JPH03246537A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain high max. image density and low min. image density by regulating the total amt. of Fe, Mn, Cu, Zn, Mg and Ca contained in gelatin used to prepare a silver halide emulsion to <=500 ppm and carrying out chemical sensitization in the presence of a specified Pd compd. CONSTITUTION:Since gelatin contains >=500 ppm metal ions as impurities in general, gelatin used to prepare an internal latent image type silver halide emulsion is purified so as to reduce the metal ion content to <=500 ppm and the purified gelatin contg. <=500 ppm, in total, of Fe, Mn, Cu, Zn, Mg and Ca as impurities is used. A prepd. photographic emulsion contg. unprefogged internal latent image type silver halide particles is chemically sensitized in the presence of a Pd compd. added by >=10<-4> mol per 1 mol silver halide. A direct positive photographic sensitive material having high max. image density and low min. image density is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a direct positive photographic light-sensitive material having an emulsion layer containing internal latent image type silver halide grains,
The present invention relates to a direct positive photographic light-sensitive material which has a high maximum image density and a low minimum image density even when stored under high temperature and high humidity.

(Prior art) A well-known method is to directly obtain a positive image by using an internal latent image type silver halide emulsion that has not been fogged in advance and performing capri processing after image exposure, or by performing surface imaging while performing fog processing. It is being

Here, the internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. Refers to emulsion.

Various techniques are known to date in this technical field. For example, U.S. Patent Nos. 2,592,250, 2.466, 957, 2,497,875,
, No. 588,982, No. 3,317,322, No. 3,
No. 761,266, No. 3,761,276, No. 3,7
The main ones are those described in British Patent No. 96,577 and the specifications of British Patent Nos. 1,151,363, 1,150,553, and 1,011,062.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

For details of the above direct positive image formation mechanism, see, for example, T.
, H. James, The Theory of the Photographic Ink Process J.
of the Photographic Proc
ess), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761.276.

In other words, due to the surface desensitization effect caused by the so-called internal latent image created inside the silver halide by the initial imagewise exposure, fogging treatment selectively creates fog nuclei only on the surface of the silver halide grains in the unexposed areas. A photographic image (
It is believed that a direct positive image) is formed.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called a "photofogging method" (for example, British Patent No. 1,151,
No. 363) and a nucleating agent (U
A method using a creating agent) is known.

Here, the "nucleating agent" is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance.

This latter method is described, for example, in ``Research Disclosure + -''.
ure) Magazine, Volume 151, No. 15162 (197
Published in November 2006), pages 76-78.

A hydrazine compound is well known as a nucleating agent used in the above-mentioned "chemical fogging method".

Further, as another nucleating agent, heterocyclic quaternary ammonium salts are known, for example, U.S. Pat. No. 3,615,615, U.S. Pat.
No. 3,759,901, No. 3,854.956, No. 4,094,683, No. 4,306,016, British Patent No. 1, No. 283.835, JP-A-52-3,426
No. 52-69,613.

Various techniques have been developed to improve the photographic properties of direct positive imaging materials using such chemical fogging methods. By using a quaternary base nucleating agent having a silver adsorption promoting group or a quaternary base nucleating agent described in JP-A No. 63-34535 and Japanese Patent Application No. 63-335544, certain effects can be achieved, e.g. A high maximum image density and a low minimum image density are obtained.

[Problem that the invention seeks to solve]

However, when direct positive photographic materials improved by the above methods are stored under high temperature and high humidity, the maximum and minimum image densities deteriorate and the S/N ratio decreases, so further improvements in these photographic performances are required. desired.

Accordingly, a first object of the present invention is to provide a direct positive photographic material that provides high maximum image density and low minimum image density.

The second object of the present invention is to create a direct positive photographic material that exhibits small changes in photographic performance such as a decrease in maximum image density and an increase in minimum image density even when the photographic material is stored under high temperature conditions. It is about providing.

[Means to solve the problem]

The above object of the present invention is to have at least one photographic emulsion layer on a support containing internal latent image type silver halide grains which are not pre-fogged, and which is developed in the presence of a nucleating agent after imagewise exposure. In a direct positive photographic light-sensitive material that can be directly processed to form a positive image, Fe+ Mn+ Cu, Zn+ contained in the gelatin used in preparing the silver halide emulsion.
The sum of Mg and Ca is 500 ppm or less, and the silver halide emulsion contains 10-4 per mole of silver halide.
This was achieved using a direct positive photographic light-sensitive material characterized by being chemically sensitized in the presence of a molar or more palladium compound.

The present invention will be explained in detail below.

Regarding the application of palladium to silver halide emulsions, see P.
hto, Sci, Eng,, 25, p63 (
(1981) reported that gold in gelatin was reduced by gold sensitization ripening in the presence of palladium, and a similar effect was reported by J. Inf. R.
ec, Mater.

16, 233 (198B), diary 37 p133 (
1974).

Further, it is described in Japanese Patent Application No. 1-26565 that the combination of palladium and reduction sensitization is effective in preventing fogging.

US Pat. No. 2,448,060 discloses that sensitivity can be increased by adding a palladium compound and ascorbic acid to the emulsion after sulfur sensitization and before coating. US Pat. No. 2,598,079 discloses that by adding a palladium compound to the emulsion after gold and sulfur sensitization and before coating, low-light sensitivity in particular can be increased. U.S. Pat. No. 2,472,627, U.S. Pat. No. 2,472,631, U.S. Pat. No. 2,566,245, and U.S. Pat. No. 2,566,263 disclose that the storage stability of sensitive materials under high temperature and high humidity is improved by adding a palladium compound after chemical sensitization of the emulsion. It is disclosed that

British Patent No. 1351309 discloses that during the silver halide grain formation process (during conversion), a noble metal salt such as palladium is added from 3XlO-' mole to 3X1 mole per mole of silver halide.
It is disclosed that 0-5 mol is added.

US Pat. No. 4,092,171 discloses that high sensitivity can be obtained and storage stability can be improved by adding an organophosphinic acid complex of a palladium compound to an emulsion.

