JP2003322940A - Silver halide color photographic light-sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic light-sensitive material improved in electrostatic fogging without impairing sharpness or processability. <P>SOLUTION: The silver halide color photographic light-sensitive material has one or more each of blue-, green- and red-sensitive emulsion layers on a support, contains a coupler of formula (I) in the blue-sensitive emulsion layers and satisfies expression a-1) 0.5≤Dmax(UV)/Dmin(UV)≤1.1 and/or b-1) 1,300≤(B-C)/A≤20,000, wherein, in formula I, Q represents a group of non- metal atoms for forming a ring; R1 and R2 each represent a substituent; m represents 0-5; and X represents H or a group capable of being split-off upon reaction with an oxidized product of a developing agent, in expression a-1), Dmax(UV)/Dmin(UV) is the smallest of the value, at a wavelength UV (UV is a certain wavelength of 340-450 nm), represented by (absorbance of yellow Dmax portion at UV)/(absorbance of yellow Dmin portion at UV), and in expression b-1), B is yellow Dmax; C is yellow Dmin; and A is an amount of the coupler of formula (I). <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a silver halide photographic sensitivity.
It relates to optical materials, more specifically sharpness and processing
Do not impair the performance of photographic materials such as
For photographic materials that have improved anti-static fog resistance
It is related. [0002] 2. Description of the Related Art A silver halide photographic light-sensitive material by a subtractive color method.
(Hereafter, it may be simply called “photosensitive material” or “photosensitive material”.
The ) In yellow, magenta and cyan
A color image is formed by the three primary color pigments. Current p-
Color using phenylenediamine color developing agent
In photography, acyl couplers are used as yellow couplers.
Acid anilide compounds are used. But these
The hue of yellow dyes obtained from these couplers is
The long wave side slash is bad, so it is reddish and pure.
It is difficult to obtain a low hue, and the dye molecules
Small extinction coefficient, large amount to obtain desired color density
Requires couplers and silver halide, and the film thickness of the photosensitive material is
The sharpness of the resulting color image may be reduced
There was a problem such as. In recent years, color photosensitive materials
With increased sensitivity, electrostatic fog occurs during shooting and manufacturing.
Often happened and improvements were desired.
Acyl groups and anilides to solve these problems
The group has been improved and more recently,
Patent document 1 describes a coupler with an improved nilide system
1-alkylcyclopropanecarbonylacetic acid anilide
Compounds and cyclic malondiamide type compounds described in Patent Document 2
Puller, pyrrole-2 described in Patent Documents 3 to 8 or the like
3-yl or indole-2 or 3-ylcarbo
Nyl acetic acid anilide couplers and the like have been proposed. these
Dyes produced from couplers have a hue and separation that are different from conventional ones.
Although the absorption coefficient has been improved, it has not been improved in terms of image storage stability.
It is not enough, and because of the complexity of the structure,
Longer, longer coupler costs, and practical problems
There was a title. In addition, Patent Documents 9 to 11, etc. 1, 2, 4
-Benzothiadiazine-1,1-dioxide bound
Acetic ester and anilide acetate couplers proposed
However, color developability is low, and absorption on the long wave side of absorption is bad.
These improvements were desired. Countermeasures against electrostatic fog
UV absorption into the photosensitive material protective layer described in Patent Document 12
Addition of collector (UV agent) is known, but further electrostatic
Increasing the amount of these UV agents to improve anti-fogging properties
Increased film thickness of sensitive material, sharpness of image, and (rapid) processing
Since it causes deterioration, it is not preferable. [0003] [Patent Document 1] Japanese Patent Laid-Open No. 4-218042 [Patent Document 2] JP-A-5-11416 [Patent Document 3] European Patent No. 935870A1
book [Patent Document 4] European Patent No. 953871A1
book [Patent Document 5] European Published Patent No. 953872A1
book [Patent Document 6] European Patent No. 953873A1
book [Patent Document 7] European Published Patent No. 953874A1
book [Patent Document 8] European Published Patent No. 953875A1
book [Patent Document 9] US Pat. No. 3,841,880 [Patent Document 10] JP-A-52-82423 [Patent Document 11] JP-A-2-28645 [Patent Document 12] JP-A-6-130549 [0004] The object of the present invention is to sharpen the object.
Improves anti-fogging performance without sacrificing temperature and processability
A photographic light-sensitive material. [0005] Means for Solving the Problems The present invention provides: (1) At least one yellow layer on each support
Blue sensitive emulsion layer containing coupler, magenta coupler
Containing green sensitive emulsion layer, red feeling containing cyan coupler
Silver halide color photographic light-sensitive material having a conductive emulsion layer
The blue-sensitive emulsion layer is represented by the following general formula (I):
At least one coupler and a-1)
And / or halogenation characterized by satisfying b-1)
Silver color photographic material, [0006] [Chemical 2] Where Q is -N = CN (R1)-
Represents a nonmetallic atom group forming a 5- to 7-membered ring. R1 is
Represents a substituent. R2 represents a substituent. m is 0 or 1 or more
It represents an integer of 5 or less. When m is 2 or more, a plurality of R2s are
They can be the same or different,
A ring may be formed. X is hydrogen atom or developing agent oxidation
Represents a group capable of leaving by a coupling reaction with a body. ) a-1) 0.5 ≦ Dmax (UV) / Dmin (UV) ≦ 1.1 (Where Dmax (UV) / Dmin (UV) is the maximum yellow color density)
Part absorbance at a certain wavelength UV) / (yellow minimum)
(Absorbance at a certain wavelength UV)
Among these numerical values, wavelength UV (UV is 340 nm or more and 450
It means the smallest value at a certain wavelength below nm. ) b-1) 1300 ≦ (BC) / A ≦ 20000 (Here, B is the maximum yellow color density, and C is the yellow maximum color density.
Represents a small color density and is transmitted when the support is a transmissive support.
Density, if the support is a reflective support, it means reflection density
The A is the amount of coupler represented by the general formula (I) (mo
l / m²). ) (2) In the general formula (I), Q is -C (-R1
1) = C (-R12) -SO₂-Or -C (-R1
1) a group represented by = C (-R12) -CO- (R1
1, R12 are bonded to each other to form 5-7 together with -C = C-
A group forming a member ring, or independently a hydrogen atom
Or a substituent)) according to (1),
Silver halide color photographic light-sensitive material, (3) The coupler represented by the general formula (I) is
It is represented by the general formula (II) and is described in (1)
Silver halide color photographic light-sensitive material, [0008] [Chemical 3] Wherein R 1, R 2, m and X are the general formulas
Represents the same as (I), R3 is a substituent, and n is 0.
Or it represents an integer of 1 or more and 4 or less. When n is 2 or more
The numbers R3 may be the same or different, and
To form a ring. (4) The support is a transmission support.
(1) None characterized by satisfying the following a-2)
(3) The silver halide color copy of any one of (3)
True photosensitive material, a-2) 0.5 ≦ Dmax (UV) / Dmin (UV) ≦ 0.9 (5) The support is a transmissive support, and the following a-2)
 And / or b-2)
The halogenation according to any one of (1) to (3)
Silver color photographic material, a-2) 0.5 ≦ Dmax (UV) / Dmin (UV) ≦ 0.9 b-2) 1700 ≦ (BC) / A ≦ 10000 (6) The support is a reflective support, and a-1)
 And / or b-3)
The halogenation according to any one of (1) to (3)
Silver color photographic material, a-1) 0.5 ≦ Dmax (UV) / Dmin (UV) ≦ 1.1 b-3) 4200 ≦ (BC) / A ≦ 20000 (7) Silver halide grains having a silver chloride content of 95 mol% or more
At least an emulsion layer containing a silver halide emulsion containing
(1) to (6)
Silver halide color photographic material, and (8) As described in (1) to (4), (5) or (7)
Silver halide color photographic light-sensitive material is imagewise exposed to black and white
It is characterized by color development after development and reversal processing.
A color image forming method is provided. In the present invention, Dmax (UV) / Dmin (UV)
But is measured as follows
It is. Fuji Photo Hui with white exposure at a color temperature of 4800 ° K
Rum Sharp Cut Filter SC-39 (Product
Name, can cut light with a wavelength shorter than 390 nm. Through
Exposure with an exposure time of 1 second and an exposure of 2000 CMS
Coloring as described below for each of the given and unexposed samples
After developing, these two exposed and unexposed samples
Measured by the following method for samples with high color density
Measured by the following method for samples with Dmax and low color density
Let the value to be Dmin. Contains color developing solution if necessary
As color development processing, transparent negative color photographic photosensitive material
When using a coating material, the development processing described in Example 1 described later is performed.
Applicable when using transmission positive type color photographic photosensitive material
Apply development processing-CR by the method described in Example 4 below.
However, when using a reflective support color photographic light-sensitive material,
The development process A described in Example 5 is applied. (Measurement method of Dmax and Dmin) Each sample after processing
10cm²40 containing 5 mg of actinase
Enzyme for 60 minutes gelatin in photographic composition layer with 20ml water at ℃
Decompose and elute photographic composition layer. After cooling to 25 ° C, 20
Extract oil-soluble components with ml of ethyl acetate. Once
-Do not use a tally evaporator under reduced pressure at 40 ° C.
Line up and contain 0.3% by weight acetic acid in a volumetric flask.
The final volume is made up to 10 ml with ethyl acetate. Actinase
The preparation of the solution from the enzymatic degradation to above is carried out in the dark.
This solution was 340 nm to 45 mm using a 1 cm quartz cell.
Measure the absorption spectrum up to 0nm, defined below
Calculate Dmax (UV) / Dmin (UV). Yellow maximum departure
The color density part is the value of the unexposed or unexposed sample.
In the density part of the sample that developed higher color with the low coupler
is there. The yellow minimum color density area is the range between exposed and unexposed.
Of the two samples, is the yellow coupler not colored?
Or the darkness of the sample that developed lower color with the yellow coupler.
The degree part. Definition of Dmax (UV) / Dmin (UV): (Yellow maximum color density)
Absorbance at a certain wavelength UV) / (yellow minimum emission)
(Absorbance at a certain wavelength UV)
Among the numerical values, wavelength UV (UV is 340 nm or more and 450 n
the smallest value). For example this
If the value is 400 nm and the minimum value is 0.5, Dmax (400
nm) / Dmin (400 nm) = 0.5. In the present invention, the range of Dmax (UV) / Dmin (UV)
Is preferably 0.50 or more and 1.10 or less, more preferably
Is 0.5 or more and 0.9 or less, more preferably 0.6 or more
1.0 or less, most preferably 0.7 or more and 0.9 or less
The The value of Dmin (UV) is large (At this time, Dmax (UV) / Dmin (UV)
Tends to reduce electrostatic fog.
preferable. However, Dmax (UV) / Dmin (UV) is less than 0.5
In this case, it is formed by coupling with the developing agent.
The dye has a low molar extinction coefficient or
Yields a yellowish color to the photosensitive material after processing.
Large and undesirable. Defined by (BC) / A in the present invention
The value to be set is preferably in the specific range. Measured below
The determination method will be described. Unexposed sample and yellow coupler included
White exposure of silver halide emulsion layer with color temperature of 4800 ° K
Sharp cut filter SC manufactured by Fuji Photo Film Co., Ltd.
An exposure amount of 200 with exposure time of 1 second through -39 (trade name)
Each sample given an exposure of 0 CMS (lx · s)
The above color development process is performed, and the yellow
Degree B and minimum coloring yellow density C
Use amount (coating amount) of the compound represented by (I) Amol /
m²(BC) / A is calculated and determined. Dark to use
For example, in the case of a reflective support photosensitive material,
Total (trade name, 436 nm, manufactured by Fuji Photo Film Co., Ltd.)
In the case of light-sensitive densitometers) and transparent support photosensitive materials, SC
D densitometer (trade name, manufactured by Fuji Photo Film Co., Ltd.)
For example). When a transmissive support is used in the present invention,
(BC) / A is preferably 1300 or more and 100
00 or less, more preferably 1700 or more and 1000
0 or less, more preferably 1800 or more and 8000 or less,
Most preferably, it is 1900 or more and 4000 or less. Main departure
In the case of using a reflective support photosensitive material in the bright
(BC) / A is preferably 4200 to 20000
More preferably 4500 or more and 10,000 or less.
Below, most preferably 4600 or more and 6500 or less. In the present invention, it is represented by the general formula (I).
Yellow coupler is in any proportion with other yellow couplers
Can be used in combination with the yellow of the present invention
The coupler ratio is preferably 10% or more by molar ratio, more
Preferably 25% or more, more preferably 50% or more,
Also preferably, it is 75% or more and 100% or less. [0017] The present invention will be described in detail below. (Dye-forming coupler) General formula of the present invention
A compound represented by (I) (in this specification, a dye-forming coupler)
Will also be described in detail. In the formula, R1 is a hydrogen atom.
Represents a substituent other than. Examples of this substituent include ha.
Logen atom, alkyl group (cycloalkyl group, bicyclo
Including alkyl groups), alkenyl groups (cycloalkenyl)
Group, including bicycloalkenyl group), alkynyl group, a
Reel group, heterocyclic group, cyano group, hydroxyl group,
Toro group, carboxyl group, alkoxy group, aryloxy
Si group, silyloxy group, heterocyclic oxy group, acyloxy
Si group, carbamoyloxy group, alkoxycarbonyl group
Xyl group, aryloxycarbonyloxy, amino group
(Including alkylamino and anilino groups), acylami
Group, aminocarbonylamino group, alkoxycarbonyl
Ruamino group, aryloxycarbonylamino group, sulfo
Famoylamino group, alkyl or arylsulfonyl
Amino group, mercapto group, alkylthio group, arylthio group
O group, heterocyclic thio group, sulfamoyl group, sulfo group,
An alkyl or arylsulfinyl group, alkyl or
Reelsulfonyl group, acyl group, aryloxycarbo
Nyl group, alkoxycarbonyl group, carbamoyl group,
Reel or heterocyclic azo group, imide group, phosphino group,
Phosphinyl group, phosphinyloxy group, phosphinyl
An amino group and a silyl group are mentioned. In addition, the above-mentioned substituent
May be further substituted with a substituent,
Examples include the above-mentioned groups. Preferably R1 is substituted or unsubstituted.
It is an alkyl group. R1 has 1 to 60 carbon atoms
Preferably, it is 6 or more and 50 or less, more preferably 11 or more and 4 or less.
0 or less is more preferable, and 16 to 30 is most preferable.
Yes. As a substituent when R1 is a substituted alkyl group,
Examples mentioned above as the substituent for R1 are given. Like
R1 is an unsubstituted alkyl group having 11 or more carbon atoms,
Or an alkoxy group or an amine at the 2nd, 3rd or 4th position.
It is an alkyl group substituted by a reeloxy group, and more preferably
Preferably, it is an unsubstituted alkyl group having 16 or more carbon atoms,
Is substituted with an alkoxy group or aryloxy group at the 3-position
An alkyl group, most preferably C₁₆H₃₃Group, C₁₈
H₃₇Group, 3-lauryloxypropyl group, or 3-
(2,4-di-t-amylphenoxy) propyl group
The In the general formula (I), Q is -N = CN.
Nonmetallic atomic group forming a 5- to 7-membered ring with (R1)-
Represents. Preferably the 5- to 7-membered ring formed is substituted or
Is an unsubstituted, monocyclic or fused heterocycle, and more
Preferably, the ring member atoms are carbon atoms, nitrogen atoms and sulfur atoms.
Selected from yellow atoms. More preferably, Q is -C
(-R11) = C (-R12) -SO₂-Or-
C (-R11) = C (-R12) -CO-
Represents a group. R11 and R12 are bonded to each other to form -C = C-
A group that forms a 5- to 7-membered ring with
Stands for a hydrogen atom or a substituent. 5 to 7 members formed
The member ring is a saturated or unsaturated ring, which is an alicyclic, aromatic
It may be a ring or a heterocycle, such as a benzene ring,
Lan ring, thiophene ring, cyclopentane ring, cyclohex
Sun ring. Further, as the substituent, the above-mentioned R1
The example given as a substituent is given. Each of these substituents
Or a ring formed by combining several substituents with each other,
Substituents (including those exemplified as the substituent for R1 described above)
May be substituted. In the general formula (I), R2 represents a hydrogen atom or less.
Represents an external substituent. Examples of this substituent include the aforementioned R1.
Examples of the substituents are as follows. Preferably
R2 represents a halogen atom (for example, a fluorine atom, a chlorine atom,
Bromine atoms), alkyl groups (eg methyl, isopropyl)
), Aryl groups (eg phenyl, naphthyl), a
Lucoxy group (eg methoxy, isopropyloxy),
Aryloxy groups (eg phenoxy), acyloxy
Groups (eg acetyloxy), amino groups (eg dimethyl)
Luamino, morpholino), acylamino groups (eg aceto
Toamide), sulfonamide groups (eg methanesulfone)
Amide, benzenesulfonamide), alkoxycarbo
Nyl group (eg methoxycarbonyl), aryloxy
Carbonyl group (eg phenoxycarbonyl), carba
Moyl group (for example, N-methylcarbamoyl, N, N-
Diethylcarbamoyl), sulfamoyl groups (eg N
-Methylsulfamoyl, N, N-diethylsulfamo
Yl), alkylsulfonyl groups (eg methanesulfonate)
), An arylsulfonyl group (for example, benzenesulfonate)
), A cyano group, a carboxyl group, and a sulfo group. Na
At least one R2 is ortho to the -CONH- group
Preferably in the ortho position, more preferably the ortho
R2 at the position is a halogen atom, alkoxy group, aryloxy
This is the case of a cis group or an alkyl group. In the general formula (I), m is 0 or more and 5 or less.
Represents an integer. When m is 2 or more, each R2 is
They can be the same or different and combine to form a ring
May be. In the general formula (I), X is a hydrogen atom or
Removable by coupling reaction with oxidized developer
Represents a group. Of these, X is a coupling with oxidized developer.
A group which can be removed by a reaction with a ring is preferred. X is developing agent
It is a group that can be removed by a coupling reaction with an oxidant.
Examples include groups leaving with nitrogen atoms and oxygen atoms.
Groups leaving, groups leaving with sulfur atoms, halogen atoms (eg
For example, chlorine atom, bromine atom) and the like. The group leaving from the nitrogen atom includes a heterocyclic ring.
Group (preferably 5-7 membered substituted or unsubstituted, saturated
Or unsaturated, aromatic (in this specification 4n + 2 cyclic
Meaning non-aromatic, having conjugated electrons)
It is a monocyclic or condensed heterocyclic group, more preferably
Is the ring atom is a carbon atom, nitrogen atom or sulfur atom
And selected from nitrogen, oxygen and sulfur atoms
5 or at least one heteroatom
Is a 6-membered heterocyclic group such as succinimide,
Rainimide, phthalimide, diglycolimide,
Roll, pyrazole, imidazole, 1,2,4-tri
Azole, tetrazole, indole, benzopyrazo
Ru, benzimidazole, benzotriazole, imida
Zolin-2,4-dione, oxazolidine-2,4-di
ON, thiazolidine-2-one, benzimidazoline-
2-one, benzoxazolin-2-one, benzothia
Zolin-2-one, 2-pyrrolin-5-one, 2-imi
Dazolin-5-one, indoline-2,3-dione,
2,6-dioxypurineparabanic acid, 1,2,4-tri
Azolidine-3,5-dione, 2-pyridone, 4-pyri
Don, 2-pyrimidone, 6-pyridazone, 2-pyrazo
2-amino-1,3,4-thiazolidine-4-o
), Carbonamide groups (eg acetamide, trifluoro)
Loacetamide), sulfonamide groups (eg methanesulfuric acid)
Honamide, benzenesulfonamide), arylazo
Groups (eg phenylazo, naphthylazo), carbamoy
A ruamino group (eg N-methylcarbamoylamino)
And so on. Of the groups leaving by a nitrogen atom, preferred
Is a heterocyclic group, more preferably a ring group.
Has 1, 2, 3 or 4 nitrogen atoms as constituent atoms
An aromatic heterocyclic group or the following general formula (L)
It is a heterocyclic group. [0025] [Formula 4] In the formula, L is from 5 to 6 together with -NC (= O)-.
