EP0520938A1 - UV-absorber containing photographic material - Google Patents

Abstract

A photographic material is described which, on a base, contains a blue-sensitive, a green-sensitive and/or a red-sensitive silver halide emulsion layer and, if appropriate, a protective layer, a layer with a UV absorber being arranged between the top silver halide emulsion layer and the protective layer or above the top silver halide emulsion layer, characterised in that the UV absorber is of the formula <IMAGE> in which the radicals R1 and R12 are as defined in Claim 1.u

Description

The present invention relates to new photographic material which contains UV absorbers, in particular of the bis-2-hydroxyphenyltriazinyl type.

Hydroxyphenylbenztriazoles previously used as UV absorbers in photographic materials showed the disadvantage that their own stability against light was insufficient. For this reason, the effectiveness of these UV absorbers decreases with increasing exposure. Furthermore, in many cases, poor chemical stability, low solubility, too high an inherent color or too low an extinction coefficient of the triazines have prevented their use in photographic materials.

A group of triazine UV absorbers has now been found which, surprisingly, has proven to be largely free from such disadvantages. They show improved stability to natural light and have the property of better protecting image dyes and color couplers against exposure to light than was possible with the hydroxyphenylbenztriazoles and triazines commonly used in photographic materials. In particular, this group of triazines is suitable for increasing the stability of the magenta and cyan layers of photographic materials, e.g. in layers, which are applied over the magenta or cyan layer, or directly embedded in the cyan layer.

The UV absorbers according to the invention can be used for all types of photosensitive material. For example, they can be used for color paper, color reversal paper, direct positive color material, color negative film, color positive film, color reversal film and others. Among other things, they are preferably used for photosensitive color material which contains a reversal substrate or which forms positives.

Furthermore, these triazines can advantageously be combined with UV absorbers of the hydroxyphenylbenzotriazole type, in particular representatives thereof which are liquid at room temperature (cf. for example US Pat. Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701). Such combinations allow considerable Reduction in the amount of oil required to incorporate the UV absorbers into the photographic layer in question. This results in a violin layer thickness or, if the layer thickness is kept constant, a higher concentration of UV absorber.

Combinations of the triazines with other types of UV absorbers such as benzophenones, oxanilides, cyanoacrylates, salicylic acid esters, acrylonitriles or thiazolines are also suitable for use in photographic materials.

In particular, photographic materials similar to those described in US-A-4,518,686 can be stabilized with good success.

entspricht, worin
die Reste R₁ unabhängig voneinander Akyl mit 1 bis 18 Kohlenstoffatomen, Alkyl mit 1 bis 18 Kohlenstoffatomen substituiert mit Hydroxyl, Alkenoxy mit 2 bis 18 Kohlenstoffatomen, -CO₂H, -CO₂R₂ und/oder -O-COR₅ durch Sauerstoff unterbrochenes Alkyl oder Hydroxyalkyl oder Glycidyloxyalkyl mit 3 bis 50 Kohlenstoffatomen, Alkenyl mit 3 bis 6 Kohlenstoffatomen, Glycidyl, eine Gruppe der Formel

Cyclopentyl, Cyclohexyl, Phenylakyl mit 1 bis 5 Kohlenstoffatomen in Alkylteil, -COR₇, -SO₂R₈ oder -CH₂CH(OH)R₉ sind, wobei R₂ Akyl mit 1 bis 18 Kohlenstoffatomen oder Sauerstoff, Schwefel oder Stickstoff unterbrochenes Akyl oder Hydroxyalkyl mit 3 bis 30 Kohlenstoffatomen, Hydroxyalkyl mit 2 bis 18 Kohlenstoffatomen, Alkenyl mit 3 bis 18 Kohlenstoffatomen, Glycidyl, Cycloalkyl mit 5 bis 8 Kohlenstoffatomen, Benzyl, Alkylphenyl mit 1 bis 12 Kohlenstoffatomen im Alkylteil, Phenyl, Furfuryl oder ein Rest der Formel -CH₂CH(OH)R₉ ist,
R₅ Alkyl mit 1 bis 18 Kohlenstoffatomen, Alkenyl mit 2 bis 18 Kohlenstoffatomen oder Phenyl ist,
R₆ Alkylen mit 2 bis 10 Kohlenstoffatomen, Phenylen oder eine Gruppe der Formel

ist,
R₇ Akyl mit 1 bis 18 Kohlenstoffatomen, Alkenyl mit 2 bis 18 Kohlenstoffatomen oder Phenyl ist,
R₈ Alkyl mit 1 bis 12 Kohlenstoffatomen, Phenyl, Naphthyl oder Akylphenyl mit 1 bis 18 Kohlenstoffatomen im Alkylteil und
R₉ Phenylalkyl mit 1 bis 6 Kohlenstoffatomen im Alkylteil oder ein Rest der Formel -CH₂OR₁₁ ist, wobei
X -O-, -S-, -SO₂-, -CH₂- oder -C(CH₃)₂- ist und
R₁₁ Cyclohexyl, Benzyl, Phenyl oder Tolyl ist, und
R₁₂ Alkyl mit 1 bis 18 Kohlenstoffatomen, Benzyl, Cyclohexyl oder eine Gruppe der Formel

oder OR₁₆ ist, worin
R₁₃, R₁₄ und R₁₅ unabhängig voneinander Wasserstoff, Akyl mit 1 bis 12 Kohlenstoffatomen oder Halogen sind, und R₁₆ Alkyl mit 1 bis 18 Kohlenstoffatomen, durch Sauerstoff unterbrochenes Alkyl mit 3 bis 18 Kohlenstoffatomen oder Akyl mit 1 bis 12 Kohlenstoffatomen substituiert mit Phenoxy, Benzyloxy oder -CO₂R₈ ist, wobei R₈ die angegebene Bedeutung hat;
oder die Reste R₁ unabhängig voneinander ein Rest der Formel -CH₂-CH(OR_x)R_y, -CH₂CH(OR_x)CH₂OR_z,

-CH₂COR_y oder -CH₂COCH₂OR_z sind, wobei
R_x H, -COR_s, -COOR_w oder -SiR_pR_qR_r,
R_y C₁-C₁₈-Alkyl oder Phenyl-C₁-C₄-Alkyl,
R_z C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl, Phenyl-C₁-C₄-Alkyl, -COR_s oder durch Sauerstoff
unterbrochenes C₁-C₂₄-Alkyl oder C₂-C₂₄-Hydroxyalkyl,
R_s C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder Phenyl,
R_w C₁-C₄-Alkyl und
R_p, R_q und R_r unabhängig voneinander C₁-C₆-Alkyl oder Phenyl bedeuten; oder
   die Reste R₁ unabhängig voneinander eine Gruppe G-II sind,
wobei II eine Gruppe der Formel

ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist: -(CH₂)_q-, -(CH₂)_q-O-, -(CH₂)_q-O-R₂₆-, -(CH₂)_q-CO-X-(CH₂)_r-, -(CH₂)_q-CO-X-(CH₂)_r-O-,

-CH₂-CH(OH)-CH₂-Y-(CH₂)_q-,
worin q und r unabhängig voneinander 1-4 und p 0-50 sind,
R₂₆ C₁-C₁₂-Alkylen, Cyclohexylen oder Phenylen bedeutet,
R₂₇ C₁-C₁₂-Alkyl, C₅-C₈-Cycloalkyl, Phenyl, C₂-C₁₃-Alkoxymethyl,
C₆-C₉-Cycloalkoxymethyl oder Phenoxymethyl bedeutet,
R₂₈ eine Gruppe der Formel G-II bedeutet,
R₂₉ Waserstoff oder Methyl ist,
X -O- oder -NR₂₃- bedeutet, worin R₂₃ Wasserstoff, C₁-C₁₂-Alkyl oder eine Gruppe -(CH₂)₃-G-II oder -(CH₂)₃-O-G-II bedeutet,
Y -O- oder -NH- bedeutet,
R₂₀, R₂₁ und R₂₂ unabhängig voneinander C₁-C₁₈-Alkyl, Cyclohexyl, Phenyl oder C₁-C₁₈-Alkoxy bedeuten.The subject of the present application is therefore photographic material containing a blue-sensitive, a green-sensitive and / or a red-sensitive silver halide emulsion layer and optionally a protection layer, a layer with a UV absorber being arranged between the uppermost silver halide emulsion layer and the protection layer, or above the uppermost silver halide emulsion layer is characterized in that the UV absorber of the formula

corresponds to what
the radicals R₁ independently of one another are alkyl having 1 to 18 carbon atoms, alkyl having 1 to 18 carbon atoms substituted by hydroxyl, alkenoxy having 2 to 18 carbon atoms, -CO₂H, -CO₂R₂ and / or -O-COR₅ by alkyl or hydroxyalkyl or glycidyloxyalkyl interrupted by oxygen 3 to 50 carbon atoms, alkenyl with 3 to 6 carbon atoms, glycidyl, a group of the formula

Cyclopentyl, cyclohexyl, phenylakyl with 1 to 5 carbon atoms in the alkyl part, -COR₇, -SO₂R₈ or -CH₂CH (OH) R₉, where R₂ is alkyl with 1 to 18 carbon atoms or oxygen, sulfur or nitrogen interrupted alkyl or hydroxyalkyl with 3 to 30 carbon atoms, hydroxyalkyl with 2 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, glycidyl, cycloalkyl with 5 to 8 carbon atoms, benzyl, alkylphenyl with 1 to 12 carbon atoms in the alkyl part, phenyl, furfuryl or a radical the formula is -CH₂CH (OH) R₉,
R₅ is alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms or phenyl,
R₆ alkylene with 2 to 10 carbon atoms, phenylene or a group of the formula

is
R₇ is alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms or phenyl,
R₈ alkyl with 1 to 12 carbon atoms, phenyl, naphthyl or Akylphenyl with 1 to 18 carbon atoms in the alkyl part and
R₉ is phenylalkyl having 1 to 6 carbon atoms in the alkyl part or a radical of the formula -CH₂OR₁₁, wherein
X is -O-, -S-, -SO₂-, -CH₂- or -C (CH₃) ₂- and
R₁₁ is cyclohexyl, benzyl, phenyl or tolyl, and
R₁₂ alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl or a group of the formula

or OR₁₆, wherein
R₁₃, R₁₄ and R₁₅ are independently hydrogen, alkyl having 1 to 12 carbon atoms or halogen, and R₁₆ alkyl having 1 to 18 carbon atoms, alkyl interrupted by oxygen having 3 to 18 carbon atoms or alkyl having 1 to 12 carbon atoms substituted with phenoxy, benzyloxy or Is -CO₂R₈, where R₈ has the meaning given;
or the radicals R₁ independently of one another are a radical of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z ,

-CH₂COR _y or -CH₂COCH₂OR _z , where
R _x H, -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₁₈-alkyl or phenyl-C₁-C₄-alkyl,
R _z C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, phenyl-C₁-C₄ alkyl, -COR _s or by oxygen
interrupted C₁-C₂₄-alkyl or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another are C₁-C₆ alkyl or phenyl; or
the radicals R 1 are independently a group G-II,
where II is a group of formula

is
and
G is a direct bond or a divalent group of one of the following formulas: - (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -O-R₂₆-, - (CH₂) _q -CO-X - (CH₂) _r -, - (CH₂) _q -CO-X- (CH₂) _r -O-,

-CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1-4 and p 0-50,
R₂₆ is C₁-C₁₂ alkylene, cyclohexylene or phenylene,
R₂₇ C₁-C₁₂ alkyl, C₅-C₈ cycloalkyl, phenyl, C₂-C₁₃ alkoxymethyl,
C₆-C₉-cycloalkoxymethyl or phenoxymethyl means
R₂₈ represents a group of the formula G-II,
R₂₉ is hydrogen or methyl,
X denotes -O- or -NR₂₃-, in which R₂₃ denotes hydrogen, C₁-C₁₂-alkyl or a group - (CH₂) ₃-G-II or - (CH₂) ₃-OG-II,
Y means -O- or -NH-,
R₂₀, R₂₁ and R₂₂ independently of one another are C₁-C₁₈ alkyl, cyclohexyl, phenyl or C₁-C₁₈ alkoxy.

und

Alkenylreste mit 2 bis 18 Kohlenstoffatomen können ein- oder, ab 4 Kohlenstoffatomen, mehrfach ungesättigt sein. Dialkylaminoalkylreste mit insgesamt 4 bis 16 Kohlenstoffatomen können beispielsweise durch die Formel

wiedergegeben werden, wobei die Summe von n₁, n₂ und n₃ 4 bis 16 ergibt, Alkylenreste mit 2 bis 10 Kohlenstoffatomen können von entsprechenden Alkylresten abgeleitet werden. Durch Sauerstoff unterbrochene Akylenreste mit 4 bis 50 Kohlenstoffatomen können z.B. der Formel

entsprechen.If substituents in the compounds of the formula (I) are alkyl having 1 to 18 carbon atoms, radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and Octadecyl and corresponding branched isomers in question. Examples are alkyl residues with 3 to 50 carbon atoms which are interrupted by oxygen, sulfur or nitrogen

and

Alkenyl radicals with 2 to 18 carbon atoms can be mono- or, from 4 carbon atoms, polyunsaturated. Dialkylaminoalkyl radicals with a total of 4 to 16 carbon atoms can be represented, for example, by the formula

are reproduced, the sum of n 1, n 2 and n 3 giving 4 to 16, alkylene radicals having 2 to 10 carbon atoms can be derived from corresponding alkyl radicals. Akylene residues with 4 to 50 carbon atoms interrupted by oxygen can, for example, of the formula

correspond.

