EP0176845B1 - Photographic recording material - Google Patents

Description

The invention relates to a photographic recording material with at least one silver halide emulsion layer, which contains novel light stabilizers for the image dyes produced during chromogenic development, in particular for yellow or pupil-colored azomethine dyes.

It is known to produce color photographic images by chromogenic development, i.e. by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances Farb so-called color developers - the oxidation product of the developer substances which is formed in accordance with the silver image reacting with the color coupler to form a dye image. Aromatic compounds containing primary amino groups, in particular those of the p-phenylenediamine type, are usually used as color developers.

It is also known that the image dyes produced by chromogenic development undergo certain changes to varying degrees under the influence of environmental conditions. This is particularly noticeable when it comes to the effects of light. As is known, the purple dyes produced from pyrazolone couplers bleach particularly strongly, while the cyan dyes produced from phenolic couplers have proven to be particularly unaffected in this regard.

There has been no lack of attempts to remedy this deficiency through special measures. In the case of the purple couplers in particular, light-stabilizing additives or a special design of the couplers have led to improved light resistance. Suitable light-stabilizing agents are essentially phenolic compounds, in particular derivatives of hydroquinone, which are either added to the couplers or linked to the coupler molecules in the form of substituents (DE-B-1 547 803, DE-A-26 17 826, DE-A -29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032).

After the lightfastness of the purple dyes produced from pyrazolone couplers had been improved in this way and approximated to those of the cyan dyes, it became increasingly important to improve the stability of the yellow azomethine dyes, so that the longer exposure to light on color photos was initially balanced Colors do not cause an uneven lack of color, which would result in the appearance of a color cast. The agents proposed for improving the lightfastness of the purple dyes are only suitable to a limited extent for the stabilization of the yellow dyes and, moreover, often have other disadvantages which make them appear unsuitable for practical use. As hydroquinones or hydroquinone derivatives, they are easily oxidizable and often give rise to undesirable coloring (yellowing) of the image whites. When stored for a long time, they are often oxidized by the action of atmospheric oxygen or other oxidizing agents and thus lose their effectiveness.

DE-A-21 46 668 describes compounds with which the light stability of chromogenically produced image dyes, and to a small extent also of the yellow dyes, can be improved.

The invention is based on the object of specifying novel light stabilizers for photographic recording materials, in particular those which are suitable for improving the light stability of the yellow image dyes produced from yellow couplers.

enthält, worin bedeuten

• G eine Hydroxygruppe oder eine alkalilabile Vorläufergruppe einer Hydroxylgruppe
• X einen Substituenten, der unter den Bedingungen der chromogenen Entwicklung nicht abgespalten wird;
• Y einen Rest einer der folqenden Formeln:
  
  
  
  
  (R' = Wasserstoff oder Alkyl
• R² = Alkyl, Aralkyl oder Aryl,
• R³ = _Alkoxy, Aroxy, Alkylamino, Arylamino oder
• ein Rest wie angegeben für R2);
• Z Wasserstoff, Alkyl, Alkoxy, Halogen oder Acylamino;
• n 1 oder 2.

The invention relates to a color photographic recording material having at least one silver halide emulsion layer and a color coupler associated therewith, characterized in that it contains a combination of a color coupler and a compound of the general formula (I) in a silver halide emulsion layer or in a non-light-sensitive binder layer adjacent thereto.

contains what mean

• G is a hydroxy group or an alkali-labile precursor group of a hydroxyl group
• X is a substituent that is not released under the conditions of chromogenic development;
• Y is a remainder of one of the following formulas:
  
  
  
  
  (R '= hydrogen or alkyl
• R ² = alkyl, aralkyl or aryl,
• R ³ = _alkox y, aroxy, alkylamino, arylamino or
• a residue as indicated for R2);
• Z is hydrogen, alkyl, alkoxy, halogen or acylamino;
• n 1 or 2.