It represents a residue that forms a membered nitrogen-containing heterocycle. these
Examples are given in the description of the heterocyclic group, and these
Is more preferable. Among them, L is a 5-membered nitrogen-containing hetero
Residues that form a ring are preferred. As the group capable of leaving by an oxygen atom, aryl
Oxy group (eg phenoxy, 1-naphthoxy), hete
Borocyclic oxy groups (eg pyridyloxy, pyrazolyloxy)
B) acyloxy group (eg acetoxy, benzoyl)
Oxy), alkoxy groups (eg methoxy, dodecylo)
Xy), a carbamoyloxy group (for example, N, N-die)
Rucarbamoyloxy, morpholinocarbamoyloxy
), An aryloxycarbonyloxy group (for example, phenoxy)
Noxycarbonyloxy), alkoxycarbonyloxy
Si group (eg methoxycarbonyloxy, ethoxycal
Bonyloxy), alkylsulfonyloxy groups (for example,
Methanesulfonyloxy), arylsulfonyloxy
Groups (eg benzenesulfonyloxy, toluenesulfo
Nyloxy) and the like. Groups leaving with an oxygen atom
Of these, preferred are an aryloxy group and an acyloxy group.
Si group and heterocyclic oxy group. Examples of the group capable of leaving by a sulfur atom include aryl.
Ruthio group (eg phenylthio, naphthylthio), hete
Borocyclic thio group (for example, tetrazolylthio, 1,3,4-thio)
Asiazolylthio, 1,3,4-oxazolylthio,
N-imidazolylthio), an alkylthio group (eg, methyl)
Ruthio, octylthio, hexadecylthio), alkyl
Sulfinyl groups (eg methanesulfinyl), aryl
Rusulfinyl group (eg benzenesulfinyl), a
A reelsulfonyl group (eg benzenesulfonyl), a
An alkylsulfonyl group such as methanesulfonyl
Can be mentioned. Of the groups leaving with a sulfur atom, preferred
Are arylthio groups, heterocyclic thio groups,
A ring thio group is more preferred. X may be substituted with a substituent,
Examples of the substituent for substituting X include those of the substituent of R1 described above.
Examples are given. X is preferably nitrogen
Groups leaving with elementary atoms, groups leaving with oxygen atoms, sulfur source
A group that leaves with a child, more preferably with a nitrogen atom
And more preferably a group that leaves with a nitrogen atom.
Are preferred in the order of the preferred groups mentioned above. X is photographic
It may be a service group. This photographically useful group includes development
Inhibitor, desilvering accelerator, redox compound, dye, coupler
-Or their precursors. In the present invention
In this case, it is preferably not a photographically useful group. coupler
Q, R1, X, to be immobilized in the photosensitive material
Or at least one of R2 has a total carbon number including substituents
It is preferably 8 or more and 50 or less, more preferably
The total carbon number is 10 or more and 40 or less. Next, the compound represented by the general formula (II) of the present invention.
Product (also referred to herein as a dye-forming coupler) in detail
explain. [0031] [Chemical formula 5] In the general formula (II), R1, R2, m,
X represents the same as described in the general formula (I).
The preferred range is also the same. In the general formula (II), R3 represents a substituent.
The Examples of this substituent include the examples of the substituent of R1 described above and
And those listed above. Preferably R3 is halogeno
Atoms (for example, fluorine, chlorine, bromine), atoms
Alkyl group (eg methyl, isopropyl), aryl group
(Eg phenyl, naphthyl), alkoxy groups (eg
Methoxy, isopropyloxy), aryloxy group
(Eg phenoxy), acyloxy groups (eg acetyl)
Ruoxy), amino groups (eg dimethylamino, morpho)
Lino), acylamino groups (eg acetamide),
Honamide group (eg methanesulfonamide, benzene)
Sulfonamide), alkoxycarbonyl groups (eg
Toxicarbonyl), aryloxycarbonyl groups (eg
For example, phenoxycarbonyl), carbamoyl group (eg
N-methylcarbamoyl, N, N-diethylcarba
Moyl), sulfamoyl groups (eg N-methylsulf
Amoyl, N, N-diethylsulfamoyl), Alky
Rusulfonyl group (eg methanesulfonyl), aryl
Sulfonyl group (eg benzenesulfonyl), cyano
Group, carboxyl group and sulfo group. N represents an integer of 0 or more and 4 or less. n is 2 or more
At the top, multiple R3s may be the same or different
Alternatively, they may combine with each other to form a ring. General formula
As a coupler represented by (I), (340n before color development)
High UV absorption density (around m to 400 nm)
The molar extinction coefficient of the dye is high, and the aforementioned UV absorption is
It is possible to use a coupler that is lower than the coupler absorption
Particularly preferred. In the present invention, the general formula (I) or
Of the couplers represented by formula (II), preferred specific examples
Although shown below, this invention is not limited to these.
Yes. The hydrogen atom at the coupling position is
The tautomers transferred onto the nitrogen of the C = N part bound to
It shall be included in the invention. [0036] [Chemical 6][0037] [Chemical 7][0038] [Chemical 8][0039] [Chemical 9][0040] Embedded image[0041] Embedded image[0042] Embedded image[0043] Embedded image[0044] Embedded image[0045] Embedded imageIn the following description, it is shown above.
Cited example compounds (also called dye-forming couplers)
Number in parentheses attached to each exemplified compound
Using (x) to display “coupler (x)”;
To do. The above general formula (I) or general formula
Specific synthesis examples of the compound represented by (II) are shown. Synthesis Example 1: Synthesis of coupler (1) Coupler (1) was synthesized by the route shown below. [0048] Embedded image38.8 g of 40% methylamine aqueous solution and
To a solution of 200 ml of cetonitrile, ortho-nitrobe under ice-cooling.
Stir 44.3 g of nzensulfonyl chloride in small portions.
While adding. Raise the system temperature to room temperature and
For 1 hour. Add ethyl acetate and water to perform liquid separation.
The machine layer was washed with dilute hydrochloric acid and saturated brine. Organic layer anhydrous
After drying over magnesium sulfate, the solvent is distilled off under reduced pressure,
Crystallization from a mixed solvent of chill and hexane yields 28.6 g of compound.
A product (A-1) was obtained. Reduced iron 44.8g, ammonium chloride
4.5g of um, 270ml of isopropanol, 45m of water
1 and heated to reflux for 1 hour. To this compound (A-
1) 25.9 g was added in small portions with stirring. More
The mixture was heated to reflux for 1 hour and then suction filtered through celite.
It was. Ethyl acetate and water are added to the filtrate for liquid separation, and the organic layer is saturated.
Washed with Japanese salt water. Organic layer with anhydrous magnesium sulfate
After drying, the solvent was distilled off under reduced pressure to give an oily product of compound (A-2)
21.5 g was obtained. Compound (A-2) 18.9 g, iminoate
Tellurium (A-0) hydrochloride 39.1 g, ethyl alcohol
The 200 ml solution was stirred for 1 day under heating to reflux. Further imino
Add 19.2 g of ether hydrochloride and add 1
Stir the day. Ethyl acetate and water are added for liquid separation, and the organic layer is separated.
Washed with dilute hydrochloric acid and saturated brine. The organic layer is anhydrous
After drying over gnesium, the solvent was distilled off under reduced pressure, ethyl acetate,
Crystallization from a hexane mixed solvent gave 21.0 g of compound (A
-3) was obtained. Compound (A-3) 5.6 g, 2-methoxy
Si-5-tetradecyloxycarbonylaniline 7.2
g. A solution of 20 ml of m-dichlorobenzene was heated under reflux.
Stir for 6 hours. After cooling, hexane was added for crystallization.
8 g of compound (A-4) was obtained. Compound (A-4) 5.
A solution of 4 g of methylene chloride in 110 ml of bromine under ice-cooling
10 ml of 0.45 ml of methylene chloride solution was added dropwise. Room
Stir at temperature for 30 minutes, then add methylene chloride and water to separate.
The organic layer was washed with saturated brine. Anhydrous magnesium sulfate
After drying with calcium, the solvent was distilled off under reduced pressure to give compound (A-5).
The crude product was obtained. 5,5-Dimethyloxazolidine-2,4
-3.5 g of dione and 3.8 ml of triethylamine in N, N-
Dissolve in 110 ml dimethylacetamide and add to room temperature
Below, all of the crude compound (A-5) synthesized earlier was
What was dissolved in 25 ml of cetonitrile was added dropwise over 10 minutes.
And stirred at room temperature for 2 hours. Add ethyl acetate and water
The organic layer was separated, and 0.1N aqueous potassium hydroxide solution, diluted
Washed with aqueous hydrochloric acid and saturated brine. Anhydrous magnesium sulfate
The solvent was distilled off under reduced pressure. Silica gel column
Mixing acetone and hexane by chromatography
Purify using solvent as the eluent and add ethyl acetate, hexa
Crystallization from a mixed solvent yields 4.7 g of coupler (1).
It was. Synthesis Example 2: Synthesis of coupler (3) Coupler (3) was synthesized by the route shown below. [0053] Embedded image3- (2,4-Di-t-amylphenoxy
Ii) propylamine 438 g, triethylamine 210
Add a solution of 1 ml of acetonitrile and 1 liter of acetonitrile under ice-cooling.
A small amount of 333 g of tonitrobenzenesulfonyl chloride
Add with stirring. Raise system temperature to room temperature
And stirred for an additional hour. Add ethyl acetate and water to separate
The organic layer was washed with dilute hydrochloric acid and saturated brine. Organic
After drying the layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure.
588 from a mixed solvent of ethyl acetate and hexane.
g of compound (B-1) was obtained. Reduced iron 84.0g, chloride
8.4 g of ammonium is 540 ml of isopropanol,
The mixture was dispersed in 90 ml of water and heated to reflux for 1 hour. Compound this
119 g of product (B-1) was added little by little with stirring.
It was. Heat for 2 hours under reflux, then absorb through Celite.
It was filtered. Ethyl acetate and water are added to the filtrate for liquid separation.
The machine layer was washed with saturated saline. The organic layer is anhydrous magnesium sulfate
After drying with calcium, the solvent was distilled off under reduced pressure to give compound (B-2).
Of oil was obtained. 111 g of compound (B-2), iminoate
(A-0) hydrochloride 68.4 g, ethyl alcohol 1
50 ml of the solution was stirred for 1 hour under heating to reflux. Further imino
Add 4.9 g of ether hydrochloride and add 30 more under reflux.
Stir for minutes. After cooling, suction filtration was carried out, and p-xylene 1 was added to the filtrate.
Add 00ml and heat for 4 hours while distilling off ethanol
Refluxed. Silica gel column chromatography of the reaction solution
-Using ethyl acetate / hexane mixed solvent as the eluent.
And purified by crystallization from methanol.
Compound (B-3) was obtained. Compound (B-3) 40.7
g, 18.5 g of 2-methoxyaniline, p-xylene 1
0 ml of the solution was stirred for 6 hours under reflux. Ethi acetate
And water, and the organic layer is diluted with dilute hydrochloric acid and saturated brine.
Washed with. After drying over anhydrous magnesium sulfate, reduce solvent
The pressure was distilled off. Silica gel column chromatography of the residue
-Using ethyl acetate / hexane mixed solvent as the eluent.
And 37.7 g of oily compound (B-4) was obtained.
Obtained. Compound (B-4) 24.8 g of methyl chloride
To a 400 ml solution of 2.1 ml of bromine under ice-cooling
35 ml of a tylene solution was added dropwise. Stir for 30 minutes under ice cooling
Then, add methylene chloride and water to separate the organic layer.
Washed with brine. Solvent after drying over anhydrous magnesium sulfate
Was distilled off under reduced pressure to obtain a crude product of the compound (B-5). 5,
5-Dimethyloxazolidine-2,4-dione 15.5
g, 16.8 ml of triethylamine was added to N, N-dimethylacetate.
Dissolved in 200 ml of toamide, synthesized earlier at room temperature
All of the crude product (B-5) was dissolved in acetonitrile 4
What was dissolved in 0 ml was added dropwise in 10 minutes and the temperature was raised to 40 ° C.
Warmed and stirred for 30 minutes. Separation with ethyl acetate and water
The organic layer was 0.1N aqueous potassium hydroxide solution, dilute hydrochloric acid.
Washed with water and saturated brine. The organic layer is anhydrous magnesium sulfate
After drying over um, the solvent was distilled off under reduced pressure. Silica gel residue
By column chromatography, acetone, hexane
Purify using the mixed solvent as eluent, and add ethyl acetate,
23.4 g of coupler (3) crystallized from a mixed solvent of xane
Got. Synthesis Example 3: Synthesis of coupler (6) Coupler (6) was synthesized by the route shown below. [0058] Embedded image21.4 g of benzylamine and acetonitrile
In a 200 ml solution, ortho-nitrobenzenesulfuric acid is cooled with ice.
Add 39.9 g of sulfonyl chloride while stirring little by little.
Added. Raise system temperature to room temperature
30 ml of ruamine was added dropwise and stirred for 1 hour. Ethi acetate
And water, and the organic layer is diluted with dilute hydrochloric acid and saturated brine.
Washed with. After drying the organic layer over anhydrous magnesium sulfate,
Evaporate the solvent under reduced pressure and remove from the mixed solvent of ethyl acetate and hexane.
Crystallization gave 31.2 g of compound (C-1). Reduced iron
44.8 g, ammonium chloride 4.5 g is isopropanol
270 ml of water and 45 ml of water, heated to reflux for 1 hour
did. To this, 29.2 g of compound (C-1) was agitated little by little.
Added with stirring. After heating at reflux for another hour,
Suction filtered through a light. Add ethyl acetate and water to the filtrate.
In addition, liquid separation was performed, and the organic layer was washed with saturated brine. Organic layer
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure,
25.5 g of an oily compound (C-2) was obtained. 19.7 g of compound (C-2), iminoate
Telline (A-0) hydrochloride 22.0 g, ethyl alcohol
The 200 ml solution was stirred for 4 hours under heating to reflux. Furthermore Imi
19.7 g of Noether hydrochloride was added and heated at reflux for 4 hours.
Stir for a while. Furthermore, p-toluenesulfonic acid monohydrate 13
g was added, and the mixture was stirred for 1 hour under reflux. Ethyl acetate, water
And the mixture is separated, and the organic layer is washed with dilute hydrochloric acid and saturated brine.
did. After drying the organic layer over anhydrous magnesium sulfate,
Evaporate under reduced pressure and crystallize from a mixed solvent of ethyl acetate and hexane.
3.2 g of compound (C-3) was obtained. Compound (C-
3) 2.9 g, 2-methoxy-5-tetradecyloxy
Carbonylaniline 2.9 g, o-dichlorobenzene 2
0 ml of the solution was stirred for 6 hours under reflux. Ethi acetate
And water, and the organic layer is diluted with dilute hydrochloric acid and saturated brine.
Washed with. After drying the organic layer over anhydrous magnesium sulfate,
The solvent was removed under reduced pressure. Silica gel column chromatography of the residue
The ethyl acetate / hexane mixed solvent is dissolved by
Purify by using as a separating solution, mixed with ethyl acetate and hexane.
Crystallization from the medium gave 3.8 g of compound (C-4). Compound (C-4) 3.4 g of methylene chloride
To 100 ml of the solution, 0.26 ml of bromine chloride under ice-cooling.
10 ml of a tylene solution was added dropwise. Stir at room temperature for 30 minutes
Then, add methylene chloride and water to separate the organic layer.
Washed with brine. Solvent after drying over anhydrous magnesium sulfate
Was distilled off under reduced pressure to obtain a crude product of compound (C-5). 1-
3.5 g of benzyl-5-ethoxyhydantoin, trie
2.1 ml of N-N-dimethylacetamide 10 ml of tilamine
This was dissolved in 0 ml, and the compound (C
-5) All of the crude product was dissolved in 20 ml of acetonitrile.
Was added dropwise over 30 minutes and stirred at 40 ° C. for 2 hours.
It was. Ethyl acetate and water are added to separate the organic layer.
Wash with constant aqueous potassium hydroxide, dilute hydrochloric acid, and saturated saline.
did. After drying over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure.
did. The residue was purified by silica gel column chromatography.
Using ethyl acetate / hexane mixed solvent as eluent
And crystallized from a mixed solvent of ethyl acetate and hexane.
3.0 g of coupler (6) was obtained. Synthesis Example 4: Synthesis of coupler (11) Coupler (11) is synthesized by the route shown below.
It was. [0063] Embedded imageCompound (D-0) (US Pat. No. 3,418,418)
Coupler 1) described in No. 80, 26.8 g, potassium carbonate
Dimethyl sulfate in a solution of 16.6 g and acetone 300 ml
The acid 13.9g was dripped and it stirred under heating-refluxing for 2 hours. Acetic acid
Ethyl and water are added for liquid separation, and the organic layer is diluted with dilute hydrochloric acid and saturated food.
Washed with brine. Dry organic layer over anhydrous magnesium sulfate
Thereafter, the solvent was distilled off under reduced pressure. Silica gel column chromatography residue
A mixture of acetone and hexane was detected by matography.
Purify using as eluent, mixed with ethyl acetate and hexane
Crystallization from the solvent gave 5.6 g of compound (D-1).
At this time, 10.9 g of compound (A-3) as a by-product
was gotten. Compound (A-3) synthesized in this way
The coupler (1) may be synthesized using 5.4 g of compound (D-1), 2-methoxy
-5-tetradecyloxycarbonylaniline 7.3
g. A solution of 50 ml of o-dichlorobenzene was heated under reflux.
Stir for 6 hours. Ethyl acetate and water are added for liquid separation, and organic
The layer was washed with dilute hydrochloric acid and saturated brine. Organic layer with anhydrous sulfur
After drying with magnesium acid, the solvent was distilled off under reduced pressure. Acetate
Crystallized from a mixed solvent of chill and methanol (D-2)
9.1 g was obtained. Compound (D-2) 4.8 g of methyl chloride
To a solution of 100 ml of lende, 0.4 ml of bromine chloride under ice-cooling
10 ml of methylene solution was added dropwise. Stir for 30 minutes under ice cooling
After adding methylene chloride and water, liquid separation was performed and the organic layer was saturated.
Washed with brine. After drying over anhydrous magnesium sulfate, dissolve
The medium was distilled off under reduced pressure to obtain a crude product of compound (D-3). 5
-3.8 g of butyloxazolidine-2,4-dione,
3.4 ml of reethylamine was added to N, N-dimethylacetamide
Compound dissolved in 100 ml and synthesized earlier at room temperature
All of the crude product of (D-3) is N, N-dimethylacetamide
What was dissolved in 50 ml was added dropwise over 30 minutes and 1 at room temperature.
Stir for hours. Ethyl acetate and water are added to separate the organic layer.
0.1N aqueous potassium hydroxide, dilute hydrochloric acid, saturated food
Washed with brine. Solvent after drying over anhydrous magnesium sulfate
Was distilled off under reduced pressure. Silica gel column chromatogram
Ace, tetrahydrofuran, hexa,
Purified using a mixed solvent as eluent, ethyl acetate,
Crystallization from a hexane mixed solvent gave coupler (11) 2.1.
g was obtained. Synthesis Example 5: Synthesis of coupler (13) Coupler (13) is synthesized by the route shown below.
It was. [0067] Embedded image Isatoic anhydride 48.9 g of acetonitrile
To 200 ml of solution, 32.2 g of benzylamine was added dropwise and stirred.
Stir. The temperature of the system is raised to 60 ° C., and further 10 minutes
Stir for a while. Ethyl acetate and water are added for liquid separation, and the organic layer is separated.
After drying over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure.
Crystallized from a mixed solvent of ether and hexane to give 54.6 g
Compound (E-1) was obtained. Compound (E-1) 24.9g, iminoether (A-
0) hydrochloride 21.6 g, p-toluenesulfonic acid monohydrate
Heat 200ml of 10.5g of ethyl alcohol in Japanese
Stir for 3 hours under reflux. After cooling, hydrochloric acid of imino ether
21.6 g of salt was added and the mixture was further stirred for 1 hour under reflux.
Ethyl acetate and water are added for liquid separation, and the organic layer is separated with anhydrous magnesium sulfate.
