JPH04362934A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To effectively suppress production of mold or fungi on a photosensitive material with a small amt. of a preventive, to improve storage property of the photosensitive material in a low cost, and moreover, to effectively suppress decoloring of color picture images obtd. by processing the photosensitive material. CONSTITUTION:A hydrophilic colloid layer on a supporting body contains at least one kind of aminoglycoside selected from gentamicin, amikacin, tobramycin, dibekacine, arbekacime, micronomicin, isepamicin, sisomicin, netilmicin, and astromicin.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to a silver halide photographic material.
Regarding fees. [Prior Art] Silver halide photographic materials include supports.
There is a silver halide emulsion layer and various auxiliary layers (undercoat layer, intermediate layer) on top.
layer, ultraviolet absorber-containing layer, filter layer, halation
(preventive layer, protective layer, backing layer, etc.) are applied.
These coated layers contain hydrophilic substances such as gelatin.
Sex colloids are used. However, hydrophilic
Lloyds rot or decompose due to the action of bacteria, mold, etc.
It is known that
When these hydrophilic colloids decay or decompose, the paint
The viscosity of the fabric solution and the physical strength of the applied film may decrease.
In addition, it is thought to be caused by decomposition products of hydrophilic colloids.
Coating failures occur and become a problem. In addition, color photosensitive materials
In this case, the color photograph obtained by color processing is
There is also the problem of discoloration due to the action of bacteria and mold.
. [0003] Therefore, conventional methods have been used to prevent bacteria, mold, etc.
Preservatives and anti-bacterial agents are used to prevent spoilage and decomposition.
is added at any stage of the manufacturing process of photographic materials.
Things have been done. Such preservatives or antibacterial
Examples of the agent include JP-A-54-27424 and JP-A-6
Various compounds such as those described in No. 3-271247 are known.
However, it must be added in large quantities to hydrophilic colloids.
If the
or problems that are harmful to the human body.
There was a problem. Neomycin, kanamycin,
Streptomycin, polymycin, framycin, etc.
It is also known that antibiotics are used, but their antibacterial ability is low and they are not very effective.
It may have to be added to certain amounts, or it may only be present in certain bacteria.
There are problems such as ineffectiveness or photographic damage.
there were. Problems to be Solved by the Invention Therefore, the problems to be solved by the present invention are as follows.
The purpose is to create an effective photographic preservative (or anti-bacterial agent) when added in small amounts.
The aim is to develop antiseptic agents) and use such preservatives to
Manufactured silver halide photographic materials of consistent quality
It is about providing. [Means for Solving the Problems] The present inventor has made extensive research
As a result, it is one of the cheapest antibiotics and is harmless to the human body.
Certain aminoglycosides such as gentamicins are unique
Even when used in small amounts, it has a remarkable preservative effect against bacteria and mold.
The aging properties of photosensitive materials and the color obtained through processing
The effect of improving image fading and further improving the coated surface condition was confirmed.
This led to the present invention. That is, the present invention provides hydrophilic
Gentamicin is present in the colloid layer.
n), Amikacin, Tobrama
Isin (Tobramycin), Dibekacin (Di
bekacin), arbekacin
), Micronomicin
, Isepamicin, Sisoma
Sisomicin, Netilmicin (Ne
tilmicin) and astromycin (Ast
of aminoglycosides selected from
A silver halide copy characterized by containing at least one kind of silver halide copy
It is a true photosensitive material. The present invention will be explained in detail below. Book
Among the aminoglycosides used in the invention, especially
Tamycin is preferred. Typical example of gentamicin
are listed below. Compound No. 1 (Gentamicin A2)
2 (Gentamicin A)
3 (Gentamicin A1)
4 (Gentamicin B)
5 (Gentamicin X2)
6 (Antibiotic JI-20A)
7 (Gentamicin B1)
8 (Antibiotic
G418) Compound No. 9 (Antibiotic JI-2
0B) 10 (gentamancin
C1) 11 (Gentamishi
C1a) 12 (Gentamai
Shin C2) 13 (Gentama
Ishin C2a) 14 (Genta
Mycin C2b) [0008] Amycin used in the present invention
Commercially available noglycosides can be used. Also, this
For information on the properties of
HE MERCK INDEX AN ENCYCLO
PEDIA OF CHEMICALS,DRUGS,
AND BIOLOGICALS) 11th edition (198
9 years) MERCK & CO. , INC. described in
There is. Regarding these manufacturing methods, for example, gentamicin
Regarding U.S. Pat. No. 3,091,572, U.S. Pat.
No. 6,704, U.S. Pat. No. 3,78 for amikacin.
No. 1,268, U.S. Pat. No. 4,10 for Arbekashi
7,424, German Patent 2,350,169, Jibekashi
German Patent No. 2,135,191, Isepa
Regarding Aisin, U.S. Patent No. 4,002,742, Mi
U.S. Pat. No. 4,045,298 for cronomycin
No., German Patent No. 2,326,781, Netilmicin
Regarding U.S. Pat. No. 4,002,742, U.S. Pat.
No. 9,882, German Patent No. 2,437,160, Perilla
Regarding mycin, see U.S. Patent No. 3,832,286, etc.
You can refer to it. The aminoglycosides used in the present invention are
, a silver halide emulsion layer coated on a support and a
At least one, preferably all, of the auxiliary layers as illustrated.
It can be contained in all layers. Aminoglycosides
is preferably dissolved in water and contains a hydrophilic colloid.
It is used by adding it to a liquid. Amount of aminoglycosides used
is preferably about 0.01 to 20 mg/m2, and 0.1 to 5
More preferred is mg/m2. [0010] The photographic light-sensitive material of the present invention has a blue-sensitive color on the support.
green-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and
At least one red-sensitive silver halide emulsion layer is applied.
can be configured. With ordinary color photographic paper,
Usually, they are coated on the support in the order listed above.
, may be in a different order. In addition, infrared sensitivity
A silver halide emulsion layer is added to at least one of the aforementioned emulsion layers.
It can be used instead. These photosensitive emulsion layers include
, a silver halide emulsion sensitive to each wavelength range, and
, a pigment that is complementary to the light it is sensitive to - that is, blue.
yellow to green, magenta to green, and shimmer to red.
Containing a so-called color coupler that forms an an-
You can perform color reproduction using the subtractive color method. However, the photosensitive layer
and the color hue of the coupler do not have the above correspondence.
It is also possible to have a different configuration. The silver halide emulsion used in the present invention is
, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, etc.
is silver chlorobromide or silver chloride, which does not substantially contain silver iodide.
It is preferable to use the following. fruit here
Qualitatively free of silver iodide means that the silver iodide content is 1 mol%.
Hereinafter, it is preferably 0.2 mol% or less. emulsion
The halogen composition of the particles may be different or the same between particles.
However, using an emulsion with equal halogen composition between grains,
This makes it easy to make the properties of each particle homogeneous. In addition, the halogen composition distribution inside the silver halide emulsion grains
Therefore, the composition of any part of the silver halide grain is
In grains with a so-called uniform structure and in silver halide grains with equal
The core of the body and the shell that surrounds it
or multiple layers] with different halogen compositions.
particles, or non-layered halo inside or on the surface of the particles.
Structures with different gene compositions (fields on the particle surface)
If there are areas of different composition on the edges, corners, or faces of the particles,
Particles with a structure in which parts are bonded together can be selected and used as appropriate.
I can do it. To obtain high sensitivity, use particles with a uniform structure.
It is also advantageous to use one of the latter two, and
It is also preferable from the viewpoint of sex. The silver halide grains are as shown above.
structure, the halogen composition differs.
Even if the boundaries between parts are clear, there may be differences in composition due to compositional differences.
It may be possible to form a mixed crystal and have an unclear boundary, or it may be aggressive.
It may also have a continuous structural change. Regarding the halogen composition of these silver chlorobromide emulsions,
silver bromide/silver chloride ratio can be used.
can. This ratio can vary widely depending on the purpose, but
, those with a silver chloride ratio of 2% or more are preferably used.
can. In addition, photosensitive materials suitable for rapid processing contain silver chloride.
A so-called high silver chloride emulsion having a high silver chloride content is preferably used. The silver chloride content of these high silver chloride emulsions is 90 mol% or more.
It is preferably 95 mol% or more, and more preferably 95 mol% or more. These high
In silver chloride emulsions, the silver bromide localized layer is
In layered or non-layered silver halide grains and/or
or a structure having it on the surface is preferable. of the above localized phase
The halogen composition is at least 10% in silver bromide content.
mol% is preferable, and more than 20 mol% is preferable.
More preferable. These localized layers are located inside the grain and inside the grain.
Can be on an edge, corner, or face of a child surface.
However, as a preferable example, it is possible to
Examples include those grown epitaxially. one
On the other hand, it minimizes the decrease in sensitivity when the photosensitive material is subjected to pressure.
