JPH01241553A - Silver halide photographic sensitive material with improved fastness of color image - Google Patents

Abstract

PURPOSE:To obtain the excellent antifading effect of the title material by incorporating a specified compd. in at least one layer of photographic constituting layers. CONSTITUTION:The compd. shown by formula I is incorporated in at least one layer of the photographic constituting layers. In formula I, R1 and R2 are each a straight chain or a branched alkyl or alkenyl group, preferably the straight chain alkyl or alkenyl group, R3 and R4 are each a straight chain or a branched alkyl group, preferably a branched alkyl group. Thus, the photographic image obtd. from the silver halide photographic sensitive material has the excellent antifading effect.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to a silver halide photographic sensitizer capable of stabilizing organic coloring substances such as dye images produced in photographic materials and obtaining robust dye images. Regarding materials.

Specifically, the present invention relates to silver halide photographic sensitizers using hydroquinone derivatives as anti-browning agents in order to improve the stability of organic coloring substances such as dye images obtained by silver halide photographic materials. Regarding materials.

[Background of the invention]

A typical color photographic material contains red, green and blue sensitive silver halide emulsion layers containing cyan, magenta and yellow couplers, respectively, in or adjacent to the layers, p- When developed with a developer containing a phenylenediamine color developing agent, a dye image is formed.

It is known to include stabilizers in color photographic materials to reduce deterioration of dye images due to the effects of light, heat and/or humidity. Published Patent Publication 62-26204
No. 7 describes the use of special bisphenol derivatives to improve the fastness of color images.

However, a problem with the above-mentioned bisphenol derivatives is that they cause hue staining in developed dye images. Furthermore, the effect of preventing fading of coloring pigments is not sufficient.

In addition, as hydroquinone derivatives, published patent publication 5
4-48538.55-69141.55-89836
Although it is described in , and considerably improves the fastness of colored dye images, it cannot be said to be sufficient.

[Purpose of the invention]

An object of the present invention is to provide a photographic material having an excellent anti-fade effect, and a further object of the present invention is to provide a photographic material containing an anti-fade agent that does not cause staining or reduce the coloring properties of the coupler. An object of the present invention is to provide a silver halide photographic material.

[Structure of the invention]

In a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, at least one of the photographic constituent layers contains a compound represented by the general formula (+). It has been found that the above object can be achieved by a silver halide photographic material having the following characteristics.

- Crotch (1) [In the formula, R8 and R1 represent an alkyl group or alkenyl group having 2 to 3 carbon atoms, and R3 and R1 represent an alkyl group having 4 to 5 carbon atoms. ] [Specific structure of the invention] -a The compound represented by formula [I] will be explained.

In general formula (1), R and R2 represent a straight or branched alkyl group or alkenyl group.

Among these, preferred are straight-chain alkyl groups or alkenyl groups.

R and R4 represent a straight-chain or branched alkyl group, preferably a branched alkyl group.

Specific examples of compounds of the present invention are shown below.

Next, typical synthesis examples of the present invention will be shown.

Synthesis Example 1 (Synthesis of Exemplary Compound 7) 12.5 g of 2.5-di-t-amylhydroquinone was mixed with 600 ml of ethanol + aj! Dissolve in NaOH46 and roughly
g was added thereto, and the mixture was heated to reflux. Add to this 177g of diethyl sulfate.
was added over 1 hour, and the mixture was further refluxed for 6 hours. Ethanol was removed under reduced pressure, and 500 mJ2 of hexane was added thereto, followed by washing with water and then drying by adding magnesium sulfate. After drying, hexane was removed under reduced pressure and recrystallized from ethanol to obtain 92 g of the desired product.

(ep, 60-81t) The structure of the target compound 7 was identified by IR, FD mass spectrum, and NMR.

