JPH04263247A - Direct positive color photographic sensitive material and image forming method using the same - Google Patents

Abstract

PURPOSE:To obtain a direct positive image having low min. density of the yellow image by incorporating a specified yellow coupler. CONSTITUTION:When at least one photographic emulsion layer contg. previously unfogged internal latent image type silver halide particles is formed on a base to obtain a direct positive photographic sensitive material capable of forming a direct positive image by imagewise exposure and development, at least one kind of acylacetamide type yellow dye forming coupler represented by the formula is incorporated into the emulsion layer. In the formula, R1 is a monovalent group and Q is a group of nonmetallic atoms required to form a 3- to 5-membered hydrocarbon ring or a 3- to 5-membered hetero ring having at least one hetero atom selected among N, O, and P in the ring in combination with C but R1 is not H or does not form a ring by bonding to Q. The amt. of the coupler used in the sensitive material is 1X10<-5>-10<-2>mol/m<2>.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention is directed to
at least one containing internal latent image type silver halide grains;
A direct positive color photographic material with two photographic emulsion layers.
For more information on the image forming method using the same, please refer to
Low minimum density (Dmin) for yellow images and color reproducibility
It relates to photosensitive materials and image forming methods with excellent
Ru. [0002] Internal latent image type halo that is not pre-fogged
After image exposure and fogging treatment using silver gende emulsion
, or perform a surface image while applying fogging treatment and directly point it.
Methods for obtaining digital images are well known. [0003] Here, the internal latent image type silver halide photograph
Emulsions are silver halide grains with photosensitive nuclei mainly inside them.
A latent image is mainly formed inside the particles by exposure to light.
A type of silver halide photographic emulsion. [0004] In this technical field, various techniques are used.
known up to now. For example, U.S. Patent No. 2,592,
No. 250, No. 2,466,957, No. 2,497,8
No. 75, No. 2,588,982, No. 3,317,32
No. 2, No. 3,761,266, No. 3,761,276
No. 3,796,577 and British Patent No. 1,15
No. 1,363, No. 1,150,553, No. 1,011
, No. 062, the main ones are those stated in each specification etc.
It is something. [0005] When these known methods are used, direct positive type and
It is possible to make relatively high-sensitivity photographic materials by
. For details on the above direct positive image formation mechanism, see, for example:
T. H. James, The Theory of the
Photographic Process” (The Theor
y of thePhotographic Proc
ess), 4th edition, Chapter 7, pp. 182-193 and US
It is described in National Patent No. 3,761,276, etc. That is, the first imagewise exposure
Surface reduction caused by so-called internal latent images that occur inside silver oxide.
Due to sensitization, silver halide in unexposed areas is removed during fogging treatment.
Fog nuclei are selectively generated only on the surface of particles, and then
Unexposed by applying normal so-called surface development processing.
It is believed that a photographic image (direct positive image) is formed on the
Ru. As mentioned above, fog nuclei are selectively generated.
As a means of
A method of applying a second exposure to the entire surface of the layer (e.g. British Patent No.
1,151,363) and the ``chemical fogging method.''
using a nucleating agent
It is known how. [0008] Here, "nucleating agent" refers to
Surface development treatment of internal latent image type silver halide emulsion
A substance that acts to directly form a positive image when
be. For this latter method, see e.g.
Disclosure” (Research Discl.
osure) Magazine, Volume 151, No. 15162 (19
Published in November 1976), pages 76-78. [0009] Used in the above-mentioned "chemical fogging method"
Hydrazine compounds are well known as nucleating agents.
. In addition, as another nucleating agent, heterocyclic quaternary ammonium
salts are known, e.g. U.S. Pat. No. 3,615,61
No. 5, No. 3,719,494, No. 3,734,738
No. 3,759,901, No. 3,854,956
, No. 4,094,683, No. 4,306,016,
British Patent No. 1,283,835, Japanese Unexamined Patent Publication No. 52-3, 4
No. 26 and No. 52-69,613
. [0010] Using such a chemical fogging method, it is possible to directly
Various techniques to improve the photographic properties of digital imaging materials
has been developed. For example, U.S. Patent No. 4,471,0
The thioacid silver halide adsorption promoting group described in No. 44
quaternary salt-based nucleating agent or JP-A No. 63-34535
Grade 4 as described in the official gazette and Japanese Patent Application No. 63-335544
Some effects can be achieved by using salt-based nucleating agents, etc.
In this case, a high maximum image density and a low minimum image density are obtained. [0011] Since direct positive photographic materials are put into practical use,
For example, if Dmax is high and Dmin is low, the contrast should not be high.
Must be. Especially if it is color reversal paper, full
Color storage for saving images from color copiers and CRTs
When used in reflective photosensitive materials such as card copies, the whiteness (
Here, whiteness refers to the color reproduction when photographing a white copy.
It is hoped that improvements will be made in Regarding whiteness,
These photosensitive materials have a limited exposure area, so the minimum image size is
Of course, the image density is important, but the gradation of the toe area is also important. feet
The harder the gradation is, the higher the whiteness is. these problems
As a method to solve the problem, for example, Japanese Patent Application Laid-Open No. 1-145647
Interior not pre-covered as disclosed in
Manganese, copper, zinc, and cadmium in latent image type silver halide grains
Highlight areas can be hardened by incorporating metal into the
If high maximum concentration and low minimum concentration can be obtained while adjusting
This effect has been found. On the other hand, conventional silver halide color photography
Materials used include yellow, magenta, and cyan couplers.
However, yellow couplers have a higher molecular absorption capacity than conventional dyes.
It requires a large amount of coupler and silver due to its small optical coefficient.
Ru. For this purpose color reversal paper, full color copier
Color hard copy for saving images from CRT or CRT,
When used in reflective photosensitive materials such as color proofs, Dm
in is impaired. Therefore, high color development (coupler
High coupling reactivity and large molecular extinction coefficient of dyes
) and has excellent spectral absorption characteristics for color images.
The development of a coupler was desired. Acyl of acylacetanilide type coupler
Based on U.S. Patent Re No. 27,848, Pivaloy
group, 7,7-dimethylnorbornane-1-carbonyl
group, 1-methylcyclohexane-1-carbonyl group, etc.
However, in JP-A-47-26133, cyclopropane-1
-carbonyl group, cyclohexane-1-carbonyl group, etc.
What is disclosed? However, these couplers
If the pulling reactivity is poor or the molecular extinction coefficient of the dye is
If it is small or the spectral absorption characteristics of the color image are inferior.
They were inferior in some respect. [Problem to be Solved by the Invention] Therefore, the object of the present invention is to
The minimum density (Dmin) of the yellow image is low and the color reproduction is
To provide a direct positive color photographic material with excellent properties.
It is in. [Means for Solving the Problems] The above objects of the present invention are as follows.
(1) direct positive color photographic material and (2) image
It has been found that this can be achieved by a forming method. (1) Internal latent image type silver halide that is not pre-fogged
at least one photographic emulsion layer containing grains on a support;
It is possible to directly form a positive image by developing after imagewise exposure.
In the direct positive photographic light-sensitive material, the emulsion layer contains one of the following:
Acylacetamide type yellow color represented by general formula (I)
characterized by containing at least one type of elementary-forming coupler
A direct positive color photographic material. General formula (I) [Formula 3] (In the formula, R1 represents a monovalent group. Q together with C is 3-
5-membered hydrocarbon ring or a small number selected from N, O, S, P
3- to 5-membered compound having at least one heteroatom in the ring
Represents a group of nonmetallic atoms necessary to form an elementary ring. however
, R1 is not a hydrogen atom and is bonded to Q.
They do not form a ring. ) (2) Direct positive color copying described in (1) above
A true photosensitive material is prepared by using a developing agent represented by the following general formula (II).
An image forming method characterized by processing with a developing treatment solution containing
Law. General formula (II) [Formula 4] (wherein, R21 represents an alkyl group, R22 represents an alkyl group
Represents a ren group. However, R21 and R22 are bonded to each other.
may form a ring. ) Acyl acetate of the present invention
The amide type yellow coupler preferably has the following general formula (Y
). General formula (Y) ##STR5## In the formula (Y), R1 is any group other than hydrogen.
a valent substituent, Q together with C represents a 3- to 5-membered hydrocarbon ring or
is at least one hetero selected from N, S, O, P
Necessary to form a 3- to 5-membered heterocycle containing atoms in the ring
R2 is a hydrogen atom, a halogen atom (
F, Cl, Br, I. The same applies in the explanation of formula (Y) below.
. ), alkoxy group, aryloxy group, alkyl group or
is an amino group, and R3 is a group that can be substituted on the benzene ring.
, X is a hydrogen atom or an oxidized product of an aromatic primary amine developer
A group that can be separated by a coupling reaction with (hereinafter referred to as a leaving group)
), and P represents an integer from 0 to 4, respectively. However, when P is multiple, multiple R3s may be the same or different.
It's okay to stay. Here, examples of R3 include halogen atom,
Alkyl group, aryl group, alkoxy group, arylox
cy group, alkoxycarbonyl group, aryloxycarbo
Nyl group, carbonamide group, sulfonamide group, carba
Moyl group, sulfamoyl group, alkylsulfonyl group,
Ureido group, sulfamoylamino group, alkoxylic
Bonylamino group, alkoxysulfonyl group, acyloxy
Cy group, nitro group, heterocyclic group, cyano group, acyl group, acyl group,
ruoxy group, alkylsulfonyloxy group, aryls
There is a sulfonyloxy group, and an example of a leaving group is a nitrogen atom.
Heterocyclic group bonded to the coupling active position, aryloxy
cy group, arylthio group, acyloxy group, alkylsulf
Honyloxy group, arylsulfonyloxy group, heterocycle
Contains an oxy group and a halogen atom. [0020] When the substituent in formula (Y) is an alkyl group,
or contains an alkyl group, unless otherwise specified.
The alkyl group can be linear, branched or cyclic, substituted.
an alkyl group that may contain unsaturated bonds even if
(e.g. methyl, isopropyl, t-butyl, cyclo
Pentyl, t-pentyl, cyclohexyl, 2-ethyl
hexyl, 1,1,3,3-tetramethylbutyl, dode
syl, hexadecyl, allyl, 3-cyclohexenyl,
Oleyl, benzyl, trifluoromethyl, hydroxy
Methylmethoxyethyl, ethoxycarbonylmethyl, fluoride
phenoxyethyl). [0021] The substituent in formula (Y) is an aryl group.
or contains an aryl group, unless otherwise specified.
The aryl group is an optionally substituted monocyclic or fused ring.
aryl groups (e.g. phenyl, 1-naphthyl, p-t)
Lyle, o-tolyl, p-chlorophenyl, 4-methoxy
Phenyl, 8-quinolyl, 4-hexadecyloxyphene
nil, pentafluorophenyl, p-hydroxyphenyl
p-cyanophenyl, 3-pentadecylphenyl,
2,4-di-t-pentylphenyl, p-methanesulfonate
(3,4-dichlorophenyl)
do. [0022] The substituent in formula (Y) is a heterocyclic group or
or a heterocyclic group, unless otherwise specified, the heterocyclic group
is at least selected from O, N, S, P, Se, Te
3- to 8-membered substituted ring containing one heteroatom
Good monocyclic or fused ring heterocyclic groups (e.g. 2-free
2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1
-imidazolyl, 1-benzotriazolyl, 2-benzo
triariazolyl, succinimide, phthalimide, 1
-benzyl-2,4-imidazolidinedione-3-yl
) means. [0023] Hereinafter, preferably used in formula (Y)
The substituents are explained below. In formula (Y), R1 is
Preferably a halogen atom, a cyano group, or both
Total number of carbon atoms that may be substituted (hereinafter abbreviated as C number) 1 to 3
0 monovalent groups (e.g. alkyl groups, alkoxy groups) or
is a monovalent group having 6 to 30 carbon atoms (e.g. aryl group, aryl group,
(aloxy group), and its substituents include, for example, halo
Gen atom, alkyl group, alkoxy group, nitro group, amino
- group, carbonamide group, sulfonamide group, acyl group
There is. In formula (Y), Q is preferably together with C.
