GB2273498A - S-Triazine UV absorbers - Google Patents

S-Triazine UV absorbers Download PDF

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GB2273498A
GB2273498A GB9324687A GB9324687A GB2273498A GB 2273498 A GB2273498 A GB 2273498A GB 9324687 A GB9324687 A GB 9324687A GB 9324687 A GB9324687 A GB 9324687A GB 2273498 A GB2273498 A GB 2273498A
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formula
compounds
compound
hydrogen
absorbers
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GB9324687D0 (en
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Vien Van Toan
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155—Organic compounds therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G03C7/3005—Combinations of couplers and photographic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Description

2273498 UV absorbers The invention relates to novel UV absorbers of the
bis- or tds-2'- hydroxyphenyltdazine type, and to the use thereof in photographic materials, inks and recording materials for ink-jet printing, and in surface coatings.
Hydroxyphenyltriazines and their use in photographic materials are known, for example, from US 3 843 37 1. However, their use in photographic materials has hitherto been prevented by still not entirely satisfactory properties, for example poor chemical stability, low solubility, excessive inherent colour or inadequate absorbence.
A group of bis- and tris-2'-hydroxyphenyltriazine UV absorbers have now been found which, surprisingly, is highly satisfactory with respect to the demands made by industry. In addition, the novel compounds are dispersible in aqueous gelatine, which simplifies their incorporation into photographic coatings and makes the use of oils superfluous. The - result is a low coating thickness or, for the same coating thickness, a higher concentration of UV absorbers. In particular, this group of triazines is suitable for increasing the stability of the magenta, cyan and yellow layer of photographic materials through incorporation into layers applied over the magenta or cyan layer or directly into the cyan layer.
The present invention thus relates to compounds of the formula R4 R3 R2 OH N N OH N RIO OR, in which the radicals Rp independently of one another, are -(CH2CHRS-0),,7R8, -CH27CH(OH)-CH270- (CH2CHRS-0),i-RS, -(CH2)rCHR6-C(O)-0-(CH2CHRS-0),,7RS or -CH27CH(CH2-OR7)O-C(O)-(CH2CHRS-0)n7R8; R2 is H, OH, Cl-CUalkyl, F or Cl; R3 is H, OR9, Cl-C12alkYl, IF or Cl; R4 is H, OR9, Cl-C12alkyl, F, Cl or, if R2 is OH, is alternatively OR,; RS is H or CH3; R6 is H or Cl-CMalkyl; R7 is ClC14alkyl or phenyl; RS is H, Cl-C14alkyl, phenyl or (Cl-C4alkyl)phenyl; R9 is Cl-C4alkyl; 1 is a number from 0 to 16 and n is a number from 1 to 16.
Any Cl-CMalkyl substituents in the compounds of the formula (1) are for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl or corresponding branched isomers.
Any (Cl-C4alkyl)phenyl substituents in the compounds of the formula (1) are radicals such as tolyl or tert-butylphenyl.
R, is preferably -CH2-CH(OH)-CH2-0-(CH2CHRS-0)n-R8 or -(CH2)1-CHR6-C(O)-0(CH2CHRS-0),CRg.
R2, R3 and R4 are preferably H or one or two Cl-C4alkyl groups.
If R2 is OH, R4 is preferably -OC'H2-CH(OH)-CH270-(CH2CHRS-0),rR8 or O(CH2)1-CHR6-C(O)-0-(CH2CHRS-O),CR8.
RS or R6 is preferably H.
R7 or R8 is preferably Cl-C8alkyl.
1 is preferably a number from 1 to 6 or 0.
n is preferably a number from 1 to 8 or 2 to 4.
Preference is given to compounds of the formula (I) in which the radicals Rp independently of one another, are -(CH2CHRS-0).7R8, -CH2-CH(OH)-CH2-0(CH2CHRS-0),rR8, -(CH2)1-CHR6-C(O)-0-(CH2CHRS-0)n-R8 or -CH2-CH(CH2-OR7)O-C(O)-(CH2CHR5-0),-R8; R2 is H, OH, Cl-C8alkyl, F or Cl; R3 is H, OR9, Cl-C8alkyl, F or Cl; R4 is H, OR9, Cl-C8alkyl, F, Cl or, if R2 is OH, is alternatively OR,; R5 is H; R6 is H or Cl-C12alkyl; R7 is Cl-C8alkyl; R8 is H or Cl-Cloalkyl; R9 is Cl-C4alkyl; 1 is a number from 0 to 12, and n is a number from 1 to 12.
Particular preference is given to compounds of the formula (I) in which the radicals R,, independently of one another, are -CH2-CH(OH)-CH2-0(CH2CBRS-O)n7R8 or -(CH2)rCHR6-C(O)-0-(CH2CHRS-0)n7RS; R2 is H, OH or ClC4alkyl; R3 is H, OR9 or Cl-C4alkyl; R4 is H, OR9, Cl-C4alkyl, F, Cl or, if R2 is OH, is alternatively OR,; R5 is H; R6 is Cl-C6alkyl; R8 is ClC4alkyl; R9 is Cl-C4alkyl; 1 is 0, and n is a number from 1 to 12.
The present invention furthermore relates to the use of a compound of the formula (I) as a light stabilizer, in particular a UV stabilizer, in photographic materials, and to the photographic material containing a compound of the formula (I); it also being possible to use a mixture of compounds of formula (I).
The novel compounds can be used in photosensitive materials of all types. For example, they can be employed for colour paper, colour reversal paper, direct-positive colour material, colour negative film, colour positive film, colour reversal film, inter alia. They are preferably used, inter alia, for photosensitive colour material which contains a reversal substrate or ffirms positives.
Furthermore, the novel triazines can be combined with further UV absorbers, in particular with those which can be dispersed in aqueous gelatine.
It is also possible to use the novel triazines with other UV absorbers, such as hydroxyphenylbenzotriazoles (cf., for example, US-A-4 853 471, USA-4 973 702, US-A-4 921966 and US-A-4 973 701), benzophenones, oxanilides, cyanoacrylates, salicylates, acrylonitriles or thiazolines, but it is advantageous to employ these other oil-dissolved UV absorbers in different layers in the photographic material than the novel UV absorbers.
In particular, photographic materials similar to those described in US-A4 518 686 can successfully be stabilized.
The present application thus relates to photographic material comprising, on a suppor a blue-sensitive, a green-sensitive andlor a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, where a layer containing a UV absorber is arranged above the uppermost silverhalide emulsion layer, wherein the UV absorber conforms to the formula In a further embodiment, the novel material contains a layer containing a UV absorber of the formula (I) arranged between the green-sensitive and the red-sensitive silver-halide emulsion layers, where a further layer containing a UV absorber of the formula (I) may be arranged above the uppermost silver-halide emulsion layer.
Good results are also achieved if the UV absorber of the formula (I) is additionally present in the red-sensitive silver-halide emulsion layer.
Preference is furthermore given to photographic materials which contain a layer containing a compound of the formula (I) above the uppermost silverhalide emulsion layer andlor between the green-sensitive and the redsensitive silver-halide emulsion layers, an oil-soluble UV absorber additionally being present in a layer containing no UV absorber of the formula (I).
It may furthermore be advantageous for all or some of said layers possibly containing a UV absorber to contain a UV absorber of the formula (I) andlor a further UV absorber which can be dispersed in aqueous gelatine, but a UV absorber of the formula (1) must be present in at least one layer.
The novel material preferably contains gelatine interlayers between the silver-halide emulsion layers.
Preference is given to photographic materials in which the silver-halide in the blue-sensitive, green-sensifive andlor red-sensitive layers is silver chloridelbromide comprising at least 90 mol % of silver chloride.
Preference is furthermore given to photographic materials in which the silver-halide emulsion layers are in the sequence blue-sensitive, greensensitive and red-sensitive silver-halide emulsion layers.
The novel photographic materials offer the advantage over materials containing benzotriazole UV absorbers, that the UV absorbers of the formula (I) are required in a relatively small amount to ensure adequate protection against UV radiation. This means that the thickness of the layers containing the UV absorbers of the formula (I) can be very thin, which has a positive effect, for example, on the sharpness of the images produced using this material.
Typical and preferred compounds of the formula (I) are shown in the table below:
R4 R3 R2 OH N N OH N Rjo& OR, Table 1
Comp. R4, R3, R2 R, No.
(1) H, H, H -CH2CH(OH)CH20(CH2CH20)7/8CH3 (2) H,H,El -CH2CH(OH)CH20(CH2CH20)IC2H5 (3) H,H,H -CH2CH(OH)CH20(CH2CH20)1C4I-I9 (4) H,H,H -CH2CH(OH)CH20(CH2CH20)2CH3 (5) CH3, H, H -CH2CH(OH)CH20(CH2CH20)2CH3 (6) H,H,H -CH2CII(OH)CH20(CH2CH20)2C2H5 (7) H, H, H -C"2CH(OH)CH20(CH2CH20)2C113 1 C2H5 (8) H, H, H -CH2CH(OH)CH20(CH2CH20)2C4I-1 (9) H, H, H -CH2CH(OH)CH20(CH2CH20)2t3CH3 (10) H, H, H -C[-'2CH(OH)CH20(CH2CH20)3CH3 (11) H, H, H -C"2CH(OH)CH20(CH2CH20)3C.2H5 (12) H,H,H -CH2CH(OH)CH20(CH2C[-120)3C4H9 (13) H, H, H -CH2CH(OH)CH20(CH2CH20)12J13CH3 (14) H,H,H -CH(CH3M0)O(CH2CH20)3CH3 (15) H, H, H -CH(CH3)C(O)O(CH2CH20)3C2H5 (16) H, H, H -CH(CH3)C(O)O(CH2CH20)3C6H13 (17) OR,, H, OH -CH2CH(OH)CH20(CH2CH20)7/8CH3 (18) OR,, H, OH -CH2CH(OH)CE120(CH2CI-120)1C2H5 (19) OR,, a OH -M2CH(OH)CH20(CH2CH20)1C4119 (20) OR,, H, OH -CH2CH(011)CEI20(CH2CH20)2CH3 (21) OR,, H, OH -CH2CH(OH)CI-I20(CI-12CE120)2C2H5 (22) OR,, H, OH -CH2CH(OH)CH20(CH2CH20)2C113/C2H5 (23) OR,, H, OH -CH2CH(OH)CH20(CH2CH20)2C4H9 (24) OR,, H, OH -CH2CH(OH)CIi2O(C112CH20)2t3C113 (25) OR,, H, OH -CE12CH(OWCH2O(CH2CH20)3CH3 (26) OR,, H, OH -CH2CH(OH)CH20(CH2CH20)3C4H9 (27) OR,, H, OH -CH2CH(OH)CH2O(CH2CH20)12J13CH3 (28) OR,, H, OH -CH(CH3)C(OP(CH2CH20)2CH3 (29) OR,, H, OH -CH(CH3)C(O)O(CH2CH20)3CH3 Yellow couplers which can be used in the novel material are preferably compounds of the formula A Q 1 R,-CO-CH-M-NHR2 (A), in which R, is alkyl or aryl, R2 is aryl, and Q is hydrogen or a group which can be eliminated by reaction with the oxidized developer.
