JPH03191340A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the resistance of a yellow color image to fading due to light and fading in the dark by incorporating at least one kind of oil soluble coupler capable of forming a dyestuff and at least one kind of specified water insoluble polymer. CONSTITUTION:At least one kind of oil soluble coupler capable of forming a dyestuff coupling with the oxidized body of an arom. prim. amine developing agent and at least one kind of water insoluble polymer represented by formula I are incorporated into at least one of silver halide emulsion layers. In the formula I, each of R<1> and R<4> is H, 1-4C lower alkyl, etc., each of R<2> and R<3> is H, aliphatic hydrocarbon, etc., L is a divalent combining group, L' is an optionally substd. hydrocarbon chain forming a ring together with O and connecting to L and A is repeating units derived from an ethylenic unsatd. monomer. The resistance of an image, especially a yellow dyestuff image to fading due to light and fading due to moisture and heat is remarkably improved.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material.
Silver halide color with improved storage stability of color images
- Regarding photographic materials, especially the storage stability of yellow images
Regarding improved silver halide color photographic materials
. (Prior technology) Color development treatment after exposing silver halide photosensitive material to light
Oxidized aromatics to silver halide by
-grade amine developing agent and dye-forming coupler react to produce color
An image is formed. In this method, subtractive color reproduction is often used.
and complementary colors to reproduce blue, green, and red tones.
Yellow, magenta and cyan color images related to
is formed. The dye image formed in this way is exposed to light for long periods of time.
may be stored and exposed to light for a long time
Although the period is short, it is stored in the dark for a long time and depends on the storage conditions.
It is known that the color fades significantly. in general
, fading in the former case is called light fading, and fading in the latter case is called dark fading.
It is called color, and color photographic materials are used as records for a long period of time.
When storing for a long time, avoid the degree of light fading and dark fading.
Yellow, magenta and cyan with minimal intensity
Comprehensive three-color fading color 7SL lance of each dye image
It is desired to maintain the initial state. however
, yellow, magenta and cyan dye image light,
The degree of fading varies depending on each of these dye images,
After long-term storage, the three colors mentioned above will fade.
Otherwise, the quality of the dye image may deteriorate.
There was an inconvenience. The degree of light fading and dark fading depends on the coupler used and other factors.
Of course it varies depending on the cause, but in many cases it is about fading.
For example, a cyan dye image is followed by a yellow dye image and a magenta image.
Zenta dye images tend to fade in the order of color, especially cyan color.
The degree of fading of the raw image is greater than that of other dye images.
, and photofading, especially in light sources rich in ultraviolet light.
The cyan dye image is followed by the yellow dye image and the magenta image.
There is a tendency for photofading to occur in the order of zenta dye images. For this reason, over a long period of time, yellow magenta
Maintain good lance of the three color lines (color and cyan).
In order to maintain the durability of the image, it is necessary to minimize the light and fading of the cyan dye image.
Therefore, photobleaching and dark-bleaching
Various attempts have been made for improvement. this
Such attempts can be broadly divided into two areas, one being
, a new coupler that can form dye images with less fading resistance
The other is to prevent fading.
The goal is to develop new additives. Among these, a new additive that can prevent fading is
Patent No. 4,203.716 etc. contain oil-soluble couplers, etc.
of the hydrophobic substance in a water-miscible organic solvent, and the solution is
The hydrophobic substance is mixed with double polymer latex.
Discloses a method for loading polymers
has been done. However, such loader pull poly
In the method using Marlatex, it is highly immiscible with water.
Especially when compared to using boiling point coupler solvents, cyanide
There is a problem that the light fastness of the image is poor. Further coupler
In order to fully impregnate and obtain sufficient maximum color density,
The disadvantage is that a large amount of polymer must be used.
be. Japanese Patent Publication No. 48-30494 describes a high-boiling coupler solution.
Instead of using organic solvent-soluble, special
A homopolymer of hydrophobic monomers with a specific structure or a specific
Couplers using copolymers with hydrophilic monomers of specific structure
-Dispersion (the particle size of the dispersed particles is approximately 0.5μ to 5μ)
photosensitive materials containing
There is a statement that the color, storage stability before processing, etc. are improved.
. However, instead of the coupler solvent,
The homopolymer of the hydrophobic monomer described in 8-30494
When used, the color development is low (especially this tendency is
Benzyl alcohol added to the developer in the example
This is noticeable in developers that do not substantially contain color accelerators such as
) and poor stability of the emulsion. one
On the other hand, copolymers with hydrophilic monomers such as acrylic acid are
However, the stability and color development of the emulsified dispersion were slightly improved.
However, it is insufficient, and copolymerization is required to improve color development.
Increasing the proportion of hydrophilic monomers in the coalescence increases discoloration (especially
There was a problem that thermal fading (at high temperatures) worsened. Ma
In addition, both polymers have a weak ability to prevent coupler crystallization.
Therefore, coupler crystals form during storage of the emulsified dispersion.
There were other disadvantages. Furthermore, in the case of Special Publication No. 4B-30494, especially the
When applied to couplers, it can be dispersed in conventional high boiling point solvents.
(so-called oil dispersion), photobleaching is significantly more pronounced than when using oil dispersion.
There was a big problem that it got worse (1.5 to 3 times). Furthermore, in the case of Special Publication No. 4B-30494,
The hue of the developed cyan dye is long-wavelength immediately after processing.
However, it easily shifts to shorter waves, especially when stored at high temperatures.
There is a problem that the hue changes over time.
It was. (Question 8 to be solved by the invention) For such problems, International Patent Publication WO38100
No. 723 contains at least an acid group in the main chain or side chain.
Water-insoluble, consisting of no repeating units (35 mol% or more)
And organic solvent soluble single or copolymer coupler
and coupler solvent to form a mixed solution and emulsify and disperse it.
This improves light and dark fading, especially for cyan images.
is disclosed. When the polymer described in the above patent is applied to yellow dye,
Although it is similarly effective in improving photobleaching,
However, it has been shown to have little effect. On the other hand, traditionally, the dark fading of couplers has been caused by cyclic ethers (especially
It is known that this can be improved by using a combination of epoxy (epoxy) compounds.
It is being Special Publication No. 58-45017, Japanese Patent Publication No. 62-
No. 75448, No. 62-75449, No. 62-754
No. 47, No. 62-■29853, No. 62-17235
No. 3, No. 62-772357, No. 62-196657
No. 64-21447, No. 64-50648, No. 64-21447, No. 64-50648, No.
No. 64-50049 discloses that the above compound is yellow mazene.
Improves dark fading of single or multiple color images of tan, cyan.
It is disclosed that it can be done. However, the combined use of such cyclic ether compounds
is effective in improving the dark fading of yellow pigments, but
There was little effect on improving photobleaching of rho dyes. In addition, the above-mentioned repeats that do not have an acid group in the main chain or side chain
Cyclic etherification to polymers with units (more than 35%)
Improvement of both photobleaching and thermal fading by using compounds together.
Although good attempts have shown some effectiveness, they have not reached a sufficient level.
It provides even better light fastness and heat fastness.
It was strongly desired. Therefore, the object of the present invention is firstly to
Both fading and dark fading have been improved, thereby making it possible to withstand high temperatures and
Dye images that exhibit excellent image storage stability even under humid conditions
To provide a silver halide photographic material that can form
be. The second object of the present invention is to reduce the degree of fading! if possible
Therefore, the overall color of yellow, magenta and cyan
It has a good fading color balance and can be stored for a long time.
A silver halide photographic material with excellent dye image quality even when
The aim is to provide fees. A third object of the present invention is to avoid adversely affecting photographic characteristics.
halo that can form dye images with improved image archiving properties without
An object of the present invention is to provide a silver germide photographic material. (Means for Solving the Problem) The above object of the present invention is to provide at least one layer of halo on a support.
Silver halide color photographic material containing a silver emulsion layer
in at least one layer of the silver halide emulsion layer.
, coupling with oxidized product of aromatic primary amine developing agent
Few oil-soluble couplers can form dyes.
Both are 1 type, and water-insoluble represented by the following formula (r)
A polymer characterized by containing at least one kind of polymer.
This was achieved using silver halide color photographic materials. General formula (1) % formula % In the formula, R1 and R4 may be the same or different, and hydrogen
Atom, lower alkyl group having 1 to 4 carbon atoms, or halogen atom
Represents a child. R2 and R3 may be the same or different, and are hydrogen atoms,
Represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, provided that
However, the total number of carbon atoms in R1 and R3 is 2 or more, and R
Even if 2 and R3 are linked to each other to form a nitrogen-containing heterocycle,
good. L represents a divalent linking group. L' forms a ring together with an oxygen atom and is connected to L.
represents a substituted or unsubstituted hydrocarbon chain. A is derived from ethylenically unsaturated monomers other than those listed above.
Represents a repeating unit. x, y, z represent the weight percentage of each component, and X is 20.
99, y represents 1 to 80.2 represents O to 50. Below, the copolymer represented by general formula (1) of the present invention will be explained.
This will be explained in detail. In the formula, R1 and R4 may be the same or different, and hydrogen
atoms, lower alkyl groups having 1 to 4 carbon atoms (e.g. methyl,
ethyl, n-propyl, n-butyl), halogen atom (
For example, chlorine atom, bromine atom), of which hydrogen atom
Particularly preferred are the child and the methyl group. R2 and R3 may be the same or different, hydrogen atom, aliphatic
represents a group hydrocarbon group or an aromatic hydrocarbon group, and these
The hydrocarbon group may be substituted. Aliphatic hydrocarbon group or aromatic group represented by R2 and R3
Hydrocarbon groups include, for example, aryl groups (e.g. phenyl
group), alkyl group, hydroxy group, alkyl group having 1 to 6 carbon atoms
Koxy group (e.g. methoxy group), halogen atom (and
(for example, a chlorine atom), a cyan group, etc. The total number of carbon atoms in the substituents represented by Rz and R3 is the coupler
, 2 to 20, especially from the point of view of affinity with hydrophobic couplers.
is preferred. A nitrogen-containing heterocycle formed by connecting R2 and R3 to each other
is preferably a 5- to 6-membered ring containing multiple nitrogen atoms as heteroatoms.