Number of carbon atoms that may be substituted with any of 3 to 5 members
3 to 30 hydrocarbon rings or at least one N, S, O
, the number of carbon atoms containing a heteroatom selected from P in the ring is 2
List the nonmetallic atomic groups necessary to form ~30 heterocycles.
Was. Also, the ring that Q forms with C has an unsaturated bond within the ring.
May contain. As an example of a ring formed by Q with C,
Cyclopropane ring, cyclobutane ring, cyclopentane ring
, cyclopropene ring, cyclobutene ring, cyclopentene
ring, oxetane ring, oxolane ring, 1,3-dioxola
These include a ring, a thietane ring, a thiolane ring, and a pyrrolidine ring. Examples of substituents include halogen atoms, hydroxyl groups, and alkyl groups.
Kyl group, aryl group, acyl group, alkoxy group, aryl group
group, cyano group, alkoxycarbonyl group, alkoxycarbonyl group,
There are kylthio and arylthio groups. In formula (Y), R2 is preferably halo
Gen atoms, any of which may be substituted, number of carbon atoms
Alkoxy group having 1 to 30, aryl having 6 to 30 carbon atoms
alkyl group having 1 to 30 carbon atoms or carbon
Represents an amino group having 0 to 30 elementary atoms, and as its substituent:
For example, halogen atoms, alkyl groups, alkoxy
group, and aryloxy group. In formula (Y), R3 is preferably H
rogene atom, any of which may be substituted, number of carbon atoms: 1
~30 alkyl group, aryl group having 6 to 30 carbon atoms
, alkoxy group having 1 to 30 carbon atoms, 2 to 30 carbon atoms
30 alkoxycarbonyl groups, having 7 to 30 carbon atoms
Aryloxycarbonyl group, carbon number 1-30
Rubonamide group, sulfonamide having 1 to 30 carbon atoms
group, carbamoyl group having 1 to 30 carbon atoms, number of carbon atoms
0-30 sulfamoyl group, carbon number 1-30 atom
Rukylsulfonyl group, aryls having 6 to 30 carbon atoms
sulfonyl group, ureido group having 1 to 30 carbon atoms, carbon atom
Sulfamoylamino group with 0 to 30 children, 2 carbon atoms
~30 alkoxycarbonylamino groups,
Heterocyclic group having 1 to 30 carbon atoms, 1 to 30 carbon atoms
Acyl group, alkylsulfonyl group having 1 to 30 carbon atoms
xy group, arylsulfonyloxy group having 6 to 30 carbon atoms
It represents a cy group, and its substituents include, for example, a halogen atom.
child, alkyl group, aryl group, heterocyclic group, alkoxy group
, aryloxy group, heterocyclicoxy group, alkylthio group
, arylthio group, heterocyclic thio group, alkylsulfonyl
group, arylsulfonyl group, acyl group, carbonamide
group, sulfonamide group, carbamoyl group, sulfamoyl group
group, alkoxycarbonylamino group, sulfamoyl group
Amino group, ureido group, cyano group, nitro group, acyl group
Oxy group, alkoxycarbonyl group, aryloxycar
Bonyl group, alkylsulfonyloxy group, arylsulfonyl group
There is a honyloxy group. In formula (Y), P is preferably
represents an integer of 1 or 2, and the substitution position of R3 is preferably the meta-position or para-position with respect to ##STR6##. In formula (Y), X is preferably a nitrogen source.
Heterocyclic group or aryl group attached to the coupling active position in the child
represents a group. When X represents a heterocyclic group,
is preferably a 5- to 7-membered monocyclic ring which may be substituted.
is a fused-ring heterocyclic group, an example of which is succinyl.
imide, maleimide, phthalimide, diglycol
imide, pyrrole, pyrazole, imidazole, 1,2
, 4-triazole, tetrazole, indole, in
dazole, benzimidazole, benzotriazole,
imidazolidine-2,4-dione, oxazolidine-2
,4-dione, thiazolidine-2,4-dione, 00
31] Imidazolidin-2-one, oxazolidine-2
-one, thiazolidin-2-one, benzimidazoline
-2-one, benzoxazolin-2-one, benzothi
Azolin-2-one, 2-pyrrolin-5-one, 2-y
midazolin-5-one, indoline-2,3-dione,
2,6-dioxypurine, parabanic acid, 1,2,4-t
Riazolidine-3,5-dione, 2-pyridone, 4-pyridone
Lydone, 2-pyrimidone, 6-pyridazone-2-pyrazo
2-amino-1,3,4-thiazolidine, 2-imino
No-1,3,4-thiazolidin-4-one, etc.
These heterocycles may be substituted. Examples of these heterocyclic substituents include
rogen atom, hydroxyl group, nitro group, cyano group, carbon
carboxyl group, sulfo group, alkyl group, aryl group,
Rukoxy group, aryloxy group, alkylthio group, ali
ruthio group, alkylsulfonyl group, arylsulfony group
group, alkoxycarbonyl group, aryloxycarboyl group
Nyl group, acyl group, acyloxy group, amino group, carbo
amide group, sulfonamide group, carbamoyl group, sulfonamide group,
famoyl group, ureido group, alkoxycarbonyl amide
and sulfamoylamino groups. X is aryluo
When representing an xy group, X is preferably an atom having 6 to 30 carbon atoms.
represents a lyloxy group, and when the above X is a heterocycle,
May be substituted with a group selected from the listed substituent groups
. As a substituent for the aryloxy group, halo
Gen atom, cyano group, nitro group, carboxyl group, tri-
Fluoromethyl group, alkoxycarbonyl group, carbonyl group
Amide group, sulfonamide group, carbamoyl group, sulfur
amoyl group, alkylsulfonyl group, arylsulfonyl group
A group or a cyano group is preferred. Next, particularly preferably used in formula (Y)
The following substituents are explained below. R1 is particularly preferably
is a halogen atom or an alkyl group, most preferably
It is a methyl group. Q is particularly preferably a ring formed together with C.
is a group of nonmetallic atoms forming a 3- to 5-membered hydrocarbon ring.
, for example, ##STR7## Here, R is a hydrogen atom, a halogen
Represents an atom or an alkyl group. However, multiple Rs are the same
It may be the same or different. Q is most preferably attached to C
Together, they form a three-membered ring. R2 is particularly preferably a chlorine atom, a fluorine atom,
elementary atoms, alkyl groups having 1 to 6 carbon atoms, (e.g. methyl
trifluoromethyl, ethyl, isopropyl, t-
butyl), alkoxy groups having 1 to 8 carbon atoms (e.g.
(toxy, ethoxy, methoxyethoxy, butoxy), or
or an aryloxy group having 6 to 24 carbon atoms (e.g.
phenoxy group, p-tolyloxy, p-methoxyphenoxy
c) and most preferably a chlorine atom, a methoxy group or
It is a trifluoromethyl group. R3 is particularly preferably a halogen atom
, alkoxy group, alkoxycarbonyl group, aryl group
Oxycarbonyl group, carbonamide group, sulfonamide
group, carbamoyl group or sulfamoyl group and most
Preferably an alkoxy group, an alkoxycarbonyl group, or a carbonyl group.
It is a carbonamide group or a sulfonamide group. X is special
is preferably represented by the following general formula (Y-1), (Y-2) or
It is a group represented by (Y-3). General formula (Y-1) [Image Omitted] In the formula (Y-1), Z represents the following. Here R4, R5, R8
, and R9 is a hydrogen atom, an alkyl group, an aryl group,
Alkoxy group, aryloxy group, alkylthio group,
Rylthio group, alkylsulfonyl group, arylsulfonyl group
represents a nyl group or an amino group, and R6 and R7 are
Hydrogen atom, alkyl group, aryl group, alkylsulfony
group, arylsulfonyl group or alkoxycarbonyl group
R10 and R11 are hydrogen atoms, alkyl groups,
represents a group or an aryl group. [0043] R10 and R11 combine with each other to form benzene.
A ring may be formed. R4 and R5, R5 and R6
, R6 and R7 or R4 and R8 are bonded to each other.
ring (e.g. cyclobutane, cyclohexane, cyclohexane)
(butane, cyclohexene, pyrrolidine, piperidine)
may be formed. of the heterocyclic group represented by formula (Y-1)
Particularly preferred is a heterocyclic group in formula (Y-1) in which Z is ##STR11##. Expressed by formula (Y-1)
The number of carbon atoms in the heterocyclic group is 2 to 30, preferably 4.
-20, more preferably 5-16. Formula (Y-2) [Image Omitted] In formula (Y-2), R12 and R1
At least one of 3 is a halogen atom, a cyano group, or a nitro group.
group, trifluoromethyl group, carboxyl group, alkoxy group
Cycarbonyl group, carbonamide group, sulfonamide group
, carbamoyl group, sulfamoyl group, alkyl sulfo
Selected from nyl group, arylsulfonyl group or acyl group
and the other is a hydrogen atom, an alkyl group, or
It may also be an alkoxy group. R14 is R12 or R
Represents a group with the same meaning as 13, and m represents an integer from 0 to 2.
. Carbon atom of aryloxy group represented by formula (Y-2)
The number of children is 6-30, preferably 6-24, more preferably
6 to 15. General formula (Y-3) [Chemical formula (Y-3)] In formula (Y-3), W together with N represents pyro
ring, pyrazole ring, imidazole ring or triazole ring
Represents a group of nonmetallic atoms necessary to form a ring. here
The ring represented by W may have a substituent, and preferred
Examples of preferred substituents include halogen atoms, nitro groups, and
group, alkoxycarbonyl group, alkyl group, aryl group
group, amino group, alkoxy group, aryloxy group or
It is a carbamoyl group. Complex expressed by formula (Y-3)
The number of carbon atoms in the ring group is 2 to 30, preferably 2 to 24, and so on.
The number is preferably 2 to 16. X is most preferably represented by the formula (
It is a group represented by Y-1). Represented by formula (Y)
Couplers are substituents R1, Q, and [Chemical formula 14] that are bonded to each other via a divalent or higher valent group.
It is also possible to form a dimer or a multimer of more than that. In this case, the carbon atom number range shown in each substituent above is
It may be outside the scope of the regulations. It is expressed by the formula (Y) below.
A specific example of a yellow coupler is shown below. [Formula 15] [Formula 15] [Formula 16] [Formula 16] [Formula 17] [Formula 18] [Formula 18] [Formula 19] [Formula 22] [Formula 23] [Formula 23] [Formula 28] [Formula 24] [Formula 25] [Formula 26] [Formula 26] ] [Chemical 29] [Chemical 30] [Chemical 31] [Chemical 32] [Chemical 32] The yellow color of the present invention represented by the formula (Y)
Puller can be synthesized by the following synthetic route. ##STR33## Here, the compound (a) is described in J. Chem
．． Soc. (C), 1968, 2548, J. Am
．． Chem. Soc. , 1934, 56, 2710
, Synthesis, 1971, 258, J. Or
g. Chem. , 1978, 43, 1729, CA, 1
Synthesized by the method described in 960,66,18533y etc.
be done. Hereinafter, compounds (b) (c) (d) (e) and (
f) can be synthesized by a conventionally known method. Examples of synthesis of couplers of the present invention are shown below. Synthesis Example 1 Synthesis G of Exemplified Compound Y-28
ottkis, D. etal, J. Am. Ch
em. Soc. , 1934, 56, 2710.