A group of yellow couplers comprises compounds of the formula A in which R, is t-butyl and R2 is a group of the formula R3 R4 -0 R5 R6 in which R3 is hydrogen, halogen, alkyl or alkoxy, and R4, RS and R6 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, carbamoyl, sulfonyl, sulfamoyl, alkylsulfonamino, acylamino, ureido, or amino.
Preference is given to compounds in which R3 is chlorine, R4 and RS are hydrogen and R6 is acylamino. These also include the compounds of the formula R8 NHCO(CHR7) 0- R X (CH3)3C-CO-CH-CO-NH -0- R5 cl in which x is from 0 to 4, R7 is hydrogen or alkyl, and R8 and R9 are alkyl.
Another group of yellow couplers conforms to the formula B R10 R1COCH(O)C0NH WCOCH(Q)COR, 1 (B), R,, R13 R12 in which R10 is hydrogen, halogen or alkoxy, R,p R12 and R13 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, carbamoyl, sulfonyl, sulfwnoyl, sulfonamido, acylamino, ureido or amino, and R, and Q are as defined above.
This includes compounds of the formula B in which R, is t-butyl, R10 is chlorine, R,, and R13 are hydrogen, and R12 is alkoxycarbonyl.
In the compounds of the formulae A and B, the leaving group Q may be hydrogen or a heterocyclic group -1< R14 in which R14 is a divalent organic group which supplements the ring to forTn a 4-7-membered ring, or Q is an -OR15 group in which R15 is alkyl, aryl, acyl or a heterocyclic radical. Typical examples of customary yellow couplers are- compounds of the formulae:
a cl (CH3)3C-CO-H-CONH -0 t-C5H1 1 WCO(CH2)P_ t-C5H, 1 a) Q = -G-C S02-0-OCH2C6H5 0 b) Q= N-CH2C6H5 0 CH(CH3)2 C) Q= -N Y, S N-SO 2-0-CH3 0 d) Q = -N) N COOCH3 CO0C6H13 e) Q= -N N cl (CH:3)3C-Uu-uti-uuNH C2 5 t-C5H11 WCO_J H- t-C5H, 1 H 0 CH3 0 CH3 CH-OC2H5 f) Q= -N g) Q= -N 0 J-benzyi 0 0 -lo- ci (CH3),3u-uu-uti-i;uNH imriuu-krl-kO-C(CH3)3 CO0C12H25 N T CH(CH3)2 ) T S WS02-0-CH3 Other examples of yellow couplers are given in US-A 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 341331, 3 369 895, 3 384 657, 3 415 652, 3 447 928, 3 551155, 3 582 322, 3 725 072, 3 891445, 3 933 501, 4 115 121, 4 401752 and 4 022 620, DE-A 1547 868, 2 057 941, 2 162 899, 2 163 813, 2 213 461, 2 219 917, 2 261361, 2 261362, 2 263 875, 2 329 587, 2 414 006 and 2 422 812, GB-A 1425 020 and 1077 874, P-A-881123 047 and EP-A-447 969.
The yellow couplers are usually used in an amount of from 0.05 to 2 mol, preferably from 0. 1 to 1 mol, per mol of silver halide.
Typical and preferred yellow couplers conform to the formulae: CH3 1 cl CH3 -C-COCHCONH- (Y-1) 1 NWO(CH2)30,& CH3 N C6H130C0 N cl CH3 1 H3C - C -CO- CHCONH (Y-2) CH3 NHCOCHO 0 N 0 U2t5 N C2H50 \ CH2-0 CH3 cl 1 CH3 - C -CO- CHCONH H3 0 (Y-3) H-CO-(CH2)3 S02 --0-OCH2-0 CH3 cl 1 CH3 - C -00CHCOW-0 1 1 (Y-4) CH3 NH-CO-(CH2)3 0 0 CH2-0 CH3 cl 1 CH3 - C.CO- CHCONH 1 CH3 NHCOCHO 0 N 0 2H5 0 CH3 CH3 -C(CH3)2C2H5 CH3 cl 1 CH3 - C -GO- CHCONH 1 1 CH3 1 4 OCHCH2SO2C12H25 0 N 0 NHC (Y-6) 'lleN CH3 0C16H37 1 k #r13 G CO- CHCONH-0 1 1 - 1 (Y-7) N 02NHCOC2H5 NHCO- 31 N cl (CH3)3CCO - CHCONH t-CSH 11 9 N-N >: --- N -0 WCO(CH2)3 t-C (Y-8) (CH3)2CH Ji- S -S02 G-0-5 CH3 CH3 OCH3 1 CH3 - G -GO- CHCONH-0 1 1 CH3 (Y-9) 0 N 0 NH-CO-CH(CH3)-CH2-SO2-Cl2H25 N-N 1 c (;4H9 Magenta couplers can be, for example, single 1-aryl-5-pyrazolones, or pyrazole derivatives which have been condensed with 5-membered heterocyclic rings, for example imidazopyrazoles, pyrazolopyrazoles, pyrazolotriazoles or pyrazolotetrazoles.
A group of magenta couplers comprises 5-pyrazolones of the formula C a, R17 0) 1 (C), N 116 as described in British Patent 2 003 473. In this formula, R16 is hydrogen, alkyl, aryl, alkenyl or a heterocyclic group, R17 is hydrogen, alkyl, aryl, a heterocyclic group, an ester group, alkoxy, alkylthio, carboxyl, arylamino, acylamino, (thio)urea, (thio)carbamoyl, guanidino or sulfonamido.
R17 is preferably a -Rls _p R20 R19 group in which R18 is imino, acylamino or ureido, R19 is hydrogen, halogen, alkyl or alkoxy, and R20 is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or urethane.
If Q' is hydrogen, the magenta coupler is tetra-equivalent with respect to the silver halide.
Typical examples of magenta couplers of this type are compounds of the formula cl 0 N cl cl cl in which R20 is as defined above, and Q, as described above, is a leaving group. These compounds are preferably in the novel material.
Further examples of tetra-equivalent magenta couplers of this type are given in US-A 2 983 608, 3 061432, 3 062 653, 3 127 269, 3 152 896, 3 311476, 3 419 39 1, 3 519 429, 3 558 319, 3 582 322, 3 615 506, 3 684 514, 3 834 908, 3 888 680, 3 891445, 3 907 571, 3 928 044, 3 930 861, 3 930 866 and 3 933 500, and JP-A-89/309 058.
If Q' in the formula C is not hydrogen, but instead a group which is eliminated during the reaction with the oxidized developer, the magenta coupler is diequivalent. In this case, Q can be, for example, halogen or a group bonded to the pyrazole ring via 0, S or N. Such di-equivalent couplers give increased colour density and are more reactive toward the oxidized developer than corresponding tetraequivalent magenta couplers.
Examples of di-equivalent magenta couplers are described in US-A 3 006 579, 3 419 391, 3 311476, 3 432 521, 3 214 437, 4 032 346, 3 701783, 4 351897, 3 227 554, EP-A-133 503, DE-A-2 944 601, JP-A-78134 044,74153 435, 74153 436,75153 372 and 751122935.
Typical and preferred magenta couplers confoiTn to the formulae cl NH-- 0 (M-1) N H-CO-(CH2)12CH3 C, C, cl 0 NH-- CH3 CH3 (M-2) N CH3 NHCO- CHO- OH w Cl 12H25 C, C, cl cl NH 0 J.
., N (M-3) N cl cl 0 N 0 18H35 0C4H9 cl NH 0 N (M4) -0 C(CH3) NH-CO-(CH2)12CH3 1 cl cl Ut'2 1 C(CH3)3 cl cl H 1 (M-S) (CH3)3C yl-y NI,, N N-N 11 CH2-CH2-CH2-SO2-Cl2H25 2 pyrazolone rings can be linked via a divalent Q, giving so-called bis- couplers. These are described, for example, in US-A-2 632 702, US-A-2 618 864, GB-A-968 461, GB-A-786 859, P-A-76137 646, 5914086, 69116 110, 69126 589, 74137 854 and 74129 638. Y is preferably an 0-alkoxyarylthio group.
As mentioned above, the magenta couplers can also be pyrazoles which have been condensed with 5-membered heterocyclic rings, so-called pyrazoloazoles. Their advantages over simple pyrazoles is that they have colours of.greater formalin resistance and purer absorption spectra.