As already mentioned, group G is either a hydroxyl group or an alkali-labile precursor group of a hydroxyl group. An alkali-labile precursor group of a hydroxyl group means a group which undergoes a conversion under the conditions of alkaline development and thereby forms a hydroxyl group. Typical examples of this are "acylated hydroxyl groups" which are hydrolyzed by alkali during development, the blocking acyl group being split off. Blocking acyl groups are derived, for example, from aliphatic or aromatic carboxylic or sulfonic acids; Examples include acetyl, dichloroacetyl, alkoxycarbonyl, pyruvoyl.

The radical represented by X which cannot be split off under the conditions of chromogenic development can be, for example, an alkyl, alkoxycarbonyl, carbamoyl, acylamino, sulfamoyl, alkylsulfonyl or arylsulfonyl radical. Those residues which are particularly suitable under the conditions of chromogenic development, i.e. at pH values between 9 and 12 not only cannot be split off, but they also do not give the light-stabilizing compound any oxidizability under these conditions (e.g. through subsequent products of development). The alkyl radicals mentioned can be straight-chain or branched and contain up to 18 carbon atoms or more; Examples are methyl, ethyl, t-butyl, 1,1,3,3-tetramethylbutyl, n-dodecyl or n-tridecyl. Such alkyl radicals can also be contained in the alkoxycarbonyl, carbamoyl, acylamino, sulfamoyl and alkylsulfonyl radicals mentioned.

The alkyl radicals represented by R ', R ² or Z can be straight-chain or branched and can contain up to 20 C atoms and optionally further substituents. Such substituents are, for example, phenoxy groups, which in turn can be further substituted by alkyl, alkoxy, hydroxyl or halogen.

An aralkyl radical represented by R ² is, for example, benzyl; an aryl radical represented by R ² is, for example, phenyl.

An alkoxy or alkylamino radical represented by R ³ can contain a straight-chain or branched, optionally substituted alkyl radical having up to 20 carbon atoms. An arylamino radical represented by R ³ is, for example, an anilino radical which may contain further substituents, such as halogen, nitro or alkyl.

A halogen substituent represented by Z is, for example, chlorine or bromine. An acylamino group represented by Z is derived from aliphatic or aromatic carboxylic or sulfonic acids.

Examples of light stabilizing compounds of the present invention are listed below.

bei der Gruppe t-CsH17 in den Verbindungen S-20 bis S-23 handelt es sich um einen Alkylrest folgender Struktur

the group t-CsH17 in the compounds S-20 to S-23 is an alkyl radical of the following structure

The compounds of formula I to be used according to the invention can be prepared by known methods, e.g. by acylation or sulfonation of the corresponding o-aminophenols, in dipolar aprotic solvents such as dimethylformamide, dimethylacetamide, hexamethylphosphoric acid triamide, N-methylpyrolidone or the like. or in dipolar solvents such as acetone, methyl ethyl ketone, acetonitrile or in protic solvents such as alcohols with the addition of base. The following production examples are given by way of example:

Preparation of compound S 3

• 76% Ausbeute
• Fp: 160°C

7.3 g of 2-amino-4-methylphenol are dissolved in 80 ml of acetone and 9.0 ml of N, N-dimethylaniline. At 0-5 ° C, 24 g of a-2,4 · diamylphenoxyicaproic acid chloride are slowly added. The mixture is stirred for a further 1 hour, the temperature slowly rising to 20 ° C. and then stirred out onto a mixture of ice, water and hydrochloric acid. It is suctioned off, dried and the residue is recrystallized from acetonitrile. 22 g of pure substance are obtained.

• 76% yield
• Mp: 160 ° C

Preparation of compound S 20

• 9 g Ausbeute
• Fp: 184-85°C

11 g of 2-amino-4-tert-octylphenol are dissolved in 50 ml of dimethylacetamide with 13 ml of triethylamine. 5.6 g of pivaloyl chloride are added at room temperature. After 1 hour, it is stirred onto 200 ml of ice water with 10 ml of concentrated hydrochloric acid. The precipitate is filtered off, washed with water and recrystallized from acetonitrile after drying.