1-Methylcyclopropanecarbo synthesized by method
25g of phosphoric acid, 100ml of methylene chloride, N,N
-3 in a mixture of 1 ml of dimethylformamide
8.1g of oxalyl chloride was added for 30 minutes at room temperature.
dripped. After dropping, react at room temperature for 2 hours and aspirate.
- Remove methylene chloride and excess oxalyl chloride under reduced pressure.
By removing 1-methylcyclopropanecarbonyl
An oil of luchloride was obtained. 6 g of magnesium, 2 ml of carbon tetrachloride
100 ml of methanol in a mixture of torr at room temperature
The mixture was added dropwise over 30 minutes at
32.6 g of ethyl 3-oxobutanoate was heated under reflux.
Add drops over 0 minutes. After dropping, heat and reflux for another 2 hours.
Methanol is completely distilled off under reduced pressure using an aspirator. Te
Add 100ml of trahydrofuran to the reaction mixture
Disperse the previously obtained 1-methylcyclopropanka at room temperature.
Add rubonyl chloride dropwise. Reaction solution after 30 minutes reaction
Extract with 300ml of ethyl acetate and dilute sulfuric acid, water
After washing, the organic layer was dried with anhydrous sodium sulfate, and the solvent was distilled off.
to give 2-(1-methylcyclopropanecarbonyl)-
55.3 g of an oily substance of ethyl 3-oxobutanoate was obtained. 2-(1-methylcyclopropanecarbonyl)
55 g of ethyl)-3-oxobutanoate, 1 ethanol
Stir 60 ml of solution at room temperature and add 30%
Drop 60ml of ammonia water over 10 minutes.
Ru. After that, stir for 1 hour and add 300ml of ethyl acetate.
After extraction with dilute hydrochloric acid, neutralization, and washing with water, the organic layer was extracted with anhydrous sulfuric acid.
After drying with sodium, the solvent was distilled off (1-methylsiloxane).
Obtained 43g of oily product of ethyl acetate (ropropanecarbonyl).
Ta. (1-methylcyclopropanecarbonyl)
34 g of ethyl acetate and N-(3-amino-4-chlorophene)
Nyl)-2-(2,4-di-t-pentylphenoxy)
Add 44.5 g of butanamide at an internal temperature of 100 to 120°C.
Heat to reflux under reduced pressure with a spirator. Reaction solution after 4 hours reaction
column chromatography using a mixed solvent of n-hexane and ethyl acetate.
49g of Exemplified Compound Y-28 was purified from tomatoes and turned into a viscous oil.
obtained as. The structure of the compound is determined by MS spectrum, NMR
Confirmed by spectrum and elemental analysis. Synthesis Example 2 Synthesis example of exemplified compound Y-1
22.8g of compound Y-28 was added to 300ml of methylene chloride.
Dissolve 5.4 g of sulfuryl chloride in 1 liter and cool on ice.
Add drops over 0 minutes. After reacting for 30 minutes, thoroughly rinse the reaction solution with water.
Wash, dry with anhydrous sodium sulfate, and concentrate to obtain Exemplary Compound Y.
-28 chloride was obtained. 1-benzyl-5-ethoxyh
Dantoin 18.7g, triethylamine 11.2ml
liter, N,N-dimethylformamide 50ml
Salt of exemplified compound Y-30 synthesized earlier in a solution of
50 ml of N,N-dimethylformaldehyde.
Add the solution dissolved in a bottle over 30 minutes at room temperature.
. After reaction at 40°C for 4 hours, the reaction solution was
Extract with 300 ml of ethyl acetate, wash with water, and add 2% trichloride.
Wash with 300 ml of ethylamine aqueous solution, and
Neutralize with dilute hydrochloric acid water. The organic layer was treated with anhydrous sodium sulfate.
After drying in a vacuum chamber, the solvent was distilled off and the resulting oil was
It was crystallized from a mixed solvent of xane and ethyl acetate. precipitated
After filtering the crystals and washing with a mixed solvent of n-hexane and ethyl acetate
, by drying, crystals of Exemplified Compound Y-1 22.8
I got g. The structure of the compound is determined by MS spectrum and NMR spectrum.
confirmed by elemental analysis. Also, the melting point is 132 ~
The temperature was 3°C. The coupler of the present invention may be used alone or in combination with two types.
- It may be used in combination of several kinds, and known yellow pigments may also be used.
It may be used in combination with a forming coupler. Couplers of the invention
can be used in any layer of photosensitive materials, but
Preferably used in a silver halide emulsion layer or its adjacent layer.
, in a light-sensitive silver halide emulsion layer is most preferred. Amount of the coupler of the present invention used in the light-sensitive material
is 1 x 10-5 mol to 10-2 mol per m2.
preferably 1 x 10-4 mol to 5 x 10-3 mol,
More preferably 2 x 10-4 mol to 2 x 10-3 mol.
be. The photosensitive material of the present invention is represented by general formula (I).
In addition to the yellow coupler, there are conventionally known couplers.
Can be used in combination with yellow coupler. Specifically after
It will be described in The color developing agent used in the present invention is one of the following:
It is represented by general formula (II). [In the above general formula (II), R21 is
represents an alkyl group, R22 represents an alkylene group,
Also, even if R21 and R22 are bonded to each other to form a ring,
good. ] The above R21 is an alkyl group having 1 to 8 carbon atoms.
preferably a methyl group, ethyl group, butyl group or
or methoxyethyl group. The above R22 is a carbon atom
Represents an alkylene group of 2 to 6, preferably ethylene
or trimethylene group. Represented by general formula (II)
Specific examples of developing agents that can be used are shown below. [Chemical formula 35] [Chemical formula 36] [Chemical formula 36] Color development represented by the above general formula (II)
The amount of the main agent to be used is preferably about 0.0% per liter of developer.
1 g to about 20 g, more preferably about 0.5 g to about 10 g
The concentration is Regarding the developer containing the developing agent of the present invention
will be described in detail later. [0087] The inside which is not covered in advance for use in the present invention
In partial latent image type silver halide emulsions, the surface of silver halide grains
is not fogged in advance, and the latent image is mainly inside the particle.
It is an emulsion containing silver halide formed in the
Specifically, a silver halide emulsion is deposited on a transparent support.
amount (0.5-3g/m2) and 0.01 less than this
Then, the following developer solution A (
Normally when developed for 5 minutes at 18°C in an internal type developer
The maximum density measured by the photographic density measurement method described above is
A silver halide emulsion coated in the same amount and exposed in the same manner as
Developed at 20°C for 6 minutes in the following developer B (surface type developer).
at least 5 times greater than the maximum concentration obtained when
Preferably, those having a concentration, more preferably at least
also has a concentration ten times greater. Internal developer A Metol
　　　　　　　　　　　　　　　　　　　　　　　　　
2g Sodium sulfite (
anhydrous)
90g
hydroquinone
　　　　　　　　　　　　　　　　　　　　　　　　　
8g Soda carbonate (monohydrate)
　　　　　　　　　　　　　　　　　　　　　　　　　
52.5g KBr
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
5g KI
　　　　　　　　　　　　　　　　　　　　　　　　　
0
．． Add 5g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1 liter surface developer B Metol
　　　　　　　　　　　　　　　　　　　　　　　　　
2.5g L-ascorbic acid
　　　　　　　　　　　　　　　　　　　　　　　　　
10g
NaBO2 ・4H2 O
　　　　　　　　　　　　　　　　　　　　　　　　　
35g KBr
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
Add 1g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1 liter 0089 Endolatent emulsion
As a specific example, for example, U.S. Patent No. 2,592,25
Conversion type halogen described in the specification for No. 0
Silver emulsion, U.S. Pat. No. 3,761,276, No. 3,8
No. 50,637, No. 3,923,513, No. 4,03
No. 5,185, No. 4,395,478, No. 4,504
, No. 570, JP-A-52-156614, JP-A No. 55-1
No. 27549, No. 53-50222, No. 56-226
No. 81, No. 59-208540, No. 60-10764
No. 1, No. 61-3137, JP-A No. 62-215272
No. 0090 Research Disclosure Magazine No. 2
3510 (issued November 1983), page 236.
In addition, U.S. Patent No. 47 having a silver chloride shell
No. 89627, Japanese Patent Application Publication No. 89627 on silver chlorobromide core-shell emulsions
No. 63-10160, No. 63-47766, patent application No. 1
No. 2467, special feature on emulsions doped with metal ions.
In 1987-191145 and JP1-52146
The core/shell type silver halide emulsions described above may be mentioned.
can. Internal latent image type core-shell silver halide emulsion
The silver halide molar ratio between the core and the shell is 20/1 or less.
/100 or more is particularly preferred. In the present invention, the cover is covered in advance.
Mn, Cu,
Zn, Cd, Pd, Bi or Periodic Table No. VIII
Contains at least one metal from the group consisting of metals belonging to the group
You may. Unfogged internal latent image of the present invention
Mn, Cu, Zn, Cd contained in type silver halide grains
, Pd, Bi or belonging to Group VIII of the periodic table
The amount of metal used is between 10-9 and 1 per mole of silver halide.
0-2 mol is preferable, and 10-7 to 10-3 mol is more preferable.
preferable. Among the above metals, lead, iridium and
Particular preference is given to using bismuth and rhodium. these
The metal is prepared by mixing a silver ion solution and a halogen aqueous solution.
When forming silver halide grains, metal ions are added to an aqueous solution or
is coexisting in the form of an organic solvent solution and incorporated into particles.
Can be done. Alternatively, after forming the particles, the metal ions can be dissolved in water.
It may be added in the form of a solution or an organic solvent solution, and then further
may be covered with silver halide. How to incorporate these metals
Regarding the law, see U.S. Patent No. 3,761,276;
, No. 395,478 and JP-A-59-216136, etc.
It is described in. The shape of the silver halide grains used in the present invention is
Cube, octahedron, dodecahedron, dodecahedron (patent application Hei 1-43
Regular crystals like 125), irregularities like spherical shapes, etc.
crystal form, as well as JP-A-1-131547 and JP-A-1-1-1.
The length/thickness ratio described in No. 58429 is 5 or more, especially 8 or more.
The upper plate-shaped grain accounts for 50% or more of the total projected area of the grain.
An overlying emulsion may also be used. In addition, these various results
Milk with complex crystal forms and mixtures thereof
It may be an agent. The composition of silver halide is silver chloride, odor
There are silver halides mixed with silver oxide, which are preferably used in the present invention.
The silver halide contained does not contain silver iodide, or even if it contains it, it is 3 mol.
% or less of salt (iodine) silver bromide, (iodine) silver chloride or (iodine) odor
It is chemical silver. Average grain size of silver halide grains (spherical
Or, for particles close to spheres, change the particle diameter to cubic particles.
In the case of
Expressed as an average of ) is 1.5μm or less and 0.1μm or less
The diameter is preferably 1.2 μm or less, and particularly preferred is 0.2 μm or less.
It is 2 μm or more. Particle size distribution may be narrow or wide.
However, the number of particles may be increased to improve graininess and sharpness.
or within ±40% of the average particle size by weight, preferably
of all particles within 30%, most preferably within ±20%.
Particle size that contains 90% or more, especially 95% or more
Developed a so-called "monodisperse" silver halide emulsion with a narrow cloth.
It is preferable to use it clearly. [0096] Also, the photosensitive material satisfies the target gradation.
In order to
Two or more types of monodispersed silver halide milk with different grain sizes
or multiple particles of the same size but with different sensitivities.
They can be mixed into layers or applied in separate layers. Sara
Two or more types of polydispersed silver halide emulsions or monodispersed silver halide emulsions
By mixing or layering combinations of emulsions and polydisperse emulsions.
