Login| Sign Up| Help| Contact|

Patent Searching and Data


Title:
COLOUR-PHOTOGRAPHIC RECORDING MATERIAL
Document Type and Number:
WIPO Patent Application WO/1995/022082
Kind Code:
A1
Abstract:
The invention relates to a colour-photographic recording material which comprises a magenta coupler and, as stabilizer, at least one compound of formula (Ia), (Ib) or (II), where the radicals are as defined in claim 1, and to the novel stabilizers.

Inventors:
JEGANATHAN SURULIAPPA (CH)
Application Number:
PCT/EP1995/000347
Publication Date:
August 17, 1995
Filing Date:
February 01, 1995
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
CIBA GEIGY AG (CH)
JEGANATHAN SURULIAPPA (CH)
International Classes:
C07D273/01; C07D291/02; C07D295/08; C07D295/096; C07F5/02; C07F7/08; C07F9/6584; G03C7/30; G03C7/392; G03C7/388; (IPC1-7): G03C7/392; C07D295/096; C07F5/02; C07F9/6584
Foreign References:
EP0273712A21988-07-06
Other References:
PATENT ABSTRACTS OF JAPAN vol. 13, no. 149 (P - 855)<3497> 12 April 1989 (1989-04-12)
B.K. WASSON ET AL.: "Bêta-Adrenergic Blocking Agents. 3-(3-Substituted-amino-2-hydroxypropoxy)-4-substituted-1,2,5-thiadiazoles", JOURNAL OF MEDICINAL CHEMISTRY, vol. 15, no. 6, pages 651 - 655
Download PDF:
Claims:
WHAT IS CLAIMED IS:
1. A colourphotographic recording material which comprises a magenta coupler and, as stabilizer, at least one compound of the formula where k is the number 0 or 1; p is a number from 1 to 18; Ri is hydrogen, CrC12alkyl, CrC12alkoxy, COR ,, COOR10 or Si(Rπ)(R12)(R13); in which R9 is CrC8alkyl, C^alkenyl or phenyl; R10 is CrC4alkyl or benzyl; and Rn, R12 and R13, independently of one another, are C1C6alkyl or phenyl; R2 is hydrogen, CrC18alkyl, OR14 or (CH2)nCOOR15; in which n is a number from 0 to 17; RJ4 is hydrogen, CrC18alkyl, C2C18alkenyl, phenylCrC4alkyl, C3C24alkyl which is interrupted by one or more O atoms, C2C14hydroxyalkyl, phenyl, which may be monosubstituted to trisubstituted by C1C4alkyl, CrC4alkoxy or halogen, or is tolyl, C5C6cycloalkyl or COR16; R15 is CjC18alkyl, C2C18alkenyl or phenyl, which may be monosubstituted to trisubstituted by C]C4alkyl, C C alkoxy or halogen; in which R16 is C C18alkyl, C2C18alkenyl or phenyl; R3, R4, R5 and R6, independently of one another, are hydrogen, CrC1 alkyl, CrC8alkoxy, C5C7cycloalkyl, phenyl, phenylCrC alkyl or halogen; R7 is hydrogen, CιC18alkyl, C2Cι alkenyl, phenylCrC4alkyl, C3C24alkyl, which is interrupted by one or more O atoms, phenyl Qalkyl, phenyl, which may be monosubstituted to trisubstituted by C C4alkyl, CrC4alkoxy or halogen, or is benzyl, a group of the formula CH2COOR23 or (CH2COO)kCH2CH(OR1)CH2R17; in which k is the number 0 or 1; m is a number from 1 to 17; R17 is as defined for R2 or is a group of the formula and RΏ is CrC8alkyl; R8 is hydrogen, CrC18alkyl or CH2R2; OO R__4 is Si(Rπ)(Ri2)(Ri3) or a group of the formu in which q is a number from 0 to 12; Rj5 is hydrogen or Cr8alkyl; X_ is O, S, SO, SO2 or NR18; in which R18 is hydrogen, CrC18alkyl, CH2CH(OH)CH2O(CrC14alkyl) or COR19; in which R19 is C^C^alkyl; and X2 is CO, BR20, PR2ι, P(O)R22, SO or SO2; in which R20, R2ι and R^ are C1C18alkyl or phenyl, which may be monosubstituted to trisubstituted by C C4alkyl, Cj alkoxy or halogen; and R2ι and R^ may alternatively be phenoxy, which may be monosubstituted to trisubstituted by Cj alkyl, CjQalkoxy or halogen; where, in the case of compounds of the formula (la) R2 may alternatively be a group of the formula .