After drying with cesium, the solvent is distilled off under reduced pressure, and ether, hexane are removed.
Crystallization from a sun mixed solvent gave 33.6 g of compound (E-
2) was obtained. 6.5 g of compound (E-2), 2-chloro-
5-dodecyloxycarbonylaniline 6.5 g p-
50 ml of xylene solution was stirred for 2 hours under heating and reflux. The
Add 0.2 g of p-toluenesulfonic acid monohydrate
And stirred for 4 hours under reflux. Add ethyl acetate and water
The organic layer was washed with 1N hydrochloric acid and saturated brine.
It was. After drying over anhydrous magnesium sulfate, the solvent is distilled off under reduced pressure.
Crystallization from a mixed solvent of ethyl acetate and hexane gave 6.7
g of compound (E-3) was obtained. Compound (E-3) 5.
To 70 ml of 5 g of methylene chloride solution, 0.4 ml of bromine under ice-cooling.
15 ml of 8 ml methylene chloride solution was added dropwise. At room temperature
After stirring for 30 minutes, methylene chloride and water were added to separate the layers,
The organic layer was washed with saturated brine. Anhydrous magnesium sulfate
After drying, the solvent was distilled off under reduced pressure to obtain a crude compound (E-4).
I got a thing. 5,5-Dimethyloxazolidine-2,4-
3.5 g of dione and 3.8 ml of triethylamine were added to N, N-di
Dissolve in 50 ml of methylacetamide and add to this at room temperature.
All the crude products of compound (E-4) synthesized in
Drops dissolved in 50 ml tilacetamide in 10 minutes
And stirred at room temperature for 1 hour. Add ethyl acetate and water
Separate the organic layer into 1N aqueous potassium carbonate solution, 1N
Washed with aqueous hydrochloric acid and saturated brine. Anhydrous magnesium sulfate
The solvent was distilled off under reduced pressure. Silica gel column
By ethyl chromatography, mixed with ethyl acetate and hexane.
Purified using mixed solvent as eluent, amorphous state
4.0 g of coupler (13) was obtained. The light-sensitive material of the present invention is a transmission type color photographic light sensitive material.
In the case of materials, there is at least one photosensitive layer on the support.
What is necessary is just to be provided. A typical example is on a support
In addition, a plurality of sensors having substantially the same color sensitivity but different sensitivities
At least one light-sensitive layer comprising a silver halide emulsion layer.
A silver halide photographic light-sensitive material. The photosensitive layer
Is sensitive to blue, green and red light
Multi-layer silver halide color photo
In photosensitive materials, the arrangement of unit photosensitive layers is generally supported.
Red color-sensitive layer, green color-sensitive layer, blue color-sensitive layer
Installed. However, depending on the purpose, the installation order is reversed.
Even if there are different photosensitive layers in the same color-sensitive layer,
The order of installation can be taken. Silver halide sensation above
Non-photosensitive layers are provided between the light-sensitive layers and on the top and bottom layers.
May be. These include couplers and DIR compounds described below.
Products, color mixing inhibitors, and the like may be included. Each unit photosensitivity
The multiple silver halide emulsion layers that make up the layer are DE 1,121,4
High sensitivity milk as described in 70 or GB 923,045
The two layers, the agent layer and the low-sensitivity emulsion layer, are sequentially felt toward the support.
It is preferable to arrange so that the luminous intensity is low. Also, JP
Sho-57-112751, 62-200350, 62-206541, 62-206543
Low sensitivity emulsion on the side away from the support as described
A high-sensitivity emulsion layer may be provided on the side close to the layer and the support. As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High
Sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity
Red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL)
Or BH / BL / GL / GH / RH / RL or BH / BL / GH /
It can be installed in the order of GL / RL / RH. Also Tokusho
As described in the 55-34932 publication,
Arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the far side
You can also Also described in JP-A-56-25738 and 62-63936
As shown, blue sensitive from the side farthest from the support
It can also be arranged in the order of layer / GL / RL / GH / RH. Also as described in Japanese Patent Publication No. 49-15495
The upper layer is the most sensitive silver halide emulsion layer and the middle layer is
Lower sensitivity silver halide emulsion layer, lower layer in the middle
A silver halide emulsion layer with lower photosensitivity than the layer is placed
However, the photosensitivity decreased gradually toward the support.
An arrangement composed of three different layers can be mentioned. like this
Even if it is composed of three layers with different sensitivities,
In the same color-sensitive layer as described in 59-202464
Medium emulsion layer / high sensitivity milk from the side away from the support
It may be arranged in the order of the agent layer / low-sensitivity emulsion layer. Other,
High sensitivity emulsion layer / Low sensitivity emulsion layer / Medium sensitivity emulsion layer, or
Arrange in order of low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer
May be. In the case of four or more layers, the above
The arrangement may be changed as follows. US to improve color reproducibility
 4,663,271, 4,705,744, 4,707,436, JP 62-1
60448, 63-89850, BL, GL, RL, etc.
Layer effect donor layer with different spectral sensitivity distribution from the main photosensitive layer
(CL) placed adjacent to or close to the main photosensitive layer
Is preferred. Preferred silver halides used in the present invention
Contains about 30 mol% or less of silver iodide, silver iodobromide, iodine
Silver chloride or silver iodochlorobromide. Especially preferred
Contains about 2 mol% to about 10 mol% of silver iodide
Silver bromide or silver iodochlorobromide. Halo in photographic emulsions
Silver halide grains have a regular shape such as a cube, octahedron, or tetrahedron.
Those with regular crystals, spherical, plate-like irregularities
Those having a crystal form or having crystal defects such as twin planes
Or a composite form thereof. Silver halide
The diameter of the projected area is about 1 even for fine particles of about 0.2 μm or less.
Large dispersion grains up to 0μm, polydisperse emulsion
However, it may be a monodisperse emulsion. Silver halide photographic emulsion usable in the present invention
For example, Research Disclosure (RD)
No. 17643 (December 1978), 22-23, “I. Emulsions”
"Emulsion preparation and types"
No. 18716 (November 1979), 648 pages, No. 307105 (1989)
(November), pp. 863-865 and Grafkide, `` Physics of Photography
And Chemistry ", published by Paul Montel (P.Glafkides, Chimie)
et Phisique Photographiques, Paul Montel, 1967)
“Emulsion Chemistry” by Duffin, published by Focal Press
(G.F. Duffin, Photographic Emulsion Chemistry, Foc
al Press, 1966), Zericman et al.
Coating ”, published by Focal Press (V. L. Zelikman, et a
l., Making and Coating Photographic Emulsion, Foca
l Prepared using the method described in Press, 1964)
be able to. US 3,574,628, 3,655,394 and GB
Monodispersed emulsions described in 1,413,748 are also preferred. Also,
Tabular grains with an aspect ratio of about 3 or more are also
It can be used clearly. Especially preferred for improving storage over time
Or 50% or more of the total projected area has an aspect ratio of 8 or more
Using emulsions occupied by silver halide tabular grains
it can. The upper limit of the aspect ratio is not particularly limited, but 30
The following is preferred. Tabular grains are written by Gatov, photographic
Fick Science and Engineering (Gu
toff, Photographic Science and Engineering), No. 14
Volumes 248-257 (1970); US 4,434,226, 4,414,31
0, 4,433,048, 4,439,520 and GB 2,112,157
It can be easily prepared by the method described. Even if the crystal structure is uniform,
May be composed of heterogeneous halogen composition, layered structure
You may have done. Composition by epitaxial bonding
Different silver halides may be joined, for example
Contact with compounds other than silver halides such as rhodium silver and lead oxide
May be combined. Also a mixture of particles of various crystal forms
May be used. The above emulsion mainly forms a latent image on the surface.
Even if the surface latent image type is formed, the internal latent image type formed inside the particle
But any type that has a latent image on the surface or inside
However, it should be a negative emulsion. internal
Of the latent image type, the core / shell described in JP-A-63-264740
The internal latent image type emulsion may be used.
No. 59-133542. The thickness of this emulsion shell
However, 3 to 40 nm is preferred.
5 to 20 nm is particularly preferable. The silver halide emulsion is usually physically ripened and modified.
Use those that have undergone academic aging and spectral sensitization. This
Additives used in such processes are RD No. 17643, No. 187
16 and No. 307105
Are summarized in the table below. The photosensitive material of the present invention includes a photosensitive material.
Grain size, grain size distribution, ha
At least one characteristic of the rogen composition, particle shape and sensitivity
Two or more types of emulsions with different characteristics are mixed in the same layer
can do. Particle surface as described in US 4,082,553
Fogged silver halide grains, US 4,626,498, JP
Silver halide fogged inside the grain described in 59-214852
Grains, colloidal silver and photosensitive silver halide emulsion layers and / or
Or apply to a substantially non-photosensitive hydrophilic colloid layer
It is preferable. Halo with fog inside or on particle
Silver-genated grains are the unexposed and exposed areas of the photosensitive material.
Any halogen that can be developed uniformly (non-imagewise)
This refers to silver halide grains, and the preparation method is US 4,626,498.
This is described in JP-A-59-214852. Particle fogging
The inner core of the core / shell type silver halide grains formed
Silver halides that have different halogen compositions
Yes. Silver halide with fogged grain inside or surface
Silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide
This can also be used. These foggy halos
The average grain size of silver halide grains is 0.01-0.75μ
m, particularly 0.05 to 0.6 μm is preferable. The particle shape is
Regular grains or polydisperse emulsions may be used, but monodisperse
Property (at least the mass of silver halide grains or the number of grains)
95% has a particle size within ± 40% of the average particle size)
It is preferable that In the present invention, the non-photosensitive fine grain silver halide is used.
Is preferably used. Non-photosensitive fine particle halogenation
Silver is sensitive during imagewise exposure to obtain dye images.
Does not light and is not substantially developed in the development process
Silver halide fine grain, pre-coated
Preferably not. Fine grain silver halide is silver bromide
The content is 0 to 100 mol%, and silver chloride and
And / or silver iodide. Preferably silver iodide
In an amount of 0.5 to 10 mol%. Fine particle halogen
Silver halide has an average grain size (average value of equivalent circle diameter of projected area)
0.01 to 0.5 μm is preferable, 0.02 to 0.2 μm is more preferable
Yes. Fine grain silver halide is the usual photosensitive silver halide
It can be prepared by the same method. Surface of silver halide grains
Does not need to be optically sensitized and has no spectral sensitization.
It is important. However, prior to adding it to the coating solution,
I.e. triazole, azaindene, ben
Zothiazolium or mercapto compounds or
It is preferable to add a known stabilizer such as a zinc compound.
Good. In this fine grain silver halide grain-containing layer,
Silver can be contained. Coating of the light-sensitive material of the present invention
Cloth silver amount is 6.0g / m²The following is preferred, 4.5 g / m²The following is the most
preferable. Photographic additives that can be used in the present invention are also RD.
The following table shows the relevant locations.
It was.   Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer 23 pages 648 pages right column 866 pages 2. Sensitivity increasing agent, right column on page 648 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868     Supersensitizer 〜Page 649, right column 4). Brightening agent 24 pages 647 pages right column 868 pages 5). Light absorber, pages 25-26, page 649, right column, page 873     Filter ~ Left column on page 650     Dye, ultraviolet     Line absorber 6). Binder 26 pages 651 pages left column 873-874 pages 7). Plasticizer and lubricant page 27 page 650 right column page 876 8). Coating aid, pages 26-27, page 650, right column, pages 875-876     Surfactant 9. Static 27 pages 650 pages right column 876-877 pages         Inhibitor Ten. Matting agents 878-879. The light-sensitive material of the present invention contains various dye-forming caps.
Can be used, but the following couplers are especially
preferable. Yellow coupler: represented by formulas (I) and (II) of EP 502,424A
Couplers represented by formulas (1) and (2) of EP 513,496A
Coupler (especially Y-28 on page 18); claim 1 of EP 568,037A
A coupler represented by the formula (I): a column of US 5,066,576
Couplers represented by general formula (I) of 45 to 55 lines of 1;
A coupler represented by general formula (I) in paragraph 0008 of 4-4-2425
-Coupler according to claim 1 on page 40 of EP 498,381A1
(Especially D-35 on page 18); represented by formula (Y) on page 4 of EP 447,969A1
Couplers (especially Y-1 (17 pages), Y-54 (41 pages)); US
Expressed by formulas (II) to (IV) on lines 36 to 58 in column 7 of 4,476,219
Couplers (particularly II-17, 19 (column 17), II-24 (color
19)). Magenta coupler; JP-A-3-9737 (L-57 (bottom right of page 11), L-
68 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257, A-4-
63 (page 134), A-4 -73, -75 (page 139); EP 486,965 M-4, -6
(Page 26), M-7 (page 27); EP 571, 959A, M-45 (page 19);
5-204106 (M-1) (page 6); Japanese Patent Laid-Open No. 4-362631, paragraph 0237, M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4, 15 (pages 14 to 16); JP-A-4-43345, C-7, 10 (page 35), 3
4, 35 (page 37), (I-1), (I-17) (pages 42-43); JP-A-6-67385
 The cap represented by the general formula (Ia) or (Ib) of claim 1
Ra. Polymer coupler: P-1, JP-A-2-44345
P-5 (page 11). Caps with moderately diffusible coloring dye
US 4,366,237, GB 2,125,570, EP 96,87
Those described in 3B, DE 3,234,533 are preferred. Of coloring pigment
Couplers for correcting unwanted absorption are EP 456,257A1
It is represented by the formula (CI), (CII), (CIII), (CIV) described on page 5.
Yellow colored cyan coupler (especially YC-86 on page 84),
Yellow colored magenta coupler ExM-7 described in the EP
(Page 202), EX-1 (page 249), EX-7 (page 251), US 4,83
Magenta colored cyan coupler CC-9 as described in 3,069
(Column 8), CC-13 (Column 10), US 4,837,136 (2)
Ram 8), expressed by the formula (A) of claim 1 of WO92 / 11575
Colorless masking couplers (especially examples on pages 36-45)
Are preferred. As a coupler for releasing a photographically useful group
Include the following. Development inhibitor releasing compounds:
In formula (I), (II), (III), (IV) described on page 11 of EP 378,236A1
Compounds represented (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP 4
A compound represented by the formula (I) described on page 7 of 36,938A2 (special
D-49 (page 51)), EP 568,037A represented by the formula (1)
Compound (especially (23) (page 11)), described on pages 5-6 of EP 440,195A2
Compounds of the formulas (I), (II), (III)
I- (1)); Bleach accelerator releasing compound: EP 310, 125A2 page 5
Compounds of the formulas (I) and (I ′) (especially (60), (6) on page 61)
1)) and the formula (I) in claim 1 of JP-A-6-59411
Compounds (especially (7) (page 7)); ligand-releasing compounds: US
An expression represented by LIG-X described in claim 1 of 4,555,478
Compound (especially compound in columns 21 to 41 of column 12); leuco color
Element-releasing compound: Compound 1 in columns 3-8 of US 4,749,641
-6; Fluorescent dye-releasing compound: Claim 1 of US 4,774,181
COUP-DYE compounds (especially compounds in columns 7 to 10)
1 to 11); Development accelerator or fogging agent releasing compound: US
It is expressed by the formula (1), (2), (3) of column 3, 4,656,123.
(Especially column 25 (I-22)) and EP 450,637A2
ExZK-2 on page 75, lines 36-38; group that becomes pigment only after leaving
Releasing compounds: US Pat. No. 4,857,447 claim 1 formula (I)
(Especially Y-1 to Y-1 in columns 25 to 36)
9). Examples of additives other than couplers include the following:
Is preferred. Oil-soluble organic compound dispersion medium: JP-A 62-21
5272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,93
(Pages 140-144); Latec for impregnation of oil-soluble organic compounds
Latex described in US 4,199,363; oxidized developer
Scavenger: US 4,978,606, column 2, rows 54-62
Compounds of formula (I) (especially I-, (1), (2), (6), (12)
(Columns 4 to 5), US 4,923,787, column 2, lines 5 to 10
(Especially compound 1 (column 3); stain inhibitor: EP
 298321A, page 4, lines 30 to 33, formulas (I) to (III), especially I-47,72,
III-1,27 (pages 24-48); antifading agent: EP 298321A A-6,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), US5,122,444, columns 25-38 II-1 to II
I-23, especially III-10, EP 471347A, pages 8-12, I-1 to III-
4, especially II-2, US 5,139,931 columns 32-40 A-1 -48,
A-39, 42; especially the amount of coloring enhancer or color mixing inhibitor used
Material to be reduced: EP 411324A, pages 5 to 24, I-1 to II-15,
Especially I-46; Formalin Scavenger: EP 477932A 24
SCV-1 to 28 on page 29, especially SCV-8; Hardener: JP-A-1-21
4845, page 17, H-1,4,6,8,14, US 4,618,573 column 13 ~
Compounds (H-1 to 54) represented by formulas (VII) to (XII)
A compound represented by the formula (6) at the lower right of page 8 of Kaihei 2-214852 (H
-1 to 76), particularly as claimed in claim 1 of H-14, US 3,325,287
Compound; Development inhibitor precursor: JP-A 62-168139
P-24, 37, 39 (pages 6-7); as described in claim 1 of US 5,019,492
Listed compounds, in particular 28, 29 of column 7; preservatives, fungicides:
US 4,923,790, columns 3 to 15, I-1 to III-43, especially II-
1,9,10,18, III-25; Stabilizer, Antifoggant: US 4,923,
793, columns 6 to 16, I-1 to (14), especially I-1, 60, (2), (1
3), US Pat.No. 4,952,483 columns 25-32 compounds 1-65, special
36: Chemical sensitizer: Triphenylphosphine Sereni
Compound 50 of JP-A-5-40324; Dye: JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-
Pages 5, 27-29 V-1-23, especially V-1, EP 445627A 33-55
Pages F-I-1 to F-II-43, especially F-I-11, F-II-8, EP 457153A
17-28 pages III-1 to 36, especially III-1,3, WO 88/04794
8 to 26 Dye-1 to 124 microcrystalline dispersion, EP 319999A 6
Compounds 1-22 on page 11 and in particular the formula of compound 1, EP 519306A
(1) Compound D-1 to 87 represented by (3) (pages 3 to 28),
Compounds 1 to 22 represented by formula (I) of US 4,268,622 (color
3-10), US4,923,788 compounds of formula (I)
(1) to (31) (columns 2 to 9); UV absorber: JP-A 46-3335
Compounds (18b) to (18r), 101 to 427 represented by the formula (1)
(Pages 6 to 9), compound represented by formula (I) of EP 520938A (3)
 To (66) (pages 10 to 44) and the compound HB represented by the formula (III)
T-1 to 10 (p. 14), EP 521823A represented by formula (1)
Compounds (1) to (31) (columns 2 to 9). The present invention relates to black and white photographic paper and black and white negative fill.
Film, X-ray film, general or movie color
-Negative film, slide or TV color
Reversal film, color paper, color positive film
And various color photosensitive materials such as color reversal paper
Can be applied to. In addition, Japanese Patent Fair 2-32615, real public
Film unit with lens described in Hei 3-39784
It is suitable for use. Suitable support usable in the present invention
Is, for example, the aforementioned RD.No.17643, page 28, the same No.18716.
Page 647, right column to page 648, left column, and No. 307105, page 879.
It is described in. The light-sensitive material of the present invention comprises a side having an emulsion layer.
The total thickness of all hydrophilic colloid layers is 28μm or less
Is preferable, 23 μm or less is more preferable, and 18 μm or less
Is more preferable, and 16 μm or less is particularly preferable. Also membrane swelling
Moisture speed T_1/2Is preferably 30 seconds or less, more preferably 20 seconds or less.
Good. T_1/2Treated with color developer at 30 ° C for 3 minutes 15 seconds
90% of the maximum swollen film thickness reached sometimes is the saturated film thickness
Defined as the time until the film thickness reaches 1/2 of that.
Film thickness was measured at 25 ° C. and 55% relative humidity (2 days).
Means film thickness, T_1/2A.Green et al.