You can also use The silver halide emulsion used in the present invention has grain
Sulfur or selenium sensitization, reduction sensitization inside or on the surface
, chemical sensitization by using noble metal sensitization alone or in combination.
can be done. As a chemical sensitization method for core particles,
Using the method described in No. 1-17488 and No. 1-17487
I can be there. As described in JP-A-1-197742
In the presence of a sea urchin mercapto compound, also 1-2549
46, No. 2-69738, Patent Application No. 1-95394
Thiosulfinic acid, sulfinic acid, sulfite as listed
may be added. For detailed specific examples, please refer to research
Disclosure magazine No. 17643-III (1
It is in the patent described on page 23 (published in December 1978). The photographic emulsion used in the present invention can be prepared by a conventional method.
Spectrally sensitized by photographic sensitizing dyes. particularly useful colors
The base is cyanine pigment, merocyanine pigment and complex merocyanine pigment.
It is a pigment that belongs to cyanine pigments, and these pigments can be used alone.
Or they can be used in combination. In addition, the above dyes and supersensitizers
may be used together. For detailed specific examples, please refer to research
Disclosure magazine No. 17643-IV (197
(Published in December 2008) in the patent described on pages 23-24, etc.
. The photographic emulsion used in the present invention contains a photosensitive material.
Prevents fogging during the manufacturing process, storage, or photo processing of materials.
Antifogging is used to prevent fogging or to stabilize photographic performance.
Inhibitors or stabilizers may be included. detailed ingredients
Examples include Research Disclosure magazine No.
17643-VI (issued December 1978) and E
．． J. “Stabilization o” by Birr
f Photographic Silver Hai
'lde Emulsion' (Focal Press
), published in 1974, etc. [0100] In the present invention, various color couplers may be used together.
can be used. A typical example of a useful color coupler
is a naphthol or phenolic compound, pyrazolo
or pyrazoloazole compounds and open chain or pyrazoloazole compounds and
is a heterocyclic ketomethylene compound. In the present invention, in combination
Available in these cyan, magenta and yellow couplers
A specific example is "Research Disclosure" magazine No.
17643 (published December 1978) 25 pages, VII
-D section, same No. 18717 (issued November 1979)
and the compounds described in JP-A No. 62-215272 and
and the patents cited in them. Among them, 5 preferably used in the present invention
-3rd place as a pyrazolone magenta coupler
5-pyra substituted with an amino group or an acylamino group
Zolone couplers (especially sulfur atom-eliminating two-equivalent couplers)
Puller). More preferred are pyrazoloazole caps.
and US Pat. No. 3,725,067, among others.
Pyrazolo[5,1-c][1,2,4]thoria described in
Sols, etc. are preferred, but due to the yellow side absorption of the coloring dye,
U.S. Pat. No. 4,500,6 due to its small size and light fastness.
The imidazo[1,2-b]pyrazoles described in No. 30 are
Even more preferred, U.S. Pat. No. 4,540,654
Pyrazolo[1,5-b][1,2,4]triazo described
are particularly preferred. Cyan coupler preferably used in the present invention
- as U.S. Patent No. 2,474,293, U.S. Patent No. 4,
052,212 etc.
Enolic coupler in U.S. Patent No. 3,772,002
An alkyl group greater than or equal to ethyl group at the meta position of the described phenol nucleus.
It is a phenolic cyan coupler with a kill group.
Other 2,5-diacylamino substituted phenolic couplers
Also preferred from the viewpoint of color image fastness. [0104] As the yellow coupler, for example,
Patent No. 3,933,501, Patent No. 4,022,620
No. 4,326,024, No. 4,401,75
No. 2, Special Publication No. 58-10739, British Patent No. 1,425
, No. 020, No. 1,476,760, etc.
is preferred. Unnecessary absorption in the short wavelength range of the generated pigment
Colored coupler to correct
Diffusive couplers, colorless couplers, couplings
DIR couplers that release development inhibitors along with the
Polymerized couplers can also be used. Photographically useful residues associated with coupling
Couplers that release
. DIR couplers that release development inhibitors are
Chi Disclosure Magazine No. 17643, VII
- Patent described in Section F, Japanese Patent Application Laid-open No. 57-151944,
57-154234, 60-184248, US special
What is described in Patent No. 4,248,962 and Unexamined Patent Publication No. 4,248,962
The one described in Sho 63-146035 is preferred. During development, a nucleating agent or development accelerator is released in the form of an image.
As a coupler, British Patent No. 2,097,140
, No. 2,131,188, JP-A-59-15763
8, 59-170840, International Application Publication (WO) 88
The one described in No./01402 is preferred. [0106] The standard amount of color coupler used is
0.001 to 1 mole per mole of silver halide
range, preferably 0.01 for yellow couplers.
to 0.5 moles, and 0.03 moles for magenta couplers.
mol to 0.5 mol, and 0.00 mol for cyan couplers.
2 to 1.0 mol. Emulsion layer of the light-sensitive material of the present invention
binders or protective colloids that can be used in
It is advantageous to use gelatin as a material, but
Other hydrophilic colloids can also be used. The photosensitive material of the present invention also contains a color antifoggant.
Alternatively, a color mixing inhibitor can be used. Representative examples of these are
Described in No. 62-215272, pages 185-193
There is. As a compound that releases a photographically useful group, JP-A-Sho et al.
No. 63-153540, No. 63-259555, patent application
No. 63-212080, patent application No. 1-64715, same
Examples include compounds described in No. 1-130986. The present invention
A color enhancer is added to improve the color development of the coupler.
Can be used. A representative example of the compound is JP-A-62-2
15272, pages 121-125.
Ru. [0108] The photosensitive material of the present invention has irradiation
and dyes that prevent halation (for example, patent application 1986-2)
No. 37985 and No. 63-240393 may also be used.
. In addition, the solid microcrystal dispersion method is used as a dye dispersion method.
Good too. ), ultraviolet absorbers, plasticizers, optical brighteners, matte
antifogging agent, air fog prevention agent, coating aid, hardening agent, antistatic agent
It is possible to add additives such as additives and slip property improvers. these
Typical examples of additives are Research Disclosure Magazine N
o. 17643 VII-XIII (December 1978
18716 (published in 1979), pp. 25-27 (published in 1979)
Published in November 2013) on pages 647-651. [0109] The present invention provides at least two different
It can also be applied to multilayer, multicolor photographic materials with spectral sensitivities. Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
At least one green-sensitive emulsion layer and one blue-sensitive emulsion layer each.
have one. You can choose the order of these layers as you like.
Bell. The preferred layer arrangement order is red sensitive, green sensitive from the support side.
Sensitivity, blue sensitivity, or green sensitivity, red sensitivity, blue sensitivity from the support side
It is gender. Also, each of the above emulsion layers has two or more layers with different sensitivities.
may be made of emulsion layers with the same color sensitivity.
A non-light sensitive layer may be present between two or more emulsion layers.
stomach. Cyan-forming coupler in red-sensitive emulsion layer, green-sensitive emulsion layer
Magenta-forming coupler in the layer and yellow in the blue-sensitive emulsion layer
Usually each contains a forming coupler, but in some cases
Add yellow coupler and magenta coupler to the green-sensitive layer.
Different combinations can be used, such as mixing them.
. [0110] The photosensitive material according to the present invention is a silver halide milk
In addition to the agent layer, there are also a protective layer, an intermediate layer, a filter layer, and a filter layer.
Add auxiliary layers such as anti-static agent, backing layer, and white reflective layer as appropriate.
It is preferable to provide one. In the photographic material of the present invention
Research disclosure for photographic emulsion layer and other layers
Magazine No. Section 17643VVII (issued in December 1978)
line) on page 28 and European Patent No. 0,102
, No. 253 and JP-A-61-97655.
is applied to. Also, Research Disclosure Magazine N
o. Apply the coating method described in Section 17643XV, pages 28-29.
can be used. [0111] The fogging treatment of the present invention is carried out by the following "light fogging method".
” and/or “chemical fogging method”. “Light?
Full-surface exposure in the fogging method, that is, fogging exposure, is imagewise exposure.
Performed after light, after or during color development processing
. That is, the imagewise exposed photosensitive material is placed in a color developing solution or
Immerse in a pre-bath of color developer or remove from these solutions.
Take it out and expose it before it dries, but the color developing solution
It is most preferable to expose inside. [0112] As a light source for fogging exposure, for example, a special
Described in 1982-137350 and 58-70223.
High color rendering (as close to white as possible) as shown
) Good light source. Light illuminance is 0.01~2000 lux
, preferably 0.05 to 30 lux, more preferably
0.05 to 5 lux is suitable. More sensitive emulsion
The more light-sensitive materials are used, the better they are for low-light exposure.
Yes. Adjustment of illuminance may be done by changing the luminous intensity of the light source.
, exposure using various filters and the distance between the photosensitive material and the light source
, the angle between the photosensitive material and the light source may be changed. Also above
The illuminance of the fogging light can be changed continuously or in steps from low to high illuminance.
It can also be increased hierarchically. [0113] Light-sensitive material is added to the color developing solution or its pre-bath solution.
The liquid is immersed into the emulsion layer of the photosensitive material, and then exposed to light.
It is better to irradiate it. After it has penetrated the liquid, it is exposed to light fog.
The time it takes to complete the process is generally 2 seconds to 2 minutes, preferably 5 seconds to
It is 1 minute, more preferably 10 seconds to 30 seconds. foggy
The exposure time for this is generally 0.01 seconds to 2 minutes, preferably
is 0.1 seconds to 1 minute, more preferably 1 second to 40 seconds.
Ru. [0114] In the present invention, so-called "chemical fog"
The nucleating agent used when applying the
It can be included in the processing solution for optical materials. Preferably the feeling
It can be included in optical materials. Here, "nucleating agent"
is internal latent image type silver halide that is not pre-fogged.
Acts during surface development of emulsion to directly form a positive image.
It is a substance that has the function of In the present invention, a nucleating agent
It is particularly preferable to carry out fogging treatment using. [0115] When incorporated into a photosensitive material, an internal latent type halide is used.
It is preferable to add it to the silver halide emulsion layer, but
, or the nucleating agent adsorbs to silver halide by diffusion during processing.
As long as other layers such as interlayer, subbing layer or back
May be added to the layer. When adding a nucleating agent to the processing solution
, developer or as described in JP-A-58-178350.
It may also be included in a low pH pre-bath such as Also, 2
More than one type of nucleating agent may be used in combination. Nucleating agent that can be used in the present invention
For example, "Research Disclosure" magazine, N
o. 22534 (January 1983) pp. 50-54, same magazine
, No. 15162 (November 1976) pp. 76-77
, same magazine, no. 23510 (November 1983) 346
- Quaternary heterocyclic compound described on pages 352, hydra
Examples include gin-based compounds. [0117] Examples of quaternary heterocyclic nucleating agents include, for example, US
Patent No. 3,615,615, Patent No. 3,719,494,
No. 3,734,738, No. 3,759,901, No. 3,759,901, No.