A high silver chloride emulsion with a silver chloride content of 90 mol% or more for the purpose of
Also, the distribution of halogen composition within the particles is small and uniform.
It is also preferably carried out to use particles with a mold structure. [0013] Also, the purpose is to reduce the amount of replenishment of the developing processing solution.
The silver chloride content of the silver halide emulsion can be further increased by
It is valid. In such cases, the silver chloride content is 98%.
Milk of nearly pure silver chloride, such as between mol% and 100 mol%
Agents are also preferably used. Silver halide used in the present invention
The average grain size of the silver halide grains contained in the emulsion (grain
The particle size is defined as the diameter of a circle equivalent to the projected area of the child,
The number average) is preferably 0.1μ to 2μ.
stomach. In addition, their particle size distribution has a coefficient of variation (particle size).
standard deviation of the particle size distribution divided by the average particle size)2
The so-called monodisperse material is 0% or less, preferably 15% or less.
preferable. At this time, in order to obtain wide latitude,
The following monodispersed emulsions may be blended in the same layer and used.
, multilayer coating is also preferably carried out. Contained in photographic emulsion
The shapes of the silver halide grains included are cubic, tetradecahedral, and
A regular crystal like an octahedron
Irregular (i
rregular) having a crystalline form, or this
It is possible to use a composite form of these. Also,
It consists of a mixture of crystals with various crystal forms.
It's okay. In the present invention, among these, the above-mentioned regular
50% or more, preferably 70% of particles having a typical crystal shape
The content is more preferably 90% or more. Ma
In addition to these, the average aspect ratio (circular equivalent diameter/thickness)
tabular grains having a diameter of 5 or more, preferably 8 or more on the projection surface
It is also preferable to use an emulsion in which the product exceeds 50% of the total grains.
Can be used. The silver halide emulsion used in the present invention is
In the process of emulsion grain formation or physical ripening, various
Valence metal ion impurities can be introduced. use
Examples of compounds include cadmium, zinc, lead, copper, and talc.
salts such as aluminum, or group VIII elements such as iron and ruthenium.
Taenium, rhodium, palladium, osmium, iridium
Examples include salts or complex salts such as aluminum, platinum, etc.
. In particular, the Group VIII elements mentioned above can be preferably used.
Ru. The amount of these compounds added varies widely depending on the purpose.
is preferably 10-9 to 10-2 mol relative to silver halide.
Yes. The silver halide emulsion used in the present invention is a conventional silver halide emulsion.
Subjected to optical and spectral sensitization. About chemical sensitization
Sulfur sensitization, which is typified by the addition of unstable sulfur compounds, and gold
Precious metal sensitization represented by sensitization, reduction sensitization, etc.
They can be used alone or in combination. For chemical sensitization
Regarding the compounds used, please refer to JP-A-62-21527.
Written in the lower right column on page 18 to the upper right column on page 22 of the specification of Publication No. 2.
Those listed above are preferably used. The silver chlorobromide emulsion used in the present invention is P. Gl
Written by afkides Chimie et Physi
que Photographique (Paul M.
ontel, 1967), G. F. Duffin
Author Photographic Emulsion Ch
emistry (published by Focal Press, 196
6 years), V. L. Written by Zelikman et al.
akingand coating photogra
phic Emulsion (Focal Press
The investigation was conducted using the method described in
can be manufactured. That is, acidic method, neutral method, and
Any method such as the Monia method may be used, and soluble silver salts and soluble silver salts may be used.
The methods for reacting halogen salts include the one-sided mixing method and the same method.
Either the time mixing method or their combination.
You may also use the law. Particles are placed in an atmosphere containing excess silver ions.
It is also possible to use a method of forming the mixture (so-called back mixing method).
can. Silver halide as a form of simultaneous mixing method
How to keep the pAg in the liquid phase constant, i.e.
It is also possible to use the so-called controlled double jet method.
Wear. According to this method, the crystal shape is regular and the particle size is
A silver halide emulsion with nearly uniformity can be obtained. [0016] Spectral sensitization is performed on each of the light-sensitive materials of the present invention.
Add spectral sensitivity to the desired light wavelength range to the emulsion of the layer
done for a purpose. In the present invention, the target spectral sensitivity
A dye that absorbs light in the wavelength range corresponding to - a spectral sensitizing dye
It is preferable to carry out this by adding. used at this time
Examples of spectral sensitizing dyes include F. M. Harmer
Author Heterocyclic compounds-
Cyanine dies and related
compounds (John Wiley & S.
onsNew York, London, 19
Examples include those described in 1964). Examples of specific compounds and spectral sensitization methods are described in the above-mentioned Japanese Patent Application Publication No.
Upper right column of page 22 of the specification of Publication No. 1982-215272~
The one described on page 38 is preferably used. To the present invention
The silver halide emulsion used depends on the manufacturing process and storage of the photosensitive material.
to prevent fogging during storage or photo processing, or
Various compounds or compounds are used to stabilize photographic performance.
Precursors such as these can be added. these compounds
A specific example is the specification of JP-A No. 62-215272 mentioned above.
Those described on pages 39 to 72 of the book are preferably used.
It will be done. The emulsion used in the present invention has a latent image mainly composed of grains.
So-called surface latent image type emulsion or latent image formed on the surface of the
This is the so-called internal latent image type emulsion in which images are mainly formed inside the grains.
It may be of any type. This invention is color
When applied to light-sensitive materials, the color light-sensitive materials may contain aromatic
Coupling with the oxidized product of group amine color developer
Yellow color that develops yellow, magenta, and cyan respectively.
Puller, magenta coupler and cyan coupler are normally used
I can stay. Cyanka preferably used in the present invention
Puller, magenta coupler and yellow coupler are
The following general formulas (C-I), (C-II), (M-I), (
M-II) and (Y). [Chemical formula 1] [Chemical formula 2] In general formulas (C-I) and (C-II),
and R1, R2 and R4 are substituted or unplaced.
represents an aliphatic, aromatic or heterocyclic group, R3, R
5 and R6 are hydrogen atoms, halogen atoms, aliphatic groups
, represents an aromatic group or an acylamino group, and R3 and R2
Non-gold that forms a nitrogen-containing 5- or 6-membered ring with
It may also represent a genus atomic group. Y1 and Y2 are hydrogen atoms or
or released during the coupling reaction with the oxidized form of the developing agent.
Represents a glutinous group. n represents 0 or 1. General formula (C-II
) is preferably an aliphatic group.
For example, methyl group, ethyl group, propyl group, butyl group
group, pentadecyl group, tert-butyl group, cyclohexyl group
Syl group, cyclohexylmethyl group, phenylthiomethyl
group, dodecyloxyphenylthiomethyl group, butanami
Examples include domethyl group and methoxymethyl group.
Ru. The above general formula (C-I) or (C-II)
A preferred example of a cyan coupler represented by is as follows.
be. In general formula (C-I), preferable R1 is ali
halogen atom, alkyl group,
Alkoxy group, aryloxy group, acylamino group, alkoxy group, aryloxy group, acylamino group,
Syl group, carbamoyl group, sulfonamide group, sulfa group
Moyl group, sulfonyl group, sulfamide group, oxycal group
Must be an aryl group substituted with a bonyl group or cyano group
is even more preferable. In general formula (C-I), R3 and
When R2 does not form a ring, R2 is preferably substituted
or an unsubstituted alkyl group or aryl group, especially
Preferred is a substituted aryloxy-substituted alkyl group.
, R3 is preferably a hydrogen atom. General formula (C-I
In I), preferred R4 is substituted or unsubstituted atom.
alkyl group, aryl group, particularly preferably substituted aryl group.
is an alkyl group substituted with hydroxyl. Preferred R5 in general formula (C-II)
is an alkyl group having 2 to 15 carbon atoms and an alkyl group having 1 or more carbon atoms.
It is a methyl group with a substituent, and the substituent is an aryl group.
ruthio group, alkylthio group, acylamino group, aryl
Oxy groups and alkyloxy groups are preferred. General formula (C-
In II), R5 is an alkyl group having 2 to 15 carbon atoms.
It is more preferable that the alkyl group has 2 to 4 carbon atoms.
It is particularly preferable that there be. In general formula (C-II)
Preferred R6 is a hydrogen atom, a halogen atom, and a chlorine atom.
Particularly preferred are atoms and fluorine atoms. General formula (C-I
) and (C-II), preferred Y1 and Y
2 is a hydrogen atom, a halogen atom, and an alkoxy atom, respectively.
group, aryloxy group, acyloxy group, sulfonamide
It is a do group. In general formula (M-I), R7 and R9 are ali
R8 represents a hydrogen atom, aliphatic or aromatic
group acyl group, aliphatic or aromatic sulfonyl group
and Y3 represents a hydrogen atom or a leaving group. R7 O
and the aryl group (preferably phenyl group) of R9.