Magents couplers of the pyrazoloazole type, which are likewise preferred, can be represented by the formula R, Q (M-7) N N\ 1 1 _z in which R, is hydrogen or a substituent, Z represents the non-metallic atoms necessary to complete a 5-membered ring containing 2 or 3 nitrogen atoms, it being possible for this ring to be substituted, and Q is hydrogen or a leaving group. Of these, preference is given to magenta couplers of the formulae R,, 0 R,, Q R,, 0 R,, 0 N N NH N N\ NH N NH N\ NH N N N=N R13)z-(R12 ==R12 R13/ (M-8) W-9) (M-10) (M- 11) in which R,,, R12 and R13, independently of one another, are, for example, hydrogen, halogen, a group of the formula -CR3, in which the radicals R, independently of one another, are hydrogen or alkyl, aryl, heterocyclyl, cyano, hydroxyl, nitro, carboxyl, amino, alkoxy, aryloxy, acylamino, alkylamino, anilino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, suifonyl, alkoxycarbonyl, heterocyclyloxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, imido, heterocyclic thio, sulfinyl, phosphonyl, aryloxycarbonyl, acyl or azolyl, preferably hydrogen; halogen (for example chlorine or bromine), a group of the formula -CR3, in which the radicals R, independently of one another, are hydrogen or alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl, 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-tamylphenoxy)propyl; aryl (for example phenyl, 4-t-butylphenyl, 2,4-di-tamylphenyl or 4-tetradecaneamidophenyl); heterocyclyl (for example 2furyl, 2-thienyl, 2-pyrimidinyl or 2-benzothiazolyl); cyano; hydroxyl, nitro; carboxyl; amino; alkoxy (for example methoxy, ethoxy, 2methoxyethoxy; 2-dodecylethoxy or 2-methanesulfonylethoxy); aryloxy (for example phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-tbutoxycarbamoylphenoxy or 3-methoxycarbamoyl); acylamino (for example acetoamido, benzamido, tetradecanamido, 2-(2,4-di-tamylphenoxy)butanamido, 4-(3-t-butyl-4-hydroxyphenoxy)butanamido or 2-(4(4-hydroxyphenylsulfonyl)phenoxy)decanamido); methylbutylamino); anilino (for example phenylamino, 2-chloroanilino, 2-chloro-5tetradecanaminoanilino, 2-chloro-S-dodecyloxycarbonylanilino, Nacetylanilino or 2-chloro-S-(alpha-(3-t-butyl-4hydroxyphenoxy)dodecanamidoanilino); ureido (for example phenylureido, methylureido or N,N-dibutylureido); sulfamoylamino (for example N,Ndipropylsulfamoylamino or N-methyl-N-decylsulfamoylamino); alkylthio (for example methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3phenoxypropylthio or 3-(4-t-butylphenoxy)propylthio); arylthio (for example phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio or 4-tetradecanamidophenylthio); alkoxycarbonylamino (for example methoxycarbonylamino or tetradecyloxycarbonylarnino); sulfonamido (for example methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido, p- toluenesulfonamido, octadecanesulfonamido or 2-methoxy-5-t- butylbenzenesulfonamido); carbamoyl (for example N-ethylcarbarnoyl, N,N- dibutylcarbamoyl, N-(Modecyloxyethyl)carbamoyl, N-methyPN- dodecylcarbamoyl or N-(3-(2,4-di-t-amylphenoxy)propyl)carbwnoyl); sulfamoyl (for example N-ethylsulfamoyl, N,N-dipropyIsulfamoyl, N-2(- dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl or N,N- diethylsulfamoyl); sulfonyl (for example methanesulfonyl, octanesulfonyl, benzenesulfonyl or toluenesulfonyl); alkoxycarbonyl (for example methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl or octadecyloxycarbonyl); heterocyclyloxy (for example 1-phenyltetrazol-5- oxy or 2-tetrahydropyranyloxy); azo (for example phenylazo, 4- methoxyphenylazo, 4-pivaloylaminophenylazo or 2-hydroxy-4- propanoylphenylazo); acyloxy (for example acetoxy); carbamoyloxy (for example N-methylcarbamoyloxy or N-phenylcarbamoyloxy); silyloxy (for example trimethylsilyloxy or dibutylmethylsilyloxy); aryloxycarbonylamino (for example phenoxycarbonylarnino); imido, (for example N-succinimido, N- phthalimido or 3-octadecenylsuccinimido); heterocyclylthio(for example 2benzothiazolylthio, 2,4-diphenoxy- 1,3,5-triazole-6-thio or 2pyridylthio); sulfinyl (for example dodecanesulfinyl, 3pentadecylphenylsuffinyl or 3-phenoxypropylsulfinyl); phosphonyl (for example- phenoxyphosphonyl, octyloxyphosphonyl or phenylphosphonyl); aryloxyccarbonyl (for example phenoxycarbonyl); acyl (for example acetyl, 3-phenylpropanoyl, benzoyl or 4-dodecyloxybenzoyl); or azolyl (for example imidazolyl, pyrazolyl or 3-chloropyrazol-l-yl).
These substituents may, if desired, be further substituted, for example by halogen or by an organic radical bonded via a C, 0, N or S atom.
Preferred groups R,, are alkyl, aryl, alkoxy, aryloxy, alkylthio, ureido, urethane and acylamino groups.
R12 can be as defined for R, j and is preferably hydrogen, alkyl, aryl, a heterocyclic ring, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acyl or cyano.
R13 can be as defined for R, j and is preferably hydrogen, alkyl, aryl, heterocyclyl, alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl, carbamoyl or acyl, in particular alkyl, aryl, heterocyclyl, alkylthio or arylthio.
Q is hydrogen or a leaving group such as halogen, alkoxy, aryloxy, acyloxy, alkyl- or arylsulfonyloxy, acylamino, alkyl- or arylsulfonamido, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl-, aryl- or heterocyclyl-Scarbamoylarnino, a 5- or 6-membered, nitrogen-containing heterocyclic radical, imido or arylazo. These groups are unsubstituted or further substituted as indicated for R, l.
Q is preferably halogen (for example fluorine, chlorine or bromine); alkoxy (for example ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropoxy, methylsulfonylethoxy or ethoxycarbonylmethoxy); aryloxy (for example 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylarninophenoxy or 2carboxyphenoxy); acyloxy (for example acetoxy, tetradecanoyloxy or benzoyloxy); alkyl- or aryIsulfonyloxy (for example methanesulfonyloxy or toluenesulfonyloxy); acylamino (for example dichloroacetylamino or heptafluorobutyrylamino); alkyl- or arylsulfonamido (for example methanesulfonamido, trifluoromethanesulfonamido or ptoluenesulfonylamido); alkoxycarbonyloxy (for example ethoxycarbonyloxy or benzyloxycarbonyloxy); aryloxycarbonyloxy (for example phenoxycarbonyloxy); alkyl-, aryl- or heterocyclyPS- (for example dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-toctylphenylthio or tetrazolylthio); carbamoylamino (for example Nmethylcarbamoylarnino or N-phenylcarbamoylarnino); a 5- or 6-membered, nitrogen-containing ring (for example imidazolyl, pyrazolyl, triazolyl, tetrazolyl or 1,2-dihydro-2-oxo-l-pyridyl); imido (for example succinimido or Hydantoinyl); or arylazo (for example phenylazo or 4methoxyphenylazo).
Q can also form corresponding bis-compounds by condensation of tetraequivalent couplers with an aldehyde or ketone. Furthermore, Q can contain photographically active groups, such as development inhibitors or development accelerators. Q is preferably halogen, alkoxy, aryloxy, alkylor arylthio, or a 5- or 6-membered, nitrogen-containing heterocyclic group which is bonded to the coupling site via a nitrogen atom.
Pyrazolotetrazoles are described in P-A-85/33 552; pyrazolopyrazoles are described in P-A-85143 695; pyrazoloirnidazoles are described in P-A85135 732, P-A-86118 949 and US-A-4 500 630; pyrazolotriazoles are described in P-A-85/186 567, P-A-86/47 957, P-A-851215 687, P-A-85/197 688, P-A-851172 982, EP-A- 119 860, EP-A- 173 256, EP-A- 178 789, EP-A178 788 and in Research Disclosure 84/24 624.
Other pyrazoloazole magenta couplers are described in: P-A-86128 947, P-A8511.40 241, P-A-851262 160, P-A-85/213 937, JP-A-87278 552, P-A-871279 340, P-A-881100 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 81120 919, 84124 531 and 85125 758.
Suitable examples of such couplers are:
Cl H CH3 C(C1-13)2C2H,5 1 1 (M-6) H3C N v Uti(;P12NI-IC0- CHOC(C1-13)2C21-1,5 N-N-N 1 C6H13 Cl H 1 (M-12) CH3 N, N N-N CHCH2-SO27C181-137 1 Ut13 Cl H CH3 N - N -I(CH2)3-' NHS02 0C12H25 Cl H 1 OCBH17 CH3 Yll:Y N 11.1 N N-N CHCH2NHS02 OC8H17 1 CH3 NHS02 -0 C81-117(t) -21 cl H C12H250 S02NH (CH2)3 N N-N- C4Hg(t) cl H 1 0C4H9 WC3H7 yly N 11. N N-N (CH2)3S02 C8HIA) cl H 1 WC3H7 yly N N 0C6H13 N-N (CH2)3S02 -0 0C4H9 NHS02t C8H17(t) cl H 1 0C4H9 WC3H7 N N-N (CH2)2NHS02 C8H17(t) cl H WC4H9 N N-N (CH2)2SO2C1SH37 H 1 0C4H9 CP4H9 Y"^ N 1%.
N-N (CH2)3S02 C8H17(t) cl H 1 0 4H9 MC4H9 Yk-_r N N N-N (CH2)3S02 C8H17M cl H P4Hg(t) WC4H9 yly N N-N- (CH2)3 NHCOCHO OH --o- 1 d C12H25 cl H 1 MC4H9 N N-N CHCH2SO2C18H37 1 UH3 0C4H9 S/0 H SH17 t C5H11(t) C2H5S V1 1..Y, N, N N-N CH2CH2NHCOCHO C5H11(t) 1 _ U4t19 cl CH30 N N CH3 N N ---IL' C - CH20 H 1 CO0C12 25 UH3 cl OCSH17 CH3 N CHCH2NHS02 0C8H17 N-N-N HS02 CBH17(t) cl CH3 N CHCH2S02 0C12H25 N-N-N cl OC8H17 CH3)rIlkr N v CH2CH2S02 N-N-N 0C8H17(t) cl 0 SH17 H CH3 N ,., 9HCH2NHS02 v CH3 N-N-N 0C8H17M cl H CH3 WC3H7 IU-UH2502C1SH37 CH ly), --- ' 3 N-N-N cl CH3 WC4H9 N 1%.