-CH₂COR_y oder -CH₂COCH₂OR_z bedeuten, wobei
R_x H, -COR_s, -COOR_w oder -SiR_pR_qR_r,
R_y C₁-C₁₈-Alkyl oder Phenyl-C₁-C₄-Alkyl,
R_z C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl, Phenyl-C₁-C₄-Alkyl, -COR_s oder durch Sauerstoff unterbrochenes C₁-C₂₄-Alkyl oder C₂-C₂₄-Hydroxyalkyl,
R_s C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder Phenyl,
R_w C₁-C₄-Alkyl und
R_p, R_q und R_r unabhängig voneinander C₁-C₆-Alkyl oder Phenyl bedeuten; oder
   die Reste R₁ unabhängig voneinander eine Gruppe G-II bedeuten,
wobei II eine Gruppe der Formel

ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist: -(CH₂)_q-, -(CH₂)_q-O-, -(CH₂)_q-O-R₂₆-, -(CH₂)_q-CO-X-(CH₂)_r-, -(CH₂)_q-CO-X-(CH₂)_r-O-,

-CH₂-CH(OH)-CH₂-Y-(CH₂)_q-,
worin q und r unabhängig voneinander 1-4 und p 0-50 sind,
R₂₆ C₁-C₁₂-Alkylen, Cyclohexylen oder Phenylen bedeutet,
R₂₇ C₁-C₁₂-Alkyl, C₅-C₈-Cycloalkyl, Phenyl, C₂-C₁₃-Alkoxymethyl, C₆-C₉-Cycloalkoxymethyl oder Phenoxymethyl bedeutet,
R₂₈ eine Gruppe der Formel G-II bedeutet,
R₂₉ Waserstoff oder Methyl ist,
X -O- oder -NR₂₃- bedeutet, worin R₂₃ Wasserstoff, C₁-C₁₂-Alkyl oder eine Gruppe -(CH₂)₃-G-II oder -(CH₂)₃-O-G-II bedeutet,
Y -O- oder -NH- bedeutet,
R₂₀, R₂₁ und R₂₂ unabhängig voneinander C₁-C₁₈-Alkyl, Cyclohexyl, Phenyl oder C₁-C₁₈-Alkoxy bedeuten; und
   R₁₂ Akyl mit 1 bis 12 Kohlenstoffatomen oder eine Gruppe der Formel

oder -OR₁₆ ist, vorzugsweise ist R₁₂ eine Gruppe der Formel

worin
R₁₃ und R₁₄ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder Chlor sind, und R₁₆ Alkyl mit 1 bis 8 Kohlenstoffatomen oder durch Sauerstoff unterbrochenes Alkyl mit 3 bis 12 Kohlenstoffatomen ist.Preferably compounds of the formula (I) are used in which the radicals R₁ independently of one another are a radical of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z ,

-CH₂COR _y or -CH₂COCH₂OR _z mean, wherein
R _x H, -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₁₈-alkyl or phenyl-C₁-C₄-alkyl,
R _{z is} C₁-C₁ Alkyl alkyl, C₂-C₁₈ alkenyl, phenyl-C₁-C₄-alkyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another are C₁-C₆ alkyl or phenyl; or
the radicals R₁ independently of one another represent a group G-II,
where II is a group of formula

is
and
G is a direct bond or a divalent group of one of the following formulas: - (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -O-R₂₆-, - (CH₂) _q -CO-X - (CH₂) _r -, - (CH₂) _q -CO-X- (CH₂) _r -O-,

-CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1-4 and p 0-50,
R₂₆ is C₁-C₁₂ alkylene, cyclohexylene or phenylene,
R₂₇ is C₁-C₁₂-alkyl, C₅-C₈-cycloalkyl, phenyl, C₂-C₁₃-alkoxymethyl, C₆-C₉-cycloalkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
R₂₉ is hydrogen or methyl,
X denotes -O- or -NR₂₃-, in which R₂₃ denotes hydrogen, C₁-C₁₂-alkyl or a group - (CH₂) ₃-G-II or - (CH₂) ₃-OG-II,
Y means -O- or -NH-,
R₂₀, R₂₁ and R₂₂ independently of one another are C₁-C₁₈ alkyl, cyclohexyl, phenyl or C₁-C₁₈ alkoxy; and
R₁₂ Akyl having 1 to 12 carbon atoms or a group of the formula

or -OR₁₆, preferably R₁₂ is a group of the formula

wherein
R₁₃ and R₁₄ are independently hydrogen, C₁-C₄ alkyl or chlorine, and R₁₆ is alkyl of 1 to 8 carbon atoms or alkyl interrupted by oxygen having 3 to 12 carbon atoms.

ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist:
-(CH₂)_q-, -(CH₂)_q-O-, -(CH₂)_q-CO-X-(CH₂)_r-,

oder -CH₂-CH(OH)-CH₂-Y-(CH₂)_q-,
worin q und r unabhängig voneinander 1, 2 oder 3 und p 0-50 sind,
R₂₇ Methyl, Phenyl, C₃-C₉-Alkoxymethyl oder Phenoxymethyl bedeutet,
R₂₈ eine Gruppe der Formel G-II bedeutet,
X und Y -O- bedeuten,
R₂₀, R₂₁ und R₂₂ unabhängig voneinander C₁-C₈-Alkyl, Phenyl oder C₁-C₈-Alkoxy bedeuten; und
R₁₂ eine Gruppe der Formel

ist, worin
R₁₃ und R₁₄ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder Chlor sind.Also preferred are compounds in which the radicals R₁ independently of one another are radicals of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z , -CH₂COR _y or -CH₂COCH₂OR _z , where
R _x H, -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₈ alkyl,
R _z C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, benzyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another are C₁-C₆-alkyl; or
R₁ represent a group G-II,
where II is a group of formula

is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -CO-X- (CH₂) _r -,

or -CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1, 2 or 3 and p are 0-50,
R₂₇ denotes methyl, phenyl, C₃-C₉ alkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
X and Y mean -O-,
R₂₀, R₂₁ and R₂₂ are independently C₁-C₁ alkyl, phenyl or C₁-C₈ alkoxy; and
R₁₂ is a group of the formula

is what
R₁₃ and R₁₄ are independently hydrogen, C₁-C₄ alkyl or chlorine.

ist
und
p 0 ist,
G eine zweiwertige Gruppe einer der folgenden Formeln ist: -(CH₂)₃-, -(CH₂)₂-O-,
-CH₂-CO-O-CH₂-, -CH₂-CH(CH₂-O-C₄H₉)-O-,

oder
-CH₂-CH(OH)-CH₂-O-(CH₂)₃-,
R₂₈ -Si(CH₃)₂R₂₂bedeutet,
R₂₀ und R₂₁ unabhängig voneinander Methyl oder Ethyl und
R₂₂ C₁-C₈-Alkyl bedeuten; und
R₁₂ eine Gruppe der Formel

ist, worin
R₁₃ und R₁₄ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder Chlor sind.Those compounds of the formula (I) are particularly preferably used in which the radicals R₁ independently of one another are a radical of the formula -CH₂-CH (OR _x ) R _y or -CH₂CH (OR _x ) CH₂OR _z , where
R _x H, -COR _s , -COOCH₃ or -Si (CH₃) ₂R _r ,
R _y C₁-C₈ alkyl,
R _z C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₄ alkyl or C₂-C₄ alkenyl and
R _r C₁-C₆ alkyl
mean; or
R₁ is a group G-II,
where II is a group of formula

is
and
p is 0,
G is a divalent group of one of the following formulas: - (CH₂) ₃-, - (CH₂) ₂-O-,
-CH₂-CO-O-CH₂-, -CH₂-CH (CH₂-O-C₄H₉) -O-,

or
-CH₂-CH (OH) -CH₂-O- (CH₂) ₃-,
R₂₈ -Si (CH₃) ₂R₂₂ means,
R₂₀ and R₂₁ independently of one another methyl or ethyl and
R₂₂ is C₁-C₈ alkyl; and
R₁₂ is a group of the formula

is what
R₁₃ and R₁₄ are independently hydrogen, C₁-C₄ alkyl or chlorine.

ist, worin
R₁₃ Wasserstoff und R₁₄ Wasserstoff, Methyl oder Chlor sind.Compounds of the formula (I) are very particularly preferably used in which the radicals R₁ independently of one another are a radical of the formula -CH₂CH (OR _x ) CH₂OR _z , where
R _x H, -COR _s , -COOCH₃ or -Si (CH₃) ₂R _r ,
R _z C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₄ alkyl or C₂-C₄ alkenyl and
R _r C₁-C₆ alkyl
mean; and
R₁₂ is a group of the formula

is what
R₁₃ is hydrogen and R₁₄ are hydrogen, methyl or chlorine.

The material according to the invention preferably contains intermediate gelatin layers between the silver halide emulsion layers.

In a further preferred embodiment, the material according to the invention contains a further layer with a UV absorber of the formula (I), which is arranged between the green and red-sensitive silver halide emulsion layer.

Good results are also achieved if the UV absorber of the formula (I) is additionally contained in the red-sensitive silver halide emulsion layer.

In the layer between the green- and red-sensitive layer and / or in the red-sensitive layer, benzotriazole compounds can advantageously be used instead of the UV absorbers of the formula (I).

worin T₁, T₂ und T₃ unabhängig voneinander Wasserstoff, Halogen, Akyl, Alkyl substituiert mit einer Carbonsäureestergruppe, Alkoxy, Aryloxy, Hydroxyl oder Acyloxy sind, und T₄ Wasserstoff, Alkoxy, Aryloxy oder Acyloxy ist.These benzotriazole compounds (HBT) preferably correspond to the formula

wherein T₁, T₂ and T₃ are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy, and T₄ is hydrogen, alkoxy, aryloxy or acyloxy.

Those compounds of formula (III) which are liquid at room temperature are particularly preferred.

entspricht, worin T₁, T₂ und T₃ unabhängig voneinander Wasserstoff, Halogen, Alkyl, Alkyl substituiert mit einer Carbonsäureestergruppe, Alkoxy, Aryloxy, Hydroxyl oder Acyloxy sind und T₄ Wasserstoff, Alkoxy, Aryloxy oder Acyloxy ist, und (b) das Material mindestens eine weitere Schicht aufweist, welche einen UV-Absorber der Formel (I) enthält.In a further aspect, the present invention also relates to photographic material containing a blue-sensitive, a green-sensitive and / or a red-sensitive silver halide emulsion layer and a protection layer, a layer with a UV absorber being arranged between the uppermost silver halide emulsion layer and the protection layer that (a) the UV absorber of the formula

where T₁, T₂ and T₃ are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy and T₄ is hydrogen, alkoxy, aryloxy or acyloxy, and (b) the material is at least one more Has layer which contains a UV absorber of the formula (I).

The further layer is preferably arranged between the green- and red-sensitive silver halide emulsion layer.

In a further preferred embodiment, the photographic material additionally contains a UV absorber of the formula (I) in the red-sensitive layer. It can also be advantageous if the UV absorber of the formula (I) in the further layer or in the red-sensitive layer is replaced by one of the formula (III); but at least one layer should contain a UV absorber of the formula (I).

Preferred photographic materials contain intermediate gelatin layers between the silver halide emulsion layers.

In a further embodiment of the present invention, the photographic material on a support contains at least 2 silver halide emulsion layers with a layer between these layers with a UV absorber, characterized in that the UV absorber corresponds to the formula (I). The two silver halide emulsion layers are preferably a green-sensitive and a red-sensitive silver halide emulsion layer. Furthermore, a corresponding material is preferred, in which the red-sensitive silver halide emulsion layer additionally contains a UV absorber of the formula (I) or (III).

Another embodiment of the present invention relates to photographic material having a red sensitive silver halide emulsion layer on a support and optionally also contains a blue-sensitive and / or green-sensitive silver halide emulsion layer, characterized in that the red-sensitive silver halide emulsion layer contains a UV absorber of the formula (I). It preferably contains a layer with a UV absorber of the formula (III) between the red-sensitive silver halide emulsion layer and the support.

