoxycarbonyl group, etc.); a carboxy group; a sulfo group; an aryl group a bonzyl group); an aryloxy group a phonoxy group, etc.); and the like.

The aryl group represented by RE 2 may include, for example, respective group of a phenyl group, a tolyl group, a p-moth- 1 L- oxyphenyl group, p-pentadecyloxyphenyl group, a p-sulfophenyl group, a p--zarbamoyl group, a phenyl group, a p-cyanophenyl group, a p-butyisulfonylphenyl group and the like.

The heterocyclic group represented by REf 2 may include, for example, a thienyl group, a furyl group, a benzofuranyl group and the like.

The amino group repres-ented by Rf is inclusive of substituted amino groups, as exemplified by an n-butylarnino group, a phenylamino group and others, The acylamino group represented by RE.~ may include, for example, a benzoyiamino group, an acetylamino group, a 2- (2,4-di-t-pentylphenoxy)butyryi1'4amino group and the like.

The imide group represented1 by REf 2 may include, for example, a phthalimide group, a succinimide group and the like, The ureido group represented by RfE- may include, for example, 2 an NI-methylureido group, an N'-.(2-c~vorophenyl)ureido group and the like, The alkoxycabonyl group represented by RE 2 may include, for example, an ethoxycarbonyl group, a hy(Iroxyethoxyethoxycarbonyl group and the like.

The carbamoyl group represented by Rf 2 is inclusive of substituted carbamoyl groups, as oxemnplited by an N-phenylcarbamoyl group, an N-p-methylsuilfonylphe-nylcarbamoyl group, an N-p-carboxytphenylcarbamoyl group and tre like.

The aryLoxy group represented by RE 2 may inc Lude, Cor example, a phenoxy group, a p-LoLyLoxy group and the Like.

The alk')Xy group represented by RE, may include, for example, a methoxy group, an ethoxy group and the like.

36 The alkyl group represented by Rf 2 may include unsibstituted J alkyl groups such as a methyl group, an ethyl group, an I n-butyl group, a t-butyl group, a dodecyl group and the like; and substituted alkyl groups. As the substituent of the Ssubstituted 9lkyl group, there may be included a halogen atom a fluorine atom, a chlorine atom, a bromine atom, etc,), a cyano group, a sulfo group, a hydroxy group, a d carboxy group, an alkoxycarbonyl group (eqg., a methoxycarbonyl group, an ethloyycarbonyl group, etc.).

RE

3 represents an alkyl. group (preferably an alkyl group having I to 12 carbon atoms), Said alkyl group is also inclusive of substituted alkyl groups Other than unsubstituted alkyl groups a methyl group, ant othyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-hexyl group, etc.), and as the substitue-nt, it may have a halogen atom a chlorine atom, a bromine atom, etc.), a cyano group, a carboxy group, a sulfo group, a sulfoalkoxy group having 1 to 6 carbon atoms a sulfopropoxy group) an alkoxycarbonyl group having 1 to 6 carbon atoms an ethcxycarbonyl group, a butoxycarbonyl group, etc.).

Rf 4 represents a substitutable group, and Qxamples of sub- 0.2 stituent may include a halogen atom, an alkyl group, an alkozy group, an aryloxy grouIp, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, etc, The halogen atom represented by Rf,4 may be, for oxample, a fluorine atom, a chlorine atom and a bromine atom; Ithe alkyl group may be, for example, Il Methyl group, an ethyl group, a t-butyt group, a mothoxymethyL. groop, a carboxymethv-i group, etc.;t the alkoxy group may be, For ex::,nple, a methoxy group, an ethoxy group, ec;the aryloxy group may be, for examplo, a phenoxy group; the alkoxycarbonyl group may be, for example, an othoxycarbonyl truup, a butoxycaroy ruoo. h abmy group may be, for example, an N,-iehl.abmy r'up, an 37- N,N-tetrar~ethYlenecarbamoy. group, a morpholinocarbaroyl I group, etc.; the sulfamoyl group may be, Eor example, an N, N-dimethylsulfamoyl group, a piperazinosulfonyl group, etc.

As the calcogen atom represented by X, there may be included, for example, an oxygen atom, a sulfur atom, a selenium atom and a tellurium atom.

The alkyl group represented by RE 5 may be the same as the alkyl group mentioned for Rf 3 Ex<amples of the aryl group represented by Rf 5 may include a phenyl group, a tolyl group, a p-sulfophenyl group, a p-carboxyphenyl group, a p-sulfamoylphenyl group and the like.

The rethine group represented by G11 L21 L431, 1 L5 and may be substituted and examples of the substituent May include a lower alkyl group having 1 to 6 carbon atoms a methyl group, an ethyl group, a propyl group, an isobutyl group, an aryl group Ce~g.9, a phenyl group, a p-tolyl group, a p-chlorophenyl group, etc. an alkoxy group having 1 to 4 carbon atom a Methoxy group, an Qthoxy group, etc an aryloxy group a phonogy group, etc, an araikyl group (ega berizyl group, a phoriethyt group, etc.),I a heterocyclic group a thienyt group, a furyi group, etc.) a oubstituted amino group a dimethyl- 2$ amino group, a teramethylenearnino group,annliogup etc.) ani atkyithio group Ia mothylthio crup and the tiko. Also, and r'4 t or L44 anid'1 can be tLnkod toqcethor to form a or G-momberod oorbon ring.

1) The cation represenited by Mt may iniclude n lka It meto l3 (Qq, Lithium, soditum, potaesoium, etc.) alkalinie earth mo-Lata k(19 magnesium, calcium 4 barium, ItLc) aImmornium or orqanv i caiono triethytanimonium, pyridin[iUm,r ppodi Muflm, morphollun, etz. arc1 id the ike.

38 specific examples of the AI dye represented by the above formula (AI 1) ar~e shown below, but the dye according to the present invention is not limited by these at all.

(Exemplary compounds) I -I) NIa 0 3S~c >CH- CH= CH CH T- T 1z~ (I 2) c ~A I- 3) -s

Q

SO~a 39 (I 4) K03S C2HS

CONH

2 1- 6) K 0 a S 4 .SOCR SOO K a 0 Q, a 6), c0 coot~f jNa 3 S -C H C C F

(CH

2 3 So 3 Na NaOS II-Q C O =S

CHH

NaQ 3 Sr,

O

II -41- I 10) 01 OH 3 N a 03S Cl

CONH

2 0 V S0 3 Na I-il1) C 3

HSO

3 Na -QC2H I 12)

(NIQ

3 S) 2 C 2,H $Qa Na 1' 42 I 13) Na 0 3 S CH C CH

C

2 SOo -Na (1-14) 0~' 0 2 4 02 4 4, 4 4 NaO 3 S <HC CHO N CzHs

SQ

3 Na 4 I (1 NaO 3 S C- Cti N 11CON H CH SOQa Na 43 I 16) N aO aS CH- CH= CH- CH C 2 H SO 4N a I 17) 0 U 0 00 o o 0 *0 00 U U 0 0 0 0*0* 0 0I 00 0 a, 0~ U 000 00 00 000 0* 0 a 00 *000 0 0*00 0 0*0100 0 0 00 X a 3 S H H z- CH CHCOOH

CZH

03jN (1I 18) K0Q 3 S CH -,cif= cl- I COOC 2 H QOdT 4 COOH 0 S03 K

I

44 I 19) NaOsS -CH- C 2 H s SOj Na SO 3 N a 1- N a 3 S c- H cH=c H cH C2H 4

SO

3 Sa IN- 0 3 S So3 Na a 4 aa a a (i -21) NaQ 3 S CH CH =CH -CH SO, N a __j

I,

45 I- 22) (NaO3S) 2 -cJC CH- CH=CH-- CO NH 2 I 23) Na 0 oS CH -CH =CH CHj GHCOC Vz~ 0115s I- 24) Na03S CH C R C

-CF

,8sO Na N aa 3

S

46- N a03 S N CI-CH=CH-CH' C (126) Te NaCS- C-H=CH-CH-UTH C 2 H $034a (127)

CH

3 Cli, X0 3 S CH -CH CH -CHN o~f

C

2 Hs 47 I- 28) C2H 5 NaO 3 s

OH

3

OH

3 00 CHO I h-aoa (1I- 29) Nao 3 s C -C =Cf-C

C

2 S 0 N a (1I- caL 8 0

I

48 I 31) Na 3 S- CH-CH=CH-CH=CH-C

C

2 H5

C

SO

0 Na (1 -32) 4> 0 0 e~oI Nao~~s CH -CH CH (OH2) SQ 3 Na a> a o aOl 00 a 00 0000 oaooa 0 0 $03 Na (I 33) NaO 3 S CH C CH- QCf COO H 303 Na 49 (1I- 34) K CONH 2 0