) v N N-N CH3 CH3 NHCOCHO S02 OH 1 -C -0 C10H21 cl CHSS02 MC4H9 v (CH2)30-0 cl N-N-NH NHCOCH 1 b C12H25 cl H OCSH17 CH3 NHS02 OCSH17 Yly Al -0 N-N-N NHS02-0 C8H17(t) 0C8H17 ffiCaH17,cxs H OC8H17 CHS CHCH2NHS02 N-N N UM3 8H17(t) - 25 0C8H17 WC8H17 S H 0C8H17 C2H50 N CHCH2NHS02 )IY '"' ri 1 N-N-N Ut3 C8H17M cl (CH3)3C yly N 11.1 N N-N CH2CH2CH2SO2CH2CHC8H17 1 1;6t'13 cl H CH3 yly N N-N CH2CH2CH20 WCOCH2CHCOOH C(CH3)3 t;I8t37 cl H c vy N 1_% N N-N CH2-CH2CH2--C MCO-CHO-(: S0.2NH OH 1 --c C12H25 cl H 1 CH3 Y1-Y N %. N N - N ---1LCHO NHS02 1 --(:: -p ;12t'25 COOH OCH3 cl H N OCH3 N-N CH2CH2CH20 -P- C5H11(t) C5H11(t) cl H CH3 (CH3)3C Y, ly N N N-N CH3 3 NHCO-CHO NHS02e4H9 1-0 C12H25 CH CY cl H 0 SH 17 1 HN CO- NH N 1 -,), CH2CH2NHS02 N-N-N C8HIA) cl H 0 4H9 1 WC3H7 JY N CH2CH2CH2S02 Y1 ir I-N C8H17(t) cl H 0C8H17 1 We4H9 N CMCH2NHS02 0C4H9 Yly 1 1 N-N-N U2t15 NHS02 C8H17(t) OCSH17 cl H t MC4H9 N CH2CH2NHS02 N-N-N CaHIA) cl cl H 9 WC4H9 N (CH2)3 NHCOCH o - C5H11(t) )1::Y 1 C10H21 N N - cl (CH2)3 NHS02 -00C12H25 1 MC4H9 N Z 1 Y1 1 N-N-NH cl H CH3 1 1 N O(CH2)3CONH(CH2)2 C N 1 11 CH3N-N-N C15H31 cl H N (OCSH11 OCH2-1)y 11.1 N 4 C13H27 C5H11(t) cl H -C H N N C13H27 cl 0C4H9 CH 3 NN CH2CH2CH2S02 C8H17(t) cl H CH3 N N ?H3 N-N- C-CH2SO2C1SH37 i CH3 cl H CH3 1 0C4H9 N yly I_. N N-N (CH2)3S02 C8HIA) cl H C5Hil(t) WC3H7 yly N N N-N CH-0 C5H11(t) 1 ;6M13 0C4H9 C8H17(t) CH3 N N-N (CH2)2SO2C12H25 cl H 1 CH3 CH3 yly N Is. N N-N 1 - CH3 2LO CH3 NH-S02C16H33 cl H 1 0C8H17 (yo-ry NI. N N-N (CH2)2NHS02 C8H17(t) cl H 1 CH3 CH3 yly NIS. N N-N CH3 CH3 NH-CO-CH_0 S02-- CH2-0 C10H21 cl CH3 MC4H9 Y1Y N.1 N-N CH3 q5Hil(t) CH3 NH-CO 1 CH-0-0- C5H, 1 (t) ;4tig cl H 1 CH3 NN% N N-N (CH2)3 -0-NH-CO-CH-0-0-SO2-0-OH 1 C10H21 0/0-CH3 H MC4H9 Y, IZ '-r N, N C.5H11(t) N-N CH-CH2NH-CO-CH-0 C5H11(t) 1 1-0- k#n3 "2"5 OCH3 Cl H 0 8H17 N 0 N 1 11 N-N CH-CH2NH-SO2 1 CH3 C8H17(t) cl CH3 N OCH2CH20C2H5 N-N CH-CH2NH-SO2 0C8H17 1 1 k#r13 NHS02-0 C8HIA) cl H CH3 q5H 11 (t) CH3 ll-C-CH2NH-CO-CH-0 --0- C5H11(t) N-N-N H, 1 U61,13 cl H 0C12H25 N CH-CH2NH-CO CH3 N'11 N-N 3 cl H q5H11(t) N CH3 CHCH2NH-CO(CH2)30 C5Hil(t) Ut'3 cl H N c CHCH2NH-COCHO H3 -1 v '), - N-N-N CH3 L;1OM21 C15H31 cl H N CH3 CHCH2NHCOCH-0 -gly), -, k;6M13 0C12H25 cl H C5H11(t) N CH-CH2NH-CO-CH-0 C5H11(t) -Ily '), - 1 (i)C3H7 1 - In UM3 1;6H13 cl H C5H11(t) N CH3' CH(CH24NH-CO-CH-0 C5H 11 (t) Ut13 U6M13 cl C5H11(t) H C5H11(t) (t)C4H9 Y CH-CH2NH-CO-CH-0 N-N-N Ut13 1 U4'19 Cyan couplers can be, for example, derivatives of phenol, of l-naphthol or of pyrazoloquinazolone. Preference is given to structures of the formula E, OH R21 R23 (E), R22 R24 OR in which 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 eliminated during the reaction with the oxidized developer. A detailed list of cyano couplers is given in US-A-4 456 681.
Examples of customary cyan couplers are the following:
t-C5H11 cl OH NHCO-CH- t-C5H11 (EA) 1 1 CH3) f C2H5 cl t-C4H9 cl OH NHCO-CH- t-C4H9 (E-2) C2H5 U4t19 cl t-CSH1 1 cl OH NHCO-CH- t-C5H, 1 (E-3) C2H5 C2H5 cl (E4) cl WCO-(CH2)14CH3 C2H5 cl F F OH t-C6H11 1 NHCO F Zt-(E3) t-CSHI, O-CH-CONH -,[: 1 F F 1 cl cl OH cl WC 1 0-6 (E-6) t-C5H O-CH-CONH 1 cl C6H13 Further examples of cyan couplers are given in the following: US-A-2 369 929, 2 423 730, 2 434 272, 2 474 293, 2 521293, 2 521908, 2 698 794, 2 706 684, 2 772 162, 2 80117 1, 2 895 826, 2 908 573, 3 034 892, 3 046 129, 3 227 550, 3 253 294, 3 311476, 3 386 3019 3 419 390, 3 458 315, 3 476 560, 3 476 563, 3 516 831, 3 560 212, 3 582 322, 3 583 97 1, 3 591383, 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 79 1, and EP-A-354 549 and EP-A-398 664.
Preference is given in the red-sensitive silver-halide emulsion layer of the novel material to cyan couplers of the formula OH Z3 NHCOZ2 (E-7) Z1COHN Z4 and/or of the formula OH (E-8) cl NHCOZ5 Z7 Z6 in which Z1 is alkyl or aryl, Z2 is alkyl, cycloalkyl, aryl, a heterocyclic group or a ballast group, 73 is hydrogen or halogen, ZI and Z3 together can form a ring, and Z4 is hydrogen or a leaving group, and Z5 is a-ballast group, Z6 is hydrogen or a leaving group, and Z7 is alkyl. - The colour developers usually used for colour-photographic materials are p-dialkylaminoanilines. Examples thereof are 4-amino-NN-diethylaniline, 3methyl-4-aminoN,N-diethylaniline, 4-ainino-N-ethyl-N-ahydroxyethylaniline, 3-methyl-4-aminoN-ethyl-N-a-hydroxyethylaniHne, 3methyl-4-amino-N-ethyl-N-a-hydroxyethylaniHne, 3-methyl-4-wnino-N-ethyl-Na-methanesulphonamidoethylaniline, 3-methyl-4-arninoN-ethyl-N-amethoxyethyl-aniline, 3-a-methanesulphonamidoethyl-4-amino-NNdiethylaniline, 3-methoxy-4-amino-N-ethyl-N-a-hydroxyethylaniHne, 3methoxy-4-aminoN-ethyl-N-a-methoxyethylaniline, 3-acetamido-4-amino-NNdiethylaniline, 4-aminoN,N-dimethylaniline, N-ethyl-N-a-[(x-(a"methoxyethoxy)ethoxy]ethyl-3-methyl- 4-aminoaniline, N-ethyl-N-a-(a'-methoxyethoxy)ethyl-3-methyl-4- wninoaniline, and the salts of such compounds, for example sulfates, hydrochlorides or toluenesulfonates.
The UV absorbers of the formula (I) and (HI) used according to the invention can be incorporated, alone or together with the colour coupler and, if desired, further additives, into the colour-photographic material by pre-dissolving them in high-boiling organic solvents. Preference is given to solvents which boil at above 16WC. Typical examples of such solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids, and alkylamides and phenols.
A low-boiling solvent is usually used in addition in order to simplify incorporation of the additives into the colour-photographic material. Examples of such solvents are esters, for example ethyl acetate, alcohols, for example butanol, ketones, for example methyl isobutyl ketone, chlorinated hydrocarbons, for example methylene chloride, or amides, for example dimethylformamide. If the additives are themselves liquid, they can also be incorporated into the photographic material without the aid of solvents.
The novel UV absorbers can, if desired, be dispersed in the gelatine layer without oil; Research Disclosure 881296 017 and 891303 070.
Further details of high-boiling solvents which can be used are given in the following publications:
Phosphates: GB-A-791 219, BE-A-755 248, JP-A-76/76 739, 78127 449, 781218 252, 78/97 573, 791148 133, 821216 177, 82193 323 and 831216 177 and EP-A265 296. Phthalates: GB-A-791 219, JP-A-77198 050, 82193 322, 821216 176, 821218 25 1, 83124 321, 83145 699, 84[79 888. Amides: GB-A-791 129, JP-A761105 -043, 77/13 600, 77161089, 84/189 556, 871239 149, US-A-928 741, EP-A-270 341, WO 88100 723. Phenols: GB-A-820 329, FR-A-1 220'657, JP-A69/69 946,7013818,751123 026, 75182 078, 78/17 914, 78/21166, 82/212 114 and 83145 699. Other oxygen-containing compounds: US-A-3 748 141, 3 779 765, JP-A-73175 126, 74/101 114, 74110 115, 75/101625, 76176 740, 77161089, EP-A-304 8 10 and BE-A-826 039. Other compounds: JP-A-72/115 369, 72/130 258, 73/127 521, 73176 592, 77113 193, 77136 294, 79/95 233, 9112748, 831105 147 and Research Disclosure 82121918.
The amount of high-boiling solvent is, for example, in the ratio of 50 mg to 2 g, preferably from 200 mg to 1 g, per & of support.