Furthermore, it can be advantageous if all or part of the layers which can contain a UV absorber have a mixture of the UV absorbers of the formulas (I) and (III).

Preferred are photographic materials which contain silver chloride bromide, which consists of at least 90 mol% silver chloride, as silver halide in the blue-sensitive, green-sensitive and / or red-sensitive layer.

Furthermore, photographic materials are preferred which contain the silver halide emulsion layers in the order of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers.

The photographic materials according to the invention offer the advantage over materials with benzotriazole UV absorbers in that the UV absorbers of the formula (I) are required in a comparatively small amount in order to ensure adequate protection against UV radiation. This means that the thickness of the layers in which the UV absorbers of the formula (I) are incorporated can be very thin, which is e.g. has a positive effect on the sharpness of the images made with this material. Obviously, the use of a comparable amount of UV absorber will result in even better protection.

Typical and preferred compounds of the formula (I) are listed in the following table:

Examples of the compounds of the formula (III) are:

worin R₁ Alkyl oder Aryl ist, R₂ Aryl ist und Q Wasserstoff oder eine Gruppe ist, die durch Reaktion mit dem oxidierten Entwickler abgespaltet werden kann.Yellow couplers which can be used in the material according to the invention are preferably compounds of the formula A.

wherein R₁ is alkyl or aryl, R₂ is aryl and Q is hydrogen or a group which can be split off by reaction with the oxidized developer.

ist, worin R₃ Wasserstoff, Halogen, Alkyl oder Alkoxy bedeutet und R₄, R₅ und R₆ Wasserstoff, Halogen, Alkyl, Alkenyl, Alkoxy, Aryl, Carboxy, Alkoxycarbonyl, eine Carbamoylgruppe, eine Sulfon- oder Sulfamoylgruppe, eine Alkylsulfonaminogruppe, Acylaminogruppe, Ureidogruppe oder Aminogruppe bedeuten.A group of yellow couplers are those compounds of the formula A in which R₁ is t-butyl and R₂ is a group of the formula

is in which R₃ is hydrogen, halogen, alkyl or alkoxy and R₄, R₅ and R₆ are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxy, alkoxycarbonyl, a carbamoyl group, a sulfone or sulfamoyl group, an alkylsulfonamino group, acylamino group, ureido group or Amino group mean.

worin x 0-4 ist, R₇ Wasserstoff oder Alkyl bedeutet und R₈ und R₉ Alkyl sind.Preferably R₃ is chlorine, R₄ and R₅ are hydrogen and R₆ is an acylamino group. This also includes the compounds of the formula

wherein x is 0-4, R₇ is hydrogen or alkyl and R₈ and R₉ are alkyl.

worin R₁₀ Wasserstoff, Halogen oder Alkoxy ist,
R₁₁, R₁₂ und R₁₃ Wasserstoff, Halogen, Akyl, Alkenyl, Alkoxy, Aryl, Carboxyl, Alkoxycarbonyl, eine Carbamoylgruppe, eine Sulfongruppe, Sulfamoylgruppe, Sulfonamidogruppe, Acylaminogruppe, Ureidogruppe oder Aminogruppe bedeuten und R₁ und Q die oben angegebene Bedeutung haben.Another group of yellow couplers corresponds to Formula B.

wherein R₁₀ is hydrogen, halogen or alkoxy,
R₁₁, R₁₂ and R₁₃ are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, a carbamoyl group, a sulfone group, sulfamoyl group, sulfonamido group, acylamino group, ureido group or amino group and R₁ and Q have the meaning given above.

These include compounds of formula B in which R₁ is t-butyl, R₁₀ is chlorine, R₁₁ and R₁₃ are hydrogen and R₁₂ is alkoxycarbonyl.

worin R₁₄ eine organische zweiwertige Gruppe ist, die den Ring zu einem 4-7-gliedrigen Ring ergänzt, oder Q ist eine Gruppe -OR₁₅, worin R₁₅ Alkyl, Aryl, Acyl oder ein heterocyclischer Rest ist.In the compounds of formula A and B the leaving group Q can be hydrogen or it is a heterocyclic group

wherein R₁₄ is an organic divalent group that complements the ring to a 4-7 membered ring, or Q is a group -OR₁₅, wherein R₁₅ is alkyl, aryl, acyl or a heterocyclic radical.

Typical examples of common yellow couplers are the compounds of the following formulas:

Further examples of yellow couplers can be found in US Pat. Nos. 2,407,210, 2,778,658, 2,875,057, 2,908,513, 2,908,573, 3,227,155, 3,227,550, 3,253,924, 3,265,506, 3,277,155, 3,408,194, 3,341,331, 3,369,895, 3,384,657, 3,415,652, 3,422,572, 3,584,357, 3,422, 252, 3,552, 3,447, 252, 3,547, 325, 3,422, 325, 3,415, 352 3,891,445, 3,933,501, 4,115,121, 4,401,752 and 4,022,620, in DE-A 1,547,868, 2,057,941, 2,162,899, 2,163,813, 2,213,461, 2,219,917, 2,261,361, 2,261,362, 2,263,875, 2,329,587, 2,414,006 and 2,422,812 in GB-A and GB 1,042,812,0,04 and 1,077,812 in GB-A and GB-A 1,042,012 and 1,422,812 in GB-A and GB-A 1,042,812,0,04 and 1,422,812 in GB-A and GB-A -A-88 / 123,047 and in EP-A-447,969.

The yellow couplers are usually used in an amount of 0.05-2 mol and preferably 0.1-1 mol per mol of silver halide.

Typical and preferred yellow couplers correspond to the formulas:

Magenta couplers can e.g. be simple 1-aryl-5-pyrazolones or pyrazole derivatives condensed with 5-membered hetero rings, e.g. Imidazopyrazole, pyrazolopyrazole, pyrazolotriazole or pyrazolotetrazole.

A group of magenta couplers are 5-pyrazolones of the formula C,

as described in British Patent 2,003,473. In it R₁₆ is hydrogen, alkyl, aryl, alkenyl or a heterocyclic group. R₁₇ is hydrogen, alkyl aryl, a heterocyclic group, an ester group, alkoxy group, alkylthio group, carboxyl group, arylamino group, acylamino group, (thio) urea group, (thio) carbamoyl group, guanidino group or sulfonamido group.

worin R₁₈ Imino, Acylamino oder Ureido ist, R₁₉ Wasserstoff, Halogen, Alkyl oder Alkoxy ist, R₂₀ Wasserstoff, Alkyl, Acylamino, Carbamoyl, Sulfamoyl, Sulfonamido, Alkoxycarbonyl, Acyloxy oder eine Urethangruppe ist.R₁₇ is preferably a group

wherein R₁₈ is imino, acylamino or ureido, R₁₉ is hydrogen, halogen, alkyl or alkoxy, R₂₀ is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group.

If Q ′ is hydrogen, the magenta coupler is tetra equivalent with respect to that Silver halide.

worin R₂₀ die oben genannten Bedeutungen hat, und Q′, wie oben beschrieben, eine Abgangsgruppe ist. Diese Verbindungen liegen bevorzugt im erfindungsgemässen Material vor.Typical examples of this type of magenta coupler are compounds of the formula

wherein R₂₀ has the meanings given above, and Q ', as described above, is a leaving group. These compounds are preferably present in the material according to the invention.

Further examples of such tetra-equivalent magenta couplers can be found in US Pat and 3,933,500 and in JP-A-89 / 309,058.

If Q ′ in formula C is not hydrogen but a group that is eliminated in the reaction with the oxidized developer, then it is a equivalent magenta coupler. In this case, Q can e.g. Halogen or a group bonded to the pyrazole ring via O, S or N. Such equivalent couplers result in a higher color density and are more reactive towards the oxidized developer than the corresponding tetra-equivalent magenta couplers.

Examples of equivalent magenta couplers are described in US-A 3,006,579, 3,419,391, 3,311,476, 3,432,521, 3,214,437, 4,032,346, 3,701,783, 4,351,897, 3,227,554, in EP-A-133,503, DE-A-2,944,601, JP-A-78/34044 , 74/53435, 74/53436, 75/53372 and 75/122935.

Typical and preferred magenta couplers correspond to the formulas

Two pyrazolone rings can be linked via a divalent Q ′ and so-called bis-couplers are then obtained. Such are e.g. described in US-A-2,632,702, US-A-2,618,864, GB-A-968,461, GB-A-786,859, JP-A-76/37646, 59/4086, 69/16110, 69/26589, 74/37854 and 74/29638. Y is preferably an O-alkoxyarylthio group.

As mentioned above, pyrazoles - so-called pyrazoloazoles - condensed with 5-membered heterocycles can also be used as magenta couplers. Their advantages over simple pyrazoles is that they have colors with greater formalin resistance and purer absorption spectra.

dargestellt werden, worin R₁ Wasserstoff oder ein Substituent ist, Z die zur Vervollständigung eines 5-gliedrigen Ringes mit 2 oder 3 Stickstoffatomen notwendigen nicht-metallischen Atome darstellt, wobei dieser Ring substituiert sein kann, und Q Wasserstoff oder eine Abgangsgruppe ist.Pyrazoloazole type magenta couplers, which are also preferred, can be represented by the formulas

are represented, wherein R₁ is hydrogen or a substituent, Z represents the non-metallic atoms necessary to complete a 5-membered ring with 2 or 3 nitrogen atoms, which ring may be substituted, and Q is hydrogen or a leaving group.

