JPS59192247A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent color stain without reducing the potographic sensitivity by incorporating a specified compound into an intermediate layer and/or an emulsion layer as a color stain inhibitor. CONSTITUTION:An intermediate layer and/or an emulsion layer contg. a compound represented by formula I or II as a color stain inhibitor is formed on a support. The preferred amount of the compound contained in the intermediate layer is 1.0X10<-3>-1.0X10<-5>mol/m<2>, and that of the compound contained in the emulsion layer is 1.0X10<-4>-1.0X10<-6>mol/m<2>. In the formulae, each of A and B is -CO- or -SO2-; R<1> is H, halogen, alkyl, alkoxy, arylsulfonamido or the like; each of R<2> and R<3> is aryl, alkyl, amino or the like; each of R<4> and R<5> is a bivalent group required to combine phenol rings or naphthol rings; R<4> may bond to B to form a disulfonyl residue or a dicarbonyl residue; R<5> may be alkylene or a dioxy residue; and each ring having substituted OH may form a naphthol ring together with a group of atoms Q.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic light-sensitive material that prevents color staining, and relates to a silver halogenide color photographic light-sensitive material containing sulfonamide phenol or naphthol derivatives as a color stain preventive agent. It is something.

In multilayer color photographic materials of the type that contain a color-forming coupler in a silver halide photographic emulsion and are developed using a color-forming developer such as It is well known that the phenomenon of so-called "color turbidity" (color mixing) occurs in which undesirable dyes are formed by migration into adjacent imaging layers. It is known that an inconvenient "color fog" phenomenon occurs due to air oxidation of the developing agent, fog of the emulsion, etc. during rough color development. In the following, this "color turbidity" and "color fog" will be collectively referred to as "color contamination."

In order to prevent color staining, various methods using hydroquinone have been proposed. For example, regarding the use of monolinear alkylhydroquinone, see US Pat. -10 Otsu 3
Regarding the use of monobranched alkylhydroquinone in No. 2, etc., see US Pat. No. 3,700, Koyu No. 3, West German Patent Publication No. 2.

14'ri, 7g7, Tokukai Sho! ;0-/jtμ3r and ≠2-106329. On the other hand, for dilinear alkylhydroquinone, U.S. Patent No. 2.72
g, 4jz No. 2,732,300, British Patent No. 7 λ, /≠6, same /, θg O.

No. 201 and “Chemical Abstract” magazine evening volume Otsu 3
1, '7h, etc., and for di-branched alkylnohydroquinone, see US Pat. No. 3,700, IA No. 3, No. 2,
No. 732,300, British Patent No. 1,011. , issue 20,
"Chemical Abstract" magazine, special HF3+ Akira!
0-/! /． lA31, Tokuko Akira. ! □-2/24t number, same 5t-μθ? There is a description in the lt issue etc.

In addition, British patent jjF describes the use of alkylnohydroquinone as a color stain inhibitor.

, zrr No. 117, No. 73-0 (corresponding U.S. Patent No. 2
.

360, 210), 117, 102, 73/,
No. 301 (corresponding U.S. Pat. No. 2,70/197) U.S. Pat.
No. 0, No. 3, 11r2, 333, West German Patent Publication 2, Evening 0! , θ/ No. (corresponding to Japanese Patent Application Laid-open No. 10337),
There is also a mention of Tokko Showyu T-G Ofl in the issue.

It is known that the "Color 1 Shu 9" phenomenon occurs in color diffusion transfer photographic materials as well as in ordinary color photographic materials, and to prevent this, the above-mentioned hydroquinones are used to improve diffusion transfer sensitivity. Hydroquinone used as an agent for preventing color turbidity of materials is described in JP-A No. 2003-110002, No. F-2/2≠.

Regarding the use of sulfonamide phenols as color clouding preventive agents for diffusion transfer sensitive materials, see Research Disclosure magazine istt2 (i273), p. 13, JP-A-Sho! j-72/! rI, JP-A-57-2≠2≠7 (corresponding U.S. patent μ, J&&.

No. 226).

In recent years, in the field of manufacturing technology for color photographic materials, in order to obtain higher quality color photographs, color contamination can be more efficiently prevented without reducing photographic sensitivity, and a thin layer is used to improve sharpness. There is a strong need for the development of new color stain inhibitors that can be added to processed photosensitive materials, do not cause any change in performance even after long-term storage, and also contribute to improving the light fastness of dye images formed by color development. desired.

The first object of the present invention is to provide a novel color stain inhibitor. A second object of the present invention is to provide a novel color stain prevention agent that efficiently removes oxidized products of color developers or charge transfer black developers. A third object of the present invention is to provide a novel color stain preventive agent that can be used to form thin-layered photosensitive materials. A fourth object of the present invention is to provide a new color stain inhibitor that does not cause any change in performance even after long-term storage. Another object of the present invention is to provide a color photographic material containing this novel color stain inhibitor.

These objects of the present invention have been achieved by incorporating compounds of the following general formulas (1) and (II) into silver halide color photographic light-sensitive materials as color stain preventive agents.

(I) (11) However, in the formula, A and B each represent 100- or -3O2-, and at least one of them is -3O2-.