The photographic layers may furthermore contain colour-cast inhibitors. These prevent the formation of colour casts, as formed, for example, due to reaction of the coupler with unintentionally oxidized developer or with by-products of the colour-formation process. Such colour-cast inhibitors are usually hydroquinine derivatives, but can also be derivatives of aminophenols, of gallic acid or of ascorbic acid. Typical examples thereof are giveri in the following publications: US-A-2 360 290, 2 336 327, 2 403 721, 2 418 613, 2 675 314, 2 701197, 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- 75192 988, 75/92 989, 75193 928, 751110 337, 8415247 and 77/146 235.
The photographic layers can also contain DIR couplers (DIR means Development Inhibition Release), which give colourless compounds with the oxidized developer. They are added to improve the sharpness and grain of the colour images.
The photographic layers in the novel material may also contain further UV absorbers. Examples of such UV absorbers are benzotriazoles, 2hydroxybenzophenones, salicylic acid esters, acrylonitrile derivatives or thiazolines. These UV absorbers are described in greater detail, for example, in the following publications: US-A-3 314 794, 3 352 68 1, 3 705 805, 3 707 375, 4 045 229, 3 700 455, 3 533 794, 3 698 907, 3 705 805, 3 738 837, 3 762 272, 4 163 671, 4 195 999, 4 309 500, 4 431726, 4 443 543, 4 576 908, 4 749 643,-GB-A-1 564 089, EP-A-190 003 and JP-A-7112784, 811111826, 8 1t27 146, 88153 543 and 88/55 542. Preferred UV absorbers are-benzotriazoles, in particular 2-(2-hydroxyphenyl)benzotriazoles.
The photographic layers may also contain phenolic compounds which act as light stabilizers for the colour image and as colour-cast inhibitors. They may be present in a photosensitive layer (colour layer) or in an interlayer, alone or together with other additives. Such compounds are described in greater detail, for example, in the following publications: US-A-3 700 455, 3 591381, 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 581326, 4 562 146, 4 559 297, GB-A-1 309 277, 1547 302, 2 023 862, 2 135 788, 2 139 370, 2 156 09 1; DE-A-2 301060, 2 347 708, 2 526 468, 2 621203, 3 323 448; DD-A-200 691, 214 468; EP-A-106799,113 124,125522,159912,161577,164030,167762,176845,246766, 320 776; P-A-741134 326, 761127 730, 76/30 462, 7713822, 771154 632, 78/10 842, 79148 535, 79170 830, 79173 032, 791147 038, 791154 325, 79/155 836, 821142 638, 831224 353, 8415246, 84172 443, 84/87 456, 841192 246, 84/192 247, 84/204 039, 841204 040, 841212 837, 841220 733, 84/222 836, 841228 249, 8612540, 8618843, 86/18 835, 86118 836, 87111456, 87142 245, 87162 157, 86/6652, 891137 258 and in Research Disclosure 79117 804.
The photographic layers may also contain certain phosphorus(HI) compounds, in particular phosphites and phosphonites. These function as light stabilizers for the colour images and as dark-storage stabilizers for magenta couplers. They are preferably added to the high-boiling solvents, together with the coupler. Such phosphorus(III) compounds are described in greater detail, for example, in the following publications: US-A-4 407 935, US-A-4 436 811, US-A-4 956 406, EP-A- 181289, P-A-73132 728, P-A7611420 and P-A-55166 741.
The photographic layers may also contain organometallic complexes which are light stabilizers for the colour images, in particular for the magenta dyes. Such compounds and combinations thereof with other additives are described in greater detail, for example, in the following publications: US-A-4 050 93 8, 4 239 843, 4 241 154, 4 242 429, 4 241155, 4 242 430, 4 273 854, 4 246 329, 4 271253, 4 242 431, 4 248 949, 4 245 195, 4 268 605, 4 246 330, 4 269 926, 4 245 018, 4 301223, 4 343 886, 4 346 165, 4 590 153; JP-A-81/167 138, 811168 652, 82/30 834, 821161744; EP- A- 137 271, 161577, 185 506; DE-A-2 853 865.
The photographic layers may also contain hydroquinone compounds. These function as light stabilizers for the colour couplers and for the colour images and as scavengers of oxidized developer in interlayers. They are used, in particular, in the magenta layer. Such hydroquinone compounds and combinations thereof with other additives are described in greater detail, for example, in the following publications: US-A-2 360 290, 2 336 327, 2 403 721, 2 418 613, 2 675 314, 2 701 197, 2 710 801, 2 732 300, 2 728 659, 2 735 765, 2 704 713, 2 937 086, 2 816 028, 3 582 333, 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 121939, 4 175 968, 4 179 293, 3 59138 1, 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, 1363 921, 2 022 274, 2 066 975, 2 071348, 2 081463, 2 117 526, 2 156 091; DE-A-2 408 168, 2 726 283, 2 639 930, 2 901520, 3 308 766, 3 320 483, 3 323 699; DD-A-216 476, 214 468, 214 469, EP-A-84 290, 110 214, 115 305, 124 915, 124 877, 144 288, 147 747, 178 165, 161577; P-A-75133 733, 75121249, 771128 130, 771146 234, 79170 036, 791133 131, 81183 742, 81/87 040, 811109 345, 831134 628, 82122 237, 821112 749, 83117 431, 83121249, 84175 249, 841149 348, 841182 785, 841180 557, 841189342,841228249, 841101650,79124019,79125823,86148856,86148857, 86127 539, 8616652, 86J72 040, 87111455, 87162 157, and Research Disclosure 79117 901, 79117 905, 79118 813, 83122 827 and 84124 014.
The photographic layers may also contain derivatives of hydroquinone ethers. These compounds function as light stabilizers and are particularly suitable for stabilizing magenta dyes. Such compounds and combinations thereof with other additives are described in greater detail, for example, in the following publications: US -A 3 285 937, 3 432 300, 3 519 429, 3 476 772, 3 591381, 3 573 052, 3 574 627, 3 573 050, 3 698 909, 3 764 337, 3 930 866, 4 113 488, 4 015 990, 4 113 495, 4 120 723, 4 155 765, 4 159 910, 4 178 184, 4 138 259, 4 174 220, 4 148 656, 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 3 85 111, 4 459 015, 4 559 297; GB-A 1347 556, 1366 441, 1547 392, 1557 237, 2 135 788; DE-A 3 214 567; DD-214 469, EP-A 161577,167 762,164 130,176 845; P-A 761123 642, 77135 633, 771147 433, 781126, 78110 430, 78153 321, 79t24 019, 79125 823, 79148 537, 79/44 521, 79156 833, 79170 036, 79170 830, 79173 032, 79195 233, 791145 530, 80121004, 80150 244, 80152 057, 80170 840, 801139 383, 81130 125, 811151936, 82134 552, 82168 833, 821204 306 821204 037, 831134 634, 831207 039, 84160 434, 841101650, 84/87 450, 841149 348, 841182 785, 86172 040, 87111455, 87162 157, 87163 149, 8612151, 8616652, 86148 855, 891309 058 and Research Disclosure 78117051.
Ex=ples of suitable stabilizers for the magenta couplers are:
CH30 CO-OC6H13 (ST-1) C6H130-OC OCH3 OH CO-OC6H13 (ST-2) C6H130-OC 0H OH CO-OC6H13 (ST-3) C6H130-OC OCH3 C3H70 (ST-4) 0C3H7 0C3H7 C3H70 C8H17 (ST-5) 0C8H17 OH (ST-6) OH -40OH (ST-7) 0 - CH-CO-OC2H5 1 -;12'25 OH C8H17 (ST-8) 0 Silver-halide emulsions which can be used are conventional silver-chlo ride, silver-bromide or silver-iodide emulsions, or mixtures thereof, such as silver chlorobromide and silver chloroiodide emulsions, in which the silver halides can have any Imown crystal forms. The use of silver- chloride emulsions is of particular importance in the novel material. The preparation of such emulsions and the sensitization thereof are described in RESEARCH DISCLOSURE, November 1989, No. 307 105. This publication furthermore mentions a number of binders for said emulsions which can also be used in the novel materials. The same applies to the supports mentioned in the publication.
The silver-halide emulsion which can be used for carrying out this invention can be sensitized for all desired wavelengths with the aid of sensitization pigments. These can be cyanine pigments, merocyanine pigments., holopolar pigments, hemicyanine pigments, styryl pigments or hemioxanol pigments.
The photosensitive material may also contain water-soluble dyes, in order, for example, to improve the clarity by preventing radiation damage. These can be oxanol dyes, hemioxanol dyes, styryl dyes, merocyanine dyes, cyanine dyes, anthraquinone dyes and azo dyes.
The novel material can also be combined with further materials, as described, for example, P-A-871215 272, 9219035, 92121840 and EP-A-429 240.
The present application also relates to the use of the compounds of the formula (I) for stabilizing ink-jet printing inks, to the stabilized inks, and to the recording material containing the compounds of the formula (I). Preferred compounds of the formula (I) are the compounds mentioned above. Examples of compounds of the formula (I) which can be used are described in greater detail under the photographic materials.
The novel inks are distinguished by good light stability. They can be used, for example, for felt-tip pens, stamp pads, fountain-pen holders and pen plotters, and in offset printing, letterpress printing, flexographic printing and intaglio printing processes, and also in colour ribbons for dot-matrix and letter-quality printing. They are preferably used in ink-jet printing processes.
Printers used in current inkJet printing processes are divided into continuous ink-jet and drop-on-demand printers, in particular bubble-jet printers. The novel inks can be used for these printers. In particular, ink-jet printing papers and forms are printed.
The novel inks may contain water-soluble solvents, for example mono-, di-, tri- or higher.ethylene glycols, propylene glycol, 1,4-butanediol, or ethers of such glycols, thiodiglycol, glycerol and ethers and esters thereof, polyglycerol, mono-, di- and triethanolamine, propanolamine, dimethylfomiamide, dimethyl sulfoxide, dimethylacetamide, Nmethylpyrrolidone, 1,3-chmethylimidazolidone, methanol, ethanol, isopropanol, n-propanol, diacetone alcohol, acetone, methyl ethyl ketone or propylene carbonate.