• 9 g yield
• Mp: 184-85 ° C

The color photographic recording materials according to the invention, in which the compounds of the present invention can advantageously be used, are preferably multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity. Emulsion layer units are understood to mean laminates of 2 or more silver halide emulsion layers of the same spectral sensitivity.

Each of the light-sensitive silver halide emulsion layers or emulsion layer units mentioned is assigned a color coupler which can react with color developer oxidation products to form a non-diffusing dye. The color couplers are expediently non-diffusing and are to be accommodated in the light-sensitive layer itself or in close proximity here. The color couplers assigned to the two or more partial layers of an emulsion layer unit do not necessarily have to be identical. You should only at the Color development gives the same color, usually a color that is complementary to the color of the light to which the photosensitive silver halide emulsion layers are sensitive.

The red-sensitive silver halide emulsion layers are therefore each assigned at least one non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or a-naphthol type. Particularly noteworthy are, for example, cyan couplers as described in US-A-2,474,293, US-A-2,367,531, US-A-2,895,826, US-A-3,772,002, EP-A-0 028 099 , EP-A-0 112 514.

The green-sensitive silver halide emulsion layers each contain at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. Particularly noteworthy are, for example, purple couplers as described in US Pat. No. 2,600,788, US Pat. No. 4,383,027, DE-A-1,547,803, DE-A-1,810,464, DE-A-2,084,665, DE-A-3 226 163.

Finally, the blue-sensitive silver halide emulsion layers each contain at least one non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping. Particularly noteworthy are, for example, yellow couplers as described in US Pat. No. 3,408,194, DE-A-2,329,587, DE-A-2,456,976.

Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publications "Color Coupler" by W. Pelz, "Messages from the research laboratories of Agfa, Leverkusen / Munich", Volume 111 (1961) p. 111 and K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971).

The color couplers can be either conventional 4-equivalent couplers or 2-equivalent couplers, which require a smaller amount of silver halide to produce the color. As is well known, 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point which is split off during the coupling. The 2-equivalent couplers which can be used according to the present invention include both those which are practically colorless and those which have an intense inherent color which disappears when the color is coupled or is replaced by the color of the image dye produced. According to the invention, the latter couplers can also be present in the light-sensitive silver halide emulsion layers and serve there as mask couplers to compensate for the undesired secondary densities of the image dyes. The 2-equivalent couplers include the known DIR couplers, which are couplers that contain a detachable residue in the coupling point, which is released as a diffusible development inhibitor or precursor of a development inhibitor when reacted with color developer oxidation products.

If required, color coupler mixtures can be used to set a desired color or reactivity. For example, water-soluble couplers can be used in combination with hydrophobic water-insoluble couplers.

The same methods that are also used for the incorporation of the compounds according to the invention are suitable for incorporating the couplers into the layers of the color photographic recording material. For example, one of the known emulsification methods is advantageously used for incorporating hydrophobic color couplers, in which, for example, color couplers are optionally dissolved in an organic solvent in the presence of a high-boiling coupler solvent or oil former and then dispersed in a gelatin solution. Examples of high-boiling coupler solvents are dibutyl phthalate and tricresyl phosphate. Further coupler solvents are described, for example, in US-A-2,322,927, US-A-3,689,271, US-A-3,764,336 and US-A-3,765,897.

It is also possible to prepare aqueous dispersions of the hydrophobic couplers and to add them to the respective casting solutions. For this purpose, aqueous slurries of the couplers are finely ground, for example by intensive stirring with the addition of sharp-edged sand and / or by using ultrasound. In this connection, reference is also made to DE-A-2 609 741.