No. 3,854,956, No. 4,094,683, No. 4
, No. 306,016, British Patent No. 1,283,835,
Special Publication No. 49-38,164, No. 52-19,452
, No. 52-47,326, JP-A-52-69,613
No. 52-3,426, No. 55-138,742
, No. 60-11,837, 0118] and the aforementioned “Research Disclosure
” Magazine No. 22534; Magazine No. 23,213 (19
(Published August 1983, pages 267-270) etc.
can give. Furthermore, as a highly active quaternary salt compound, JP-A-6
No. 3-121042, No. 63-301942, JP
No. 1-191132, No. 2-101450, No. 2-7
Use those described in No. 9038 and No. 2-101451.
be able to. In particular, the quaternary class represented by the following general formula (N)
Heterocyclic nucleating agents are preferred. General formula (N) [0119] [0120] In the formula, Z forms a 5- to 6-membered heterocycle;
represents a group of nonmetallic atoms necessary for
It may be R1 is an aliphatic group, R2 is water
It is an elementary atom, an aliphatic group, or an aromatic group. R1 and R
2 may be substituted with a substituent. Also, R2 is
Furthermore, it may be combined with the heterocycle completed by Z to form a ring.
stomach. However, among the groups represented by R1, R2 and Z,
, at least one is an alkynyl group, an acyl group, a hydra group,
contains a gin group or a hydrazone group, or R1 and R
2 to form a 6-membered ring, and the dihydropyridinium skeleton is
Form. Furthermore, substituents of R1, R2 and Z
At least one of them has a group that promotes adsorption to silver halide.
You may. Y is a counter ion for charge balance
, n is 0 or 1. As a heterocycle completed by Z
, for example, quinolinium, benzothiazolium, benz
imidazolium, pyridinium, acridinium,
nanthridinium, and isoquinolinium nuclei are mentioned.
Ru. More preferred are quinolinium and benzothiazolium.
most preferably quinolinium. [0122] As a substituent for Z, an alkyl group, an alkyl group,
Nyl group, aralkyl group, aryl group, alkynyl group,
droxy group, alkoxy group, aryloxy group, halogen
atom, amino group, alkylthio group, arylthio group,
Acyloxy group, acylamino group, sulfonyl group, sulfonyl group
Honyloxy group, sulfonylamino group, carboxyl group
, acyl group, carbamoyl group, sulfamoyl group, sulfamoyl group,
Ho group, cyano group, ureido group, urethane group, carbonate ester
group, hydrazine group, hydrazone group, or imino group.
What can I say? [0123] The substituent of Z may be connected via a suitable linking group.
. The aliphatic groups of R1 and R2 preferably have 1 carbon number.
~18 unsubstituted alkyl groups and carbon atoms in alkyl moieties
It is a substituted alkyl group having 1 to 18 in number. Represented by R2
The aromatic group to be used preferably has 6 to 20 carbon atoms.
, for example, phenyl group, naphthyl group, etc. [0124] Even if the substituents of R1, R2 and Z have
Thioamide group is a good adsorption promoting group to silver halide.
, mercapto group or 5- to 6-membered nitrogen-containing heterocyclic group
can be given. The thioamide group is preferably acyclic
Thioamide group (e.g. thiourethane group, thiourido group)
etc.). [0125] As the mercapto group, especially heterocyclic mer
Capto group (e.g. 5-mercaptotetrazole, 3-mercapto group)
Lucapto-1,2,4-triazole, 2-mercapto
1,3,4-thiadiazole, 2-mercapto-1,3
, 4-oxadiazole, etc.) are preferred. 5 or 6
Examples of nitrogen-containing heterocycles include nitrogen, oxygen, sulfur, and carbon.
Preferably, a combination of
For example, benzotriazoles and aminothiatria
I can give you zor. Promotion of adsorption to these silver halides
The radical may be present via a linking group. As a linking group, for example, [
[0126] [0127] etc. are mentioned. Preferably as R2
is an aliphatic group, most preferably a methyl group, a substituted methyl group,
or a heterocycle further completed by Z to form a ring
This is the case. Group represented by R1, R2 and Z
or at least one substituent on the ring is an alkynyl group
or when it is an acyl group, or when R1 and R2 and
may connect to form a dihydropyridinium bone core.
Preferably, it further contains at least one alkynyl group
are preferable, and particularly a propargyl group is most preferable. As the counter ion Y for charge balance,
, such as bromide ion, chloride ion, iodide ion, p-to
Luenesulfonate ion, ethylsulfonate ion, peroxide
Chlorate ion, trifluoromethanesulfonate ion,
Thiocyanine ion, boron tetrafluoride ion, lithium hexafluoride
Examples include ions. Represented by general formula (N)
Specific examples of compounds are listed below, but are limited to these:
Do not mean. (C-1) 5-ethoxy-2-methyl
-1-propargylquinolinium bromide (C-2
) 2,4-diethyl-1-propargylquinolinium
Mu Bromide (C-3) 3,4-dimethyl-dihydropyride [2
,1-b]benzothiazolium bromide (C-4)
6-ethoxythiocarbonylamino-2-methyl-
1-propargylquinolinium trifluoromethane
Sulfate 0130 (C-5) 6-(5-benzotriazo
carboxamide)-2-methyl-1-propargyl
Quinolinium trifluoromethane sulfate (C-
6) 6-(5-mercaptotetrazol-1-yl
)-2-Methyl-1-propargylquinolinium yo
(C-7) 6-ethoxythiocarbonylamino-2
-(2-methyl-1-propenyl)-1-propargyl
Quinolinium trifluoromethanesulfonate [0]
131] (C-8) 10-propargyl-1,2,
3,4-tetrahydroacridinium trifluoro
Methanesulfonate (C-9) 7-ethoxythiocarbonylamino-1
0-propargyl-1,2,3,4-tetrahydroac
Lysinium trifluoromethanesulfonate (C-
10) 7-[3-(5-mercaptotetrazole-
1-yl)benzamide]-10-propargyl-1,
2,3,4-tetrahydroacridinium Bencro
[0132] (C-11) 7-(5-Mercaptote)
Torazol-1-yl)-9-methyl-10-propal
Gyl-1,2,3,4-tetrahydroacridiniumbu
Lomido (C-12) 7-ethoxythiocarbonylamino-
10-propargyl-1,2-dihydroacridinium
Trifluoromethanesulfonate (C-13) 10-propargyl-7-[3-(1
,2,3,4-thiatriazol-5-ylamino)be
nzamide]-1,2,3,4-tetrahydroacridi
perchlorate 0133 (C-14) 7-(3-cyclohexy
methoxythiocarbonylaminobenzamide)-10
-propargyl-1,2,3,4-tetrahydroacrylate
Zinium trifluoromethanesulfonate (C-1
5) 7-(3-methoxythiocarbonylaminoben)
zuamide)-10-propargyl-1,2,3,4-te
Trihydroacridinium trifluoromethanesul
Honato 0134 (C-16) 7-[3-(3-ethoxy)
cythiocarbonylaminophenyl)ureido]-10-
Propargyl-1,2,3,4-tetrahydroacridi
trifluoromethanesulfonate (C-17
) 7-(3-ethoxythiocarbonylaminobenze
(sulfonamide)-10-propargyl-1,2,3
,4-tetrahydroacridinium trifluoromethane
Sulfonate 0135 (C-18) 7-[3-{3-[3-
(5-mercaptotetrazol-1-yl)phenyl]
ureido}benzamide]-10-propargyl-1,
2,3,4-tetrahydroacridinium triflu
Oromethanesulfonate (C-19) 7-[3-(5-mercapto-1,3
,4-thiadiazol-1-ylamino)benzamide
]-10-propargyl-1,2,3,4-tetrahydride
Roacridinium trifluoromethanesulfonate
(C-20) 7-[3-(3-butyl
thioureido)benzamide]-10-propargyl-
1,2,3,4-tetrahydroacridinium triflu
Oromethanesulfonate (C-21) 6-(3-ethoxythiocarbonyla)
minobenzamide)-1-propargyl-2,3-tri
Methylenequinolinium Trifluoromethanesulfona
Examples of hydrazine compounds include
The aforementioned Research Disclosure magazine No. 15,1
62 (published November 1976, pp. 76-77) and
Magazine No. 23,510 (issued November 1983 34
Examples include those described on pages 6 to 352). Change
Specifically, the following patent specifications are mentioned.
Can be done. First, hydrazide having a silver halide adsorption group
Examples of nucleating agents include, for example, U.S. Patent No. 4,03
No. 0,925, No. 4,080,207, No. 4,0
No. 31,127, No. 3,718,470, No. 4,
No. 269,929, No. 4,276,364, No. 4
, No. 278,748, No. 4,385,108, No. 4,385,108, No.
No. 4,459,347, British Patent No. 2,011,391
B, JP-A-54-74,729, JP-A No. 55-163,
No. 533, No. 55-74, 536, and No. 60-17
No. 9,734, No. 63-231441, etc.
can be mentioned. Other hydrazine-based nucleating agents include, for example:
For example, Japanese Patent Application Publication No. 57-86,829, U.S. Patent No. 4,560
, No. 638, No. 4,478,928, and even No. 2
, No. 563,785 and No. 2,588,982.
Compounds include: As a highly active hydrazine compound
JP-A-63-231441 and JP-A No. 234244
, No. 234245, No. 234246, No. 20425
No. 6, Patent Application No. 63-167773, No. 63-2001
Examples include the compound described in No. 89. [0140] Representative hydrazine-based nucleating agents are shown below.
. (B-1) 1-formyl-2-{4-[3-(2-
methoxyphenyl)ureido]-phenyl}hydrazine
(B-2) 1-formyl-2-{4-[3-(5-
Mercaptotetrazol-1-yl)benzamide]
phenyl}hydrazine (B-3) 1-formyl-2-[4-{3-[3-
(5-mercaptotetrazol-1-yl)phenyl]
[Ureido}phenyl]hydrazine [0141] Quaternary heterocyclic compounds are the main nucleating agents.
This is preferable in that the effects of the invention are greatly exhibited. quaternary heterocyclic system
The compound and a hydrazine compound may be used together. Nucleating agent
When adding to the processing solution, add it to the developer or JP-A-58-
In a low pH prebath as described in No. 178350,
May be contained. When adding a nucleating agent to the processing solution,
The amount used is preferably 10-8 to 10-3 mol per liter.
preferably, more preferably 10-7 to 10-1 mol.
. In the present invention, the nucleating agent is a silver halide emulsion.
Although it may be contained in the hydrophilic colloid layer adjacent to the layer,
It is preferably contained in the silver halide emulsion layer. the
The amount added depends on the characteristics of the silver halide emulsion actually used,
It varies depending on the chemical structure of the nucleating agent and development conditions, so
in a silver halide emulsion, although it can vary over a wide range.
from about 1 x 10-8 mole to about 1 x 10-2 mole per mole of silver.
A range of
1 x 10-7 mole to about 1 x 10-3 mole. [0143] When using a nucleating agent, promote the action of the nucleating agent.
It is preferred to use a nucleation accelerator to promote the process. Construction
A nucleating agent is a substance that has virtually no function as a nucleating agent, but
Promotes the action of nucleating agents to directly increase the maximum density of positive images
and/or the development time required to obtain a constant direct positive image.
It refers to a substance that acts to speed up time. [0144] Such a nucleation accelerator may optionally include
Substituted with alkali metal atom or ammonium group
Tetraza having at least one mercapto group
Indenes, triazaindenes and pentazaindenes
and JP-A-63-106656, pages 5 to 16.
Mention may be made of the compounds described. Also, JP-A-63-
No. 226652, No. 63-106656, No. 63-8
Examples include the compounds described in No. 740. Built below
Here are some specific examples of nuclear accelerators. embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image .
However, it can be contained inside the photosensitive material.
Latent image-type silver halide emulsions and other hydrophilic colloid layers (
It is preferable to include it in an intermediate layer, a protective layer, etc.). Particularly preferred is the silver halide emulsion or its adjacent layer.
be. The amount of nucleation accelerator added is 1 per mole of silver halide.
Preferably 0-6 to 10-2 mol, more preferably 10
-5 to 10-2 moles. [0149] The nucleation accelerator may also be added to the processing solution, that is, the developer.
or when added to the pre-bath, 10-
Preferably 8 to 10-3 mol, more preferably 10-7
~10-4 mol. Also, two or more types of nucleation accelerators may be combined.
