DE19541941A1 - Colour photographic silver halide material with reduced fading of yellow dye in light - Google Patents

Abstract

In colour photographic silver halide (AgX) material with a base, blue-, green- and red-sensitive layers containing yellow, magenta and cyan couplers respectively and light-insensitive layer(s), at least one blue-sensitive layer contains a malonic ester half amide derivative of formula (I) as yellow coupler and at least one of the light-sensitive and light-insensitive layers contains a 2-(2'-hydroxyphenyl)-4-phenyl-6-substituted-1,3,5-triazine of formula (II) as ultraviolet (UV) absorber; in which R, R1 = an optionally substituted alkyl, aryl or heterocyclic group; R2 = hydrogen (H) or R1; X = a group eliminated on reaction of (I) with the oxidation product of the colour developer; R<1>, R<3> = H, halogen, hydroxyl (OH), mercapto, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR<5>R<6>, alkoxycarbonyl, carbamoyl or sulphamoyl; R<2> = H, OH, halogen or alkyl; R<4> = alkyl, alkoxy, alkylthio, aryloxy, arylthio or a group of formula (III); R<5> = H, alkyl or aryl; R<6> = H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulphamoyl or sulphonyl; and m, n, o = 1, 2, 3 or 4.

Description

The invention relates to a color photographic material containing special yellow couplers and contains special UV absorbers.

It is known (US 5,338,654) Malonesterhalbamide as yellow coupler in farbfoto to use graphic silver halide materials. It has been shown that the from these yellow couplers formed yellow dyes in combination with her conventional UV absorbers show disadvantages.

It has now been found that these disadvantages are due to the use have a novel UV absorber repaired.

The invention therefore relates to a color photographic silver halide material with a support, at least one blue-sensitive, yellow-coupling layer, at least one green-sensitive, magenta-coupling layer, at least one red-sensitive, cyan-coupling layer and at least one non-light sensitive layer, characterized in that at least one blue-sensitive yellow coupling layer of a yellow coupler of the formula (I)

contains, in which
R is an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group or an unsubstituted or substituted heterocyclic group,
X is a group which is split off in the reaction of the yellow coupler with the oxidation product of the color developer,
R₁ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group or an unsubstituted or substituted heterocyclic group,
R₂ is hydrogen or R₁
and at least one of the photosensitive and non-photosensitive layers comprises a UV absorber of formula (II)

contains, in which
R¹ and R³ are H, halogen, hydroxy, mercapto, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR⁵-R⁶, alkoxycarbonyl, carbamoyl or sulfamoyl;
R² is H, hydroxy, halo or alkyl;
R⁴ is alkyl, alkoxy, alkylthio, aryloxy, arylthio or a radical of the formula

R⁵ is H, alkyl or aryl;
R⁶ is H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl or sulfonyl;
m, n and o (same or different) are 1, 2, 3 or 4
and wherein a plurality of R¹, R² and R³ are the same or different.

The alkyl and aryl groups may be further substituted.

In a preferred embodiment of the invention, the hydroxy correspond phenyl-UV absorber of the formula III

wherein
R³¹ is H, alkyl, aryl or acyl;
R³², R³⁵ and R³⁸ halogen, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio or acylamino;
R³³, R³⁴, R³⁶ and R³⁷ (same or different) H, -OH or a radical such as R³²;
l, n and o denote 0, 1 or 2.

An alkyl radical represented by or contained in R³¹ to R³⁸ may be straight be chain, branched or cyclic and 1-36, preferably 1-20 C-atoms contain. A represented by or R³¹ to R³⁵ or contained therein alkyl or Aryl may in turn be substituted; possible substituents are those for R³² specified groups. A represented by R³¹ to R³⁵ or contained therein Acyl may be derived from an aliphatic or aromatic carbon or Sulfonic acid, a carbonic acid half ester, a carbamine or sulfamine acid, a phosphoric or phosphonic acid. Several radicals R³², R³⁵ and R³⁵ kön be the same or different; these radicals are preferably alkyl, aryl, Acylamino, acyloxy, halogen and / or alkoxy.  