JP-A No. 61-67845 discloses monodisperse core-shell type silver halide grains in which the silver iodobromide content is different in the vicinity of the surface and in the interior, using a chalcogen sensitizer, a gold sensitizer, and an aqueous solution of palladium. A method for making a silver halide emulsion is disclosed which is chemically sensitized in the presence of at least one sex salt.

The inventors of the present invention have developed a photographic emulsion containing internal latent image type silver halide grains that have not been shaken or shaken by halogenation! By chemically sensitizing the material in the presence of a palladium compound of 101 moles per 11 moles or more, a direct positive photographic light-sensitive material having a high maximum image density and a low minimum image density can be obtained, and by using such a photographic emulsion, It is also effective to some extent in preventing deterioration of the maximum and minimum image density when the photographic material is stored under high temperature and high humidity.As a result of further investigation, we found that Fe and Mn, which are contained as impurities in the photographic emulsion, , Cu+ If metal ions such as Zn, Mg, and Ca are small, the photosensitive material can be stored at high temperatures to obtain a sufficiently high maximum image density and a sufficiently low minimum image density, and such a photographic emulsion can be obtained. However, the emulsion contains Fe+ Mn and Cu+ Zn as impurities.
.

The present invention was completed based on the finding that gelatin containing a total of 500 ppm or less of Mg and Ca is particularly effective.

Gelatin generally contains 500 ppm or more of the metal ions mentioned above as impurities. The gelatin used to prepare the internal latent image type silver halide emulsion in the present invention is purified to contain these metal ions to 500 ppm or less.

Such gelatin can be obtained by deionization by ion exchange or the like. For example, the content of the metal ions can be reduced by heating an aqueous gelatin solution and bringing it into contact with an ion exchange resin while stirring.

Metal elements in gelatin are usually cations, so these can be removed by using H3 type cation exchange resin, but some metal elements may form negative complex salts. Therefore, in such a case, it can be removed using an OH-type anion exchange resin. For more information on these methods, please refer to the Nippon Kagaku Yoshin ``Experimental Chemistry Course 2''.
, Basic Techniques nJ Maruzen (1956), pp. 151-202, Nippon Kagaku Yoshin, "New Experimental Chemistry Course 1, Basic Operations I" Maruzen (1975), pp. 463-497, etc. for details. Furthermore, if this alone is insufficient, the content of metal impurities can be further reduced by using a chelate resin and performing techniques such as solvent extraction and foam separation. These methods are described, for example, in Nippon Kagaku Yosen's Experimental Chemistry Course (Continued) 2 Separation and Purification J (1967).

In the present invention, a silver halide emulsion containing internal latent image type silver halide that has not been fogged in advance is
Although it is not clear what kind of action the metal ions contained as impurities in the emulsion have during chemical sensitization in the presence of 10-4 mol or more of a palladium compound per mol of A, it is difficult to prepare a silver halide emulsion. Sometimes, if untreated gelatin is used, that is, the content of the metal ions is increased, the maximum image density and minimum image density will slightly deteriorate when the obtained direct positive photographic light-sensitive material is stored under high temperature and high humidity.・The metal ion content of silver halide is 500a
When adjusted using gelatin that has been treated to have a pH of below pH 1, the deterioration of image density under the above-mentioned high temperature and high humidity conditions is significantly prevented, and it has a high maximum image density and a low minimum image density,
A direct positive photographic material with a high S/N ratio can be obtained.

Examples of palladium compounds used in the chemical aggradation of the photographic emulsion in the present invention include the following compounds. That is, KzPd(J4, (NH4) zPdcl b
, NazPdCla, or (NH4)zPdcL, are preferred, but PdCl2, PdCZ, .2HzO, Pd
(NHz) afJz, (Nl(a) zPdclz.

Pd1z, Pd(O)I)2, Pd(SO2), Pd
(NOi)z, NazPd(NOx)z, and CNH
s) zPdcl a, can also be used. Preferably, these compounds are water soluble.

Although the palladium compound may be added at any time before chemical sensitization, it is particularly desirable to add it during the core or shell chemical sensitization step.

The amount of the palladium compound added is 10-4 mol or more, particularly 10-4 mol to 10 mol, per mol of silver halide in the photographic emulsion, and if this amount is less than to-' mol, the desired maximum image density and minimum image Concentration cannot be obtained.

The direct positive photographic light-sensitive material of the present invention is a type of window material in which a positive image is formed directly by developing in the presence of a nucleating agent after imagewise exposure, and the nucleating agent is generally directly incorporated into the positive photographic light-sensitive material. Contain.

In the present invention, when a nucleating agent is contained in a photographic light-sensitive material, a solution of a water-miscible organic solvent such as alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), ketones (e.g. acetone), etc. Alternatively, if it is water-soluble, it may be added to the hydrophilic colloid solution as an aqueous solution.

A solution containing these nucleating agents is converted into a hydrophilic colloid solution (
For example, when added to a silver halide emulsion), -S
This is done in the following steps.

That is, a solution containing a nucleating agent is added while stirring a gelatin aqueous solution weighed in a predetermined amount using a commercially available ordinary stirrer. In this case, if necessary, addition may be performed while controlling the temperature.

When the nucleating agent is added to the aqueous gelatin solution, for example, if the solution is a silver halide emulsion, the timing of adding the nucleating agent to the aqueous gelatin solution is from the start of chemical ripening to
It may be carried out at any time before coating, but it is preferably carried out after chemical ripening is completed. If the couplers used in the present invention are oil-soluble, such couplers can be dissolved in high boiling organic solvents.
It is preferable to dissolve the solution using a low-boiling organic solvent if necessary, emulsify and disperse this solution in an aqueous gelatin solution, and then add the dispersion to the silver halide emulsion. It is particularly preferred that the nucleating agent be added immediately before the emulsified dispersion containing the coupler is added.

The nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably contained in the silver halide emulsion layer. The amount added depends on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range, but the i! Approximately lXl0 per mole
A range of -' moles to about 1X10-' moles is useful in practice, with a preferred range of about 1 x 10-7 moles to about 1X10-' moles per mole of silver.