Photographic Science and Engineering
Alling (Photogr.Sci.Eng.), Volume 19, 2, 124-129
To use the described type of spherometer
More measurable. T_1/2Gelati as a binder
Add a hardener to the skin, or
It can be adjusted by changing. Also swelling
The rate is preferably 150 to 400%. The swelling rate is the one I mentioned earlier
From the maximum swollen film thickness under conditions, the formula: (maximum swollen film thickness-film
(Thickness) / film thickness. The light-sensitive material of the present invention comprises a side having an emulsion layer.
On the other side, a hydrophilic core with a total dry film thickness of 2 μm to 20 μm.
It is preferable to provide a Lloyd layer (referred to as a back layer).
In this back layer, the aforementioned light absorber, filter dye,
UV absorber, antistatic agent, hardener, binder
-Including plasticizers, lubricants, coating aids, and surfactants.
It is preferable. The swelling rate of this back layer is 150-500%
Is preferred. The light-sensitive material of the present invention has the above-mentioned RD.
Pages 28-29, No. 18716, column 651, left column to right column, and column N
o.307105 by ordinary methods described on pages 880-881
It can be developed. Next, the color negative film used in the present invention.
A processing solution for rumm will be described. Used in the present invention
For the color developer, page 9, upper right column, line 1 of JP-A-4-21739
The compounds listed in page 11, lower left column, line 4 can be used.
The Especially as a color developing agent for quick processing
Is 2-methyl-4- [N-ethyl-N- (2-hydro
Xylethyl) amino] aniline, 2-methyl-4- [N
-Ethyl-N- (3-hydroxypropyl) amino] a
Nilin, 2-methyl-4- [N-ethyl-N- (4-H
Droxybutyl) amino] aniline is preferred. these
The color developing agent is 1 liter of color developer (hereinafter referred to as “L”).
Also written. ) Use within the range of 0.01 to 0.08 mole
In particular, 0.015 to 0.06 mol, more preferably 0.0
It is preferable to use in the range of 2 to 0.05 mol. Again
The color developer replenisher contains 1.1 to 3 times the color density.
It is preferable to contain an image active agent, particularly 1.3 to 2.5.
It is preferable to contain a double. As a preservative for the color developer, hydroxy
Luamine can be used widely, but requires higher preservability
In this case, alkyl group, hydroxyalkyl group, sulfo group
Has a substituent such as an alkyl group or carboxyalkyl group
Hydroxylamine derivatives are preferred, specifically
N, N-di (sulfoethyl) hydroxylamine, monomer
Tylhydroxylamine, dimethylhydroxylamine
, Monoethylhydroxylamine, diethylhydroxyl
Ruamine, N, N-di (carboxyethyl) hydroxyl
Amines are preferred. Of these, N, N-di (s)
Ruphoethyl) hydroxylamine is preferred. These are hi
May be used in combination with droxylamine, but preferably
Use one or more types instead of roxylamine
It is preferable. Preservative is 0.02-0.2 mol per liter
It is preferable to use in a range, particularly 0.03-0.15 mol,
Furthermore, it is preferable to use in the range of 0.04 to 0.1 mol.
Yes. In the replenisher, the same as in the case of the color developing agent.
In addition, a preservative at a concentration 1.1 to 3 times the mother liquor (treatment tank solution)
It is preferable to contain. The color developer contains an oxide of the color developing agent.
Sulphites are used as tarring inhibitors. Sulfite
Is preferably used in the range of 0.01 to 0.05 mole per liter.
In particular, the range of 0.02 to 0.04 mol is preferable. Replenisher
In this case, use it at a concentration 1.1 to 3 times higher than these.
Is preferred. The pH of the color developer is in the range of 9.8 to 11.0.
Is preferable, but 10.0 to 10.5 is particularly preferable.
In liquid, high value in the range of 0.1 to 1.0 from these values
It is preferable to set to. To stabilize such pH
Carbonate, phosphate, sulfosalicylic acid
Known buffering agents such as salts and borates are used. Coloring
The replenishment amount of the image liquid is 1m of photosensitive material.²80-1300mL is preferred
However, from the viewpoint of reducing the environmental pollution load, the lesser
Is preferred, specifically 80 to 600 mL, more preferably 80 to 400 mL.
preferable. The bromide ion concentration in the color developer is
Usually, it is 0.01-0.06 mole per liter, but keeps sensitivity.
While suppressing fogging and improving discrimination
And for the purpose of improving graininess,
It is preferable to set to 0.015 to 0.03 mol. Bromide
When setting the ON concentration to such a range,
Should contain the bromide ion calculated by the following formula
Yes. However, when C is negative, the replenisher contains bromide ion.
It is preferable not to contain any hydrogen. C = A-W / V C: Concentration of bromide ion in color developer replenisher (mol / L) A: Bromide ion concentration (molar) in the target color developer
/ L) W: 1m²If the photosensitive material is color developed,
Amount of bromide ion eluted from the color developer (mol) V: 1m²Replenishment amount of color developer replenisher for various photosensitive materials
(L). In addition, when the replenishment amount is reduced or high bromide
If the ion concentration is set, it is a method to increase the sensitivity.
1-phenyl-3-pyrazolidone and 1-phenyl-
2-methyl-2-hydroxymethyl-3-pyrazolidone
And pyrazolidones represented by 3,6-dithia-1,8
-Thioether compounds such as octanediol
It is also preferred to use any development accelerator. In the present invention
Japanese Patent Application Laid-Open No. 4-125558 discloses a processing solution having bleaching ability.
The compounds listed in page 16, lower left column, line 16 to page 7, lower left column, line 6
Processing conditions can be applied. Bleach is redox
It is preferable that the position is 150 mV or more.
Are preferably those described in JP-A-5-72694 and JP-A-5-17312.
In particular, 1,3-diaminopropanetetraacetic acid, JP-A-5-17
Ferric complex salt of the compound of Example 1 on page 7 of No. 3312 is preferred
Yes. In order to improve the biodegradability of the bleaching agent
Are disclosed in JP-A-4-51845, 4-268552, EP588,289, 591,
934, bleaching compound ferric complex described in JP-A-6-208213
It is preferable to use it as an agent. The concentration of these bleaches
The degree is preferably 0.05-0.3 mol per liter of liquid with bleaching ability.
Especially for the purpose of reducing environmental emissions
It is preferable to design at 0.1 mol to 0.15 mol. Also bleaching ability
When the solution having a bleaching solution is 0.2 mol to 1 mol per liter
It is preferable to contain bromide
It is preferable to contain a mole. As a replenisher for a solution having bleaching ability, basically,
The concentration of each component calculated by the following formula is included. this
Thus, the concentration in the mother liquor can be kept constant. CR = CT × (V1 + V2) / V1 + CP CR: concentration of the component in the replenisher CT: Concentration of components in mother liquor (treatment tank liquid) CP: Concentration of components consumed during processing V1: 1m²Replenisher for bleaching light sensitive materials
Replenishment volume (mL) V2: 1m²Brought in from the previous bath by the photosensitive material
(ML). In addition, the bleaching solution contains a pH buffer.
In particular, succinic acid, maleic acid, malon
Dicals with low odor such as acid, glutaric acid and adipic acid
It is preferable to contain a boronic acid. Also, JP-A-53-9
Known bleaching described in 5630, RD No. 17129, US 3,893,858
It is also preferred to use accelerators. Photosensitive material for bleaching solution
1m²May be replenished with 50-1000mL of bleach replenisher
Preferably, especially 80-500 mL, more preferably 100-300 mL supplement.
It is preferable to charge. Air bleach
Preferably. Regarding a processing solution having a fixing ability, Japanese Patent Application Laid-Open (JP-A) No. Hei 11 (1999).
4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19
The compounds and processing conditions can be applied. Special
In addition, in order to improve the fixing speed and preservability, JP-A-6-30
1169 compounds represented by general formulas (I) and (II)
Alternatively, it can be used in combination with a processing solution that has fixing ability.
Are preferred. Also p-toluenesulfinate
Therefore, use sulfinic acid described in JP-A-1-224762.
In any case, it is preferable in terms of improving the preservation property. Liquid with bleaching ability
In order to improve desilvering properties, click
It is preferable to use ammonium as the on-
For the purpose of reducing pollution, ammonium is reduced or reduced.
B is preferable. For bleaching, bleach-fixing, and fixing processes
The jet agitation described in JP-A-1-309059
It is particularly preferred. Of the replenisher in the bleach-fixing or fixing step
Replenishment amount is 1m photosensitive material²100-1000mL per
Preferably 150 to 700 mL, particularly preferably 200 to 600 mL.
The Various silver recovery units are installed in the bleach-fixing and fixing processes.
It is preferred to collect silver by installing on line or offline
That's right. By installing inline, the silver concentration in the liquid
As a result, the amount of replenishment can be reduced.
it can. In addition, silver is collected offline and the remaining liquid is used as a replenisher.
It is also preferable to reuse it. Bleach fixing process and fixing process
The process can consist of multiple processing tanks, each tank
It is preferable to use a multi-stage countercurrent system with cascade piping.
Yes. Generally 2 tanks due to the balance with the size of the developing machine
The cascade configuration is efficient, the front tank and the rear tank
The ratio of treatment times in the tanks of 0.5: 1 to 1: 0.5
It is preferable to be in the range, in particular 0.8: 1 to 1: 0.8.
A range is preferred. For bleach-fixing solutions and fixing solutions,
A free chelating agent that is not a metal complex from the above viewpoint
It is preferable that these chelating agents and
The biodegradable chelating agent described for the bleach solution.
It is preferable to use it. Regarding the water washing and stabilization process,
JP 4-125558, page 12, lower right column, line 6 to page 13, lower right column, page 16
The contents described in the row can be preferably applied. Special
In addition, EP 504,60 replaces formaldehyde in the stabilizer.
9, azolylmethylamines described in 519,190 and JP
Use N-methylol azoles described in Hei 4-362943
Or magenta couplers with two equivalents
A surfactant solution that does not contain image stabilizers such as dehydride
It is preferable from the viewpoint of maintenance of the work environment. Ma
In addition, dust adheres to the magnetic recording layer applied to the photosensitive material.
In order to reduce this, the stabilizer described in JP-A-6-289559 is preferred.
Can be used. Washing with water and the replenishment amount of the stabilizing solution are as follows.
m²80 to 1000 mL per unit is preferable, particularly 100 to 500 mL.
In addition, 150 to 300 mL is necessary for washing and stabilizing
This is a preferable range in terms of reducing waste liquid for environmental conservation.
The In processing with such replenishment amount,
Thiabendazole, 1, to prevent rear and pupae reproduction
2-benzoisothiazolin-3-one, 5-chloro-2-
Known antifungal agents such as methylisothiazolin-3-one
And antibiotics such as gentamicin, ion exchange resin, etc.
It is preferable to use water deionized by.
Deionized water and antibacterial agents and antibiotics can be used in combination.
It is effective. The liquid in the water washing or stabilizing liquid tank is
JP-A-3-46652, 3-53246, 3-355542, 3-111448,
The reverse osmosis membrane treatment described in 3-1226030 is performed to reduce the replenishment amount.
The reverse osmosis membrane in this case is a low pressure
A reverse osmosis membrane is preferred. For processing in the present invention
Is disclosed in the Japan Society for Invention and Innovation Technical Bulletin No. 94-4992.
It is especially preferred to perform evaporation correction of the treated liquid
Yes. In particular, based on (Formula-1) on page 2,
A method of correcting using boundary temperature and humidity information is preferred.
Yes. The water used for evaporation correction is taken from the water replenishment tank.
In this case, it is recommended to remove the water as replenishment water.
It is preferable to use ionic water. As the treatment agent used in the present invention, the above-mentioned treatment agents are used.
From the third page, right column, line 15 to page 4, left column, line 32
Those are preferred. Moreover, as a developing machine used for this,
Film processor described in lines 22 to 28 in the right column on page 3
-Is preferred. Preferred treatment agents for carrying out the present invention
For specific examples of dynamic developing machines and evaporation correction methods,
From the 11th page, right column, line 11 to the 7th page, right column, last line
It is listed. Supply form of treatment agent used in the present invention
Is a solution in concentrated form or concentrated form,
Or granule, powder, tablet, paste, emulsion, etc.
It may be a form. As an example of such a treatment agent,
63-17453 discloses a liquid agent contained in a low oxygen permeable container,
4-19655 and 4-230748 are vacuum-packed powder or
Granules, 4-221951, condyles containing water-soluble polymer
JP-A 51-61837, JP-A 6-102628 discloses tablets, JP
57-500485 discloses a paste-like treatment agent,
Either can be used preferably, but is it easy to use?
Use a liquid that has been prepared in advance for use.
It is preferable. In the container for storing these treatment agents,
Ethylene, polypropylene, PVC, polyester
Tylene terephthalate, nylon, etc. alone or
Used as a composite material. These are the required oxygen permeability.
It is selected according to the transient level. Color developer etc.
For liquids that are susceptible to oxidation, materials with low oxygen permeability are preferred.
More specifically, polyethylene terephthalate and poly
A composite material of ethylene and nylon is preferred. These materials
The material is 500-1500μm thick, used for containers, and oxygen permeable.
20 mL / m transient²・ 24hrs ・ atm or less is preferred
Yes. Next, the color reversal film used in the present invention.
The processing solution for the liquid will be described. For color reversal film
As for the processing of, known technology issued by Aztec Co., Ltd.
Issue 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and
Page 15 line 8 to page 24 line 2
Any of the contents can be preferably applied. Kara
-Adjust image stabilizers for reversal film processing
Contained in bath or final bath. Such as image stabilizer
In addition to formalin, formaldehyde sodium bisulfite
Thorium and N-methylolazoles
Formaldehyde sodium sulfite from the viewpoint of working environment
Or N-methylolazoles are preferred, N-methylo
As the azole azoles, N-methylol triazo is particularly useful.
Is preferred. Also for color negative film processing
Color developer, bleach, fixer, washing water, etc.
Is also preferred for processing color reversal film
Can be applied. Preferred color reversal film including the above contents
E-manufactured by Eastman Kodak Company
6 treatment agent and CR-56 treatment of Fuji Photo Film Co., Ltd.
Agents (both are trade names). Next, the magnetic recording preferably used in the present invention.
The recording layer will be described. Magnetic recording layer means magnetic particles
Aqueous or organic solvent-based coating liquid dispersed in binder
Is coated on a support. Used in the present invention
Magnetic particles are γFe₂O_ThreeFerromagnetic iron oxide such as Co-coated γF
e₂O_Three, Co-coated magnetite, Co-containing magnetite, strong magnetic
Chrome dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal
Ba ferrite, Sr ferrite, Pb ferrite, Ca blowjob
Can be used. Co-coated γFe₂O_ThreeCo adherence strength such as
Magnetic iron oxide is preferred. The shape is needle-like, rice grain, sphere
The shape may be any of a shape, a cube shape, a plate shape, and the like. S in specific surface area
_BETAt 20m²/ g or more is preferable, 30m²/ g or more is particularly preferred
Yes. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10^Four
~ 3.0 × 10^FiveA / m, particularly preferably 4.0 × 10^Four~ 2.5 ×
Ten^FivemA / m. Ferromagnetic particles, silica and / or
May be surface-treated with alumina or an organic material.
Further, the magnetic particles are as described in JP-A-6-61032
Silane coupling agent or titanium coupling on the surface
It may be treated with an adhesive. JP-A-4-259911, 5-8165
Magnetic particles with inorganic and organic coatings on the surface described in No. 2
Can also be used. The binder used for the magnetic particles is a special one.
Thermoplastic resins and thermosetting resins described in Kaihei 4-19569
Ray-curable resin, reactive resin, acid, alkali or biodegradation
Polymer, natural polymer (cellulose derivative, sugar derivative)
Body etc.) and their mixtures can be used
The Tg of the above resin is -40 ° C to 300 ° C, and the mass average molecular weight is
20,000 to 1,000,000. For example, vinyl copolymer, cellulose
Cellulose acetate, cellulose triacetate, cellulose
Cellulose acetate propionate, cellulose acetate
Cells such as butyrate and cellulose tripropionate
Loose derivatives, acrylic resin, polyvinyl acetal tree
Fats can be mentioned, and gelatin is also preferred. Especially cell
Loose di (tri) acetate is preferred. binder
Epoxy, aziridine, and isocyanate racks
It can be cured by adding a crosslinking agent. Isocyanine
As the salt-based crosslinking agent, tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate, hexa
Methylene diisocyanate, xylylene diisocyanate
Isocyanates, etc., these isocyanates
Products of alcohols and polyalcohols (eg tolylene)
Of 3 mol of diisocyanate and 1 mol of trimethylolpropane
Reaction product), and condensation of these isocyanates
For example, polyisocyanate produced from
For example, it is described in JP-A-6-59357. Disperse the above-mentioned magnetic material in the binder.
The method described in JP-A-6-35092
In addition, kneaders, pin type mills and annular type mills are preferred.
A combination is also preferable. Dispersant described in JP-A-5-088283
In addition, other known dispersants can be used. Magnetic recording layer
The thickness is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm,
More preferably, it is 0.3 μm to 3 μm. Magnetic particles and bar
The mass ratio of the inder is preferably from 0.5: 100 to 60: 100
More preferably, it is 1: 100-30: 100. Magnetic particles
The coating amount is 0.005-3g / m², Preferably 0.01-2g / m²The
More preferably, 0.02 to 0.5 g / m²It is. Permeation of magnetic recording layer
The overyellow density is preferably 0.01 to 0.50, and 0.03 to 0.20.
Is more preferable, and 0.04 to 0.15 is particularly preferable. Magnetic recording
The layer is coated or printed on the back side of the photographic support.
Or it can provide in stripe form. Magnetic recording layer
Air doctor, blade, air
A knife, squeeze, impregnation, reverse roll, transformer
Fur roll, gravure, kiss, cast, spray,
Dips, bars, extrusions, etc. are available
A coating solution described in JP-A-5-341436 is preferable. For the magnetic recording layer, improved lubricity, curl adjustment,
Combines functions such as antistatic, adhesion prevention, and head polishing
Or provide another functional layer for these functions.
And at least one of the particles may be Morse.
Abrasives of non-spherical inorganic particles having a hardness of 5 or more are preferred. Non
The composition of spherical inorganic particles includes aluminum oxide, oxidation
Chrome, silicon dioxide, titanium dioxide, silicon carbide
Oxide such as silicon carbide, carbide such as silicon carbide, titanium carbide, die
A fine powder such as almond is preferred. These abrasives are
Surface of silane coupling agent or titanium coupling
It may be treated with an agent. These particles are added to the magnetic recording layer.
In addition, an overcoat on the magnetic recording layer (example
For example, a protective layer or a lubricant layer may be used. Use at this time
The binders mentioned above can be used, preferably magnetic.
The same binder as the recording layer is preferable. Has a magnetic recording layer
US 5,336,589, 5,250,404,
 5,229,259, 5,215,874, EP 466,130
The Next, a support used in the present invention, preferably
Describes the polyester support, but the photosensitive material described later,
Details including processing, cartridges and examples
For example, published technical bulletin, public technical number 94-6023 (Invention Association; 199
4.3.15.). The polyester used in the present invention
Steal is preferably a diol component and an aromatic dicarboxylic acid
And 2,6 as aromatic dicarboxylic acids
-, 1,5-, 1,4-, and 2,7-naphthalenedica
Rubonic acid, terephthalic acid, isophthalic acid, phthalic acid, di
Diethylene glycol and triethylene glycol as all
Coal, cyclohexanedimethanol, bisphenol
A and bisphenol are mentioned. With this polymer
Polyethylene terephthalate, polyethylene naphthalate
Phthalate, polycyclohexanedimethanol terephthal
Homopolymers such as rate can be mentioned. Especially good
The best one is 50 mol% 2,6-naphthalenedicarboxylic acid
Polyester containing ˜100 mol%. Especially preferred
New is polyethylene 2,6-naphthalate.
The average molecular weight range is about 5,000 to 200,000. Main departure
Bright polyester has a Tg of 50 ° C or higher and 90 ° C or lower.
Above is preferred. Next, the polyester support has a curl.
In order to make it harder, the heat treatment temperature is 40 ° C or more and less than Tg, more preferable
The heat treatment is preferably performed at Tg−20 ° C. or more and less than Tg. Heat treatment
It may be carried out at a constant temperature within this temperature range and should not be cooled.