The permissible substituents are the permissible positions for substituent R1.
Same as substituent, and when there are two or more substituents, they are the same
But they can be different. R8 is preferably a hydrogen atom
, aliphatic acyl group or sulfonyl group, particularly preferred
Preferably it is a hydrogen atom. Preferred Y3 is sulfur, acid
It is a type that leaves either an elementary or a nitrogen atom.
For example, U.S. Patent No. 4,351,897 and International Publication No.
Sulfur as described in WO88/04795
The atomic dissociation type is particularly preferred. In general formula (M-II), R10 is water
Represents an elementary atom or a substituent. Y4 is a hydrogen atom or
Represents degrouping, with halogen atoms and arylthio groups being particularly preferred.
Yes. Za, Zb and Zc are methine, substituted methine, =N- or
represents -NH-, and represents the Za-Zb bond and Zb-Zc bond.
One of them is a double bond and the other is a single bond. Zb
-If the Zc bond is a carbon-carbon double bond, it is aromatic.
Including cases where it is part of a ring. 2 amounts with R10 or Y4
When forming a multimer with more than
When Zc is a substituted methine, the amount of the substituted methine is 2.
This includes the case where a multimer of more than one body is formed. General formula (M-I
Among the pyrazoloazole couplers represented by I)
Low yellow side absorption and light fastness of the coloring dye
The imidazo described in US Pat. No. 4,500,630
1,2-b] pyrazoles are preferred and are described in U.S. Pat.
Pyrazolo[1,5-b][1] described in No. 540,654
, 2, 4] triazoles are particularly preferred. [0024] Others described in Japanese Patent Application Laid-Open No. 61-65245
A branched alkyl group such as
directly linked to the 2, 3 or 6 position of the pyrazolotriazole cap
Ra, as described in JP-A No. 61-65246.
Pyrazoloazole cap containing a sulfonamide group
Ra, as described in JP-A No. 61-147254.
Pione with alkoxyphenylsulfonamide ballast group
Lazoloazole coupler and European Patent (Publication) No. 226,
6 as described in No. 849 and No. 294,785.
Pyrazolotris with an alkoxy or aryloxy group in position
Preference is given to using azole couplers. In the general formula (Y), R11 is halogen
atom, alkoxy group, trifluoromethyl group or ali
R12 represents a hydrogen atom, a halogen atom, or
Represents an alkoxy group. A is -NHCOR13, -NHS
O2 -R13, -SO2 NHR13, -COOR1
3, -SO2 N-R13 (R14). however,
R13 and R14 are each an alkyl group, an aryl group or
represents an acyl group. Y5 represents a leaving group. R12 and R
13.As a substituent for R14, the permissible substituents for R1 are
The leaving group Y5 is preferably an acid substituent.
A type that leaves either an elementary atom or a nitrogen atom
The nitrogen atom-eliminating type is particularly preferable. General formulas (C-I), (C-II), (M-I), (M-
Specific examples of couplers represented by II) and (Y) are shown below.
Listed below. [Formula 3] [Formula 3] [Formula 4] [Formula 4] [Formula 5] [Formula 5] [Formula 6] [Formula 7] [Formula 7] [Formula 10] [Formula 11] [Formula 11] [Formula 11] [Formula 12] [Formula 13] [Formula 14] [Formula 14] [Formula 14] ] [Chemical 17] [Chemical 18] [Chemical 19] [Chemical 19] [Chemical 19] [Chemical 20] [Chemical 21] [0045] [Chemical 22] [0046] [Chemical 23] [0047] Represented by the above general formulas (C-I) to (Y)
The coupler is contained in the silver halide emulsion layer that constitutes the photosensitive layer.
, usually 0.1 to 1.0 mol per mol of silver halide,
Preferably it is contained in an amount of 0.1 to 0.5 mol. The present invention
In order to add the above-mentioned coupler to the photosensitive layer, known methods can be used.
Various techniques can be applied. Normally oil pump
Added using the oil-in-water dispersion method known as the Rotect method.
After dissolving in the solvent, gelatin containing surfactant can be
Emulsify and disperse in Chin aqueous solution. or contain surfactants.
Add water or gelatin aqueous solution to the coupler solution,
It may also be made into an oil-in-water dispersion with phase inversion. Also Arca
Re-soluble couplers can be used in the so-called Fischer dispersion method.
It can also be dispersed. From the coupler dispersion, distillation,
Low boiling point can be obtained through methods such as water washing or ultrafiltration.
After removing the organic solvent, it may be mixed with a photographic emulsion. As a dispersion medium for such a coupler, the dielectric constant (25℃)
2-20, high boiling point with refractive index (25℃) 1.5-1.7
Using organic solvents and/or water-insoluble polymer compounds
is preferable. As the high boiling point organic solvent, preferably the following
High boiling point organic solvents represented by general formulas (A) to (E) are used.
It will be done. ##STR24## where W1, W2 and W3 are
Substituted or unsubstituted alkyl group, cycloalkyl
group, alkenyl group, aryl group or heterocyclic group.
, W4 represents W1, OW1 or S-W1
, n is an integer from 1 to 5, and when n is 2 or more, W
4 may be the same or different from each other, and the general formula (E
), W1 and W2 may form a fused ring
). The high boiling point organic solvent that can be used in the present invention has the general formula (A)
Or other than (E), the melting point is 100℃ or less and the boiling point is 14
A compound that is immiscible with water above 0°C and is a good solvent for couplers.
If so, you can use it. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher.
more preferably 170°C or higher. These high boiling
For details on organic solvents, see JP-A No. 62-21527.
In the lower right column of page 137 to the upper right column of page 144 of the published specification No. 2
Are listed. [0050] These couplers also have the above-mentioned high boiling point.
Loadable latex in the presence or absence of organic solvents
polymers (e.g. U.S. Pat. No. 4,203,716)
or by impregnating it with a water-insoluble but organic solvent-soluble polymer.
Dissolve in reamer and emulsify and disperse in hydrophilic colloid aqueous solution.
can be done. Preferably International Publication WO88/0072
The homopolymer or homopolymer described on pages 12 to 30 of Specification No. 3
Copolymers are used, especially acrylamide-based polymers.
The use of is preferred from the viewpoint of color image stabilization and the like. Using the present invention
The photosensitive materials produced are treated with hydrochloric acid as a color fog preventive agent.
Quinone derivatives, aminophenol derivatives, gallic acid derivatives
It may contain ascorbic acid derivatives, etc. The photosensitive material of the present invention contains various anti-fading agents.
can be used. i.e. cyan, magenta and/or
Or Hydro as an organic anti-fade agent for yellow images.
Quinones, 6-hydroxychromans, 5-hydroxy
Coumarans, spirochromans, p-alkoxyphenos
Hindered phenols and bisphenols
Nols, gallic acid derivatives, methylenedioxybenzene
aminophenols, hindered amines and
The phenolic hydroxyl group of each of these compounds is silylated or alkylated.
Typical examples are ether or ester derivatives.
can be mentioned. Also, (bissalicylaldoximato)
Nickel complex and (bis-N,N-dialkyldithio
metal complexes such as carbamate) nickel complexes, etc.
Can be used. Specific examples of organic anti-fading agents are disclosed in the following patents.
It is stated in the detailed description. Hydroquinones are disclosed in US Pat. No. 2,360.
, No. 290, No. 2,418,613, No. 2,70
No. 0,453, No. 2,701,197, No. 2,7
No. 28,659, No. 2,732,300, No. 2,
No. 735,765, No. 3,982,944, No. 4
, 430,425, British Patent No. 1,363,921
, U.S. Patent No. 2,710,801, U.S. Patent No. 2,816,
028 etc., 6-hydroxychromans, 5-hydro
Roxycoumarans and spirochromans are covered by U.S. Patent No. 3,
No. 432,300, No. 3,573,050, No. 3
, No. 574,627, No. 3,698,909, No. 3,698,909, No. 3,698,909, No.
No. 3,764,337, JP-A-52-152225, etc.
However, spiroindanes are disclosed in U.S. Patent No. 4,360,58.
No. 9, p-alkoxyphenols are disclosed in U.S. Patent No. 2,
No. 735,765, British Patent No. 2,066,975;
JP 59-10539, JP 57-19765
etc., hindered phenols are disclosed in U.S. Patent No. 3,70.
No. 0,455, JP-A-52-72224, U.S. Patent No. 4
, No. 228, 235, Special Publication No. 52-6623, etc.
Gallic acid derivatives, methylenedioxybenzenes, amino
Phenols are each covered by U.S. Patent No. 3,457,079.
No. 4,332,886, Special Publication No. 56-2114
No. 4, etc., and hindered amines are disclosed in U.S. Patent Nos. 3 and 33.