As the nucleating agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating smooth silver halide can be used. Two or more types of nucleating agents may be used in combination. To explain in more detail, examples of the nucleating agent include [
Research Disclosure+-J (Research
h Disclosure) Magazine No. 22゜534
(Published in January 1983, pages 50-54), and these are broadly classified into three types: hydrazine compounds, quaternary heterocyclic compounds, and other compounds, but in the present invention, Particularly preferred are heterocyclic compounds.

As the hydrazine compound, for example, the above-mentioned research
Disclosure Magazine No. 15.162 (1976
Published in November, pp. 76-77) and the same magazine No. 2351
0 (published November 1983, pages 346-352). More specifically, those described in the following patent specifications can be mentioned. First, examples of hydrazine-based nucleating agents having a silver halide adsorption group include U.S. Pat. No. 4,030,925 and U.S. Pat.
．． No. 080,207, No. 4,031,127, No. 3,718.470, No. 4,269,929, No. 4,276.364, No. 4,278,748,
No. 4,385.108, No. 4,459.347, British Patent No. 2.011,391B, Japanese Unexamined Patent Publication No. 1983-7
No. 4.729, No. 55-163, No. 533, No. 55-
No. 74,536, and No. 60-179.734, No. 6
Examples include those described in No. 3-231441.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86,829, U.S. Pat. No. 4,560,638,
4,478,928, and 2,563,7
Examples include the compounds described in No. 85 and No. 2,588,982.

As quaternary heterocyclic nucleating agents, for example, U.S. Patent No. 3.61
No. 5.615, No. 3,719,494, No. 3,734
, No. 738, No. 3,759,901, No. 3,854,
No. 956, No. 4,094,683, No. 4,306,0
No. 16, British Patent No. 1,283.835, Special Publication No. 1973-
38.164, 52-19,452, 52-4
7.326, JP-A-52-69.613, JP-A No. 52-
No. 3.426, No. 55-138.742, No. 60-1
No. 1,837, and the aforementioned r)) Search Disclosure +-J Magazine No. 22534; Intermediate No. 23,
213 (published August 1983, pages 267-270).

Quaternary heterocyclic nucleating agents are considered to have weak adsorptivity, and in this case, the effects of the present invention are greatly exhibited.

In particular, in the present invention, quaternary heterocyclic compounds represented by the following general formulas ([) and (II) are preferred.

General formula (1) (wherein, Z represents a nonmetallic atomic group necessary to form a 5- to 6-membered heterocycle, and Z may be substituted with a substituent. R1 is an aliphatic group; , R2 is a hydrogen atom, an aliphatic group or an aromatic group. R1 and R2 may be substituted with a substituent. In addition, R2 is further combined with the heterocycle completed by Z to form a ring. However, R1, R2
At least one of the groups represented by and Z contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazine group, or R1 and R2 form a 6-membered ring to form a dihydropyridinium skeleton. Further, at least one of the substituents R1, R1 and Z is halogen (IJ
It may have a group that promotes adsorption to I. Y is a counterion for charge balance, and n is O or 1.

More specifically, the heterocycle completed by Z includes, for example, quinolinium, hendithiazolium, henzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indo Mention may be made of rhenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxacillium, naphthooxacillium and benzoxacillium nuclei. Substituents for Z include alkyl groups, alkenyl groups,
Aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryloxy group, halogen atom,
Amino group, alkylthio group, arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group,
Examples include a cyano group, ureido group, urethane group, carbonate ester, hydrazine group, hydrazone group, and imino group. As the substituent for Z, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different.

Moreover, the above-mentioned substituents may be further substituted with these substituents.

Furthermore, as a substituent for Z, a heterocyclic quaternary ammonium group completed with Z via a suitable linking group may be included. In this case, it takes a so-called dimer structure.

Preferable examples of the heterocycle completed by 2 include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium.

The aliphatic groups represented by R1 and R: are an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl portion. Examples of the substituent include those described as the substituent for Z.

The aromatic group represented by R2 has 6 to 20 carbon atoms, such as phenyl group and naphthyl group. N
Examples of the substituent include those mentioned as substituents for Z.H2 is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group, or a heterocycle further completed by 2 to form a ring. This is the case.

At least one of the groups represented by R1, pZ and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazine group, or R1 and R2 form a 6-membered ring, and the dihydropyridinium core , which may be substituted with the group described above as a substituent for the group represented by Z.

At least one of the substituents to the group or ring represented by R1, y* and Z is an alkynyl group or an acyl group, or R1 and Rt are linked to form a dihydropyridinium core. Preferably, it further contains at least one alkynyl group, most preferably a propargyl group.

The adsorption-promoting group to silver halide possessed by the substituents R', "and Z is preferably represented by X'-(L'),-, where xl is a group promoting adsorption to silver halide, Ll is a divalent linking group, and m is O or l.

Preferred examples of the adsorption-promoting group to silver halide represented by χ1 include a thioamide group, a mercapto group, and a 5- to 6-membered nitrogen-containing heterocyclic group.

These may be substituted with the substituents mentioned above for Z. The thioamide group is preferably an acyclic thioamide group (e.g., thiourethane group, thiourido group, etc.)
It is.

The mercapto group of
, 3,4-thiadiazole, 2-mercapto 1.3.4
-oxadiazole, etc.) are preferred.

The 5- to 6-ji nitrogen-containing heterocycle represented by xl is one consisting of a combination of nitrogen, oxygen, sulfur, and carbon, and preferably produces iminosilver, such as benzotriazole and aminothiazole.

The divalent linking group represented by Ll includes C, N, S,
It is an atom or atomic group containing at least one type of 0.

Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, 0- -S--NH--
SO! N= -C0SO, - (these groups may have a substituent), etc. alone or in combination. NH (arylene) 1 8HCNH- Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion , thiocyanide ion, boron tetrafluoride ion, phosphorus hexafluoride ion, etc.