You may heat-process. This heat treatment time is 0.1 hour or more.
Upper 1500 hours or less, more preferably 0.5 hours or more 200 hours
Or less. The heat treatment of the support is carried out in the form of a roll
Alternatively, it may be carried out while being conveyed in a web form.
Provide unevenness on the surface (eg SnO₂And Sb₂O_FiveNo conductivity such as
The surface shape may be improved by applying fine particles. Another end
Winding by knurling the part and raising only the edges slightly
Hope to devise measures such as preventing the core from being cut off
Good. These heat treatments are performed after forming the support, after the surface treatment,
After applying the back layer (antistatic agent, slip agent, etc.), undercoat application
It may be performed at any later stage. Preferred is antistatic
After applying the stop agent. This polyester has UV absorber
You may knead. To prevent light piping,
Mitsubishi Chemical's Diaresin (trade name), Nippon Kayaku's Kayase
t (trade name) and other dyes commercially available for polyester
The purpose is achieved by kneading the material or pigment
Is possible. Next, in the present invention, the support and the light-sensitive material constituting layer are contacted.
In order to make it wear, it is preferable to surface-treat. Chemical shop
, Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment
, High frequency treatment, glow discharge treatment, active plasma treatment,
Laser treatment, mixed acid treatment, ozone oxidation treatment, etc.
An activation process is mentioned. Preferred among surface treatments
UV irradiation treatment, flame treatment, corona treatment, glow treatment
Is. Next, the primer method will be described.
Two or more layers may be used. As binder for undercoat layer, salt
Vinyl chloride, vinylidene chloride, butadiene, methacryl
Among acids, acrylic acid, itaconic acid, maleic anhydride, etc.
Starting with copolymers selected from monomers selected from
Polyethyleneimine, epoxy resin, grafting
Examples include gelatin, nitrocellulose, and gelatin.
Resorcin and p-chloro as compounds to swell the support
There is ruphenol. As a gelatin hardener for the undercoat layer
Are chromium salts (such as chromium alum), aldehydes (such as
Mualdehyde, glutaraldehyde, etc.), isocyania
Nates, active halogen compounds (2,4-dichloro-6
-Hydroxy-S-triazine, etc.), epichlorohydride
List phosphorous resins, active vinyl sulfone compounds, etc.
Can do. SiO₂, TiO₂, Inorganic fine particles or polymethyl
Tacrylate copolymer fine particles (0.01-10μm) mat
You may make it contain as an agent. In the present invention, an antistatic agent is preferred.
Used. These antistatic agents include carbo
Polymers containing acids and carboxylates and sulfonates;
List thionic polymers and ionic surfactant compounds
You can. Most preferred as antistatic agent
ZnO, TiO₂, SnO₂, Al₂O_Three, In₂O_Three, SiO₂, MgO, Ba
O, MoO_Three, V₂O_FiveAt least one volume selected from
Resistivity is 10⁷Ω · cm or less, more preferably 10^FiveΩ ・ cm or less
A particle size of 0.001 to 1.0 μm
Or fine particles of these complex oxides (Sb, P, B, In, S, Si, C, etc.)
Particles, sol-like metal oxides, or composites of these
Fine oxide particles. As content to photosensitive material, 5-5
00mg / m²Is particularly preferably 10 to 350 mg / m²In
The Conductive crystalline oxide or composite oxide thereof and vine
The ratio of the amount of der is preferably 1/300 to 100/1, more preferably
Is 1/100 to 100/5. The light-sensitive material of the present invention is preferably slippery.
Yes. The slip agent-containing layer can be used on both the photosensitive layer surface and the back surface.
And are preferred. The preferred sliding property is a dynamic friction coefficient of 0.
25 or less and 0.01 or more. The measurement at this time is a step with a diameter of 5 mm.
Represents the value when transported at 60 cm / min for a ballless ball (25
℃, 60% RH). In this evaluation, the photosensitive layer surface is used as a counterpart material.
Even if it is replaced with, the value is almost the same level. Used in the present invention
Possible slip agents include polyorganosiloxane, high grade
Fatty acid amide, higher fatty acid metal salt, higher fatty acid and higher fatty acid
Polyorganosiloxane, such as ester of rucol
As polydimethylsiloxane, polydiethylsiloxane
Xylene, polystyrylmethylsiloxane, polymethylphenol
For example, phenylsiloxane can be used. As an additive layer
The outermost layer of the emulsion layer and the back layer are preferable. Especially polyji
Esters with methyl siloxane or long chain alkyl groups
preferable. The photosensitive material of the present invention preferably has a matting agent.
That's right. Matting agent can be used on either emulsion side or back side
Although it is good, it is particularly preferable to add it to the outermost layer on the emulsion side.
The matting agent may be soluble or insoluble in the processing solution.
Preferably, both are used together. For example, polymethyl
Methacrylate, poly (methyl methacrylate / metac
Rylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles, etc.
Is preferred. The particle size is preferably 0.8-10 μm.
The particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.1.
It is preferable that more than 90% of the total number of particles is contained during
Yes. In order to improve matting properties, fine particles of 0.8μm or less
It is also preferable to add them simultaneously, for example polymethyl methacrylate
Relate (0.2μm), poly (methyl methacrylate / medium
Tacrylic acid = 9/1 (molar ratio), 0.3μm)), polystyrene
Particles (0.25μm) and colloidal silica (0.03μm)
Can be mentioned. Next, the film patrol used in the present invention.
I will write about Ne. Main material of patrone used in the present invention
The material may be metal or synthetic plastic. Preferred plastic
The stick material is polystyrene, polyethylene, polypropylene
Examples include pyrene and polyphenyl ether. Furthermore, the present invention
The cartridge may contain various antistatic agents.
-Bon black, metal oxide particles, nonion, anio
, Cationic and betaine surfactants or polymers
Can be preferably used. These are antistatic
The cartridges are described in JP-A-1-1251253 and 1-312538.
ing. Especially the resistance at 25 ℃ and 25% RH is 10¹²Less than Ω is preferred
That's right. Plastic patrone usually provides light shielding
For this purpose, a plastic kneaded with carbon black or pigments
Produced using sticks. The size of the patrone is now
The size of 135 can be used as it is.
Current 135 size 25mm cartridge diameter is 22mm or less
It is also effective. Patrone case volume
Is 30cm^ThreeLess preferably 25cm^ThreePreferably
Yes. Used for cartridges and cartridge cases
The mass of the plastic is preferably 5 to 15 g. Further, the spool used in the present invention is rotated.
Then, a patrone that sends out the film may be used. Hui
The rum tip is stored in the cartridge body, and the spool shaft
By rotating in the film feed direction, the film
Structure that feeds the tip of the cartridge out of the port of the cartridge
But you can. These are disclosed in US 4,834,306 and 5,226,613
Has been. The photographic film used in the present invention is before development.
So-called raw film or developed photo
It may be a film. Also, raw film and developed photographic film.
The film may be stored in the same new patrone,
Different patrone may be used. The color photographic light-sensitive material of the present invention is an Advan.
For strike photo system (hereinafter referred to as AP system)
Also suitable as a negative film, Fuji Photo Film
NEXIA A, NEXI manufactured by FUJIFILM Corporation
A F, NEXIA H (trade name, ISO 200/100/400 in order)
Uni film is processed into AP system format and dedicated
The thing stored in the cartridge can be mentioned. This
These AP system cartridge films are
Rum's Epion series (Epion 300Z (trade name), etc.)
It is used by loading in the camera for AP system. Also,
The color photographic light-sensitive material of the present invention is Fujika Fujifilm.
Ran like a super slim (product name)
It is also suitable for a film with a scratch. Taken by these
The following processes are used in the minilab system.
After being printed. (1) Reception (exposed Cartri
(2) Detachment
(From the cartridge, remove the film from the intermediate
(3) Film development (4) Rear touch
Process (Developed negative film is replaced with the original cartridge.
(5) Print (C / H / P3 type print and
Ndex print on color paper [preferably Fuji
Continuous automatic printing on SUPER FA8 (trade name)
(6) Verification and shipment (cartridge and index pre
The printer is checked with the ID number and shipped with the print). These systems include Fuji Film.
Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Freon
Tiers (both trade names) are preferred. Minilab Chan
FP922AL / FP562B / F as Pion film processor
P562B, AL / FP362B / FP362B, AL (all are trade names)
Recommended treatment chemical is Fuji Color Just It CN-16L
And CN-16Q (both are trade names). Printer Pro
As a seser, PP3008AR / PP3008A / PP1828AR / PP1828A /
PP1258AR / PP1258A / PP728AR / PP728A (All trade names)
Recommended treatment chemicals are Fuji Color Just It
CP-47L and CP-40FAII (both are trade names). Flow
In the entear system, the scanner and image processor
-SP-1000 and laser printer & paper processor
-LP-1000P or laser printer LP-1000W
The trade name is also used as the deviation. Used in the detach process
Rear toucher used in toucher and rear touch process
Are Fujifilm DT200 / DT100 and AT200 / AT respectively.
100 (both are trade names) is preferred. The AP system is a Fujifilm digital card.
Inside the mage workstation Aladdin1000 (product name)
You can also enjoy it with the photo joy system
The For example, Aladdin 1000 (trade name) developed AP system
System cartridge film directly or negative film
Image information of rum, positive film and print
Lum Scanner FE-550 (trade name) and flat head
Digital data obtained using the CANER PE-550 (trade name)
The tall image data can be easily processed and edited.
The data is based on the light-fixing thermal color printing method.
Digital color printer NC-550AL (trade name) and laser
-Potography 3000 (product of exposure heat development transfer method)
Name) or through a film recorder
Can be output as a print by lab equipment.
Aladdin 1000 is also a floppy disk for digital information directly.
(Registered trademark) disc, Zip disc, or CD
It is also possible to output to CD-R via iter. On the other hand, at home, the developed AP system car
Photo film AP made by Fujifilm
-1 (product name) just to load photos on TV
FUJIFILM photo scanner AS-1 (product)
Name information), image information can be continuously transferred to a personal computer at high speed.
Can also be imported. Also, film, print or
To input solid objects to a computer,
Photovision FV-10 / FV-5 (trade name) can be used. Further
Floppy (registered trademark) disk, Zip disk, C
The image information recorded on the D-R or hard disk is
Fujifilm application software photo facts
Various processing on a personal computer using Lee (trade name)
You can squeeze. Print high-quality prints from your computer
Fuji Electric's light-fixing thermal color printing method
Irum digital color printer NC-2 / NC-2D (product)
Name) is preferred. Developed AP system cartridge
To store film, Fuji Color Pocket Album
AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartry
Wedge file 16 (both are trade names) is preferred. The present invention is applied to a reflection (support) type photosensitive material.
The halogenation in the silver halide emulsion used.
Silver particles are preferably substantially cubic with {100} faces
Or tetradecahedral crystal particles (they have rounded vertices)
Or may have a higher surface) or 8
The faceted crystal grains, or 50% or more of the total projected area is {1
00} plane or {111} plane aspect ratio of 2 or more
The upper tabular grains are preferred. Aspect ratio is the projection plane
It is the value obtained by dividing the diameter of the circle corresponding to the product by the thickness of the particle.
In the present invention, the cube or {100} plane is the main plane.
Tabular grains or tabular grains having a {111} plane as the main plane
Child is preferably applied. Silver halide emulsions include silver chloride and bromide.
Silver, silver iodobromide, silver salt (iodo) bromide emulsions and the like are used.
From the viewpoint of rapid processability, the silver chloride content is 90 mol% or less.
Silver chloride, silver chlorobromide, silver chloroiodide, or chlorobromoiodide milk on
Agent, more preferably silver chloride content 95% mol
More preferably, the silver chloride content is 98 mol% or more
Silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide milk
Agents are preferred. Among such silver halide emulsions,
In the shell portion of the silver halide grains, 0.
01-0.50 mol%, more preferably 0.05-0.
High sensitivity is also obtained with 40 mol% silver iodochloride phase.
Therefore, it is preferable because it is excellent in aptitude for high illumination exposure. Also halo
0.2-5 moles per mole of total silver on the surface of silver halide grains
%, More preferably 0.5-3 mol% of silver bromide localized phase
It has high sensitivity and stable photographic performance.
It is particularly preferable because it can be realized. Reflective (support) type silver halide color photograph
Silver halide emulsions and other applied in light-sensitive materials
Materials (additives, etc.) and photographic composition layers (layer arrangement, etc.)
And processing methods applied to process this photosensitive material
As processing additives, JP-A-62-215272
No. 1, JP-A-2-33144, European Patent EP 0,35
Those described in US Pat. No. 5,660A2, especially European patents
What is described in EP0,355,660A2
Preferably used. Furthermore, JP-A-5-34889
No., No. 4-359249, No. 4-313753, No.
4-270344, 5-66527, 4-34
No. 548, No. 4-145433, No. 2-854, No.
1-158431, 2-90145, 3-19
4539, 2-93641, European Patent Publication No. 05
Silver halide color photographic feel as described in 20457A2 etc.
An optical material and a processing method thereof are also preferable. In particular, the reflection type support and silver halide described above are used.
Heterogeneous gold doped into emulsions and even silver halide grains
Ion species, storage stabilizers or fog in silver halide emulsions
Inhibitor, chemical sensitization (sensitizer), spectral sensitization (spectral sensitization)
Agent), cyan, magenta, yellow coupler and its milk
Dispersion method, color image preservability improving agent (anti-stain agent and anti-fading agent)
Stopper), dye (colored layer), gelatin seed, photosensitive material layer structure
The table below shows the composition and pH of the photosensitive material film.
Those described in each part of the publication are particularly preferably applicable. [0124] [Table 1]Reflection (support) type silver halide color photograph
The photosensitive material is an exposure and development system described in the following publicly known materials.
It can be preferably used in combination with
As the developing system, JP-A-10-333253 is disclosed.
Automatic printing and developing system described in Japanese Patent No.
Photosensitive material conveying apparatus described in JP-A-00-10206,
Recording including the image reading device described in No. 11-215312
System, JP-A-11-88619 and JP-A-10
-The color image recording system described in No. -202950
Exposure system described in JP-A-10-210206
Digital photo print system including interval diagnosis method, and
And an image recording apparatus described in JP 2000-310822 A
A photo print system including Preferred scanning exposure method applicable to the present invention
Are described in detail in the publications listed in the table above.
ing. The photosensitive material of the present invention is exposed to a printer.
In the case of Bands described in US Pat. No. 4,880,726
It is preferable to use a top filter. This
As a result, light color mixing is removed and color reproducibility is remarkably improved. In the present invention, European Patent EP 0789
As described in 270A1 and EP 0789480A1
Before adding image information to the
You can pre-expose the print pattern and apply copy restrictions.
Yes. In the processing of the light-sensitive material of the present invention, JP-A-2-
207250, page 26, lower right column, line 1 to page 34, upper right column
9th line, and page 5, upper left column 1 of JP-A-4-97355
7th to 18th page, lower right column, line 20
The method is preferably applicable. Also used in this developer
As a preservative, the chemicals described in the publications listed in the above table are used.
A compound is preferably used. Typically, the hue and white background in the present invention are
Fuji Photo Film Co., Ltd. as a color development process when prescribing
Minilab "PP350 (trade name)", C as treatment agent
Using P48S chemical (trade name)
Replenish color development by imagewise exposure from a negative density film
Continue processing until the volume of the liquid reaches twice the capacity of the color developer tank
Some of them are treated with the treated liquid. Treatment agent
Chemicals include CP45X manufactured by Fuji Photo Film Co., Ltd.
CP47L, Eastman Kodak RA-100,
RA-4 (both are trade names) may be used. [0131] Examples of the present invention will be described below. However, the present invention
Is not limited to this embodiment. Example 1 Support The support used in this example was prepared by the following method.
It was. 1) First layer and undercoat layer About 90μm thick polyethylene naphthalate support
The processing atmosphere pressure is 2.66 × 10 6 on each of both surfaces.
Pa, H in atmospheric gas₂O partial pressure 75%, discharge frequency 3
0 kHz, output 2500 W, processing strength 0.5 kV · A ·
Min / m²Glow discharge treatment was applied. On this support,
As the first layer, a coating solution having the following composition is used as JP 58-4589.
5 mL / m using the bar coating method described in No. 1²Coating
It was applied in the amount of cloth.     Conductive fine particle dispersion (SnO₂/ Sb₂O_FiveParticle concentration 50 parts by mass         10% aqueous dispersion. Primary particle size of 0.005μm         Secondary aggregate with an average particle size of 0.05μm)     Gelatin 0.5 parts by mass     49 parts by weight of water     Polyglycerol polyglycidyl ether 0.16 parts by mass     Poly (degree of polymerization 20) oxyethylene 0.1 part by mass             Sorbitan monolaurate. Furthermore, after coating the first layer, the diameter is 20 cm.
Wrapped around a stainless steel core, 110 ° C (PEN support
Tg: 119 ° C) for 48 hours and heat history
After the neal treatment, the support is sandwiched and the side opposite the first layer side
Bar coating with a coating solution of the following composition as an undercoat layer for emulsion
10 mL / m using the method²It applied with the application quantity of.     Gelatin 1.01 parts by weight     Salicylic acid 0.30 parts by mass     Resorcin 0.40 parts by mass     Poly (degree of polymerization 10) oxyethylene nonylphenyl ether                                                     0.11 parts by mass     3.53 parts by weight of water     Methanol 84.57 parts by mass     n-propanol 10.08 parts by mass. Furthermore, the second and third layers, which will be described later, are coated in order on the first layer.
And finally, oppose color negative photosensitive material with the composition described below
Transparent with silver halide emulsion layer by coating on the side
A bright magnetic recording medium was produced. 2) Second layer (transparent magnetic recording layer) Magnetic dispersion Co-coated γ-Fe₂O_ThreeMagnetic material (average major axis length: 0.25μ
m, S_BET : 39m²/ G, Hc: 6.56 × 10^FourA /
m, σs: 77.1 Am²/ Kg, σr: 37.4 Am²
/ Kg) 1100 parts by weight, 220 parts by weight of water and silane
Pulling agent [3- (Poly (Polymerization degree 10) oxyethini
L) Oxypropyl trimethoxysilane] 165 mass
And knead well with an open kneader for 3 hours
It was. This roughly dispersed viscous liquid is dried at 70 ° C for one day.
After removing the salt water, heat treatment was performed at 110 ° C. for 1 hour,
Treated magnetic particles were prepared. Furthermore, with the following prescription, again open kneader
And kneading for 4 hours.     Surface-treated magnetic particles 855 g     Diacetylcellulose 25.3 g     Methyl ethyl ketone 136.3 g     Cyclohexanone 136.3 g Furthermore, with the following prescription, a sand mill (1 / 4G sand)
Mill) and finely dispersed at 2000 rpm for 4 hours. Mede
For the via, 1 mmφ glass beads were used.     45 g of the above kneaded liquid     Diacetylcellulose 23.7 g     Methyl ethyl ketone 127.7 g     Cyclohexanone 127.7 g Furthermore, the magnetic substance containing intermediate liquid was produced with the following prescription. Production of magnetic substance-containing intermediate solution     Magnetic material fine dispersion 674 g     Diacetylcellulose solution 24280 g (Solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)     Cyclohexanone 46 g After mixing these, stirring with a disperser,
Containing intermediate solution ”was prepared. The α-alumina abrasive of the present invention having the following formulation
A dispersion was prepared.   (A) Sumiko Random AA-1.5 (trade name) (average primary particle size 1.5 μm, Specific surface area 1.3m² / G) Preparation of particle dispersion   Sumiko Random AA-1.5 152g   Silane coupling agent KBM903 (trade name, manufactured by Shin-Etsu Silicon Co.)                                                       0.48g   Diacetylcellulose solution 227.52 g   (Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) In the above formulation, a ceramic coated sand mill (1 /
4G sand mill), 800rpm, 4 hours fine
Distributed. Use 1mmΦ zirconia beads for the media
It was. (B) Colloidal silica particle dispersion (fine
particle) Using “MEK-ST (trade name)” manufactured by Nissan Chemical Co., Ltd.
did. This is a standard solution using methyl ethyl ketone as a dispersion medium.