In the formula, the ratio 1 is a hydrogen atom, a hydrogen atom (e.g. chlorine,
(bromine, fluorine, etc.), alkyl groups (), rogene atoms, hydroxyl groups, alkoxy groups, etc., and preferably those with a total number of carbon atoms of /, / j-, such as methyl group, ethyl group , t-butyl group, n-hair tatecyl group, etc.), an alkoxy group (which may be substituted with a halogen atom, hydrogen group, aryl group, etc., and preferably has a total carbon number of /-10, such as a methoxy group) , ethoxy group, butoxy group, etc.), acylamino group (the acyl group may be substituted with an alkyl group, an aryl group, etc., and preferably has a total number of carbon atoms of 2 to 30, such as the following groups) acetylamino group, benzoylamino group, α-(2, gouge-t-amylphenoxy)propanamide group, etc.), alkylthio group (halogen atom,
It may be substituted with a hydroxyl group, an alkoxy group, etc., preferably one with a total number of carbon atoms of /-20, such as a methylthio group, a hexadecylthio group, an alkoxycarbonyl group (an alkoxy group is a halogen atom, a hydroxyl group, an aryl group, etc.) may be substituted with, preferably those having a total number of carbon atoms of 2 to 20, such as a methoxycarbonyl group,
ethoxycarbonyl group, etc.), aryloxycarbonyl group (aryl group may be substituted with an alkyl group, chlorine, alkoxy group, etc., and preferably has a total number of carbon atoms of 7 to 30, for example, phenoxycarbonyl M- 1
etc.), sulfamoylamino group (sulfamoyl group may be substituted with an alkyl group, aryl group, etc., and preferably has a total number of carbon atoms of 0-, !0, such as NH2SO2Nl-1- group, N, N-dizolopylsulfamoylamino group, etc.), carbamoylamino group (carbamoyl group may be sandwiched by an alkyl group, aryl group, etc., and preferably has a total number of carbon atoms of 2 to 0), For example, N1.(2CONH- group, N-7enylcarpamoylamino)k-1, etc.), arylsulfonamide group (aryl group may be substituted with alkoxy group, alkyl group, etc.), Number of carbons is 6
~3Q, such as goo(n-dobcycloxy) phenylsulfonamide group, p-tolylsulfonamide group,
(μm dodecyl phenyl sulfonamide group, etc.), alkyl sulfonamide group (the alkyl group may have a substituent such as a halogen atom, a hydroxyl group, an alkoxy group, etc., and preferably has a total number of carbon atoms of /-20, e.g. methane sulfonamide group, n-octanesulfonamide group, etc.), acyl group (preferably those having an alkyl group or aryl group having -5 to 20 carbon atoms, such as an acetyl group, an ethercarbonyl group, etc.), a sulfonyl group (preferably those having an alkyl group or aryl group having 1-2θ carbon atoms, such as p-toluenesulfonyl group), carbamoyl group (preferably having an alkyl group or aryl group having 1 to 20 carbon atoms, such as di-n -ocnalcarpamoyl group, etc.).

In the general formula (I), R and R are each a substituted or unsubstituted aryl group (aryl group is a halogen atom, an alkyl group,
It may be further substituted with an alkoxy group or the like.

The total number of carbon atoms is preferably t to 30. For example, g-(n-dobusyloxy)phenyl&, p-)IJsil, 3+4
t-di-chlorophenyl group, μm dodecylphenyl group), alkyl group (the alkyl group may be further substituted with a halogen atom, hydroxyl group, aryloxy group, alkoxy group, etc. Total number of carbon atoms/~3Q) Also (7)
75E Good 4 Good. For example, methyl group, trifluoromethyl group, n-hexadecyl group, /-(m-pentadecylphenoxy)propyl group, etc.), amino group (amine group may be substituted with alkyl group, aryl group, etc.) The total number of carbon atoms is preferably θ to 30.For example, dimethylamino group, dipropylamine group, etc.) may be included, and they may be the same or different.

几 and 几 are divalent groups that connect two phenol rings or naphthol rings.几4 cooperates with B to form a disulfonyl residue (preferably having 3 to 3 carbon atoms.
, J-henzendisulfonyl group, / 1j-Anthanedisulfonyl group, μ', 4L"-(l.

diphenoxybutane) disulfonyl group, etc.), diacyl residue (preferably carbon number λ to 2Q, e.g. oxalyl group, malonyl group, sebacoyl group, phthaloyl group, terephthaloyl group, etc.), disulfamoyl residue (carbon number 1),
~3θ is preferred. For example, Id-8OzNH(-CH2+
4NH8O2-! ), disulfonyl residue (number of carbon atoms/~
30 is preferred. For example, R5 may be a substituted or unsubstituted alkylene group (preferably having 1 to 20 carbon atoms, such as an ethermethylene group), a dioxy residue (preferably having 1 to 20 carbon atoms, such as an IA-butanedioquine group, etc.), or a ditheo residue. group (preferably has 7 to 20 carbon atoms, such as l, ≠-butane ditheo group, etc.), dioxycarbonyl residue (preferably has 7 to 20 carbon atoms,
2Q is preferred. For example, -CON
H+CH2+4NHCO- etc.).

The ring substituted with an OH group may form a naphthol ring from the atomic groups Q and K.