R₁₁, R₁₂ und R₁₃ bedeuten unabhängig voneinander beispielsweise Wasserstoff, Halogen, eine Gruppe der Formel -CR₃, worin die Reste R unabhängig voneinander Wasserstoff oder Alkyl sind, Aryl, Heterocyclyl, Cyano, Hydroxy, Nitro, Carboxyl, Amino, Alkoxy, Aryloxy, Acylamino, Alkylamino, Anilino, Ureido, Sulfamoylamino, Alkylthio, Arylthio, Alkoxycarbonylamino, Sulfonamido, Carbamoyl, Sulfamoyl, Sulfonyl, Alkoxycarbonyl, Heterocyclyl-oxy, Azo, Acyloxy, Carbamoyloxy, Silyloxy, Aryloxycarbonylamino, Imido, heterocyclische Ring-thio, Sulfinyl, Phosphonyl, Aryloxycarbonyl, Acyl oder Azolyl, und vorzugsweise Wasserstoff; Halogen (z.B. Chlor, Brom), eine Gruppe der Formel -CR₃, worin die Reste R unabhängig voneinander Wasserstoff oder Alkyl sind, Aralkyl, Alkenyl, Alkinyl, Cycloalkyl oder Cycloalkenyl und besonders bevorzugt Methyl, Ethyl, Propyl, Isopropyl, t-Butyl, Tridecyl, 2-Methansulfonylethyl, 3-(3-Pentadecylphenoxy)propyl, 3-(4-(2-(4-(4-Hydroxyphenylsulfonyl)phenoxy)dodecanamido)phenyl)propyl, 2-Ethoxytridecyl, Trifluoromethyl, Cyclopentyl, 3-(2,4-Di-t-Amylphenoxy)propyl); Aryl (z.B. Phenyl, 4-t-Butylphenyl, 2,4-Di-t-amylphenyl, 4-Tetradecaneamidophenyl); Heterocyclyl (z.B. 2-Furyl, 2-Thienyl, 2-Pyrimidinyl, 2-Benzothiazolyl); Cyano; Hydroxy, Nitro; Carboxy; Amino; Alkoxy (z.B. Methoxy, Ethoxy, 2-Methoxyethoxy; 2-Dodecylethoxy, 2-Methansulfonylethoxy); Aryloxy (z.B. Phenoxy, 2-Methylphenoxy, 4-t-Butylphenoxy , 3-Nitrophenoxy, 3-t-Butyloxycarbamoylphenoxy, 3-Methoxycarbamoyl); Acylamino (z.B. Acetoamido, Benzamido, Tetradecanamido, 2-(2,4-Di-t-amylphenoxy)-butanamido, 4-(3-t-Butyl-4-hydroxyphenoxy)butanamido, 2-(4-(4-Hydroxyphenylsulfonyl)phenoxy)decanamido); Methylbutylamino); Anilino (z.B. Phenylamino, 2-Chloranilino, 2-Chloro-5-tetradecanaminoanilino, 2-Chloro-5-dodecyloxycarbonylanilino, N-Acetylanilino, 2-Chloro-5-(alpha-(3-t-butyl-4-hydroxyphenoxy)dodecanamido-anilino); Ureido (z.B. Phenylureido, Methylureido, N,N-Dibutylureido); Sulfamoylamino (z.B. N,N-Dipropylsulfamoylamino, N-Methyl-N-decylsulfamoylamino); Alkylthio (z.B. Methylthio, Octylthio, Tetradecylthio, 2-Phenoxyethylthio, 3-Phenoxypropylthio, 3-(4-t-Butylphenoxy)propylthio); Arylthio (z.B. Phenylthio, 2-Butoxy-5-t-octylphenylthio, 3-Pentadecylphenylthio, 2-Carboxyphenylthio, 4-Tetradecanamidophenylthio); Alkoxycarbonylamino (z.B. Methoxycarbonylamino, Tetradecyloxycarbonylamino); Sulfonamido (z.B. Methansulfonamido, Hexadecansulfonamido, Benzolsulfonamido, p-Toluolsulfonamido, Octadecansulfonamido, 2-Methyloxy-5-t-butylbenzolsulfonamido); Carbamoyl (z.B. N-Ethylcarbamoyl, N,N-Dibutylcarbamoyl, N-(2-Dodecyloxyethyl)carbamoyl, N-Methyl-N-dodecylcarbamoyl, N-(3-(2,4-Di-t-Amylphenoxy)propyl)carbamoyl); Sulfamoyl (z.B. N-Ethylsulfamoyl, N,N-Dipropylsulfamoyl, N-2(-Dodecyloxyethyl)sulfamoyl, N-Ethyl-N-dodecylsulfamoyl, N,N-Diethylsulfamoyl); Sulfonyl (z.B. Methansulfonyl, Octansulfonyl, Benzolsulfonyl, Toluolsulfonyl); Alkoxycarbonyl (z.B. Methoxycarbonyl, Butoxycarbonyl, Dodecyloxycarbonyl, Octadecyloxycarbonyl); heterocyclische Ringoxy (z.B. 1-Phenyltetrazol-5-oxy, 2-Tetrahydropyranyloxy); Azo (z.B. Phenylazo, 4-Methoxyphenylazo, 4-Pivaloylaminophenylazo, 2-Hydroxy-4-propanoylphenylazo); Acyloxy (z.B. Acetoxy); Carbamoyloxy (z.B. N-Methylcarbamoyloxy, N-Phenylcarbamoyloxy); Silyloxy (z.B. Trimethylsilyloxy, Dibutylmethylsilyloxy); Aryloxycarbonylamino (z.B. Phenoxycarbonylamino); Imido (z.B. N-Succinimido, N-Phthalimido, 3-Octadecenylsuccinimido); heterocyclische Ring-thio (z.B. 2-Benzothiazolylthio, 2,4-Diphenyloxy- 1,3,5-triazol-6-thio, 2-Pyridylthio); Sulfinyl (z.B. Dodecansulfinyl, 3-Pentadecylphenylsulfinyl, 3-Phenoxypropylsulfinyl); Phosphonyl (z.B. Phenoxyphosphonyl, Octyloxyphosphonyl, Phenylphosphonyl); Aryloxycarbonyl (z.B. Phenoxycarbonyl); Acyl (z.B. Acetyl, 3-Phenylpropanoyl, Benzoyl, 4-Dodecyloxybenzoyl); Azolyl (z.B. Imidazolyl, Pyrazolyl, 3-Chloro-pyrazol-1-yl).Of these, magenta couplers of the formulas are preferred

R₁₁, R₁₂ and R₁₃ independently of one another, for example, hydrogen, halogen, a group of formula -CR₃, wherein the radicals R are independently hydrogen or alkyl, aryl, heterocyclyl, cyano, hydroxy, nitro, carboxyl, amino, alkoxy, aryloxy, acylamino , Alkylamino, anilino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclyl-oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, sulfonyl, imido Aryloxycarbonyl, acyl or azolyl, and preferably hydrogen; Halogen (eg chlorine, bromine), a group of the formula -CR₃, in which the radicals R are independently of one another hydrogen or alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl and particularly preferably methyl, ethyl, propyl, isopropyl, t-butyl, Tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- (4- (2- (4- (4-hydroxyphenylsulfonyl) phenoxy) dodecanamido) phenyl) propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- ( 2,4-di-t-amylphenoxy) propyl); Aryl (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecaneamidophenyl); Heterocyclyl (e.g. 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl); Cyano; Hydroxy, nitro; Carboxy; Amino; Alkoxy (e.g. methoxy, ethoxy, 2-methoxyethoxy; 2-dodecylethoxy, 2-methanesulfonylethoxy); Aryloxy (e.g. phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); Acylamino (e.g. acetoamido, benzamido, tetradecanamido, 2- (2,4-di-t-amylphenoxy) butanamido, 4- (3-t-butyl-4-hydroxyphenoxy) butanamido, 2- (4- (4-hydroxyphenylsulfonyl)) phenoxy) decanamido); Methylbutylamino); Anilino (e.g. phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- (alpha- (3-t-butyl-4-hydroxyphenoxy) dodecanamido -anilino); ureido (e.g. phenylureido, methylureido, N, N-dibutylureido); sulfamoylamino (e.g. N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino); alkylthio (e.g. methylthio, octylthio, tetradecylthio, 3-phenoxyethyl -Phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio); arylthio (e.g. phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio); Alkoxycarbonylamino (e.g. methoxycarbonylamino, tetradecyloxycarbonylamino); Sulfonamido (e.g. methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido, p-toluenesulfonamido, octadecanesulfonamido, 2-methyloxy-5-t-butylbenzenesulfonamido); Carbamoyl (e.g. N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- (3- (2,4-di-t-amylphenoxy) propyl) carbamoyl) ; Sulfamoyl (e.g. N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-2 (-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl); Sulfonyl (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); Alkoxycarbonyl (e.g. methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl); heterocyclic ringoxy (e.g. 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy); Azo (e.g. phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); Acyloxy (e.g. acetoxy); Carbamoyloxy (e.g. N-methylcarbamoyloxy, N-phenylcarbamoyloxy); Silyloxy (e.g. trimethylsilyloxy, dibutylmethylsilyloxy); Aryloxycarbonylamino (e.g. phenoxycarbonylamino); Imido (e.g. N-succinimido, N-phthalimido, 3-octadecenylsuccinimido); heterocyclic ring thio (e.g. 2-benzothiazolylthio, 2,4-diphenyloxy-1,3,5-triazol-6-thio, 2-pyridylthio); Sulfinyl (e.g. dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl); Phosphonyl (e.g. phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); Aryloxycarbonyl (e.g. phenoxycarbonyl); Acyl (e.g. acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl); Azolyl (e.g. imidazolyl, pyrazolyl, 3-chloropyrazol-1-yl).

These substituents are optionally further substituted, for example by halogen or by an organic radical bonded via a C, O, N or S atom.

The preferred groups R₁₁ are alkyl, aryl, alkoxy, aryloxy, alkylthio, ureido, urethane and acylamino groups.

R₁₂ can have the meaning of R₁₁ and is preferably hydrogen, alkyl, aryl, a heterocyclic ring, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acyl or cyano.

R₁₃ can have the meaning of R₁₁ and is preferably hydrogen, alkyl, aryl, heterocyclic, alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl, carbamoyl or acyl, preferably alkyl, aryl, heterocyclic, alkylthio or arylthio.

Q is hydrogen or a leaving group such as halogen, alkoxy, aryloxy, acyloxy, Alkyl- or arylsulfonyloxy, acylamino, alkyl- or aryl-sulfonamido, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl-, aryl- or heterocyclyl-S-carbamoylamino, a 5- or 6-membered nitrogen-containing heterocyclic radical, imido and arylazo. These groups are optionally further substituted as shown for R₁₁.

Preferably Q is halogen (e.g. fluorine, chlorine, bromine); Alkoxy (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy); Aryloxy (e.g. 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy); Acyloxy (e.g. acetoxy, tetradecanoyloxy, benzoyloxy); Alkyl or aryl sulfonyloxy (e.g. methanesulfonyloxy, toluenesulfonyloxy); Acylamino (e.g. dichloroacetylamino, heptafluorobutyrylamino); Alkyl or arylsulfonamido (e.g. methanesulfonamido, trifluoromethanesulfonamido, p-toluenesulfonylamido); Alkoxycarbonyloxy (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy); Aryloxycarbonyloxy (e.g. phenoxycarbonyloxy); Alkyl, aryl or heterocyclyl-S- (e.g. dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio); Carbamoylamino (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino); 5- or 6-membered nitrogen-containing ring (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl); Imido (e.g. succinimido, hydantoinyl); Arylazo (e.g. phenylazo, 4-methoxyphenylazo).

Q can also form corresponding bis-compounds by condensing 4 equivalent couplers with an aldehyde or ketone. Furthermore, Q can contain photographically active groups such as development inhibitors or development accelerators. Preferably Q is halogen, alkoxy, aryloxy, alkyl, arylthio, or a 5- or 6-membered nitrogen-containing heterocyclic group which is attached to the coupling site via a nitrogen atom.

Pyrazolo-tetrazoles are described in JP-A-85/33552; Pyrazolo-pyrazole in JP-A-85 / 43,695; Pyrazolo-imidazoles in JP-A-85/35732, JP-A-86/18949 and US-A-4,500,630; Pyrazolo-triazoles in JP-A-85 / 186,567, JP-A-86/47957, JP-A-85 / 215,687, JP-A-85 / 197,688, JP-A-85 / 172,982, EP-A-119,860 , EP-A-173,256, EP-A-178,789, EP-A-178,788 and in Research Disclosure 84 / 24,624.

Further pyrazoloazole magenta couplers are described in: JP-A-86 / 28,947, JP-A-85 / 140,241, JP-A-85 / 262,160, JP-A-85 / 213,937, JP-A-87 / 278,552, JP-A-87 / 279,340, JP-A-88 / 100,457, EP-A-177,765, EP-A-176,804, EP-A-170,164, EP-A-164,130, EP-A-178,794, DE-A- 3,516,996, DE-A-3,508,766 and Research Disclosure 81/20919, 84/24531 and 85/25758.

Suitable examples of such couplers are:

worin R₂₁, R₂₂, R₂₃ und R₂₄ Wasserstoff, Halogen, Alkyl, Carbamoyl, Amino, Sulfonamido, Phosphoramido oder Ureido sind. R₂₁ ist vorzugsweise H oder Cl, R₂₂ ist vorzugsweise eine Alkyl- oder Aminogruppe. R₂₃ ist vorzugsweise eine Aminogruppe und R₂₄ ist vorzugsweise Wasserstoff. Q˝ ist Wasserstoff oder eine Abgangsgruppe, die bei der Reaktion mit den oxidierten Entwickler abgespalten wird. Eine ausführliche Aufzählung von Cyankupplern ist im US-A-4,456,681 zu finden.Cyan couplers can be, for example, derivatives of phenol, 1-naphthol or pyrazoloquinazolone. Structures of the formula E are preferred

wherein R₂₁, R₂₂, R₂₃ and R₂₄ are hydrogen, halogen, alkyl, carbamoyl, amino, sulfonamido, phosphoramido or ureido. R₂₁ is preferably H or Cl, R₂₂ is preferably an alkyl or amino group. R₂₃ is preferably an amino group and R₂₄ is preferably hydrogen. Q˝ is hydrogen or a leaving group which is split off in the reaction with the oxidized developer. A detailed list of cyan couplers can be found in US-A-4,456,681.

Examples of common cyan couplers are the following:

Further examples of cyan couplers can be found in the following US-A-: 2,369,929, 2,423,730, 2,434,272, 2,474,293, 2,521,293, 2,521,908, 2,698,794, 2,706,684, 2,772,162, 2,801,171, 2,895,826, 2,908,573, 3,034,892, 3,046,129, 3,294,550, 3,253 3,311,476, 3,386,301, 3,419,390, 3,458,315, 3,476,560, 3,476,563, 3,516,831, 3,560,212, 3,582,322, 3,583,971, 3,591,383, 3,619,196, 3,632,347, 3,652,286, 3,737,326, 3,758,308, 3,839,044, 3,880,661, 4,004,929, 4, 124.396, 4,333,999, 4,463,086, 4,456,681, 4,873,183 and 4,923,791 and in EP-A-354,549 and EP-A-398,664.

und/oder oder Formel

zum Einsatz, worin
Z₁ Alkyl, Aryl, Z₂ Alkyl, Cycloalkyl, Aryl, eine heterocyclische Gruppe, oder eine Ballastgruppe, Z₃ Wasserstoff oder Halogen ist, Z₁ und Z₃ zusammen einen Ring bilden können, und Z₄ Wasserstoff oder eine Abgangsgruppe ist, und Z₅ eine Ballastgruppe, Z₆ Wasserstoff oder eine Abgangsgruppe und Zr Alkyl ist.In the red-sensitive silver halide emulsion layer of the material according to the invention there are preferably cyan couplers of the formula

and / or or formula

to use, in which
Z₁ alkyl, aryl, Z₂ alkyl, cycloalkyl, aryl, a heterocyclic group, or a ballast group, Z₃ is hydrogen or halogen, Z₁ and Z₃ together can form a ring, and Z₄ is hydrogen or a leaving group, and Z₅ is a ballast group, Z₆ hydrogen or a leaving group and Zr is alkyl.