It can also be used. For known photographs that can be used in the present invention
The additive is the aforementioned Research Disclosure No. 1
7643 (December 1978) and the same No. 1871
6 (November 1979), and the relevant items
The locations are summarized in the table below. [0150] Additive type
RD17643 RD187161
chemical sensitizer
Page 23 Page 648 Right column 2 Feeling
Increasing agent
Same as above 3
Spectral sensitizers, supersensitizers pages 23-24
Page 648 right column~
　　　　　　　　　　　　　　　　　　　　　　　　　
Page 649, right column 4
brightener
Page 24 5 Antifogging agent, stabilizer
Pages 24-25 Page 649 Right column 6
Light absorbers, filter dyes, pages 25-26
Page 649 right column ~ Ultraviolet absorber
　　　　　　　　　　　　　　　　　　　　　　　　　
Page 650 left column 7 Stain inhibitor
Page 25 right column
Page 650 left to right column 8 Dye image stabilizer
Page 25 9 Hardener
26 pages
Page 651 left column 10 binder
26 pages
Same as above 11 Plasticizer, lubricant
27 pages 6
Page 50, right column 12 Coating aids, surfactants
Pages 26-27 Same as above 13
Static inhibitor
Page 27 Same as above 0152
In the photographic material of the present invention, the photographic emulsion layer and other layers are
Plastic film commonly used in photographic materials
flexible supports such as paper, cloth, or glass, ceramic, or gold.
applied to a rigid support such as a genus. as a flexible support
Cellulose nitrate, cellulose acetate, and vinegar are useful.
Cellulose acetate, polystyrene, polyvinyl chloride, polyester
Half combination of polyethylene terephthalate, polycarbonate, etc.
films made of synthetic or synthetic polymers, baryta layers or
is an α-olefin polymer (e.g. polyethylene, poly
Coating propylene, ethylene/butene copolymer), etc.
is laminated paper, etc. The support uses dyes and pigments.
It may also be colored. Silver halide photographic emulsion layer and other hydrophilic properties
The colloid layer can be applied using, for example, dip coating, roller
-Known coating methods, curtain coating methods, extrusion coating methods, etc.
Various methods can be used. Also, if necessary,
Accordingly, U.S. Patent Nos. 2,681,294 and 2,76179
No. 1, No. 3526528, No. 3508947, etc.
Multiple layers may be applied simultaneously by the method described in . The latent type emulsion-containing photographic material of the present invention has a surface
Directly obtain a positive image by developing with a developer
be able to. The development process with surface developer is essentially
Generally, latent images or fog nuclei on the surface of silver halide grains
It is induced by [0155] The color developer of the present invention contains, as a preservative,
Sodium sulfite, potassium sulfite, sodium bisulfite
potassium bisulfite, sodium metasulfite, metasulfite
sulfites such as potassium sulfate, and also the carbonyl of the present invention.
Compound sulfite adducts can be added as needed.
Ru. [0156] The preferred amount added is 1 liter of color developer.
0.5g to 10g per bottle, more preferably 1g to 5g.
Ru. [0157] Furthermore, the color developing agent of the present invention can be directly used for preservation.
Various hydroxylamines,
Hydroxamic acids described in No. 61-186559, No. 61
-170756-described hydrazines and 63-21
Hydrazine derivatives and hydroxylua described in No. 7270
Min derivatives, No. 61-188742 and No. 61-20
Phenols described in No. 3253, No. 61-188741
α-Hydroxyketones and α-aminoketones listed in the No.
, and/or various saccharides described in No. 61-180616
It is preferable to add. In addition, in combination with the above compounds,
Patent application No. 61-147823, No. 61-166674
, No. 61-165621, No. 61-164515,
No. 61-170789, No. 0158] and No. 61-168159, etc.
Noamines, No. 61-173595, No. 61-164
Diamines described in No. 515, No. 61-186560, etc.
61-165621 and 61-16978
Polyamines described in No. 9, described in No. 61-188619
polyamines, nitro as described in No. 61-197760
Xyradicals, No. 61-186561, and No. 61-
Alcohols described in No. 197419, No. 61-1989
Oximes described in No. 87 and No. 61-265149
Preference is given to using the tertiary amines mentioned. [0159] Other preservatives include JP-A-57-441
Various metals described in No. 48 and No. 57-53749,
Salicylic acids described in JP-A-59-180588, JP-A-59-180588
Alkanolamines described in No. 54-3532, JP-A No. 54-3532
Polyethyleneimines described in No. 56-94349, rice
Aromatic polyhydro described in National Patent No. 3,746,544
It may contain an xy compound or the like as necessary. To the present invention
The color developer used preferably has a pH of 9 to 12,
More preferably, it is 9 to 11.0, and the color developer
may contain other known developer component compounds.
I can do that. [0160] In order to maintain the above pH, various buffers are used.
It is preferable to use As buffering agents, especially carbonates,
Phosphate, tetraborate, hydroxybenzoate are dissolved
It has excellent buffering ability in the high pH range of pH 9.0 or higher, and
Examples include sodium carbonate, potassium carbonate, and bicarbonate.
Sodium, potassium bicarbonate, trisodium phosphate, lye
Tripotassium phosphate, disodium phosphate, dipotassium phosphate
Sodium borate, Potassium borate, Sodium tetraborate
borax, potassium tetraborate, o-hydroxy
Sodium Benzoate (Sodium Salicylate), O-H
Potassium droxybenzoate, 5-sulfo-2-hydroxy
Sodium cybenzoate (sodium 5-sulfosalicylate)
), potassium 5-sulfo-2-hydroxybenzoate (
Potassium 5-sulfosalicylate), etc.
Wear. [0161] The amount of the buffer added to the color developer is 0.
．． It is preferably 1 mol/liter or more, especially 0
．． Must be 1 mol/liter to 0.4 mol/liter
is particularly preferred. In addition, there is calcium in the color developer.
As an anti-settling agent for aluminum and magnesium, or as a color
Various chelating agents are used to improve the stability of the developer.
be able to. [0162] As the chelating agent, an organic acid compound is preferable.
For example, Japanese Patent Publications No. 48-30496 and No. 44-30
Aminopolycarboxylic acids described in No. 232, JP-A-56-
No. 97347, Special Publication No. 56-39359 and West German patent
Organic phosphonic acids described in No. 2,227,639, JP-A No. 2,227,639
No. 52-102726, No. 53-42730, No. 5
No. 4-121127, No. 55-126241 and No. 5
Phosphonocarboxylic acids described in No. 5-659506 etc.,
Others JP-A-58-195845, JP-A No. 58-2034
40 and Special Publication No. 53-40900, etc.
[0163] Specific examples include nitrilotriacetic acid, diethyl
Lentriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,
N,N-trimethylenephosphonic acid, ethylenediamine-
N,N,N',N'-tetramethylenephosphonic acid, tri
cyclohexanediaminetetraacetic acid, 1,2-diamino
Propane tetraacetic acid, glycol ether diamine tetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2-
Phosphonobutane-1,2,4-tricarboxylic acid, 1-hyperoxylic acid
Droxyethylidene-1,1-diphosphonic acid, N,N'
-Bis(2-hydroxybenzyl)ethylenediamine-
N,N'-diacetate is mentioned. [0164] The amount of these chelating agents added depends on color development.
It is sufficient as long as the amount is sufficient to sequester the metal ions in the liquid.
. For example, it is about 0.1 g to 10 g per liter. Other development accelerators include Japanese Patent Publication No. 37-16088
, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
Thioether compounds expressed in No. 813,247 etc.
, JP-A-52-49829 and JP-A-50-15554
p-phenylenediamine compound represented by JP-A-Sho
No. 50-137726, 0165] Japanese Patent Publication No. 1974-30074, Japanese Patent Publication No. 1983-
No. 156826 and No. 52-43429, etc.
Quaternary ammonium salts, U.S. Patent No. 2,494,9
No. 03, No. 3,128,182, No. 4,230,79
No. 6, No. 3,253,919, Special Publication No. 41-1143
No. 1, U.S. Patent No. 2,482,546, U.S. Patent No. 2,596
, No. 926 and No. 3,582,346, etc.
compound, Japanese Patent Publication No. 37-16088, No. 42-25
No. 201, U.S. Patent No. 3,128,183, Special Publication No. 4
No. 1-11431, No. 42-23883 and US Patent
Polyalkylene represented by No. 3,532,501 etc.
Oxide, other 1-phenyl-3-pyrazolidones
, imidazoles, etc. can be added as necessary.
Wear. [0166] In the present invention, any optional
Antifoggants can be added. As an antifoggant, salt
Aluminum salts such as sodium chloride, potassium bromide, and potassium iodide
Potash metal halides and organic antifoggants can be used.
Ru. Examples of organic antifoggants include benzotriazo
6-nitrobenzimidazole, 5-nitroin
Indazole, 5-methylbenzotriazole, 5-di
Trobenzotriazole, 5-chloro-benzotriazole
2-thiazolyl-benzimidazole, 2-thia
Zolylmethyl-benzimidazole, indazole, hydrogen
Nitrogen-containing substances such as droxyazindolizine and adenine
Rocyclic compounds can be cited as a representative example. [0167] The color developer used in the present invention contains fluorescent
Preferably, it contains a photobrightener. As a fluorescent whitening agent
, 4,4'-diamino-2,2'-disulfostilbene
type compounds are preferred. The amount added is preferably 0 to 5 g/liter.
Preferably, it is 0.1 g to 4 g/liter. Also, if necessary
Alkyl sulfonic acids, aryl phosphonic acids, aliphatic
Added various surfactants such as carboxylic acid and aromatic carboxylic acid.
You can also add it. [0168] The processing temperature of the color developer of the present invention is 20~
The temperature is 50°C, preferably 30 to 40°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 4 minutes. Replenishment amount is small
20 to 600 per m2 of photosensitive material.
ml Preferably 50 to 400 ml
Ru. Next, the desilvering step in the present invention will be explained.
do. The desilvering process generally includes a bleaching process, a fixing process, and a fixing process.
Bleaching process - bleach-fixing process, bleaching process - bleach-fixing process, bleaching
Any process such as a fixing process may be used. Desilvering process
The heating time is 1 minute 30 seconds or less, more preferably 15 seconds to 60 seconds.
Seconds. Desilvering process Bleaching solution used in the desilvering process, bleach-fixing
The liquid and fixer will be explained. Used in bleach or bleach-fix solutions
Any bleaching agent can be used as the bleaching agent.
However, especially organic complex salts of iron(III) (e.g. ethylenedia
Amino acids such as aminetetraacetic acid and diethylenetriaminepentaacetic acid
Polycarboxylic acids, aminopolyphosphonic acids, phosphonoca
(complex salts such as carboxylic acids and organic phosphonic acids) or
Organic acids such as citric acid, tartaric acid, malic acid; persulfates;
Hydrogen oxide is particularly preferred from the viewpoint of bleaching power and prevention of environmental pollution.
Delicious. Useful for forming organic complexes of iron(III)
aminopolycarboxylic acid, aminopolyphosphonic acid,
If you list organic phosphonic acids or their salts, [
0171 Ethylenediaminetetraacetic acid, diethyleneditriacetic acid
Aminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, pro-
Pyrenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexa
diaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid
, glycol ether diamine tetraacetic acid, etc.