The substituents on the phenol ring and naphthol ring may be substituted at any position on the ring.

The compound represented by the general formula (I) or (II) has two sulfonamidophenol or nanthol skeletons in the molecule, and therefore has a large reducing ability and can prevent color staining with a small amount of addition. Suitable for use in colored photographic materials.

Among the compounds represented by the general formula (I) or (II), those having a phenol ring are most effective, and among them, the compounds of the following general formulas (Kawa) to (X) are preferred.

(Ill) (IV) (V) (Vl) (■) (■) (iX) (X) ~R is the same as the definition of general formula (IJ, (n)).

In the compounds included in (m), (IV), and (■) of the above general formulas, R1 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl basis,
Sulfonyl groups and carbamoyl groups are preferred.

In the compounds included in the above general formulas (V), (VI), and (■), 几1 is a hydrogen atom, an alkyl group, an acylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoylamino group, A carbamoylamino group, an acyl group, or a carbamoyl group is preferable, and as one that does not cause color development due to oxidative coupling with a color developer in color development, 几1 is an alkyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an acyl group. , a carbamoyl group is particularly preferred.

Of the 9 compounds represented by the above general formulas (In) to (X), the general formulas (ill), (IV), (V)
, (Vl) are preferred, and those of general formulas (III) and (IV) are most preferred.

It is particularly preferable that A and B in the above general formula are both -802-.

When the compound of the present invention is used as a color turbidity prevention agent in an intermediate layer, 1. It is preferable to use Oy, lO~/, Ox/θ-5 mol/m2, and when using a milking layer as a color fog preventive agent, it is preferable to use it at a concentration of /, 0x10 per layer.
~/, 0x10'mol/m2, but is not limited thereto. Furthermore, it can be added to both the intermediate layer and the emulsion layer to prevent color turbidity and color fog.

Specific examples of the compounds of general formulas (1) and (n) according to the present invention are shown below, but the present invention is not limited thereto.

Here, A, B, R, R, R, R, R are the same as defined in general formula (I), 1). X
is a group known to retain hydrogen or a hydroxyl group (for example, benzyl group), and a protective group can be introduced before the above reaction and removed after the above reaction, if necessary. R2
-A-CJ, C1-B-R' -B-(ffl are all acid chlorides of acids having -A-, -B-J(, -B- residues, respectively).

Reaction (A-/), (A-3), (B/).

(B-3) is an amidation reaction using aniline and acid chloride, and generally uses a deoxidizing agent (e.g. triethylamine, pyridine, ≠-(dimethylamino)pyridine, DBU, etc.)
The reaction is carried out in the presence of an aprotic polar solvent (eg, acetonitrile, dimethylformamide, dimethylacetamide, etc.). However, in the above route, when X is hydrogen, the deoxidizing agent is preferably a weakly basic crosslinker (such as pyridine) in order to obtain reaction selectivity. The reaction temperature is o
A temperature between 6C and solvent reflux is preferred.

Reactions (A-2) and (B-2) are reduction reactions of nitro groups to amino groups, and can generally be carried out by catalytic hydrogenation with hydrogen gas or reduction with metals (e.g. tin, iron, etc.). can.

Next, examples of synthesis of compounds according to the present invention will be shown.

Synthesis Example 1 Synthesis steps of exemplified compound (6)! NH20C12H2s A B Dissolve aniline A (/j, Hirof') in 10 mQ of pyridine, stir, and add solid sulfonyl chloride B (3
1,, It) was added. A slight exotherm was observed. This mixture was heated at reflux temperature for 1 hour and then allowed to cool for 70 minutes. 1f without it! , ice water containing salt p100mQ! ;
The mixture was slowly poured into 00mu under stirring. The precipitated crystals were collected, washed with water, and dried to give yellow crystals C≠72.
I got it.

Step 2 Nitrophenol C in 200mu of isopropanol
(≠72) and reduced iron (2 nights?) were added and heated to reflux while stirring. 1θml of concentrated hydrochloric acid was gradually added dropwise thereto, and after stirring with JOff, it was left to cool and 300ml of ethyl acetate was added.
mQ and 300 mσ of Tachijuso water were added to remove the solid content. The ether acetate layer was separated, washed with water, and then condensed to obtain blackish brown crude crystals. Recrystallized from methanol after treatment with activated carbon to obtain light brown crystals D3? I got it.

Amine phenol D (J2.4!
? ) was dissolved and stirred, and sulfonyl chloride E (//, Ofi/) was gradually added while cooling on ice.

After the addition, the mixture was heated at reflux temperature for 1 hour and then
It was left to cool for 0 minutes. Next, the mixture was gradually poured onto an ice-water solution θOmQ containing 100 rnQ of hydrochloric acid while stirring. The precipitated crystals were collected, washed with water, and dried to obtain crude crystals.

After treatment with activated carbon, white crystals F239 were obtained by recrystallization from acetonitrile.

Calculated value C as C64H86N4014S4:
tO, I3 H: t, rt N: lt, lI3 actual value C: AO, Otsu 7H:, 4.72 N:≠, 3/Synthesis example 2
Synthesis step I of exemplified compound (5)
Dissolve and stir, and add sulfonyl chloride E (22,
0? ) was added. Thereafter, the same operation as in step 1 of Synthesis Example 1 was performed to obtain Takadai crystal G339.