These compounds and their synthesis methods are described in, for example, Research Disclo
sure magazine N1122.534 (published January 1983,
50-54 pages), and the patents cited in Nα23.213 (published in August 1983, pages 267-270), Japanese Patent Publications No. 49-38.164, No. 52-19,452, No. 52-47. , No. 326, JP-A-52-69,613,
523, 426, 55-138.742, 6
No. 0-11,837, U.S. Pat. No. 4,306,016, and U.S. Pat. No. 4,471.044.

Specific examples of the compound represented by general formula (1) are listed below, but the invention is not limited thereto.

(III-1-2) 5-ethoxy-2-methyl-1
-Propargylquinolinium Bromide (N-1-2) 2.4-Dimethyl-1-Propargylquinolinium Bromide (N, l-3) 2-Methyl-1-(3-C2-(4
-methylphenyl)hydrazonocobutyl)quinolinium iosito(N-1-4) 3.4-dimethyl-dihydropyrido[
2,1-bl benzothiazolium bromide (N-1-5) 6-ethoxythiocarbonylamino-
2-methyl=1-propargylquinolinium trifluoromethanesulfonate (N-1-6) 2-methyl-6-(3-phenylthioureido)-1-propargylquinolinium bromide (N-4-7) 6- (5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-8) 6- (3-(2-mercaptoethyl)ureidocou 2-methyl-1-propargyl Quinolinium trifluoromethanesulfonate (N-1-9) 6- (3-(3-(5-mercapto-1゜3.4-thiadiazol-2-ylthio)propylthureido)-2-methyl-1- Pro ■ ■ ■ ■ ■ ■ Pargyl quinolinium trifluoromethanesulfonate 10) 6-(5-mercaptotetrazol 1-yl)-2-methyl-1-propargyl quinolinium iosito 11) 1-propargyl-2-( 1-propenyl) quinolinium trifluoromethanesulfonate 12) 6-nitoxythiocarponylamino 2-(2-methyl-1-propenyl)-1 propargylquinolinium trifluoromethanesulfonate 13) 10-propargyl-1,2,3 , 4-tetrahydroacridinium trifluoromethanesulfonate 14) 7-nidoxythiocarbonylamino 10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 15) 6-nitoxythiocarbonylamino 1 -Propargyl-2,3-pentamethylenequinolinium trifluoromethanesulfonate (N-I-16) 7-(3-(5-mercaptotetrazol-1-yl)benzamide]-10-propargyl-1,2,3 ,4-tetrahydroacridinium
Perchlorate (N-1-17) 6- (3-(5-mercaptotetrazol-1-yl)benzamide]-1-propargyl-2,3-pentamethylenequinolinium bromide (N-I-18) 7- ( 5-mercaptotetrazol-1-yl)-19-methyl-10-propargyl-
1,2,3,4-tetrahydroacridinium bromide (N-1-19) 7-(3-(N-(2-(5-mercapto-1,3,4-thiadiazol-2-yl)ethyl [Carbamoyl)propanamidocou 10-propargyl-1,2,3,4-tetrahydroacridinium (N4-20) 6-(5-mercaptotetrazol-1-yl)-4-methyl-1-propargyl-2,3-
Pentamethylene quinolinium bromide (N4-21) 7-nitoxythiocarbonylamino lO-propargyl-1,2-dihydroacridinium trifluoromethanesulfonate (N-1-22)
7-(5-mercaptotetrazol-1-yl)-9
-Methyl-10-propargyl-1,2-dihydroacridinium hexafluorophosphate (N-1-23) 7-(3-(5-mercaptotetrazol-1-yl)benzamide]-10-propargyl- 1,2-dihydroacridinium bromide (N-1-24) 10-propargyl-7-(3-
(1,2,3゜4-thiatriazol-5-ylamino)benzamide)-1,2,3,4-tetrahydroacridinium perchlorate (N-1-25) 7- (3-cyclohexylmethoxy thiocarbonylaminobenzamide)-10propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-1-26) 7-(3-isopropoxythiocarbonylaminobenzamide)-1O-propargyl-L2 .3.4-Tetrahydroacridinium trifluoromethanesulfonate (N-I-27) 7-(3-methoxythiocarbonylaminobenzamide)-10-propargyl 1.2
,3.4-tetrahydroacridinium trifluoromethanesulfonate (N-1-28) 7-(3,-(3-ethoxythiocarbonylaminophenyl)ureido]-10-propargyl-1,2,3,4- Tetrahydroacridinium trifluoromethanesulfonate (N-1-29) 7-(3-ethoxythiocarbonylaminobenzenesulfonamide)-10-propargyl-L2.3.4-tetrahydroacridinium ■ ■ ■ ■ Nitrifluoromethanesulfonate Naat30) 7
- (3-(3-[3-(5-mercaptotetrazol-1-yl)phenyl]ureido)benzamide]-1
0-Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 31) 7-(3-(5-mercapto-1,3,4thiadiazol-1-ylamino)benzamide]-IO
-Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 32) 7-(3-(3-butylthioureido)benzamide)-10-propargyl-1,2゜3.4-tetrahydroacrylate Zinium trifluoromethanesulfonate 33) 6-(3-ethoxythiocarbonylaminobenzamide)-1-propargyl 2.3-trimethylenequinolinium trifluoromethanesulfonate General formula (n) (wherein, R1' is an aliphatic group, aromatic group, or heterocyclic group, Hz represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group,
or represents an amino group; G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (HN=C); R23 and R1 are both hydrogen atoms, or one is a hydrogen atom and the other is Represents any one of an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, but includes G, +p*, R-4, and hydrazine nitrogen to form a hydrazone structure<>N-*=c
) may be formed. Furthermore, the groups mentioned above may be substituted with a substituent if possible.) To explain in more detail, Rz' may be substituted with a substituent, and examples of the substituent include the following. . These groups may be further substituted. For example, an alkyl group, an aralkyl group, an alkoxy group, an alkyl or aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group, a sulfamoyl group. , carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group, sulfanyl group, hydroxy group, halogen atom, cyano group, sulfo group,
These include carboxyl groups and phosphoric acid amide groups. Among these, ureido groups and sulfonylamino groups are particularly preferred.