Synthesis Example 2 (Synthesis of Exemplified Compound 8) 2.5-di-t-amylhydroquinone was dissolved in 300 mf of I-propyl alcohol, and 41 g of potassium hydroxide was added thereto, followed by heating to 70 to 80°C. 82.5 g of allyl bromide was added dropwise to this over 1 hour, and then 2
heated for an hour. After hot filtration of the precipitated salt, I-propyl alcohol was removed under reduced pressure, and 300% of hexane was added to this.
After adding mA, it was washed with water and then dried by adding magnesium sulfate. After drying, hexane was removed under reduced pressure, the residue was subjected to column chromatography, and further recrystallized from methanol to obtain 50 g of the desired product. (mp, 31~
(32°C) The structure of the target compound 8 was identified by IR, FD mass spectrum and NMR.

The amount of the anti-fading agent used in the present invention is preferably 5 to 400 mol%, more preferably 10 to 300 mol%, based on the organic coloring substance.

The organic coloring substance used in the silver halide photographic light-sensitive material of the present invention is 300 nm to 800 nm in methanol solution.
m, preferably at least 1 between 400 nm and 700 nm
Water-soluble dyes such as basic dyes, acid dyes, direct dyes, soluble vat dyes, and mordant dyes, sulfur dyes, vat dyes, and oil-soluble dyes have two absorption maxima. ,
It includes all dyes belonging to the classification of dyeing properties such as disperse dyes, azoic dyes, insoluble dyes such as oxidative dyes, and reactive dyes.

Among these dyes, the dyes preferably used in the present invention include quinone imine dyes (azine dyes, oxazine dyes, thiazine dyes, etc.), methine and polymethine dyes (dianine dyes, azomethine dyes, etc.), azo dyes, anthraquinone dyes, indoaniline and indophenol dye,
It includes dyes belonging to chemical structural classes such as indicoid dyes, carbonium dyes, and formazan dyes.

The organic coloring substance in the present invention includes image-forming dyes used in the field of photography, such as color couplers, DRR compounds, DDR couplers, amitracine compounds, dyes formed from dye developers, dyes for silver dye bleaching, etc. All inclusive.

Preferred dyes for use as organic colorants in the present invention include anthraquinone, quinoneimine, azo, methine,
These include polymethine, indoaniline, indophenol and formazan dyes.

The dyes most preferably used in the present invention are methine and polymethine dyes and indoaniline and indophenol dyes. This dye includes compounds having the following groups.

Among the above groups, the benzene ring may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, or an amino group in the dye.

The foregoing couplers include those of the yellow, magenta and cyan dye-forming types. This coupler is described, for example, in U.S. Pat.
Even if it is a so-called 4-equivalent type as described in No. 5, or a 2-equivalent type in which the coupling position is substituted with a substituent (split-off group) that can be separated during the coupling reaction. good.

Preferred examples of yellow dye image-forming couplers in the present invention include benzoylacetanilide type and piparoylacetanilide type couplers, and examples of magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type, imidazopyrazole type and pyrazolopyrazole type couplers. ,
There are pyrazolotetrazole-based, pyrazolinobenzimidazole-based, and indasilone-based couplers, and cyan dye image-forming couplers include phenol-based, naphthol-based, and pyrazoloquinazolone-based couplers.

Examples of cholera yellow, magenta, and cyan dye-forming couplers are well known in the photographic industry;
The present invention includes all these known couplers.

Next, typical examples of yellow couplers are listed.

Y-4 C11゜Y-Nire's yellow coupler is, for example, West German Published Patent Application No. 2.0.
No. 570941, West German Published Patent No. 2,163.812,
JP 47-26133, JP 48-29432, JP 50-65321, JP 51-3631, JP 51-5
No. 0734, No. 51-102636, No. 48-6 (i
No. 835, No. 48-94432, No. 49-1229, No. 49-10736, Special Publication No. 51-33410,
It includes the compounds described in Japanese Patent No. 52-25733, etc., and can be synthesized according to the methods described therein.

Next, a typical blackbody example of a magenta coupler is given.