Step 2 Reduced iron 0HOH Using nitrophenol G (jJf/), the same procedure as in Synthesis Example 1 and Step 2 was carried out using aminophenol H (,!
71) was obtained.

+ φ 〒 White crystals J229 were obtained by the same operation as in Step 3 of Synthesis Example 1 using aminophenol H (/l, 4c9) and sulfonyl chloride I (/t, 29)f.

Calculated value as C56t-■7ON4014S4
C: rr, (AI H: 4./J N: gJ7 actual measurement IU
C: jf, /7 H: j, 91r N: lA, 7A
In order to introduce the compound of the invention into the constituent layers such as the emulsion layer and the intermediate layer, the known methods used for introducing the coupler into the emulsion can be applied.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl lauryl amide) , fatty acid esters (e.g. dibutoxyethyl sacinate, diocter azelate),
) rifsinate esters (e.g. tributyl trimesate), etc., or lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl acetate, secondary butyl alcohol, methyl isobutyl ketone, After being dissolved in β-ethoxyether acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point solvent and low boiling point solvent may be mixed and used.

The color stain inhibitor of the present invention is a halogenated type that forms a color image through oxidative coupling between an aromatic primary amine developer (for example, a phenylene diamine derivative or an amine phenol derivative) and a color-forming coupler in color development processing. Shows effectiveness in preventing color staining of color photographic materials.

As a color-forming coupler used in this type of color photosensitive material, for example, magenta coupler! - There are pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers Examples include naphthol couplers and phenol couplers. These couplers introduce a hydrophobic group called a ballast group into the molecule,
It is preferably used because it can be bonded to a polymer chain to make it non-diffusible.

The coupler may be either 1-equivalent or 2-equivalent to the scissors ion. It may also be a colored coupler that has a color correction effect, or a coupler that suppresses and releases (2) radiation during development (so-called DIR coupler).

A specific example of a magenta coloring coupler is disclosed in U.S. Patent No. 2゜too.
, 'yrtr issue, same 2. Flr3. AOr No., same J,
Ot2, tjj issue, same 3. / 27. No. 24P, No. 3, 3/I, No. 76, No. 3. ≠lri, 3ri No. 1, same!
,! IP, No. 2, 3. ! ! ♂, 3/9 issue, same j
, No. 112.322, 3,411.

rot- No. J, r31/-, No. 901, No. 3.1
9/, No. 44F, West German patent/, 110.1 Atlt.
No., West Germany, d(OLS), z, 4l-Dr,
ttj issue, same 2. It/7. Hari, same, 2. ≠／♂、
No. 52, 2. l/, 244. ut7, special public showament 4A
og.

No. 31, Tokukai Sho! /-20♂26, same J' 2- j
rY, No. 22, No. 119-/2?131, No. 17027 of the same turf, No. 3jt of the same to-is, No. 131 of the same! 2−μλ
/2/ issue, Getter 7 Hiro 0 Koza issue, same! 0-60233
No., same ta l-2t Jtu1 no., giant 141-jjt/22
This is what is listed in the issue.

A specific example of a yellow coloring coupler is given in US Pat.
No. 7, Ta, 3, 2! o6, same 3゜p-o♂, /9
≠ No. 3. Taro 1. /jyo issue, same 3,! Zako, 322
No., No. 3, 7, No. 072, No. J, lr9/, 4
Au! No., West German Patent T, sa7. rtr No. 2.21, No. 917, No. 2, xAt, No. JAt, No. 2. II/'t, No. 004, English 11th match/, lt2
Ta, oxo issue, special public show j/-10713 issue, 4! i' Vice Showa g 7-j A/J No. 3, 44I-73/9
7@, same j/-1O2t31. Same issue! 0-I J 4
! No. 7, same! 0-/233! No. 42, same 0-/
30 g No. 412, same j/-2/ J' 27
issue, O-za 7t on the same evening! θ, same! 2-J', 7-Hiro issue 2μ, 7-Hiro issue 32-//E-21 issue, etc.

Specific examples of cyan couplers are listed in US patents 2 and 3.

No. 2, No. 2.4t3≠, No. 272, No. λ, μ7It
, No. 293, same 2,! No. 21.901, 2゜♂5F
Ta, ♂ No. 2, same! , 0317. fri No. 2, same! ,! '
//, No. 4t7A, 3. l! ♂, 31! No. J,
p7A, jAj issue, same 3, jrY3.97/issue, same! , JRI/, 3t No. 3, J, 717, Hiroshi//, No. 41.0044.12P, -i German patent, condyle (O
LS) 2.4</4L, No. 130, 2. ”!4t.

No. 322, JP-A No. 1'-49131, same j/-2t0
J41, same l♂-IO! ! No., same, 1/-/1st 2g
Is it the same Tanou? No. 62≠, which is described in No. 2-2OF32.

As a colored coupler, for example, US Patent 3゜1/-
76,! ;1.0, 2.12/,'? Or, No. 3,03μ9g22, Tokko Sho 4L≠-2O1t, No. 3g-, 22333, No. 4'2-//3041, No. 3,03μt1, Tokko Sho! ;/-2A03μ
Specification of No. 2-≠2.12/Specification of West German patent gj (OLS) 2, IA/r, ? !
r Y fAL7) can be used.