I can do that. These compounds include sodium, potassium,
Either lithium or ammonium salt may be used. these
Among the compounds, ethylenediaminetetraacetic acid, diethylene
triaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1
, 3-diaminopropanetetraacetic acid, methyliminodiacetic acid
Iron(III) complex salts are preferred because they have high bleaching power. Among these, the organic complex salt of iron(III) is
Rapid processing ferric phosphate, etc. and aminopolycarboxylic acid, amino
Chelates such as nopolyphosphonic acid and phosphonocarboxylic acid
Even if a ferric ion complex is formed in solution using
good. In addition, chelating agents form ferric ion complex salts.
It may be used in excess. Among iron complexes, aminopoly
Recarboxylic acid iron complex is preferred, and the amount added is 0.0
1 to 1.0 mol/liter, preferably 0.05 to 0.5
It is 0 mol/liter. Bleach solution, bleach-fix solution and/or
or these pre-baths contain various compounds as bleach accelerators.
can be used. For example, US Pat. No. 3,893,858
Specification, German Patent No. 1,290,812, Pat.
Publication No. 53-95630, Research Disclosure
Mail listed in the magazine number 17129 (July 1978 issue)
Compounds with capto groups or disulfide bonds, and
Publication No. 45-8506, Japanese Unexamined Patent Publication No. 52-20832, same
No. 53-32735, U.S. Patent No. 3,706,561
Thiourea-based compounds, or iodine, bromine ions, etc.
Preferred are halides such as chlorine and the like because they have excellent bleaching power. [0175] In addition, the bleaching solution or bleaching agent used in the present invention
The white fixer contains bromides (e.g. potassium bromide, sodium bromide).
thorium, ammonium bromide) or chloride (e.g.
potassium chloride, sodium chloride, ammonium chloride) or
or iodide (e.g. ammonium iodide).
may contain a oxidizing agent. Boric acid, borax, metal as necessary.
Sodium borate, acetic acid, sodium acetate, sodium carbonate
um, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
pH buffers such as citric acid, sodium citrate, and tartaric acid
one or more inorganic acids, organic acids, and these
Alkali metal or ammonium salts or ammonium nitrate
Corrosion inhibitors such as aluminum and guanidine may be added.
I can do that. [0176] Used in the bleach-fix solution or fixing solution according to the present invention.
The fixing agent used is a known fixing agent, namely sodium thiosulfate.
Thiosulfates such as ammonium thiosulfate, ammonium thiosulfate;
Salts such as sodium annate and ammonium thiocyanate
Osocyanate; ethylene bisthioglycolic acid, 3,6
-Thioethers such as dithia-1,8-octanediol
Water-soluble silver halides such as silver compounds and thioureas
It is a solubilizing agent, and can be used singly or in combination of two or more.
can be used. [0177] Also, described in JP-A-55-155354
fixed fixing agents and large amounts of halides such as potassium iodide.
A special bleach-fix solution consisting of a combination of
be able to. In the present invention, thiosulfate, especially thiosulfate,
Preference is given to using ammonium sulfate salts. per liter
The amount of the fixing agent is preferably 0.3 to 2 mol, more preferably 0.3 to 2 mol.
Preferably, it is in the range of 0.5 to 1.0 mol. bleach-fix solution
Or, the pH range of the fixer is preferably 3 to 10, and furthermore,
5 to 9 are particularly preferred. [0178] The bleach-fix solution also contains various other fluorescent enhancers.
Whitening agent, antifoaming agent or surfactant, polyvinylpyrrolid
It can contain organic solvents such as alcohol, methanol, etc.
. [0179] The bleach-fixing solution and fixing solution in the present invention are
Sulfites as agents (e.g. sodium sulfite, sulfite
potassium, ammonium sulfite, etc.), bisulfite (
For example, ammonium bisulfite, sodium bisulfite,
potassium bisulfite, etc.), metabisulfite (e.g.
Potassium Metabisulfite, Sodium Metabisulfite, Meta
Release of sulfite ions such as ammonium bisulfite, etc.)
Contains compounds. These compounds are converted to sulfite ions
and about 0.02 to 0.50 mol/liter.
is preferable, more preferably 0.04 to 0.40 mo
per liter. [0180] As a preservative, sulfite is commonly added.
However, other substances such as ascorbic acid and carbonyl bicarbonate
By adding sulfuric acid adducts or carbonyl compounds, etc.
Also good. In addition, buffering agents, optical brighteners, chelating agents, and antifoaming agents
A fungicide, a fungicide, etc. may be added as necessary. [0181] Aqueous liquid and/or stabilization in the treatment of the present invention
After desilvering treatment such as fixing or bleach-fixing, aqueous solution and/or
It is common to perform stabilization treatment. [0182] The amount of water used in the washing process depends on the characteristics of the photosensitive material.
(e.g. depending on the material used such as coupler), usage, washing water temperature
, number of washing tanks (number of stages), replenishment methods such as countercurrent and forward flow,
It can be set in a wide range depending on various other conditions. This way
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
, Journal of the Society of
Motion Picture and Television
Journal of the Engineers
Society of Motion Picture
e and Television Engineer
s) Volume 64, p. 248-253 (May 1955 issue
) can be obtained using the method described in . Usually multi-stage
The number of stages in the flow system is preferably 2 to 6, particularly 2 to 4.
preferable. [0183] According to the multi-stage countercurrent method, the amount of washing water can be increased widely.
For example, 0.5 liters per m2 of photosensitive material.
1 liter to less than 1 liter is possible. Water stagnation in the tank
Due to increased residence time, bacteria proliferate and the resulting suspended
Problems such as objects adhering to the photosensitive material occur. The power of the present invention
There are solutions to these problems in the processing of color-sensitive materials.
Calcium described in JP-A No. 62-288838
, using methods to reduce magnesium extremely effectively.
can be done. [0184] Also, the method described in Japanese Patent Application Laid-Open No. 57-8542
Sothiazolone compounds and thiabendazoles, 61-
Chlorinated sodium isocyanurate described in No. 120145
Chlorine-based disinfectants such as Umu, etc., in Japanese Patent Application Laid-Open No. 61-267761
Benzotriazole, copper ion, etc. written by Hiroshi Horiguchi.
"Chemistry of antibacterial and fungicidal agents", edited by Sanitation Technology Association, "sterilization and killing of microorganisms"
"Bacteria and Antifungal Technology", edited by the Japanese Society of Antibacterial and Antifungal Agents, "Encyclopedia of Antibacterial and Antifungal Agents"
” can also be used. [0185] Furthermore, the washing water contains surfactant as a draining agent.
as a sex agent and as a water softener, such as EDTA.
A coating agent can be used. Continue with the above washing process or
Alternatively, it is possible to directly treat with stabilizing solution without going through the water washing process.
Ru. A compound with image stabilization function is added to the stabilizing liquid.
For example, aldehyde compounds such as formalin
and buffering agent to adjust membrane pH suitable for dye stabilization.
and ammonium compounds. Also, the battery in liquid
Prevents bacterial growth and provides anti-mildew properties to photosensitive materials after processing
Therefore, the various fungicides and fungicides mentioned above can be used.
can. [0186] Furthermore, surfactants, optical brighteners, and hardeners are added.
You can also add In processing the photosensitive material of the present invention
, if the stabilization is carried out directly without going through a water washing step,
JP-A-57-8543, 58-14834, 60-
All known methods described in No. 220345 etc. are used.
be able to. Others: 1-hydroxyethylidene-1,
1-diphosphonic acid, ethylenediamine tetramethylene phosphonic acid
Chelating agents such as phosphoric acid, magnesium and bismuth compounds
It is also a preferable embodiment to use it. Desilvering in the present invention
The so-called washing liquid or stabilizing liquid used after treatment
A rinsing solution is also used. [0188] The pH of the water washing step or stabilization step is 4 to 10.
and preferably 5 to 8. Temperature is for photosensitive materials
Various settings can be made depending on the application, characteristics, etc., but generally the temperature is 15 to 45℃.
Preferably it is 20-40°C. You can set the time arbitrarily.
The shorter the length, the better. Preferably 30 seconds to 3 minutes, more preferably
Preferably, it is 30 seconds to 2 minutes. The smaller the amount of refill, the better.
preferred from the viewpoints of cleaning costs, reduced emissions, ease of handling, etc.
Moreover, the effects of the present invention are also great. [0189] The specific preferred amount of replenishment is as follows:
0.5 to 50 times the amount brought in from the front bath per area, preferably
Preferably it is 3 to 40 times. or 1m2 of photosensitive material
1 liter or less, preferably 500 ml or less per
It's below. Also, replenishment may be performed continuously or intermittently.
You can. [0190] The liquid used in the water washing and/or stabilization step is as follows:
Furthermore, it can also be used in a pre-process. For this example, multi-stage
The overflow of washing water is reduced by using the counter-current method.
It flows into the pre-bath bleach-fixing bath, and the bleach-fixing bath contains concentrated
One way to do this is to replenish the fluid and reduce the amount of waste fluid. [Example] Example 1 Preparation of sample 101 Paper support laminated on both sides with polyethylene (thickness 10
0 micron) on the front side, apply the following layers 1 to 11 on the back side.
Color photographic effect with layer 12 to layer 13 applied on the side
Created optical materials. The polyethylene on the first layer coating side is acidic.
Titanium chloride (4 g/m2) was used as a white pigment, and a trace amount (
Contains 0.003g/m2) of ultramarine as a blue tinting dye.
(The chromaticity of the surface of the support is 8 in L*, a*, b* system.
They were 8.0, -0.20, and -0.75. ). (Photosensitive layer composition) The components and coating amount (g/
m2 unit). However, the amount of sensitizing dye added is 1 mo of silver.
Expressed in moles per liter. Regarding silver halide, silver
Shows the converted coating amount. The emulsions used in each layer are listed below.
Change the particle size by changing the temperature according to the manufacturing method of EM-1
It was made by However, the emulsion in the 11th layer is surface chemically sensitized.