N

NaO, 3 S SQ0 Na (I

CH-

(CR 03ooa N'a0~s -36) 0 0,

Q

3

C

2

H

5 s so I 37) C2H 5 aS 0

SO

3 Na (I1 38) 0 o 0 p u 0 0 o *~o 0 0

S\O

3 (I 39) 0 p' 0 C 0 0 00 (CHz~oSOojNa 's~i Na 51 I -40) (OHa) 3 S Na Ka 0 O -41) CU C 2 4 SO aNa SO0 Na (I1 42) OR CfI.iQO 2 C~fls SO~a NaQu$ 52 (1I 43) I 44) Na03S S0 Na 9Uf CH3 CIIco CU* 7 0. N I 02us 53 (I46) CH CH CONH 2

C

2

H

5 1 IN ao SOO Na (47) 0 H CHQHH C -CH 2 0H O TGi-flR=CH CH oCl

N

0 54 (I 49) CH -CH;=CH- CH (CHz),SO 3 Na Na (1I C H C j C i C

C

4 He~ K03s, 51) CH= C C coxf-e- co, N~a NaoaS" SQa Na 55 I -5'2) -CH-CH=GH-CH K0 3

S

3

H

7 0 H=CH-C CI -53) 2 CFzCF 13 Na S 0 Na I 541)

CHS

cCCH CH -CH OH(H3

CH

3 O N (g)SNa

NN

NaQ~s SO 3 Na 736 I C- CH CH CHT C 2

H

5 s CHzCOOC 2

H

I 56) r Se

CI{

2 =0CH ,ce-C~I-C~T C~dr

I~

K03S S0aK (I1 57) c( Te CH Ch C H N KO~S S0 3

K

57

CH

3

CH

3 HO CH -CH CH- CH /CNH2

(CH

2 4 SOiUNa

SQ

3 Na SO 3 Na

-N

CH -CH CH-C H

CF

3 0410 SO a a CfN C- CH CH H- CH CR SO4a NaO 3

S'

II 58 (I 61) CH 3

CH

3 CH CH CH G AI;1 C-il C i CH i C 2I 2A C H 3 N' a0 3 S S S0 3 N a 62) 9 3r 9999 99 9P

CHL

3 O N f-

C:

C11 CH l CH-CH= CH-c-

CONH

2

H

4

OH

-OH

NaO 3 S C 33N '25 The Al dye represeit;ed by the above formula (Al 1) can be fit. easily synth(sized according to the synthetic methods as described in U.S. Patents No. 2,493,747 and No. 3,148,187.

Nextf, the forqitia (Al is to be described.

The alkyl group represented by W is inclusive oE those having subs~ituents and may includle, for example,.straight or branched groups such as a methyl group, an ethyl group, an isobutyl group, etc.; cyclic groups such as a cyclopentyl group, a cyctohexyL group, etc.; substituted alkyl groups such as an allyl group, a benzyl group, a 2-hydroxyethyl group, a hydr- 59 oxyethoxyethyl group, a 2-methylsulfonylethyl group, a 2carbamoylethyl group, a 2-sulfamoylethyl group, a 2-(N,Ndimethylamino)ethyl group, a 2-cyanoethyl group, a 2-(22,23tetrafluoro)propyloxyethyl group, a 3-ethoxycarbonylpropyl group, a 3-succinimidopropyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a carboxymethyl group, a carboxyethyl group, a p-sulfobenzyl group, a p-carboxyphenethyl group, etc. The heterocyclic group represented by W is inclusive of aromatic and saturated types, including substituted or unsubsituted groups such as a 1,1-dioxothiolanyl group, a 2group, a 6-sulfo-2-benzothiazolyl group, a 2-pyridyl group, a 2-pyrimidyl group, etc., but W may be preferably a group substituted with an acidic group.

The alkyl group represented by Rf 2 is inclusive of those "o°o having substituent, and examples thereof may be straight or branched groups such as a methyl group, an ethyl group, a t-butyl group, a dodecyl group, a 2-ethylhexyl group and the like; substituted alkyl group such as an allyl group, a benzyl group, a carbamoylethyl group, an ethoxycarbonylmethyl group, a cyanomethyl group, a 2-sulfamoylethyl group, a 2-phenoxyethyl group, a carboxymethyl group, a p-sulfobenzyl group and the like.

As the aryl group, a heterocyclic group, an amino group, an acylamino group, an imide group, an ureido group, a carboxy group, an alkoxycarbonyl group, a carbamoy! group, an aryloxy group, an alkoxy group, a hydroxy group and a cyano group, those mentioned as examples for Rf 2 in the above formula (AI I) can be enumerated as specific examples, respectively.

The alkyl group represented by Rf 3 is inclusive of those having substituents, and examples thereof may include a methyl group, an ethyl group, a 2-(2,2,3,3-tetrafiuoopropyloxy)ethyl group, an allyl group, a benzyl group, an ethoxycarbonylethyl group, a 2-hydroxyethyl group, a carbamoylp.- 60 methyl group, a 2-cyanoethyl group, a carboxymethyl group, a p-carboxyphenethyl group, a p-sulfobenzyl group, a 3-sulfopropyl group, a 2-sulfoethyl group, a 4-sulfobutyl group, etc., preferably alkyl groups substituted with acidic group such as a carboxymethyl group, a p'-carboxyphenethyl group, a p-sulfobenzyl group, a 3-sulfopropyl. group, a 2-sulfoethyl group, a 4-sulfobutyl group, etc.

For Rf 4 1, Rf 5 1, L 1 to L 6and m, the respective descriptions for Rf 4 f Rf 5 'K to L 6 and mn are applicable.

In the following, specific examples of the AI dye represented by the formula (AI 1) are set fort., (Exemplary compounds) 00 0, 00 C H~ (CfC! 2 XSO 3Na

S

C2H$O C O 0 CH1 S03 Iv 61 -3 -4 N a O a S

O

C

2 H 4 (1 0 CE1 2 COC2HS 0 00 0 0 0 0 0 44 jig 4 00 o 4 0 044 44 4 4 4 I 4 4 4 4 4 44 6 Na~oS, (CHI)aSO~Na S0-CF 62 -7 \-CH -CH

CONH

2

CH

3 Q (CH03)SO 3 Na

CH.

2 SOpNa I' 8) 0 0 Se ~~Cfl-CH-

CH

3 0 I

(QH

2

>COOI

CC)~$Q~

3 Na 0'0 0 '0 0 00 000 (11 -9 CH 3Oa N AN

(CR

2 63 I I 0 CH -CH-

(CH

2 )OS0INa 0 so Na 0 sS CH O 3 NaOi S~ 'R~t SO 3Na, o I 12) HOOC 64 I-13) -CH 0 C Hl

HOQC

C

2 H1 4 C00011 3 1 (I 14) ~2 4ao 8-H+SO A oi 2 H 44 G 65 I 6) CH- CH= CR- CHI (C 2 3 SO3Na 2 3SO3Na (I 17) C[2Cf{ 2

OCH

2

CF

2 CF2H CH CH- CH- CH o 8

N

CHC

CH

2 cH- COOn

A

I -I "P.

HOOC C2[+SO3 Na0 CONif SO 3

N~

'7 66 19)

CO

CHO CH= CH-

OH

(CH

2 ),S0 3

K

S0 3

K

(V c~ CH-- CR=CH- CH) ff OM\ -cooH

C

2

HSO

3 Xa 0 CH2CF 3 (f 21) CHO

CHO

N

7 ~SOa N a (CfH) 4

SO

3 Na C2 COO CH 67 (I 22)

OH

3 CHa INa 3S a c C H -CH=CH CH C H 2

COOC

2 H s

(OH

2 3 SOA a 00 0

C

2 CCH3N (I 24) cCH C H C H CH CON1\.,

(CHOOSO

3

CH

2 Cff2CH 2

SQOX

68 (1 Nao, sCH: 3

CH,

N -CH -CH =CH -CH COOC 2

H

CH

3 41 W1 -26) C2H CH-CH=CH-CH

C

S/

N

$lot'-27) NaOS3 C H c H c H c c H H CH 8 02 H 5

N

C2HsU

-IN

69 0113 CHI s Na0 3

S

(CH2) 4

SO

3 Xa

C

2 1140 H 44 t (1 29) CHI CHI CII ~CH= CH-C, aC' OHI

OH

0211 11 25 In the frormula (Al II), Rf 6 and Rf 6 each represent a 4 hydrogen atom or an alkyl group, an aryl. group or a heterocycic group which may be each substituted, and the aryl group may be a 4-sulfophenyl group, a 4-(cL-sulfobutyl)phenyl group, a 3-suifophenyl group, a 2,5-disulfophenyl group, a 3,5-disuifophenyl group, a 6,8-disuifo-'2-naphthyi group, a 4,8-disulfo-2-naphthyl group, a 3,5-dicarboxypheniyl group, a it-dicarboxyphenyt group, etc., and the aryl group can have a suLifo group, a suiloalkyL group, a cavboxy group, an alkyt group having 1 to 5 carbon atoms a methyL group, an ethyl group, etc.), a halogen atom, (e.gs, a chlorine atom, a bromine atom, etc.), an aikoxy group having 1 to 4 carbon 70 atoms a methoxy group, an ethoxy group, etc.), or a phenoxy group, and others.