As a DIR coupler, for example, U.S. Pat. Ta S4L, same 3. AI7,221, 3.7
01.7g No. 3, No. 3,790, No. 3 and 4, No. 3/A3
'2,3 Hiroyu issue, West German patent application ((,) L S )ko, μ/μ, No. 006, 1nj2,4 ta≠, 30/ issue,
1 ril, 2, 'A evening u, 32! P issue,
British patent yr3. ttst issue, JP-A-5.2-6262
≠ No., same μ Turco No. 233j, Special Publication No. 31-1411
What is not described in No. 41 can be put to practical use.

The color stain preventing agent of the present invention is useful for preventing color stains in so-called diffusion transfer type halogenated button color photographic materials. Dye image-forming compounds that can be used in this Jl+J photosensitive material include, for example, dye developers, dye-releasing redox compounds, and (1) DR couplers. , Dohiro, θJ-5, 4
/2g issue, -”gu, 07t,! No. 27, same gu, l! λ,
No. 153, 4μ.

/3! , No. 92F, Japanese Unexamined Patent Publication No. 13/41932! r number,
11m1! / -/ 04' 3 'l No. 3, same! ;3-'t1.730, same za-/30/22,
Same 33-311? Compounds described in Japanese Patent Application No. Shoj≠-guri No. 72g, Takota Orot No. 15 μm 9//za No. 7, etc. can be used.

The compound of the present invention may be used in combination with known color stain inhibitors, such as hydroquinone derivatives, amine phenol derivatives, gallic acid derivatives, and ascorbic acid derivatives.

A specific example is the US patent No. 3tO,2';? No. 0, No. 2
．． 33t, No. 327, same 2.110! , 72/No. 2, U,/I, A/3, No. 2, 1,
71.3 no Hiro No. 2,70/, /ri No. 7, same co, 7
041.

No. 7/3, 2.72g, No. 6j'2, 2,732g.
No. 300, 2.73jr, 31. JT issue, Tokukai Sho! ;
0-9291#, same jtO-92!1119, same!
;0-93 Octopus g No., No. 30-110337, Same Ta,
7. -/ll-6235, Special Public ShojTO-231/3
It is stated in the number etc.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a ≠-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a penzoxazole compound, and an ultraviolet absorbing polymer can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer.

For other photographic silver halide emulsions that can be used in the color sensitive material of the present invention, their preparation methods, and photographic additives (or photographic materials), please refer to [Re5erc
h L)isclosurej magazine, 7111Vt(1
November 1971) ``A of emulsion'' described in items 22 to 37
i and type", "Washing of emulsions", "Chemical sensitization", "Antifoggants and stabilizers", "Hardeners", "Supports", "
"plasticizers and lubricants", "coating aids", "matting agents",
"Sensitizer J", "Spectral sensitizer", "Addition method", "Absorption and filter dye J", "Coating method J", etc. can be applied.

For color image formation, negative-positive method (for example, “Jou
rnal of the 5ociety o
fMotion Picture and Tel
evision Engineers lx / volume (1
913), pp. 667-701), develop with a developer containing a black and white developing agent to create a negative 0 image,
A color reversal process in which the dye-containing photographic emulsion layer is then developed after exposure by subjecting it to at least one uniform flashing or other suitable fogging treatment, followed by color development to obtain a dye-positive image. A method such as the color consideration whitening method is used, in which a trowel surface fP is created and this is used as a bleaching catalyst to bleach the dye.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (for example, Hiro-amino-N, N-dietheraniline, 3-methyl-≠-amino-N, N-diethylaniline, ≠-amino-N- Ethyl-β-hydroquinetheraniline, 3-methyl-guaminoh-ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-ethyl-N-
β-methanesulfamide ethylaniline, t-amino-
3-methyl-N-ethyl-N-β-methoxyetheraniline, etc.) can be used.

In addition, F, A, Mason-J'Photogr.
aphicProcessing Chemistry
(Published by Focal Press, /Ytt) 22t
~No2 pages, US patent! .

/93,0/Evening issue, same 2. J Octopus, No. 36, Tokukai Shomu
Those described in r-tlA233 and the like may be used.

The color developing solution may also contain pH softeners such as alkali metal salts, carbonates, borates and phosphates, development inhibitors such as bromides, iodides and antifoggants.
1i! It may contain an I agent or an antifoggant. In addition, if necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, color mark forming couplers, competitive couplers, etc. , fogging agents such as sodium borohydride, auxiliary developers such as l-phenyl-3-pyrazolidone, viscosity-imparting agents, U.S. Patent≠, θ13.72
Polycarboxylic acid chelating agent described in No. 3, West German Publication No. 1
) LS) z, 42 Co., and the antioxidant described in Tata No. O, etc. may be included.

After color development, the mushroom emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As bleaching agents, compounds of polyvalent metals such as iron (1), cobalt (I[t), chromium (2), and copper (IT), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate,
Iron (m)-! f or Kobal) (m), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /,!
- Aminopolycarboxylic acids such as diamino-2-pronoξnortetraacetic acid or complex salts of organic acids such as citric acid, silicic acid, and malic acid; persulfates, permanganate salts; nitrone phenol, etc. can be used. .