Dispersion of colloidal silica with an average primary particle size of 0.015 μm
It is a liquid and has a solid content of 30%. Preparation of second layer coating solution   The above magnetic substance-containing intermediate solution 19053 g   Diacetylcellulose solution 264 g (Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)   Colloidal silica dispersion “MEK-ST” [dispersion b] 128 g   (Solid content 30%)   AA-1.5 dispersion [dispersion a] 12 g   Millionate MR-400 (trade name, manufactured by Nippon Polyurethane Co., Ltd.) Diluent (Solid content 20%, diluent solvent: methyl ethyl ketone / cyclohexanone = 1/1)                                                               203g   Methyl ethyl ketone 170 g   Cyclohexanone 170 g Apply the above mixed and stirred coating solution with a wire bar.
Amount 29.3 mL / m²It applied so that it might become. Drying is 1
Performed at 10 ° C. The thickness of the magnetic layer after drying is 1.0
It was μm. 3) Third layer (including higher fatty acid ester slip agent)
Layered) Preparation of dispersion solution of slip agent The following solution is heated and dissolved at 100 ° C.
Disperse with a homogenizer to prepare a dispersion stock solution of slip agent.
It was.   A liquid       The following compound 399 mass parts         C₆H₁₃CH (OH) (CH₂)_TenCOOC₅₀H₁₀₁       171 parts by mass of the following compound         n-C₅₀H₁₀₁O (CH₂CH₂O)₁₆H         830 parts by mass of cyclohexanone.   Liquid         Cyclohexanone 8600 parts by mass. Preparation of spherical inorganic particle dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.
It was. Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (trade name, manufactured by Shin-Etsu Silicon Co.)       Compound 1-1: (CH_ThreeO)_ThreeSi- (CH₂)_Three-NH₂)                                                     5.53 parts by mass Compound 1 2.93 parts by mass [0142] Embedded image[0143] Seahosta KEP50 88.00 parts by mass (Trade name, amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).   After stirring for 10 minutes according to the above formulation, the following is added. 252.93 parts by mass of diacetone alcohol Ultrasonic homogenizer while cooling and stirring the above solution
"SONIFIER450 (trade name, BRANSON
For 3 hours, and spherical inorganic particle dispersion
Liquid c1 was completed. Preparation of spherical organic polymer particle dispersion Spherical organic polymer particle dispersion [c2] with the following formulation
Produced.   XC99-A8808 (trade name, manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysilos) Xanthan particles, average particle size 0.9 μm) 60 parts by mass   120 parts by mass of methyl ethyl ketone   120 parts by mass of cyclohexanone (Solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ultrasonic homogenizer “SONI” with ice cooling and stirring
Using “FIER450” (manufactured by BRANSON)
Disperse for 2 hours to complete spherical organic polymer particle dispersion c2.
It was. Production of third layer coating solution Add the following to 542 g of the lubricant dispersion stock solution and apply the third layer.
Liquid.   Diacetone alcohol 5950 g   Cyclohexanone 176 g   Ethyl acetate 1700 g   Seahosta KEP50 dispersion [c1] 53.1 g   300 g of the above spherical organic polymer particle dispersion [c2]   FC431 2.65 g     (Trade name, 3M, solid content 50%, solvent: ethyl acetate)   BYK310 5.3 g     (Trade name, manufactured by BYK Chemi Japan Co., Ltd., solid content 25%). 10.35 mL / m of the third layer coating solution on the second layer²
After coating at 110 ° C and further drying at 97 ° C, 3
After drying for a minute. 4) Coating of photosensitive layer Next, on the opposite side of the back layer obtained above, the following composition
Each layer was applied in multiple layers to produce a color negative film. (Composition of photosensitive layer) The number corresponding to each component is g / m.²single
The amount of coating expressed in terms of
The calculated coating amount is shown.   First layer (first antihalation layer)   Black colloidal silver Silver 0.122   0.07 μm silver iodobromide emulsion Silver 0.01   Gelatin 0.919   ExM-1 0.066   ExC-1 0.002   ExC-3 0.002   Cpd-2 0.001   F-8 0.001   HBS-1 0.050   HBS-2 0.002 [0147]   Second layer (second antihalation layer)   Black colloidal silver Silver 0.055   Gelatin 0.425   ExF-1 0.002   F-8 0.001   Solid disperse dye ExF-7 0.120   HBS-1 0.074   Third layer (intermediate layer)   ExC-2 0.050   Cpd-1 0.090   Polyethyl acrylate latex 0.200   HBS-1 0.100   Gelatin 0.700 [0148]   4th layer (low sensitivity red sensitive emulsion layer)   Em-D Silver 0.577   Em-C Silver 0.347   ExC-1 0.188   ExC-2 0.011   ExC-3 0.075   ExC-4 0.121   ExC-5 0.010   ExC-6 0.007   ExC-8 0.050   ExC-9 0.020   Cpd-2 0.025   Cpd-4 0.025   UV-2 0.047   UV-3 0.086   UV-4 0.018   HBS-1 0.245   HBS-5 0.038   Gelatin 0.994 [0149]   5th layer (medium sensitivity red emulsion layer)   Em-B Silver 0.431   Em-C Silver 0.432   ExC-1 0.154   ExC-2 0.068   ExC-3 0.018   ExC-4 0.103   ExC-5 0.023   ExC-6 0.010   ExC-8 0.016   ExC-9 0.005   Cpd-2 0.036   Cpd-4 0.009   Cpd-7 0.082   HBS-1 0.129   Gelatin 0.882 [0150]   6th layer (high-sensitivity red-sensitive emulsion layer)   Em-A Silver 1.108   ExC-1 0.180   ExC-3 0.035   ExC-6 0.029   ExC-8 0.110   ExC-9 0.020   Cpd-2 0.064   Cpd-4 0.008   Cpd-7 0.028   HBS-1 0.329   HBS-2 0.120   Gelatin 1.245 [0151]   7th layer (intermediate layer)   Cpd-1 0.094   Cpd-6 0.369   Solid disperse dye ExF-4 0.030   HBS-1 0.049   Polyethyl acrylate latex 0.088   Gelatin 0.886 [0152]   Eighth layer (a layer that gives a layered effect to the red-sensitive layer)   Em-J Silver 0.153   Em-K Silver 0.153   Cpd-4 0.030   ExM-2 0.120   ExM-3 0.016   ExM-4 0.026   ExY-1 0.016   ExY-4 0.036   ExC-7 0.026   HBS-1 0.218   HBS-3 0.003   HBS-5 0.030   Gelatin 0.610 [0153]   9th layer (low sensitivity green emulsion layer)   Em-H Silver 0.333   Em-G Silver 0.329   Em-I Silver 0.088   ExM-2 0.378   ExM-3 0.047   ExY-1 0.017   ExC-7 0.007   HBS-1 0.098   HBS-3 0.010   HBS-4 0.077   HBS-5 0.548   Cpd-5 0.010   Gelatin 1.470 [0154]   10th layer (medium sensitive green sensitive emulsion layer)   Em-F Silver 0.457   ExM-2 0.032   ExM-3 0.029   ExM-4 0.029   ExY-3 0.007   ExC-6 0.010   ExC-7 0.012   ExC-8 0.010   HBS-1 0.065   HBS-3 0.002   HBS-4 0.020   HBS-5 0.020   Cpd-5 0.004   Gelatin 0.446 [0155]   11th layer (high sensitivity green emulsion layer)   Em-E silver 0.794   ExC-6 0.002   ExC-8 0.010   ExM-1 0.013   ExM-2 0.011   ExM-3 0.030   ExM-4 0.017   ExY-3 0.003   Cpd-3 0.004   Cpd-4 0.007   Cpd-5 0.010   HBS-1 0.148   HBS-3 0.003   HBS-4 0.020   HBS-5 0.037   Polyethyl acrylate latex 0.099   Gelatin 0.939 [0156]   12th layer (yellow filter layer)   Cpd-1 0.094   Solid disperse dye ExF-2 0.070   Solid disperse dye ExF-5 0.010   Oil-soluble dye ExF-6 0.010   HBS-1 0.049   Gelatin 0.630 [0157]   13th layer (low sensitivity blue-sensitive emulsion layer)   Em-O Silver 0.112   Em-M Silver 0.300   Em-N Silver 0.260   ExC-1 0.027   ExC-7 0.013   ExY-1 0.002   ExY-2 0.890   ExY-4 0.058   Cpd-2 0.100   Cpd-3 0.004   HBS-1 0.222   HBS-5 0.074   Gelatin 1.553 [0158]   14th layer (high sensitivity blue-sensitive emulsion layer)   Em-L Silver 0.714   ExY-2 0.211   ExY-4 0.068   Cpd-2 0.075   Cpd-3 0.001   HBS-1 0.124   Gelatin 0.678 [0159]   15th layer (first protective layer)   0.07 μm silver iodobromide emulsion Silver 0.301   UV-1 0.211   UV-2 0.132   UV-3 0.198   UV-4 0.026   F-11 0.009   S-1 0.086   HBS-1 0.175   HBS-4 0.050   Gelatin 1.984 [0160]   16th layer (second protective layer)   H-1 0.400   B-1 (diameter 1.7 μm) 0.050   B-2 (diameter 1.7 μm) 0.150   B-3 0.050   S-1 0.200   Gelatin 0.750 Furthermore, preservability, processability, and pressure are appropriately applied to each layer.
Improve resistance, antibacterial and antibacterial properties, antistatic properties and coatability
For W-1 to W-6, B-4 to B-6, F
-1 to F-18 and lead salts, platinum salts, iridium
Salts and rhodium salts are contained. Preparation of dispersion of organic solid disperse dye The ExF-2 of the 12th layer was dispersed by the following method.   ExF-2 wet cake (including 17.6% by weight water) 2.800 kg   Sodium octylphenyldiethoxymethanesulfonate   (31 mass% aqueous solution) 0.376 kg   F-15 (7% aqueous solution) 0.011 kg   4.020 kg of water   Total 7.210kg (Adjusted to pH = 7.2 with NaOH) Stir the slurry having the above composition with a dissolver.
After coarse dispersion, the agitator mill LMK-4 (product
Name), peripheral speed 10 m / s, discharge rate 0.6 kg / mi
n, with a filling rate of 80% for zirconia beads of 0.3 mm diameter
Disperse until the absorbance ratio of the liquid dispersion is 0.29, solid fine particles
A child dispersion was obtained. The average particle size of the fine dye particles is 0.29 μm
Met. Similarly, for ExF-4 and ExF-7
A solid dispersion was obtained. The average particle size of the fine dye particles is
They were 0.28 μm and 0.49 μm. ExF-5 is Europe
Microprecipitation described in Example 1 of State Patent No. 549,489A
(Microprecipitation) for distribution method
More dispersed. The average particle size was 0.06 μm. [0164] [Table 2] In Table 2, emulsions Em-A to Em-C are
Spectral sensitizing dyes 1 to 3 are added in an optimal amount, optimally gold sensitization,
Sulfur-sensitized and selenium-sensitized. Emulsions Em-E to Em
-G is added with an optimal amount of spectral sensitizing dyes 4-6, optimally gold
Sensitization, sulfur sensitization, and selenium sensitization. Emulsion Em-J
Spectral sensitizing dyes 7 and 8 are added in an optimal amount to optimally increase gold
Sensation, sulfur sensitization, selenium sensitization. Emulsion Em-L
Spectral sensitizing dyes 9 to 11 are added in an optimal amount, and gold is optimally increased.
Sensation, sulfur sensitization, selenium sensitization. Emulsion Em-O
Spectral sensitizing dyes 10-12 are added in an optimal amount, and gold is optimized
Feeling, sulfur sensitized. Emulsions Em-D, Em-H, E
m-I, Em-K, Em-M, and Em-N are the amounts listed in Table 3.
Optimum amount of photosensitizing dye added, optimal gold sensitization, sulfur enhancement
Sense, selenium sensitization. [0166] [Table 3] The sensitizing dyes listed in Table 3 are shown below. [0168] Embedded image [0169] Embedded image [0170] Embedded image [0171] Embedded image [0172] Embedded image [0173] Embedded image [0174] Embedded image[0175] Embedded image [0176] Embedded image [0177] Embedded image [0178] Embedded image [0179] Embedded image [0180] Embedded imageFor the preparation of tabular grains, JP-A-1-1584.
Using low molecular weight gelatin according to the example described in No. 26
Yes. Emulsions Em-A to Em-K contain optimum amounts of Ir and Fe
Contains. Emulsions Em-L to Em-O
Reduced sensitization. For tabular grains, use a high-voltage electron microscope.
When used, it is described in JP-A-3-237450.
Such dislocation lines are observed. Emulsions Em-A to Em-C,
Em-J is in accordance with the examples described in JP-A-6-11784.
Dislocations are introduced using an iodide ion releasing agent. emulsion
Em-E is a magnetic cup described in JP-A-10-43570
Immediately before addition in a separate chamber with a ring induction stirrer
Dislocations are introduced using the prepared silver iodide fine particles.
The compounds used for each layer are shown below. [0182] Embedded image[0183] Embedded image[0184] Embedded image[0185] Embedded image[0186] Embedded image[0187] Embedded image[0188] Embedded image[0189] Embedded image[0190] Embedded image[0191] Embedded imageThe silver halide color photographic light-sensitive material described above is used.
Sample 101 is designated. Development is automatically performed by Fuji Photo Film Co., Ltd.
Performed as follows using imager FP-360B (trade name)
It was. Do not flush the overflow solution of the bleaching bath
And modified to discharge to the waste liquid tank. This FP
-360B is an open technique 94-4992 (incorporated corporation invention)
Evaporation correction means described in the Association) is installed. The treatment process and the treatment liquid composition are shown below.   (Processing process)     Process Processing time Processing temperature Replenishment amount * Tank capacity   Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5 L   Whitening 50 seconds 38.0 ℃ 5 mL 5L   Fixing (1) 50 seconds 38.0 ℃ ─ 5L   Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L   Washing with water 30 seconds 38.0 ℃ 17 mL 3L   Stable (1) 20 seconds 38.0 ℃ ─ 3L   Stable (2) 20 seconds 38.0 ℃ 15 mL 3L   Dry 1 min 30 sec 60.0 ° C   * The replenishment amount is 35 mm of photosensitive material per 1.1 m width (equivalent to one shot per 24). Stabilizer and fixer are counter-current from (2) to (1)
In this case, all the overflow water of the washing water is led to the fixing bath (2).
I entered. The amount of developer brought into the bleaching process, bleach solution
To the fixing process and to the washing process of the fixing solution
The amount brought in is 35mm per photosensitive material and 1.1m wide.
2.5 mL, 2.0 mL, and 2.0 mL. Ma
The crossover time is 6 seconds.
The time is included in the processing time of the previous process. The opening area of the processor is 10 with a color developer.
0cm², 120cm with bleach²About 1 other processing solution
00cm²Met. The composition of the treatment liquid is shown below.   (Color developer) Tank solution (g) Replenisher (g)   Diethylenetriaminepentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3mg −   4-hydroxy-6-methyl-1,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-Methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18. [0195]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-diaminopropanetetraacetic acid second     Iron ammonium monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia] 4.6 4.0. (Fixing (1) Tank liquid) The above-mentioned bleaching tank liquid
And 5:95 (volume ratio) mixture of the following fixing tank solution. (PH 6.8)   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240 mL 720 mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45 (Washing water) H-type strongly acidic cation exchange with tap water
Replacement resin (Rum & Haas Amberlite IR-
120B, trade name) and OH type strongly basic anion exchange tree
Filled with fat (same Amberlite IR-400, trade name)
Calcium and magnesium by passing through a mixed bed column
The ion concentration is treated to 3 mg / L or less, followed by dichloride
Sodium sodium cyanate 20mg / L and sodium sulfate
150 mg / L was added. The pH of this solution is 6.5-
It was in the range of 7.5. [0198]   (Stabilizer) Tank fluid and replenisher common (Unit: g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl ether 0.2     (Average polymerization degree 10)   1,2-Benzisothiazoline-3-one sodium 0.10   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   Add water and add 1.0L   pH 8.5 As shown in Table 4, from the sample 101, the thirteenth
The same except that ExY-2 of layer 14 and 14th layer are replaced
Samples 102 to 115 were prepared, and the relative humidity at 25 ° C.
Stored at 65% for 7 days. Use these samples for
The performance was examined. (Evaluation 1 Dmax (UV) / Dmin
(UV) Calculation) White exposure at color temperature 4800 ° K Fuji
SHARP CUT FILTER SC-39
Through the exposure time of 1 second, the exposure is 2000 CMS.
The aforementioned color development processing is performed on the sample that has been given light and the unexposed sample.
Of these two exposed and unexposed samples, the color density is
Dmax, color density of the higher (exposed sample in this example)
The lower one (unexposed sample in this example) was defined as Dmin.
10cm of each sample after treatment ²5 mg actina
Photographic gelatin in 20 ml of water containing 40 ° C.
Was digested for 60 minutes to elute the photographic composition layer. 25 ° C
After cooling, extract oil-soluble components using 20 ml of ethyl acetate.
Put out. Once at 40 ° C using a rotary evaporator
Dry up under reduced pressure, 0.3 quality in volumetric flask
Complete the volume with ethyl acetate containing 10% acetic acid.
It was. Solution preparation from enzymatic degradation with actinase
Was carried out in the dark. Using this solution in a 1 cm quartz cell
Measure absorption spectrum from 340nm to 450nm
Calculate and determine Dmax (UV) / Dmin (UV) as defined below.
It was. Definition of Dmax (UV) / Dmin (UV): "(yellow maximum color development
Absorbance at a certain wavelength UV of concentration part / (yellow
(Absorbance at a certain wavelength UV)
Among the numerical values, the wavelength UV (UV is 340 nm or more 4
The smallest value at a certain wavelength of 50 nm or less. ”
Justified. (Evaluation 2 (BC) / Calculation of A) Evaluation 1
Using the sample used in step 1, the maximum color development area (Dmax)
That is, in this example, the yellow density B of the exposed sample)
And minimum color development (Dmin) (that is, unexposed in this embodiment)
The yellow density C of the sample is measured using an SCD meter.
It was. Application amount Amol / of the compound represented by the general formula (I)
m²(BC) / A was calculated and determined. (Evaluation 3: Static fogging)
Processed into a roll and atmosphere with 10% relative humidity at 25 ° C under no light
No exposure after rewinding at 100 m / min under ambient air
The processing was performed in the development processing step. Sample after treatment (D
min) and visually detect the number of electrostatic fog generated.
It was. Against the number of electrostatic fog generated on sample 101
The relative values (percentage) are shown in the table. [0203] [Table 4]Table 4 clearly shows that the photosensitive material of the present invention is electrostatic.
It turns out that it is excellent in feeling. Example 2 As shown in Table 5, the 15th layer from each sample of Example 1
The sample was prepared in the same manner except that
In addition to evaluations 1, 2, and 3 as in Example 1, the following
Evaluation was performed. Also described in JP-A-6-130549
The same evaluation was performed on the sample. 15th layer (first protective layer)   0.07 μm silver iodobromide emulsion Silver 0.301   UV-1 0.175   UV-2 0.110   UV-3 0.164   UV-4 0.022   F-11 0.009   S-1 0.086   HBS-1 0.175   HBS-4 0.050   Gelatin 1.647 (Evaluation 4 Sharpness Evaluation) Using the above sample
After writing MTF evaluation pattern with white exposure
The color development processing was performed in the same manner. Magenta density fresh
The sharpness is shown as a relative value to the sample 101. Numeric value is large
The higher the sharpness, the better. [0207] [Table 5] From Table 5, the silver halide photographic materials of the present invention are
It is clear that it is excellent in electrostatic fog and sharpness. Example 3 Samples prepared in Example 1 and Example 2 were 35 mm wide.
Processed into rolls and packed in patrone, relative humidity 10%
Camera paste that sends film at high speed at room temperature 25 ℃
Each tested sample was developed using the process described above.
When the subsequent fogging was evaluated, Example 1 and Example 2
In samples that were effective against electrostatic fogging,
I couldn't. Example 4 (Preparation of multilayer sample) Preparation of silver halide color photographic material, sample CR01 Back layer application 205 μm thick triacetyl with primer on both sides
Apply the following back layer on one side of the cellulose support.