May contain oxygen atoms in addition to elementary atoms and nitrogen atoms,
For example, rings such as piperidine, morpholine, pyrrolidine, etc.
can be mentioned. Polymer bag represented by general formula (1) used in the present invention
Specific examples of monomers include N-ethyl acrylamide,
N-(n-propyl)acrylamide, N-isopropyl
Acrylamide, N-(n-butyl)acrylamide,
N-(tert-butyl)acrylamide, N-(n-
octyl)acrylamide, N-(isoamyl)acrylic
Ruamide, N(Lert-octyl)acrylamide,
N-lauryl acrylamide, N-cyclohexyl acrylamide
Rylamide, N-benzylacrylamide, N-phenylene
lyacrylamide, N-(1,1-dimethyl-3-hydro)
(roxybutylacrylamide), N,N-diethyl acrylamide
Rylamide, NN-dioctyl acrylamide, N-(
1,1-dimethyl-3-oxobutyl)acrylamide
, N-acryloylmorpholine, N-methyl-N'-a
Kryloylpiperazine, N-ethyl N'-acryloyl
Lupiperazine, N-acryloylpiperidine, N-(β
-morpholinoethyl)acrylamide, N-(tert
-butyl) methacrylamide, N(tert-o)
(cutyl) methacrylamide, N-benzyl methacrylamide
de, N-cyclohexylmethacrylamide, N-phenylene
N,N-diethylmethacrylamide, N,N-diethylmethacrylamide
Do, N. N-dipropyl methacrylamide, N-methyl N-phenylene
Nylmethacrylamide, N-methacryloyl-N'-methacrylamide
Tilbiperazine, N-methacryloylpiperidine, 4-
Methacryloyl-26 dimethylmorpholine, N-methac
Liloyl-N'-ethylpiperazine and the like. L is preferably divalent having from 1 to about 20 carbon atoms.
represents a linking group, specifically, −4x”h, (J'
-X")-,(J"-x')-1(J'-X')-, (
It is represented by J'3-1. x', x'', x', x' are the same
-coo--oco-5 CON- (R' is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms)
, or a substituted alkyl group preferably having 1 to 6 carbon atoms.
represent. L -CO--so, -R5R5R5 5otN--N-Co N 5ot-R% (R5 has the same meaning as above), -N-R' - (R' is above)
R' is an alkyl group preferably having 1 to about 4 carbon atoms;
Ren group), -N-R" -N- (R'R6 is the same as above
, R7 is a hydrogen atom, an alkyl group (preferably 1 carbon number)
~6), substituted alkyl group (preferably 1 to 6 carbon atoms)
, RS R'1 -O--3---N-Co-N R5R'+ R5R5 N-5o, -N--NCO, --0CON (R3,
R? is synonymous with the above). JI JI Jff, J4 are the same but different
alkylene group, substituted alkylene group, aryle group, alkylene group, substituted alkylene group,
group, substituted arylene group, aralkylene group, substituted aral
Represents a kylene group. p, q, r, s, and t are O or l
However, they will never be 0 at the same time. As an example of a substituent that may be further substituted in (7) above,
These include halogen atoms, nitro groups, cyano groups, and alkyl groups.
, substituted alkyl group, alkoxy group, substituted alkoxy group,
-NHCOR" (R- is an alkyl group,
Substituted alkyl group, phenyl group, substituted phenyl group, aralkyl group
(represents a substituted aralkyl group), -NH5O,R@
(R1 has the same meaning as above), -5oR"(R" is above
(same meaning as above), -SO□R” (R” has the same meaning as above),
-COR” group (R”, Rlo may be the same or different)
hydrogen atom, alkyl group, substituted alkyl group.
phenyl group, substituted phenyl group, aralkyl group, 9 (R9 and Rlo are the same as above), amino group (alkyl group)
(may be substituted with), hydroxyl group or hydrolyzed to form hydroxyl
Examples include groups forming a group. Of the linking groups represented by, phenylene is particularly preferred.
groups (for example, 0-phenylene group, p-phenylene group, m-
phenylene group), arylene has 1 to about 12 substituents.
The alkylene group that may be represented by -CO□-Rlg (however,
Rlg is an optionally substituted alkylene group, phenylene
or arylene alkylene group), CO□-R~ (R13 is synonymous with Rlg), -CO□-
R"-OC-R'COCO□-R"(R" is synonymous with 1 R"), -CONH-R"- (However, LR"4t above
), -CON-R12 (however, R1
, Rlg represents the same as above, ), C0NH-R
Eye-COO-R”-(R”, R eye represents the same as above.
), etc. L' forms a ring together with the oxygen atom and is connected to Katsushi.
represents a substituted or unsubstituted hydrocarbon chain. The ring formed by 13' and oxygen atom is 3 to 8
A membered ring is preferable, and the oxygen-containing ring formed is
Substituted by a substituent selected from the same group as mentioned in
It may be Of the rings formed by L' and oxygen atoms, especially
Preferred are epoxy rings, tetrahydrofuran rings, and tetrahydrofuran rings.
It is a lahydropyran ring. 4 Below, -(expressed as cnzch h in formula (1)
Examples of monomers that provide repeating units are given, but are not limited to
It is not something that will be done. CH. As a copolymerizable ethylenically unsaturated monomer represented by A,
For example, acrylic esters, methacrylic acid
Esters, allyl compounds, vinyl ethers, vinyl
Esters, vinyl heterocyclic compounds, styrenes, male
acid esters, fumaric acid esters, itaconic acid esters
esters, croton esters, olefins, etc.
Ru. Specific examples thereof are methyl acrylate, ethyl acrylate,
Acrylate, n-propyl acrylate, isopropyl
Acrylate, n-butyl acrylate, octyl acrylate
rylate, 2-chloroethyl acrylate, 2-cyano
Ethyl acrylate, benzyl acrylate, cyclohexyl acrylate
Xyl acrylate, phenyl acrylate, methyl acrylate
Tacrylate, ethyl methacrylate, n-propyl methacrylate
tacrylate, isopropyl methacrylate, n-butylene
lumetafurylate, octyl methacrylate, to cyclo
xyl methacrylate, benzyl methacrylate, 3-
Sulfopropyl methacrylate, allyl acetate, capryl
Allyl acid, allyl caproate, allyl laurate, rest
Allyl fragrant, allyl butyl ether, allyl phenyl ether
ether, methyl vinyl ether, butyl vinyl ether
, octyl vinyl ether, methoxyethyl vinyl ether
ter, 2-chloroethyl vinyl ether, 2-hydroxy
ethyl vinyl ether, (2-dimethylaminoethyl
) vinyl ether, vinyl trilyl ether, vinyl trilyl ether
ether, vinyl chlorphenyl ether, vinyl ether
Cetate, vinyl propionate, vinyl butyrate,
Vinyl isobutyrate, vinyl caproate, vinyl
loracetate, vinylmethoxyacetate, vinylph
phenyl acetate, vinyl acetoacetate, vinyl la
Cutate, vinyl benzoate, vinyl naphthoate, styrene
P-acetoxystyrene, P-methylstyrene, p
-methyl vinylbenzoate, crotonamide, crotonic acid
Butyl, glycerin monocrotonate, methylvinyl chloride
ton, phenyl vinyl ketone, ethylene, propylene,
1-butene, dicyclopentadiene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-pentene, etc.
Methyl conate, ethyl itaconate, diethyl itaconate
, etc., methyl sorbate, dibutyl maleate, male
Halogens such as octyl inate, diptyl fumarate, etc.
olefins, such as vinyl chloride, vinylide chloride
unsaturated nitriles, such as isoprene, isoprene, etc.
Krylonitrile, methacrylonitrile, etc. are included and are necessary.
Two or more types can also be used depending on the situation. Among these monomers, polymer solubility, lipophilicity, and phobicity
In view of the affinity of water-based couplers, acrylic acid ester
esters or methacrylic acid esters, vinyl esters
Particularly preferred are the following. x, y, z represent the weight percentage of each component, and χ is 20.
99, preferably 3o to 95, y is 1 to 99, preferably 3o to 95, y is 1 to 99
80. Preferably 5 to 70. z is O to 50, good
Preferably, it is in the range of 0 to 30. The polymers of the present invention can be produced by various polymerization methods, e.g.
Made by liquid polymerization, precipitation polymerization, suspension polymerization, and bulk polymerization.
Ru. In addition, the method for initiating polymerization is to use a radical initiator.
method, method of irradiation with light or radiation, method of thermal polymerization, etc.
Ru. These polymerization methods and polymerization initiation methods are described, for example, by Sadada Tsuruta.
2. Revised edition of “Polymer synthesis reactions” (Nikkan Kogyo Shimbun series, 19
71). Among the above polymerization methods, especially those using radical initiators,
A liquid polymerization method or a suspension polymerization method is preferred. Solvents used in the solution polymerization method include, for example, ethyl acetate,
Methanol, ethanol, 1-propertool, 2-propertool
Patur, acetone, dioxane, NN-dimethylform
Muamide, N,N-dimethylacetamide, toluene,
Various organic solvents such as n-hexane, acetonitrile, etc.
It can be used alone or in a mixture of two or more, or in combination with water.
A mixed solvent may also be used. The polymerization temperature depends on the molecular weight of the polymer produced, the type of initiator, etc.
It is necessary to set it in relation to
Although it is possible to exceed ℃, it is usually in the range of 3℃ to 100℃.
Polymerize. As the radical initiator used for polymerization, for example, 2
．． 2'-azobisisobutyronitrile, 2.2'-azo
Biz(2,4-dimethylvaleronitrile), 2,2'-
Azobis(2-amidinopropane) dihydrochloride
, 4,4'-azobis(4-cyano-pentanoinqua)
Azo initiators such as
Peroxide initiators such as oxides are preferred. The amount of initiator is adjusted depending on the molecular weight of the polymer, but
The range is preferably 0.0 l-10 mol% based on the nomer.
, especially 0.01 to 1. A range of 0 mol% is particularly preferred.
. Preferred examples of the polymer represented by the general formula (r) of the present invention are
Although shown below, the present invention is not limited thereto.
stomach. (All composition ratios represent weight percentage ratios). -(CH,CH)-8 (CH2C)-. (P 6. 7) (P-12) x / y = 70 / 30 (P-13) A C1 (ICH) -. Hs+cozc)−. (P-14) x / y / z = 60 / 20 / 20 (
P8) CH. CI(3x/y/z-60/20/20(P-
9) CH, CH)-, CH2Ctihy x/y/=90/I 0 (P 10. 11) (-1 x/y=50150 (P 15) CH. x/3' = 80/20 (P 16) !/7=65/35 (P-17) x / y / z = 65 / 15 / 20 (
P-18) (P-21) L 5 (P-19) (P-20) X#/Z = 60/30/10 Hs x/y/z = 60/10/30X
/)'/Z-45/45/10 Polymer coupler (
The usage ratio (weight ratio) to (in the same layer) is 1:20.
The range of 201 is preferable, more preferably 1:lO or
and l:1. In addition, the number average molecular weight of this polymer is preferably about 1 million or less.
More preferably, it is about 200,000 or less. The coupler used in the present invention will be explained below. Particularly preferred with the polymer represented by the general formula (1) of the present invention
The yellow coupler, which is a good combination, is oil protector.
A typical example is the acylacetamide type coupler.
Can be mentioned. A specific example is U.S. Patent No. 2,407,2
No. 10, No. 2.875.057 and No. 3,26
5,506 etc. The present invention includes two patents.
It is preferred to use yellow couplers, as described in U.S. Pat.
No. 408.194, No. 3,447,928, No. 3
．． No. 933,501 and No. 4,022゜620, etc.
There is an oxygen atom dissociation type yellow coupler described in
Japanese Patent Publication No. 5B-10739, U.S. Patent No. 4,401
, No. 752, No. 4,326.024, RD1805
3 (April 1974), British Patent No. 1,425,02
No. 0, West German Application No. 2.219,917, No. 2,
No. 261,361, No. 2.329,587 and No.
Nitrogen atom detachment described in No. 2゜433.812 etc.
A typical example is the type yellow coupler. α-pivaloylacetanilide couplers are color-forming dyes.
It has excellent fastness, especially light fastness, while α-benzoic
Ruacetanilide couplers provide high color density
. More preferred as a yellow coupler used in the present invention
The yellow color represented by the following formula (II) is
It's a puller. General formula (II) CH. In the direct formula CH, R1 is substituted or unsubstituted N-phenylcarba.
represents a moyl group, and Zll represents an aromatic primary amine color developer.