Examples of preferred UV absorbers correspond to the formulas II-1 to II-19:

In Formula I, the following definitions are preferred:

wherein R₄ in particular an over

bound Ballast residue, preferably a C₁₀H₂₁- to C₂₀H₄₁-alkyl radical.

Examples of couplers of the formula I are:

Preference is given to low molecular weight or polymeric acid group-containing oil formers used as an oil former for the hydroxylphenyltriazine UV absorbers of formula II, d. H. acid group-containing oil former and the UV absorber of the formula II expediently in the form of a common emulsifier in the casting solution for the layer in question dispersed. The quantities used are for all layers together 50 to 1500 mg / m², preferably 200 to 700 mg / m² for the UV absorber and 50 to 1500 mg / m², preferably 100 to 500 mg / m² for the acid group-containing oil former. The combination of Hydroxylphenyltriazin UV Ab Sorber of the formula II and acid group-containing oil former is preferred above or in the light-sensitive layer farthest from the support Silver halide emulsion layer used.

The recording material according to the invention has significantly improved absorption tion properties in the range of UV light. The with the help of the invention according to oil-dispersed hydroxyphenyltriazine UV absorber have a  significantly higher absorption compared to the dispersion with conven oil producers. Thus, the possibility for the same effect is lower Use quantities and thereby reduce the layer thickness.

Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color-sensitive materials for the color diffusion transfer method or the Sil berfarbbleich method.

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. As a carrier In particular, thin films and films are suitable. An overview of carriers materials and on their front and back applied auxiliary layers is in Research Disclosure 37,254, Part 1 (1995), p. 285.

The color photographic materials usually contain at least one red each sensitive, green-sensitive and blue-sensitive silver halide emulsions layer and optionally intermediate layers and protective layers.

Depending on the type of photographic material, these layers may be different be arranged. This is illustrated for the main products:

Color photographic films such as color negative films and color reversal films exhibit the sequence indicated below on the carrier 2 or 3 rotempfind pale cyan silver halide emulsion layers, 2 or 3 greenemp sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue sensitive, yellow coupling silver halide emulsion layers. The layers same spectral sensitivity differ in their photographic Emp sensitivity, with the less sensitive sublayers usually closer are arranged to the carrier than the higher sensitive sub-layers.

Between the green-sensitive and blue-sensitive layers is more common a yellow filter layer attached, the blue light prevents it, in the to reach underlying layers.  

The possibilities of different layer arrangements and their effects The photographic properties are described in J. Int. Rec. Mats., 1994, Vol. 22, pages 183 to 193 described.

Color photographic paper, which is generally much less sensitive to light as a color photographic film, has the order given below usually a blue-sensitive, yellow-coupling silver halo on the support genisemulsion layer, a green sensitive, purplish coupling silver halide emulsion layer and a red-sensitive, cyan silver halide emulsion layer on; the yellow filter layer can be omitted.

Deviations from the number and arrangement of the photosensitive layers can to achieve certain results. For example, you can all highly sensitive layers to a layer package and all low-sensitivity layers to another layer package in a photographic film summarized to increase the sensitivity (DE 25 30 645).

Essential constituents of the photographic emulsion layers are binders, Silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37 254, Part 2 (1995), p. 286.

Information on suitable silver halide emulsions, their preparation, ripening, Stabilization and spectral sensitization including appropriate spectral sensitizers can be found in Research Disclosure 37,254, Part 3 (1995), p. 286 and in Research Disclosure 37 038, Part XV (1995), p. 89.

Photographic materials with camera sensitivity usually include Sil Berbromidiodidemulsionen, which may also contain small amounts of silver chloride can contain. Photographic copying materials contain either silver chloride bromide emulsions containing up to 80 mol% AgBr or silver chlorobromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37 254, Part 4 (1995), p288 and Research Disclosure 37038, part 11 (1995), p80. The maximum absorption of those from the couplers and the color developer oxide  formed dyes is preferably in the following areas: Yellow coupler 430 to 460 nm, magenta coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.

In color photographic films, to improve sensitivity, Graininess, sharpness and color separation are often used in the compounds Reaction with the developer oxidation product release compounds, the foto are graphically effective, z. B. DIR couplers which are a development inhibitor columns.