The color developers commonly used for color photographic materials are p-dialkylaminoanilines. Examples include 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-α-hydroxyethylaniline, 3-methyl-4-amino-N -ethyl-N-α-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-α-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-α-methanesulphonamidoethylaniline, 3-methyl-4 -amino-N-ethyl-N-α-methoxyethyl-aniline, 3-α-methanesulphonamidoethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-α-hydroxyethylaniline, 3 Methoxy-4-amino-N-ethyl-N-α-methoxyethylaniline, 3-acetamido-4-amino-N, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-α- [α ′ - (α˝-methoxyethoxy) ethoxy] ethyl-3-methyl-4-aminoaniline, N-ethyl-N-α- (α '-Methoxyethoxy) ethyl-3-methyl-4-aminoaniline, and the salts of such compounds, such as sulfates, hydrochlorides or toluenesulfonates

The UV absorbers of the formulas (I) and (III) used according to the invention can be incorporated into the color photographic material alone or together with the color coupler and, if appropriate, further additives, by pre-dissolving them in high-boiling organic solvents. Solvents boiling above 160 ° C. are preferably used. Typical examples of such solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids, and also alkylamides and phenols.

In most cases, a low-boiling solvent is also used to facilitate the incorporation of the additives into the color photographic material. Examples of such solvents are esters such as e.g. Ethyl acetate, alcohols such as e.g. Butanol, ketones such as Methyl isobutyl ketone, chlorinated hydrocarbons such as e.g. Methylene chloride, or amides such as e.g. Dimethylformamide. If the additives themselves are liquid, they can also be incorporated into the photo material without the use of solvents.

The UV absorbers according to the invention can optionally be dispersed without 0l in the gelatin layer; Research Disclosure 88/296017 and 89/303070.

Further details on usable high-boiling solvents can be found in the following publications:
Phosphates: GB-A-791,219, BE-A-755,248, JP-A-76/76739, 78/27449, 78 / 218,252, 78/97573, 79 / 148,133, 82 / 216,177, 82/93323 and 83 / 216,177 and EP-A265,296. Phthalates: GB-A-791,219, JP-A-77/98050, 82/93322, 82 / 216,176, 82 / 218,251, 83/24321, 83/45699, 84/79888.
Amides: GB-A-791,129, JP-A-76 / 105,043, 77/13600, 77/61089, 84 / 189,556, 87/239, 149, US-A-928,741, EP-A-270,341, WO 88/00723 .
Phenols: GB-A-820,329, FR-A-1,220,657, JP-A-69/69946, 70/3818, 75 / 123,026, 75/82078, 78/17914, 78/21166, 82 / 212,114 and 83/45699.

Other oxygen-containing compounds: US-A-3,748,141, 3,779,765, JP-A-73/75126,
74 / 101,114, 74/10115, 75 / 101,625, 76/76740, 77/61089, EP-A-304,810 and BE-A-826,039.

Other compounds: JP-A-72 / 115,369, 72 / 130,258, 73 / 127,521, 73/76592, 77/13193, 77/36294, 79/95233, 91 / 2,748, 83 / 105,147 and Research Disclosure 82/21918.

The amount of high boiling solvent is e.g. in the range of 50 mg to 2 g per m² of support, preferably from 200 mg to 1 g per m².

The photographic layers may also contain color fog inhibitors. These prevent the formation of color veils, such as those caused by the reaction of the coupler with inadvertently oxidized developer or with by-products of the color formation process. Such color fog inhibitors are mostly hydroquinine derivatives, but can also be derivatives of aminophenols, of gallic acid or of ascorbic acid. Typical examples of this can be found in the following publications:
US-A-2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,365; EP-A-124,877, EP-A-277,589, EP-A-338,785; JP-A-75/92988, 75/92989, 75/93928, 75 / 110,337, 84 / 5,247 and 77 / 146,235.

The photographic layers may also be so-called DIR couplers (DIR means D evelopment I nhibition R elease) contain give the colorless compounds with the oxidized developer. They are added to improve the sharpness and graininess of the color images.

The photographic layers in the material according to the invention can also contain further UV absorbers. Examples of such UV absorbers are benzotriazoles, 2-hydroxybenzophenones, salicylic acid esters, acrylonitrile derivatives or thiazolines. Such UV absorbers are explained in more detail, for example, in the following publications: US Pat. 4,749,643, GB-A-1,564,089, EP-A-190,003 and JP-A-71/2784, 81 / 111,826, 81/27, 146, 88 / 53,543 and 88 / 55,542. Preferred UV absorbers are benzotriazoles, in particular 2- (2-hydroxyphenyl) benzotriazoles and preferably those of the formula (III) shown above.

The photographic layers can also contain phenolic compounds which act as light stabilizers for the color image and as agents against color fog. They can be contained in a light-sensitive layer (color layer) or in an intermediate layer, alone or together with other additives. Such connections are e.g. in the following publications: US-A-3,700,455, 3,591,381, 3,573,052, 4,030,931, 4,174,220, 4,178, 184, 4,228,235, 4,279,990, 4,346,165, 4,366,226, 4,447,523, 4,528,264, 4,581,326, 4,562,146, 4,559,297, GB-A-1,302,277 , 2,023,862, 2,135,788, 2,139,370, 2,156,091; DE-A-2,301,060, 2,347,708, 2,526,468, 2,621,203, 3,323,448; DD-A-200,691, 214,468; EP-A-106,799, 113,124, 125,522, 159,912, 161,577, 164,030, 167,762, 176,845, 246,766, 320,776; JP-A-74 / 134,326, 76 / 127,730, 76/30462, 77/3822, 77 / 154,632, 78/10842, 79/48535, 79/70830, 79/73032, 79 / 147,038, 79 / 154,325, 79 / 155.836, 82 / 142.638, 83 / 224.353, 84/5246, 84/72443, 84/87456, 84 / 192.246, 84 / 192.247, 84 / 204.039, 84 / 204.040, 84 / 212.837, 84 / 220.733, 84 / 222.836, 84 / 228,249, 86/2540, 86/8843, 86/18835, 86/18836, 87/11456, 87/42245, 87/62157, 86/6652, 89 / 137,258 and in Research Disclosure 79/17804.

The photographic layers can also contain certain phosphorus III compounds, especially phosphites and phosphonites. These act as light stabilizers for the color images and as a dark storage stabilizer for magenta couplers. They are preferably added to the high-boiling solvents together with the coupler. Such phosphorus III compounds are e.g. described in greater detail in the following publications: US-A-4,407,935, US-A-4,436,811, US-A-4,956,406, EP-A-181,289, JP-A-73/32728, JP-A-76/1420 and JP-A -55/66741.

The photographic layers can also contain organometallic complexes which are light stabilizers for the color images, in particular for the magenta dyes. Such compounds and their combination with other additives are e.g. described in more detail in the following publications: US Pat. JP-A-81 / 167,138, 81 / 168,652, 82/30834, 82 / 161,744; EP-A-137,271, 161,577, 185,506; DE-A-2,853,865.

The photographic layers can also contain hydroquinone compounds. These act as light stabilizers for the color couplers and for the color images and as scavengers for oxidized developers in the intermediate layers. You will mainly be in the Magenta layer used. Such hydroquinone compounds and their combinations with other additives are described in more detail in, for example, the following publications: US Pat. 3,637,393, 3,700,453, 3,960,570, 3,935,016, 3,930,866, 4,065,435, 3,982,944, 4,232,114, 4,121,939, 4,175,968, 4,179,293, 3,591,381, 3,573,052, 4,279,990, 4,429,031, 4,346,165, 4,360,589, 4,346,167, 4,385,111, 4,416,978, 4,430,425, 4,277,558, 4,489,155, 4,504,572, 4,559,297, FR-A-885,982; GB-A-891,158, 1,156,167, 1,363,921, 2,022,274, 2,066,975, 2,071,348, 2,081,463, 2, 117,526, 2,156,091; DE-A-2,408,168, 2,726,283, 2,639,930, 2,901,520, 3,308,766, 3,320,483, 3,323,699; DD-A-216,476, 214,468, 214,469, EP-A-84290, 110,214, 115,305, 124,915, 124,877, 144,288, 147,747, 178,165, 161,577; JP-A-75/33733, 75/21249, 77 / 128,130, 77 / 146,234, 79/70036, 79 / 133,131, 81/83742, 81/87040, 81 / 109,345, 83 / 134,628, 82/22237, 82 / 112.749, 83/17431, 83/21249, 84/75249, 84 / 149.348, 84 / 182.785, 84 / 180.557, 84 / 189.342, 84 / 228.249, 84 / 101.650, 79/24019, 79/25823, 86/48856, 86/48857, 86/27539, 86/6652, 86/72040, 87/11455, 87/62157, as well as in Research Disclosure 79/17901, 79/17905, 79/18813, 83/22827 and 84/24014.

The photographic layers can also contain derivatives of hydroquinone ethers. These compounds act as light stabilizers and are particularly suitable for stabilizing magenta dyes. Such compounds and their combination with other additives are e.g. described in more detail in the following publications: US Pat , 4,207,111, 4,254,216, 4, 134,011, 4,273,864, 4,264,720, 4,279,990, 4,332,886, 4,436,165, 4,360,589, 4,416,978, 4,385,111, 4,459,015, 4,559,297; GB-A 1,347,556, 1,366,441, 1,547,392, 1,557,237, 2,135,788; DE-A 3,214,567; DD-214,469, EP-A 161,577, 167,762, 164,130, 176,845; JP-A 76 / 123,642, 77/35633, 77 / 147,433, 78/126, 78/10430, 78/53321, 79/24019, 79/25823, 79/48537, 79/44521, 79/56833, 79/70036 , 79/70830, 79/73032, 79/95233, 79 / 145,530, 80/21004, 80/50244, 80/52057, 80/70840, 80 / 139,383, 81/30125, 81 / 151,936, 82/34552, 82 / 68833, 82 / 204,306 82 / 204,037, 83 / 134,634, 83 / 207,039, 84/60434, 84 / 101,650, 84/87450, 84 / 149,348, 84 / 182,785, 86/72040, 87/11455, 87/62157, 87/63149, 86/2151, 86/6652, 86/48855, 89 / 309,058 and in Research Disclosure 78/17051.

Examples of stabilizers for the magenta couplers are:

Usual silver chloride, bromide or iodide emulsions can be used as silver halide emulsions or mixtures thereof such as silver chlorobromide and silver chloroiodide emulsions, in which the silver halides can have all known crystal forms. The use of silver chloride emulsions is of particular importance in the material according to the invention. The preparation of such emulsions and their sensitization are described in RESEARCH DISCLOSURE, November 1989, No. 307.105. This publication also mentions a number of binders for the emulsions mentioned, which can also be used in the materials according to the invention. The same applies to the carriers mentioned in the publication.

The silver halide emulsion which can be used in the practice of this invention can be sensitized to any desired wavelength by means of sensitizing pigments. Cyanine pigments, merocyanine pigments, holopolar pigments, hemicyanine pigments, styryl pigments or hemioxanol pigments can be used for this purpose.

Water-soluble dyes may be included in the photosensitive material to improve clarity, for example, by preventing radiation damage. Oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, anthraquinone dyes and azo dyes can be used for this.

Other materials such as those described in JP-A-87/2 15,272, 92 / 9,035, 92 / 21,840 and EP-A-429,240 can also be used with the material according to the invention.

The present invention also relates to compounds

worin R₁ Alkyl mit 1 bis 18 Kohlenstoffatomen, durch Sauerstoff unterbrochenes Alkyl oder Hydroxyalkyl mit 3 bis 50 Kohlenstoffatomen oder -CH₂CH(OH)R₉ ist, worin R₉ Phenylalkyl mit 1 bis 6 Kohlenstoffatomen im Akylteil oder -CH₂OR₁₁ ist, worin R₁₁ Cyclohexyl, Tolyl, Phenyl oder Benzyl ist, und R₁₂ -OR₁₆ ist, worin R₁₆ Alkyl mit 1 bis 18 Kohlenstoffatomen oder durch Sauerstoff unterbrochenes Alkyl mit 3 bis 18 Kohlenstoffatomen ist.of the formula

wherein R₁ is alkyl having 1 to 18 carbon atoms, oxygen-interrupted alkyl or hydroxyalkyl having 3 to 50 carbon atoms or -CH₂CH (OH) R,, wherein R₉ is phenylalkyl having 1 to 6 carbon atoms in the alkyl part or -CH₂OR₁₁, wherein R₁₁ is cyclohexyl, tolyl, Is phenyl or benzyl, and R₁₂ is -OR₁₆, wherein R₁₆ is alkyl of 1 to 18 carbon atoms or oxygen-interrupted alkyl of 3 to 18 carbon atoms.