Represents a group that can be separated in reaction with the oxidized form of the image agent
. N-phenylcarbamoy of R11 in general formula (■)
Substituents on the phenyl group include aliphatic groups (
For example, methyl, allyl, cyclopentyl), heterocyclic groups
(e.g. 2-pyridyl, 2-imidazolyl, 2-furyl)
, 6-quinolyl), aliphatic oxy groups (e.g. methoxy
, 2-methoxyethoxy, 2-propenyloxy), aromatic
aromatic oxy groups (e.g. 2,4-di-tert-amylph)
phenoxy, 4-cyanophenoxy, 2-chlorophenoxy
), acyl groups (e.g. acetyl, benzoyl),
Ster groups (e.g., butoxycarbonyl, hexadecyl
Oxycarbonyl, phenoxycarbonyl, dodecyl
Oxy, carbonylmethoxycarbonyl, acetoxy, benzene
nzoyloxy, tetradecyloxysulfonyl, hexyloxy
(e.g., sadecanesulfonyloxy), amido groups (e.g.,
Acetylamino, dodecane sulfonamide, α-(2゜
4-di-tert-pentylphenoxy)butanamide
, r-(2,4-di-tert-pentylphenoxy)
Butanamide, N-tetradecylcarbamoyl, N,N
-Dihexyl Rubamoyl, N-Butanesulfamoyl
, N-methyl-N-tetradecanesulfamoyl), i
Mido group (e.g. succinimide, N-hydantoynyl
, 3-hexadecenylsuccinimide), ureido group (
For example, phenylureido, N,N-dimethylureide
, N-(3-(2,4-di-tert-pentylphenol)
xy)propyl)ureido), aliphatic or aromatic
sulfonyl groups (e.g. methanesulfonyl, phenylsulfonyl)
Honyl, dodecanesulfonyl, 2-butoxy-5-te
rt-octylbenzenesulfonyl), aliphatic or
Aromatic thio groups (e.g., phenylthio, ethylthio,
xadecylthio, 4-(2,4-di-tert-pheno
(oxyacetamido)benzylthio), hydroxy group,
Sulfonic acid groups, halogen atoms (e.g. fluorine, chlorine, odor
element), and when there are two or more substituents, the same but different
You may - In formula (n), Zll represents a coupling-off group
For example, a halogen atom (e.g.
fluorine, chlorine, bromine), alkoxy groups (e.g. dodecyl
Oxy, dodecyloxycarbonylmethoxy, methoxy
Carbamoylmethoxy, carboxypropyloxy, methoxy
tansulfonyloxy), aryloxy groups (e.g.
4-methylphenoxy, 4-terL-butylphenoxy
cy, 4-methanesulfonylphenoxy, 4-(4-ben
Zyloxyphenylsulfonyl) phenoxy, 4- (
4-hydroxyphenylsulfonyl)phenoxy, 4-
methoxycarbonylphenoxy), acyloxy group (e.g.
For example, acetoxy, tetrazokayloxy, benzoy
(e.g., methanesulfoxy), sulfonyloxy (e.g., methanesulfoxy),
Honyloxy, toluenesulfonyloxy), amide group
(e.g. dichloroacetylamino, methanesulfonyl
amino), alkoxycarbonyloxy groups (e.g.
Toxycarbonyloxy, benzyloxycarbonyloxy
(xy), iri-ruoxycarponyloxy group (e.g.
phenoxycarbonyloxy), aliphatic or aromatic
Thio groups (e.g. phenylthio, dodecylthio, benzylthio)
ruthio, 2-butoxy-5-tert-octylpheny
ruthio, 2゜5-di-octyloxyphenylthio, 2
-(2-ethoxyethoxy)-5-tert-octyl
phenylthio, tetrazolylthio), imide groups (e.g.
, succinimide, hydantoinyl, 2゜4-dioxo
Oxazolidin-3-yl, 3-benzyl-4-ethoxy
cyhydantoin-1-yl, 3-benzylhydantoin
-1-yl, l-benzyl-2-phenyl-3,5-di
Oxo-1,24-triacylidin-4-yl, 3-benzene
N-dyl-4-ethoxyhydantoin-1-yl, N-dimethyl
Bare rings (e.g. 1-pyrazolyl group, l-benzotriazo
Lyle, 5-chloro-1,2,4-triazol-1-y
), aromatic azo groups (e.g. phenylazo), etc.
Yes, these leaving groups contain photographically useful groups.
Good too. Photographically useful groups include, for example, those that release development inhibitors.
groups, groups that release development accelerators, aromatic azo groups (e.g.
phenylazo). R11 or Zll of general formula (I[) is a dimer or its
It is also possible to form a multimer of more than one. Particularly preferred as the leaving group represented by Z are
Aryloxy group, imide group or other N-heterocycle
It is. Among these, imide groups and N-heterocycles are more preferred.
especially - leaving groups represented by formulas (bi) to (■')
is preferred. (+') (17') (IIF
') In the formula, R1, I'? yz, Rat, R, each hydrogen
N child, halogen atom, carboxylic acid ester group, amino group
, alkyl group, alkylthio group, alkoxy group, alkyl
Rusulfonyl group, alkylsulfinyl group, carboxylic acid
group, sulfonic acid group, unsubstituted or substituted phenyl group
or a heterocycle, and these groups may be the same or different.
good. Ro is carbamoy #M (Nx it: N-fu
phenylcarbamoyl). The nonmetallic atoms required to form a membered ring or a 6-membered ring
represent More preferable specific examples of the general formula (■') are the following formulas (V') ~
It is represented by (■′). R1at et W. In the formula, R+e+ and Log are hydrogen atoms and alkyl groups, respectively.
, aryl group, alkoxy group, aryloxy group or
Represents a hydroxy group, R1゜1, R1゜4 and R1
゜ and each hydrogen atom represent an alkyl group, an aryl group, an aral group,
Represents a kill group or an acyl group, W, , is oxygen or
Represents a sulfur atom. - More preferred yellow couplers of formula (II)
is represented by the following formula (n-A) or (If-B)
Ru. General formula (II-A) group, ester group, amide group, imide group, or halogen
Atoms are preferred. A specific example of the 5-membered ring formed by Xl is the general formula (V
' n, (■′) and (■′), but especially −
Formulas (V') and (■') are preferred, - formula (V')
), particularly preferred is RIIl and Rlo.
Which represents a substituent where one is not a hydrogen atom?
Ru. General formula (ff-B) Iz In the formula, X1□ is a group of nonmetallic atoms necessary to form a 5-membered ring
represents. RI! is the substituted N-phenylcar defined above
Represents a substituent of a bamoyl group, among which an aliphatic group,
In the aliphatic oxy group, aromatic oxy formula, R13 is halogen
atom, alkoxy group, trifluoromethyl group or ali
R represents a hydrogen atom, a halogen atom or
represents an alkoxy group, A is -NHCOR,,, -N)
(So, -R,S, -5o, NHR, , -COOR,
,,So! Represents NRIS. However, RIS and RI6
It represents an alkyl group, an aryl group or an acyl group, respectively. R
o has the same meaning as ni (■'). Next, specific examples of the compound represented by general formula (II) will be shown.
However, the compounds of the present invention are not limited thereto. (Y-1) (Y-2) (Y-3) SO□ (Y-6) OOH (Y-12) (Y-13) (Y-8) (Y 9) 0OCHx C00+1 11 (Y-10) (Y 11) (Y-15) (Y-16) (Y 17) (Y 19) (Y-18) (Y-20) (Y 21) Next, cyan couplers preferably used in the present invention
, the magenta coupler has the following formula (C-I), ((,
-II), (M-1), (M-11)
be. General formula (C-1> I General formula (C-II) 0■Ytomi General formula (M-1) General formula (M-11) In general formulas (C-r) and (C-11), R1,
Rz and R4 are substituted or unsubstituted aliphatic, aromatic
or represents a heterocyclic group, Rs, Rs and R4 are hydrogen atoms
child, halogen atom, aliphatic group, aromatic group or acyl atom
represents a mino group, and R1 together with R2 is a nitrogen-containing 5-membered ring or
may represent a group of nonmetallic atoms forming a 6-membered ring. Yl
,Y! is a coupling with a hydrogen atom or an oxidized form of a developing agent.
Represents a group that can be separated during an oxidation reaction, n represents O or l
. R2 in general formula (C-U) is an aliphatic group
For example, methyl group, ethyl group, propylene group
group, butyl group, pentadecyl group, tert-butyl group
, cyclohexyl group, cyclohexylmethyl group, phenyl
ruthiomethyl group, dodecyloxyphenylthiomethyl group
, butanamidomethyl group, methoxymethyl group, etc.
can be done. - the system represented by the formula (C-N or (C-1f))
Preferred examples of uncouplers are as follows. -a formula (preferred R in C-H is an aryl group, a complex
It is a bare ring group, such as halogen atom, alkyl group, alkoxy
group, aryloxy group, acylamino group, acyl group, carbon
rubamoyl group, sulfonamide group, sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group.
Delicious. In general formula (C-1), R1 and R2 do not form a ring
, R2 is preferably substituted or unsubstituted alkyl
group, aryl group, particularly preferably T1. tA ant
R is preferably an alkyl group substituted with
It is a hydrogen atom. - In formula (C-11), R4 is preferably substituted or
is an unsubstituted alkyl group or aryl group, and is particularly preferred.
or a substituted aryloxy-substituted alkyl group. In the general formula (C-ff), R2 preferably has 2 to 2 carbon atoms.
Having an alkyl group of I5 and a substituent having 1 or more carbon atoms
It is a methyl group, and substituents include an arylthio group and an alkyl group.
Kylthio group, acylamino group, aryloxy group, alkyl
Kyloxy group is preferred. - In formula (C-11), R1 is an atom having 2 to I5 carbon atoms.
More preferably, it is an alkyl group, and has 2 to 4 carbon atoms.
Particularly preferred is an alkyl group. In general formula (C-IF), preferred R6 is a hydrogen atom,
Halogen atoms, especially chlorine and fluorine atoms
preferable. - In formulas (C-I) and (C-n)
Preferred Yl and Y2 are hydrogen atoms and halogen atoms, respectively.
atom, alkoxy group, aryloxy group, acyloxy group
They are a cy group and a sulfonamide group. In general formula (M-1), R1 and R9 are aryl
represents a group, and R6 is a hydrogen atom, an aliphatic or aromatic atom.
Represents a syl group, aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group. R6 and R1
Permissible substitutions on aryl groups (preferably phenyl groups)
The groups are the same as the permissible substituents for the substituent R,
and when there are two or more substituents, they may be the same or different.
Re is preferably a hydrogen atom, an aliphatic acyl
group or sulfonyl group, particularly preferably a hydrogen atom
It is. Preferred Y is sulfur, oxygen or nitrogen atom
For example, the US patent
No. 4,351.897 and International Publication WO3810479
The sulfur atom detachment type as described in No. 5 is particularly preferred.