The sulfo group may be bonded through a divalent organic group to an aryl group to form, for example, a 4-(4-sulfophenoxy)phenyl group, a 4-(2-sulfoethyl)phenoxy group, a 3-(sulfomethylamino)phenyl group, a 4-(2-sulfoethoxy)phenyl group and the like.

The alkyl group represented by Rf 6 and Rf 6 may be either straight, branched or cyclic, having preferably 1 to 4 carbon o0 atoms, such as an ethyl group, a f3-sulfoethyl group and the 09 like.

15 Examples of the heterocyclic group may include a 2-(6-sulfo)benzothiazolyl group, a 2-(6-sulfo)benzoxazo, yl group and the like, which may have subscituents such as a halogen atom a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group a methyl group, an ethyl group, etc.), an aryl group a phenyl group, etc.), a carboxyl group, a sulfo group, a hydroxy group, an alkoxy group a phenoxy group, etc.).

i r "ge: Rf and Rf each represent a hydroxy group; an alkoxy group having 1 to 4 carbon atoms a metho.:y group, an ethoxy group, an isopropoxy group, an n-butyl group, etc.); a substituted alkoxy group such as alkoxy groups having 1 to 4 carbon atoms substituted with a halogen atom or an alkoxy group with up to 2 carbon atoms a -chloroethoxy group, a 8methoxyethoxy group, etr.); a cyano group; a trifluoromethyl group; -COORfa; -CONHRf a; -NHICORfa (where Rfa represents a hydrogen atom; an alkyl group, preferably an a' Yxy group having 1. to 4 carbon atoms; or an aryl group such as a phenyl group, a naphthyl group, and said alkyl group and aryl group may have a sulfo group or a carboxy group as the substituent); an amino group; a substituted amino group substituted 71 with an alkyl group having 1 to 4 cabon atoms an ethylamino group, a dimethylamino group, a diethylamino group, a di-n-butylamino group, etc.); or a cyclic amino

(CH

2 group represented by: -N X (CH2) q (where p and q each represent an integer of 1 or 2, and X represents an oxygen atom, a sulfur atom or -CH 2 group) a morpholino group, a piperidino group, a piperazino group, etc.).

The methine group represented by L may be substituted with an alkyl group having 1 to 4 carbon atoms a methyl group, o0 an ethyl group, an isopropyl group, a tert-butyl group, etc.) 15 or an aryl group a phenyl group, a tolyl group, etc.) Also, at least one of a sulfo group, a sulfoalkyl group and a carboxy group of the compounds may form salts with alkali metals sodium, potassium, etc.), alkaline earth metals calcium, magnesium, etc.), ammonium or organic bases a diethylamino group, a triethylamino group, a morpholino group, a pyridinyl group, a piperidinyl group, etc.). n Srepresents 0, 1 or 2. m represents 0 or 1.

i 2j Specific examples of the compound represented by the above formula (AI II) are shown below, but the present invention j is not limited by these at all.

.i 72 (Exemplary compounds) ON C-C =CH- C-C CN, O HO~~~ S0 3 KS0 (11- 2)

CX-C-C=CH-CH=CH-C--CN

N 0 HON KQ3S S0 3 K K0 3 S S0 3

K

C X- C- C C H- CH C H- C- C-C X S 11 S K 0 S S 0 3

K

-73 (1 4 CN- 0-0= CH- C-C- CN NaMa SO 3 Na *0 #4 00 4 0 0 4 0 00 *4 0 14 0908 04 94 (11 -5 NaOO( COONa COO Na 0 0O Na 14 90 14 14 14 flit (1-)oo COO- SO 31N 2

SO

3 Vi2 503 a 74 -7) HOOC- CH- C-C- CoCH s I X I I o o o (11-8) o ts RONC- C--C CH CH CH- C-C COOH 0 II II S*3 $03K 9j HOO C -0 OH -CtHOH 011CH C- C--C-COO 1 II IIHo Soo K

CH

5 QOC-C--C=CH--CH=CH-CH= CU- C-C-COOCglH 0 N "C 0 o Pa 0CK S0O o0 0 0060 H 09 NN

HO

19.) S~N L f-C=ci H C 76

I-S)

HO-C-C=CH-CH=CH-CH=CH- C-C-OH 0 HO S03K S03., (114) PvOOC-C-C:,;CH -CH;7-CH -CH CH C-CCOH 0 HO X, NHCU~SON~ .XtCHSsNa 1115) S0a N SOa It 16 HNCO- C-C= CH- CH= CH-C-C-CONH 2 l~-1 HO "NA S03K S0 3

K

HO

Q11aCONt1 -C-C QH- OR= OR Ctt: CH C-C- N" 1c 0CII 3 III HO 4 K So a K 78 (-19) H, NCO- C C=CH- CH= CHCH= CH-C--CONH 2 0I H IN, S0 3 K so a It (1120) HOO-C-C=CR-CH=CR-CR=Cfl-- OCH KOI S

K

(t-21) ClioCQNR QH O CH C-C-NCOC11 3 79 H -22) 04 44 o 0 *0 o i 0* *0 *ee* 0 *0 4, 0 4 0o 4 4 4 HOOC-C-C CH -CH OH C-C-COOH S0 3 K 3 3 K0 3 S K0 3

S

(123) C z H 00C C-C H C H CH -C-C -COC H N oz 0 H SQ3A S0 3

K

24) S0 3 K so", SOaK SOOK (1125)

(C

4 Hs) 2 N-C-C=Cl- CH=CH- CH=CH-C-C- IN(C 4 .H9- fl)2 4S03( 0 3

K

I (Ri -26) 0 2 N- CH CH C CH C1 C-C-N 0H

HON

SO

3 NH4NCH) So 3 NCH

KO

3 S NHCO- C-C=CH-CH=CH- C CONH- \SOK 1 -1 N' C 0 HO/ N,--N H H 44 (II 29)

KO

3 S- \NHCO- C-C=H CHCH= CH- C-C- coqH- HO ii SI0 CHCH:$SOK CHCHeSO 3

K

In the formula (AI III), c represents an integer of 1 to 3, W represents an oxygen atom ald a sulfur atom, L represents a methine group, RE 3 1 to Rf 34 each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a heterocyclic group, of which at least one is substituent other than a hydrogen atom, The methine group represented by L can include those as described in the item of the formula (Al 11).

The alkyl group represented by Rf 3 1 to RE34 may include the same alkyl groups as mentioned for RE 6 and RE 6 in the item of the formula (AI II), and said alkyl groups may include various substituents to be introduced into the groups of a sulfo, a carboxy, a hydroxy, an alkoxy, an alkoxycarbonyl, a 82 cyano and a sulfonyl. The aryl gropu represented by Rf 3 1 to Rf 3 4 may be preferably a phenyl group, and the substituent to be introduced onto the phenyl group may include vairous ones mentione as the substituent to be introduced into the groups of Rf 6 and Rf 6 in the item of the formula (AI II), and it is desired to have at least one of a sulfo group, a carboxy group, a sulfamoyl group on the aromatic ring.

The aralkyl group represented by Rf 3 to Rf 3 4 may be preferably a benzyl group a phenethyl group, and the substituent to be introduced into the heterocyclic group may include the ,0 same substituents on the aryl group of Rf 3 1 to Rf 3 4 as desai cribed above.

0 ,15 The group represented by Rf 31 to Rf 3 4 may be preferably an alkyl group or an aryl group, and further the barbituric acid i and the thiobarbituric acid represented by the formula (AI III) should desirably have at least one of a carboxy group, a sulfo group and a sulfamoyl group within one molecule, pre- S 20 ferably of the symmetric type.

I

Typrical specific examples of the compounds represented by Sthe above formula (AI III) are shown below, but the present invention is not limited by these at all, (Exemplary compounds) (if- i) CH, COOH CHt 2COO o o 0 0 O-K- 0 H -1 0 o o

I

-83 CH~C0OH CH 2 C00H 0 0 CH~c~OH1 CHZCOOH H CH

Q

0 nO (M fa-o4) o l 2 CO CHI: 2

CCQH

*1~I so~ll SO IN

I

so 2 N if z 84 Off- 5

CH

2 C00H 2COOH OH- OH

C

4 ,He -n C4iH- (MlI- 6

CH

2

COOH

00 00 N" q tir2Cnt1 OH-CH= CH Cfl=CW C. -n, i (il- 7 Mg cC00!{ 0% 11 off C =CH- H,-C73-, 110 In the formula (AI IV), I represents an integer of 1 or more, L represents a methine group, Rf 41 has the same meaning as Rf 6 and Rf 6 in the formula (AI II), preferably an alkyl group and an aryl group, which aryl group should desirably have at least one sulfo group.

Rf 42 can introduce all of the substituents shown for Rf 7 and Rf 7 0 in the formula (AI II), preferably selected from an alkyl group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, a ureido group, an acylamino group, an imide group and a cyano group.

Rf 43 represents -OZ 1 group or group, where Zl, Z2 and z 3 2 3 each representa hydrogen atom, an alkyl group, Z 2 and Z 3 being either the same or different or bonded together to form a ring.