Of these, preference is given to those compounds in which R₁ is alkyl having 1 to 8 carbon atoms, alkyl interrupted by oxygen or hydroxyalkyl having 3 to 20 carbon atoms or -CH₂CH (OH) R₉, where R₉ is CH₂OR₁₁, wherein R₁₁ is benzyl, and R₁₂ is -OR₁₆ , wherein R₁₆ is alkyl having 1 to 8 carbon atoms or alkyl interrupted by oxygen having 3 to 10 carbon atoms.

worin R₁ unabhängig voneinander einen Rest der Formel -CH₂-CH(OR_x)R_y, -CH₂CH(OR_x)CH₂OR_z,

-CH₂COR_y oder -CH₂COCH₂OR_z bedeuten, wobei
R_x -COR_s, -COOR_w oder -SiR_pR_qR_r,
R_y C₁-C₁₈-Alkyl oder Phenyl-C₁-C₄-Alkyl,
R_z C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl, Phenyl-C₁-C₄-Alkyl, -COR_s oder durch Sauerstoff
unterbrochenes C₁-C₂₄-Alkyl oder C₂-C₂₄-Hydroxyalkyl,
R_s C₁-C₁₈-Alkyl, C₂-C₁₈-Alkenyl oder Phenyl,
R_w C₁-C₄-Alkyl und
R_p, R_q und R_r unabhängig voneinander C₁-C₆-Alkyl oder Phenyl bedeuten; oder
   die Reste R₁ unabhängig voneinander eine Gruppe G-II bedeuten, wobei II eine Gruppe der Formel

ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist: -(CH₂)_q-, -(CH₂)_q-O-, -(CH₂)_q-O-R₂₆-, -(CH₂)_q-CO-X-(CH₂)_r-, -(CH₂)_q-CO(X-(CH₂)_r-O-,

-CH₂-CH(OH)-CH₂-Y-(CH₂)_q-,
worin q und r unabhängig voneinander 1-4 und p 0-50 sind,
R₂₆ C₁-C₁₂-Alkylen, Cyclohexylen oder Phenylen bedeutet,
R₂₇ C₁-C₁₂-Alkyl, C₅-C₈-Cycloalkyl, Phenyl, C₂-C₁₃-Alkoxymethyl,
C₆-C₉-Cycloalkoxymethyl oder Phenoxymethyl bedeutet,
R₂₈ eine Gruppe der Formel G-II bedeutet,
R₂₉ Waserstoff oder Methyl ist,
X -O- oder -NR₂₃- bedeutet, worin R₂₃ Wasserstoff, C₁-C₁₂-Alkyl oder eine Gruppe -(CH₂)₃-G-II oder -(CH₂)₃-O-G-II bedeutet,
Y -O- oder -NH- bedeutet,
R₂₀, R₂₁ und R₂₂ unabhängig voneinander C₁-C₁₈-Alkyl, Cyclohexyl, Phenyl oder C₁-C₁₈-Alkoxy bedeuten; und
R₁₂ Alkyl mit 1 bis 12 Kohlenstoffatomen oder eine Gruppe der Formel

oder -OR₁₆ ist, vorzugsweise ist R₁₂ eine Gruppe der Formel

worin R₁₃ und R₁₄ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder Chlor sind, und R₁₆ Alkyl mit 1 bis 8 Kohlenstoffatomen oder durch Sauerstoff unterbrochenes Alkyl mit 3 bis 12 Kohlenstoffatomen ist.The present invention further relates to compounds of the formula

wherein R₁ independently of one another is a radical of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z ,

-CH₂COR _y or -CH₂COCH₂OR _z mean, wherein
R _x -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₁₈-alkyl or phenyl-C₁-C₄-alkyl,
R _z C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, phenyl-C₁-C₄ alkyl, -COR _s or by oxygen
interrupted C₁-C₂₄-alkyl or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another are C₁-C₆ alkyl or phenyl; or
the radicals R₁ independently of one another represent a group G-II, II being a group of the formula

is
and
G is a direct bond or a divalent group of one of the following formulas: - (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -O-R₂₆-, - (CH₂) _q -CO-X - (CH₂) _r -, - (CH₂) _q -CO (X- (CH₂) _r -O-,

-CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1-4 and p 0-50,
R₂₆ is C₁-C₁₂ alkylene, cyclohexylene or phenylene,
R₂₇ C₁-C₁₂ alkyl, C₅-C₈ cycloalkyl, phenyl, C₂-C₁₃ alkoxymethyl,
C₆-C₉-cycloalkoxymethyl or phenoxymethyl means
R₂₈ represents a group of the formula G-II,
R₂₉ is hydrogen or methyl,
X denotes -O- or -NR₂₃-, in which R₂₃ denotes hydrogen, C₁-C₁₂-alkyl or a group - (CH₂) ₃-G-II or - (CH₂) ₃-OG-II,
Y means -O- or -NH-,
R₂₀, R₂₁ and R₂₂ independently of one another are C₁-C₁₈ alkyl, cyclohexyl, phenyl or C₁-C₁₈ alkoxy; and
R₁₂ alkyl having 1 to 12 carbon atoms or a group of the formula

or -OR₁₆, preferably R₁₂ is a group of the formula

wherein R₁₃ and R₁₄ are independently hydrogen, C₁-C₄-alkyl or chlorine, and R₁₆ is alkyl having 1 to 8 carbon atoms or alkyl interrupted by oxygen having 3 to 12 carbon atoms.

ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist:
-(CH₂)_q-, -(CH₂)q-O-, -(CH₂)_q-CO-X-(CH₂)_r-,

oder -CH₂-CH(OH)-CH₂-Y-(CH₂)_q-,
worin q und r unabhängig voneinander 1, 2 oder 3 und p 0-50 sind,
R₂₇ Methyl, Phenyl, C₃-C₉-Alkoxymethyl oder Phenoxymethyl bedeutet,
R₂₈ eine Gruppe der Formel G-II bedeutet,
X und Y -O- bedeuten,
R₂₇, R₂₁ und R₂₂ unabhängig voneinander C₁-C₈-Alkyl, Phenyl oder C₁-C₈-Alkoxy bedeuten; und
R₁₂ eine Gruppe der Formel

ist, worin
R₁₃ und R₁₄ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder Chlor sind.Particularly preferred are the compounds in which the radicals R₁ independently of one another are the radicals of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z , -CH₂COR _y or -CH₂COCH₂OR _z , where
R _x -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₈ alkyl,
R _z C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, benzyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another C₁-C₆-alkyl
mean; or
R₁ represent a group G-II,
where II is a group of formula

is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH₂) _q -, - (CH₂) qO-, - (CH₂) _q -CO-X- (CH₂) _r -,

or -CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1, 2 or 3 and p are 0-50,
R₂₇ denotes methyl, phenyl, C₃-C₉ alkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
X and Y mean -O-,
R₂₇, R₂₁ and R₂₂ are independently C₁-C₁ alkyl, phenyl or C₁-C₈ alkoxy; and
R₁₂ is a group of the formula

is what
R₁₃ and R₁₄ are independently hydrogen, C₁-C₄ alkyl or chlorine.

Further preferred compounds are those as mentioned in the description of the photographic material.

The following examples further illustrate the invention.

Example 1:

A gelatin layer, which contains silver bromide, a magenta coupler and a stabilizer, is first applied to a carrier material coated with polyethylene, then a gelatin layer, which contains the UV absorber of the formula (I) (top layer).

The gelatin layers contain the following components (per m² carrier material):

2,4-dichloro-6-hydroxytriazine is used as the hardener, the sodium salt of diisobutylnaphthalenesulfonic acid as the wetting agent.

The amounts of magenta coupler and stabilizer are given in Table 2.

A step wedge with a density difference of 0.15 logE per step is exposed on each of the samples thus obtained and then processed in accordance with the manufacturer's instructions in processing process E + 2 from Kodak for negative color papers.

After exposure and processing, the reflectance density in green for the magenta step is measured with a density between 0.9 and 1.1 of the wedge. Then the wedge is exposed in a Atlas exposure device with a total of 45 kJ / cm² and the remission density is measured again.

The dye loss (-ΔD) in% is given in Table 2.

A smaller decrease in the magenta density is found in the samples which contain a UV absorber according to the invention.

Example 2:

The procedure is as in Example 1, but without a stabilizer and using a cyan coupler. The composition of the gelatin layers (per m²) is as follows:

The amounts of the cyan coupler are given in Table 3:
After exposure and processing as described in Example 1, the reflectance density in red for the cyan level is measured with a density between 0.9 and 1.1 of the wedge. Then the wedge is exposed in a Atlas exposure device with a total of 30 kJ / cm² and the remission density is measured again. The dye density loss (-ΔD) in% is given in Table 3.

A smaller decrease in the density of the cyan dye can be found in the samples which contain a UV absorber according to the invention.

Example 3:

The procedure is as in Example 1, but without a stabilizer and using a yellow coupler.

The composition of the gelatin layers (per m²) is as follows:

The amount of yellow coupler is given in Table 4.

After exposure and processing as described in Example 1, the reflectance density in blue is measured for the yellow level with a density between 0.9 and 1.1 of the wedge. Then the wedge is exposed in a Atlas exposure device with a total of 15 kJ / cm² and the remission density is measured again. The dye loss (-ΔD) in% is given in Table 4.

A smaller decrease in the yellow dye density can be found in the samples which contain a UV absorber according to the invention.

Example 4:

The procedure is as in Example 1.

The amounts of magenta coupler and stabilizer are given in Table 5.

The reflectance density in blue for yellowing is measured. Then the wedge is exposed in a Atlas exposure device with a total of 15 kJ / cm², the reflectance density (in blue) is measured again and the yellow dye increase (-ΔD _B ) is calculated. The yellowing is shown in Table 5.

Less yellowing is found in the samples which contain a UV absorber according to the invention.

Example 5:

The amount of UV absorber listed in the table below is dissolved in 2 ml of ethyl acetate. 1 ml of this solution is mixed with 9 ml of an aqueous gelatin solution (which contains 27.6 g / l gelatin and 6.8 g / l of an 8% aqueous solution of 4,8-diisobutylnaphthalene-2-sulfonic acid (sodium salt) as a wetting agent ) mixed. This mixture is emulsified with ultrasound for 3 minutes. 7.5 ml of this UV absorber emulsion is mixed with 4.5 ml of an aqueous hardener solution (consisting of 0.24% of 2-hydroxy-4,6-dichloro-1,3,5-triazine, potassium salt). 8 ml of this emulsion are poured onto a polyester carrier (13x18 cm). The cast is hardened for 7 days at room temperature. Values for the maximum density in the range of 330-380 nm are now recorded with a UV spectrometer. Then the sample is exposed in an Atlas exposure device with a total of 60 kJ / cm², the maximum density is determined again and the difference (-DD in%) between the corresponding values is calculated:

Example 6:

• ① belichtet man nur 30 kJ/cm²
• ② mischt man UV-Absorber der Erfindung (150 mg) mit Hydroxybenztriazole (150 mg)

Is carried out as in Example 1 but

• ① one exposes only 30 kJ / cm²
• Man mixing the UV absorber of the invention (150 mg) with hydroxybenzotriazoles (150 mg)

Example 7:

A gelatin layer which contains silver bromide, a cyan coupler and a UV absorber of the formula (I) is applied to a carrier material coated with polyethylene. The gelatin layer contains the following components (per m² carrier material)

After exposure and processing as described in Example 1, the reflectance density in red for the cyan level is measured with a density between 0.9 and 1.1 of the wedge. Then it is exposed to wedge in an Atlas exposure device with 30 kJ / cm² and the remission density is measured again. The dye loss (-ΔD) in% is given in Table Y.

Example 8:

If the procedure is as in Example 4, but the UV absorber of the invention (150 mg) is mixed with a hydroxybenzotriazole (150 mg)

Example 9:

If you carry out as in Example 4 but additionally add a stabilizer of the following formula

Example 10:

If the procedure is as in Example 9, but the UV absorber of the invention (150 mg) is mixed with a hydroxybenzotriazole (150 mg)

Example 11:

A photographic material with the following layer structure is produced:

The gelatin layers consist of the following components (per m² carrier material):

Blue sensitive layer

First layer of gelatin

Green sensitive layer

Second layer of gelatin

Red sensitive layer

A protective layer is made with and without UV absorber

The corresponding compounds according to Example 1 are used as hardeners and wetting agents.