The compounds according to the invention are preferably used together with yellow couplers; however, effects are also achieved when used in combination with magenta couplers or with cyan couplers. For this purpose, they can be dissolved in an oil former together with the respective color couplers and added to the respective casting solution in the form of such a common solution. However, they can also be added to the casting solution in the form of a separate solution in an oil former. Advantageous results can be achieved if 5 to 200% by weight, preferably 20 to 100% by weight, of the compound according to the invention, in each case based on the amount of the color coupler used, are used.

Compound I and the assigned color coupler are preferably in the same layer. However, it is also possible to introduce them into adjacent layers.

To stabilize the image dyes produced from the color couplers, the color photographic recording material can additionally contain other known stabilizing agents, for example UV absorbers and agents which fade the dyes, in particular under the action of light, Prevent or delay heat or moisture. For example, phenol derivatives, hydroquinone derivatives, p-alkoxyphenol derivatives, pyrogallol derivatives, gallic acid derivatives, 5-hydroxycoumaran derivatives, 6-hydroxychromane derivatives and 5-hydroxyindane derivatives have been described as being suitable for this purpose.

As already mentioned, the compound according to the invention is preferably used in combination with yellow couplers. These are in particular hydrophobic yellow couplers with good solubility in hydrophobic or hydrophilic oil formers. The yellow couplers are preferably derived from a-pivaloyl or a-benzoyiacetanilides. Examples of such yellow couplers are listed below.

The intermediate layers arranged between the light-sensitive silver halide emulsion layers, the binder of which preferably consists of gelatin, may contain compounds which are capable of reacting with color developer oxidation products and which thus prevent undesired diffusion of the color developer oxidation products. Examples of such compounds are non-diffusing reducing agents, e.g. Hydroquinone derivatives which, when reacted with the color developer oxidation products, do not give any dye remaining in the layers, or color couplers which give a soluble dye which is washed out of the layers during color photographic processing. Further suitable compounds for suppressing the undesired diffusion of color developer oxidation products are described, for example, in the monograph "Stabilization of Photographic Silver Halide Emulsions" by E. J. Birr, The Focal Press, 1st Edition 1974, pages 116 to 122.

With regard to further suitable additives for the color photographic recording according to the invention materials or one of their layers, reference is made to the article in the magazine "Product Licensing Index", volume 92, December 1971, pages 107 to 110.

The recording materials according to the invention can be developed with the usual color developer compounds, in particular those of the p-phenylenediamine series with a primary amino group, e.g. 4-amino-N, N-dimethylaniline, 4-amino-N, N-diethylaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-3-methyl-N-methyl-N- (ß -methylsulfonamidoethyl) aniline, 4-amino-N-ethyl-N- (ß-hydroxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (ß-hydroxyethyl) aniline, 4-amino- 3-methyl-N-ethyl-N- (ß-methoxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (ß-methylsulfonamidoethyl) aniline, 4-amino-N-butyl-N- (w-sulfobutyl) aniline, 4-amino-3-methyl-N-isopropyl-N- (w-sulfobutyl) aniline.

Other suitable color developers are described, for example, in J. Amer. Chem. Soc., 73, 3200-3125 (1951).

example 1 Color photographic materials were prepared as follows. a) Production of the color coupler emulgate

8 mmol of color coupler are dissolved in the same amount of face dibutyl phthalate and three times the amount by weight of ethyl acetate in the presence of 0.15 g of sulfosuccinic acid dioctyl ester at a temperature of 50 to 75 ° C. If necessary, the light-stabilizing compound to be tested is also added to the solution in the amount shown in the table. The solution is then stirred into 150 g of 7.5% aqueous gelatin solution at about 40 ° C. and dispersed therein.

b) Production of the color photographic recording materials to be tested

The emulsify produced under a is mixed with a silver halide emulsion which contains 8.2 g of silver in the form of silver halide, 9.2 g of gelatin and 0.04 g of sodium dodecylbenzenesulfonate. The total volume is adjusted to 350 ml with water. The casting solution prepared in this way is poured onto a layer of cellulose triacetate.

c) processing and evaluation

After drying, the material is exposed behind a step wedge and color developed as usual.