Uμ Cα しμ a しμ M−9 These magenta couplers are described, for example, in U.S. Pat.
4.514, British Patent No. 1,183,515, Japanese Patent Publication No. 40-6031, No. 40-6035, British Patent No. 44-15
No. 754, I! IJ No. 45-40757, No. 46-1
9032, JP-A No. 50-130.41, JP-A No. 53-1
No. 29035, No. 51-37646, No. 55-624
No. 54, US Patent No. 3.725.067, British Patent No. 1,
No. 252,418, No. 1,334.515, Japanese Unexamined Patent Publication No. 1973
No. 9-171956, No. 59-162548, No. 60
-43659, 60-33552 Research Disclosure No. 24626 (1984),
Patent Application No. 59-243007, No. 59-243008, No. 59-243009, No. 59-243012,
It includes the compounds described in No. 60-70197, No. 60-70198, etc., and can be synthesized according to the methods described therein.

Although there are no particular limitations on the cyan coupler, a cyan coupler based on enol is preferred.

A typical example of a cyan coupler is given below.

C-Nirella's cyan couplers are described, for example, in U.S. Pat. No. 2,423.
No. 730, No. 2,801.171, Japanese Unexamined Patent Publication No. 1983-11
No. 2038, No. 50-134644, No. 53-109
No. 630, No. 54-55380, No. 56-65134
No. 56-80045, No. 57-155538,
No. 57-204545, No. 58-98731, No. 5
9-31953, etc., and can be synthesized according to the methods described therein.

When such couplers are used in the present invention, dyes are formed from these couplers by reaction with an oxidized I; aromatic primary amine silver halide developer.

The above developers include aminophenol and phenylenediamine, and these developers can be used in combination.

The above-mentioned anti-fading agent of the present invention is preferably present in the color photographic material, particularly in the organic coloring substance or the layer in which it is formed, or in a layer adjacent thereto.

The methods effective for dispersing these compounds of this invention are the same as those used for dispersing couplers.

The compounds used in the present invention are generally oil-soluble and are commonly used in U.S. Pat.
191 and 2,304,940, it is preferable to dissolve it in a high boiling point solvent and, if necessary, in combination with a low boiling point solvent, disperse it, and add it to the wood-philic colloid solution. If necessary, there is no problem in using a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known dye image fading preventive agent.
Compounds described in Publication No. 4 and the like can be mentioned. At this time, there is no problem even if two or more kinds of compounds of the present invention are mixed.

The silver halide emulsion used in the photographic light-sensitive material of the present invention generally has silver halide grains dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide,
Silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof.

[Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these.

Margin Example 1 A multicolor silver halide photographic light-sensitive material was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side to obtain Sample 1.

1st N: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-1-benzylimidazolidin-3-yl)
-2-chloro-5-[r-(2,4-di-t-amylphenoxy)butyramide 1 acetanilide at 5.8B/
100cm", blue-sensitive silver chlorobromide emulsion (containing 85 mol% of s7 bromide) converted to silver is 3.21/100cs+"
, dibutyl phthalate 3.5B7100cs+”,
And gelatin was coated to give a coater of 13.5 mg/100 cm.

2nd layer: Middle layer 2.5-external t-octylhydroquinone 0.5+mg
/1OOc11! , dibutyl phthalate 0.5mg/
100cm” and gelatin 9.Oleg/100
cys".

Third layer: green-sensitive silver halide emulsion layer containing the magenta coupler (M-14) at 3.5 mg/10
0cm+! , green-sensitive silver bromide emulsion (containing 80 mol% silver bromide) converted to silver is 2-5111g/100cm+1,
Dibutyl phthalate 3.0 mg/100 cIN
and gelatin were coated at a concentration of 12.0 Img/100 cm.

4th layer: 0.7w1g of 2-(2-hydroxy-3,5-di-butylphenyl)benzotriazole as an intermediate layer UV absorber
/ 100 cm”, 6.0% dimethyl phthalate.
0mg/100cm'', 2.5-G t-octylhydroquinone at 0.5mg/100cIN'', and gelatin at 12.0I1g/100cII''.

5th layer: red-sensitive silver halide emulsion layer as cyan coupler 2-[α-(2,4-G-
(pentylphenoxy)butanamide) -4,6-dichloro-5-ethylphenol red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver: 3.0-g/100 cm" Tricresyl phosphate 3.5 myH7 1 0 0
cm” and gelatin 11.5 mg/100
cm'.

6th N: Protective layer gelatin 8. 0 tag/100 am".