No. 6,135, No. 4,268,593, British Patent No.
No. 1,326,889, No. 1,354,313, No.
No. 1,410,846, Special Publication No. 51-1420, Special Publication No.
Kaisho No. 58-114036, Kaisho No. 59-53846,
No. 59-78344, etc., metal complexes are described in US Patent No.
No. 4,050,938, No. 4,241,155, English
Each is described in National Patent No. 2,027,731(A), etc.
It is listed. These compounds each have a corresponding
Usually 5 to 100% by weight of the coupler is added to the color coupler.
The purpose is achieved by co-emulsifying with - and adding it to the photosensitive layer.
can be achieved. Cyan dye image heat and especially light
In order to prevent deterioration due to
It is recommended to introduce UV absorbers into the layers on both sides adjacent to the
more effective. As the ultraviolet absorber, substituted with aryl group
benzotriazole compounds (e.g., U.S. Pat.
, 533,794), 4-thiazolidone
compounds (e.g., U.S. Pat. No. 3,314,794;
3,352,681), benzophenone
Compounds (e.g. those described in JP-A-46-2784)
, cinnamate ester compounds (e.g. U.S. Pat. No. 3,70
Nos. 5,805 and 3,707,395
), butadiene compounds (U.S. Pat. No. 4,045,229
) or benzoxazole compounds
(For example, U.S. Patent Nos. 3,406,070 and 3,67
7,672 and 4,271,307)
can be used. UV-absorbing couplers (e.g.
α-naphthol cyan dye-forming couplers) and purple
A polymer absorbing external radiation may also be used. these purple
The external radiation absorber may be mordanted in a specific layer. Among them, benzotriazo substituted with the above aryl group
A metal compound is preferred. [0054] In addition to the aforementioned couplers, in particular the following
Preference is given to using such compounds. Especially Pyrazoloa
Preferably used in combination with a sol coupler. That is, color development processing
Chemically bonds with the aromatic amine developing agent that remains after processing.
produces a chemically inert and virtually colorless compound.
Compound (F) remaining after color development processing
chemically combines with the oxidized form of an aromatic amine color developing agent.
produces a chemically inert and virtually colorless compound.
It is possible to use compound (G) simultaneously or singly, e.g.
If there is no residual color developing agent or solvent in the film during storage after processing,
The reaction between the oxidized form of
This is preferable in terms of preventing the occurrence of tein and other side effects. Preferred compounds as compound (F) are p-anisidine and
The second-order reaction rate constant k2 (trioctylphosate at 80°C
during phase) is 1.0 liter/mol ・sec ~
Reaction within the range of 1 x 10-5 liter/mol sec
It is a corresponding compound. The second-order reaction rate constant is based on JP-A-63-158545.
It can be measured by the method described in . If k2 is larger than this range, the compound
It becomes unstable, reacts with gelatin and water, and decomposes.
Sometimes I put it away. On the other hand, if k2 is smaller than this range,
If the
Prevents the side effects of aromatic amine developing agents that remain as a product.
Sometimes you can't stop it. Such compounds (
F) is more preferably represented by the following general formula (FI) or (
FII). General formula (FI) R1 -(A)n -X General formula (FII) R2 -C(-B)=Y In the formula, R1 and R2 are each an aliphatic group
, aromatic group, or heterocyclic group. n is 1 or 0
represents. A reacts with the aromatic amine developer and forms a chemical bond.
, and X represents a group that reacts with an aromatic amine developer.
represents a group that leaves in response. B is a hydrogen atom, an aliphatic group,
Aromatic group, heterocyclic group, acyl group, or sulfonyl group
, Y represents the aromatic amine developing agent with the general formula (FII
) represents a group that promotes addition to the compound. child
Here, R1 and X, Y and R2 or B are bonded to each other.
It may also have a cyclic structure. Residual aromatic amine developing agent
Among the methods of chemical bonding with
It is an addition reaction. Formulas represented by general formulas (FI) and (FII)
For specific examples of compounds, see JP-A-63-158545.
, No. 62-283338, European Patent Publication No. 29832
Described in specifications such as No. 1 and No. 277589.
Preferably. On the other hand, the aroma that remains after color development processing
Chemically combines with the oxidized form of group amine developing agent to form a chemically
Compound (G), which produces an inert and colorless compound.
More preferable ones can be represented by the following general formula (GI).
Wear. General formula (GI) R-Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group.
vinegar. Z is a nucleophilic group or decomposes in the photosensitive material to become nucleophilic
represents a group that releases a group. Represented by general formula (GI)
The compound in which Z is Pearson's nucleophilic nCH3I
Value (R.G. Pearson, et al., J.Am
．． Chem. Soc. , 90, 319 (1968))
5 or more groups or groups derived therefrom are preferred.
stomach. Regarding specific examples of compounds represented by general formula (GI)
European Patent Publication No. 255722, JP-A-62-14
No. 3048, No. 62-229145, Patent Application No. 1-23
No. 0039, No. 1-57259, European Patent Publication No. 298
Items listed in No. 321, No. 277589, etc.
is preferred. Also, the above compound (G) and compound (F)
For details on the combination of
It is described in. [0058] The photosensitive material produced using the present invention has parenteral
As a filter dye or as an irradiation agent in aqueous colloid layers.
For various purposes such as prevention of oxidation and halation.
Contains water-soluble dyes and dyes that become water-soluble through photographic processing.
You may do so. Such dyes include oxonol dyes.
dye, hemioxonol dye, styryl dye, merocyanide
cyanine dyes, cyanine dyes and azo dyes. inside
Even oxonol dyes, hemioxonol dyes and melo
Cyanine dyes are useful. Emulsion layer of the light-sensitive material of the present invention
as a binder or protective colloid that can be used in
It is advantageous to use gelatin, but other parents
Aqueous colloids can be used alone or with gelatin
can. In the present invention, gelatin is lime-treated
However, it can also be treated with acid.
. For details on how to make gelatin, see Arthur Vuis, The
Macromolecular chemistry of gelatin (
Academic Press, published in 1964)
. The support used in the present invention is usually a photographic support.
Cellulose nitrate filaments used in photosensitive materials
Transparent films such as lume and polyethylene terephthalate
or reflective supports can be used. For the purpose of this invention
, the use of reflective supports is more preferred. Used in the present invention
"Reflective support" is a silver halide emulsion with increased reflectivity.
This refers to something that sharpens the pigment image formed in the layer.
Such reflective supports include titanium oxide, zinc oxide, etc.
Avoid light-reflecting substances such as lead, calcium carbonate, and calcium sulfate.
Items coated with dispersed hydrophobic resin or light reflective substances
The one using a hydrophobic resin containing dispersion of as a support is
included. For example, baryta paper, polyethylene coated paper,
Polypropylene synthetic paper, with reflective layer or reflective
Transparent supports that are used in conjunction with transparent substances, such as glass plates and polyester
Tylene terephthalate, cellulose triacetate or nitric acid
Polyester film such as cellulose, polyamide film
film, polycarbonate film, polystyrene film
lum, vinyl chloride resin, etc. [0060] As other reflective supports, specular reflective
Or use a support with a type 2 diffuse reflective metal surface.
can be done. Metal surfaces exhibit spectral reflection in the visible wavelength range.
It is best to have an emissivity of 0.5 or more, and the metal surface can be roughened.
Alternatively, it is preferable to use metal powder to make it diffusely reflective. Applicable
Metals include aluminum, tin, silver, magnesium, and
The surface is rolled, vapor-deposited, or plated.
On the surface of a metal plate, metal foil, or thin metal layer obtained by
It's good. Among others, metals are obtained by vapor deposition on other substrates.
It is better. Water-resistant resins, especially thermoplastics, are used on metal surfaces.
It is preferable to provide a synthetic resin layer. Metal of the support of the present invention
It is best to provide an antistatic layer on the side opposite to the side with the surface.
. Details of such supports can be found, for example, in JP-A-Sho.
No. 61-210346, No. 63-24247, No. 63
-24251 and 63-24255 etc.
ing. These supports can be selected as appropriate depending on the purpose of use.
Wear. [0061] As the light-reflecting substance, the presence of a surfactant
It is best to thoroughly knead the white pigment at the bottom of the pigment particles.
Use one whose surface has been treated with di- to tetrahydric alcohol.
is preferable. Specified unit area of white pigment fine particles
The occupied area ratio (%) of
Divide the area into adjacent unit areas of 6 μm x 6 μm,
Occupied area ratio of fine particles projected on the unit area (%)
(Ri) can be determined by measuring. Occupied area ratio
The coefficient of variation of the ratio (%) with respect to the average value (R) of Ri is
It can be determined by the ratio s/R of the standard deviation s of Ri.
come. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined by the following equation. The present invention
The coefficient of variation of the occupied area ratio (%) of pigment fine particles is
It is preferably 0.15 or less, particularly 0.12 or less. 0.08
The dispersibility of the particles is considered to be “uniform” in the following cases:
I can say that. Used in the development process of the photosensitive material of the present invention
The color developer is preferably an aromatic primary amine color developer.