Three step wedges with a density difference of 0.15 kJ per step are each exposed on the three samples 104-106 (with blue, green or red light).

The process is then carried out in accordance with processing process EP2 (Kodak) for negative color papers.

After exposure and processing, the reflectance densities are measured in red for the cyan level, in green for the magenta level and in blue for the yellow level at a density between 0.9 and 1.1 of the wedges. Then the wedges are exposed in an Atlas exposure device with a total of 15 kJ / cm² and the remission densities are measured again.

The remission density of the magenta wedge is measured before and after the exposure in blue for yellowing.

The presence of the UV absorbers reduces the loss of dye density of the cyan, magenta and yellow image dye and yellowing.

Example 12:

A photographic material with the following layer structure is produced:

The gelatin layers consist of the following components (per m² carrier material):

Blue sensitive layer

α- (3-Benzyl-4-ethoxyhydantoin-1-yl) -α-pivaloyl-2-chloro-5- [α- (2,4-di-t-amylphenoxy) butanamido] acetanilide (400 mg)
α- (1-Butyl-phenylurazol-4-yl) -α-pivaloyl-5- (3-dodecanesulfonyl-2-methylpropanamido) -2-methoxyacetamide (400 mg)
Dibutyl phthalate (130 mg)
Dinonyl phthalate (130 mg)
Gelatin (1200 mg)
1,5-dioxa-3-ethyl-3- [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] -8,10-diphenyl-9-thia- [5,5] spiroundecane (150 mg)
Bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate (150 mg)
3,5-di-t-butyl-4-hydroxy- (2,4-di-t-amylphenyl) benzoate (150 mg)
Poly (Nt-butylacrylamide) (50 mg)
blue-sensitive silver chlorobromide emulsion (240 mg)

First layer of gelatin

Gelatin (1000 mg)
2,5-di-t-octylhydroquinone (100 mg)
5- [2,5-Dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoic acid hexyl ester (100 mg)
Dibutyl phthalate (200 mg)
Diisodecyl phthalate (200 mg)

Green sensitive layer

7-chloro-2- {2- [2- (2,4-di-t-amylphenoxy) octanamido] -1-methylethyl} -6-methyl-1H-pyrazolo [1,5-b] [1,2, 4] triazole (100 mg)
6-t-Butyl-7-chloro-3- (3-dodecanesulfonylpropyl) -1H-pyrazolo [5,1-o] [1,2,4] triazole (100 mg)
Dibutyl phthalate (100 mg)
Dicresyl phosphate (100 mg)
Trioctyl phosphate (100 mg)
Gelatin (1400 mg)
3,3,3 ′, 3′-tetramethyl-5,5 ′, 6,6′-tetrapropoxy-1,1′-spirobiindane (100 mg)
4- (i-tridecyloxyphenyl) thiomorpholine-1,1-dioxide (100 mg)
4,4'-butylidene-bis (3-methyl-6-t-butylphenol) (50 mg)
2,2′-isobutylidene bis (4,6-dimethylphenol) (10 mg)
3,5-dichloro-4- (hexadecyloxycarbonyloxy) ethylbenzoate (20 mg)
3,5-bis [3- (2,4-di-t-amylphenoxy) propylcarbamoyl] sodium benzenesulfinate (20 mg)
green-sensitive silver chlorobromide emulsion (150 mg)

Second layer of gelatin

Gelatin (1000 mg)
5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) benz-1,2,3-triazole (200 mg)
2- (3-dodecyl-2-hydroxy-5-methylphenyl) benz-1,2,3-triazole (200 mg)
Trinonyl phosphate (300 mg)
2,5-di-t-octylhydroquinone (50 mg)
5- [2,5-Dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoic acid hexyl ester (50 mg)

Red sensitive layer

2- [α- (2,4-di-t-amylphenoxy) butanamido] -4,6-di-chloro-5-ethylphenol (150 mg)
2,4-dichloro-3-ethyl-6-hexadecanamidophenol (150 mg)
4-chloro-2- (1,2,3,4,5-pentafluorobenzamido) -5- [2- (2,4-di-t-amylphenoxy) -3-methylbutanamido] phenol (100 mg)
Dioctyl phthalate (100 mg)
Dicyclohexyl phthalate (100 mg)
Gelatin (1200 mg)
5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) benz-1,2,3-triazole (100 mg)
2- (3-dodecyl-2-hydroxy-5-methylphenyl) benz-1,2,3-triazole (100 mg)
3,5-di-t-butyl-4-hydroxy- (2,4-di-t-amylphenyl) benzoate (50 mg)
Poly (Nt-butylacrylamide) (300 mg)
N, N-Diethyl-2,4-di-t-amylphenoxyacetamide (100 mg)
2,5-di-t-octylhydroquinone (50 mg)
red sensitive silver chlorobromide emulsion (200 mg)

The top layer is made with and without UV absorber

with UV absorber:
2,5-di-t-octylhydroquinone (20 mg)
5- [2,5-Dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoic acid hexyl ester (20 mg)
Gelatin (400 mg)
Trinonyl phosphate (120 mg)
UV absorber compound no. (3) (200 mg)
without UV absorber:
Gelatin (800 mg)

2,4-dichloro-6-hydroxytriazine is used as the hardener, the sodium salt of diisobutylnaphthalenesulfonic acid as the wetting agent.

Three step wedges with a density difference of 0.15 kJ per step are exposed on the 2 samples (with blue, green or red light).

The process is then carried out in accordance with processing process RA-4 (Kodak) for color papers.

After exposure and processing, the reflectance densities are measured in red for the cyan level, in green for the magenta level and in blue for the yellow level at a density between 0.9 and 1.1 of the wedges. Then the wedges are exposed in an Atlas exposure device with a total of 15 kJ / cm² and the remission densities are measured again.

The remission density of the magenta wedge is measured before and after the exposure in blue for yellowing.

The presence of the UV absorbers reduces the loss of dye density of the cyan, magenta and yellow image dye.

Example 13:

Production of
2,4-di- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -6-methoxy-1,3,5-triazine 10 g of 2,4-di- (2,4-dihydroxyphenyl ) -6-methoxy-1,3,5-triazine are stirred with 100 ml of butyl glycidyl ether and 0.20 g of tetrabutylammonium bromide at 130 ° C for three hours. The mixture is then allowed to cool to 80 ° C., mixed with 100 ml of ethyl acetate and 2.0 g of Prolith Rapid, filtered through diatomaceous earth and the solvent is removed under reduced pressure. The excess butyl glycidyl ether is then distilled off under vacuum. This gives 2,4-di- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -6-methoxy-1,3,5-triazine that, after recrystallization from ethanol, has a melting point of 108- 109 ° C.

If 2-ethylhexylglycidyl ether is used instead of butylglycidyl ether, 2,4-di- {2-hydroxy-4- [3- (2-ethylhexoxy) -2-hydroxypropoxy] phenyl} -6-methoxy-1,3,5- triazine with a melting point of 98-99 ° C.

Example 14:

wobei R₁₀₀

entsprichtProduction of

where R₁₀₀

corresponds

Elementaranalyse:

C₅₁H₇₉N₃O₈Si₂

Berechnet:

C 66,7; H 8,67; N 4,57 %

Gefunden:

C 66,38; H 8,80; N 4,42 %

To a solution of 15 g of 2,4-bis [2-hydroxy-4- (2-hydroxy-3-butoxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine and 7.15 g of imidazole in 100 ml of N, N'-dimethylacetamide is added dropwise to 9.4 g of thexyl-dimethylchlorosilane under nitrogen. After 12 hours at room temperature, the reaction mixture is evaporated in a Rotavapor. The residue is taken up in 200 ml of ethyl acetate. After the filtration, the filtrate is concentrated and the crude product obtained is purified on silica gel (mobile solvent: hexane / ethyl acetate 20: 1). 3.5 g of the compound are obtained as a slightly yellow resin.

Elemental analysis:

C₅₁H₇₉N₃O₈Si₂

Calculated:

C 66.7; H 8.67; N 4.57%

Found:

C 66.38; H 8.80; N 4.42%

Example 15:

Preparation of a mixture of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine and 2,4- Bis [2-hydroxy-4- (3 '- (2-ethylhexyloxy) -2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine
A mixture of 20.0 g of 2,4-bis [2,4-dihydroxyphenyl] -6-phenyl-1,3,5-triazine, 7.7 g of n-butyl glycidyl ether, 10.9 g of 2- Ethylhexyl glycidyl ether and 2.0 g of phosphorus triphenylethyl bromide are kept in 100 ml of mesitylene for 5 hours at 150 ° C. Mesitylene is removed with the Rotavapor and the crude product is taken up in 50 ml of ethyl acetate.

Elementaranalyse:

C₃₉H₅₁N₃O₈

Berechnet:

C 67,90; H 7,45; N 6,09 %

Gefunden:

C 67,64; H 7,43; N 6,02 %

The solution is poured onto a layer of silica gel (2 cm) and eluted with 200 ml of ethyl acetate. After the solvent has been removed, the product is recrystallized from 60 ml of ethyl acetate and 28.9 g of the mixture of the compounds are obtained as a light yellow solid (mp. 66-70 ° C.).

Elemental analysis:

C₃₉H₅₁N₃O₈

Calculated:

C 67.90; H 7.45; N 6.09%

Found:

C 67.64; H 7.43; N 6.02%

Example 16:

Elementaranalyse:

C₃₉H₄₇N₃O₁₂

Berechnet:

C 62,47; H 6,32; N 5,60 %

Gefunden:

C 62,34; H 6,41; N 5,39 %

Preparation of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-methoxycarbonyloxypropoxy) phenyl] -6-phenyl 1,3,5-triazine A mixture of 5.0 g 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine, 8.7 g of methyl chloroformate and 2 Drops of pyridine are kept in 50 ml of toluene at 100 ° C. for 40 hours. The mixture is evaporated on a Rotavapor and purified on a silica gel column with ethyl acetate / petroleum ether (1: 1). 3.3 g of the compound are obtained as a slightly yellow resin.

Elemental analysis:

C₃₉H₄₇N₃O₁₂

Calculated:

C 62.47; H 6.32; N 5.60%

Found:

C 62.34; H 6.41; N 5.39%

Example 17:

Elementaranalyse:

C₄₅H₅₉N₃O₁₀

Berechnet:

C 67,40; H 7,41; N 5,23 %

Gefunden:

C 67,32; H 7,61; N 5,14 %

Preparation of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-valeroyloxypropoxy) phenyl] -6-phenyl-1,3,5-triazine
A mixture of 5.0 g of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine, 2 , 2 g of valeroyl chloride and 5 drops of pyridine is kept in 50 ml of toluene for 5 hours at 80-85 ° C, HCl escaping. The mixture is evaporated on a Rotavapor and purified on a silica gel column (silica gel 60, 230-400 mesh) with ethyl acetate / petroleum ether (4: 1). 4.4 g of the compound are obtained as a slightly yellow, thick oil.

Elemental analysis:

C₄₅H₅₉N₃O₁₀

Calculated:

C 67.40; H 7.41; N 5.23%

Found:

C 67.32; H 7.61; N 5.14%

Example 18:

Elementaranalyse:

C₃₉H₄₇N₃O₁₀

Berechnet:

C 65,26; H 6,60; N 5,85 %

Gefunden:

C 64,85; H 6,76; N 5,60 %

Preparation of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-acetoxypropoxy) phenyl] -6-phenyl-1,3,5-triazine
A mixture of 4.0 g of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine, 1 , 6 g of acetyl chloride and 2 drops of pyridine is kept in 50 ml of toluene for 4 hours at 60 ° C, HCl escaping. The mixture is evaporated on a Rotavapor, taken up in 300 ml of ethyl acetate and filtered through a layer of silica gel (1 cm; silica gel 60, 230-400 mesh). After the solvent has been stripped off, 4.4 g of the compound are obtained as a slightly yellow resin.