The alkyl group represented by ZI, Z 2 and Z 3 may include, for example, a methyl group, an ethyl group, a butyl group, a hydrQxyalkyl group a hydroxyethyl group, etc.), an alkoxyalkyl group a -ethoxyethyl group, etc.), a carboxyalkyl group a f-carboxyethyl group, etc.), an alkoxycarbonylalkyl group a 3-ethoxycarbonylethyl group, etc.), a cyanoalkyl group a group, etc.), a sulfoalkyl group a -sulfoethyl group, a y-sulfopropyl group, etc.) and the like.

S

2 and Z 3 may be bonded together to form a 5- or 6-membered ring, specifically a morpholino group, a piperidino group, a pyrrolidino group, etc.

Rf 44 represents a hydrogen atom, an alkyl group, a chlorine atom, an alkoxy group, and the alkoxy group may be exemplified by a methoxy group, an ethoxy group, etc, 86 Typical specific examples of the above formula (AI IV) are shown below, but the present invention is not limited by these at all.

(Exemplary compounds) (IV-1

HOH

4 Ca C CZfi 4 SO3Na 0 0 0 Ni COh O.N (IV 2) 000 CQ H 2 SO 3 N a 87 (TV 4

HOOC

~CHCH=CH

\<H

Soo Na g~q 41 ~a I I *1 *4 1 41 41 44 (IV- 5 H 3

C

CR

3

N<

S0jNa I 4.411 441444 4 1 (IV- 6 HOOC {f}CH N IOez CH: OONa d~~Yrl*~IIP*PUII~-.- 88 (I -7)

C

2

H

'c 2 1 S0O3 8) 4 04 I HNQCHN

C,-CHI

C'H H 4 SO Xa 1 803 Na ,42 5* The compounds reposen ed by the above formula (Al It), (Al III) Or (Al IV) can be synThesized according to the synthetic methods as described in U.S. Patents No, 3,575,704, No. 3,247,127, No. 3,540,887 and No, 3,653,905, Japanese Provisional Patent Publications No. 85130/1973, No, 99620/- 1974, No, 111640/1984, No, 111641/1984 and. NQ. 17083/1984.

The AT dye according to the present invention has the property of beLng decoicred in the photographic development processing bath by The peesence of hydroxylamnine.

The AI dye oF t he present Invention can be used as the irL-adiation preventive dye contained in The 19 t-~sonsitiLve 89 silver halide emulsion, or alternatively as the filter dye or the halation preventive dye contained in the non-sensitive hydrophilic colloid layer. Also, two or more kinds of the dyes of the present invention may be used in combination depending ont he purpose of use or also combined with other dyes. The dye according to the present invention can be contained in the light-sensitive silver halide emulsion layer or other hydrophilic colloid layers easily according to conventional methods. Generally, the dye or an organic or inorganic alkali salt of the dye can be dissolved in water to make up an aqueous dye solution with an appropriate concentration, which is then added into a coating solution, followed by coating according to a known method to incorporate :4 the dye in the photographic material. The amount of these 15 dyes contained, which may differ depending on the purpose of 2 use, is generally 1 to 800 mg coated per 1 m of area of the photographic material.

In addition to the AI dye of the present invention, further other dyes may be used in combination, Examples of dyes available in combination may include the pyrazoloneoxonol dyes disclosed in U.S. Patent No. 2,274,782; the diarylazo dyes disclosed in U.S. Patent No, 2,956,879; the styryl dyes or the butadienyl dyes disclosed in U.S. patents No, 3,423,207 and No. 3,384487,; the merocyanine dyes disclosed in U.S. Patent No. 2,527,583; the merocyanine dyes and oxonol dyes disclosed in U.S. Patents No. 3,486,897, No. 3,652,284 and No. 3,718,472; the enaminohemioxonol dyes disclosed in U.S. Patent No. 3,796,661; and the dyes disclosed in GB Patents No. 584,609 and No. 1,177,429; Japanese Provisional Patent Publications No. 85130/1973, No. 99620/1974 and No.

L14420/1974; and U.S. Patents No, 2,533,472, No, 3,148,187, No. 3,177,078, No. 3,247,127, No. 3,540,887, No. 3,575,704 and No. 3,653,905.

Hydroxylamine in the present invention is ordinarily used in 90 the form of a salt such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, etc.

The color developing solution to be used in the present invention as mentioned above has a hydroxylamine concentration generally of, for example, 0.05 g/liter or higher, more preferably 0.07 g/liter to 4 g/liter, particularly preferably 0,2 g/liter to 4 g/liter.

In the silver halide emulsion of the present invention, for the pcurpose of preventing fogging during the preparation steps, storage or photogrpahic processing of the lightsensitive material or maintaining stably the photographic performance, during chemical aging, on completion of chemical aging and/or after completion of chemical aging, until coating of the silver halide emulsion, compounds known as antifoggants or stabilizers known in the field of photography can be added.

As the binder (or protective colloid) in the silver halide emulsion of the present invention, gelatin may be advantageously used, but hydrophilic colloids such as gelatin derivatives, graft polymers of graft with other polymers, other proteins, sugar derivatives, cellulose derivatives, synthetic 5 hydrophilic polymeric materials such as polymers or copolymors can be also used.

The photographic emulsion layer and other hydrophtlic collold layers in the Light-sensitive material by of the silver halide emulsion of the presenent invention (hueoinafter called the light-sensitive material of the present invention) can be hardened by cross-linking the binder (or protective colloid) molecules and by use of one or more kinds of film hardener for enhancing fiLm strength. The film hardencr can be added in an amount which can effect film hardoning to the extent which requires no addition Ln the processLng solution, but it 91 is also possible to add a film hardener in the processing solution.

In the silver halide emulsion laver and/or other hydrophili.colloid layers in the light-sensitive material of the present invention, a plasticizer can be added for enhancement of flexibility.

In the Photographic emulsion layer and other hydrophilic colloid layers in the light-sensitive material of the present invention, a dispersion (latex) of a water ins-oluble or difficulItly soluble synthetic copolymer can be contained, In the emulsion layer in the light-sensitive material of the prese-nt invention, in the color development processing, a dye forming COuIpler which undergoes couipling reaction with the oxidized product of an aromatic primary amine developing agent (ega p-phenyle nediamine deritive, an aminopheonol derivative, etQ.) to form a dye is used. said dye forming couplers are ordinarily selected so as to form dyes which absor'b sensitive spectral lights of the emulsion layers for the respective emulsion layer.s, ancl A yellow dye forming.

coupler is used in tho blue-oensitivo emulsion layer, a magenta dye forming coupler in the g reen- sens Itive emulsion layer', and a cya1n dye forming Coupler in the rod-sensitivo emulsion, layer, However, depending on the purpose, a lightsensi~tve silver halide color photogra!phi materiL c,-n be also prepareO In a manner dife rent from the abovo combinations' These dye forming couplers may be either tetravalent type whtich recquires 4 molecules or silver tons to be reduced focr Cration of one molecule of dyee or divnlent type whih requires only 2 molecules of oilver Ions to be roduced, Inr 3 the col(Ior CorMing coupler, it 'Ls possibLe to Locorpor(' to compounds capcible of releasing photographically usefuL Fraq- 92 ments such as development acelerators, bleaching accelerators, developers, silver halide dissolving agents, tone controllers, film hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and sensitivity reducers. Colored (rcqplers having the efEfect of color correction for these color forming coulers, or DIR couplers which release development inhibitor with development to improve sharpnes.- or graininess of image may be also used in combination. in this case, the DIR coupler should be preferably one which forms a dye of the same type as the dye formed from the color forming coupler used in the same emulsion layer, but different dyes may be also formed when turbidit*' of the color is not conspicuous. In place of DIR compound cpoduc of andeveoing aen onormea cio ithst oo.J.ompouned cpablec of undevegoing then couplngrmeaton with ta Compundsimultaneous with release of a development inhibitor maybealso used.

Acolorless coupler which undergoes Lhe coupling reaction wih theoxidized product of an atomatic primary amine developing agent but does not form a dye c-in be also used in combination with the color forming couplor.

The support to be used for the light-sensitive viaf (rial of 2$ the ptesent Invention, may include flexible, reflective supports suc h as paes ynthetic papers laminated with 'lfin polyor (egpolyethylene,. poLypropylene othylen butone cOpolyer), oto.

4 films Comprising semi-synthetic or Ad ~synithetic polymers such as; cellulose acetate cellulose nitrata, polystyrene, polyvinyl chloridEj polyothylene-' tore phthath, PolyCa1rbo.nato, polyamide, etc.ot fleXible- suppor _S of thf films provided wt.h reflective lay7orot gllaosses motals;' fearthonwcjres' etLc:.

3$ The tgtsstvomaterial o-C the presnt iniventionu can e eXposed by use of on otoctromognotic wave in the s3peCtral Ii [1 93 p @0 q~ O 0 000I eq 0 Ltgion to which the emulsion layers ,onstituting the lightsensitive have sensitivities. As the light source, all of the light source known in the art may be available, including; natural light (sunlUqht), tungsten lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cakhode ray tube flying spot, various laser beams, fluorescent diode light, electron beam, X-ray, lights emitted from phosphors excited by gamma-ray, alpha-ray, etc.