It is an alkaline aqueous solution whose main component is a developing agent. this
Aminophenol compounds are also used as color developing agents.
p-phenylenediamine compounds are preferred.
A typical example is 3-methyl-4-amino
No-N,N-diethylaniline, 3-methyl-4-amino
no-N-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-methane
Sulfonamidoethylaniline, 3-methyl-4-ami
No-N-ethyl-β-methoxyethylaniline and this
sulfate, hydrochloride or p-toluenesulfonate
Examples include. Among these, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethyl
Niline sulfate is preferred. These compounds are used depending on the purpose.
Two or more types can also be used together. [0064] The color developing solution contains alkali metal carbonates,
pH buffers such as borates or phosphates, chloride salts
, bromide salts, iodide salts, benzimidazoles, benzo
Development inhibitors such as thiazoles or mercapto compounds
It generally contains a detergent or an antifoggant. In addition, if necessary, hydroxylamine, diethylhydride
Roxylamine, sulfite, N,N-biscarboxyme
Hydrazines such as tylhydrazine, phenyl semicals
Bazides, triethanolamine, catechol sulfone
Various preservatives such as acids, ethylene glycol, diethyl
Organic solvents such as glycol, benzyl alcohol,
Polyethylene glycol, quaternary ammonium salt, amine
Development accelerators, dye-forming couplers, competitive couplers such as
-, auxiliary development such as 1-phenyl-3-pyrazolidone
Main drug, viscosity enhancer, aminopolycarboxylic acid, aminopolycarboxylic acid
Phosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid
Various chelating agents such as ethylene
Diaminetetraacetic acid, nitrilotriacetic acid, diethylenetriamine
pentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxy
Ethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylene
phosphonic acid, ethylenediamine-N,N,N,N-te
Tramethylenephosphonic acid, ethylenediamine-di(o-
Typical examples include hydroxyphenylacetic acid) and their salts.
can be mentioned. [0065] Also, when performing inversion processing, it is usually black and white.
After imaging, color development is performed. This black and white developer contains
Dihydroxybenzenes such as hydroquinone, 1-phenylene
3-pyrazolidones such as nyl-3-pyrazolidone or
is an aminophenol such as N-methyl-p-aminophenol.
Known black and white developing agents such as nols may be used alone or in combination.
Can be used together. These color developing solutions and
The pH of black and white developer is generally 9 to 12.
. In addition, the amount of replenishment of these developers depends on the color photo being processed.
It depends on the photosensitive material, but in general, the amount per square meter of photosensitive material is
3 liters or less per day, and the bromide ion concentration in the replenisher is
By reducing the volume, the volume can be reduced to 500ml or less.
Can also be done. When reducing the amount of replenishment, the air in the treatment tank
Liquid evaporation, air acid by reducing the contact area of
It is preferable to prevent this from occurring. [0066] Contact area between photographic processing solution and air in processing tank
can be expressed by the aperture ratio defined below. That is,
, Opening ratio = contact area between processing liquid and air (cm2)/processing liquid
Capacity (cm3) The above aperture ratio is preferably 0.1 or less;
It is preferably 0.001 to 0.05. in this way
One way to reduce the aperture ratio is to use photographic processing liquid in the processing tank.
In addition to providing a shield such as a floating lid on the surface,
Method using a movable lid described in No. 033, JP-A-63
The slit development treatment method described in No.-216050
can be mentioned. Reducing the aperture ratio increases color development
Not only the development and black and white development processes, but also the subsequent processes,
For example, all processes such as bleaching, bleach-fixing, fixing, washing, stabilization, etc.
It is preferable to apply it in all steps. Also, developing
We decided to use a method to suppress the accumulation of bromide ions in the liquid.
It is also possible to further reduce the amount of replenishment. During color development processing
The time period is usually set between 2 and 5 minutes, but with high temperature and high pH,
By using a high concentration of color developing agent,
Furthermore, processing time can also be shortened. The photographic emulsion layer after color development is usually bleached.
It will be done. The bleaching process may be carried out simultaneously with the fixing process.
(Bleach-fixing treatment) may be carried out separately. further processing
In order to speed up the process, bleach-fixing treatment is applied after bleaching.
It may be a method. Furthermore, it is processed in two continuous bleach-fixing baths.
fixing before bleach-fixing, or
Bleaching after bleach-fixing may also be carried out depending on the purpose.
It can be done. As a bleaching agent, for example, iron (III) etc.
Polyvalent metal compounds, peracids, quinones, nitro compounds, etc.
is used. Typical bleaching agents include those containing iron (III).
organic complex salts, e.g. ethylenediaminetetraacetic acid, diethylenetetraacetic acid
lyaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyl
liminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol
Aminopolycarbonate such as recall ether diamine tetraacetic acid, etc.
Rubonic acids or citric acid, tartaric acid, malic acid, etc.
Complex salts etc. can be used. Of these, ethylene
Diaminetetraacetic acid iron (III) complex salt, and 1,3-diamine
Iron(III) nopropane tetraacetate Complex salts and other amino acids
Nopolycarboxylic acid iron(III) complex salts can be used for rapid processing and environmental pollution.
Preferable from the viewpoint of preventing staining. Furthermore, aminopolycarbonate
Acid iron(III) complex salts can be used both in bleaching solutions and in bleach-fixing solutions.
It is also particularly useful. These aminopolycarbons
p of bleach or bleach-fix solutions using acid iron(III) complex salts
H is usually 4.0 to 8, but it is
It is also possible to process at an even lower pH. Bleach solutions, bleach-fix solutions and their prebaths include
, a bleach accelerator can be used if necessary. Specific examples of useful bleach accelerators are described in
Yes: U.S. Patent No. 3,893,858, West German Patent No. 1
, No. 290,812, No. 2,059,988, JP-A-Sho
No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623
, No. 53-28426, Research Disclosure
-No. Described in No. 17129 (July 1978) etc.
A compound having a mercapto group or a disulfide group;
Thiazolidine induction described in JP-A-50-140129
Body; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832
No. 53-32735, U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,127
, No. 715, and the iodination described in JP-A-58-16,235.
Salt; West German Patent No. 966,410, West German Patent No. 2,748,4
Polyoxyethylene compounds described in No. 30;
Polyamine compound described in No. 5-8836; other JP-A-Sho
No. 49-40,943, No. 49-59,644, No. 5
No. 3-94,927, No. 54-35,727, No. 55
-26,506, 58-163,940
compound; bromide ion, etc. can be used. Among them, Mercap
Compounds with a disulfide group or a disulfide group have a promoting effect.
Preferred from a large standpoint, especially U.S. Pat. No. 3,893,8
No. 58, West German Patent No. 1,290,812, JP-A-53
-95,630 is preferred. Furthermore, rice
Compounds described in National Patent No. 4,552,834 are also preferred.
stomach. These bleach accelerators may be added to the photosensitive material. These are used when bleaching and fixing color photosensitive materials for photography.
Bleach accelerators are particularly effective. In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution contain
contains an organic acid to prevent bleaching stains.
It is preferable. Particularly preferred organic acids have an acid dissociation constant (
pKa) is 2 to 5, specifically acetic acid,
Ropionic acid and the like are preferred. Used in fixer and bleach-fixer
Examples of fixing agents include thiosulfate, thiocyanate, and thiosulfate.
Oether compounds, thioureas, large amounts of iodide salts, etc.
However, the use of thiosulfates is common.
ammonium thiosulfate is the most widely used
. Also, thiosulfates, thiocyanates, thioethers
Combination use of compounds, thiourea, etc. is also preferred. Fixer and bleach
Fixer preservatives include sulfites, bisulfites, and calcium.
Bonyl bisulfite adduct or European Patent No. 294769
The sulfinic acid compounds described in item A are preferred. Furthermore, fixed
Various amino acids are added to the depositing liquid and bleach-fixing liquid for the purpose of stabilizing the liquid.
Addition of polycarboxylic acids and organic phosphonic acids is preferable.
. In the present invention, the fixing solution or bleach-fixing solution has a pH of
Compounds with a pKa of 6.0 to 9.0, preferably
For example, imidazole, 1-methylimidazole, 1-ethyl imidazole,
Imides such as tylimidazole and 2-methylimidazole
Adding dazoles from 0.1 to 10 mol/liter
is preferred. [0070] The total time of the desilvering process is
It is preferable that the length be as short as possible. The preferred time is 1 minute to 3 minutes.
minutes, more preferably 1 to 2 minutes. Also, the processing temperature
is 25°C to 50°C, preferably 35°C to 45°C. In the preferred temperature range, the desilvering rate increases and
The generation of stains after treatment is effectively prevented. For the desilvering process
It is preferable that the agitation is as strong as possible.