Delicious. - In formula (M-11), RI8 is a hydrogen atom or
Represents a substituent. Y4 represents a hydrogen atom or a substituent, and
A halogen atom or an arylthio group is preferable. Za, Z
b and Zc are methine, substituted methine, =N- or -NH
- represents one of Za-Zb bond and Zb-Zc bond
is a double bond and the other is a single bond. Zb-Zc connection
If the bond is a carbon-carbon double bond, it is part of an aromatic ring.
Including cases where If R1゜ or Y4 is a dimer or more,
When forming a polymer, Za, Zb or Zc may also be placed.
When it is a substituted methine, it is a dimer or more of the substituted methine.
Including the case where a polymer is formed. -11G Pyrazoloazole system represented by formula (MU)
Among the couplers, the yellow side absorption of the coloring dye is low.
No. 4,500.630 for light fastness and light fastness.
The imidazo(1,2-b)pyrazoles described are preferably
, pyrazolo (
1,5,-b)(1°2.4)) riazoles are particularly preferred.
Yes. In addition, as described in Japanese Patent Application Laid-Open No. 61-65245
The branched alkyl group is 2.3 or
Directly connected to the 6th place is the pyrazolotriazole coupler, Tokukai Sho
No. 61-65246.
Pyrazoloazole coupler containing an amide group, JP-A-Sho
Alkoxif as described in No. 61-147254
Pyrazoloazole with enyl sulfonamide ballast group
Coupler, European Patent (Publication) No. 226.849 and the like
Alkoki in the 6th position as described in No. 294,785
Pyrazolotriazole caps with cy or aryloxy groups
The use of lar is preferred. - Formulas (C-1), (C-11), (M-1), (M-
Specific examples of couplers represented by 11) are listed below.
. (C-1) (C-2) (C-3) (C-4) (C-9) (C-10) Shi! (C-7) (C-12) (C-14) (C-15) (C-20) (C-21) (C-22) Ushiko (C-17) (C-18) ( C-19) (M-1) (M-2) (M-3) I t I 2 (M-6) (M-7) (M-8) I C) 13 CH. death! Next, the high boiling point cap that is immiscible with water used in the present invention is
The color solvent will be explained in detail. The high-boiling coupler solvents that can be used in the present invention include the following-
Compounds represented by formula (III) to general formula (■) are preferred.
However, in other cases, the melting point is less than i o o ”c, the boiling point is
A compound that is immiscible with water and has a temperature of 140°C or higher, and is a coupler.
- Any good solvent can be used. High boiling coupler solvent
The melting point is preferably below 80"C.High boiling point coupler
The boiling point of the solvent is preferably 160°C or higher, and more
Preferably it is 170°C or higher. General formula (III) I ■ enemy t-o-p=. One general formula (rV) h, -coow. General formula (V) General formula (Vl) General formula (■) 11, -o-wt General formula (■) HO-11゜In the formula, Wl, Wz and W are each substituted or
Unsubstituted alkyl group, cycloalkyl group, alkenyl
group, aryl group or heterocyclic group, W4 is W
l, OWl, or S-W. , n is an integer from 1 to 5, and n is 2 or more
When , W4 can be the same or different, and - number
In formula (■), Wl and Wa are connected to each other to form a condensed ring.
may be formed. W is a substituted or unsubstituted alkyl group or ali
represents a metal group, and the total number of carbon atoms constituting W is 12 or more.
be. If the melting point of the coupler solvent exceeds approximately 100°C,
, crystallization of the coupler tends to occur, and color development is further improved.
They also tend to be less effective. Additionally, the boiling point of the coupler solvent is below approximately 140°C.
In some cases, the photographic emulsion evaporates easily when applied and dried.
In order to prevent this, the coupler and the present invention are incorporated as oil droplets in the photographic emulsion layer.
It is difficult to coexist with the polymer, and as a result, the effects of the present invention are
is difficult to obtain. Also, if the coupler solvent used is miscible with water,
Obtained when applying a true emulsion layer, or after applying and drying
When photo-processing photosensitive materials, the coupler may be attached to other photographic layers.
It may move or leak into the processing solution, causing color mixing and fogging.
This causes a decrease in raw and maximum color density. In the present invention, the amount of high-boiling coupler solvent used is
varies over a wide range depending on the type and amount of polymer
However, by weight, the high-boiling coupler dissolution/coupler ratio is
Preferably 0.05-20, more preferably 0.1-20
10. Also, the high boiling coupler solvent/polymer ratio is preferably
preferably 0.02 to 40, more preferably 0.0
It is 5-20. Also, high-boiling coupler solvents alone
Can also be used in combination. -C Among the compounds represented by formulas ([1) to (■), -
Formulas (III), (IV) and (V) are preferably represented by W1 to W8 in general formulas (II[) to (■)
Substituted or unsubstituted alkyl group, cycloalkyl
Examples of groups, alkenyl groups, aryl groups and heterocyclic groups
- The groups exemplified with respect to formula (n) can be applied.
. Also, an epoxy group may be bonded to the alkyl group.
. Specific examples of high-boiling coupler solvents used in the present invention are listed below.
are shown, but are not limited to these. (SI) 0=PnOC-Hq-n)s(S
-2) 0=P(OCHzC1'1zCHCH3) 5(S-3
) O-Pi0CbHIff n)i 0-P-EOC,)Ill n)i (S 10) O Cape-(OCqHI*-2). 17) 18) (S 12) 0=P(OC+++lLc+-yu). (S-19) (S-14) C,H. (S-20) (S 15) (S-21) /\ 0=P-E-0(C)Itell-CM (S-22) C,H. 0・P÷QC! 1zcHcdL ) (S 23) (S-24) (S-25) (S-30) zHs (S-31) (S-32) (S 33) (S-26) (S-27) (S 28) zHs zHs (S-35) (S-36) (S-37) (S-38) C14゜(S-40) (S-41) (S 42) (S-43) (S 44) (S- 49) cttcoocot (CP zcF t) tH1 CHCOOCHt (CFzCFt) J (S-51) (S-52) (s-53) (S-45) (S CI, 0CO 46) CHzCOOCJq C-C00C,H. CHzCOOCJw Js HO-C-COOCHzCHCJ* CHzCOOCHtCHCJ* C! HS (S-47) (S-48) (S-54) (S-55) (S 56) (S-57) (S-58) C+! HzsO)1 C+J(!zOH 570H C+oHttO(Cut)sO(CHi)zOH(S-
61) CI3 (CHz) +, C1 (S-62) CH3 (CHz) + sBr (S-63) (S-67) (S-64) (S-68) (S-65) (S-69) ( S-70) (S-66) CsH+wCHC1(CHz)7cOOcJq(n)\
/ (blank space below) containing the above coupler, high boiling coupler solvent and polymer.
In order to obtain an emulsified dispersion of lipophilic fine particles having
can be prepared by the following method. Synthesized by solution polymerization, emulsion polymerization, suspension polymerization, etc.
non-crosslinked, so-called linear polymers, high boiling
The point coupler solvent and coupler are co-completed in an auxiliary organic solvent.
After total dissolution, the solution is poured into water, preferably in a hydrophilic solution.
in an aqueous gelatin solution, more preferably in an aqueous gelatin solution.
With the help of powder, ultrasonic waves, colloid mills, etc.
It is dispersed in the form of particles and incorporated into a silver halide emulsion. be
or dispersion aids such as surfactants, polymers of the present invention, and high boiling points.
Water in the coupler solvent and in the auxiliary organic solvent containing the coupler.
Or add a hydrophilic colloid aqueous solution such as gelatin aqueous solution.
, it may also be an oil-in-water dispersion with phase inversion. prepared
From the dispersion, distillation, noodle washing or ultrafiltration are performed.
By which method, after removing the auxiliary organic solvent, the photographic emulsion
May be mixed with The auxiliary organic solvent here refers to emulsion
Organic solvent useful for dispersion, drying process during coating, and the above-mentioned
is substantially removed from the photosensitive material by the method of
It is suitable for low-boiling point organic solvents or water.
Use a solvent that has a certain level of solubility and can be removed by washing with water, etc.
cormorant. As auxiliary organic solvents, ethyl acetate and butyl acetate can be used.
Acetate of lower alcohols such as ethyl propionate
alcohol, secondary butyl alcohol, methyl ethyl ketone, methyl
Leisobutyl ketone, β-ethoxyethyl acetate, metal
Tyrcellosolve acetate, methylcarpitol acetate
Methylcarpitol propioto and cyclohexane
Examples include non. Additionally, if necessary, organic solvents that are completely miscible with water, e.g.
For example, methyl alcohol, ethyl alcohol, acetone
or tetrahydrofuran can also be used in combination. Also, these organic solvents may be used in combination of two or more.
be able to. The average particle diameter of the lipophilic fine particles obtained in this way is 0.
．． 04μ to 2μ is preferable, more preferably 0.0μ
It is from 6μ to 0.4μ. The particle size of lipophilic particles is, for example
For example, using a measuring device such as the Nanosizer manufactured by Coulter in the UK.
Can be measured. The lipophilic fine particles of the present invention contain various photographic hydrophobic substances.
It can be included. Examples of hydrophobic substances for photography
are colored couplers, colorless couplers, developers, developing
agent precursor, development inhibitor precursor, ultraviolet absorption
agents, development accelerators, tone control agents such as hydroquinones, and dyes.
agent, dye release agent, antioxidant, optical brightener, anti-fading agent
etc. In addition, these hydrophobic substances may be used in combination with each other.
It's okay to stay. Also, from couplers, high boiling coupler solvents and polymers.
Photographic hydrophobic substance contained in the lipophilic fine particles of the present invention
As a quality, compounds of the following general formulas (A) to -r formula (C)
further enhances the effect of improving color development and reducing fading of the present invention.
It is particularly useful in A represents a divalent electron-withdrawing group, R1 is substituted or
Unsubstituted alkyl group, substituted or unsubstituted aryl group
, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxy group
Substituted aryloxy group, substituted or unsubstituted alkyl group
Ruamino group, substituted or unsubstituted anilino group, also substituted
Alternatively, it represents an unsubstituted heterocyclic group. l is 1 or 2
is an integer. R2 is a substituted or unsubstituted alkyl group,
Substituted or unsubstituted alkoxy group, hydroxyl group,
It represents a halogen atom, and m is an integer from 0 to 4. Q
is a benzene ring or a hexacyclic ring which may be fused to a phenol ring.
Represents the ring of terrorism. H 4 In the general formula (B), R3, R4, and Rs each represent water.
Elementary atoms, halogen atoms, nitro groups, hydroxyl groups, substituted or
is an unsubstituted alkyl group, alkoxy group, aryl group,
It is an aryloxy group or an acylamino group. 01(X-3) -C In formula (C), R-1Rt is each a hydrogen atom
, substituted or unsubstituted alkyl group, alkoxy group or
is an acyl group, and X is -CO- or 1000-
and n is an integer of 1 to 4. Below, compounds represented by general formulas (A) to -general formula B)
Specific examples will be given, but the invention is not limited to these. X-1) X-5) X-6) X-2) X-7) X-11) X-8) X-12) X-9) X-13) X-10) X-14) Present invention Halogenation used in silver halide emulsions related to
Silver includes silver chloride, silver iodobromide, silver bromide, silver chlorobromide, and silver salt.
Any compound used in conventional silver halide emulsions such as silver iodobromide
Includes: The color photographic material of the present invention uses a color coupler.