It was. 1st layer binder: acid-treated gelatin (isoelectric point 9.0) 1.00 g         Polymer latex P-2 (average particle size 0.1 μm) 0.13 g         Polymer latex: P-3 (average particle size 0.2 μm) 0.23 g         UV absorber U-1 0.030g         UV absorber U-3 0.010g         UV absorber U-4 0.020g         High-boiling organic solvent Oil-2 0.030g         Surfactant W-3 0.010g         Surfactant W-6 3.0mg [0211] Second layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.10 g         Polymer latex: P-3 (average particle size 0.2 μm) 0.11 g         UV absorber U-1 0.030g         UV absorber U-3 0.010g         UV absorber U-4 0.020g         High-boiling organic solvent Oil-2 0.030g         Surfactant W-3 0.010g         Surfactant W-6 3.0mg         Dye D-2 0.10 g         Dye D-10 0.12g         Potassium sulfate 0.25g         Calcium chloride 0.5mg         Sodium hydroxide 0.03g [0212] 3rd layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.30 g         Surfactant W-3 0.020g         Potassium sulfate 0.30g         Sodium hydroxide 0.03g 4th layer Binder: Lime-processed gelatin (isoelectric point 5.4) 1.15g         1: 9 copolymer of methacrylic acid and methyl methacrylate             (Average particle size 2.0μm) 0.040g         6: 4 copolymer of methacrylic acid and methyl methacrylate             (Average particle size 2.0μm) 0.030g         Surfactant W-3 0.060g         Surfactant W-2 0.010g         Curing agent H-1 0.23g Coating of photosensitive emulsion layer The photosensitive milk shown below is on the opposite side of the back layer.
An agent layer was applied to obtain a sample CR01. The number is m²Per
Represents the amount of addition. The effect of the added compound is described
Not limited to usage. First layer: Antihalation layer Black colloidal silver 0.20g Gelatin 2.50g Compound Cpd-B 0.050g UV absorber U-1 0.050g UV absorber U-3 0.10g UV absorber U-4 0.030g UV absorber U-5 0.050g UV absorber U-7 0.10g Compound Cpd-F 0.20g High boiling point organic solvent Oil-1 0.10g High-boiling organic solvent Oil-2 0.15g High boiling point organic solvent Oil-5 0.010g Dye D-4 1.0mg Dye D-8 2.5mg 0.05g microcrystalline solid dispersion of dye E-1 Second layer: intermediate layer Gelatin 1.8g Compound Cpd-M 0.20g Compound Cpd-F 0.050g Compound Cpd-K 3.0mg UV absorber U-6 6.0mg High boiling point organic solvent Oil-3 0.010g High boiling point organic solvent Oil-4 0.010g High boiling point organic solvent Oil-6 0.10g High boiling point organic solvent Oil-7 2.0mg Dye D-7 4.0mg Third layer: intermediate layer Gelatin 0.40g Compound Cpd-D 0.020g High boiling point organic solvent Oil-3 0.010g High boiling point organic solvent Oil-8 0.010g Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.15g Emulsion B Silver amount 0.15g Emulsion C Silver amount 0.15g Gelatin 0.80g Coupler C-1 0.10g Coupler C-2 7.0mg Coupler C-10 2.0mg UV absorber U-3 0.010g Compound Cpd-I 5.0mg Compound Cpd-D 3.0mg Compound Cpd-J 2.0mg High boiling point organic solvent Oil-10 0.030g Additive P-1 5.0 mg Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion C Silver amount 0.15g Emulsion D Silver amount 0.15g Silver bromide emulsion coated inside (cube, sphere equivalent average particle diameter
0.11μm) Silver amount 3.0mg Gelatin 0.70g Coupler C-1 0.15g Coupler C-2 7.0mg Compound Cpd-D 3.0mg UV absorber U-3 0.010g High-boiling organic solvent Oil-10 0.030g additive
P-1 7.0mg Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion E Silver amount 0.20g Emulsion F Silver amount 0.20g Gelatin 1.50g Coupler C-1 0.60g Coupler C-2 0.025g Coupler C-3 0.020g Coupler C-9 5.0mg UV absorber U-1 0.010g UV absorber U-2 0.010g High boiling point organic solvent Oil-6 0.030g High boiling point organic solvent Oil-9 0.020g High-boiling organic solvent Oil-10 0.20g Compound Cpd-D 5.0mg Compound Cpd-K 1.0 mg Compound Cpd-F 0.030g Compound Cpd-L 1.0mg Compound Cpd-R 0.030g Additive P-1 0.010g Additive P-4 0.030g Seventh layer: Intermediate layer Gelatin 0.60g 0.10g of additive P-2 Dye D-5 0.020g Dye D-9 6.0mg Compound Cpd-I 0.010g Compound Cpd-O 3.0mg Compound Cpd-P 5.0mg High boiling point organic solvent Oil-6 0.050g 8th layer: Middle layer Yellow colloidal silver Silver amount 0.010g Gelatin 1.30g Additive P-2 0.05g UV absorber U-1 0.010g UV absorber U-2 0.030g Compound Cpd-A 0.050g Compound Cpd-D 0.030g Compound Cpd-M 0.10 g High boiling point organic solvent Oil-3 0.010g High boiling point organic solvent Oil-6 0.10g Ninth layer: Low-sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.15g Emulsion H Silver amount 0.30g Emulsion I Silver amount 0.15g Gelatin 1.30g Coupler C-4 0.10g Coupler C-5 0.030g Compound Cpd-A 5.0mg Compound Cpd-B 0.020g Compound Cpd-G 2.5mg Compound Cpd-F 0.010g Compound Cpd-K 2.0mg High-boiling organic solvent Oil-2 0.040g Additive P-1 5.0mg Layer 10: Medium sensitivity green sensitive emulsion layer Emulsion I Silver amount 0.20g Emulsion J Silver amount 0.20g Silver bromide emulsion coated inside (cube, sphere equivalent average particle diameter
0.11μm) Silver amount 3.0mg Gelatin 0.50g Coupler C-4 0.15g Coupler C-5 0.050g Coupler C-6 0.010g Compound Cpd-A 5.0mg Compound Cpd-B 0.020g High-boiling organic solvent Oil-2 0.020g Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver amount 0.40g Gelatin 1.20g Coupler C-4 0.50g Coupler C-5 0.20g Coupler C-7 0.050g Compound Cpd-B 0.030g Compound Cpd-F 0.010g High boiling point organic solvent Oil-2 0.050g High boiling point organic solvent Oil-9 0.020g 12th layer: Yellow filter layer Yellow colloidal silver Silver amount 5.0mg Gelatin 1.0g Compound Cpd-C 0.010g Compound Cpd-M 0.030g High-boiling organic solvent Oil-1 0.020g High boiling point organic solvent Oil-6 0.040g 0.20 g of microcrystalline solid dispersion of dye E-2 13th layer: Intermediate layer Gelatin 0.40g Compound Cpd-Q 0.20g Dye D-6 4.0mg 14th layer: Low sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.15g Emulsion M Silver amount 0.10g Emulsion N Silver amount 0.10g Gelatin 0.80g Coupler C-8 0.30g Compound Cpd-B 0.10 g Compound Cpd-I 8.0mg Compound Cpd-K 1.0mg UV absorber U-6 0.010g High boiling point organic solvent Oil-2 0.010g 15th layer: Medium sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.10g Emulsion O Silver amount 0.20g Gelatin 0.80g Coupler C-8 0.30g Compound Cpd-B 0.10 g Compound Cpd-E 0.030g Compound Cpd-N 2.0 mg High boiling point organic solvent Oil-2 0.010g 16th layer: High sensitivity blue-sensitive emulsion layer Emulsion P Silver amount 0.20g Emulsion Q Silver amount 0.25g 2.00g gelatin Coupler C-8 1.40g Coupler C-2 0.010g High-boiling organic solvent Oil-2 0.030g UV absorber U-6 0.10g Compound Cpd-E 0.20g Compound Cpd-N 5.0mg Seventeenth layer: First protective layer Gelatin 1.00g UV absorber U-1 0.10g UV absorber U-2 0.050g UV absorber U-5 0.10g UV absorber U-7 0.10g Compound Cpd-B 0.020g Compound Cpd-O 5.0mg Compound Cpd-A 0.030g Compound Cpd-H 0.20g Dye D-1 8.0mg Dye D-2 0.010g Dye D-3 0.010g High boiling point organic solvent Oil-3 0.10g 18th layer: 2nd protective layer Colloidal silver Silver amount 2.5mg Fine-grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1
Mol%) Silver amount 0.10g Gelatin 0.80g UV absorber U-1 0.030g UV absorber U-6 0.030g High boiling point organic solvent Oil-3 0.010g 19th layer: 3rd protective layer Gelatin 1.00g 0.10 g of polymethyl methacrylate (average particle size 1.5 μm) 6: 4 copolymerization of methyl methacrylate and methacrylic acid
Body (average particle size 1.5μ) 0.15g Silicone oil SO-1 0.20g Surfactant W-1 3.0mg Surfactant W-2 8.0mg Surfactant W-3 0.040g Surfactant W-7 0.015g In addition to the above composition, the additive F-
1-F-9 was added. In addition to the above composition, each layer
Gelatin hardener H-1 and surfactant for coating and emulsification
W-3, W-4, W-5, W-6 were added. Further prevention
Phenol, 1,2-benzisothia as antifungal agent
Zolin-3-one, 2-phenoxyethanol, phene
Add chilled alcohol, p-benzoic acid butyl ester
It was. [0227] [Table 6][0228] [Table 7] [0229] [Table 8][0230] [Table 9] [0231] [Table 10][0232] Embedded image [0233] Embedded image [0234] Embedded image[0235] Embedded image[0236] Embedded image[0237] Embedded image[0238] Embedded image[0239] Embedded image[0240] Embedded image[0241] Embedded image[0242] Embedded image[0243] Embedded image[0244] Embedded image[0245] Embedded image[0246] Embedded image[0247] Embedded image[0248] Embedded image[0249] Embedded imagePreparation of dispersion of organic solid disperse dye (Preparation of dispersion of dye E-1) Wetke of dye E-1
BASF (P) made by BASF
luronic F88 (trade name) (ethylene oxide-propylene
100 g of oxide block copolymer) and water
The mixture was stirred to 4000 g. Next, Imex
To Ultraviscomil (UVM-2, trade name) manufactured by
Filled with 1700 ml of zirconia beads with an average particle size of 0.5 mm
The peripheral speed is about 10 m / sec through the slurry, and the discharge amount is 0.
The mixture was pulverized at 51 / min for 2 hours. Remove the beads by filtration,
After adding water and diluting to a dye concentration of 3%, for stabilization
Heated at 90 ° C. for 10 hours. Average dye fine particles obtained
The particle size is 0.30 μm and the breadth of particle size distribution (particle size
Standard deviation × 100 / average particle diameter) was 20%. (Preparation of solid dispersion of dye E-2) Water 3
Add 1400g E-2 wet cake containing 0% by weight
270g of W-4 and stirred, E-2 concentration 40 mass
% Slurry. Next, crusher, Imex Co., Ltd.
Ultra-viscomill (UVM-2, trade name) average grain
Filled with 1700 ml of 0.5 mm zirconia beads
And the peripheral speed is about 10m / sec through the slurry, discharge rate
E-2 solid ground at 0.5 liter / min for 8 hours
A fine particle dispersion was obtained. This is ion-exchanged water, 20 mass
% To obtain a solid fine particle dispersion. Average particle size
Was 0.15 μm. Next, from sample CR01
The 14, 15, 16-layer coupler C-8 is shown in Table 11.
Replacement samples CR02 to CR07 were prepared as described above. Mosquito
When replacing the puller, C-8 of sample CR01
The number of moles was replaced with 0.9 times. So
In addition to the above, additives other than those specifically indicated were changed from sample CR01.
There wasn't. When used for the following evaluations,
Store the photosensitive material for 14 days at 25 ° C and 55%.
I went later. [0252] [Table 11] (Sample evaluation) Calculation of Dmax (UV) / Dmin (UV) Samples CR01 to CR07 are 10.5 cm x 12.5 cm
Prepare two pieces that have been cut into two pieces, one of which has a color temperature of 4
Sharp made by Fuji Photo Film with white exposure at 800 ° K
Dew with 1 second exposure time through cut filter SC-39
After exposure with a light intensity of 2000 CMS,
Image processing-CR applied (the entire surface gives the lowest density;
Bottom, sample with the lowest concentration). The other one is unexposed.
In addition, processing after reversal processing in development processing-CR
(The entire surface gives the maximum density of each sensitive material;
Bottom, maximum concentration sample). Created as above, the most
As described in Example 1 for the low concentration sample and the maximum concentration sample
A small piece was punched and extracted, and the ultraviolet light absorption was measured. This
The value of Dmax (UV) / Dmin (UV) obtained
The results are shown in Table 12. Evaluation of electrostatic fog Samples CR01 to CR07 were 12.7 cm wide x 200 m
Each roll is processed at 25 ° C relative humidity under no light.
After rewinding at 100 m / min in a 10% atmosphere
In addition, it was processed with development processing-CR without exposure (however, the first
Performed by sensitized development with 1 development time extended to 13 minutes
) Electrostatic fog generated after treatment (white in black background)
Number) was detected visually. Occurs in sample CR01
Table 1 shows the relative values when the number of electrostatic fog is 1.0.
It is shown in 2. The smaller the number, the less electrostatic fogging is preferred.
That's right. [0255] [Table 12] According to Table 12, the photosensitive material of the present invention was used.
It can be seen that there is little electrostatic fog. (Development processing -CR)       Processing time Time Temperature Tank capacity Replenishment amount       First development 6 minutes 38 ° C 37 liters 2200 ml / m²       First washing 2 minutes 38 ℃ 16 liters 4000 ml / m²       Reversal 2 minutes 38 ℃ 17 liters 1100 ml / m²       Color development 6 minutes 38 ℃ 30 liters 2200 milliliters / m²       Pre-bleaching 2 minutes 38 ℃ 19 liters 1100 ml / m²       Whitening 6 minutes 38 ℃ 30 liters 220 ml / m²       Settling time 4 minutes 38 ℃ 29 liters 1100 ml / m²       Second washing 4 minutes 38 ℃ 35 liters 4000 ml / m²       Final rinse 1 minute 25 ° C 19 liters 1100 ml / m² The composition of each treatment solution was as follows. [First developer] [Tank solution] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 1.5 g 1.5 g   Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g   Sodium sulfite 30 g 30 g   Hydroquinone potassium monosulfonate 20 g 20 g   Potassium carbonate 15 g 20 g   Potassium bicarbonate 12 g 15 g   1-phenyl-4-methyl-4-hydroxymethyl     -3-pyrazolidone 1.5 g 2.0 g   Potassium bromide 2.5 g 1.4 g   Potassium thiocyanate 1.2 g 1.2 g   Potassium iodide 2.0 mg −   Diethylene glycol 13 g 15 g   Add water 1000ml 1000ml pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide. [0257] [Reversing liquid] [Tank liquid] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid tank solution ・ Same as 3.0 g of sodium salt   Stannous chloride dihydrate 1.0 g   p-Aminophenol 0.1 g   Sodium hydroxide 8 g   Glacial acetic acid 15ml   1000ml with water     pH 5.80 The pH was adjusted with acetic acid or sodium hydroxide. [Color developer] [Tank solution] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 2.0 g 2.0 g   Sodium sulfite 6.0 g 6.0 g   Trisodium phosphate, 12 hydrate 22 g 22 g   Potassium bromide 1.0 g −   Potassium iodide 30 mg −   Sodium hydroxide 12.0 g 12.0 g   Citrazic acid 0.5 g 0.5 g   N-ethyl-N- (β-methanesulfonamidoethyl)     -3-Methyl-4-aminoaniline, 3/2 sulfuric acid,     Monohydrate 10 g 10 g   3,6-dithiaoctane-1,8-diol 0.7 g 0.7 g   Add water 1000ml 1000ml   pH 11.90 12.00 The pH was adjusted with sulfuric acid or potassium hydroxide. [Pre-bleaching] [Tank liquid] [Replenisher]   Ethylenediaminetetraacetic acid, disodium salt, dihydrate 8.0 g 8.0 g   Sodium sulfite 6.0 g 8.0 g   1-thioglycerol 0.4 g 0.4 g   Formaldehyde sodium bisulfite adduct 30 g 35 g   Add water 1000ml 1000ml   pH 6.50 6.50 The pH was adjusted with acetic acid or sodium hydroxide. [Bleaching solution] [Tank solution] [Replenisher solution]   Ethylenediaminetetraacetic acid, disodium salt, dihydrate 2.0 g 4.0 g   Ethylenediaminetetraacetic acid / Fe (III) / Ammonium     ・ Dihydrate 120 g 240 g   Potassium bromide 100 g 200 g   Ammonium nitrate 10 g 20 g   Add water 1000ml 1000ml   pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide. [Fixing solution] [Tank solution] [Replenisher solution]   Ammonium thiosulfate 80 g Same as tank liquid   Sodium sulfite 5.0 g 〃   Sodium bisulfite 5.0 g 〃   1000ml with water     pH 6.60 The pH was adjusted with acetic acid or aqueous ammonia. [Stabilizer] [Tank fluid] [Replenisher]   1,2-Benzisothiazolin-3-one 0.02g 0.03g   Polyoxyethylene-p-monononylphenyl ether     (Average polymerization degree 10) 0.3 g 0.3 g   Polymaleic acid (average molecular weight 2,000) 0.1 g 0.15 g   Add water 1000ml 1000ml     pH 7.0 7.0 In the above development process, each bath continuously circulates the liquid.
Furthermore, the bottom of each tank has a diameter of 0.3 mm.
Place foamed tubes with small holes at 1 cm intervals, and continuously nitrogen
The raw gas was bubbled and stirred. The pre-bleaching bath and the second washing bath
No foaming stirring was performed. Example 5 (Preparation of the present invention blue-sensitive layer emulsion A) 98.9 mol% of silver chloride
  Halogen composition of 1 mol% silver bromide and 0.1 mol% silver iodide
The average side length is 0.70 μm, and the side length variation coefficient is 8%.
Of silver halide cubic grains were formed. Spectral sensitizing dye
1 and 2 are each 2.5 × 10^-FourMol / Ag mol
2.0 × 10^-FourMol / Ag mol was added. During particle formation
K_ThreeIrCl_Five(H₂O), K_FourRu (CN)₆,
K_FourFe (CN)₆Thiosulfonic acid compound-1, thio
Sodium sulfate, gold sensitizer-1, and mercapto compound
-1 and 2 were used in optimum amounts. In this way, high-sensitivity emulsion A
-1 was produced. Similarly, the average side length is 0.55 μm,
Cubic grains having a side length variation coefficient of 9% were formed. Spectral sensitization
In addition, the chemical sensitization is corrected by adjusting the specific surface area (side length ratio).
0.7 / 0.55 = 1.27 times)
Thus, low sensitivity side emulsion A-2 was prepared. [0259] Embedded image(Preparation of green-sensitive layer emulsion C) Emulsion A-1
And lower the temperature at the time of grain formation and the types of sensitizing dye
Same as the preparation conditions for Emulsions A-1 and 2 except that
In this way, high-sensitivity emulsion C-1 for green-sensitive layer, low-sensitivity emulsion C-2
It was created. [0261] Embedded imageThe particle size on the sensitive side is 0.40 on the average side length.
μm The low-sensitivity side has an average side length of 0.30 μm. That strange
The dynamic coefficients were all 8%. Sensitizing dye D is halogenated
3.0 x 1 for large emulsions per mole of silver halide
0 ^-Four3.6 × 10 for small, small emulsions^-FourMo
In addition, a large amount of sensitizing dye E is added per mole of silver halide.
4.0x10 for is emulsion^-FiveMole, small size emulsion
7.0 × 10 for^-FiveMole was added. (Preparation of Emulsion E for Red Sensitive Layer) During Emulsion with Emulsion A-1
And change the type of sensitizing dye as follows
Except for the above, the redness was the same as the preparation conditions of Emulsions A-1 and
High-sensitivity emulsion E-1 and low-sensitivity emulsion E-2
It was. [0263] Embedded image As for the particle size, the sensitive side has an average side length of 0.38.