The novel inks contain dyes, as also known for the dyeing of natural fibres. Examples which may be mentioned are monoazo, disazo or polyazo dyes, reactive dyes, tdphenylmethane dyes, xanthene dyes and phthalocyanine dyes. Specific examples thereof are Food Black 2, C.I. Direct Black 19, C.I. Sulphur Black 1, Acid Red 35, Acid Red 14, Acid Red 52, Acid Yellow 17, Acid Yellow 23 and copper phthalocyanines, furthermore Direct Black 38, Direct Black 168, Acid Red 249, Direct Red 227, Direct Yellow 86, Direct Yellow 132, Acid Blue 9, Direct Blue 86, Direct Blue 199, Reactive Red 24, Reactive Red 40 and Reactive Red 159, and the azo dyes mentioned in EP-A-366 121.
The inks may also contain further conventional additives, for example binders, surfactants, biocides, corrosion inhibitors., sequestrants, pH buffers or conductive additives. They may also contain further UV absorbers or light stabilizers, for example the compounds mentioned in US 5 073 448, US 5 089 050 or in particular in US 5 096 489 and US 5 124 723. In general, however, the novel addition of a stabilizer of the formula (I) is sufficient to stabilize the inks.
Also known are ink-jet printing inks which comprise more than one phase. JP-A-0 1170 675, 0 1182 379, 0 1182 380, 0 1182 381 and 0 1193 376 describe inks which comprise an aqueous phase, in which the dye is dissolved, and an emulsion of oil drops, which contain the UV absorbers and, if desired, also antioxidants. In JP-A-0 1170 673 and 0 1182 382, the oil phase containing UV absorbers is microencapsulated, and the dye is dissolved in the aqueous phase. By contrast, oil-soluble dyes can be dissolved in an oil together with UV absorbers and, if desired, antioxidants. The oil is either emulsified or dispersed in an aqueous phase, as described, for example, in JP-A-0 1170 674 and 0 1170 672. The compounds of the formula (I) are highly suitable for the stabilization of. such inks; they are water-soluble and can be dissolved in the aqueous phase.
The novel inks preferably contain 0.0 1-30 % by weight, in particular 0. 1-20 % by weight, of at least one compound of the formula (I).
Preferred inks contain compounds of the formula (I) as indicated in the description of the preferred compounds.
The compounds can easily be incorporated into inks and recording materials.
The novel recording materials, which are preferably used for the ink-jet printing process and which contain a compound of the formula (1), comprise a support with a surface which can be printed by ink jet. The support is usually paper or a plastic film and is normally coated on one side with a material which is capable of accepting inks. This layer preferably contains SiO2 and polyvinyl alcohol.
Uncoated paper can likewise be employed. In this case, the paper simultaneously serves as support material and ink-accepting layer. It is furthermore possible to use materials comprising cellulose fibres and textile fibre materials, for example cotton fabric or mixed cotton fabric made from cotton and polyacrylamide or polyester, which contain compounds of the formula (I) for ink-jet printing.
The recording materials may also be transparent, as in the case of projection films.
The compounds of the formula (I) can be incorporated into the support material as early as during production thereof, for example by addition to the paper pulp during the production of paper. A second method of application is the spraying of the support material with a solution of the compound of the formula (I). This is an aqueous solution or a solution in a readily volatile organic solvent. The use of emulsions or dispersions is also possible.
Preferably, however, a coating composition with high dye affinity is applied to the support material, and in this case the compounds of the formula (I) are added to this coating composition. The coating compositions generally comprise a solid filler, a binder and conventional additives.
The filler is the major constituent of the coating composition by amount. Examples of suitable fillers are Si02, kaolin, talc, clay, calcium silicate, magnesium silicate, aluminium silicate, gypsum.. zeolite, bentonite, diatomaceous earth, vermiculite, starch or the surfacemodified SiO2 described in JP-A-601260 377. Small amounts of white pigments, for example titanium dioxide, barytes, magnesium oxide, lime, chalk or magnesium carbonate, can be used with the filler in the coating composition if they do not greatly reduce the density of the ink-jet print.
Coating compositions which are intended for transparent, projectable, recording materials cannot contain light-scattering particles, such as pigments and fillers.
The binder binds the fillers to one another and to the support material. Examples of customary binders are water-soluble polymers, for example polyvinyl alcohol, partially hydrolysed polyvinyl acetate, cellulose ethers, polyvinylpyrrolidone and copolymers thereof, polyethylene oxide, salts of polyacrylic acid, sodium alginate, oxidized starch, gelatine, casein, vegetable gum, dextrin, albumin, dispersions and polyacrylates or acrylate-methacrylate copolymers, latexes of natural or synthetic rubber, poly(meth)acrylamide, polyvinyl ethers, polyvinyl esters, copolymers of maleic acid, melamin resins, urea resins or chemically modified polyvinyl alcohols, as described in JP-A-611134 290 and JP-A-611134 291.
An additional dye receptor or a mordant which improves the fixing of the dye through the coating may be added to the binder. Dye receptors for acidic dyes are of a cationic or amphoteric nature. Examples of cationic receptors are polymeric ammonium compounds.
for example polyvinylbenzyltdmethylammonium chloride, polydiallyldimethylammonium chloride, polymethacryloxyethyldimethylhydroxyethylammonium chloride, polyvinylbenzylmethylimidazolium chloride, polyvinylbenzylpicolinium chloride and polyvinylbenzyltributylammonium chloride. Other examples are basic polymers, for example poly(dimethylaminoethyl) methacrylate, polyalkylenepolyamines and condensation products thereof with dicyandiamide, amine-epichlorohydrin polycondensates, or the compounds described in JP-A-57-36 692, 57-64 591, 57-187 289, 57-191084, 58-177 390, 58-208 357, 59-20 696, 59-33 176, 59-96 987, 59-198 188, 60-49 990, 6071796, 60-72 785, 60-161 188, 60-187 582, 60-189 481, 60-189 482, 61-14 979, 61-43 593, 61-57 379, 61-57 380, 61-58 788, 61-61887, 61-63 477, 6172 58 1, 61-95 977, 61-134 291, 62-37 181 or US-A-4 547 405 and 4 554 181 and DE-A-3 417 582. An example of amphoteric dye receptors is gelatine.
The coating with high dye affinity may contain a number of additives, for example antioxidants, further light stabilizers (including UY absorbers), viscosity improvers, optical brighteners, biocides andlor antistatics.
Examples of suitable antioxidants are, in particular, sterically hindered phenols, hydroquinones and hydroquinone ethers, for example the antioxidants mentioned in GB-A-2 088 777, US 5 073 488, US 5 089 050 and JP-A-60-72 785, 60-72 786 and 60-71796.
Examples of suitable light stabilizers are, in particular, organonickel compounds and sterically hindered amines, for example the light stabilizers mentioned in JP-A-58-152 072, 61-146 591, 61-163 8 86, 60-72 785 and 61-146 591 and GB-A-2 088 777, JP 59-169 883 and 61-177 279. Suitable UV absorbers which can be added to a coating composition in combination with compounds of the formula (I) are described, for example, in Research Disclosure No. 24239 (1984), page 284, GB-A-2 088 777 and EPA-0 280 650. Particularly the UV absorbers of the 2hydroxyphenylbenzottiazole class and very particularly 2-(2'-hydroxy-3', 5'-di-t-amylphenyl)benzotriazole and 2-(2'-hydroxy-3'-t-butyl-5'(polyglycol propionate)phenyl)benzotriazole are suitable for use together with compounds of the formula (I) or (11) in recording materials for inkjet printing. The UV absorbers can be added to the coating composition as emulsions or dispersions.
The coating composition is generally applied to the support, for example paper, and dried by heating. As mentioned above, the compounds of the formula (I) can also be applied to the recording material in a separate operation, alone or together with other components described above, as an aqueous solution. Application can take place by spraying, sizing in a sizing press, a separate pouring operation or by immersion in a trough. After such post-treatment of the recording material, an additional drying operation is necessary.
The recording material preferably contains from 1 to lfflffl Mg1M2, in particular from 50 to 2000 Mg1M2, of at least one compound of the formula (1).
The present invention furthermore relates to the use of a compound of the formula (I) for stabilizing organic materials and in particular surface coatings against damage by, in particular, radiation (UV light), and to the stabilized organic material or coating itself. Preferred compounds of the formula (I) are mentioned above under the description of the compounds. Examples of compounds of the formula (I) which can be used are described in greater detail under the photographic materials.
The use of the compound of the formula (I) is particularly preferred in surface coatings as described in US-A-5,106,891 (col. 6, line 55, to col. 7, line 62; incorporated herein by reference). Very particular pr6ference. is given to the use of a compound of the formula (I) in automotive paints.
The use of a compound of the formula (1) for stabilizing organic materials and in particular surface coatings can also take place together with sterically hindered amines of the polyalkylpiperidine type. Suitable compounds from the series consisting of derivatives of polyalkylpiperidines contain at least one group of the formula (HA) RCH2 CH3 R - N (RA) RCH2 CH3 in which R is hydrogen or methyl. Examples of such compounds are given in US-A-5,106,891 (col. 10, line 1, to col. 27, line 45; incorporated herein by reference). In addition to or instead of the sterically hindered amines, it is advantageous to use a UV absorber from the series consisting of the hydroxyphenylbenzotriazoles, hydroxyphenylbenzophenones, oxanilides or further hydroxyphenyl-striazines with a compound of the formula (I).
The organic materials or surface coatings stabilized according to the invention preferably contain 0.02-5 % by weight, particularly preferably 0.05-3 % by weight, of a compound of the formula (1), based on the polymer weight (solid).
The present invention furthermore relates to a process for the preparation of the novel compounds of the formula R4 R3 R2 OH N N OH N RIO& OR, Examples of processes for the preparation of the starting compounds: aa) Reaction of epichlorohydrin with HO-(CH2C1120).7R8 with addition of a base (for 0 example NaOH) to give CH2-0-(CH2CH270)n-R8, where Rg and n are as defined under the formula (I). bb) Reaction of HO-(CH2CH20),-RS with COC12 to give Cl-Q0)0-(CH2CH20).-RS, where R8 and n we as defined under the formula (I).
The other starting compounds are known or can be obtained by processes known from the literature.
Examples of processes for the preparation of the compounds of the formula (I):
0 al.) Reaction of a bisresorcinyltriazine with L, CH2-0-(CH2CH270)n-R8 to give R4 R3 R2 OH N N OH N 1 R10 Zll OR, where R, is CH2-CH(OH)-CH2-0-(CH2CH2-0).-R8, where R2, R3, R4, R8 and n are as defined under the formula (I).