These groups may be linked to each other to form a ring when possible.

R1' is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group (eg, phenyl group, naphthyl group, etc.).

Among the groups represented by R2Z, preferred are a hydrogen atom, an alkyl group (e.g. methyl group), an aralkyl group (e.g. 0-hydroxybenzyl group etc.) or an aryl group (
For example, 2-hydroxymethylphenyl group, etc.), and a hydrogen atom is particularly preferred.

As the substituent for R1, in addition to the substituents listed for H2I, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

These substituents may be further substituted with these substituents. Further, if possible, these groups may be linked to each other to form a ring.

Among lpl and Rzz, lpl may contain a diffusion-resistant group such as a coupler, a so-called ballast group, and it is particularly preferable to link with a ureido group or a sulfamino group.

Group X” that promotes adsorption to the surface of silver halide grains
+ L"ht. Here, X2 represents the same meaning as χ1 in general formula CI), and is preferably a thioamide group (excluding thiosemicarbazide and its substituted products), a mercapto group, or a 5- to It is a 6-membered nitrogen-containing heterocyclic group.L2 represents a divalent linking group, and is represented by the general formula [1
) has the same meaning as Ll. I! 12 is O or 1.

More preferably, x2 is an acyclic thioamide group (e.g., thioureido group, thiourethane group, etc.), a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, such as a 2-mercaptothiadiazole group, a 3-mercapto-1
, 2,4-) lyazole group, 5-mercaptotetrazole group, 2-mercapto1.3.4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or nitrogen-containing heterocyclic group (e.g. group, benzimidazole group, indazole group, etc.).

The most preferable X2 varies depending on the photosensitive material used.6For example, in a color photosensitive material, when using a coloring material (so-called coupler) that forms a dye through a force/sampling reaction with an oxidized form of a p-phenylenediamine developer, ×2
As such, a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver is preferable. In addition, in color sensitive materials, by cross-oxidizing the oxidized developer,
When using a coloring material that produces a diffusible dye (a so-called DRR compound), x2 is preferably an acyclic thioamide group or a mercapto-substituted nitrogen-containing heterocycle. Furthermore, in a black-and-white sensitive material, x2 is preferably a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver.

Hydrogen atoms are most preferred as R23 and R14.

G in general formula (II) is most preferably a carbonyl group.

Further, as the general formula (If), those having an adsorption group to silver halide, or those having a ureido group or a sulfonylamino group are more preferable.

Examples of these compounds and their synthesis methods are as follows: Examples of hydrazine nucleating agents having a silver halide adsorption group include, for example, U.S. Pat.
, No. 207, No. 4,031,127, No. 3,71
No. 8,470, No. 4,269,929, No. 4,2
No. 76.364, No. 4.278,748, No. 4,
385.108, 4,459.347, 4.
No. 478.922, No. 4,550,632, British Patent No. 2.011,391B, JP-A-54-74,729
No. 55-163,533, No. 55-74,536
No. 60-179,734.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86,829, U.S. Pat. No. 4,560,638, U.S. Pat. No. 4,478,928, and even U.S. Pat.
No. 785 and No. 2.588.982.

Specific examples of the compound represented by the general formula [■] are shown below.
However, the present invention is not limited to the following compounds.

(N-If4) 1-formyl-2-(4-(3-(
2methoxyphenyl)ureido]-phenyl)hydrazine (N-It-2) 1-formyl-2-(4-(3-
(3(3-(2,4-di-tert-pentylphenoxy)propylthureido)phenylsulfonylaminoco-phenyl)hydrazine (N-11-3) 1-formyl-2-(4-(3-
(5mercaptotetrazol-1-yl) benzamido]phenyl)hydrazine (N-11-4) 1-formyl-2-(4-(3-
(3(5mercaptotetrazol-1-yl)phenylthureido)phenyl]hydrazine1-formyl-2-C4-(3-(N (5,-mercapto-4-methyl-1,2,4triazole-3- yl)carbamoyl]propanamido)phenyl)hydrazine 1-formyl-2-(4-(3-(N-[4-(3-mercapto-1,2,4-triazol-4-yl)phenylcarbamoyl)-propane Amido]phenyl)hydrazine.

1-formyl-2-[4-(3-(N (5-mercapto-1,3,4-thiadiazole-2-
yl)carbamoyl]propanamido)phenyl]-hydrazine (N-It-8) 2-(4-(benzotriazole-5carboxamido)phenyl]-1-formylhydrazine 5) 6) ■■-7) (N-It-8) (N-■-9) 2- (4-(3-(N-(benzotriazole-5-carboxamido)carbamoyl)propanamido)phenyl] l-formylhydrazine (N-11-10) l-formyl-2- (4-[1
-(N-phenylcarbamoyl)thiosemicarbazide]
phenyl)hydrazine (N-1-11) 1-formyl-2-(4-(3-
(3phenylthioureido)henzamido)phenyl)
Hydrazine (N-n-12) 1-formyl-2-(4-(3-
hexylureido) phenyl) hydrazine (N-n-13) 1-formyl-2-(4-(3-
(5-mercaptotetrazol-1-yl)benzenesulfonamide]phenyl)hydrazine (N-11-14) 1-formyl-2-(4-(3
-(3-(3-(5-mercaptotetrazol-1-yl)phenylthureido)benzenesulfonamide]phenyl)hydrazine (N-If-15) l-formyl-2-(4-(3
-(3-(2,4-di-tert-pentylphenoxy)propylthureido)phenylene]hydrazine(N-n-16) 1-(2-hydroxymethylbenzoyl)-2-(4-(3-(5- Mercaptotetrazol-1-yl)benzamido]phenyl)hydrazine (N-If-17) 1-(2-hydroxymethylbenzoyl)-2-(4-(3-(5-mercaptotetrazol-1-yl)benzene, sulfonamide , do]phenyl)hydrazine (N-11-18)2- (4-(
a-(3-(3-(5-mercaptotetrazole-1-
yl) phenylthureido) benzenesulfonamide]
phenyl) -1-(2-methanesulfonamidobenzoyl)hydrazine (N-11-18) N-(4-(2-formylhydrazino)phenyl]diphenylphosphoramidate (N ■ 1) (N ! 3) (N ■ 4) ozc CH (N !-5) CH1C=C)l (N ■ 6) cnzc=c.