No Lippmann emulsion was used. 1st layer (antihalation layer) Black colloidal silver
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.10 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.70 second
Layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.70 0194 3rd layer (red sensitive layer) Red sensitizing dye (ExS-1, 2, 3 each in equal amounts, total 5
．． Silver bromide (average grain size) spectrally sensitized with
size 0.40μ, particle size distribution 10%, octahedral)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.28 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…1
．． 00 Cyan coupler (ExC-1, 2, 3 in 1:
1:0.2) ...0.30 [0195] Antifading agent (Cpd-1, 2, 3, 4, 30 each equivalent amount
) …0.18 Stain prevention
Stopping agent (Equivalent amounts of Cpd-5 and 15)
…0.003 Coupler dispersion medium (C
pd-6)
...0.30 coupler solvent
(Equivalent amounts of Solv-1, 3, and 5)
…0.12 0196 4th layer (middle layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...1.00 Color mixing prevention agent (Cpd-
7)
...0.08 Color mixing prevention agent
Solvent (Equivalent amounts of Solv-4 and 5)
…0.16 Polymer latex
(Cpd-8)
…0.100197 5th layer (green-sensitive layer) Green sensitizing dye (ExS-4 2.6×10-4)
silver bromide spectrally sensitized with (average grain size 0.40μ,
Particle size distribution 10%, octahedral)
...0.25 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.80 magenta
Puller (equal amounts of ExM-1, 2, and 3)
...0.11 Yellow coupler (E
xY-2)
…0.03 Anti-fading agent (Cp
Equal amounts of d-9, 26, and 30)
...0.15 [0198] Stain inhibitor (Cpd-10, 11, 12, 13
10: ...0.025
7:7:1 ratio) Coupler dispersion medium (
Cpd-6)
…0.05 coupler solution
Solvate (Equivalent amounts of Solv-4 and Solv-6)
…0.15 0199 6th layer (intermediate layer) 7th layer (yellow filter layer) same as 4th layer Yellow colloidal silver (particle size 100 Å)
...0.12 ze
latin
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.70 Color mixing prevention agent (Cpd-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.03 Color mixing inhibitor solvent (
Solv-4, 5 equivalents)
...0.10 Polymer latex (
Cpd-8)
...0.070200] 8th layer (medium)
Interlayer) Same as the 4th layer 0201 9th layer (blue sensitive layer) Blue sensitizing dye (Equivalent amount of each ExS-5 and 6, total 3.5
silver bromide (average grain size
0.60μ, particle size distribution 11%, octahedral)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.40 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.8
0 Yellow coupler (ExY-1)
…0
．． 35 Anti-fading agent (Cpd-14)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.10 Anti-fading agent (Cpd-30)
　　　　　　　　　　　　　　　　　　　　　　　　　
…0.05 Stain inhibitor (Cpd-
5, 15 in a 1:5 ratio) …0
．． 007 Coupler dispersion medium (Cpd-6)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.05 Coupler solvent (Solv-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.100202] 10th layer (ultraviolet absorber content) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...1.00 Ultraviolet absorber (Cpd
-2, 4, 16 equivalents)
...0.50 Color mixing prevention agent (Cpd-7, 17
equal amount of each)
...0.03 Dispersion medium (Cpd-6)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.02 UV absorber solvent
(Equivalent amounts of Solv-2 and 7)
...0.08 Anti-irradiation dye
(Cpd-18, 19, 20, 21, ...0.05
27 to 10:10:13:15:2
0 ratio) 11th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0)
．． 1μ) ...0.03 Polyvinyl alcohol
acrylic modified copolymer (molecular weight 50,000)
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.01 polymethyl meta
Acrylate particles (average particle size 2.4μ) and silicon oxide
Equivalent amount of elementary (average particle size 5μ)
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.05 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
…1.80 ze
Latin curing agent (equal amounts of H-1 and H-2)
...0.18 0204
] 12th layer (back layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
...2.50 Ultraviolet absorber (Cpd
-2, 4, 16 equivalents)
...0.50 Dye (Cpd-18, 19, 2
Equal amounts of 0, 21, 27) …0.06
13th layer (back layer protective layer) Polymethyl methacrylate particles (average particle size 2
．． 4μ) and silicon oxide (average particle size 5μ) equivalent amount
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.05 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
...2.00 Gelatin hardening agent (H-1, H-2, etc.)
quantity)...
0.14 How to make emulsion EM-1: Mix an aqueous solution of potassium bromide and silver nitrate with an aqueous gelatin solution.
They were added at the same time at 65°C for 15 minutes with thorough stirring,
Octahedral silver bromide grains having an average grain size of 0.23μ were obtained. this
0.3 g of 3,4-dimethyl-1,3 per mole of silver
-Thiazoline-2-thione was added. 1 silver in this emulsion
6 mg sodium thiosulfate and 7 mg gold chloride per mole
Add acid (tetrahydrate) in sequence and heat at 75°C for 80 minutes.
A chemical sensitization treatment was carried out. The particles obtained in this way
As a core, grow it further in the same precipitation environment as the first time.
, the final octahedral monodisperse core/shape with an average particle size of 0.4μ
A silver bromide emulsion was obtained. The coefficient of variation of particle size is approximately 10
%Met. This emulsion contains 1.5 mg of thiol per mole of silver.
Add sodium sulfate and 1.5 mg of chloroauric acid (tetrahydrate).
After chemical sensitization by heating at 60℃ for 60 minutes,
A partial latent image type silver halide emulsion was obtained. Each photosensitive layer contains ExZK-1 as a nucleating agent.
and ExZK-2 to silver halide at 10-3, respectively.
, 10-2% by weight, Cpd-22,2 as a nucleation accelerator
8 and 29 were each used in an amount of 10-2% by weight. Furthermore, each layer contains milk.
Alkanol XC (Du Pont
) and sodium alkylbenzenesulfonate,
Succinic esters and Magefac as coating aids
F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. halogen
In the layer containing silver oxide and colloidal silver, (Cpd-
Equivalent amounts of 23, 24, and 25) were used. Specify this sample as the sample number.
No. 101. The compounds used in the examples are shown below. [Formula 42] [Formula 43] [Formula 43] [Formula 44] [Formula 45] [Formula 45] [Formula 46] [Formula 49] [Formula 50] [Formula 50] [Formula 50] [Formula 51] [Formula 52] [Formula 52] [Formula 53] [Formula 53] [Formula 54] [Formula 54] [Formula 54] -ethylhexyl) sebacate Solv-2 Trinonyl phosphate Solv-3 Di(3-methylhexyl) phthalate Solv-4 Tricresyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate Solv-7 Di(2-ethylhexyl) ) Phthalate H-1 1,2-bis(vinylsulfonylacetamido)ethane
H-2 4,6-dichloro-2-hydroxy-1,3,5-tri
Azine Na salt 0223 ExZK-1 7-(3-ethoxythiocarbonylaminobenzamide
)-9-methyl-10propargyl-1,2,3,4-
Tetrahydroacridinium trifluoromethane
Ruhonato ExZK-2 2-[4-{3-[3-{3-[5-{3-[2-chrome
rho-5-(1-dodecyloxycarbonyl ethoxylic
(bonyl)phenylcarbamoyl]-4-hydroxy-1
-naphthylthio}tetrazol-1-yl]phenyl}
ureido]benzenesulfonamide}phenyl]-1-
Preparation of formylhydrazine samples 102 to 107 Instead of the coupler added to the ninth layer of sample 101,
The comparative compound shown in 1 and the coupler compound of the present invention were
Do the same thing except that the number of moles of is replaced with equal moles of
Samples 102 to 107 were produced. Preparation of samples 108-111 Samples 104-1
Coating amount of the present invention coupler of No. 07, coating amount of silver from 10% to 30%
% to lower the yellow maximum image density (Dmax)
Samples 108 to 111 were prepared in the same manner except that the following adjustments were made.
did. [0225] 101 to 111 produced in this way
Apply gradation exposure through an optical wedge and perform the following development process.
(Processing step A) was performed. These processed streams
maximum yellow image density (Dmax) and
The yellow minimum image density (Dmin) was measured. Preparation of samples 112-118 Samples 101-1
Gradation exposure of 03, 108 to 111 through an optical wedge
and the developing agent of the color developing solution was D-2 (4.2 g of mother liquor).
Sample 112 was prepared in the same manner except that the replenisher solution was changed to 5.6 g).
~118 were produced. Preparation of samples 119-122 Samples 115-1
18 through an optical wedge to give gradation exposure and color development.
The developing agent in the solution was D-3 (4.5 g of mother solution, 6.0 g of replenisher
) Samples 119 to 122 were prepared in the same manner except that
Ta. These results are shown in Table 1. Processing step A: Cumulative replenishment of liquid using an automatic processor as described below.
Continuous processing was carried out until the volume was three times the tank capacity. [0228] Processing time Time Temperature
Degree Tank capacity Refill amount Color development
Development 135 seconds 38℃ 30
Liter 240ml/m2
Bleach fixing 60 seconds 35℃
15 liters 300ml/m2
Washing with water (1) 40 seconds 35℃
10 liters --- Water
Washing (2) 40 seconds 35℃
3 liters 320ml/m2
Drying 30 seconds 75
℃0229 The washing water replenishment method is to supplement the washing bath (2).
Transfer the overflow liquid from the washing bath (2) to the washing bath (1).
A so-called countercurrent replenishment method was adopted, which leads to At this time, the photosensitive material
transfer of the bleach-fix solution from the bleach-fix bath to the washing bath (1).
The carry-on amount is 35ml/m2, and it is bleach-rated.
The ratio of the amount of washing water replenishment to the amount of liquid brought in is 9.1
It was double that. The composition of each treatment liquid was as follows. (Color developer)
　　　　　　　　　　　　　　　　　　　　　　　　　
Mother liquor Replenisher D-sorbitol
　　　　　　　　　　　　　　　　　　　　　　　　　
0.15g 0.20g
Sodium naphthalene sulfonate/formalin
0.15g 0.20g
Condensate Ethylenediaminetetrakismethylenephosphone
1.5 g 1.5 g
acid diethylene glycol
12.0ml
16.0ml benzyl alcohol
　　　　　　　　　　　　　　　　　　　　　　　　　
13.5ml 18.0ml
potassium bromide
0.80
g --- benzotriazole
　　　　　　　　　　　　　　　　　　　　　　　　　
0.003g 0.004g Sodium sulfite
thorium
2.4 g 3
．． 2 g N,N-bis(carboxymethyl)hydra
Gin 6.0 g 8.0
g0231 D-glucose
2.0 g
2.4 g triethanolamine
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0 g 8.0 g N-ethyl
Ru-N-(β-methasulfonamide)
6.3 g 8.4 g Chill)-3
-Methyl-4-aminoaniline sulfate Potassium carbonate
30.0
g 25.0 g Optical brightener (Diaminos
Chilbene type) 1.0
g 1.2 g add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml 1000ml
liter pH (25℃)
1
0.50 11.00 0232] (Bleach-fix solution)
　　　　　　　　　　　　　　　　　　　　　　　　　
Mother liquor Replenisher Ethylenediamine 4 vinegar
Acid/disodium/diwater 4.0 g
Same as mother liquor Salt Ethylenediaminetetraacetic acid/Fe(III)/Ammonia
70.0 g Ni-dihydrate ammonium thiosulfate (700 g/liter)
180ml
Sodium p-toluenesulfinate
20.0 g sodium bisulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
20.0 g 5-mercapto-1,3,
4-triazole 0.5 g Nitrogen
ammonium acid
Add 10.0 g water
Yes
1000ml
pH (25℃)
6.20 [
[0233] Tap water for both washing water mother liquor and replenisher was added to H-type strongly acidic cation exchange resin.
(Amberlight IR-120 manufactured by Rohm and Haas)
B) and OH type anion exchange resin (Amberlite I)
Water is passed through a mixed bed column packed with R-400) to remove calcium.
and magnesium ion concentration to 3 mg/liter or less.
treated with sodium isocyanurate dichloride followed by
20mg/liter and sodium sulfate 1.5g/liter
was added. The pH of this solution is in the range of 6.5 to 7.5.
there were. [Table 1] [0235] From the results in Table 1, the compound of the present invention (sample N
o. 104-107) are comparative compounds (sample No. 101)
~103) The maximum image density (Dmax) is higher than that of
Therefore, when adjusting by lowering the maximum image density (Dmax)
(Samples No. 108 to 111) have minimum image density (Dm
It is clear that in ) is low. Furthermore, the development of the present invention
Comparative compounds (test samples)
Fee No. 112 to 114) are the minimum image density (Dmin
) becomes high, whereas the compound of the present invention (sample No. 1
15 to 122) have a low minimum image density (Dmin).
The effect is even more obvious.

Claims (2)

[Claims] 1. A direct positive film having at least one photographic emulsion layer containing internal latent image type silver halide grains which are not pre-fogged on a support, and which can be developed directly after imagewise exposure to form a positive image. 1. A direct positive color photographic material, characterized in that the emulsion layer contains at least one kind of acylacetamide type yellow dye-forming coupler represented by the following general formula (I). General formula (I) [Formula 1] (In the formula, R1 represents a monovalent group. Q together with C is 3-
Represents a group of nonmetallic atoms necessary to form a 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle having at least one heteroatom selected from N, O, S, and P in the ring. However, R1 is not a hydrogen atom and does not combine with Q to form a ring. ) 2. An image forming method comprising processing the direct positive color photographic material according to claim 1 with a developing solution containing a developing agent represented by the following general formula (II). General formula (II) [Formula 2] (In the formula, R21 represents an alkyl group, and R22 represents an alkylene group. However, R21 and R22 may be bonded to each other to form a ring.)