Of these, potassium ferricyanide, ethylenediaminetetraacetate rD < (ill) sodium and ethylenediaminetetraethane 1:, (II!) ammonium are particularly useful. Ethylenediamide tetraacetate fk (Jl, I
) Complex salts are useful both in stand-alone bleaching solutions and in -bath bleaching solutions.

For bleaching or egg white fixers, US Patent 3.0≠2,! 2
No. 0, pq13, lit/, ? tt issue, special public Sho U
! -FSOt issue, Tokko Akira≠! - and 131. In addition to the thiol compound described in JP-A-13-6J732, various additives can also be added.

When the present invention is used in a diffusion transfer method, it can also be processed with a viscous developer.

This viscous developer solution is a scissors-like composition containing the processing components necessary for the development (2) of the halogenated emulsion and the formation of a diffusion-transferred color wood image, and the main solvent is water. It may also contain other hydrophilic solvents such as methanol and methyl cellosolve. The processing composition has a pH necessary to cause development of the emulsion layer.
and the acids produced during the development and dye image formation processes (
For example, it contains a sufficient amount of alkali to neutralize hydrohalic acids such as hydrobromic acid, carboxylic acids such as acetic acid, etc.). Examples of alkalis include alkali metal or alkaline earth metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine, or amines. pH of about 72 or higher at room temperature, especially p.
) (/ It is desirable to contain a caustic alkali at a concentration of 17 or higher.Furthermore, a suitable casing composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, or sodium carboxymethyl cellulose. These polymers can be added to the treatment composition at room temperature to more than 1 voice, preferably in the hundreds (
The present invention will be described in more detail with reference to Examples below.

Example 1 Preparation of Film A On a baryta paper support coated on both sides with polyethylene,
Yellow coupler α-piparoyl-α (2
, Gujiokin-j,! ;'-dimethyloxazolidin-3-yl)-2-chloro-5-(α-(2,4I-di-tert-pentylphenoxy)butanamide] acetanilide-containing blue-sensitive chlorobrominated buttonhole layer with 3.θμ
Coated to a thickness of ζ (Coupler coating amount 0, A I A x
/ 0 mol/m.

Application record 3. ♂xlo mol/m, silver bromide 7
0 mol, 30 mol of chloride), on which a gelatin layer was applied as a second layer to a thickness of /, jμ, and a third layer of magenta coupler /- (2°, A-
) A gelatin layer containing chlorophenyl)-3-(nochloro-(!-tetradecanamide)anilinol-s-pyrazolone was coated to a thickness of J,/μ (coupler coated 00 × 10−3 mol). /m2) Film B Same as film A except that the second layer contains 2.!-G-t-octylhydroquinone (
Hydroquinone application 'F/kl#riXl0-4mol/m
2) to produce film B.

The following film C-F was made.

Film C In the above film A, the second layer contains the exemplary compound of the present invention (
5) (coating amount: Ox / 0' mol /
Same as film A except m2).

Film D In the above film A, the second layer contains the exemplary compound of the present invention (
Same as film A except that it contains 6) (coating amount: 0x10 mol/m ).

Film E Compound application in film D itA, 0x10 morph m
2 things.

Film F: Compound coating amount in Film D: 2.0x10-5 mol/
m2 thing.

Films A to F produced in this manner were sequentially exposed to light through wedges having different gray tones and subjected to the following processing.

Processing process Color development processing 3 minutes 30 seconds 33°C bleach-fixing processing 1 minute 30 seconds 336C water washing 3
Minutes 2g~350C color developer benzyl alcohol /jmQ diethylenetriamine! Acetic acid! 2 KBr O, da 2N a
2 S 03 j f/
Na2COa 3oy hydroxylamine acid salt 29 Hiro-amino-3
-Methyl-N- β-(methanesulfonamide) Etheraniline・372H2804・H2Og, 19 Adjust to 10100O with water pH 10.1 White fixer Ammonium thiosilicate (70wt%) /jOmQ Na 2 S 03
j 9Na(Fe(EDTA)) u09
Add EDTA and make 2 ml/000 ml p)) 4. f The density of each developed sample was measured using a green filter (degree of magenta color development). The magenta color mixture in the yellow coloring area was investigated by determining the difference between the magenta density at the maximum yellow coloring density and the magenta density at the lowest yellow coloring density.

The table below shows the terminology.

A smaller number indicates less color mixture. Therefore, the compound of the present invention has excellent ability to prevent color mixing (color fog),
It is clear that sufficient effects can be achieved with a small amount of entanglement.

Example 2 Preparation of Film A Yellow coupler α-2 baloyl-α (2° μm dioxota, ri'-dimethyloxazolidin-3-yl)-2 on a paper support coated on both sides with polyethylene.
-Chloro-5-(α-(,2゜hiro-di-t-pentylphenoxy)phthenamide]acetanilide-containing blue-sensitive brominated a emulsion layer was applied to a dry thickness of 3 μm (coupler coating amount: 01 tIA!) , x IQ-3 mol/m2, coated silver amount 3.11 x 10-3 mol/m2, silver chlorobromide)
The helogen composition was 70 moles of bromide complex and 30 moles of chloride complex, and a gelatin layer was applied thereon to a dry film thickness of 7 μm.