The processed samples are then covered with a UV protective film and irradiated in a Xenotest device to determine the light fastness (40% relative humidity; 25 ° C; 100,000 Ix.h.). The UV protective film was made as follows. A layer of 1.5 g of gelatin, 0.65 g of compound A (UV absorber) of the following formula was placed on a transparent cellulose triacetate film provided with an adhesive layer

0.07 g dicotyl hydroquinone and 0.36 g tricresyl phosphate applied. The amounts relate to 1 m ² .

Developer A contains 2-amino-5- (N-ethyl-N-methanesulfonamidoethylamino) toluene as a color developer. Developer B contains 2-amino-5- (N-ethyl-N-hydroxyethylamino) toluene as a color developer. substance. The results (percentage decrease in color density) are shown in Table 1.

Example 2

The procedure was as in Example 1. For comparison, the following compounds were also tested, which were known as light-stabilizing agents for the purple dyes produced from pyrazolone couplers.

Compound Y-4 was used as a coupler. The results obtained with developer A are shown in Table 2 below.

Example 3 Stabilization of purple and teal dyes.

The procedure was as in Example 1. The following color couplers were used.

The results are shown in Table 3.

It can be seen from Table 3 that Compound S-3 also has a certain stabilizing effect on the lightfastness of the magenta and cyan dyes. Naturally, this effect is comparatively small with the already more stable cyan dyes.

Example 4

• 1. Eine blauempfindliche gelbkupplerhaltige Silberhalogenidemulsionsschicht aus 0,55 g AgN0₃ mit 0,72 g Verbindbung Y-4, 0,22 g Trikresylphosphat und 1,7 g Gelatine.
• 2. Eine Zwischenschicht mit 1,2 g Gelatine, 0,07 Dioctylhydrochinon und 0,04 g Trikresylphosphat.
• 3. Eine grünsensibilisierte purpurkupplerhaltige Silberhalogenidemulsionsschicht aus 0,5 g AgN0₃ mit 0,45 g Verbindung M-2 (Purpurkuppler),
  
  0,22 g Verbindung V-1 Lichtstabilisator, 0,36 g Dibutylphthalat und 1,5 g Gelatine.
• 4. Eine UV-Schutzschicht mit 1,5 g Gelatine, 0,65 g Verbindung A (UV-Absorber), 0,07 Dioctylhydrochinon und 0,36 g Trikresylphosphat.
• 5. Eine rotsensibilisierte blaugrünkupplerhaltige Silberhalogenidemulsionsschicht aus 0,4 g AgN0₃ mit 0,35 g Verbindung C-3 Blaugrünkuppler,
  
  0,14 g Dibutylphthalat und 1,4 g Gelatin.
• 6. Eine Deckschicht mit 1,2 g Gelatine.

The following layers were applied in succession to a polyethylene-coated paper provided with an adhesive layer (the stated amounts relate to 1 m ² ).

• 1. A blue-sensitive yellow coupler-containing silver halide emulsion layer consisting of 0.55 g AgN0 ₃ with 0.72 g compound Y-4, 0.22 g tricresyl phosphate and 1.7 g gelatin.
• 2. An intermediate layer with 1.2 g gelatin, 0.07 dioctyl hydroquinone and 0.04 g tricresyl phosphate.
• 3. A green-sensitized purple coupler-containing silver halide emulsion layer consisting of 0.5 g AgN0 ₃ with 0.45 g compound M-2 (purple coupler),
  
  0.22 g of compound V-1 light stabilizer, 0.36 g of dibutyl phthalate and 1.5 g of gelatin.
• 4. A UV protective layer with 1.5 g of gelatin, 0.65 g of compound A (UV absorber), 0.07 dioctyl hydroquinone and 0.36 g of tricresyl phosphate.
• 5. A red-sensitized cyan coupler-containing silver halide emulsion layer composed of 0.4 g AgN0 ₃ with 0.35 g of compound C-3 cyan coupler,
  
  0.14 g dibutyl phthalate and 1.4 g gelatin.
• 6. A top layer with 1.2 g gelatin.

