JPS5814832A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To prevent stains and to elevate sensitivity, by adding a water-soluble and nondecolorable dye having a specified absorption peak to at least one layer of a silver halide photosensitive material containing a specified 2-equivalent magenta coupler. CONSTITUTION:A water-soluble and nondecolorable dye, such as formula III, having a 580-620nm absorption peak is added in an aq. alkaline soln. by 0.1- 100mg/m<2> to a silver halide color photosensitive material containing a 2-equiv. magenta coupler of 4-arylthio-5-pyrazolone, such as formula II, represented by general formulaIin which Ar is phenyl substd. by a halogen, alkyl, alkoxy, alkoxycarbonyl, or cyano group; R1 is H, halogen, hydroxy, alkyl, aryl, or the like; M is 1-5, when m>=2, each of R1 may be equal or different; and Y is acylamino or anilino. The obtained color photosensitive material is enhanced in sharpness and sensitivity, and prevented almost from stains.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photosensitive material containing a 2-equivalent magenta coupler r.

For silver halide color light-sensitive materials, it is necessary to use a 2-equivalent coupler in order to improve sharpness and developability, and a 2-equivalent magenta coupler is described in US Pat. ．． 2:2
7. ! It is also disclosed in issue J≠. Among these, ≠-Arylthio! -Pyrazolone couplers are advantageous in terms of sensitivity and two-strike effects.

Although this coupler has considerably improved staining (color staining caused by unreacted residual coupler gradually changing and developing color) compared to other two-spot magenta couplers, it is still not satisfactory. Also, is the sting generated from the ≠−diluthiol J-pyrazolone coupler the previously known sting? Additives that prevent this were not able to prevent it much.

JP-A No. 3/10 discloses a technique for whitening the white background of photographic paper using an oil-soluble dye, but this specification does not include guarylthio! - There is no specific disclosure of pyrazolones or disadvantages thereof, nor is there any disclosure of water-bathable dyes.

The purpose of the present invention is, first, to prevent the stain r that occurs when using the Hiro-arylthio-,1-birazoronko damage macenta coupler 7, and second, to improve the sharpness by utilizing this prevention technology. An object of the present invention is to provide a color light-sensitive material with a high sieve sensitivity and almost no staining.

The object of the present invention is to provide an absorption peak of at least one l- in a color photosensitive material containing a 2-equivalent magenta coupler 7 represented by the following general formula (1).
This was achieved by adding a water-bathable non-decolorizing dye at 0 nm.

The water-resistant, non-decolorizing dyeing of the present invention uses anthraquinone-based, azo-based, and phthalocyanine-based dyes with water-washable groups (e.g., carboxylic acid groups, sulfones, phosphoric acids, and their metal salts such as sodium and potassium). ) r It is worth it.

Even if two or more types of dyes of the present invention are mixed, it is sufficient that the absorption peak at that time is between StO and A-20 nm.

The dye of the present invention can be added in a water bath solution or alkaline water #4, and the amount of addition is o, i to i0 onrg/m2, preferably /-10yng/m2.

General formula (I) Ar In the formula, Ar represents a phenyl group in which at least 7 or more halogen atoms, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cyano group are dusted with W, and FL represents a hydrogen atom, a halogen atom, An acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an alkoxycarbonyl group, a hydroxy group, an alkyl group, an alkoxy group, or an aryl group, m is 1
from! When m is 2 or more, the roues may be the same or different. Y represents an acyl 7ξ group or anilino group.

Among the compounds represented by the general formula (I), particularly preferred compounds can be represented by the general formula (■).

General formula (11) In the formula, Ar has the same meaning as in general formula (11), R2 represents an argyl group, and X represents a halogen atom or alkoxy! ('?r expression, L(
, 3 represents a water bond, a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, or an alkyl group, and 1(・
4 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, a sulfone diamide group, a sulfamoyl group, a carbamoyl group, a diacylamino group, an alkoxycarbonyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, an alkanesulfonyl group, an aryl Represents a sulfonyl group, an alkylthio group, an arylthio group, a -ter-alkyloxycarbonylamino group, an alkylureido group, a sulfonyl group, a nitro group, a carboxy group or a trichloromethyl group. Hail integer t from n l-i / to -.