EXAMPLES

The present invention is described in detail below by referring to Examples, by which the present invention is not limited at all.

Example 1 On a resin-coated paper support, the respective layers shown below were successively applied from the support side to prepare a sample, Layer I Cyan forming red-sensitive silver halide emulsion layer According to the method shown in Japanese Provisional Patent Publication No. 127548/19$0, an internal latent image type silver halide emulsion was prepared. More specifically, 175 ml of a 2.1 mole aqueous solution of potassium chloride containing 10 g of gelatil and 175 ml of a 2 mo'e aqueous solutoin of silver nitrate were added at the same time over 10 minutes while being controlled at 60 After physical agi ig for 10 minutes, 200 ml of a 2 mole aqueous solution of potassium bromide was added, followed further by physical aging for 10 minutes. Subsequently, after removal of watersoluble halides by washing with water, 10 g of gelatin was added, and the total amount was made up to 50r m, by addition of water. The silver chloride shell was coated by adding at 94 the same time 100 ml of a 2 mole aqueous silver nitrate and 100 ml of a 2.1 mole aqueous solution of potassium chloride at 60 oC to the conversion type silver chlorobromide emulsion over 5 minutes, and then washed with water to obtain a silver chlorobromide core/shell emulsion containing 61 mole of silver bromide.

As the cyan coupler, 70 g of 2,4-dichloro-3-methyl-6-[o- (2,4-di-tert-amylphenoxy)butyramido]phenol (Cyan coupler C 2 g of 2,5-di-tert-octylhydroquinone, 50 g of dibutyl phthalate and 140 g of ethyl acetate were mixed and dissolved, and the resultant solution was added into a gelatin solution containing sodium isopropylnaphthalene sulfonate to be dispersed by emulsification.

Subsequently, the dispersion was added to the above emulsion Spreviously spectrally sensitized with the dyes and (b) 0, shown below, 1 g of potassium 2,5-dihydroxy-4-sec-octadecyl- Sbenzene sulfonate was added, followed by addition of bis- (vinylsulfonylmethyl)ether as the film hardener, and the mixture was applied to a silver quantity f ,00 mg/m 2 and a coupler quantity of 460 mg/m 2 Dye S CAfl S-CI C

(CH

2 )3SOaNa C(H2)S0 3 Dye S C2115 IC HH I -I-CH-CCH Layer 2 Intermediate layer: A 2.5 of gelat.Ln solution (100 ml) containing 5 g of gray colloidal silver and 10 g of quinone dispersed in dibutyl phthalate was coated to a collaid silver quantity of 400 mg/mi.

Layer 3 Magent forming green-sensitive silver halide emulsion layer; As the magenta coupler, 40 g of 1-(2,4,6-trichlorophenyl)-3-(2-chloro--5-octadecylsuccinimidoanilino)-5-pyrazolone, 1 g of 2,5-di-tert--octylhydroquinone (Magenta coupler M 1) 75 9 of dioctyl phthalate and 30 g of ethyl acetate were mixed and dissolved, and the resultant solution was P 0 0 added inti a gelatin solution containing sodium isopropylnaphthalene sulfonate tQ be dispersed by emulsification.

subsequently, the dispersion was added to the above emulsion previously spectrally sensitized with the dyes (c'I and (d) shown below, 1 g of potassium 2,S-dihydroxy-4-sec,,octade-cylbenzene sulfonate was added, followed by addition of bis- (vinyisulfonylmethyl)ether as the film hardener, and the mixture was coited to a -silver quantity of 400 g/m, and a 2 coupler quantity off 400 mg/m Dye

CH

U I

(CH

2 3S0bNa (OH ~Xso< Dye Wd):

=CH

(Mflaso 3 -96 Layer 4 Yellow filter layer: gelatin solution containing 5 g of yellow colloid silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was coated to a colloid silver 2 quantity of 200 mg/n Layer 5 Yellow forming blue-sensit!.ve silver halide emulsion layer: As the yellow coupler, 80 g of a~-[4-(l-benzyl-2-phenyl- 3,5-dioxo-l,2,4-triazolidinyl) (2,4-di-tert-amylphenoxy)butylamido.Iacetanilide (Yellow coupler Y 1 g of 2,5-di-tdrt-octylhydroquinone, 80 g of dibuty! phthalate and 200 g of ethyl acetate were mixed and dissolved, and the resultant solution was added into a gelatin solution containing sodium isopropylnaphthalene sulfonate to be dispersed by emulsification. Subsequently, the dispersi~on was added to the above emulsion, 1 g of potassium dihydroxy-4-sec-octadecylbenzene sulfonate was added, followed by addition of bis(vinylsulfonylmethyl)ether as the film hardener, and the mixture was coated to a silver quantity of 380 mg/rn 2 and a coupler quantity of 530 mg/rn 2 Layer 6 Protective layer This layer was coated to a gelatin quantity of 200 mg/rn In the respective layers, saponin was contained as the coating aid to prepare Sample 1.

(Y 1) 010 35O0 2 Q 1 t C 4 -97- Next, according to the method described in Japanese Patent Publication No. 7772/1971, the three kinds of silver chlorobromide emulsions A, B and C shown below were prepared, chemically sensitized respectively with the use of sodium sulfate penta hydrate, and 4-hydroxy-l,3,3a,7-tetrazaindene was added as the stabilizer: A: containing 80 mole of silver bromide; B: containing 70 mole of silver bromide; and C: containing 80 mole of silver bromide.

For B, the above dyes and were further added to give a green-sensitive silver chlorobromide emulsion For C, the above dyes and were further added to give a red-sensitive silver chlorobromide emulsion On a paper svpport laminated on both surfaces with a polyethylene, the respective layers shown below were successively provided by coating.

Layer 1 a layer containing 1.2 g/m 2 of gelatin, 0.32 gam of (calculated on silver, hereinafter the same) of a bluesensitive silver chlorobromide emulsion (containing 80 mole of silver bromide) and 0.80 g/m of a yellow coupler (Y 1) dissolved in 0.50 g/m 2 of dioctyl phthalate.

2 Layer 2 an intermediate layer comprising 0.70 g/m of gelatin.

I 2 30 Layer 3 a layer containing 1.25 g/m of gelatin, 0.25 g/m2 of a green-sensitive silver chlorobromide emulsion (containing 70 mole of siLver bromide) and 0.62 gim 2 oE a magenta coupler (M 1) dissoloved in 0.30 g/m 2 of dioctyl phthalate.

intermediate layer comprising 0.20 /m 2 f Layer 4 an intermediate layer comprising 0.20 g/m 2 of gelatin. alyr -9 2 o eai,03 Layer 5..alyrcontaining 1.20 9m o eai,03 g/m 2 fardsniiesilver chiorobromide emulsion (otiig80 mole %of silver bromide) (CI) and 0.4S g/M 2 of a cyan coupler (C 1)dissoloved in 0.20 g/m 2of dioctyl phthala te, Layer 6 a layer containing 1.00 g/m 2of gelatin, and 0.30 f Q/ f a Uk/-ray absorber dissolved in 0.20 g/m 2of dioctyl phthalate.

Layer 7 a layer containing 0.50 9/m 2of gelatin.

As the film hardener, 2,4-dichlorQ-6-hydroxy-s-tria~iie sodium was added in the layers 2, 4 and 7 each in an amount of 0.017 9 per I g of gelatin.

4 (Mv 1) 1 8 3

S

I

(C 1) OHh (t x H COC H .4 99 (UV 1)

OH

C

5

H

1 1 (t) As described above, Sample II of color paper (negative-type light-sensitive silver halide color photographic material) was prepared.

The above Sample I and Sample II were cut into widths of 82 mm, and the Sample I was given uniform image exposure by an automatic color paper printer with the use of a positive obtained by camera photographing of a color reversal film with ASAl00, followed by color development, while the Sample II was given uniform image exposure by an automatic color printer with the use of a negative obtained by camera photographing of a color negative film with ASAlOO, and each sample was tested by use of an automatic developing machine shown in Fig. 1, Fig. I is a schematic illustration showing one example of sutomatic developing machine which can be used for processing 125 of the present invention, and as shown in the Figure, the main automatic developing machine 1 is constituted of a paper feeding section2, a photographic processing section 3 and a drying section 4.

The light-sonsitive silver halide photographic material which is a sample according to the present example is formed in a roll and housed in a dark box 6. The light-sensitive siLver halide photographic material 5 withdrawn from the dark box 6 was subjected to development processing at the photographic processing section 3 while being conveyed by a series of rollers rotating in pressure contact therewith.