An instant hardening agent is hardened by covering it with a 10% strength aqueous solution.

Recording material 1 is obtained. Recording material 2 is also prepared in a corresponding manner, with the only difference that layer 1 additionally contains 0.22 g of compound S-3.

• 1. Farbentwicklung - 3,5 min
  • 15 ml Benzylalkohol
  • 15 ml Ethylenglykol
  • 3 g Hydroxylaminsulfat
  • 4,5 g 3-Methyl-4-amino-N-ethyl-N-(ß-methansulfonamidoethyl)-anilinsulfat
  • 32 g K₂C0₃
  • 2 g K₂S0₃
  • 0,6 g KBr
  • 1 g Dinatriumsalz der 1-Hydroxyethylidin-1,1-disulfonsäure
  • auf 1000 ml auffüllen mit Wasser; pH 10,2.
• 2. Bleichfixierbad - 1,5 min
  • 35 ml Ammoniaklösung (28%ig)
  • 30 g EDTA
  • 15 g Na₂S0₃
  • 100 g Ammoniumthiosulfat
  • 60 g Natrium-(EDTA)-eisen-III-komplex
  • auf 1000 ml auffüllen mit Wasser; pH 7.

The two materials 1 (prior art) and 2 (according to the invention) were exposed to blue light behind a step wedge and developed as follows (bath temperature 33 ° C.):

• 1. Color development - 3.5 min
  • 15 ml of benzyl alcohol
  • 15 ml ethylene glycol
  • 3 g of hydroxylamine sulfate
  • 4.5 g of 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate
  • 32 g K ₂ C0 ₃
  • 2 g K ₂ S0 ₃
  • 0.6 g KBr
  • 1 g of disodium salt of 1-hydroxyethylidine-1,1-disulfonic acid
  • make up to 1000 ml with water; pH 10.2.
• 2. bleach-fix bath - 1.5 min
  • 35 ml ammonia solution (28%)
  • 30 g EDTA
  • 15 g Na ₂ S0 ₃
  • 100 g ammonium thiosulfate
  • 60 g sodium (EDTA) iron III complex
  • make up to 1000 ml with water; pH 7.

3.Water - 3 min.

The yellow color parts obtained were measured and the levels of the densities 0.8 and 1.0 were marked. The wedges were then irradiated in a Xenotest device with a quantity of light of 15.10 ⁶ 1x.h. The marked steps were then measured again. The results are shown in the table.

The addition according to the invention thus results in an approximately 40% reduction in the loss of color density.

Claims (3)

1. A colour photographic recording material comprising at least one silver halide emulsion layer and a colour coupler associated therewith, characterized in that, in one silver halide emulsion layer or an adjacent non-photosensitive binder layer, it contains a combination of a colour coupler and a compound corresponding to general formula I

in which

G is a hydroxyl group or an alkali-labile precursor group of a hydroxyl group;

X is a substituent which is not eliminate under chromogenic development conditions;

Y is a substituent corresponding to the following formulae

―SO₂―NR¹―R²

―CO―NR¹―R²

―NR¹―CO―R³

―NR¹―SO₂―R³

(R' = hydrogen or alkyl

R² = alkyl, aralkyl or aryl,

R³ = alkoxy, aroxy, alkylamino, arylamino or a substituent as defined for R²);

Z is hydrogen, alkyl, alkoxy, halogen or acylamino;

n is 1 or 2.

2. A recording material as claimed in claim 1, characterized in that the colour coupler is a yellow coupler.

3. A recording material as claimed in claim 1 or 2, characterized in that, in formula I in claim 1, X is an alkyl, alkoxycarbonyl, carbamoyl, sulfamoyl, alkylsulfonyl or arylsulfonyl group.