A wide variety of photosensitive materials, including photosensitive materials for shadows, photosensitive materials for printing, and photosensitive materials for movies.
It can be applied to various types of color sensitive materials. That is, color negative filter
color reversal film, color paper, color reversal
Paper, color positive film, autopositive color sensitive material
, sensitive materials for color diffusion transfer method, color sensitive materials for heat development, etc.
Reflective supports may be used, but are particularly suitable for the present invention.
Focusing on motsu color sensitive materials (typically color paper)
This will be explained in detail below. The color photographic material of the present invention has a blue-sensitive halo on the support.
Silver halide emulsion layer, green silver halide emulsion layer and redness
A structure in which at least one silver halide emulsion layer is coated.
can be achieved. In general color photographic paper, the support
Normally it is painted on top in the above order, but this
May also be in a different order than the infrared-sensitive halogen
a silver emulsion layer in place of at least one of the foregoing emulsion layers;
Can be used. These photosensitive emulsion layers contain
Silver halide emulsions sensitive to each wavelength range and photosensitive
A pigment that has a complementary color relationship with the light that
yellow, magenta against green and cyan against red.
The color can be reduced by containing a so-called color coupler that forms
It is possible to perform legal color reproduction. However, the photosensitive layer and cap
The color hue of color is a composition that does not have the above correspondence.
It's good as well. The silver halide emulsion used in the present invention is substantially iodine.
Silver chlorobromide or silver chloride that does not contain silver chloride
It can be preferably used. Here, silver iodide is essentially
Not containing means that the silver iodide content is 1 mol% or less, preferably
refers to the halogen composition of the emulsion, which is 0.2 mol% or less.
may be different or equal between particles, but between particles
Using emulsions with equal halogen composition, each grain has
It is easy to make the properties homogeneous. Also, halogenated
Regarding the halogen composition distribution inside silver emulsion grains,
The so-called uniform composition is the same in every part of the silver oxide grain.
The grains with a mold structure and the core inside the silver halide grains.
with a shell (M) [-layer or layers] surrounding it.
Particles with a so-called laminated structure with different halogen compositions, or
Different halogen compositions inside or on the surface of the particles in a non-layered manner
A structure with a part (the edge of the particle if it is on the particle surface)
, a structure in which parts of different compositions are joined on a corner or surface
) can be appropriately selected and used. high feeling
In order to obtain a higher degree of
It is advantageous to use
If the new silver halide grains have the above structure,
In this case, the boundary between parts that differ in halogen composition is
Even if there is a clear boundary, mixed crystals may be formed due to compositional differences, resulting in failure.
Structures that may have clear boundaries or are actively continuous
It may be something with some variation. Regarding the halogen composition of these silver chlorobromide emulsions,
Those having a bromide w1/silver chloride ratio can be used. child
The ratio of silver chloride can vary widely depending on the purpose, but the silver chloride ratio
Those having a ratio of 2% or more can be preferably used. In addition, photosensitive materials suitable for rapid processing contain high silver chloride content.
A so-called high silver chloride emulsion is preferably used. This is high salt
The silver chloride content of the silver emulsion is preferably 90 mol% or more,
More preferably 95 mol% or more. In such high silver chloride emulsions, the silver bromide localized layer is described first.
Inside the silver halide grains in a sticky layered or non-layered manner
and/or have a structure on the surface, preferably
The halogen composition of the localized layer has a low silver bromide content.
It is preferably at least 10 mol%, and more than 20 mol%.
It is more preferable that these localized layers
inside the particle, on the edge, corner, or surface of the particle surface.
However, in one preferred example, particles can be
Some of them are epitaxially grown.
can. On the other hand, it is possible to minimize the decrease in sensitivity when photosensitive materials are subjected to pressure.
High silver chloride milk with a silver chloride content of 90 mol% or more for the purpose of
In addition, the distribution of halogen composition within particles is small and even.
It is also preferred to use particles of monomorphic structure. In addition, in order to reduce the amount of replenishment of processing solution,
It is also effective to further increase the silver chloride content of the silver emulsion. In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferred.
used. Halogenation contained in the silver halide emulsion used in the present invention
Average particle size of silver particles (circle equivalent to the projected area of the particles)
Particle size is determined by the diameter and the number average is taken)
is preferably 0.1 μ to 2 μ. In addition, their particle size distribution has a coefficient of variation (particle size
standard deviation of the distribution divided by the average particle size) 20%
Hereinafter, a so-called monodisperse material of 15% or less is preferable.
In this case, in order to obtain wide latitude, the above
Monodispersed emulsions may be blended in the same layer, or heavy
Layer coating is also preferably carried out. The shape of silver halide grains contained in photographic emulsions is cubic.
, regular (regu) such as a tetradecahedron or an octahedron.
lar) something that has a crystalline shape, such as spherical, plate-like, etc.
having an irregular crystal shape;
Alternatively, it is possible to use a combination of these forms.
Wear. Also, a mixture of crystals with various crystal forms.
In the present invention, among these,
Preferably, 50% or more of the particles have the above-mentioned regular crystal shape.
or 70% or more, more preferably 90% or more
It's good. In addition to these, the average aspect ratio (yen equivalent diameter/
Tabular grains with a thickness of 5 or more, preferably 8 or more are projected
Emulsions whose area exceeds 50% of the total grains are also preferred.
It can be used in many ways. The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chfie eL Ph1sique Photo
ographique (Paul Nonte 1 company)
(Published, 1967), G., F. Duffin, Ph.
oto-graphic Ewulsion Che+
*1try (Published by Focal Press, 196
6 years), V, L, Zelikman eL al.
AuthorMaking and Coating Photog
raphkc Earluldron CFocal P
using the method described in
8, i.e. acidic method, neutral
method, ammonia method, etc. may be used, and soluble root salt method may be used.
The reaction method for reacting with soluble halogen salt is one-sided mixing.
legal, simultaneous mixed method, and combinations thereof.
It is also possible to use a different method to place zero particles in an atmosphere with excess silver ions.
Using a method of forming under air (so-called back mixing method)
You can also Halogen as a form of simultaneous mixing method
A method for keeping pAg constant in the liquid phase produced by silver oxide.
In other words, the so-called Chondrold double jet method is used.
You can also do that. According to this method, the crystal shape is regular and grainy.
It is possible to obtain a silver halide emulsion with a nearly uniform grain size.
Wear. The silver halide emulsion used in the present invention is characterized by its emulsion grain formation.
or various polyvalent metal ions in the process of physical ripening.
Impurities can be introduced. Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Ruthenium, rhodium, palladium, osmium, iridium
Examples include salts or complex salts of dium, platinum, etc.
Ru. In particular, the above Group Ⅰ elements can be preferably used.
. The amount of these compounds added can vary widely depending on the purpose.
is preferably 101 to 104 mol based on silver halide.
stomach. The silver halide emulsion used in the present invention is usually chemically sensitized.
and spectral sensitization. Regarding chemical sensitization methods, the addition of unstable sulfur compounds is a typical method.
sulfur aggravation, noble metal aggravation represented by gold sensitization,
Alternatively, reduction sensitization can be used alone or in combination.
can. Regarding compounds used for chemical sensitization,
Lower right column on page 18 of specification of Publication No. 1982-215272~
Those described in the upper right column of page 22 are preferably used. Spectral sensitization is applied to the emulsion of each layer in the light-sensitive material of the present invention.
This is done for the purpose of imparting spectral sensitivity to the desired wavelength range.
In the present invention, the wave corresponding to the desired spectral sensitivity is
A dye that absorbs light in a long range - adding a spectral sensitizing dye
The spectral enhancement color used at this time is preferably
For example, Het by F. M. Rareer.
erocyclic compounds-Cyani
ne dies and re! ated cospo
unds (John Wiley l 5ons (N
ew York, London), 1964)
The following can be mentioned. concrete
Examples of compounds and spectral enhancement methods are described in the above-mentioned JP-A-62-
215272 Publication Specification, page 22, upper right column to page 38
Those described in are preferably used. The silver halide emulsion used in the present invention includes
Preventing fogging during processing, storage or photo processing,
Alternatively, various compounds may be used to stabilize photographic performance.
or their precursors can be added. these
A specific example of the compound is described in the above-mentioned JP-A No. 62-215272.
Those described on pages 39 to 72 of the publication specification are preferred.
Often used. In the emulsion used in the present invention, latent images are mainly formed on the grain surfaces.
The so-called surface latent image type emulsion, or the latent image mainly consists of grains.
Which type of so-called surface latent image emulsion is formed inside the emulsion?
It may be from a pool. The photosensitive material produced using the present invention contains a color antifoggant and
Hydroquinone derivatives, aminophenol derivatives
Contains gallic acid derivatives, ascorbic acid derivatives, etc.
You can. Various anti-fading agents may be used in the photosensitive material of the present invention.
I can do it. i.e. cyan, magenta and/or yellow
Organic anti-fading agents for images include hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
spirochromans, p-alkoxyphenols, bis
Hindered phenols, mainly phenols,
Edible acid derivatives, methylenedioxybenzenes, aminof
Enols, hindered amines, and each of these compounds T
The phenolic hydroxyl group of h is silylated or alkylated.
Typical examples include ether or ester derivatives.
Ru. Also, (bissalicylaldoximide) nickel complex
and (bis-N, N-dialkyldithiorubama)
g) Metal complexes such as nickel In can also be used.
Ru. Specific examples of anti-fading agents are described in the patent specifications below.
It is. Hydroquinones are U.S. Patent No. 2,360,290,
Same No. 2,418.613, Same No. 2.700.453
, No. 2,701.197, No. 2.728.659
No. 2,732.300, No. 2,735.76
No. 5, No. 3.982.944, No. 4.430.4
No. 25, British Patent Section 1.363.921, U.S. Pat.
No. 2.710,801, No. 2,816.028, etc.
, 6-hydroxychromans, 5-hydroxykumara
and spirochromans are disclosed in U.S. Patent No. 3.432.30.
No. 0, No. 3,573.050, No. 3,574,6
No. 27, same No. 3,698. . No. 909, No. 3,764,337, Japanese Unexamined Patent Publication No. 52-1
No. 52225, etc., spiroindanes are disclosed in US Patent No. 4.
．． 360.589, p-alkoxyphenols are
U.S. Patent Section 2,735.765, British Patent Section 2,06
No. 6.975, JP-A-59-10539, JP-A-57
-19765 etc., hindered phenols are
Patent tube No. 3.700.455, JP-A-52-72224
No., U.S. Patent No. 4,228,235, Special Publication No. 1983-1986
No. 23, etc., gallic acid derivatives, methylenedioxyben
Zens and aminophenols are disclosed in US Patent No. 3, respectively.
No. 457.079, No. 4.332,886, Tokukosho
No. 56-21144, etc., hindered amines are
Patent No. 3,336,135, Patent No. 4,268.593
No. 1,326.889, British Patent Section No. 1,354
, No. 313, No. 1, No. 410.846, Special Publication No. 1973-
No. 1420, JP-A-58-114036, JP-A No. 59-
No. 53846, No. 59-78344, etc., metal complexes
The body is U.S. Patent No. 4.050.938, U.S. Patent No. 4,241
゜155, British Patent Section 2,027,731(^) etc.
Each is listed in which. These compounds are
Usually 5 to 100 for each corresponding color coupler
% by weight is co-emulsified with the coupler and added to the photosensitive layer.