Yes. As a specific method for strengthening stirring, see
Spraying a processing liquid onto the emulsion surface of a photosensitive material described in No. 183460
The method of colliding the flows and the method of
A method of increasing the stirring effect using a rotating means, and furthermore,
While the provided wiper blade is in contact with the emulsion surface.
By moving the photosensitive material and creating turbulence on the emulsion surface,
A method to improve the stirring effect by improving the circulation flow of the entire processing liquid
One method is to increase the amount. This kind of stirring improves
The method is whether it is a bleach solution, a bleach-fix solution, or a fix solution.
is also valid. Improved stirring is achieved by bleaching and fixing into the emulsion film.
It is thought that this will speed up the supply of the agent and increase the desilvering rate as a result.
available. In addition, the above-mentioned agitation improvement means uses a bleach accelerator.
More effective when used and significantly increases the promoting effect
or eliminate the fixation inhibiting effect of bleach accelerators.
I can do it. [0071] Automatic developing machine used for the photosensitive material of the present invention
JP-A-60-191257, JP-A No. 60-19125
No. 8, photosensitive material conveyor described in No. 60-191259
Preferably, it has steps. The above-mentioned JP-A-60-1
As described in No. 91257, such means of conveyance are
The carry-over of processing liquid from the bath to the post-bath can be significantly reduced.
Highly effective in preventing deterioration of liquid performance. This kind of effect is
Shorten processing time in each process and reduce processing solution replenishment amount
It is particularly effective for Silver halide color photographic effect of the present invention
After desilvering, optical materials undergo water washing and/or stabilization processes.
is common. The amount of water used in the washing process is determined by
characteristics (e.g., depending on the materials used, such as couplers), uses, and
including washing water temperature, number of washing tanks (number of stages), countercurrent flow, forward flow, etc.
A wide range of settings can be made depending on the replenishment method and various other conditions.
obtain. Of these, the number of water washing tanks in the multi-stage countercurrent method and
Regarding the relationship between water volume, please refer to the Journal of the Soc.
iety of Motion Picture a
nd Television Engineers No.
Volume 64, P. 248-253 (May 1955 issue)
You can find it using the method listed below. Many of the documents mentioned above
According to the stage counterflow method, the amount of washing water can be significantly reduced, but
Due to the increased residence time of water in the tank, bacteria
The bacteria may propagate and the resulting floating matter may adhere to the photosensitive material.
A problem arises. In processing the color photosensitive material of the present invention
, as a solution to this problem, Japanese Patent Application Laid-Open No. 62-288
, No. 838, the calcium ions and magnesium ions described in
It is possible to use extremely effective methods to reduce
Ru. Also, isothiae described in JP-A No. 57-8,542
Zolone compounds, thiabendazoles, chlorinated isocyanates
Chlorine-based disinfectants such as sodium nurate, and other benzoate
Riazor et al., Hiroshi Horiguchi, “Chemistry of antibacterial and fungicidal agents” (198
6th year) Sankyo Publishing, Hygiene Technology Society, ed. “Sterilization and sterilization of microorganisms,
Anti-mold technology” (1982) Society of Industrial Engineers, Japan Anti-bacterial and anti-mold science
Disinfectants listed in the Society's "Encyclopedia of Antibacterial and Antifungal Agents" (1986)
You can also use Washing water in processing the photosensitive material of the present invention
The pH is 4-9, preferably 5-8. washing with water
Water temperature and water washing time can also be set in various ways depending on the characteristics of the photosensitive material, application, etc.
However, in general, at 15 to 45°C for 20 seconds to 10 minutes,
Preferably, the temperature range is 30 seconds to 5 minutes at 25 to 40°C.
It will be done. Furthermore, the photosensitive material of the present invention can be directly washed instead of washing with water.
It can also be treated with a stabilizing solution. Such cheap
In the standardization process, JP-A-57-8543 and JP-A-57-8543
-14834, publicly known as described in 60-220345
All methods can be used. In addition, the water washing
Following the treatment, further stabilization treatment may be performed;
and is used as the final bath for color photosensitive materials for photography.
, lists stabilizing baths containing dye stabilizers and surfactants.
be able to. As a dye stabilizer, formalin and glue are used.
Aldehydes such as rutaraldehyde, N-methylol
compound, hexamethylenetetramine or aldehyde
Examples include sulfite adducts. In this stable bath
Various chelating agents and antifungal agents can also be added. [0073] O
The bar flow liquid is not reused in other processes such as desilvering process.
You can also In processing using automatic processing machines etc.
, if each of the above treatment liquids is concentrated by evaporation, water
It is preferable to correct the concentration by adding Halogen of the present invention
Silver oxide color light-sensitive materials have the potential to simplify and speed up processing.
A color developing agent may be incorporated therein. In order to incorporate
It is preferable to use various precursors of color developing agents.
stomach. For example, in US Pat. No. 3,342,597,
Doaniline compound, No. 3,342,599, Lisa
Disclosure No. 14,850 and the same
No. 15,159, the Schiff base type compound described in
Aldol compounds described in No. 13,924, U.S. Pat.
, 719,492, JP-A-53-1
Examples include the urethane compounds described in No. 35628.
Wear. The silver halide color photosensitive material of the present invention can be used as necessary.
Accordingly, various types of 1-phenylene are added for the purpose of promoting color development.
Ru-3-pyrazolidones may be incorporated therein. typicalization
The compound is disclosed in JP-A-56-64339 and JP-A-57-14454.
No. 7, and No. 58-115438, etc.
Ru. [0074] Various processing solutions in the present invention can be used at temperatures ranging from 10°C to 50°C.
Used at ℃. Normally the temperature is between 33°C and 38°C.
Standard, but use higher temperatures to speed up processing and increase processing time
It is possible to shorten the time, or conversely lower the temperature to improve image quality or reduce processing liquid.
An improvement in the stability of can be achieved. Moreover, the present invention
The silver halide photosensitive material is disclosed in U.S. Patent No. 4,500,62.
No. 6, JP-A-60-133449, JP-A No. 59-2184
No. 43, No. 61-238056, European Patent No. 210,6
Also suitable for heat-developable photosensitive materials such as those described in No. 60A2.
Can be used. [Example] The following is a more detailed explanation using examples.
However, the present invention is not limited thereto. Example 1 As shown in Table 2, a 16% by weight gelatin aqueous solution was
Compounds A, B, C listed in Table 1 as samples (sample 1),
D: 0.01% by weight, 0.1% by weight based on solid gelatin
%, make samples (2 to 13) so that it is 1.0% by weight.
We conducted an experiment to compare their antiseptic properties. as a measure of corruption
The number of bacteria present in 1 ml of gelatin aqueous solution was determined using Nutoi.
ENT agar medium at 40℃ in incubator
The cells were cultured and the number of colonies was counted. [Table 1] [Table 2] [Table 2] [Table 3] [Table 4] [Table 4] The results obtained are shown in Table 3. However, bacterial test
The standard level is based on the criteria shown in Table 4. This is it
When compound A is used as a preservative, compound B,
Despite the amount being 1/100 compared to C and D, the bacteria were not generated.
It can be seen that the antiseptic effect is excellent. Also, mold
were put into samples 1 to 13 and the breeding status was investigated.
In samples 2 to 4, mold growth was remarkable compared to samples 1 and 5 to 13.
It was also confirmed that it has high anti-mold properties. Example 2 A roller was applied to the surface of a paper support laminated on both sides with polyethylene.
After the sodium discharge treatment, dodecylbenzenesulfonate sodium
A gelatin undercoat layer containing thorium is provided, and various photocoating layers are applied.
Multilayer color prints with the layer structure shown below by applying true constituent layers
Paper was made. The coating solution was prepared as follows. First layer coating solution prepared Yellow coupler (ExY) 19.1g and color image stability
agent (Cpd-1) 4.4g, color image stabilizer (Cpd-12)
) and 0.7 g of color image stabilizer (Cpd-7) with vinegar.
27.2cc of ethyl acid and solvent (Solv-3)
Add and dissolve 4.1 g each of Solv-7 and
Add a solution of 10% sodium dodecylbenzenesulfonate
Emulsified in 185cc of 10% gelatin aqueous solution containing 8cc
An emulsified dispersion A was prepared by dispersing the mixture. On the other hand, silver chlorobromide emulsion
A (cubic, large size milk with an average particle size of 0.88 μm)
3:7 mixture of agent A and 0.70 μm small size emulsion A
(silver molar ratio). The coefficient of variation of particle size distribution is 0, respectively.