~~-_---rirrrr-rirruL-~rr--L 100 In the present example, the photographic processing section 3 is constituted of four processing tanks, namely a development processing tank 7, a bleach-fixing processing tank 8 and stabilizing tanks 9 and The stabilizing tanks 9 and 9' are two-tank countercurrent system. On the other hand, the exposure device 11 is detected by the sensor 13 when an internal latent image type direct positive sensitive material is used as the light-sensitive silver halide photographic material, and fog exposure can be given during development processing by lighting on the fluorescent lamp 12, but no fog exposure is given when a negative-type sensitive material is used, The exposed light-sensitive silver halide photographic material 5 is subjected to processing in the respective processing tanks for predetermined periods of time in the photographic processing section 3, then delivered to the drying section 4 to be dried therein and thereafter cut by a cutting member 14 into predetermined lengths before discharged out of the device, In the Figure, 15 is a waste-solution storage section and 16 is a supplemental solution storage section.

2S.. The processing conditions are as followst jProcessing conditions Processing rcessing step. temperature Procesgn. time 1. Color develop- 38 "C 2 minutes ment (note 1) 2. Bleach-fixing 35 oC 50 seconds 3. Stabilizing 32 C 1 minute (note 1) Whole surface exposure was set so that irradiation was effected for 10 seconds after the sample was _i 101 introduced into the color developing solution.

As the processing solutions, the processing solutions having the compositions shown below were used.

1 5 (Color developing solution) Benzyl alcohol Ethylene glycol Hydroxylamine derivative indicated in Table I 3-Methyl4-amino-N-ethyl-N- (f-methanesulfonamidoethyl)aniline sulfate 3-MNethyl-4-amino-N-ethyl-N-hydroxyethylaniline sulfate Potassium carbonate Potassium F:tlfite (50 solution) Potassium bromide Polyphosphorio acid (TPPS) Water 16 ml 16 ml 5 9 5,7 9 2g 25 g 6 ml 1.0 9 3,0 g added to 1 liter (pEI 10.2) (Supplemental color developing sol ution) Benzyl alcohol 20 ml Ethylene glycol 20 ml H1ydroxylamine derivative indicated in Table 1 5 g 3-Mo thyl-4-ani no-N-e thyl-- methanesulfonamidothyl)aniline sulfate (CD 3) 6.8 g 3-Methyl-4-amino-N-e thyl-N-hydroxyethylaniline sulfate (CD 41 2.4 9 Potassium carbonate 25 Potassium sulfito (50 75 solution) 7.5 [11l Po:lyphosphoric acid (TPPS) 4.0 g (made up to one liter with water and adjuste to pNl 10.60 ith potassium hydroxide or sulfuric acid) *cr- 102 (Bleach-fixing solution) Iron (III) ammonium ethylenediaminetetraacetate 70 g Ammonium sulfite 5.0 g Ammonium thiosulfate 150 g Aqueous ammonia (28 10 ml (made up to one liter with water and adjusted to pH with acetic acid or aqueous ammonia) (Supplemental bleach-fixing solution) Iron (III) ammonium ethylenediaminetetraacetate 80 g Ammonium sulfite 10 g Ammonium thiosulfate 190 g "o"115 Aqueous ammonia (28 10 ml (made up to one liter with water and adjusted to pH a7.0 with acetic acid or aqueous ammonia) (Stabilizing solution and supplemental stabilizing solution) 2-Methyl-4-isothiazolin-3-one 0.01 g l-Hlydroxyethylidene-l, -diphosphonic acid l1. g (made up to one liter with water and adjusted to pH with potassium hydroxide) The supplemental color developing solution is supplemented in an amount of 3.2 ml per 100 cm of the light-sensitive material, and the supplemental bleach-fixing solution in an amount of 3.2 ml per 100 cm 2 of the light-sensitive material.

Also, the supplemental stabilizing solution is supplemented in an amount of 3.2 ml per 100 cm of the light-sensitive material. The stabilizing solution is made the two-tank counbercurrent system and supplemented to the final tank, In the processing line 1, Sample I is continuously processed until the total amount of the supplemental color developing solution becomes two-fold amount of the color developing tank (hereinafter referred to as 2-round), while in the processing 103 line 2, Sample. II is subjected to 2-round continuous processing, and in the processing line 3, 2-round continuous processing was performed while processing alternatively 3 m of 2 Sample I and 3 m of Sample II.

For observation of photographic characteristics, Sample I and Sample II subjected to wedge exposure were processed at the processing initiation time and completion of 2-round of the respective lines.

The maximum density and the minimum density of yellow of the samples obtained by processing are shown in Table 1.

0 a Q 1 i Table 1 ~1 Pr Hvdrox Sample I (yellow density) Sample II (yellow density) ameri- amine Processing i- -Processing mi- 2-round mental cess- deriva- tiation time 2 tiation time No :x'lg tive aiM I Minimum Maximum Minimum Maximum Minimum Maximum Minimum (i ~S aID 1 ensitvr densitv densitv densi 2 -densitv density -densitv Idensity B (Coin 2.13 0.13 2.10 0-13 1 2.45 0.08 2.43 0.08 parative) (Goin 2-10 0.12 2.08 0_13 244 0_07 2.42 0.07 carative 3(Com- 3 2-12 0.2 1.90 0-16 2.45 0-08 2-44 0.07 SIE( 3 2.11.: 0.12 2.09: 1- f2.5 9 0.130-12 1.90 200..

vthisn (2 2.0 01 .0 01 2.47 j 0.06 j 2.44 0.-07 2.11 0-13 2.09 0.13 2.46 T 0.07 2.44 0.07 (Thi 3 .12.1 0.13 2.46 1 0.06 2.43 0.06 invn't~on) H~ 2 2.13 0.12 2,07 02 2.4S 0.07 2.44 0.07 6vnThi 3 17) 2.12 0-13 2.11 0.12 2.46 0.07 2.42 0.06 1 (This 2 1)ion 3 (18) 2.11 0.12 2.06 0.13 2.46 0.06 2.44 0.07 inveni4 (Ti 3 (20) 2.13 0.12 2.12 0-13 2.45 0.08 2.43 0.07 invention)! t__I

_I

2 (T__his (hs 3 (23) 2.14 0_12 2-09 0.12 2.47 0.07 2.46 0.08 -inventionr______ 105 As is apparent from Table 1, in Sample II, there is substantially no abnormality such as lowering in the maximum dye density of yellow accompanied with continuous processing or increase of yellow stain in all of the processing lines, but abnormality particularly in the processing line 3 is great in Sample I. However, it can be understood that lowering in the maximum dye density of yellow and increase of yellow stain can be prevented by addition of the compound of the present invention.

xample2 Into the second layer in Sample I of Example 1 was added mg/m 2 of the exemplary Al dye (II into the third layer 10 mg/m 2 of (11 and similarly into the second layer of Sample II 10 mg/mn 2 of (II 8) and into the fifth layer mg/m 2 of (II and the same evaluation as in Exampl 1I was conducted for tests No. 1, 2, 3, 4, 6, 7, 9 and II.

Hlowever, here, in place of yellow dye density, the maximum densities of magenta and cyan dyes were measured. The results are shown in Table 2.

'LL- i i L' C -i e.a 0 0O 000.

a' C Table 2 Pros- Hvdroxvl Sample I (magenta, cvan density) Sample II (magenta, cyan density) Experi- amrine, jrcesing mi- Processing i 2-round amle sscsii ni 2-rund 2-roundn im mental deriva- tation time tiation t No. tIves ~agenta Cyan Iagenta ICan Kagenta Cyan Magenta F Cyan lne derisity..densitv density densitv Idensitv density densityI density I3(Cn- i 2.25 2.26 2.16 2-21 2.33 1 2.22 2.31 I 2.21 J parative) (Con- 2 1~ 2 2.21 2.24 2-j8 1~ 2-23 2.34 2-21 -i2.32 2. 220 parative (or- T 223 2.27 203 2.01 2.33 2-23 2.31 2.23 iparative) 3 2.213 122 16 (This 2.25 2.18 2.2 2.32 2.21 2.32 2.22 invention 3This 2.24 2.26 2-20 1 2-23 2.35 2.22 2.31 2.21 invention 18 (This 223 2.33 2.24 2.31 2.24 32.1) -3 724 2.21 2,21 invention)i 1(3 19 (This 3 (17) 2-22 2-25 2.20 2 2 2423 invention) T (This 31 (20) 223 2.23, 219 12.20 2.35 .22 2.32 2.21 inventio L r I I 107- As is apparent from Table 2, as compared with Sample II, the maximum densities of magenta and cyan dyes are remarkable lowered particularly in the processing line 3, but it can be understood that addition of the compound of the present invention brings about improvements to great extent.

In this example, when (II 16), (II 17), (II 22) and (II 23) were used in place of the exemplary compound (II 8) of AT dye, and (II. 10), (II 12), (II 13) and (II 19) in place of the exemplary compound (II substantially the same results were obtained.

Example 3 By using Samples I and 1I1 employed in Example 1, the same processing treatments were repeated -s in Example 1 and the same evaluation as In Example 1 was conducted.

However, here, in place of hydroxylamine sulfate in the color developing solution and the supplemental color developing solution, hydroxylamines as shown Table 3 were employed in amounts shown in Table 3.