You can achieve your goals. Cyan dye image heat
In particular, to prevent deterioration caused by light, cyan emitting
The UV absorber is introduced into the color layer and the adjacent layers on both sides.
It is more effective to enter As a UV absorber, benzene substituted with an aryl group is used.
Triazole compounds (e.g. U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g.
For example, U.S. Patent No. 3,314,794, U.S. Pat.
681), benzophenone compounds (e.g.
(Japanese Patent Publication No. 46-2784 Togeki 3), cinnamic acid
Stell compounds (e.g. U.S. Pat. No. 3,705°805)
, No. 3,707,395), Butaje
compound (as described in U.S. Pat. No. 4,045,229)
,'``t-)''), or benzoachyl M-ol compounds (e.g.
Patent tube No. 3,406.070 No. 3,677.672
4.271.307) shall be used.
I can do it. UV-absorbing couplers (e.g. α-naphtho)
color-based cyan dye-forming couplers) and ultraviolet-absorbing
These UV absorbers may be made of polymers, etc.
A specific layer may be mordanted. Among them, benzotriazo substituted with the above-mentioned oryl group
A metal compound is preferred. In addition to the above-mentioned couplers, the following compounds may also be used:
Preferably used, especially pyrazoloazole couplers
It is preferable to use it in combination with -. In other words, the aromatic amine developer remaining after color development processing
Chemically combined with drugs to be chemically inert and virtually colorless
Compound (F) that produces the compound and/or color developer
Oxidation of aromatic amine color developing agent remaining after image processing
Chemically bound to the body, chemically inert and virtually colorless
Using the compound (G) that produces the compound simultaneously or singly
For example, residual color development in the film during storage after processing may occur.
Color development due to the reaction between a developing agent or its oxidized product and a coupler
Prevents staining and other side effects caused by pigment production
preferred above. Preferred compounds as compound (F) are p-anisidine and
The second-order reaction rate constant t + z (trioctylphosate at 80°C
during sface) is 1. Oj! /mol-sec-I
A compound that reacts in the range of X10-' 1 /mol・sec
It is a compound. The second-order reaction rate constant is based on JP-A-63-158545.
It can be measured by the method described in . If kt is larger than this range, the compound itself is unstable.
may react with gelatin or water and decompose.
Ru. On the other hand, if R2 is smaller than this range, the remaining aroma
It reacts slowly with group amine developing agents and remains as a result.
Can prevent side effects of aromatic amine developing agents.
Sometimes there isn't. More preferable compounds (F) are as follows:
It can be expressed as (Fl) or (Fn). General formula (FI) R+ (A)-X General formula (Fll) R1-C禦Y In the formula, R3 and R7 are each an aliphatic group, an aromatic group, or
represents a heterocyclic group, n represents 1 or O. A reacts with an aromatic amine developer to form a chemical bond.
X represents a group that reacts with an aromatic amine developer and is released.
Represents a group that leaves, B is a hydrogen atom, an aliphatic group, an aromatic group
, represents a heterocyclic group, acyl group, or sulfonyl group,
Y is a compound in which the aromatic amine developing agent has the general formula (FIr)
represents a group that promotes addition to a compound, where R8
and X, Y and R5 or B are bonded to each other to form a cyclic structure
It's okay to be. Of the methods that chemically bond with residual aromatic amine developing agents
The typical examples are substitution reactions and addition reactions. Compounds represented by general formulas (F I) and (F ff)
For examples, see JP-A-63-158545 and JP-A-63-158545.
2-283338, European Patent Publication No. 298321,
Those described in specifications such as No. 277589 are preferred.
Delicious. On the other hand, the aromatic amine developer that remains after color development processing
Chemically bonded with the oxidized form of the drug, making it chemically inert and colorless
A more preferable compound (G) is
It can be represented by the following - binding margin CGI). General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group.
Z is a nucleophilic group or decomposes in the photosensitive material to become nucleophilic.
represents a group that releases a group of
The compound whose Z is Pearson's nucleophilicity °C Hs I value (
R.G., Pearson+ et al., J.
Am. Che-, Soc, fl, 319 (1968)
) is preferably 5 or more, or a group derived therefrom.
Delicious. -Specific examples of compounds expressed by Tsuzuriyo (CHI)
European Patent Publication No. 255722, Japanese Patent Publication No. 143-1983
No. 048, No. 62-229145, Patent Application No. 63-13
No. 6724, No. 62-214681, European Patent Publication 2
Described in No. 98321, No. 277589, etc.
Preferably. Further, details of the combination of the above compound (G) and compound (F)
Details are described in European Patent Publication No. 277589.
There is. The photosensitive material produced using the present invention contains hydrophilic colloids.
As a filter dye or as an irradiation layer
Water-soluble dyes and
May contain dyes that become water-soluble through photographic processing.
However, such dyes include oxonol dyes, hemioxonol dyes,
Sonol dye, styryl dye, merocyanine dye, shea
Included are nin dyes and azo dyes. Among them, Oxono
color dyes, hemioxonol dyes and merocyanine dyes
is useful. Binder that can be used in the emulsion layer of the light-sensitive material of the present invention
Alternatively, it is recommended to use gelatin as a protective colloid.
However, other hydrophilic colloids alone or with
Can be used with latin. In the present invention, gelatin may be lime-treated or acid-treated.
gelatin, whichever is processed using
For details on the manufacturing method of
Recular Chemistry of Gelatin (Academy)
Tsuku Press, published in 1964). The support used in the present invention is usually used for photographic materials.
Cellulose nitrate film and polyester film
Transparent films and reflective supports such as tyrene terephthalate
For purposes of the present invention, reflective supports can be used.
It is more preferable to use the "reflective support" used in the present invention.
is the color formed in the silver halide emulsion layer by increasing its reflectivity.
This type of reflective support refers to something that makes the original image clearer.
titanium oxide, zinc oxide, and calcium carbonate on a support.
Hydrophobic material containing dispersed light-reflecting substances such as aluminum, calcium sulfate, etc.
Those coated with a transparent resin or those containing a dispersed light-reflecting substance.
0 including those using aqueous resin as a support e.g.
, baryta paper, polyethylene-coated paper, polypropylene-based
Synthetic paper, with a reflective layer, or with reflective materials
Transparent support, e.g. glass plate, polyethylene terephthalate
cellulose triacetate or cellulose nitrate.
Polyester film, polyamide film, polycarbonate
Bonate film, polystyrene film, vinyl chloride
There are resins, etc. As other reflective supports, specular reflective or type 2
Supports with reflective metal surfaces can be used.
Wear. The metal surface has a spectral reflectance of 0.0 in the visible wavelength range.
5 or more is better, and the metal surface is roughened or metal
As the metal, it is preferable to make it diffusely reflective using powder.
is aluminum, tin, silver, magnesium or their alloys
The surface is obtained by rolling, vapor deposition, plating, etc.
may be the surface of a metal plate, metal foil, or thin metal layer
. Among these, gold is best obtained by vapor depositing metal on other substrates.
A layer of water-resistant resin, especially thermoplastic resin, is placed on the metal surface.
0 side with a metal surface of the support of the invention
It is better to provide an antistatic layer on the opposite side of the
For details of the support, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc. These supports can be appropriately selected depending on the purpose of use. As a light-reflecting substance, a white pigment in the presence of a surfactant is used.
It is best to thoroughly knead the pigment particles, and also coat the surface of the pigment particles with
It is preferable to use one treated with tetrahydric alcohol.
. Occupancy area ratio per specified unit area of white pigment fine particles
The ratio (%) most typically refers to the observed area,
Divide into 6-×6- unit areas and project onto that unit area.
Measure the occupied area ratio (%) (R+) of fine particles
You can ask for it. The coefficient of variation of the occupied area ratio (%) is
, the ratio of the standard deviation S of Ri to the average value (R) of R+
It can be determined by s/R. target unit
The number of position areas (n) is preferably 6 or more, so the variation coefficient
The number S/π can be found by In the present invention, the occupied area ratio (%) of pigment fine particles is
The coefficient of variation is preferably 0.15 or less, particularly 0.12 or less.
, if it is 0.08 or less, the dispersibility of the particles is substantially "uniform".
It can be said that there is one. The color developing solution used in the development of the photosensitive material of the present invention is preferably
Preferably, the main ingredient is an aromatic primary amine color developing agent.
It is an alkaline aqueous solution. As this color developing agent
Aminophenol compounds are also useful;
Preferably, phenylenediamine compounds are used;
An example table is 3-methyl-4-amino-N,N-diethyl
Luaniline, 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-a
Mino-N-ethyl-N-β-methanesulfonamidoethyl
Luaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates and salts
Examples include acid salts and p-toluenesulfonate salts. Two or more of these compounds can be used in combination depending on the purpose.
Wear. The color developer is an alkali metal carbonate or phosphate.
pHil street agents such as bromide salts, iodide salts, benzene
Midazoles, benzothiazoles or mercapto
Contains development inhibitors or antifoggants such as compounds.
It is common to Also, if necessary, hydroxyl
Amine, diethylhydroxylamine, sulfite, N,
Hydrazine such as N-biscarboxymethylhydrazine
, phenylsemicarbazides, triethanolamine
, various preservatives such as catechol sulfonic acids, ethylene
organic solvents such as glycol, diethylene glycol,
Benzyl alcohol, polyethylene glycol, quaternary alcohol
Development accelerators such as ammonium salts, amine necks, dye formation
coupler, competitive coupler 1-phenyl-3-pyrazolide
Auxiliary developing agents such as
Bonic acid, aminopolyphosphonic acid, alkylphosphonic acid,
Various chelating agents such as phosphonocarboxylic acids
, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediamine
Tetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxy
siethylidene-1,1-diphosphonic acid, nitrilo-N,
N,N-trimethylenephosphonic acid, ethylenediamine-
N,N,N'N'-tetramethylenephosphonic acid, ethylene
Glycol (0-hydroxyphenylacetic acid) and it
A typical example is the salt of In addition, when performing reversal processing, it is usually black and white development and reversal processing.
After processing, 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. The pH of these color developing solutions and black and white developing solutions is 9 to 12.
Some things are common. Also, the amount of replenishment of these developers
Although it depends on the color photographic material to be processed, it is generally
31 or less per 11 square meters of light material, and in the replenisher
500 by reducing the bromide ion concentration of
It can also be less than d. When reducing the replenishment amount
By reducing the contact area with the air in the treatment tank,
It is preferable to prevent evaporation and air oxidation of
The contact area between the photographic processing solution and the air is determined by the opening defined below.
It can be expressed in words. In other words, the aperture ratio - processing liquid and air
Contact area with air (cm”)/Volume of processing liquid! (cm’) The above aperture ratio is preferably 0.1 or less, and more preferably
Preferably it is o, oot to 0.05. As a method to reduce the aperture ratio in this way, the treatment tank
In addition to installing a shield such as a floating lid on the surface of the photographic processing solution,
Using the movable lid described in Application No. 62-241342
method, the slitting method described in JP-A No. 63-216050.
Examples include development processing methods. Reducing the aperture ratio is effective for both color development and black and white development.
Not only the process, but also the subsequent processes, such as bleaching and bleach fixation.
Applicable to all processes such as application, fixation, washing, stabilization, etc.