Film BA-E In addition to the above yellow coupler, the compound of the present invention (511
(6) l (711 (14 each 0.02×/θ-3
Films BE were prepared in the same manner as film A except that mol/m2 was added.

Each of the above films was exposed through a wedge with a varying degree of gray reduction and subjected to the same process as in Example 1, except that color development was performed at 3g 0c for 3 minutes. Ta. After the treatment, the yellow density was measured, and the maximum density (1) max) and minimum VA degree (Dmin) were determined.

The results are shown in the table below.

Table 2 Films B-E using the compounds of the present invention have lower minimum density than Film A, indicating that color fog is improved.

The above film A-E (jl total relative humidity before light is 0chi,
After being stored for 3 days at a temperature of O0C and subjected to the same Aft light treatment as above, a decrease in the maximum density and an increase in the minimum density were observed for film A, whereas film B In this case, both the maximum concentration and the minimum 0 degree change were very small.

Example 3 Film A Film samples were obtained by coating emulsion layers and auxiliary layers in the following order on a triacetyl cellulose support.

<7th layer: low red-sensitivity emulsion layer> Cyan coupler NO (heptafluorobutyl 7'
mid-t-z-(x'-(J",≠"-di-t-aminophenoxy)bunalamide)phenol 1oof) licresyl phosphate 100cc and ethyl acetate/0
Dissolved in 0 cc, 10 Chiselatin aqueous solution/stain (silver 70
Contains 9 gelatin tOf, iodine content ≠,! (mol%) and coated to a dry film thickness of 2-μ.

<Second layer Highly red sensitive emulsion layer> Cyan coupler emulsion ioo used in layer 27.

2 to red-sensitive highly sensitive silver iodobromide hole AIJ / kg (button 70
9 (containing gelatin Otsu 09, iodine content ≠ 5 moles) and coated to a dry film thickness of 2 μm.

<Third layer middle rNJ layer>
Vcf & 10% gelatin aqueous solution/j (Li and 1
- 700 g of the emulsion obtained by stirring and emulsifying was mixed with l# of IO gelatin and coated to give a dry film of j♀/2μ.

<μth layer low green-sensitive emulsion layer> Magenta coupler/-(2,II, O-trichlorophenyl)-3-(3-(,z, 4L-di-t-amylphenoxyacetamide)benzamide)- The emulsion obtained in the first JPJ was prepared in the same manner except that terpyrazolone/2!9 was used, and the resulting emulsion was subjected to green-sensitive silver iodobromide filtration.
j/kg ([Stock] 709 gelatin t.

9 and the iodine content was 2.5 molar) and coated to give a dry film thickness of θμ.

<5th layer Highly green sensitive emulsion layer> Magenta coupler emulsion used in the ≠ layer 1QOO? was mixed with an edge-sensitive highly iodine silver bromide emulsion (containing Button 709 Seratin tO9 and 2.5 mol % of iodine) and coated to a dry film thickness of 2 μm.

<Layer middle layer> Emulsion 700 qto gelatin lA1 used in the third layer
The mixture was mixed and applied to a dry film thickness of 01 μm.

<7j Special Yellow Filter Single Layer> A gelatin solution containing yellow colloidal steel was applied to a dry film thickness of lμ.

<Layer low sensitivity W pore agent layer> Yellow coupler α(pivaloyl)-α-(/-penzyl-1-ethoxy-3-hydantoinyl)-2-chloro-! -Dodecylox 7carbonylacetanilide 702
Emulsion 1009 obtained in the same manner as the emulsion of the first layer was mixed with a blue-sensitive silver iodobromide emulsion/kg (silver 709 containing gelatin t09 with an iodine content of 2.5 moles). The film was coated to give a dry film thickness of λ and θμ.

<7th layer - Highly sensitive red-sensitive emulsion layer> 1 ooot of the same emulsion used in the G layer was made into a blue-sensitive highly sensitive silver iodobromide emulsion/ky (contains 7 oys of silver and toy gelatin, the iodine content is 2.j mol) Mix to dry film thickness,
It was applied so that θμ.

<10th Layer, 2nd Protective Layer> One volume of the emulsion used in the third layer was mixed with one volume of 10% gelatin and coated to give a dry film thickness/μ.

<1st/layer 1st acquisition layer> Fine-grain silver iodobromide emulsion (grain size o
A 10% gelatin aqueous solution containing 7 mol of iodine) was prepared at a silver coating weight of 0.3 f/m and a dry film thickness of l.
It was applied so that it became μ.

Films B to C... Exemplary compound of the present invention (5) 9 f6) in place of di-t-octylhydroquinone
Films B-C were made the same as film A except that emulsions containing the following were used for the third, sixth, and tenth layers, respectively.

The films A to C above were exposed to red light through a wedge with varying gray density and subjected to the following reversal development process.

Processing recipe Processing process Time Temperature First development t' 310C Water washing 2'〃Reversal
2' 〃Color development 4'
tt adjustment 2' Bleach 1r' t
t fixation g ' tt water
washing μ′ 〃stable l
′ The composition of the room temperature drying solution is as follows.