The supplemental color developing solution is supplemented in 2 an amount o.f 2.0 ml per 100 cm of the light-sensitive material. Also, the color development is carried out at a processing temperature of 40 0 C since the development level is inactive at 2-round.

Also, additives in the color developing solution and the supplemental color developing solution, and amounts thereof are showni in Table 3, 6~e t 0 0 00 0 Table 3 Pro- Sample I (maximum density) taliaio 2-roundrovl mena cssHdrx- Additives Processing No.er -n amines iniYelowns itvun 21 13 J13 (5g/1) -2.11 1.97 22 3 13 (5g/1)Tn ethanol-2.3-0 22 3 amine (10g/1) 21 23 1 13 (S5g/1) PAI 1 2.12 2.09 24 j3 1l7 (5g/l) j- J 2.11 1.95 3 7(g1 Triethanol- 2.120 25 3 117_(5g/l amine, (10g/1) 2.1.0 26 3 17 PA 2-12 2.10 27 3 ~20 (5q/l) J-2.12 1.94 18 3 20g1 Triethanol- 1 2.13 21 28 120 (Sg/1)amine (10q/1)21 29 3 20(5g/1) PAT 1 j 2.14 2.12 1 1 120 1 g/1) Table 3 (Contd) Pro- Sample I (maximum density) Experi- Hd l Yellow density mental .Additives Processing No. ing amines initiation 2-round line time 3 1(/1 2. 1.95 T Triethanol- 31 3 1 5g/1) 2.13 2.11 f amine (10g/) 32 T 1 (5g/1 PAIl1 2.13 2.10 33 3 2(.11 1.98 3 (2g/l) 34 33 13 (6g/l) Triethanol- 2.13 2.09 1 (2q/1) amine (109/I)21 13 (9/1 PA 3 1 (6g/l PM 2-13 2.10 Hydroxyla mine suN4 2.13 1.95 fate(3g/l)_ I 1 Hydroxyl- 1Triethanol- 37 3 amine sul-J amine 2.13 2.10 fate(3g/ 1)i(10/l1)

I

Hdro,P1l- 38 3 amine suli PI -1 2.14 2.11 fate(3/1)j g) 110 As is apparent from Table 3, by using various hydroxylamine derivatives in place of hydroxylamine sulfate, while lowering of the maximum dye density of yellow in Sample I becomes large, it can be understood that addition of the additives of a poly(alkylamine) or an alkanolamine effectively prevents the lowering of the maximum dye density of yellow.

Example 4 o 10 a l 00 0 "0 00 00 0 0 S0 ft i 0 't 0 0-i i <0 Sample IV was prepared in the same manner as in Sample I in 2 Example 1 except that, in Layer 1, 10 mg/m 2 of the exemplary compound (II 9) of AI dye was added in addition to 1 g of potassium 2,5-dihydroxy-4-sec--otadecylbenzene sulfonate and, in Layer 3, 15 mg/m of the exemplary compound (II 8) of AI 15 dye was added in addition to 1 g of potassium 4-sec-octadecylbenzene sulfonate in addition to 1 g of potassium 2,5-dihydroxy-4-sec-octadecylbenzene sulfonate.

Further, into the second layer in Sample IIT. of Example I was 20 added 15 mg/m 2 of the exemplary compound (II 8) of AI dye, and into the fourth layer in Sample II of Example 1 was added 10 mg/m 2 of the exemplary compound (II 9) of AI dye, to prepare Sample V, and the same evaluation as in Example 1 was conducted with the processing conditions as in Example 1 25 except for using hydroxylamine sulfate in the color developing solution and the supplemental color developing solution with an amount shown in Table In the processing line 1, Sample IV is continuously processed until the total amount of the supplemental color developing solution becomes two-fold amount of the color developing tank during 10 days (hereinafter referred to as 2-round), while in the processing line 2, Sample V is subjected to 2-round continuous processing during 10 days, and in the processing line 3, 2-round continuous processing was performed during days while processing alternatively 3 m 2 of Sample IV and 3 U U 04 0 000 U U 0 00 U U 4 1 2 m of Sample V.

For observation of photographic characteristics, Sample IV and Sample V subjected to wedge exposure were processed at the processing initiation time and completion of 2-round of jthe respective lines.

The maximum density and the minimum densities of magenta (M) and cyan of the samples obtained by processing are shown in Table 4.

Table 4 HydroxylS Pro- amine Sample Sample V Experi- cess- sulfate Processing 2 -round Processing 2-round mental ing (g/l col initiation time I _nitiation time No- line or devel. Magenta. Cyan Magentaj Cvan I Magenta Cyan fMagent yan sol.1 enstv enstvdenitv desit Idensitvi densitv Idensitv densitv 39 (Com- 2,24 2.25 2.15 2.18 2.32 2.20 2.31 2.19 parative) 1 1 (Com- 2 2.26 217 2.18 2.33 2.22 2.33 2.21 parative) _-23 41 (Cor- 3 23 2-25 2.02 2-05 2.33 2.21 2.31 2.20 42 (Com- paratie) 42parate- 30.01 2.22 2.24 2.06 2.09 2.32 2.21 2.31 2.21 43 (Cor- 3 0.03 2.22 2.23 2.11 2.14 2.32 2.21 2.30 220 44 (This 3 0.05 2.21 2.23 2.18 2.20 2.32 2.21 2.31 2.20 invention) 3 (This 3 0.1 2.21 2.22 2-19 2 21 2-31 2.21 2.30 2.19 46 (This 1-0 2.19 2.19 2.18 2.19 2.30 2.20 2.29 2.19 invention) I 47 (This 1 5.0 2.17 2-19 2-17__1 2.29 2.19 2.29 2.18 inventionl 219 2_29 2.29 invention 3 10.0 1 2.15 2.18 2.15 2.18 T28 2.18 2.2- 2.17 2.2n218 .2iJ .1 it r-a lu~~.a 113 As is apparent from Table 4, in Sample IV, there is substantially no lowering in magenta and cyan maximum dye densities accompanied with continuous processing in all of the processing lines, but in Sample IV, lowering in density particularly in the processing line 3 is great. However, it can be understood that lowering in the maximum dye densities of magenta and cyan can be effectively prevented by addition of 0.05 g of hydroxylamine sulfate per liter of the color developing solution.

Example 0 if The same evaluation as in Example 1 was conducted except for S' using AI dyes as shown in Table 5 in place of AI dyes (II 15 8) and (II 9) used in Example 4.

Comparative Al 1 Oi 0 NliHCHS0 a Nao0S S03Na ,aOM SCH-iH 0 OQ Comparative AI 2 o i 1 ICOCFIl SoSNa SANa SO. na Table Tdye Sample IV i- 9 Processing I 2-round substi- initiation time tute {Magenta Cyan. Ma genta ICyan degnsity densitv density densit -~tive 2-18 2 2.04 2.06 TT 1-0~ 2-18 2.20 T2.17 2__18 7~ T-12 2-20 22 219 2.20 2 1- 13 2-19 2.20 2.17 2.19 3j1 T-19~ 2.18 2.21 2.17 2.19 11-19j 2-20 2.21 220.0 000 0 000 0 000 O 00 0 00 0 0 0 0 0 0 0 *0 0 Table 5 (Contd) 116 As is apparent from Table 5, in Sample IV, there can be seen lowering in maximum dye density in Comparative AI dye, but in the AI dye of the present invention, lowering in dnr.ity can hardly be seen. Also, in Sample V, it can be understood that lowering in the maximum dye density accompanied with continuous processing can hardly be admitted.

asb a S a 1_;_1

Claims (14)

1. A method for common development processing of two kinds of light-sensitive silver halide photographic material which comprises the step of development processing an internal latent type direct positive light-sensitive silver halide photographic material and a negative-type light-sensitive silver halide photographic material in the same development processing bath, and the step of applying whole surface exposure on said internal latent type direct positive light- sensitive silver halide photogrphic material during devel- opment processing of said internal latent type direct posi- tive light-sensitive silver halide photographic material, characterized in that said developing processing solution contains a compound represented by the formula shown below: \N-on 12 wherein R 1 and R 2 each represent hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent or may be combined with each other to form a heterocyclic ring.