More specifically, Ar is a substituted phenyl group, and the substituents include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, etc.), an alkyl group having 1 to 22 carbon atoms (for example, a methyl group).

ethyl group, tetradecyl group, t-butyl group, etc.), alkoxy groups having 1 to 22 carbon atoms (e.g., methoxy group, ethoxy group, octyloxy group, dodecyloxy group, etc.),
An alkoxycarbonyl group having λ to -23 carbon atoms (for example,
methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group, etc.) or cyano group.

To explain X in more detail, dodecyloxy group, etc.)
r represents.

io-R4 in more detail, R4 is a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, fluorine atom, etc.), a linear or branched alkyl group (e.g. methyl group, t
-butyl group, tetradecyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, λ-ethylhexyloxy group, tetradecyloxy group, etc.), cylamino group (e.g., acetamide group, benzamide group, zotanamide group, tetradecane group) Amide group, α-(2, Hirojit
ert-amylphenoxy)acetamide group, α-(2
9μm Di-tert-amylphenoquine)butyramide group, α-(3-pentadecylphenoxy)hexanamide group, α-(4A-hydroxy-J-tert-7'tylphenoxy)tetradecanamide group, 2-oquine-virolidine- l-yl group (% co-oxo, tetradecylpyrrolidin-l-yl group, N-methyl-tetradecanamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonand group, p-)luenesulfone Rindo group, octane sulfonamide group, p
-dodecylbenzenesulfonylamide group, N-methyl-tetradecanesulfonamido group, etc.), sulfamoyl group (e.g., N-methylsulfamoyl group, N-hexadecylsulfamoyl group, N-C3-(dodecyl oxy)-propyl]sulfamoyl group, N-(4'-(@
21≠-di-tert-amylphenoxy)butyl]sulfamoyl group, N-methyl-N-tetradecylsulfuryl group), carbamoyl L (e.g., hemethyl-rbamoyl group, N-octadecylcarbamoyl M,
N-(≠-(-1μm sheet tert-amylphenolic)phthyl]carbamoyl &, N-methyl-he-tetradecylcarbamoyl group, etc.), dianrylamino group (N-succinimide group, N-phthalimide group, -2,j -dioxo-7-oxazolidinyl group, 3-dodecyl-.

! -dioquine/-hydantoinyl group, 3-(N-acetyl-he-dodecylamino)succinimide group, etc.)
, an alkoxycarbonyl group (e.g.

methoxycarbonyl group, tetradecyloxycarbonyl group, benzyloxycarbonyl group, etc.)% alkoxysulfonyl group (e.g., meth#'/sulfonyl group,
octyloxysulfonyl group, tetradecyloxysulfonyl group, etc.), arylo"cis"bonyl M(
For example, Id, phenoxysulfonyl group, 2.41-dit
ert-amylphenoxysulfonyl group, etc.% alkanesulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, λ-ethylhexanesulfonyl group,
hexadecanesulfonyl group, etc.), ryorylsulfonyl group (e.g., benzenesulfonyl group, Hiro-nonylbenzenesulfonyl group, etc.), alkylthio group (e.g.,
Ethylthio group, hexylthio group.

Benzylthio group, tetradecylthio &, '-(-.

p-Q-tert-methylphenoxy)ethylthio group,
), arylthio & (e.g. phenylthio group, 1
)-)lylthio group, etc.), alkyloxycarbonylamino, If! i (for example, ethyloxycarbonylamino group, benzyloxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido group (for example, N-methylureido group, N,N-dimethylureido group) , N-methyl-N-dodecylureido M, N-hexadecylureido%, N,N-dioctadecylureido group, etc.), acyl group (e.g., ryocetyl group, benzoyl group, octadecanoyl group, p-dodecane Midobenzoyl group, etc.)
, nido group, carboxy group or trichloromethyl group?
represent. However, among the above substituents, those defined as alkyl groups have 7 to 31.2 carbon atoms, and those defined as aryl groups have 6 to 315 carbon atoms.