(N ■-7) c) ltc=CH (N ■-8) cozc=　c.

(N ■ 9) H2C CH (N ■ 10) 舖 CHzC=cH (N ■ 11) H2C B (N ■ 12) (Jl, cE to CH (N ■ 13) CH, CE CH (N ■ 14) cttzc=CH (N ■ 15) CH2C3CH (N ■ 16) 11 cozc=CH (N-1-17) 1 cozc=c.

(N-! 18) CLC=CH (N-1-19) CH1C3CH (N!-20) CH (N 1-21) ozc C)! (N [22) 9■ ozc CH (N-1-23) q■ ozc C)l (N I-24) (N 1-25) (N 1-26) (N-1-27) 1 CH2C mi C11 cnzc=CH nzc O CH,C=CH (N-1-29) 1 (N 1-32) ctizc= CH cozc2CH Cl, (:=CH CH,C=CH( (N ■ (N ■ N 33) l) Cfl 3 ■ 3) I1 HzC H (N ■ 4) lI H3 (N ■ 6) (N ■ 8) (N ■ 10) (N ■ 11) (N ■ 12) (N ■ 13) I (N ■ 14) (N ■ 15) (N-II -16) (N-II -17) (N-II -18) (N-II -19) An image-type silver halide emulsion is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and forms a latent image mainly inside the grains.More specifically,
A certain amount (0.5 to 3
g/%) and exposed to light for a fixed time of 0.01 to 10 seconds, as shown below in developer A (internal developer).
The maximum density measured by a normal photographic density measurement method when developed at 18°C for 5 minutes was determined by using the following developer B for a silver halide emulsion coated in the same amount and exposed in the same manner as above.
It is preferable that the density is at least 5 times greater than the maximum density obtained when developed for 6 minutes at 20°C in (surface-type developer), and more preferably it is less (both 10 times greater). be.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-
water salt) 52.5 gKBr
5 gKI
O, add 5g water
11 Surface type image solution Metol 2.5 g L-ascorbic acid 10 g NaBOt ・
4H 0 35 gKBr
Add lg water
Specific examples of internal type emulsions include conversion type silver halide emulsions described in US Pat. No. 2,592.250, US Pat. No. 3,761,276, US Pat. No. 637, No. 3,923.513, No. 4,035.185,
4,395,478, 4,504,570, JP-A-52-156614, JP-A-55-127549,
No. 53-60222, No. 56-22681, No. 59
-208540, 60407641, 61-3
137, No. 62-215272, and Research Disclosure Magazine No. 23510 (issued November 1983) P2S5, core/shell type silver halide emulsions can be mentioned.

The internal latent image type silver halide grains of the present invention may be a conversion type emulsion or a core/shell type emulsion.
It is preferable to have a core/shell laminated structure in terms of easy control of gradation, etc. The core and shell preferably contain silver bromide and 10 mol% or less, preferably 16 mol% or less of silver iodide. consisting of silver bromide, silver iodobromide or silver chloroiodobromide, or silver chloride, silver chlorobromide, the core may be of the so-called converted type or a normal grain, halogen of the core and shell. Silver halide emulsions having a core/shell type structure, which may have the same or different compositions, are disclosed, for example, in JP-A-55-127549 and US Pat.
．． 395.478 and German Patent No. 2.332,80
The emulsions described in No. 202 and the like can be used as appropriate.

The silver halide grains of the present invention contain at least 10@-4 moles of palladium compound per mole of silver halide.

The palladium compound may be added at any point in the unfogged internal latent image emulsion used in the present invention. It is preferable to add it during chemical sensitization.

When a silver ion solution and an aqueous halogen solution are mixed to form silver halide particles, the palladium compound can be made to coexist in the form of an aqueous solution or an organic solvent solution and incorporated into the particles.

Alternatively, the palladium compound may be added in the form of an aqueous or organic solvent solution after the grains are formed and then further coated with silver halide.

The method of adding palladium is described in U.S. Patent No. 3.
, 761,276, U.S. Pat. No. 4,395,478, and Japanese Patent Application Laid-Open No. 59-216136.

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the refinement is taken as the grain size and the projected area is calculated as the average): 1.5 - or less and preferably 0.1n or more, particularly preferably 1.2- or less and 0.2n or more. The particle size distribution may be narrow or wide, but in order to improve graininess and sharpness, the particle number or weight should be within ±40% of the average particle size (more preferably ±40%).
In the present invention, a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution in which 90% or more, especially 95% or more of all grains fall within 30%, most preferably ±20%, is used in the present invention. is preferred. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers.

Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and an emulsion in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more, account for 50% or more of the total projected area of the grains may be used. An emulsion consisting of a mixture of these various crystal forms may also be used.

Silver halide compositions include silver chloride, silver bromide, and mixed silver halides.The silver halide preferably used in the present invention does not contain silver iodide or contains less than 3 mol% of salt (iodide). ) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium aggravation, reduction sensitization, noble metal sensitization, etc. alone or in combination.

For detailed examples, see Research Disclosure Magazine No. 17643 m (published December 1978)2
It is in the patent described in 23 etc.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. A detailed example can be found, for example, in the patent described in Research Disclosure Magazine No. '17643-IV (published December 1978), pages 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed examples, see Research Disclosure Magazine No. 17643-
Vl (published December 1978) and E, J, Bi
“5 tabilization of Photo” written by rr.
graphic 5ilver Halide Em
ulsions” (Focal Press), 197
It is written in the 4th annual issue.

A variety of color couplers can be used to form direct positive color images in the present invention. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention are given in "Research Disclosure" magazine No. 17643 (published December 1978) p.
25, Section 1-D, No. 18717 (published in November 1979) and JP-A-62-215272 and the patents cited therein.