C) Reaction of a bisresorcinyltdazine with R6-CH(Br)-C(O)O-R20 to give R4 R3 R2 OH N N OH N 1 -- R2TO(O)C-CH(R6)-O& O-CH(R6)-C(O)OR20 and subsequent esterification thereof by means of HO-(CH2CH2-0),,-R8 to give the novel compound R4 R3 R2 OH N N OH N R8-0(0)C-CH(R6)-O O-CH(R6)-C(O)O-RS where R2, R3, R4, R6, R8 and n are as defined under the formula (I).
b) Reaction of 4 R3 R2 OH N N OH N 1 - _;,, 1 R7-O-CH2-CH(OH)-CH2-0 O-CH2-CH(OH)-CH2-0-R7 R4 R3 R2 with Cl-Q0)0-(CH2CH20)n-RS to give OH N N OH R10& OR, where R, is CH2-CH(C112OR7)-O-C(O)-(CH2CH2-0),,7R8 whew R2, R3, R4, R7, RS and n are as defined under the formula (I).
Analogous preparation processes can also be used to give the novel compounds derived from trisresorcinyltriazine.
The examples below illustrate the invention in greater detail, without representing a limitation.
Example 1: Preparation of heptaethylene glycol cc-methyl-o--t-glycidyl ether 12.0 g (0.30 mol) of sodium hydroxide are dissolved virtually completely in 105.1 g (0.30 mol) of polyethylene glycol (350) monomethyl ether over the course of 3 hours at 80C with stirring. The mixture is cooled to 25Q and 83.2 g (0.90 mol) of epichlorohydrin (Fluka, 99.5 %) are added with vigorous stirring, and the temperature of the exothermic reaction is kept below 40C by cooling with an ice bath from time to time.
After one hour, the reaction mixture is heated to 75'C, held at this temperature for 2 hours and cooled to SO'C, and the resultant salt (NaCI) is filtered off. The excess epichlorohydrin is removed at 1 10T/15 mm and subsequently at 1 10T/0.5 mm, giving 0 L CH2-0-(CH2CH2-0)7T4CH3 as a slightly viscous, pale yellow liquid.
Example 2: Preparation of 2-phenyl-4,6-bis [2-hydroxy-4- (3'(methoxyheptaethoxy)2'-hydroxypropoxy 1 phenyl] - 1,3,5-tdazine [compound (I)] A mixture of 10.0 g of 2-phenyl-4,6-bis(2,4-dihydroxy)phenyl)-1,3,5triazine, 25.8 g of heptaethylene glycol a-methyl-w-glycidyl ether and 1. 10 g of ethyl triphenylphosphoniurn bromide is kept at 140C for 5 hours in 100 mI of mesitylene. The mixture is evaporated on a Rotavapor and transferred onto a silica gel column (0=6 cm, h=35 cm; silica gel 60, 230400 mesh) and eluted with a mixture of methylene chloride/methanol (95/5). Removal of the solvent (11 O'C/0.0 1 mm) from the main fraction gives 27. 7 g (87.9 %) of the compound of the formula OH N N OH N RO& OR where R = CH2CH(OH)-CH2-0(CH2CH20)7.54-CH3, as a viscous pale yellow oil.
Elemental analysis:Csg.2H91.4N3023.1 Calculated: C 58.53; H 7.58; N 3.46 %Found: C 57.29; H 7.84; N 2.83 % By using the corresponding starting compounds, the compounds listed in Table 2 below can be prepared analogously to the above procedure.
Table 2:
Comp. Formula (MW) (2) C3SH43N3010 Calculated C 63.15; H 6.51; N 6.31 % (665.75) Found C 63.23; H 6.77; N 6.07 % (3) C39H51N3010 Calculated C 64.89; H 7.12; N 5.82 % (721.86) Found C 65.04; H 7.09; N 5.81 % (4) C37H47N3012 Calculated C 61.23; H 6.53; N 5.79 % (725.80) Found C 60.93, H 6.88; N 5.45 % (6) C39H51N3012 Calculated C 62.14; H 6.82; N 5.57 % (753.85) Found C 61.89; H 7.04; N 5.37 % (8) C43H59N3012 Calculated C 63.77; H 7.34; N 5.19 % (809.96) Found C 63.60; H 7.37; N 5. 13 % (9) C39H51N3013 Calculated C 60.85; H 6.68; N 5.46 % (769.85) Found C 60.58; H 6.79; N 5.15 % (10) C41H55N3014 Calculated C 60.51; H 6.8 1; N 5.16 % (813.90) Found C 60.30; H 6.78; N 5.65 % (11) C43H59N3014 Calculated C 61.34; H 7.06; N 4.99 % (841.96) Found C 60.82; H 7.13; N 4.72 % (12) C47H67N3014 Calculated C 62.86; H 7.52; N 4.68 % (898.07) Found C 63.02; H 7.64; N 4.43 % (13) C-nH127N3032 Calculated C 57.56; H 7.97; N 2.62 % (1606.87) Found C 56.87; H 8.25; N 2.33 % (15) C43H55N3014 Calculated C 61.64; H 6.62; N 5.01 % (837.93) Found C 61.35; H 6.69; N 4.99 % (16) C43H55N3010 Calculated C 66.73; H 7.16; N 5.43 % (773.93) Found C 66.67; H 7.20; N 5.24 % (17) C81H135N3036 Calculated C 56.33; H 7.88; N 2.43 % (1726.97) Found C 55.64; H 8.03; N 2.12 % (18) C42H57N3015 Calculated C 59.78; H 6.8 1; N 4.98 % (843.93) Found C 59.73; H 6.89; N 5.05 % (19) C48H69N3015 Calculated C 62.12; H 7.49; N 4.53 % (928.10) Found C 62.13; H 7.49; N 4.53 % (20) C4SH63N3018 Calculated C 57.87; H 6.80; N 4.50 % (934.01) Found C 57.93; H 6.79; N 4.44 % Table 2:
Comp. Formula (MW) (21) C48H69N3018 Calculated C 59.07; H 7.13; N 4.30 % (976.09) Found C 58.88; H 7.07; N 4.29 % (23) C54H8IN3018 Calculated C 61.17; H 7.70; N 3.96 % (1060.26) Found C 60.95; H 7.63; N 4.00 % (24) C48H69N3019-5 Calculated C 57.65; H 6.95; N 4.20 % (1000.09) Found C 57.55; H 6.82; N 4.24 % (25) C51H75N3021 Calculated C 57.45; H 7.09; N 3.94 % (1066.17) Found C 57.17; H 7.16; N 3.75 % (26) C6A3N3021 Calculated C 60.44; H 7.86; N 3.52 % (1192.42) Found C 60.38; H 7.87; N 3.62 % (27) C105H1S3N3048 Calculated C 55.91; H 8.18; N 1.86 % (2255.62) Found C 54.84; H 8.38; N 1.37 % (28) C4SHS7N3018 Calculated C 58.25; H 6.19; N 4.53 % (927.97) Found C 58.13; H 6.21; N 4.33 % (29) C51H69N3021 Calculated C 57.78; H 6.56; N 3.96 % (1060.12) Found C 57.49; H 6.84; N 3.28 % ExaTRIe 3: The novel UY absorbers are incorporated with stirring into a water-borne varnish of the following composition:
Bayhydrol@ VP LS 2986 E (45 72.0 Cymel@ 327 (90 %)2) 15.4 Butyl diglycol 10.44 Fluorad(D FC 170 (100 % in water)3) 0.72 Lanco-Thix PUR 214) 0.72 Byk 301 0.72 100.0 Acrylate resin (Bayer, D) 2) Melamine resin (American Cyanamid, USA) 3) Wetting agent (3M, D) 4) Thickener (Langer & Co., D) 5) Flow-control agent (Byk-Chemie, D) The varnish prepared in this way is thinned with water to a spraying consistency and applied to a prepared substrate (coil-coated aluminium sheet, automotive filler, water-borne silver-metallic base coat).
The coating is dried for about 20 minutes at room temperature, and for 20 minutes at 7WC and then baked for 20 minutes at 1.40'C, giving a dry film thickness of about 35-40 gm.
The comparison used is a varnish produced in the same way but containing no UV absorber.
The samples are weathered in a Xenon-weatherometerO unit (Atlas Corp.) (cycle: CAM 180) The gloss (DIN 67530) and cracking (TNO scale) are measured.
Table 3:
stabilization 20 gloss after-hours 0 400 800 1200 unstabilized 90 33 28 10 1.5 % of compound (4) 92 88 83 76 1.5 % of compound (11) 88 82 77 72 1.5 % of compound (12) 92 88 83 76 1.5 % of compound (21) 92 90 88 83 1.5 % of compound (25) 91 85 78 73 1.5 % of compound (26)l 86 82 73 70 % based on the solids content The stabilized formulations exhibit better gloss retention and less cracking than the comparison example which shows cracking after 1200 hours.
Example 4: The novel UY absorbers are pre-dissolved in about 5-10 g of xylene and incorporated into a varnish of the following composition:
Uracron@ 2263 XB (50 %)') 54.5 Cymel@ 327 (90 %)2) 16.3 Butyl glycol acetate 5.5 Xylene 19.4 n-Butanol 3.3 Baysilon(g)A (1 % in xylene)3) 1 100.0 1) Acrylate resin (DSM, NL) 2) Melamine resin (American Cyanamid, USA) 3) Flow-control agent (Bayer, D) The varnish prepared in this way is thinned to a spraying consistency using butyl glycol acetateln-butanollxylene (116113) and applied to a prepared substrate (coil-coated aluminium sheet, automotive filler, silver-metallic base coat). After a drying time of about 15 minutes, the coating is baked at OWC for 30 minutes, giving a dry film thickness of about 40-45 gm.
The comparison used is a varnish produced in the same way but containing no UY absorber.
The samples are weathered in a UWON0 unit (Atlas Corp.) (UVB-313 lamps; cycle: 8 h UV, 70'C; 4 h cond., SO'C).
The 20' gloss (DIN 67530) is measured. The stabilized samples exhibit better gloss retention than the unstabilized comparison sample.
The results are shown in Table 4.