μm The low-sensitive side has an average side length of 0.32 μm.
The coefficient of variation was 9% and 10%, respectively. Sensitizing dye G
And H, each large size per mole of silver halide
8.0 × 10 for emulsion^-FiveMole, small size emulsion
10.7 × 10^-FiveMole was added. In addition,
Compound I per red halide emulsion layer per mole of silver halide
3.0 × 10^-3Mole was added. ) [0265] Embedded imageFirst layer coating solution preparation 57 g yellow coupler (ExY), color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, low color image
Fixed agent (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
g 21 g of solvent (Solv-1) and 80 m of ethyl acetate
1 g of this solution was dissolved in 4 g of dodecylbenzenesulfone.
23.5 mass% gelatin aqueous solution 22 containing sodium acid
Emulsified and dispersed in 0 g with a high-speed stirring emulsifier (dissolver)
Then, water was added to prepare 900 g of emulsified dispersion A. one
On the other hand, the emulsion dispersion A and the emulsions A-1 and A-2 are mixed.
Dissolve and prepare the first layer coating solution to have the composition described below.
It was. The emulsion coating amount indicates the silver coating amount. 2nd to 2nd layers
Prepare the coating solution for the seven layers in the same way as the coating solution for the first layer.
It was. As gelatin hardener for each layer, 1-oxy-3,
5-dichloro-s-triazine sodium salt (H-
1), (H-2), and (H-3) were used. Also in each layer
(Ab-1), (Ab-2), (Ab-3), and (A
b-4) is 15.0 mg / m in total²60.
0 mg / m², 5.0 mg / m²And 10.0 mg / m²
It added so that it might become. [0267] Embedded image [0268] Embedded image Further, 1- (3-methylureidopheny
) -5-mercaptotetrazole, second layer, fourth
Layer, 6th layer and 7th layer, 0.2 mg /
m²0.2 mg / m²0.6 mg / m²0.1 mg
/ M²It added so that it might become. Blue sensitive emulsion layers and
4-hydroxy-6-methyl- for the green sensitive emulsion layer
1,3,3a, 7-tetrazaindene, each halo
1 x 10 per mole of silver halide^-FourMol, 2 × 10^-FourMo
Added. In addition, methacrylic acid and acrylic acid are added to the red-sensitive emulsion layer.
Copolymer latex of butyl yllate (mass ratio 1: 1, flat
Average molecular weight 200000-400000) 0.05 g /
m²Was added. Also, the second, fourth and sixth layers
Tecor-3,5-disulfonate disodium
6mg / m²6 mg / m²18 mg / m²It will be
It was added. In order to prevent irradiation,
The following dyes were added (the amount in parenthesis represents the coating amount). [0270] Embedded image(Layer Structure) The structure of each layer is shown below. number
The letter is the coating amount (g / m²). Silver halide emulsion
Represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [White pigment (TiO 2 on the first layer side polyethylene resin)₂;
16% by mass, ZnO; 4% by mass)) and increased fluorescence
Whitening agent (4,4'-bis (5-methylbenzoxazoly
Le) Stilbene. Content 0.03% by mass), bluish dye
(Ultramarine, 0.33% by mass). polyethylene
The amount of resin is 29.2 g / m²] [0272]   First layer (blue sensitive emulsion layer)     Silver chlorobromoiodide emulsion A (gold-sulfur sensitized cube, large size emulsion A-1 and small size 3: 7 mixture (silver molar ratio) with emulsion A-2. )                                                           0.24     Gelatin 1.25     Yellow coupler (ExY) 0.57     Color image stabilizer (Cpd-1) 0.07     Color image stabilizer (Cpd-2) 0.04     Color image stabilizer (Cpd-3) 0.07     Color image stabilizer (Cpd-8) 0.02     Solvent (Solv-1) 0.21   Second layer (color mixing prevention layer)     Gelatin 1.15     Color mixing inhibitor (Cpd-4) 0.10     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.07     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.12     Solvent (Solv-5) 0.11 [0273]   Third layer (green sensitive emulsion layer)     Silver chlorobromoiodide emulsion C (gold-sulfur sensitized cube, large size emulsion C-1 and small size 1: 3 mixture (silver molar ratio) with emulsion C-2. )                                                           0.14     Gelatin 1.21     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.003     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.01     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.09     Solvent (Solv-4) 0.18     Solvent (Solv-5) 0.17   Fourth layer (color mixing prevention layer)     Gelatin 0.68     Color mixing inhibitor (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.011     Color image stabilizer (Cpd-6) 0.08     Color image stabilizer (Cpd-7) 0.04     Solvent (Solv-1) 0.02     Solvent (Solv-2) 0.07     Solvent (Solv-5) 0.065 [0274]   5th layer (red-sensitive emulsion layer)     Silver chlorobromoiodide emulsion E (gold-sulfur sensitized cube, large size emulsion E-1 and small size 5: 5 mixture (silver molar ratio) with emulsion E-2. )                                                           0.16     Gelatin 0.95     Cyan coupler (ExC-1) 0.023     Cyan coupler (ExC-2) 0.05     Cyan coupler (ExC-3) 0.17     Ultraviolet absorber (UV-A) 0.055     Color image stabilizer (Cpd-1) 0.22     Color image stabilizer (Cpd-7) 0.003     Color image stabilizer (Cpd-9) 0.01     Color image stabilizer (Cpd-12) 0.01     Solvent (Solv-8) 0.05 [0275]   Sixth layer (UV absorbing layer)     Gelatin 0.46     Ultraviolet absorber (UV-B) 0.35     Compound (S1-4) 0.0015     Solvent (Solv-7) 0.18   Seventh layer (protective layer)     Gelatin 1.00     Acrylic-modified copolymer of polyvinyl alcohol     (Denature degree 17%) 0.4     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.02 [0276] Embedded image [0277] Embedded image[0278] Embedded image[0279] Embedded image[0280] Embedded image[0281] Embedded image[0282] Embedded image[0283] Embedded image[0284] Embedded image [0285] Embedded imageIn the sample P101 prepared as described above,
On the other hand, sample P10 in which the composition of the first layer was changed as follows:
2 to P105 was created. First layer of sample P102 (blue sensitive emulsion layer)     Silver chlorobromoiodide emulsion A (gold-sulfur sensitized cube, large size emulsion A-1 and small size 3: 7 mixture (silver molar ratio) with emulsion A-2. )                                                           0.24     Gelatin 1.25     Yellow coupler (ExY) 0.57     Color image stabilizer (Cpd-2) 0.06     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-20) 0.11     Solvent (Solv-9) 0.36 [0287] First layer of sample P103 (blue sensitive emulsion layer)     Silver chlorobromoiodide emulsion A (gold-sulfur sensitized cube, large size emulsion A-1 and small size 3: 7 mixture (silver molar ratio) with emulsion A-2. )                                                           0.15     Gelatin 1.25     Yellow coupler (Exemplary Compound 3) 0.30     Color image stabilizer (Cpd-2) 0.06     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-20) 0.11     Solvent (Solv-9) 0.36 For sample P104 to sample P105, sample P103
Yellow couplers shown in Table 13
Changed to be equimolar. The photosensitive material P103 is 127 mm wide.
Minilab made by Fuji Photo Film Co., Ltd.
Using printer processor PP350 (trade name)
Imagewise exposure from the negative density film
Of the color developer replenisher used in the following processing steps.
Continuous processing until the capacity is twice the capacity of the color developer tank
(Running test) was conducted. Treatment liquid composition and process time
The light-sensitive material was evaluated by performing the following two different processes. Processing using the processing solution below processing step A
A.       Processing temperature Temperature Time Replenishment amount *       Color development 38.5 ° C 45 seconds 45 mL       Bleach fixing 38.0 ° C 45 seconds 35 mL       Rinse 1 38.0 ° C. 20 seconds −       Rinse 2 38.0 ° C. 20 seconds −       Rinse 3 ** 38.0 ° C 20 seconds-       Rinse 4 ** 38.0 ° C 20 seconds 121mL       Dry 80 ° C (note) * Photosensitive material 1m²Replenishment amount per ** Phosphorus screening system RC50D (trade name) manufactured by Fuji Photo Film Co., Ltd. ) Is attached to the rinse 3, the rinse solution is taken out from the rinse 3, and reverse osmosis by a pump Send to module (RC50D). The permeated water sent in the tank is supplied to the rinse 4, Return the concentrate to rinse 3. The amount of permeated water to the reverse osmosis module is 50 to 300 mL / The pump pressure was adjusted to maintain the minute, and the temperature was circulated for 10 hours per day. Rinse A 4-tank counterflow system from 1 to 4 was adopted. The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] 800 ml of water 800 ml Optical brightener (FL-1) 2.2g 5.1g Optical brightener (FL-2) 0.35 g 1.75 g Triisopropanolamine 8.8g 8.8g Polyethylene glycol average molecular weight 300 10.0 g 10.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.20g Potassium chloride 10.0 g − 4,5-dihydroxybenzene-   Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate   Ethyl) hydroxylamine 8.5 g 14.0 g 4-Amino-3-methyl-N-ethyl-N-   (Β-Methanesulfonamidoethyl) aniline   ・ 3/2 sulfate ・ Monohydride 4.8g 14.0g Potassium carbonate 26.3g 26.3g Add water for a total volume of 1000 mL 1000 mL pH (adjusted with sulfuric acid and KOH at 25 ° C) 10.15 [Bleaching fixer] [Tank solution] [Replenisher] 800 ml of water 800 ml Ammonium thiosulfate (750 g / L) 107 mL 214 mL m-Carboxybenzenesulfinic acid 8.3 g 16.5 g Ethylenediamine tetraammonium iron (III) acetate 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1g 46.2g Add water for a total volume of 1000 mL 1000 mL pH (adjusted with nitric acid and aqueous ammonia at 25 ° C.) 6.5 6.5  [Rinse solution] [Tank solution] [Replenisher solution] Chlorinated isocyanurate sodium 0.02g 0.02g Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL pH (25 ° C.) 6.5 6.5 Processing step B Sample P103 is processed into a 127 mm wide roll and processed
Fuji Photo Film so that time and processing temperature can be changed
Minilab printer processor PP350
Photosensitive materials using experimental processing equipment modified from (trade name)
Imagewise exposure is performed from a negative film with an average density.
The volume of color developer replenisher used in the processing process
Continuous processing (running test) until the image tank capacity is doubled
Strike). Treatment using this running treatment liquid
It was set as the process B.     Processing temperature Temperature Time Replenishment amount *     Color development 45.0 ℃ 20 seconds 45mL     Bleach fixing 40.0 ℃ 20 seconds 35mL     Rinse 1 40.0 ° C 8 seconds-     Rinse 2 40.0 ° C 8 seconds-     Rinse 3 ** 40.0 ° C 8 seconds-     Rinse 4 ** 38.0 ° C 8 seconds 121mL     Drying 80 ℃ 15 seconds (note) * Photosensitive material 1m²Replenishment amount per ** Rinse the Fuji Screening Corporation RC 50D phosphorus screening system 3 is attached, the rinse liquid is taken out from the rinse 3, and the reverse osmosis module is pumped To (RC50D). The permeated water sent in the tank is supplied to the rinse 4, and the concentrate is recycled. Return to step 3. The permeate flow rate to the reverse osmosis module is maintained at 50 to 300 mL / min. The pump pressure was adjusted so that the temperature was circulated for 10 hours per day. Rinse from 1 to 4 4 tank countercurrent system. The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] 800 ml of water 800 ml Optical brightener (FL-3) 4.0g 8.0g Residual color reducing agent (SR-1) 3.0 g 5.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 10.0 g 10.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.10g Potassium chloride 10.0 g − 4,5-dihydroxybenzene-   Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate   Ethyl) hydroxylamine 8.5 g 14.0 g 4-Amino-3-methyl-N-ethyl-N-   (Β-Methanesulfonamidoethyl) aniline   ・ 3/2 sulfate ・ Monohydride 7.0g 19.0g Potassium carbonate 26.3g 26.3g Add water for a total volume of 1000 mL 1000 mL pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.25 12.6 [0292] [Bleaching fixer] [Tank solution] [Replenisher] 800 ml of water 800 ml Ammonium thiosulfate (750 g / L) 107 mL 214 mL Succinic acid 29.5g 59.0g Ethylenediamine tetraammonium iron (III) acetate 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1g 46.2g Add water for a total volume of 1000 mL 1000 mL pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.00 6.00  [Rinse solution] [Tank solution] [Replenisher solution] Chlorinated isocyanurate sodium 0.02g 0.02g Deionized water (conductivity 5μS / cm or less) 1000mL 1000mL pH (25 ° C.) 6.5 6.5 Process C Using the processing solution of processing step B in the running state,
The processing speed was shortened by changing the transfer speed of the sir to 1.8 times.
The process was designated as process step C. The compounds used are shown below.
The [0293] Embedded imageSamples P101 to P105 are coated with photosensitive material.
After 10 days storage at 25 ° C and 55% relative humidity conditions
Evaluation was performed. (Evaluation 1 Rapid processing suitability (Dmax processing fluctuation)) Each sample
465 with an exposure time of 1/10000 sec.
Blue through nm bandpass filter and optical wedge
Was given a separate exposure. Each exposed sample is treated in the following three types:
Process under the physical conditions and measure the maximum density of the yellow coloring area.
Fast processability and process stability were evaluated. Process B and
And processing step A of the maximum density of the yellow coloring portion of processing step C
The relative value (percentage) with respect to the maximum concentration was calculated. (Evaluation 2: Calculation of Dmax (UV) / Dmin (UV)) Color temperature 4800
Sharp cut made by Fuji Photo Film with white exposure at ° K
1 second exposure time through filter SC-39 (trade name)
And the sample that was exposed to an exposure amount of 2000 CMS and no exposure
Each of the light samples was subjected to the color development processing A described above, and these
Of the exposed and unexposed samples, the one with the higher color density (this
In the example, the exposed sample is Dmax, the one with the lower color density.
Let Dmin be an unexposed sample in this embodiment. After processing
For each sample, the UV concentration is measured in the same manner as in Example 1. Definition of Dmax (UV) / Dmin (UV): “(Maximum yellow color density
Part absorbance at a certain wavelength UV) / (yellow minimum)
(Absorbance at a certain wavelength UV)
Among these numerical values, wavelength UV (UV is 340 nm or more and 450
The smallest value at a certain wavelength below nm. Defined by
It is. (Evaluation 3 (BC) / A calculation) Sample of evaluation 2 is used.
Maximum color development area (Dmax) (ie exposure in this embodiment)
Sample) yellow density B and minimum color development (Dmin)
(Ie, unexposed sample in this example)
Degree C is HPD densitometer (Fuji Photo Film 436n
m). Compound represented by general formula (I)
Application amount Amol / m²Calculate (BC) / A using
Set. Table 13 shows the results of evaluations 1, 2, and 3. [0295] [Table 13]According to Table 13, yellow of the general formula (I)
When the light-sensitive material of the present invention containing a coupler is used, rapid processing is possible.
It can be seen that there are few fluctuations in the maximum concentration of. Example 6 In sample P101 of Example 5, only the composition of the first layer is
Samples P201 to P210 changed as described above were prepared. First layer of sample P201 (blue sensitive emulsion layer)     Silver chloride emulsion A (gold-sulfur sensitized cube, large size emulsion A-1 and small size milk 3: 7 mixture (silver molar ratio) with agent A-2. )                                                           0.20     Gelatin 1.25     Yellow coupler (Exemplary Compound 3) 0.15     Yellow coupler (ExY) 0.28     Color image stabilizer (Cpd-2) 0.06     Color image stabilizer (Cpd-3) 0.07     Color image stabilizer (Cpd-20) 0.11     Solvent (Solv-9) 0.36 [0298] First layer of sample P202 (blue sensitive emulsion layer)     Silver chloride emulsion A (gold-sulfur sensitized cube, large size emulsion A-1 and small size milk 3: 7 mixture (silver molar ratio) with agent A-2. )                                                           0.22     Gelatin 1.25     Yellow coupler (Exemplary Compound 3) 0.08     Yellow coupler (ExY) 0.42     Color image stabilizer (Cpd-2) 0.06     Color image stabilizer (Cpd-3) 0.07     Color image stabilizer (Cpd-20) 0.11     Solvent (Solv-9) 0.36 For sample P203 to sample P210, sample P103
Yellow couplers shown in Table 14
Changed to be equimolar. Samples P101 to P105 of Example 5 and
Using the above P201 to 210, 25 ° C. after applying the photosensitive material
-12.7c after 10 days storage at -55% relative humidity
Processed into a roll of m width x 200 m, according to Example 5
Evaluations 2 and 3 were performed, and the following evaluation 4 was performed. [Evaluation 4: Static fogging] Each roll is 10 ° C under no light.
Rewind at 100 m / min in an atmosphere with a humidity of 25%
Thereafter, the treatment was performed in the treatment step B without exposure. place
Visually detect the number of electrostatic fog generated on a white background after treatment
did. Against the number of electrostatic fog generated on sample P101
Table 14 shows the relative values (percentage). [0300] [Table 14]According to Table 14, the photosensitive material of the present invention was used.
It can be seen that there is little electrostatic fog. Example 7 In the samples of Examples 5 and 6, the composition of the fifth layer is as follows:
Samples changed as described above were prepared, and in accordance with Examples 5 and 6
As a result of the evaluation, rapid processing suitability and electrostatic fog resistance
It was found to be excellent. 5th layer (red-sensitive emulsion layer)     Silver chlorobromide emulsion E (gold-sulfur sensitized cube, large size emulsion E-1 and small size 5: 5 mixture with emulsion E-2 (silver molar ratio). )                                                           0.10     Gelatin 1.11     Cyan coupler (ExC-1) 0.02     Cyan coupler (ExC-3) 0.01     Cyan coupler (ExC-4) 0.11     Cyan coupler (ExC-5) 0.01     Color image stabilizer (Cpd-1) 0.01     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.01     Color image stabilizer (Cpd-17) 0.01     Color image stabilizer (Cpd-18) 0.07     Color image stabilizer (Cpd-20) 0.01     UV absorber (UV-7) 0.01     Solvent (Solv-5) 0.1 [0303] Embedded image[0304] The silver halide color photographic light-sensitive material of the present invention.
The material is excellent in anti-static fogging. According to the present invention
For example, anti-fogging and sharpness of images that can be formed.
And maintain good processing without losing the processability of the photosensitive material.
Can be improved.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroyuki Yoneyama             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. (72) Inventor Kiyoshi Takeuchi             210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo             Within Film Co., Ltd. F-term (reference) 2H016 AB03 BE02

Claims (1)

What is claimed is: 1. A blue sensitive emulsion layer containing at least one yellow coupler, a green sensitive emulsion layer containing a magenta coupler, and a red sensitive emulsion layer containing a cyan coupler on the support. A silver halide color photographic light-sensitive material having at least one coupler represented by the following general formula (I) in the blue-sensitive emulsion layer:
A silver halide color photographic light-sensitive material satisfying a-1) and / or b-1). [Chemical 1] (In the formula, Q represents a group of nonmetallic atoms that form a 5- to 7-membered ring with —N═C—N (R1) —, R1 represents a substituent, R2 represents a substituent, and m is 0 or Represents an integer of 1 to 5. When m is 2 or more, a plurality of R2s may be the same or different and may be bonded to each other to form a ring, and X is a hydrogen atom or an oxidized developer. A-1) 0.5 ≦ Dmax (UV) / Dmin (UV) ≦ 1.1 (where Dmax (UV) / Dmin (UV) is the maximum of yellow) Among the numerical values represented by the absorbance at a certain wavelength UV of the color density portion / (the absorbance at a certain wavelength UV of the yellow minimum color density portion), the wavelength UV (UV is from 340 nm to 450 nm)
It means the smallest value at a certain wavelength below nm. B-1) 1300 ≦ (BC) / A ≦ 20000 (where B represents the yellow maximum color density, C represents the yellow minimum color density, and when the support is a transmission support, the transmission density, the support) Means the reflection density when A is a reflective support, and A is the amount of the coupler represented by the general formula (I) (mo
l / m ² ). )