Colored couplers are used to correct unnecessary absorption in the short wavelength range of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, colorless couplers, DIR couplers that release a development inhibitor along with the coupling reaction, and so on. Polymerized couplers can also be used.

In the present invention, when the gelatin layer containing a nucleating agent is a silver halide emulsion layer, as described above, the coupler is
It is preferable that the emulsion is emulsified and dispersed separately from the silver halide emulsion containing the nucleating agent and then added to the silver halide emulsion containing the nucleating agent. The organic solvent solution of the coupler may contain a color image stabilizer, a hydroquinone derivative, and an ultraviolet absorber, if necessary. Examples of high boiling organic solvents that dissolve couplers include U.S. Pat. No. 2,322,027
The solvents described in No. 1, etc. and known solvents can be used. for example,
Phthalate esters (dibutyl phthalate, dicyclohexyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylhenzoate, etc.) ), amides (such as N,N-diethyldodecanamide), alcohols or phenols (such as isostearyl alcohol), and the like. Examples of low boiling point solvents include ethyl acetate, methyl ethyl ketone, and cyclohexane. The dissolved coupler solution contains a hydrophilic solution such as gelatin containing anionic surfactants such as alkylhenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate. The mixture is mixed with an aqueous solution containing a binder and emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc.

The process of latex dispersion method etc. is disclosed in U.S. Patent No. 41993.
No. 63, West German Patent Application No. 2.541,274 and No. 2
．． It is also described in No. 541,230. Furthermore, gelatin is advantageously used as a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the rhodapul latex polymer described in U.S. Pat. No. 4,203,716 or the light-sensitive material of the present invention. However, other hydrophilic colloids can also be used.

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Typical examples of these are JP-A No. 62-215272 6oo~
It is described on page 663.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 374-391.

The light-sensitive materials of the present invention include dyes for preventing irradiation and halation, ultraviolet absorbers, desensitizers, optical brighteners, matting agents, air capping inhibitors, coating aids, hardeners,
Antistatic agents, slippery improvers, etc. can be added.

Representative examples of these additives are found in Research Disclosure Magazine No. 17643-xrM (December 1978).
P25-27, and 1B716 (19
Published in November 1979) on pages 647-651.

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

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Furthermore, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. good. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

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

In the method for producing a photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are prepared in Research Disclosure Magazine No. 176.
43V ■ (issued December 1978), page 28, European Patent No. 0,102,253, and JP-A-61
-97655. Further, the coating method described in Research Disclosure Magazine No. 17643X, Section V, pages 28 to 29 can be used.

The present invention can be applied to the production of various color photosensitive materials.

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to "Research Disclosure" magazine No. 1712.
3 (published in July 1978), it can also be applied to black-and-white photosensitive materials using a mixture of three color couplers.

Furthermore, the present invention can also be applied to the production of black and white photographic materials.

Examples of black-and-white ('B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-2600.
B/- direct positive photographic material described in No. 39 (
Examples include X-ray photosensitive materials, duplex photosensitive materials, micro photosensitive materials, photographic photosensitive materials, and printing photosensitive materials.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Mention may be made of β-methoxyethylaniline and its sulfates, hydrochlorides or P-)luenesulfonates. Two or more of these compounds can also be used in combination depending on the purpose.

The pH of these color developing solutions is 9 to 12, preferably 9.5 to 11.5.

After color development, the photographic emulsion layer is usually subjected to desilvering treatment.

The desilvering treatment may be carried out simultaneously with bleaching and fixing (bleaching and fixing) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose.

The light-sensitive material obtained according to the present invention is generally subjected to a water washing and/or stabilization process after desilvering.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent/forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal of the S.

Society of Motion Picture a
nd Te1evision Engineers
It can be determined by the method described in Vol. 64, pp. 248-253 (May 1955 issue).

The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent.

On the other hand, various known developing agents can be used to develop the black-and-white light-sensitive material according to the present invention. That is, polyhydroxybenzenes, such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol; aminophenols,
For example, p-aminophenol, N-methyl-P-aminophenol, 2,4-diaminophenol; 3-pyrazolidones, such as 1-phenyl-3-pyrazolidone, l-phenyl-4,4'-dimethyl-3 -pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone; ascorbic acids and the like can be used alone or in combination. Also, JP-A-58-5
The developer described in No. 5928 can also be used.

For detailed examples of developers, preservatives, buffers, and development methods for black-and-white photosensitive materials, please refer to "
Research Disclosure” Magazine No. 17643
(Published in December 1978) It is described in sections x■ to XxI.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to only these examples.

111 of EM-1 (Using regular alkali-treated gelatin) An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution with vigorous stirring at 75°C over 15 minutes.
Octahedral silver bromide grains with an average grain size of 0.35 μm were obtained. followed by 0.3 g of 3,4-dimethyl-1,3 per mole of silver.
-Thiazoline-2-thione was added. 1 silver in this emulsion
Chemical sensitization treatment was performed by sequentially adding 61 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole and heating at 75° C. for 80 minutes.

The grains thus obtained were used as cores and further grown in the same precipitation environment as the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 μm. The coefficient of variation in particle size was approximately 10%.

To this emulsion were added 1.5 B of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver, and the mixture was heated to 60°C.
A chemical sensitization treatment was carried out by heating for 60 minutes to obtain an internal latent image type silver halide emulsion.

U of EM-2 (Using normal alkali-treated gelatin) Add palladium just before flocculation (Na3) t
pdct Same as EM-1 except that 44 x 10-' mol 1 mol Ag and 2 x 10-' mol 1 mol-6 g of potassium thiocyanate were added.

i of EM-3 (Fe, Mn, Cu, Zn,
Gelatin (ion exchange treated so that the sum of Mg and Ca is 1100 pp or less) Amount of EM-4. 1 EM-3 to which no palladium compound was added.

-11 of EM-5 In EM-3, (NHa) zPd (J a to lX
The content of 10-' mole of Ag and palladium compound is lower than the specified amount of the present invention.

Same as EM-2 except that the above gelatin was used.

The metal ion content of each gelatin mentioned above is as follows.