Elemental analysis:

C₃₉H₄₇N₃O₁₀

Calculated:

C 65.26; H 6.60; N 5.85%

Found:

C 64.85; H 6.76; N 5.60%

Claims (13)

Photographic material containing on a support a blue-sensitive, a green-sensitive and / or a red-sensitive silver halide emulsion layer and optionally a protection layer, a layer with a UV absorber being arranged between the uppermost silver halide emulsion layer and the protection layer, or above the uppermost silver halide emulsion layer, characterized in that that the UV absorber of the formula

corresponds to what
the radicals R₁ independently of one another alkyl having 1 to 18 carbon atoms, alkyl having 1 to 18 carbon atoms substituted by hydroxyl, alkenoxy having 2 to 18 carbon atoms, -CO₂H, -CO₂R₂ and / or -O-COR₅ by alkyl or hydroxyalkyl or glycidyloxyalkyl interrupted by oxygen 3 to 50 carbon atoms, alkenyl with 3 to 6 carbon atoms, glycidyl, a group of the formula

Cyclopentyl, cyclohexyl, phenylalkyl with 1 to 5 carbon atoms in the alkyl part, -COR₇, SO₂R₈ or -CH₂CH (OH) R₉, where R₂ is alkyl with 1 to 18 carbon atoms or oxygen, sulfur or nitrogen interrupted alkyl or hydroxyalkyl with 3 to 30 carbon atoms, Hydroxyalkyl with 2 to 18 carbon atoms, alkenyl with 3 to 18 carbon atoms, glycidyl, cycloalkyl with 5 to 8 carbon atoms, benzyl, alkylphenyl with 1 to 12 carbon atoms in the alkyl part, phenyl, furfuryl or a radical of the formula -CH₂CH (OH) R₉, R₅ is alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms or phenyl,
R₆ alkylene with 2 to 10 carbon atoms, phenylene or a group of the formula

is
R₇ is alkyl with 1 to 18 carbon atoms, alkenyl with 2 to 18 carbon atoms or phenyl,
R₈ alkyl with 1 to 12 carbon atoms, phenyl, naphthyl or alkylphenyl with 1 to 18 carbon atoms in the alkyl part and
R₉ is phenylalkyl having 1 to 6 carbon atoms in the alkyl part or a radical of the formula -CH₂OR₁₁, wherein
X is -O-, -S-, -SO₂, -CH₂- or -C (CH₃) ₂- and
R₁₁ is cyclohexyl, benzyl, phenyl or tolyl, and
R₁₂ alkyl having 1 to 18 carbon atoms, benzyl, cyclohexyl or a group of the formula

or OR₁₆, wherein
R₁₃, R₁₄ and R₁₅ are independently hydrogen, alkyl having 1 to 12 carbon atoms or halogen, and R₁₆ alkyl having 1 to 18 carbon atoms, alkyl interrupted by oxygen having 3 to 18 carbon atoms or alkyl having 1 to 12 carbon atoms substituted with phenoxy, benzyloxy or Is -CO₂R₈, where R₈ has the meaning given;
or the radicals R₁ independently of one another are a radical of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z ,

-CH₂COR _y or -CH₂COCH₂OR _z , where
R _x H, -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₁₈-alkyl or phenyl-C₁-C₄-alkyl,
R _{z is} C₁-C₁ Alkyl alkyl, C₂-C₁₈ alkenyl, phenyl-C₁-C₄-alkyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another C₁-C₆ alkyl or phenyl
mean; or
the radicals R₁ are independently a group G-II, II being a group of the formula

is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -O-R₂₆-, - (CH₂) _q -CO-X- (CH₂) _r -, - (CH₂) _q -CO -X- (CH₂) _r -O-,

-CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1-4 and p 0-50,
R₂₆ is C₁-C₁₂ alkylene, cyclohexylene or phenylene,
R₂₇ is C₁-C₁₂-alkyl, C₅-C₈-cycloalkyl, phenyl, C₂-C₁₃-alkoxymethyl, C₆-C₉-cycloalkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
R₂₉ is hydrogen or methyl,
X denotes -O- or -NR₂₃-, in which R₂₃ denotes hydrogen, C₁-C₁₂-alkyl or a group - (CH₂) ₃-G-II or - (CH₂) ₃-OG-II,
Y means -O- or -NH-,
R₂₀, R₂₁ and R₂₂ independently of one another are C₁-C₁₈ alkyl, cyclohexyl, phenyl or C₁-C₁₈ alkoxy. Photographic material according to claim 1, characterized in that the radicals R₁ independently of one another are a radical of the formula -CH₂-CH (OR _x ) R _y ,
-CH₂CH (OR _x ) CH₂OR _z ,

-CH₂COR _y or -CH₂COCH₂OR _z mean, wherein
R _x H, -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₁₈-alkyl or phenyl-C₁-C₄-alkyl,
R _{z is} C₁-C₁ Alkyl alkyl, C₂-C₁₈ alkenyl, phenyl-C₁-C₄-alkyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another are C₁-C₆ alkyl or phenyl; or
the radicals R₁ independently of one another represent a group G-II,
where II is a group of formula

is
and
G is a direct bond or a divalent group of one of the following formulas: - (CH₂) _q -, - (CH₂) _q -O-, (CH₂) _q -O-R₂₆-, - (CH₂) _q -CO-X- (CH₂) _r -, (CH₂) _q -CO-X- (CH₂) _r -O-,

-CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1-4 and p 0-50,
R₂₆ is C₁-C₁₂ alkylene, cyclohexylene or phenylene,
R₂₇ is C₁-C₁₂-alkyl, C₅-C₈-cycloalkyl, phenyl, C₂-C₁₃-alkoxymethyl, C₆-C₉-cycloalkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
R₂₉ is hydrogen or methyl,
X denotes -O- or -NR₂₃-, in which R₂₃ denotes hydrogen, C₁-C₁₂-alkyl or a group - (CH₂) ₃-G-II or - (CH₂) ₃-OG-II,
Y means -O- or -NH-,
R₂₀, R₂₁ and R₂₂ independently of one another are C₁-C₁₈ alkyl, cyclohexyl, phenyl or
Is C₁-C₁₈ alkoxy; and
R₁₂ alkyl having 1 to 12 carbon atoms or a group of the formula

or -OR₁₆, preferably R₁₂ is a group of the formula

wherein R₁₃ and R₁₄ are independently hydrogen, C₁-C₄-alkyl or chlorine, and R₁₆ is alkyl having 1 to 8 carbon atoms or alkyl interrupted by oxygen having 3 to 12 carbon atoms. Photographic material according to claim 1, characterized in that the radicals R₁ independently of one another are radicals of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z , -CH₂COR _y or -CH₂COCH₂OR _z mean, wherein
R _x H, -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₈ alkyl,
R _z C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, benzyl, -COR _s or interrupted by oxygen
C₁-C₂₄-alkyl or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another C₁-C₆-alkyl
mean; or
R₁ represent a group G-II,
where II is a group of formula

is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -CO-X- (CH₂) _r -,

or -CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1, 2 or 3 and p are 0-50,
R₂₇ denotes methyl, phenyl, C₃-C₉ alkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
X and Y mean -O-,
R₂₀, R₂₁ and R₂₂ independently of one another C₁-C₈-alkyl, phenyl or C₁-C₈-alkoxy
mean; and
R₁₂ is a group of the formula

is what
R₁₃ and R₁₄ are independently hydrogen, C₁-C₄ alkyl or chlorine. A photographic material as claimed in claim 1, which contains a further layer with a UV absorber of the formula (I) which is arranged between the green and red-sensitive silver halide emulsion layer, or wherein the UV absorber of the formula (I) additionally contains in the red-sensitive silver halide emulsion layer is characterized in that it contains in the further layer and / or in the red-sensitive silver halide emulsion layer instead of the UV absorber of the formula (I) a UV absorber of the benzotriazole type, in particular of the formula

wherein T₁, T₂ and T₃ are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy and T₄ is hydrogen, alkoxy, aryloxy or acyloxy. Photographic material containing on a support a blue-sensitive, a green-sensitive and / or a red-sensitive silver halide emulsion layer and a protection layer, a layer with a UV absorber being arranged between the uppermost silver halide emulsion layer and the protection layer, characterized in that (a) the UV Absorber of the formula

where T₁, T₂ and T₃ are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy and T₄ is hydrogen, alkoxy, aryloxy or acyloxy, and (b) the material is at least one more Has layer which contains a UV absorber of the formula (I). Photographic material containing on a support at least 2 silver halide emulsion layers with a layer between these layers with a UV absorber, characterized in that the UV absorber of the formula (I) corresponds. Photographic material containing on a support a red-sensitive silver halide emulsion layer and optionally a blue-sensitive and / or green-sensitive silver halide emulsion layer, characterized in that the red-sensitive silver halide emulsion layer contains a UV absorber of the formula (I). Photographic material according to one of Claims 1 to 7, characterized in that a mixture of the UV absorbers of the formulas (I) and (III) is present in the layers which can contain a UV absorber. Photographic material according to claim 1, 5, 6 or 7, characterized in that the red-sensitive silver halide emulsion layer is a cyan coupler of the formula

and / or the formula

contains what
Z₁ alkyl, aryl, Z₂ alkyl, cycloalkyl, aryl, a heterocyclic group, or a ballast group, Z₃ is hydrogen or halogen, Z₁ and Z₃ together can form a ring, and Z₄ is hydrogen or a leaving group, and Z₅ is a ballast group, Z₆ hydrogen or a leaving group and Z₇ is alkyl. Photographic material according to claim 1, 5, 6 or 7, characterized in that the green-sensitive silver halide emulsion layer is a magenta coupler of the formula

contains wherein R₁ is hydrogen or a substituent, Z represents the non-metallic atoms necessary to complete a 5-membered ring with 2 or 3 nitrogen atoms, which ring may be substituted, and Q is hydrogen or a leaving group. Photographic material according to claim 1, 5, 6 or 7, characterized in that the green-sensitive silver halide emulsion layer is a magenta coupler of the formula

contains, wherein R₂₀ is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group and Q 'is a leaving group. Compounds of the formula

wherein R₁ independently of one another is a radical of the formula -CH₂-CH (OR _x ) _y , -CH₂CH (OR _x ) CH₂OR _z ,

-CH₂COR _y or -CH₂COCH₂OR _z mean, wherein
R _x -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₁₈-alkyl or phenyl-C₁-C₄-alkyl,
R _{z is} C₁-C₁ Alkyl alkyl, C₂-C₁₈ alkenyl, phenyl-C₁-C₄-alkyl, -COR _s or C₁-C₂₄-alkyl interrupted by oxygen or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another C₁-C₆ alkyl or phenyl
mean; or
the radicals R₁ independently of one another represent a group G-II, II being a group of the formula

is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -O-R₂₆-, - (CH₂) _q -CO-X- (CH₂) _r -, - (CH₂) _q -CO -X- (CH₂) _r -O-,

-CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1-4 and p 0-50,
R₂₆ is C₁-C₁₂ alkylene, cyclohexylene or phenylene,
R₂₇ is C₁-C₁₂-alkyl, C₅-C₈-cycloalkyl, phenyl, C₂-C₁₃-alkoxymethyl, C₆-C₉-cycloalkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
R₂₉ is hydrogen or methyl,
X denotes -O- or -NR₂₃-, in which R₂₃ denotes hydrogen, C₁-C₁₂-alkyl or a group - (CH₂) ₃-G-II or - (CH₂) ₃-OG-II,
Y means -O- or -NH-,
R₂₀, R₂₁ and R₂₂ independently of one another are C₁-C₁₈ alkyl, cyclohexyl, phenyl or C₁-C₁₈ alkoxy; and
R₁₂ alkyl having 1 to 12 carbon atoms or a group of the formula

or -OR₁₆, preferably R₁₂ is a group of the formula

wherein
R₁₃ and R₁₄ are independently hydrogen, C₁-C₄ alkyl or chlorine, and R₁₆ is alkyl of 1 to 8 carbon atoms or alkyl interrupted by oxygen having 3 to 12 carbon atoms. Compounds according to claim 12, wherein the radicals R₁ independently of one another are radicals of the formula -CH₂-CH (OR _x ) R _y , -CH₂CH (OR _x ) CH₂OR _z , -CH₂COR _y or -CH₂COCH₂OR _z , where
R _x -COR _s , -COOR _w or -SiR _p R _q R _r ,
R _y C₁-C₈ alkyl,
R₇ C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, benzyl, -COR _s or interrupted by oxygen
C₁-C₂₄-alkyl or C₂-C₂₄-hydroxyalkyl,
R _s C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl,
R _w C₁-C₄ alkyl and
R _p , R _q and R _r independently of one another are C₁-C₆-alkyl; or
R₁ is a group G-II, II being a group of the formula

is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH₂) _q -, - (CH₂) _q -O-, - (CH₂) _q -CO-X- (CH₂) _r -,

or -CH₂-CH (OH) -CH₂-Y- (CH₂) _q -,
wherein q and r are independently 1, 2 or 3 and p are 0-50,
R₂₇ denotes methyl, phenyl, C₃-C₉ alkoxymethyl or phenoxymethyl,
R₂₈ represents a group of the formula G-II,
X and Y mean -O-,
R₂₀, R₂₁ and R₂₂ independently of one another C₁-C₈-alkyl, phenyl or C₁-C₈-alkoxy
mean; and
R₁₂ is a group of the formula

is what
R₁₃ and R₁₄ are independently hydrogen, C₁-C₄ alkyl or chlorine.