To explain H・2 in more detail, R12 is charcoal 18
/--22 alkyl groups (e.g., methyl group, propyl group, butyl group, J-methynethyl group, methoxymethyl group, hexyl group, coethylhexyl group, dodecyl group,
hexadecyl group, λ-(-2° gauge-tert-amylphenoxy)ethyl group, 2-dodecyloxyethyl group, etc.), aryl group (e.g. phenyl group, α- or β-naphthyl group, ≠ -tolyl group, etc.) r.

H2S represents a hydrogen atom, a hydroxy group, a ``2'' (having the same meaning as , 4), a rogene atom, an alkyl group, an alkoxy group, or an aryl group.

-1[(l) among the couplers, H・2
It is particularly preferable that the sum of the carbon numbers of and (3) is 6 or more in terms of achieving the object of the present invention.

Typical coupler compound examples of the present invention are shown below, but are not limited to (i, 1, etc.).

−/j゛− 2) 1 3) 76− ≠ ) UC4H9 (! j ) (ε 77− 6 ) (1! 7) α −/I− ” t−Jc8ti, 7
Ce''.) CB1117-ltar θ) 6g //) -, 20- jin e 27- flash○ insult-2λ- α/G) α −,2j− 2,2) () 26−λ3) (,e 211L) 27−koyo) Cノ26) 1,2/−,27) −g) (τ −,2terλ−) 30 ) t 30- 31) (,'g 3.2) 3 l- 33) 34() -J +2- 3ri α 36) G' 33- 37) (1 31) (Z -3 Hiroshi-! 35- HiroO) e ≠l) Cso36-u2) Shi11 ≠3) <l37- Stine is formed by a chemical reaction between unreacted couplers and substances remaining in the processed sample. This is due to the color produced by the colored substances.The whiteness of the photographic paper is affected by the color.There are various methods for measuring whiteness, but here we will use the CIE method.
The X value and X value of the chromaticity diagram were used. The CTFJ chromaticity diagram is described in Chapter 7, Section 3 of the new Color Science Handbook. In terms of color, it looks white when X is about 0.31
0°y is around 0.321, and the closer it is to this value, the whiter it looks.

The emulsion used in the present invention is P, C by G1afkides.
bimie et i'hysique Photo
ographique (published by Paul Monte1)
1267), G, F'.

Photographic Emuls by Duffin
ionChemistry (The k'ocalP
ress (published in 1936), V, L, Zeme kman
Making and Coating by et al.
Photographic Emulsion (The
It can be prepared using the method described in I'ocal Press, 196≠). In other words, any of the acidic method, neutral method, ammonium method, etc. can be used, and the methods for reacting complex salts with soluble halogens include one-sided mixing method, simultaneous mixing method, and combinations thereof. Any of the following may be used.

A method (so-called back mixing method) in which particles are formed into a J structure with an excess of silver ions can also be used.

As one type of simultaneous mixing method, a method in which silver halide is maintained at a pAgv level in the phase along which it is produced, that is, a so-called Chondrold double jet method can also be used.

According to this method, a silver halide emulsion having a uniform crystal shape and a nearly uniform grain size can be obtained.

Silver halide emulsions of 1M or more that have been prepared separately may be mixed and used.

It can be introduced into the Cub'7-f silver halide emulsion layer used in the present invention by known methods such as those described in US Patent λ, J, 2.
The method described in No. 2.027 can be used. For example, phthalic acid alkyl ester (dibutyl phthalate),
dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphoryl),)
! cresyl phosphate, diocnaldutylphosphate).