Information on such compounds, in particular couplers, can be found in Research Disclosure 37,254, Part 5 (1995), p. 290 and Research Disclosure 37,038, Part XIV (1995), p. 86.

Most hydrophobic color couplers, but also other hydrophobic components the layers are usually in high boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in a aqueous binder solution (usually gelatin solution) emulsified and are after drying the layers as fine droplets (0.05 to 0.8 microns through knife) in the layers.

Suitable high-boiling organic solvents, methods for incorporation into the layers of a photographic material and other methods, chemical To introduce compounds into photographic layers can be found in Research Disclosure 37,254, Part 6 (1995), p. 292.

The usually between layers of different spectral sensitivity arranged non-photosensitive intermediate layers may contain agents, the unwanted diffusion of developer oxidation products from a photosensitive in another photosensitive layer with different prevent spectral sensitization.

Suitable compounds (white couplers, scavengers or EOP scavengers) can be found in Research Disclosure 37,254, Part 7 (1995), p. 292 and in Research Disclosure 37 038, Part 111 (1995), p. 84.  

The photographic material may further include whiteners, spacers, filter dyes, formalin scavengers, sunscreens, antioxidants, D _MIN dyes, additives to improve dye, coupler and whitening stability, as well as to reduce color fog, plasticizers (latices), biocides, and others th.

Suitable compounds can be found in Research Disclosure 37 254, Part 8 (1995), P. 292 and Research Disclosure 37038, parts IV, V, VI, VII, X, M and XIII (1995), p. 84 ff.

The layers of color photographic materials are usually cured, i. H., the binder used, preferably gelatin, by suitable crosslinked chemical processes.

Suitable hardener substances can be found in Research Disclosure 37 254, Part 9 (1995), p. 294 and Research Disclosure 37 038, Part XII (1995), p. 86.

After imagewise exposure, color photographic materials become their character ter accordingly processed according to different methods. Details of the Procedures and required chemicals are in Research Disclosure 37,254, Part 10 (1995), p. 294 and Research Disclosure 37,038, parts XVI to XXIII (1995), p. 95 et seq., Together with exemplary materials.

In a preferred embodiment, at least one silver halide is included emulsion layer, preferably a blue-sensitive, yellow coupling silver halide emulsion layer and especially those containing the yellow coupler of the formula (I), a silver halide emulsion whose silver halide is at least 50% of the projected area of platelet-form AgCl granules and (100) major surfaces. Platelet shape means that the diameter ratio of the Circular projection surface to thickness of granules (aspect ratio) at least 2, preferably 5 to 20.

Examples example 1

A multilayer color photographic recording material was produced, by applying to a substrate made of paper coated on both sides with polyethylene the following layers were applied in the order given. All Quantities refer to 1 m², the amount of silver is as AgNO₃ give:

1st layer (substrate layer)

0.10 g of gelatin

2nd layer (blue-sensitive layer)

blue-sensitive silver halide emulsion (99.5 mole% chloride and 0.5 mole% bromide, mean grain diameter 0.9 μm)
0.50 g of AgNO₃ and
1.25 g of gelatin
0.42 g yellow coupler Y-1
0.18 g yellow coupler Y-2
0.50 g of tricresyl phosphate (TKP)
0.10 g stabilizer ST-3
0.70 mg Bluesensitizer Se-1
0.30 mg stabilizer ST-4

3rd layer (intermediate layer)

1.10 g of gelatin
0.06 g of oxform scavenger O-1
0.06 g of oxform scavenger O-2
0.12 g TKP

4th layer (green-sensitive layer)

green sensitized silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.47 μm)
0.25 g of AgNO₃ and
1.20 g of gelatin
0.25 g magenta coupler M-1
0.25 g stabilizer ST-1
0.20 g stabilizer ST-2
0.50 g of dibutyl adipate
0.70 mg green sensitizer Se-2
0.50 mg stabilizer ST-5

5th layer (UV protection layer)

1.15 g of gelatin
0.50 g UV absorber UV-1
0.10 g UV absorber UV-2
0.03 g of oxform scavenger O-1
0.03 g of oxform scavenger O-2
0.35 g TKP