Table 4: -
Stabilization 20 gloss after hours UWON0 0 800.1200 1600 2000 Unstabilized 87 55 15 1.5 % of compound (1) 88 74 80 79 51 1.5 % of compound (17) 87 71 73 52 39 1.5 % of compound (1) 87 84 84 85 83 0.7 % of Tinuvin 292 1.5 % of compound (17) 87 83 79 83 82 0.7 % of Tinuvin 292 % based on the solids content of the varnish sterically hindered amine (Ciba-Geigy, CH) Example 5: Gelatine layers of the following. composition (per m2) are applied to a polyester support:
Component Amount Gelatine 1200 mg Hardening material 40 mg Dispersant 100 mg Compound of the formula (1) 400 mg The hardening material is 2-hydroxy-4,6-dichloro-1,3,5-triazine. The dispersant is sodium-4,8-diisobutyl-naphthalene-2-sulfonate.
The prepared coatings are dried and hardened at 20C for 7 days.
When compounds (1), (15) or (17) are used, clear transparent photographic layers are obtained.
Example 6: Preparation of 2-phenyl-4,6-bis[2-hydroxy-4{(methoxytriethoxycarbonyl)-2-ethoxy}phenyll1,3,5-triazine [Compound (14)l A mixture of 10.0 g (17 mmol) of 2-phenyl-4,6-bis[2-hydroxy-4(ethoxycarbonyl)2-ethoxy)phenyl] - 1,3,5-triazine, 18.1 g (110 mmol) triethylene glycol monomethyl ether and 0.4 g (1.6 mmol) of dibutyltin oxide are kept at 120 'C for 16 hours, during which ethanol is removed using a I-Eckmann condenser. The mixture is evaporated on a Rotavapor and transferred to a silica gel column (0=6 em, h=35 em; silica gel 60, 230400 mesh) and eluted with ethyl acetate. Removal of the solvent (150'C10. 1 mm) from the main fraction gives 11.8 g (84 % yield) of the compound of formula OH N N OH (14), N RO& OR where R = CH(CH3)-C(O)0-(CH2CH20)3-CH3, as a viscous, pale yellow oil.
Elemental analysis:C41H.51N3014 Calculated: C 60.8 1; H 6.35; N 5. 19 % Found: C 60.75; H 6.36; N 5.03 % WHAT IS CLARVW IS:
1. A compound of the formula R4 R3 R2 OH N N OH RIO OR, in which the radicals R,, independently of one another, are -(CH2CERS-0),,7RS, -CI12-CH(OH)-CH2- 0-(CH2CHRS-0),7RS, -(CH2)rCHR6-C(O)-0-(CH2CHRS-0),,7R8 Or -CI12-CH(CH2- OR7)-O-C(O)-(C112CHRS-0)n-R8; R2 is a OH, Cl-C12alkyl, F or Cl; R3 is H, OR9, Cl-C12alkyl, F or Cl; R4 is H, OR9, Cl-C12aRVI, F, Cl or, if R2 is OH, is alternatively OR,; R,5 is H or CH3; R6 is H or Cl-CMalkyl; R7 is Cl-C14alkyl or phenyl; R8 is H, Cl-C14alkyl, phenyl or Cl-C4alkylphenyl; R9 is Cl-C4alkyl; 1 is a number from 0 to 16 and n is a number from 1 to 16.
2. A compound according to claim 1, wherein, in the formula (1), the radicals R,, indeendently of one another, are -(CH2CHRS-0)n7R8, CHrCH(OH)-CH270-(CH2C]HRS-0)n7R8, -(C112)1-CHR6-C(O)-0-(CH2CHRS-0)n7R8 Or -CH2-CH(C112-OR7)-O-C(O)-(CH2CHR:5-0)n7R8; R2 is H, OH, Cl- - C8alkyl, F or Cl; R3 is H, OR9, Cl-C8alkyl, F or Cl; R4 is H, OR9, Cl-C8alkyl, F, Cl or, if R2 is OH, is alternatively OR,; R5 is H; R6 is H or Cl-C12alkyl; R7 is Cl-C8alkyl; R8 is H or Cl-Cloalkyl; Rg.is Cl-C4alkyl; 1 is a number from 0 to 12, and n is a number from 1 to 12.
3. A compound according to claim 1, wherein, in the formula (1), the radicals R,, independently of one another, are -CH2-CH(OH)-CH2-0-(CH2CHRS0),i-R8 or -(CH2)1-CHR6-C(O)-0-(CH2CHRS-0)n-R8; R2 is H, OH or Cl-C4alkyl; R3 is H, OR9 or Cl-C4alkyl; R4 is H, OR9, Cl-C4alkyl, F, Cl or, if R2 is OH, is alternatively OR,; RS is H; R6 is Cl-C6alkyl; R8 is Cl-C4alkyl; R9 is Cl-C4alkyl; 1 is 0, and n is a number from 1 to 12.
4. A photographic material containing a compound of the formula (I) as defined in any one of claims 1 to 3. 5. A photographic material according to claim 4, comprising, on a support, a blue-sensitive, a green-sensitive andlor a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, where a layer containing a UV absorber is arranged above the uppermost silver-halide emulsion layer, wherein the UV absorber conforms to the formula (I).
6. A photographic material according to claim 4, comprising, on a support, a blue-sensitive, a green-sensitive andlor a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, in which a layer containing a UV absorber of the formula (I) is arranged between the greensensitive and the red-sensitive silver-halide emulsion layers, where a further layer containing a UV absorber of the formula (I) may be arranged above the uppermost silver-halide emulsion layer.
7. A photographic material according to claim 4, comprising, on a support, a 0 blue-sensitive, a green-sensitive andlor a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, where a layer containing a UV absorber of the formula (I) is arranged above the uppermost silver-halide emulsion layer or where a layer containing a UY absorber of the formula (I) is arranged between the green-sensitive and the red-sensitive silver-halide emulsion layers, wherein a UY absorber of the formula (I) is additionally present in the red-sensitive silverhalide emulsion layer.
8. A photographic material according to claim 4, comprising, on a support, a blue-sensitive, a green-sensitive andlor a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, wherein a cyan coupler of the formula (E-7) Z3;:%p, 1 NHCOZ2 lkl-l Z1COHN andlor of the formula OH cl WCOZ5 (E-8) 7# 6 in which Z1 is alkyl or aryl, 7,2 is alkyl, cycloalkyl, aryl, a heterocyclic group or a ballast group, 2 is hydrogen or halogen, Z1 and 2 together can form a ring, and Z4 is hydrogen or a leaving group, and Z5 is- a ballast group, Z6 is hydrogen or a leaving group, and 2 is alkyl, is present in the red-sensitive silver-halide emulsion layer.
9. A photographic material according to claim 4, comprising, on a support, a blue-sensitive, a green-sensitive andlor a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, wherein a magenta coupler of the formula R, (M-7) N N\ _Z in which R, is hydrogen or a substituent, Z represents the non-metallic atoms necessary to complete a 5-membered ring containing 2 or 3 nitrogen atoms, it being possible for this ring to be substituted, and Q is hydrogen or a leaving group, is present in the green-sensitive silver- halide emulsion layer.
10. A photographic material according to claim 4, comprising, on a support, a blue-sensitive, a green-sensitive andlor a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, wherein a magenta coupler of the formula cl 0, NH--o 0, N R20 cl cl in which R20 is hydrogen, alkyl, acylamino, carbamoyl, sulfarnoyl, sulfonarnido, alkoxycarbonyl, acyloxy or a urethane group, and Q' is a leaving group, is present in the green-sensitive silver-halide emulsion layer.
11. A stabilized ink-jet printing, ink, comprising an effective amount of a compound of the fonnula(I) as defined in any one of claims 1 to 3.
12. A recording material for ink-iet printing, which contains at least one compound of the formula(I) as defined in any one of claims 1 to 3.
13. A stabilized organic material comprising a compound of the formula (I) as defined in any one of claims 1 to 3.
14. A stabilized organic material according to claim 13, which is a surface coating.
15. A stabilized organic material according to claim 13, which is an automotive paint.
16. A stabilized organic material according to claim 13, which contains, in addition to a compound of the formula (I), a sterically hindered amine.
17. A stabilized organic material according to claim 13, which contains, in addition to a compound of the formula (1), a sterically hindered amine andlor a further UV absorber from the series consisting of hydroxyphenylbenzotdazoles, hydroxyphenylb--nzophenones, oxanilides and further hydroxyphenyl-s-triazines.
18. A compound according to claim 1 substantially as hereinbefore described with reference to any one of the foregoing Examples.
Z
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US5556973A (en) * 1994-07-27 1996-09-17 Ciba-Geigy Corporation Red-shifted tris-aryl-s-triazines and compositions stabilized therewith
US5637706A (en) * 1994-07-27 1997-06-10 Ciba-Geigy Corporation Compositions stabilized with red-shifted tris-aryl-s-triazines
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US5668200A (en) * 1995-01-18 1997-09-16 Ciba-Geigy Corporation Stabilizer combination
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US6841670B2 (en) 1995-03-15 2005-01-11 Ciba Specialty Chemicals Corporation Biphenyl-substituted triazines
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WO1998003489A1 (en) * 1996-07-18 1998-01-29 Ciba Specialty Chemicals Holding Inc. Polyoxyalkene substituted and bridged triazine, benzotriazole and benzophenone derivatives as uv absorbers
EP1266889A2 (en) * 1996-07-18 2002-12-18 Ciba SC Holding AG Polyoxyalkylene substituted and bridged triazine and benzotriazole derivatives
US6653484B2 (en) 1996-07-18 2003-11-25 Ciba Specialty Chemicals Corporation Polyoxyalkylene substituted and bridged benzotriazole derivatives
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US5962452A (en) * 1997-05-16 1999-10-05 Ciba Specialty Chemicals Corporation Resorcinyl-triazines
US6913712B2 (en) 1999-12-23 2005-07-05 Ciba Specialty Chemicals Corp. Stabilizer mixture

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ITMI932530A0 (en) 1993-12-02
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JPH06211813A (en) 1994-08-02
ITMI932530A1 (en) 1995-06-02
DE4340725B4 (en) 2005-11-24
NL9302097A (en) 1994-07-01
GB9324687D0 (en) 1994-01-19
BE1006797A5 (en) 1994-12-13
FR2698870A1 (en) 1994-06-10

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