It is preferable to do so. Additionally, measures are taken to suppress the accumulation of bromide ions in the developer.
By doing so, the amount of replenishment can also be reduced. The time for color development processing is usually set between 2 and 5 minutes.
However, high temperature, high pH, and high concentration of color developing agent are used.
It is also possible to further reduce processing time by using
Wear. After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be carried out simultaneously with fixing treatment.
fusing treatment), which may be carried out separately, and which is more rapid in processing.
In order to achieve
It can also be treated with two consecutive bleach-fix baths.
and fixing before bleach-fixing or bleach-fixing.
Depending on the purpose, bleaching can be carried out after the dyeing process.
Wear. As a bleaching agent, for example, polyvalent metals such as iron (1)
Typical bleaching agents include iron (I) compounds, etc.
II), such as ethylenediaminetetraacetic acid, di
Ethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid
Acetic acid, methyliminodiacetic acid, 1. 3-diaminopropa
glycol ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, etc.
Aminopolycarboxylic acids or citric acid, tartaric acid,
Complex salts such as malic acid can be used. these
Of these, including ethylenediamine ferric acetate(m)iff salt
Aminopolycarboxylic acid iron(I[I) complex salt can be rapidly processed.
and aminopolymer, which is preferable from the viewpoint of preventing environmental pollution.
Iron carboxylate (Iff) complex salts can be used in bleaching solutions as well.
It is also particularly useful in fixers. These aminopoly
Iron(III) carboxylate t! Bleach solution or bleaching with salt
The pH of the fixer is usually 4.0 to 8.0, but
For faster processing, processing can also be performed at lower pH.
Ru. Bleach solution, bleach-fix solution, and their pre-baths may contain
bleach accelerators can be used. 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, JP-A-53-95630, Lisa
Arch Disclosure Floor No. 17, 129 (1978
Mercapto group or disulfide described in
Compounds having a bond; described in JP-A-50-140129
Thiazolidine derivatives described in US Pat. No. 3,706,56
Thiourea derivatives described in No. 1; JP-A-58-16235
Iodide salt described in No. 2.748.430; West German Patent No. 2.748.430
Polyoxyethylene compounds described in: Japanese Patent Publication No. 45-8
Polyamine compounds described in No. 836; bromide ions, etc.
can be used. Among them, mercapto group or disulfide group
Compounds having a do group are preferred from the viewpoint of a large promoting effect.
, especially U.S. Patent No. 3,893.858, West German Patent No. 1
．． No. 290,812, described in JP-A-53-95630
Also preferred are the compounds of U.S. Pat. No. 4,552.8.
Compounds described in No. 34 are also preferred, these bleach accelerators
may be added to light-sensitive materials, color impression for fl shadows
These bleach accelerators are especially useful when bleach-fixing photomaterials.
It is valid. As a fixing agent, thiosulfate, thiocyanate, thioether
Examples include tel-based compounds, thioureas, large amounts of iodide salts, etc.
However, the use of thiosulfates is common and
Ammonium thiosulfate is the most widely used. bleaching
Preservatives for the fixer include sulfite, bisulfite, p-
4 Sulfine fIl like luenesulfinic acid! ! be
Alternatively, carbonyl bisulfite adducts are preferred. The silver halide color photographic light-sensitive material of the present invention is subjected to desilvering treatment.
After that, it is common to undergo a water washing and/or stabilization process. The amount of water used in the washing process is determined by the characteristics of the photosensitive material (e.g.
(depending on the materials used), usage, washing water temperature, washing
Number of tanks (number of stages), replenishment methods such as counterflow, forward flow, etc.
It can be set over a wide range depending on various conditions. Of these, many
The relationship between the number of washing tanks and the amount of water in the stage counterflow method is Jo
Urnalof the 5ociety of Mo
tion Picture and Te1svisi
on Engineers Vol. 64, p. 248-2
53 (May 1955 issue)
I can do that. According to the multi-stage countercurrent method described in the above literature, the amount of washing water can be increased.
The residence time of water in the tank may be increased.
As a result, bacteria proliferate and the resulting suspended matter becomes photosensitive.
Color sensitization of the present invention may cause problems such as adhesion to materials.
As a solution to such problems in material processing,
Calcium ion described in JP-A No. 62-288838
, a highly effective method to reduce magnesium ions
Can be used. Also, in JP-A No. 57-8542
The isothiazolone compounds and thiabendazoles listed above,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Other benzotriazoles, etc., written by Hiroshi Horiguchi,
Gaku J (1986) Sankyo Publishing, Hygiene Technology Gold Wire [Misei
Sterilization, sterilization, and anti-mold technology J (1982) Industrial technology
Japan Antibacterial and Antifungal Society, “Encyclopedia of Antibacterial and Antifungal Agents” (198
6) can also be used. The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. Washing water temperature, during washing
Although the time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.,
Generally, zθ seconds to IO minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The photosensitive material of the present invention can be directly washed with a stabilizing solution instead of washing with water.
You can also process it as follows. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
No. 3, No. 5B-14834, No. 60-220345
All known methods described in can be used. Further, following the water washing treatment, a further stabilization treatment may be performed.
An example of this is the final bath for color photosensitive materials for imaging.
A safe substance containing formalin and surfactant used as
One example is regular bathing. Various chelating agents and antifungal agents may also be added to this stable bath.
can. Overflow due to water washing and/or replenishment of stabilizing solution
The solution can also be reused in other processes such as the desilvering process.
Ru. The silver halide color light-sensitive material of the present invention has simplification of processing.
It is also possible to incorporate a color developing agent for the purpose of speeding up the process.
For storage, various precursors of color developing agents are used.
0 e.g. U.S. Pat. No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
and the Schiff base-type compounds described in No. 15,159;
Aldol compounds described in No. 13,924, U.S. Pat.
．． Metal complex described in No. 719,492, JP-A-53-13
Examples include urethane compounds described in No. 5628.
Ru. The silver halide color photosensitive material of the present invention can be used as needed.
, various 1-phenyl-3 for the purpose of promoting color development.
- Typical compounds that may contain pyrazolidones are:
JP-A-56-64339, JP-A No. 57-144547,
and No. 58-115438. The various processing solutions used in the present invention can be used at temperatures between 10°C and 50°C.
The standard temperature is usually between 33°C and 38°C.
However, higher temperatures can be used to accelerate the process and shorten the process time.
On the other hand, it is possible to lower the temperature to improve image quality and improve the stability of the processing solution.
can achieve good results. In addition, West German Patent No. 2,226,7 was developed to save silver on photosensitive materials.
No. 70 or U.S. Pat. No. 3,674,499.
Treatment using cobalt intensification or hydrogen peroxide intensification
You can. (Example) The present invention will be specifically explained below with reference to Examples.
The invention is not limited to this. Example 1 The following was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper A having the layer structure shown in FIG. Coating liquid
was prepared as follows. 19.1 g of yellow coupler compound example (Y-7) was added to acetic acid.
Add 27.2 cc of ethyl and solvent (Solv-3) to 8.
Add 2g and dissolve, and add 10% dodecylbenzene to this solution.
10% gelatin in water containing 8 cc of sodium sulfonate
The mixture was emulsified and dispersed in 185 cc of liquid. On the other hand, silver chlorobromide emulsion (
Silver bromide 80.0 mol%, cubic; average grain size 0.8
5 μm, coefficient of variation 0.08, silver bromide 80.0%
, cubic; average particle size 0.62 μm, coefficient of variation 0°
07 in a ratio of 1:3 (Ag molar ratio))
Add 1 silver of the blue-sensitizing dye shown below to the sulfur-sensitized product.
Prepared by adding 5,0XIO-' mole per mole
. The above emulsified dispersion and this emulsion are mixed and dissolved, and the following is carried out.
A coating solution for the first layer was prepared to have the composition shown below. The coating liquid for the second to seventh calendar months is the same as the coating liquid for the -layer.
Prepared by method. The gelatin hardening agent for each layer is 1-oxygen.
C-3,5-dichloro-5-) riazine sodium salt
Using. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer so, e (5.0XIO-' mole per mole of halogenated SN)
For the green-sensitive emulsion layer and the red-sensitive emulsion layer, add the following compounds to silver halide.
2.6 x 10-' moles were added per mole. SO, θ 5OsH' N(CtHs)z (4.0XIO-' mol per mol of silver halide)
and so, e SOsH-N(CJs)s (halogenated 1! per mole?, 0XIO-' mole)
C, NS ■θ CsH++ (Ol
, 1-(5-methylureidophenyl)-5-mercap
Each totetrazole is halogenated! ! i! per mole
per 4.0X10-' mol, 3.0XIO-1 mol, 1
．． 0XIO-% mole also 2-methyl-5-t-octyl
Hydroquinone per mole of halogenated wA
8XlO-"moles, 2x104moles, 2X10-"moles
Added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy
-6-methyl-1,3,3a,7-chitrazaindene
1.2X10-" per mole of silver halide, respectively
Mol, 1. In addition, the following mercaptoimimizer was added to the red-sensitive emulsion layer.
2 x 10-' moles per mole of silver halide
and the following mercaptothiadiazoles as silver halides.
4X10-' moles were added per mole. The following dyes are added to the emulsion layer to prevent irradiation.
added. 03K SO3 and SO,K SO,K (Layer composition) The composition of each layer is shown below, and the numbers are coating amounts (g/rrr)
The silver halide emulsion represents the silver conversion X coating weight. Support polyethylene laminated paper [white pigment (TiOz) and blue on the polyethylene on the first layer side
Contains taste dye (ulmarine blue)] Layer 1 (blue-sensitive layer) Silver chlorobromide emulsion described above (AgBr: 80 mol%) 0.26 Gelatin 1, 83 Yellow
Coupler compound example (Y-7) 0.83 Solv-
3) 0.36 second N (color mixing prevention layer) Gelatin 0.99 color mixing prevention layer
Agent (Cpd-4) 0.08? Container (So
lv-1,) 0.