In the above sample 1, the compound of the present invention was added to the 3rd M4 in the first
Multilayer samples 2 to 12 were created by adding the combinations shown in the table at a ratio of 100 mol % to CP.

After exposing the sample obtained above through an optical model according to a conventional method,
The treatment was carried out in the following steps.

[Processing process] Processing temperature Processing time Color development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Wash with water for 1 minute and 30 seconds at 33°C 3
Separate axis drying 50-80°C for 2 minutes The components of each treatment solution are as follows.

[Color developer]

Benzyl alcohol 12I11 diethylene glycol 10d Potassium carbonate 25H Sodium bromide
0.6g anhydrous sodium sulfite 2.0g hydroxylamine sulfate
2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g water was added to make 12, and the pH was adjusted to 10.2 with NaOH.

[Bleach-fix solution]

Ammonium thiosulfate 120g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3g EDTA ferric ammonium salt 65g Add water to make 12, ptt
Adjusted to 6.7-6.8.

The concentrations of Samples 1 to 12 treated above were measured using a densitometer (model KD-7 R manufactured by Konica Corporation) under the following conditions.

Each of the above-mentioned processed samples was exposed to a xenon fade meter for 16 days to examine the light fastness of the dye image.

Comparative compound 1 (compound described in JP-A-54-48538) 2 (compound described in JP-A-55-89836) 3 (compound described in JP-A-55-69141) Sushi 51111L1 Compound A ( Table 1 From the results in Table 1, the use of the compound of the present invention is effective in stabilizing magenta dye images formed from magenta couplers, and Y-stin in unexposed areas is also improved. Ta.

Example 2 Chloride 1 was substituted for each silver halide emulsion used in Example 1.
A sample similar to Sample 1 of Example 1 (Sample 13
-28) were prepared.

Samples 13 to 28 were exposed to light according to a conventional method and then subjected to the following treatments.

Processing process Processing temperature Processing time Color development
34.7±0.3℃ 45 seconds bleach fixing 34.7
±0.5℃ 45 seconds stabilization 30~34℃ 9
Drying for 0 seconds 60-80℃ 60 seconds [Color developer] Pure water 800Jd Triethanolamine 8gN, N
-diethylhydroxyamine 5g potassium chloride 2gN-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4- Aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
30g potassium sulfite
0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add pure water to make the overall view 12 and adjust to p 1110.2.

[Bleach-fix solution]

Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100af ammonium sulfite (40% solution) 27.5d Adjust the pH to 5.7 with potassium carbonate or glacial acetic acid and add water. Let the total amount be 11.

Stabilizing liquid C] 5-chloro-2-methyl-4=isothiazolin-3-one 1g 1-hydroxyethylidene-1゜l-diphosphonic acid 2g Add water to make it 12, and adjust the pH to 7 with sulfuric acid or potassium hydroxide.
．． Adjust to 0.

The light resistance of each sample after treatment was evaluated in the same manner as in Example 1.

The results are shown in Table 2.

(The following is a blank space) Table 2 As is clear from Table 2, the samples using the exemplary compounds according to the present invention exhibited good light fastness of color images, and good color images were obtained.

Example 3 Similarly to the magenta coupler of Example 2, when the color image stabilizer of the present invention was added to the yellow coupler and cyan coupler of the present invention, good light fastness of color images was exhibited. Also, good color images were obtained.

[Effects of the Invention] The present invention provides that, by using a specific hydroquinone derivative as a stabilizer for a dye capable of forming an image, photographic images obtained from a silver halide photographic light-sensitive material have an excellent browning prevention effect. .

Applicant: Konica Co., Ltd. Representative Patent Attorney: Miki Nakajima, Yu and two others

Claims (1)

[Scope of Claims] A silver halide photographic material having a photographic constituent layer including at least one silver halide emulsion layer on a support, in which at least one of the photographic constituent layers is represented by the general formula [I]. A silver halide photographic material containing a compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 represent an alkyl group or an alkenyl group having 2 to 3 carbon atoms. R_3 and R_4 represent an alkyl group having 4 to 5 carbon atoms. ]