Citrate esters (e.g. acetyl tributyl citrate), benzoate esters (e.g. octyl benzoate)
, alkylamides (e.g. diethyl laurylamide)
, monofatty acid ester derivatives (e.g., dibutyl esters, di-octyl esters), Nisder mesinates (e.g., tributyl trimesate), or organic baths with a boiling point of about 30°C to /JO0C. After being dissolved in a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl fropionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethyne ethyl acetate, methylseron ruduacetate, etc., it is dispersed in a hydrophilic colloid. Ru. The above-mentioned high boiling point organic F6 medium and low boiling point ') Pi medium may be mixed for use.

Further, the dispersion method using a polymer described in Japanese Patent Application Publication No. 113 and Japanese Patent Application Publication No. 2007-110003 can be used.

When the coupler has an acid group such as carboxylic acid or sulfmenic acid, it is introduced into the hydrophilic colloid as an alkaline water bath.

Example 1゜Magenta coupler 7-(co,4',&-)lichlorophenyl)-J-((2-rio-j-tetradecanamide)anilinoJ-41-((2-n-butoxy-t −
t-octyl)phenylthio)-11 birazoline! −
On (Coupler 1) 1092 tricundyl phosphate θmQ, [1ethyl phosphate 〇mti K! This m solution was emulsified and dispersed in gelatin bath solution/θ02 containing t/% sodium dodecylbenzenesulfonate aqueous solution ♂m9'2.

Next, this emulsified dispersion r green-sensitive chlorobromide emulsion (BrjO
mol qb) and added with sodium dodecylbenzenesulfonate as a coating aid to obtain a coating solution for the third layer shown in Table 7.

Using this coating solution r, a multilayer color photosensitive material r having the structure shown in Table 7 was prepared as Sample A.

Dyes in the second layer - 2), J), Za) and comparative dyes -≠
l - Aqueous solution of 20.2% is acidified and the amount of coating is j tng.
It was added to the sea urchin which became 7m2. Using such a first layer, samples B, C, and C were prepared in the same manner as sample A, respectively.
D, Ey, created.

Also, a coupler (3) in place of the third layer coupler (5),
Samples h', Q, and () were made corresponding to each sample using the comparative coupler r and otherwise in the same manner as sample B.

These samples A to 111 were passed through a continuous wedge r at /θOθlux for 1 second without light, and then treated with the following treatment solution.

Developer benzyl alcohol /jml! diethylenetriaminej acetic acid yo2KBr
O,tty~a28
03 19~a2Cυ3
3Cg hydroxylamine @ acid l 2y Hiro-amino-3-methyl-N
-Ethyl-N-β-(methanesulfonamide)ethylaniline・3/2H28U4・H2O≠, tf-da λ- Make 7000 mQ with water p I-1/0,
/Bleach-fix solution Nao@Ammonium E acid (70wt%) lyo0rnQN a 2
SU a”Na(f
+'e(EDTA)] 4AoyEDT
A 4'9 10 with water
'00m (set to 1) pH 7, a' processing culm Temperature Time Developer 33° 3 minutes 30 seconds White fixer
33° 1 minute 30 seconds water washing 2i-
3j 0 3 minutes - Hiroshi 3 - Each sample on which a dye image had been formed in this way was irradiated with light using a fluorescent lamp at an illuminance of 20,000 lux for a week. The X value and y value r of the CIE chromaticity table were determined and the values are summarized in Table λ.

A 15) / 0.3/l" 0.
32g Comparative Example B (5) Dye, 2) 0.3
0g 0.3.26 Invention C(5) Dye J)
0. J/θ 0,3-za 〃D(5) Dye J) 0.309 0.32A ttE(5)
Comparative dye 0.3/≠ 0.32g Comparative example F (3
) Dye 2) 0.30 0.327 Invention G
Comparative coupler dye, 2) 0.310 0.32t
Comparative Example From the above table, it can be seen that the samples of the present invention have a high degree of processed whiteness.

Patent applicant: Fuji Photo Film Co., Ltd. -≠ 6-

Claims (1)

[Claims] Guarylthio! - Silver halide color sensitive material containing pyrazolone 2 and magenta coupler R has at least one water-bathable non-decolorizing dye R in at least one layer, and its absorption peak is
Silver halogenide color light-sensitive material characterized by the fact that it is on ln.