Fe 7.7 3.3 gate n
1.30CuO,40
,2 Zn O,50 Mg 229.7 0.8Ca
2720 3.32959.6pp
paper support laminated on both sides with polyethylene (thickness 10
A color photographic material was prepared in which the following first to third layers were coated on the front side of the film (0 micron). 4g/s of titanium oxide was added to the polyethylene on the first layer coating side as a white pigment.
+" or 0.003 g/mz of ultramarine blue as a dye.

(Photosensitive layer composition) The components and coating amount (in units of g/m2) are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (low sensitivity red sensitive layer) Gelatin cyan coupler (ExS-1, 2 in 1:1) Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) Anti-stinting agent (Cp
d-5) Coupler dispersion medium (Cpd-6) Coupler solvent (Solv-1, 2, 3 equivalents) 1.2 0.45 ---0.27 0.0045 ---0.045 0.18 2 layers (ultraviolet absorption layer) Gelatin ultraviolet absorber (Cpd-2, 4, 16 equivalents) Color mixing inhibitor (Cpd-7, 17 equivalents) Dispersion medium (Cpd-6) Ultraviolet absorber solvent (Solv-2, 7 equivalents) anti-irradiation dye (Cpd-1819, 20, 21, 27
(10:10:13:15:20 ratio) 0.80 0.50 0.03 0.02 0.08 0.05 Third layer (protective layer) Gelatin -1,05 gelatin hardener (H-1 , H-2 equivalent) ---0,18 In the above photosensitive material, the emulsions EM1 and EM-2 are added to the first layer emulsion.
, and EM-3 were used, respectively.

Photosensitive material 1: Emulsion EM-1 (comparative example) 1
〃EM-2() 3: 〃EM-3 (Example) 〃 4: 48M-5 (Comparative example) 〃 5:
〃EM-6() The compounds used in the examples are shown below.

ExS-1 ExS-2 ・N(CJs)z xS 3 ・N(CJs)s Cpd 0 Cpd pti-a Cpd-4 Cpd H υi Cpd (CHI-CH)-r- (n= 100-1000) CONHCaHq( t) Cpd-=7 H Cpd 6 Cpd 8 Cpd 9 (CHzhSOz(C1h)zsOJ Cpd 0 Cpd 1 pct 7 ExC21 ExC~2 Solv-1 di(2-ethylhexyl) sehaket 5olv-2) Linonyl phosphate 5olv~3 Di(3-methylhexyl)phthalate 5olv-7 Di(2-ethylhexyl)phthalate H-11,2-bis(vinylsulfonylacetamide)
Ethane H-246-dichloro-2-hydroxy-135-triazine Na salt After exposure to the silver halide color produced as described above, continuous processing was performed using an automatic processor in the manner described below.

Processing process Color development, bleaching, fixing, washing with water (1) Washing with water (2) Time Temperature Mother liquor tank capacity Replenishment amount 135 seconds 38°C1〃M! 300IR1/
m240〃33//3〃300 40〃 33〃 3〃 40〃33〃3〃320 The replenishment method of flush water is to replenish the flush water to the flush bath (2),
A so-called countercurrent replenishment system was adopted in which the overflow liquid of 2) was led to the washing bath (1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fix bath for photosensitive materials is 3
5 d/m'', and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

Kotonoritozo Mother Liquor Replenisher Solvit 0.15g 0.20g Diethylene Glycol Hensyl Alcohol Potassium Bromide Henstriazole Sodium Sulfite NN-Bis(carboxymethyl)hydrazine D-Glucose Triethanolamine 12.0 d 13.5 1d 0 .80g 0.003g 2.4g 6.0g 2.0g 6.0g 16.0g 18,0IR1 0,004g 3.2g 8.0g 2.4g 8.0g Potassium carbonate 30.0g 25.0g pH (25°C) 10.25 10.75 Probe 1 solution Mother solution replenisher Disodium dihydrate Ammonium thiosulfate (700 g/l) 80 Sodium P-toluenesulfinate 20.0 g Sodium bisulfite 20.0 g 5- Mercaptotriazole ■ 3゜-0.5g Ammonium nitrate 10.0g Add water to 00M pH (25°C) 6.20 Add water to both mother liquor and replenisher. The calcium and magnesium ion concentration was reduced to 3 mfl/l or less by passing water through a hotbed column filled with Amberlite R-120B) and OH type anion exchange resin (Amberlite IR-400), and then Sodium dichloride isocyanurate 20mg/It and sodium sulfate 1.5g/j! was added. The pH of this liquid was in the range of 6.5 to 7.5.

Table 1 shows the results obtained by measuring the maximum image density ([1max) and minimum image density (Dmin) of the cyan image of each material obtained as described above.

Table 1 Incubation test> Sample of photosensitive material 1.2.3 at 45°C 185%R)
After storage (incubation) in an atmosphere of I for 2 days, exposure and processing were carried out in the same manner as above, and the cyan image density of the obtained dye image was measured. The results are shown in Table 2.

Table [Effects of the Invention] As is clear from the above results, according to the present invention, when preparing a silver halide emulsion, purified gelatin with a metal ion content of 500 ppm or less is used, and 1X per mole of silver halide is used.
A light-sensitive material chemically sensitized in the presence of 10-' moles or more of a palladium compound has a metal ion concentration of 500p in gelatin.
p+m or more, and/or the Pd compound is
Compared to light-sensitive materials using emulsions chemically sensitized in an amount of less than 0-' mole, Dmax decreases less under high temperature and high humidity, and direct positive images have high []+wax and l]win close to can be formed.

Claims (1)

[Claims] (1) Having at least one photographic emulsion layer containing internal latent image type silver halide grains that have not been fogged in advance on a support, and after imagewise exposure, developing in the presence of a nucleating agent and directly In a direct positive photographic light-sensitive material capable of forming a positive image, the total amount of Fe, Mn, Cu, Zn, Mg and Ca contained in the gelatin used in preparing the silver halide emulsion is 5.
00 ppm or less, and the silver halide emulsion is chemically sensitized in the presence of 10^-^4 moles or more of a palladium compound per mole of silver halide.