16 Solvent (Sol v-4) 0.
08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (AgBr90 mol%, cubic, average grain
One with a size of 0.47 μm and a coefficient of variation of 01I2, and one with an Ag
90 mol% Br, cubic, average particle size 0.36 μm
, with a coefficient of variation of 0°09 in a ratio of 1:1 (Ag mol
ratio)) mixed with 0.16 gelatin
Chin 1.79 magenta
Puller (ExM) 0.32 color image stabilizer (C
pd-1) 0.02 color image stabilizer (Cpd-
2) 0.20 color image stabilizer (Cp d-3)
0. 01 color image stabilizer (Cpd-6)
0.03 color image stabilizer (Cpd-7)
0.04 Solvent (Solv-2) 0.
65 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorption
Absorbent (UV-1) 0.47 Color mixture prevention (C
pd-4) 0.05 solvent (Solv-5)
0.24 Fifth layer (red feeling N) Silver chlorobromide emulsion (AgBr70 mol%, cubic, average grain
One with a size of 0.49 μm and a coefficient of variation of 0°08, and one with an Ag
70 mol% Br, cubic, average particle size 0.34 μm
5 The coefficient of variation 01IO and the ratio of 1=2 (Ag mol
ratio)) 0.23 lati
1.34 cyan coupler
(ExC) 0.30 color image stabilizer (Cpd
-5) 0.17 solvent (So I v-6)
0.20 6th layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet absorption
Agent (UV-1) 0.16 Color mixture prevention agent (Cp
d-4) 0.02 solvent (Solv-5)
0.08 7th N<protective layer) Gelatin 1.33 Polyviny
Acrylic modified copolymer of alcohol (modification degree 17%)
0.17 liquid paraffin
0.03 (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer 11 (Cpd 4) Color mixture prevention agent (Cpd 6) Color image stabilizer 11 C11 (Cpd 5) Color Image Stabilizer (Cpd) Color Image Stabilizer C (Cpd 8) Comparative Compound H1 1+CI+, -C, 0OCHs '2:4:4 mixture (weight ratio) with an average molecular weight of 50,000 (cpd 9) (So 1 1) Melt CI+3 ICH□=C square. C00C411q(n) Average molecule N50,000 (UV 1) Ultraviolet absorber (Sol 2) Solvent (S. 3) 4: 2: 4 mixture of solvents (weight ratio) (Solv-4) Solvent (ExM) Magenta coupler (Solv) -5) Solvent C00CIIHI? (CHz)s COOCII11? C.I. 0.11°(n) (Solv-6) Solvent Cs1 (+7C11C1l(CHz)tcOOcs)I
+t\1 (Solv-7) solvent/\CHt3 (CHt)? -CIl -CIl (CH
g) , -CON (C,H9) 2(Ex C)
Cyan coupler Next, the additives shown in Table 1 were added to the emulsified dispersion.
Sample B was prepared in the same manner as Sample A except that the solvent was changed.
-H was created. A sensitometer (manufactured by Fuji Photo Film Co., Ltd., FW
H type, color temperature of the light source is 3200'K), and the sensor is
Gradation exposure for tometry was provided. The exposure at this time is O,]
Do this so that the exposure amount is 250CJIS with an exposure time of seconds.
It was. After exposure, the sample undergoes the following processing steps and processing solution composition.
The process is done using a liquid and an automatic developing machine. Fushi1Jko42J2IkoLm Text:] υ1 color development
37℃ 3 minutes 30 seconds bleach constant @ 33℃
Washing with water for 1 minute and 30 seconds 24-34°C Drying 70-80°C The composition of each treatment liquid is as follows. Sadatenu 1 cliff water diethylene triamine pentaacetic acid nitrilotriacetic acid benzyl alcohol diethylene glycol sodium sulfite potassium bromide potassium carbonate N-ethyl = N- (β-methanesulfonamidoethyl)-3-methyl 4-aminoaniline sulfate hydroxylamine sulfate 3 minutes 1 minute 00-1,0g 2.0g 5M1 10-2,Og 1,0g 0g 4,5g 3,0g Add water and adjust pH (25℃)

[East 100 (1+z 10.25 Wed 40
〇-Ammonium thiosulfate (700g/jri 15
0m Sodium sulfite 18g Ethylenediaminetetraacetate Iron (III) Ammonium 55g Ethylenediaminetetraacetate Thorium acetate 5g Add water 1000mp100℃)
6.70 The yellow dye concentration of each sample obtained was measured using a reflection densitometer through a blue filter.
The residual density ratio at an initial yellow density of 2.0 was measured when stored for 6 days and when stored under sunlight for 1 month, and is shown in Table 1. Table 1 shows that the photosensitive material containing the epoxy group-containing polymer of the present invention simultaneously and significantly improves yellow photofading and thermal fading. Example 2 Multilayer color photographic paper A having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. 19.1 g of yellow coupler compound example (Y-7), 27.2 cc of ethyl acetate and 8.2 g of solvent (Solvl)
was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 10% sodium dodecylhenzenesulfonate (g cc). On the other hand, silver chlorobromide emulsions (cubic, with an average grain size of 0.88 μm and 0.70 μm)
The coefficient of variation of the particle size distribution of the 3-near mixture (silver molar ratio) with those of 0.08 and 0.10. Silver bromide 0 for each emulsion
．． For large-sized emulsions, 2.0 x 10-' moles of each of the blue-sensitive sensitizing dyes shown below (containing 2 mol % locally on the grain surface) were added per 1 mol of silver, and for small-sized emulsions, , 2.5×10 −4 mol of each were added and sulfur sensitized was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. l-oxy-3,5-dichloro-3-triazine sodium salt was used as the gelatin hardener for each layer. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer 50s e 5OsH-N (CtHs) 5(
CHri4 (CHriJ SO3θ 5O3)IN(CJs)z (per mole of halogenated SS, 2.0X10-' moles each for large size emulsions, and 2.0X10-' moles each for small size emulsions) .5X10-' mole)) 3 sensitive emulsion layers Red-sensitive emulsion layer (4.0XIO-' mole for large size emulsions and 5.6 for small size emulsions per mole of silver halide)
XlO-' mol) and C2H4Ie csH+ (0.9xlQ-' mol per mol of silver halide for large size emulsions and 1 xlQ-' mol for small size emulsions)
．． For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6X10-'' mole per mole of silver halide. 0x10-' mole, or 1 for small size emulsions
．． In addition, 1-(5-methylureidophenyl)5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at a rate of 8.0% per mole of silver halide, respectively.
5X10-'mol, 7.7XIO-'mol, 2.5Xl
O-' moles were added. The following dyes were added to the emulsion layer to prevent irradiation. and (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/n ()), and the silver halide emulsion represents the silver equivalent coating amount. Support polyethylene laminate paper [first layer side polyethylene Contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] Layer 1 (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Solvent (Solv-1) ＞
0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-4> 0.08 Solvent (Sol
v-1) 0.16 solvent (Solv-4
) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.55 μm
A 1:3 mixture of 0.39 μm and 0.39 μm (Ag
molar ratio) 9 The coefficient of variation of the particle size distribution is 0.10 and 0.
08, each emulsion contained 0.8 mol% of AgBr locally on the grain surface) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd
-1) 0.03 color image stabilizer (Cpd-2
) 0.15 color image stabilizer (Cpd-3)
0.02 color image stabilizer (Cpd-7>
0.02 solvent (Solv-2)
0140 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (
Cpd-4) 0.05 Solvent (Solv-
5) 0.24 fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.58 μm
Ql:4 mixture (Ag
molar ratio) 0 The coefficient of variation of the particle size distribution is 0.09 and 0.0.
LL Each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) 0.23 Gelatin 1.34 Cyan coupler (
ExC) 0.32 color image stabilizer (Cpd-
5) 0.17 color image stabilizer (Cpd-7>
0.04 solvent (So Iv-6>
0. 15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing prevention agent (
Cpd-4) 0.02 Solvent (Solv-
5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
0.17 liquid paraffin
0.03 (E ) Color image stabilizer and L CHi H3 R=CzHs and C, Hq (Cpd 6) Color image stabilizer 11 (Cpd 7) Color image stabilizer (Cpd 8) Comparative compound (CI□ C1 + square. C00C41 (q ( n) Average molecular weight 50,000 (Cpd 4) Color mixing inhibitor H (cpa 5) '2:4:4 mixture of color image stabilizer (weight ratio) (UV-1) Ultraviolet absorber (Solv-1) Solvent (Solv -2) Solvent (Solv-6) Solvent (Solv-7) (Solv-4) fJ medium (Solv-5>Solvent C00CsH+t (CFb). C00C8H1? Next, regarding the coupler emulsion dispersion of the first layer, Samples B to J were prepared in the same manner as sample A except that the additives shown in the table were added and the coupler solvent was changed.
The color temperature of the light source was 3200"K), and the gradation exposure of a three-color separation filter for sensitometry was applied.The exposure at this time was 611 for 0.1 seconds, resulting in an exposure amount of 250 CMS. After exposure, the sample was subjected to continuous processing (running test) using a paper processing machine until the tank capacity for color development was refilled twice as much in the next processing step. PfM 0 x 1 main color development 35°C 45 seconds 16111t171 bleaching room 30~35°C 45 seconds 215TII117 m!
Rinse■ 30-35℃ 20 seconds □ 10/rinse■ 30-35℃ 20 seconds □ 1 (1 rinse■
30-35℃ 20 seconds 350M1101 drying 7
0 to 80°C for 60 seconds Tetra filtered water 800 * 8oOd ethylenediamine-N,N. N',N'-tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015 g Triethanolamine 8.0g 12.0g Sodium chloride 1. 4g potassium carbonate
25g25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4 aminoaniline sulfate 5.0g 7.0gNN
-Bis(carboxymethyl)hydrazine 5.5g 7.0g Fluorescent brightener (WHITEX 4B. Manufactured by Sumitomo Chemical) 1. Og 2.0g
Add water 1o001d 100
0 pH (25℃) 10.05 10.
45M11XJ1 (tank fluid and refill fluid are the same) water
400 d ammonium thiosulfate (700g/l) 100
d Sodium sulfite 17 g
Iron (III) ethylenediaminetetraacetate Ammonium disodium ethylenediaminetetraacetate 5 g g Add water 1ooo MIl
pH (25℃) 6.0 Yunoa (tank liquid and replenisher are the same) Ion exchange water (calcium and magnesium are 3p each)
pvl or less) The yellow dye concentration of each sample obtained was measured with a reflection densitometer through a blue filter.Then, the sample was stored at 80° C. and 75% RH for 30 days, and
Initial yellow density 2 when stored under sunlight for 3 months
．． The residual rate of concentration at 0 was measured and shown in Table 2. Table 2 shows that the photosensitive material containing the epoxy group-containing polymer of the present invention simultaneously and significantly improves yellow photofading and thermal fading. (Effects of the Invention) According to the present invention, a color photograph in which both photobleaching and thermal fading are simultaneously and significantly improved can be obtained. This effect is particularly remarkable in yellow dye images.

Claims (3)

[Claims] (1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one oil-soluble coupler capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developing agent and the following general formula [I] are present in at least one of the silver halide emulsion layers. 1. A silver halide color photographic material containing at least one water-insoluble polymer represented by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^4 may be the same or different,
Represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a halogen atom. R^2 and R^3 may be the same or different and represent a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. However, the total number of carbon atoms of R^1 and R^3 is 2 or more,
Further, R^2 and R^3 may be linked to each other to form a nitrogen-containing heterocycle. L represents a divalent linking group. L' constitutes a ring together with an oxygen atom, and represents a substituted or unsubstituted hydrocarbon chain connected to L. A represents a repeating unit derived from an ethylenically unsaturated monomer other than those mentioned above. x, y, and z represent the weight percentage of each component, where x represents 20 to 99, y represents 1 to 80, and z represents 0 to 50. (2) The silver halide emulsion layer comprises at least one of the oil-soluble couplers, a coupler solvent that is immiscible with water and has a melting point of 100°C or lower and a boiling point of 140°C or higher, and the general formula [I]. 2. The silver halide color photographic light-sensitive material according to claim 1, which contains the silver halide color photographic material in the form of lipophilic fine particles obtained by emulsifying and dispersing a solution in which the expressed polymer is dissolved. (3) Claim characterized in that the oil-soluble coupler is a yellow coupler represented by the following general formula [II] (
The silver halide color photographic material described in 1) or (2). General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1^1 represents an N-arylcarbamoyl group, and Z^1^1 is a hydrogen atom or an aromatic primary amine color developing agent. Represents a group that can be separated by reaction with an oxidant of