．． 08 and 0.10, each size emulsion contains 0.3 mol of silver bromide
% localized on a part of the particle surface) was prepared. this milk
The agent contains blue-sensitive sensitizing dyes A and B shown below per mole of silver.
2.0 x 10-
4 mol, and for small size emulsion A, 2.
5×10 −4 mol was added. Also, the conversion of this emulsion
Scientific ripening was performed with the addition of sulfur sensitizers and gold sensitizers. Before
Mix and dissolve the emulsified dispersion A and this silver chlorobromide emulsion A.
A first layer coating solution was prepared to have the composition shown below.
. [0082] The coating liquid for the second to seventh layers is also applied as the first layer.
It was prepared in the same manner as the liquid. As a gelatin hardening agent for each layer
1-oxy-3,5-dichloro-s-triazine
Sodium salt was used. In addition, Cpd-10 and C
The total amount of PD-11 was 25.0 mg/m2 and 50 mg/m2, respectively.
．． It was added at a concentration of 0 mg/m2. Each photosensitive emulsion layer
The following spectral sensitizing dyes were used in the silver chlorobromide emulsion.
Ta. [Chemical 25] [Chemical 26] [Chemical 27] [Chemical 27] Also, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer,
For the emulsion layer, 1-(5-methylureidophenyl)-
5-mercaptotetrazole to 1 silver halide each
8.5 x 10-5 mol, 7.7 x 10-4 mol per mole
2.5 x 10-4 mol was added. Also, blue-sensitive emulsion
4-hydroxy-6-methyl for the green-sensitive emulsion layer and the green-sensitive emulsion layer.
-1,3,3a,7-tetrazaindene each with halo
1 x 10-4 mol and 2 x 10-4 mol per mol of silver germide
4 mol was added. Also, to prevent irritation
Add the following dyes (coating amounts are shown in parentheses) to the emulsion layer.
did. (Layer structure) The composition of each layer is shown below. numbers
represents the coating amount (g/m2). Silver halide emulsions are converted into silver.
Represents the calculated coating amount. Support polyethylene laminate paper [white pigment (TIO2) and polyethylene on the first layer side]
First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A described above
　　　　　　　　　　　　　　　　　　　　　　　　　
0.30 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.86 Yellow mosquito
Puller (ExY)
0.82 Color image
Stabilizer (Cpd-1)
0.19
Solvent (Solv-3)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.18 Solvent (Solv-7)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.18 Color image stabilizer (Cpd-7
)
0.06 second layer (color mixing prevention layer)
) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.99 Color mixing prevention agent (Cpd-5
)
0.08 Solvent
-1)
0.16 melt
Solv-4
0
．． Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.55μ
m large size emulsion B and 0.m large size emulsion B. 39μm small size
A 1:3 mixture (Ag molar ratio) with Emulsion B. particle size
The coefficient of variation of the distribution is 0.10 and 0.08, respectively.
, each size emulsion contains 0.8 mol% AgBr.
localized on a part of the child surface)
0.12 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.24 Magenta Taka
Puller (ExM)
0.23 Color image
Stabilizer (Cpd-2)
0.03
Color image stabilizer (Cpd-3)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.16 Color image stabilizer (Cpd-4)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Color image stabilizer (Cpd-9)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Solvent (Solv-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.40 Fourth layer (ultraviolet light
Absorbent layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.58 Ultraviolet absorber (UV-1
)
0.47 Color mixing prevention agent (C
pd-5)
0.05 Solvent (
Solv-5)
0.2
4. Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0.58μ
m large size emulsion C and 0.m large size emulsion C. 45μm small size
1:4 mixture (Ag molar ratio) with Emulsion C. particle size
The coefficient of variation of the distribution is 0.09 and 0.11, each size
Both emulsions contain 0.6 mol% of AgBr on the grain surface.
localized in some parts)
0.23 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.34
Uncoupler (ExC)
0.3
2 Color image stabilizer (Cpd-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03 Color image stabilizer (Cpd-4)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Color image stabilizer (Cpd-6)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.18 Color image stabilizer (Cpd-
7)
0.40 Color image stabilizer (
Cpd-8)
0.05 solvent
(Solv-6)
0.
14 Sixth layer (ultraviolet absorption layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.53 Ultraviolet absorber (UV-1
)
0.16 Color mixing prevention agent (C
pd-5)
0.02 Solvent (
Solv-5)
0.0
8 Seventh layer (protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.33 Polyvinyl alcohol
Acrylic modified copolymer (degree of modification 17%) 0.17
liquid paraffin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03 [0098] [0099] This sample was designated as 101, and the preservative Cpd-10
and Cpd-11, the present invention compound no.
10 to 12 (1:1:1 weight ratio) and sample 1
02 was created. However, the total amount of the mixture is 0.5mg/
m2 was added. The test obtained in this way
Examine the photographic characteristics of materials 102 and 102 using the following method.
Ta. First, a sensitometer (manufactured by Fuji Photo Film Co., Ltd.,
FWH type, light source color temperature 3200°K),
Provided gradation exposure for 3-color separation filter for cytometry
. The exposure at this time was 250 CMS with an exposure time of 0.1 seconds.
I made sure to get the right amount of exposure. After exposure, the sample is
The following processing steps and processing liquid composition are carried out using a super processing machine.
Use this solution and refill twice the capacity of the color development tank.
Continuous processing (running test) was carried out until the end. Treatment process temperature
Time Replenisher* Tank capacity Color
Image 35℃ 45 seconds
161ml 17 liter bleach fixing
30~35℃ 45 seconds
215ml 17 Rinse■
30-35℃ 20 seconds
−10 〃 Rinse■
30~35℃ 20 seconds -
10 〃 Rinse■ 3
0~35℃ 20 seconds 350ml
10 Drying 7
0 to 80℃ 60 seconds *The amount of replenishment depends on the exposure to light.
Per 1 m2 of material (3 tanks countercurrent method from rinse ■→■
And so. )0100 The composition of each treatment solution is as follows.
be. color developer
tank liquid
replenisher water
　　　　　　　　　　　　　　　　　　　　　　　　　
800ml 800ml
Tilenediamine-N,N,N,N-tetramethylene
Renphosphonic acid
1.5g 2.0g
potassium bromide
0.015g
- Triethanolamine
8.
0g 12.0g Sodium chloride
　　　　　　　　　　　　　　　　　　　　　　　　　
1.4g - carbonate
Rium
25g
25g N-ethyl-N-(β-methanesulfone
(amidoethyl)-3-methyl-4-amino
Aniline sulfate
5.0g
7.0g N,N-bis(carboxymethyl)
hydra gin
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0g 5.0g N,N-di(
Sulfoethyl) hydroxyl amine/1Na
　　　　　　　　　　　　　　　　　　　　　　　　　
4.0g 5.0g Fireflies
Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical)
1.0g 2.0g
add water
1000ml
1000ml pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
10.05 10.45 [
Bleach-fix solution (tank solution and replenisher are the same) Water
　　　　　　　　　　　　　　　　　　　　　　　　　
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml ammonium thiosulfate (700ml)
g/liter)
100ml sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
17g ethylenediamine tetra
Iron(III) acetate ammonium
55g ethylenediaminetetra vinegar
acid disodium
5g ammonium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
40g
add water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
6.0 Rinse liquid (ta)
(same solution for tank fluid and replenisher) Ion-exchanged water (3 for calcium and magnesium each)
ppm or less) Concentration measurement of the sample treated in this way
The relative sensitivities of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer were determined. one
On the other hand, the untreated sample was aged for 1 month at 35°C and 60%.
After that, the same processing as above was performed to measure the photographic performance, and the sensitivity was determined.
I looked into it. The above results are shown in Table 5. [Table 5] Example 3 The following was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown in Figure 1 was prepared. The coating liquid is
It was prepared as follows. First layer coating solution prepared Yellow coupler (ExY) 19.1g and color image stability
Agent (Cpd-1) 3.8g and (Cpd-7) 1.9
27.2 cc of ethyl acetate and solvent (Solv-3
) and (Solv-6) were added and dissolved, and this solution
10% sodium dodecylbenzenesulfonate 8c
emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c.
(Emulsified dispersion A). On the other hand, silver chlorobromide emulsion (sulfur sensitized)
Silver bromide 80.0 mol%, cubic; average grain size
Emulsion of 0.85 μm, coefficient of variation 0.08 and sulfur sensitized
Silver bromide 80.0 mol%, cubic; average grain size 0
．． 62 μm, emulsion with a coefficient of variation of 0.07 in a ratio of 1:4.
(Mixed at Ag molar ratio), the blue-sensitive sensitizing dye shown below
5.0 x 10-4 mol per mol of silver was added.
Manufactured. The above emulsified dispersion A and this silver chlorobromide emulsion are mixed.
The first layer is mixed and melted so that it has the composition shown in the layer structure described below.