6th layer (red-sensitive layer)

red sensitized silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.5 μm)
0.30 g of AgNO₃ and
1.00 g of gelatin
0.46 g cyan coupler BG-1
0.46 g TKP
0.03 mg of red sensitizer Se-3
0.60 mg stabilizer ST-6

7th layer (UV protection layer)

0.35 g of gelatin
0.15 g UV absorber UV-1
0.03 g UV absorber UV-2
0.09 g TKP

8th layer (protective layer)

0.90 g of gelatin
0.05 g whitener W-1
0.07 g of polyvinylpyrrolidone
1.20 mg of silicone oil
2.50 mg spacer (polymethylmethacrylate)
0.30 g of hardener H-1

The color photographic recording material is exposed through a step wedge. In this case, additional filters in the beam path of the exposure unit brought so that the wedge appears neutral at an optical density of D = 0.6. The exposed material is processed according to the following scheme:

The processing baths were prepared according to the following procedure:

Color developer solution Tetraethylene glycol | 20.0 g N, N-diethyl 4.0 g N-ethyl-N- (2-methanesulfonamido) ethyl-4-amino-3-methyl benzene sulphate 5.0 g potassium 0.2 g potassium carbonate 30.0 g polymaleic 2.5 g hydroxyethane 0.2 g Whitening agent (4,4'-diaminostilbenesulfonic acid derivative) 2.0 g potassium 0.02 g

Make up with water to 1000 ml, pH with KOH or H₂SO₄ to pH 10.2 to adjust.

Bleichfixierbadlösung Ammonium thiosulphate | 75.0 g   sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 45.0 g

make up with water to 1000 ml, pH with ammonia (25 wt .-%) or Adjust acetic acid to pH 6.0.

Example 2

As Example 1, but with 0.6 g yellow coupler GB-1 instead of Y-1 and Y-2.

Example 3

As Example 1, but with UV absorber II-1 instead of the UV absorber mixture from UV-1 and UV-2 in the 7th layer in the same amount.

Example 4

As example 3, but with 0.6 g yellow coupler GB-1 instead of Y-1 and Y-2.

The 4 processed samples were normalized with the light of daylight Xenon lamp irradiated with 20 × 10⁶ lux-h and then the percentage of return Yellow density determined. There were the following results.

Table 1

(V = comparison, E = according to the invention)

As can be seen, the UV absorber II-1 according to the invention has the yellow coupler mixture Y-1 + Y-2 no advantage over the prior art on. The light stability of the yellow coupler GB-1 of the present invention is in use This mixture unsatisfactory. Surprisingly, it is greatly improved, when using the UV absorber II-1 according to the invention.

Substances used in the examples:

Claims (2)

A color photographic silver halide material comprising a support, at least one blue-sensitive, yellow coupling layer, at least one green sensitive, magenta coupling layer, at least one red-sensitive, cyan coupling layer, and at least one non-photosensitive layer, characterized in that at least one blue-sensitive, yellow-coupling layer a yellow coupler of the formula (I)
contains, in which R is an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group or an unsubstituted or substituted heterocyclic group,
X is a group which is split off in the reaction of the yellow coupler with the oxidation product of the color developer,
R₁ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group or an unsubstituted or substituted heterocyclic group,
R₂ is hydrogen or R₁
and at least one of the photosensitive and non-photosensitive layers comprises a UV absorber of formula (II) contains, in which
R₁ and R³ are H, halogen, hydroxy, mercapto, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR⁵-R⁶, alkoxycarbonyl, carbamoyl or sulfamoyl;
R² is H, hydroxy, halo or alkyl;
R⁴ is alkyl, alkoxy, alkylthio, aryloxy, arylthio or a radical of the formula R⁵ is H, alkyl or aryl;
R⁶ is H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl or sulfonyl;
m, n and o (same or different) are 1, 2, 3 or 4
and wherein a plurality of R¹, R² and R³ are the same or different. The silver halide color photographic material of claim 1, wherein the ultraviolet absorber is of the formula (III) wherein
R³¹ is H, alkyl, aryl or acyl;
R³², R³⁵ and R³⁸ halogen, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio or acylamino;
R³³, R³⁴, R³⁶ and R³⁷ (same or different) H, -OH or a radical such as R³²;
i, n and o denote 0, 1 or 2.