2. The method according to Claim 1, wherein said internal ]'Ient type direct positive light-sensitive silver halide pnotographic material and said negative-type light-sensitive silver halide photographic material contains at least one of AI dye selected from the group consisting of the compounds represented by the formulae (At (At (AI It), (At III) and (At IV) shown below: 118 L fl 3 L 2 (L s (1O S)M0 f 2 (AI I) (Rf l )p (SQ(M) 9 0n 0 00 0 tO wherein X represents a chalcogen atorm, C11 grop, 3 REs 1/ N\ group, 142, f,3( T4V L 5 ard L8 each represent a meLhlne group; Rf 5 represent an alkyl group or an aryl group; RE 1 represents a :3ubsiltuLable group; RE2 repre- sents an aryl group, a heAe~-ocyclic group, an amino group, an acylamino group, an imide group, a ureido group, a carboxyl group, an aikoxyoarbonyl group, a carbamoyl group, an alkoxy group, an aryloxy group, a hydroxy group, an alkyl group or a cyano group; RE 3 represents an alkyl group; Rf 4 represents a substl- tuLable group;# M roprosenLs a hydrogen atom or a cation; I represents 01 or 2; rn repronts 0, 1 or 2;1 n 1 n 2 and n 3 each reproent 0 or 1; p ropresents an in, oq r cA O Lo 5; and q reProeen'- an Integer of 0 to providcji thal mu 0, 0 0 00 R 21f (Rrf 4 A (O S) h SL (L L- 4 L l W wheveln W represents a hydrogon at a m, an iIkylV group or a hoteracyclic group; Rf 2 r o prosce n alkyl group, an Ory1 group, a hoborocyclic group, an amino group, an 8 99 000 0 8 as 8 00 119 acylamino group, an imide group, a ureido group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, an aryloxy group, an alkoxy group, a hydroxy group or a cyano group; Rf 3 represents an alkyl group; Rf represents a substitutable group; X represents 013 Ci 3 a chalcogen atom, IC\ \N group, group, L, L21 .13r L 4 1 and L each represent a methine group; represents an alkyl group or an aryl group; M represents a hydrogen atom or a cation; m represents 0, I or 2; nl, a2 and n 3 each represent 0 or 1; and q represents an integer of 0 tO 4, R if K L-L H Rf 0 H 'J (AI II) (CH 2 )M (CH 2 I I US A wherein RE 6 and R 6' each represent a hydrogen atom, an alkyl group, an aryl group or a heterocylic group; RE7 and RE each represent a hydroxy groun, an alkoxy group, a substituted alkoxy group, a cyano group, a trifluoromethyl group, -COORf 8 -CONHRfE 8 -NHCORE, an amino group, a substituted amino group, subastituted with a alkyl group having 1 to 4 carbon atoms or a cyclic 011 3 I(CI2)' amino group represented by: -N \X (where 2 and g each represent 1 or 2, and X rapresents an oxygen atoni, a sulfur atom or -CtI2- grup); RE 8 represents a hydrogen atom, an alkyl group or an aryl group; L represents a methine group; r represents 120 0, 1, 2; and m represents 0 or 1, Rf 34 0 0 I II Hfa 0 OH Rf 33 N, NC (AI III) Rfs 2 a q 4 a 4t o* p 4 4, p 44 wherein r represents an integer of 1 to 3; W represents an oxygen atom or a sulfur atom; L represents a methine group; Rf 31 to Rf 3 4 each represent a hydrogen atom, an alkyl group, an aryl group, an aralky! group or a hetero- cylic group, of which at least one is a substituent other than the hydrogen atom, Rf4-.- L L -Rf 4 3 0" 4 I Rf44 (AI IV) Rf 4 I whe.ein I cepresents an integer of 1 or 2; L represents a methine group; Rf 41 represents an alkyl group, an aryl group or a heterocyclic group; Rf 42 represents a hydroxy griup, an alkyl group, an alkoxy group, a substituted alkoxy group, a cyano group, a trifluoromethyl group, -COORf -CONHIRf8, -NHCORf 8 an amino group, a substi- tuted amino group substituted with an alkyl group having 1 to 4 carbon atoms, or a cyclic amino group represented (CH[2) by: )x (CH2 q (where 2 and q each represent 1 or 2, and X represents an oxygen atom, a sulfur atom or -CH 2 group); Rfr represents a hydrogen atom, an alkyl group or an aryl group; RE 43 represents -OZ 1 group or a group: -121 -N Z2 group; Z 1 Z 2 and Zeach represent a hydrogen z 3 atom or an alkyl group, Z 2 and Z 3 may be either the same or different, or can be bonded togethIer to form a ring; Rf 44 represents a hydrogen atom, an alKyl group, a chlorine atom or an alkoxy group.

3. The method according to claim 2, wherein said AI dye is the compoundi represented by the formula of (Al-i) and (Al-Il).

4. The method according to any one of claims I to 3 wherein the said hydroxylamine compound is selected from OJe group consisting of: N 2 -OH HO-C 2 H 4 -NH-OH CH 3 -NH-OH HOOC-C 2 H 4 NH-OH C 2 H 5 -NH-OH (OW. HO 3 S-C 2 H 4 NH-OH i so-C 3 H 7 NH-OH (11) H 2 N-C 3 H 6 NH-OH C 3 H 7 '-NI-OH (12) C 2 H 5 -O-C 2 H 4 -NH-QH HO-CH 2 NH-OH (13) HO-C 2 H 4 -O-C 2 H 4 -NH-OH CH 3 C 2 H 4 -NH-OH (14) CH(15) C CH O (16) a 3(17) C N-OH N-OH CUH7 CH3Q2 2 H 4 (18) C H 5 (19) n-C H 7 N-OH N-OH C2~ P7 II I I C 6 1 122 (22) (24) (26) (28) iso-C 3H7 N-OH iso--C 3H 7/ H 3OC 2H 41,N O 3 2H N-OH t0IC 2H 7 N-OH HO 3SC 3H 7 NH23 246 N-OH NH 2C 3H61l n-OH H N-OH \-I (21) (23) (27) (29) (31) (33) N-OH CH 302 H 4~ 3H20 2 H4 CHHOC H C2 H C2 H4 NN-OH N-OH HC 2 H 2 2 4 HOX3 C 5H 1 N-OH H C H N-OH (32) HO-N N-OH (34) H 3 C-N N-OH

5. The method according to any one of claims I to 4, wherein said hydroxylamine compound is contained In said developing solution in an amount of M.5 g/liter or more. cc 123

6. The method according to any one of claims 1 to 5, wherein said hydroxylamine compound is contained in an amount of 0.1 to 50 g/liter of the developing solution.

7. The method according to any one of claims 1 to 6 wherein said hydroxylamine compound is contained said developing solution in an amount of 0.07 g/llter to 4 g/liter,

8. The method according to any one of claims 1 to 7, wherein said developing solution contains at least one of a poly(alkyleneimine) and an alkanolamine.

9. The method according to claim 8, wherein said poly(alkyleneimine) is a compound represented by the formula: R ip2 R N- (P I) pl n wherein R p represents an alkylene group having 1 to 6 carbon atoms; Rp 2 represents an alkyl group; and n Is an integer of 500 to 20,000. The method according to claim 8, wherein said polyalkanolamine is a compound represented by the formula: 0 0 S 0 0 00 o o whereIn Rp3 represents a hydroxyalky1 group having 2 to 6 carbon atoms, i 0 R p3 -N (P 0 0 0 0 0 o wherein Rp 3 represents a hydroxyalkyl group having 2 to 6 carbon atoms, Rp4 and Rp5 each represent a hyd'ogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl o0 i group or a formula: -CnH 2 n- n in the above formula 0 00 being ain integer of 1 to 6, X and Z each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to ,0 0 6 carbon atoms. o 0

11. The method according to any one of claims 1 to 10 wherein said hydroxylamine compound Is NH 2 -OH. i x, i 124

12. The method according to any one of claims 1 to 11, wherein said developing solution further contains a sulflte or a sulfite ion releasing compound.

13. The method according to Claim 12, wherein said sulfite of said sulfite ion releasing compound is selected from the group consisting of potassium sulfite, sodium sulfite, ammonium sulfite, sodium metabisulfite, potassium metabisulfite, sulforous acid adduct of formaldehyde, sulfurous acid adduct of acetaldehyde and sulfurous acid adduct of glutaraldehyde.

14. The method according to claim 12 or claim 13, wherein said sulfite of said sulfite Ion releasing compound is contained in the range from 1.0 x 10 4 to 1.0 x 10-1 mole/liter of the color developing solution. A method according to any one of claims 1 to 10 or 12 to 14 wherein R l and R 2 of said hydroxylamine compound cannot be hydrogen at the same time.

16. A method for common development processing of two kinds of light-sensitive silver halide photographic material which comprises the step of development processing an internal latent type direct positive light-sensitive silver halide photographic material and a negative-type light-sensitive silver halide photographic material in the same development processing bath, and the step of applying whole surface exposure on said internal latent type direct positive light-sensitive silver halide photographic material during development processing of said Internal latent type direct positive light-sensitive silver halide photographic material, characterized in that said developing processing solution contains a hydroxylamine compound represented by the formula shown below: S R N-OH (A) R 2 wherein R1 and R2 each represent hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent or may be combined with each other to form a heterocyclic ring, substantially as herein described with reference to Example 1 and any one of Experiments 4 to 2, Example 2 K 7 1'2 7 y V I l 125 and any one of Experiments 16 to 20, Example 3 and any one of Experiments 21 to 28, Example 4 and any one of Experiments 44 to 48 or Example 5 and any one of Experiments 50 to 54 or 56 to DATED this SECOND day of. MAY 1990 Konlshlroku Photo Industry Co., Ltd. Patent Attorneys for the Applicant SPRUSON FERGUSON 04 Q0 00 0 0 0 0000 0 0 00 00 a Ot t 4 44 S4 t ~t F.? ,Ir P ii ii I I- r 711 2y Ir~~l