7th developer water 700
mQ Sodium tetrapolyphosphate -19 Sodium sulfite 209 Hydroquinone monosulfite L-to3o9 Sodium carbonate (l hydrate) 302/-Phenyl μmethyl- Hydroxylmethyl-3 Pyrazolidone 22 Potassium bromide 2. ! Potassium dithiocyanate /, 2g potassium iodide (o
, t% solution) Add 2 ml of water
1000mQ (100O, t) anti-1 liquid water 70
0 mlNitrilo-N-N-N-)lintereneoschinic acid/INa salt 39Stannic chloride (dihydrate)/pp-aminophenol. , /9 sodium hydroxide
♂2glacial acetic acid
/ , t mD.

Add water and lθ00 proof color developer water 70
0mQ Sodium Tetrapolyphosphate 2? Sodium sulfite 7g Sodium phosphate (lλ hydrate) 3t9 Potassium bromide
/f/potassium iodide (067%
solution) taOmQ sodium hydroxide
32 Citrazic acid
2N Ethyl-N-(β-methanesulfonamidoethyl)-3 Methyl-guaminotriline nitrate //9 Ethylenediamine 32 Add water
10100O.

Adjustment liquid water 700
ml + Sodium Kayite /2
fl Ethylenediamine, sodium tetraacetate (dihydrate) ♂2thioglycerin 0. lAmQ glacial acetic acid
Add 3ml water
lO100O bleach solution water zo
o″′pSodium ethylenediaminetetraacetate (dihydrate) 2.Of/Iron ethylenediaminetetraacetate (DI) Ammonium (dihydrate) 120.09
Potassium bromide 100.02 Add water 1000m
Sodium nitrate j, OF? Sodium bisulfite! , 09 Add water
1000m9 stable liquid water r0
0mQ formalin (37% by weight) j, Om
Q Fuji Drywell j, Om
Addition of ice water / 000 mD Each developed film was measured once using a filter to check the maximum color density (Dmax) and minimum density (Dmin). Also, use a blue filter and a green filter, respectively. The maximum degree of color development of the green-sensitive layer and the green-sensitive layer was investigated.

The results are shown in the table below.

From Table 3, it can be seen that when the compound of the present invention is used, the minimum density value of the red sensitive layer is lowered. This result shows that color staining is prevented by using the compound of the present invention.

Procedural amendment, Commissioner of the Patent Office 1, Indication of the case Showa! Patent Application No. TTA30 2, Title of invention: Color photographic light-sensitive material 3, Relationship with the person making the amendment Case: Patent applicant Location: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Amendment We will submit an engraving of the amended specification (with no changes to the content) of Specification 5.

Procedural amendment, Commissioner of the Patent Office 1, Indication of the case Showa! Patent application No. 61, 30
No. 2, Name of the invention Color photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Subject of the amendment `` Column 5 of "Detailed Description of the Invention" Contents of Amendment (1) The structural formula of compound α9 on page 2μ of the present specification is amended as follows.

(tic　c　l’J　*　.

(tjcIJs.

(2) Same book, page 37, line 11 "Effective" ``Efficacy j and correct it.

(3) Same book, page 3, line 74 rResearchJ rResearchJ and correct it.

(4) Same book, page j2, line 74 "Word table" "result" and correct it.

(5) In the color mixture column of Table 1 on page j 3 of the same book, indicate “-〇, 7J
Correct "J" to "f-0,7JJ".

(6) Same book, page 60, line 1 “Connective” "Continuous" and correct it.

The above procedural amendment was filed on July 76, 1999, Mr. Commissioner of the Japan Patent Office.
No. 7, No. 2, Title of the invention Color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Special r [Notification of representative name of applicant ( 4, Subject of amendment Column 5 of “Detailed description of the invention” of the specification) Details of the amendment (1) In the specification jA negative 14, the line "amide/-" is corrected to "amide)-".

(2) Same book, page 56, line 1j "t-amino" "t-amil" and correct it.

(3) On page 56 of the same book, in the third line from the bottom, after 9j, insert the emulsion obtained by mixing and emulsifying the emulsion SOO? into a red-sensitive silver iodobromide emulsion/9.J in full. do.

(4) Same book, page 61, line 14 "Oschinic acid" "Phosphonic acid"

Claims (2)

[Claims] (1) As a color stain preventive agent, use the following general formula (I) or (II).
) A silver halide color photographic material characterized by containing a compound represented by: (I) (II) However, in the formula, A and B each represent -CO- or -802-, and at least one of them is -802-. R1 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an arylsulfonamide group, an alkylsulfonamide group, an acylamino group,
an alkylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoylamino group, a carbamoylamino group, an acyl group, a sulfonyl group, a carbamoyl group; B2 and B3 each represent a substituted or unsubstituted aryl group, alkyl group, or amino group, and may be the same or different. R and R are divalent groups necessary to connect two phenol rings or naphthol rings, and R cooperates with B to form a disulfonyl residue, dicarbonyl residue, disulfamoyl residue, or dicarpamoyl residue. do.几 stands for substituted or unsubstituted alkylene groups, dioxy residues, dithio residues, dioxycarbonyl residues, and dicarpamoyl residues. The ring substituted with an OH group may form a naphthol ring with the atomic group Q. (2) A silver halide color photographic material according to claim 1, wherein both A and B in general formula (I) or (II) are -802-.