A layer coating solution was prepared. The coating liquid for layers 2 to 7 is also
It was prepared in the same manner as the single layer coating solution. In addition, the gelatin of each layer
As a tin curing agent, 1-oxy-3,5-dichloro-s
- Triazine sodium salt was used. of each photosensitive emulsion layer.
The following spectral sensitizing dyes are used in silver chlorobromide emulsions.
Ta. [Chemical formula 37] [Chemical formula 38] [Chemical formula 38] Also, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer,
In the emulsion layer, 1-(5-methylureidophenyl)-5
- one mole of silver halide each
4.0 x 10-5 mol, 3.0 x 10-4 mol per mol
, 1.0 x 10-4 mol and 2-methyl-5-t-oc
Chirhydroquinone per mole of silver halide, respectively
8 x 10-3 mol, 2 x 10-3 mol, 1 x 10-3
Mol added. In addition, in the blue-sensitive emulsion layer and the green-sensitive emulsion layer,
4-hydroxy-6-methyl-1,3,3a,7-tet
1. each of razaindene per mole of silver halide.
2×10 −2 mol and 1.1×10 −2 mol were added. Ma
The red-sensitive emulsion layer contains the following mercaptoimidazole
compound and mercaptothiadiazole compound respectively.
2 x 10-4 mol, 4 x 10-4 mol per mol of silver
was added. [Chemical formula 39] [Chemical formula 40] In addition, all emulsions from the first layer to the seventh layer
Compound I shown in Table 6 is added to prevent rot and mold formation.
and II were added respectively to create samples 201 and 202.
Ta. [Table 6] (Layer composition) The composition of each layer is shown below. numbers
represents the coating amount (g/m2). Silver halide emulsions are converted into silver.
Represents the calculated coating amount. Support polyethylene laminate paper [white pigment (TIO2) 1 on the polyethylene on the first layer side
Contains 4.7% by weight and 0.3% by weight of blue dye (ulmarine blue)]
First layer (blue-sensitive emulsion layer) The aforementioned silver chlorobromide emulsion (AgBr: 80 mol%)
0.30 Zera
Chin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.15 Yellow coupler (ExY)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.68 Color image stabilizer (Cpd-1)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.14 Color image stabilizer (Cp
d-7)
0.07 Solvent (S
olv-3)
0.14
Solvent (Solv-6)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.14 Second layer (color mixing prevention layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.34 Color mixing inhibitor (Cpd-5
)
0.04 Solvent
-1)
0.10 melt
Solv-4
0
．． 10 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion (AgBr90 mol%, cubic, average
Particle size 0.47μm, coefficient of variation 0.12
Emulsion with 90 mol% AgBr, cubic, average grain size
1 with an emulsion of 0.36 μm and a coefficient of variation of 0.09.
: Mixed at a ratio of 1 (Ag molar ratio)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1
3 Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.48 Magenta coupler (E
xM)
0.27 Color image stabilizer (C
pd-2)
0.04 Color image stability
Fixing agent (Cpd-3)
0.20
Color image stabilizer (Cpd-4)
0
．． 01 Color image stabilizer (Cpd-8)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.03 Color image stabilizer (Cpd-9)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.08 Solvent (Solv-2)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.65 fourth layer (ultraviolet absorption
layer) gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.44 Ultraviolet absorber (UV-1
)
0.52 Color mixing prevention agent (C
pd-5)
0.06 Solvent (
Solv-5)
0.2
6. Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (AgBr70 mol%, cubic, average
Particle size 0.49μm, coefficient of variation 0.08
Emulsion with 70 mol% AgBr, cubic, average grain size
1 with an emulsion of 0.34 μm and a coefficient of variation of 0.10.
:2 ratio (Ag molar ratio))
　　　　　　　　　　　　　　　　　　　　　　　　　
0.2
0 gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.85 Cyan coupler (Ex
C)
0.28 Color image stabilizer (
Cpd-6)
0.56 color image
Stabilizer (Cpd-7)
0.27
Color image stabilizer (Cpd-8)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Color image stabilizer (Cpd-9)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.02 Solvent (Solv-6)
　　　　　　　　　　　　　　　　　　　　　　　　　
0.17 Sixth layer (ultraviolet absorption layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.39 Ultraviolet absorber (UV-1
)
0.16 Color mixing prevention agent (C
pd-5)
0.02 Solvent (
Solv-5)
0.0
8 Seventh layer (protective layer) Gelatin
　　　　　　　　　　　　　　　　　　　　　　　　　
1.26 Polyvinyl alcohol
Acrylic modified copolymer (modification degree 17%) 0.05
liquid paraffin
　　　　　　　　　　　　　　　　　　　　　　　　　
0.020114 (Cpd-1) Color image stability
(Same as Example 2) (Cpd-2) Color image stabilizer (Same as Cpd-9 in Example 2)
(Cpd-3) Color image stabilizer (same as in Example 2) (
Cpd-4) Color image stabilizer 1,4-dihydroxy-2
-hexadecyl-5-benzenesulfonic acid sodium salt
(Cpd-5) Color mixing inhibitor (same as Example 2) (
Cpd-6) Color image stabilizer (same as above) (Cpd-7) Color image stabilizer (same as in Example 2: However
(average molecular weight is 80,000) (Cpd-8) Color image stabilizer (same as Cpd-4 in Example 2)
(Cpd-9) Color image stabilizer (same as Cpd-2 in Example 2)
(UV-1) Ultraviolet absorber (same as in Example 2) (
Solv-1), (Solv-3), (Solv-4)
and (Solv-5) are respectively those of Example 2.
same. [Chemical Formula 41] [Chemical Formula 41] [Chemical Formula 43] [Chemical Formula 43] First, each sample was tested with a sensitometer (Fuji Photo Film).
Co., Ltd., FWH type, light source color temperature 3200°K)
The gradation of the three-color separation filter used for sensitometry
gave exposure. The exposure at this time was 2 with an exposure time of 0.1 seconds.
The exposure amount was set to 50 CMS. Exposure ends
The sample was prepared using the following processing steps and processing solution composition.
Processing was performed using an automatic processor. The composition of each treatment liquid is as follows. color developer water
　　　　　　　　　　　　　　　　　　　　　　　　　
800ml diethylenetri
amine pentaacetic acid
1.0g Nitrilo
triacetic acid
2
．． 0g benzyl alcohol
　　　　　　　　　　　　　　　　　　　　　　　　　
15ml diethylene glycol
　　　　　　　　　　　　　　　　　　　　　　　　　
10ml sulfite
sodium
2
．． 0g potassium bromide
　　　　　　　　　　　　　　　　　　　　　　　　　
1.0g potassium carbonate
　　　　　　　　　　　　　　　　　　　　　　　　　
30g
N-ethyl-N-(β-methanesulfonamide
(doethyl)-3-methyl-4-amino aniline
sulfate
4.5
g Hydroxylamine sulfate
　　　　　　　　　　　　　　　　　　　　　　　　　
3.0g Fluorescent whitening agent (WHITEX 4B,
Made by Yukagaku)
Add 1.0g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml pH
(25℃)
1
0.25 Bleach-fix water
　　　　　　　　　　　　　　　　　　　　　　　　　
400ml ammonium thiosulfate
Ni (700g/liter)
150ml sodium sulfite
　　　　　　　　　　　　　　　　　　　　　　　　　
18g Echi
Iron(III) diaminetetraacetate Ammonium
Mu
　　　　　　　　　　　　　　　　　　　　　　　　　
55g Ethylenediaminetetraacetic acid dibasic acid
thorium
Add 5g water
　　　　　　　　　　　　　　　　　　　　　　　　　
1000ml
pH (25℃)
　　　　　　　　　　　　　　　　　　　　　　　　　
6.70 For samples thus treated, the concentration
Perform measurements to find the relative sensitivity of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer.
I met. On the other hand, the untreated sample was kept at 30℃60% for 1 month.
After aging, the same treatment as above was applied and the photographic performance was measured.
, the sensitivity was investigated. The above results are shown in Table 7. [Table 7] [Effects of the Invention] The effects of the present invention on photographic materials
Mold and bacteria can be suppressed inexpensively and effectively in small quantities. Ma
In addition, by using the antibacterial and antibacterial agent of the present invention, photosensitive
It is possible to improve the aging properties of materials and also to reduce the amount of carbon obtained through processing.
Fading of color images can also be effectively suppressed. Furthermore, the coating surface is bad.
There is no problem with conversion.

Claims (1)

[Claims] Claim 1: In the hydrophilic colloid layer on the support, gentamicin, amikacin, tobramycin, dibekacin, arbekacin, micronomycin, isepamycin,
A silver halide photographic material comprising at least one aminoglycoside selected from sisomicin, netilmicin and astromycin.