2. A colourphotographic recording material according to claim 1, which comprises, as stabilizer, at least one compound of the formula (la), (lb) or (II), where k is the number 0 or 1; p is a number from 2 to 12; Rj is hydrogen; R2 is CrC18alkyl or OR14; in which R14 is hydrogen, CrC18alkyl, C2C18alkenyl, C3C24alkyl which is interrupted by one or more O atoms, phenyl, which may be monosubstituted to trisubstituted by alkyl or C C4alkoxy, or is tolyl or C5C6cycloalkyl; R3, R4, R5 and R6, independently of one another, are hydrogen, CrC12alkyl or CιC8 alkoxy; R7 is CjC salkyl, C2C18alkenyl, a group of the formula CH2COOR2J or (CH2COO)kCH2CH(OR1)CΗ2R17; in which k is the number 0 or 1; m is a number from 1 to 17; R17 is as defined for R2 or is a group of the formula 0(CH2COO) CH2CH(OR1)CH20(CH2) — and R^ is CrC8alkyl; R8 is hydrogen, CrC8alkyl or CH2R2; OO in which q is a number from 0 to 6; Rπ, R12 and R13, independently of one another, are C1C6alkyl or phenyl; and R25 is hydrogen or CrC18alkyl; X! is O, S, SO, SO2 or NR18; in which R18 is CH2CH(OH)CH2O(CrC14alkyl); and X2 is CO, BR20, PR2ι or P(O)R22; in which R20, R2 and R22 are phenyl, which may be monosubstituted to trisubstituted by C C alkyl or alkoxy; and R2 and R^ may alternatively be phenoxy, which may be monosubstituted to trisubstituted by CιC alkyl or C1C4alkoxy; where, in the case of compounds of the formula (la), R2 may alternatively be a group of the formula 0(CH2COO) CH2CH(OR1)CH20(CH2) _ .
3. A colourphotographic recording material according to claim 1, which contains further organic stabilizers, UV absorbers, optical brighteners, light stabilizers, colour cast inhibitors and/or plasticizers.
4. A colourphotographic recording material according to claim 3, which comprises, as further organic stabilizers, a compound of the formula P in which Rj and R2, independently of one another, are hydrogen, acyl or alkyl; Ra, Rb and Rc, independently of one another, are H, alkyl, cycloalkyl, aryl, halogen, alkoxy, aroxy, acyloxy, alkylthio, arylthio, acyl, sulfonyl, sulfamoyl, acylamino, sulfonylamino or nitro; A is a bond, S =£ O] m f alkylene or NR^, Rd is alkyl or acyl; and m is 0, 1 or 2; or a compound of the formula S A in which R1 is hydrogen; R2 is phenyl or Rx and R2 are methyl; q is 0, 1 or 2; and X is a divalent radical which supplements the ring of the formula S A to form a tetrahydrothiopyran ring; or a compound of the formula SB R3S(CpH2p)ZR4 in which R3 is alkyl, aryl or a (CpH2p)ZR4 group; p is 112; Z is COO or OCO; and R is a univalent, divalent, trivalent or tetravalent group; or a compound of the formula HQ in which Re and Rd, independently of one another, are alkyl or cycloalkyl; and Rf and Rg, independently of one another, are as defined for Ra, Rb and Rc; or a compound of the formula RE in which Rjand R„., independently of one another, are H, acyl or alkyl; or Rj and ^ are bonded together to a POaryl radical; and Rh, R;, RJ and Rk, independently of one another, are as defined for Ra, Rb and R<., with the proviso that at least one of the radicals R_ and Rj is not alkyl.
5. A compound of the formula where k is the number 0 or 1; p is a number from 1 to 18; Rj is hydrogen, CrC12alkyl, CrC12alkoxy, COR9, COOR10 or Si(R„)(R12)(Rι3); in which R9 is C C8alkyl, C2C 8alkenyl or phenyl; Rio is C C alkyl or benzyl; and Rn, R12 and Rι3, independently of one another, are CiCgalkyl or phenyl; R2 is hydrogen, CrC18alkyl, ORι4 or (CH^CCOR^; in which n is a number from 0 to 17; R1 is hydrogen, CιC18alkyl, C2C18alkenyl, phenylCrC4alkyl, C3C2 alkyl which is interrupted by one or more O atoms, C^C^hydroxyalkyl, phenyl, which may be monosubstituted to trisubstituted by CιC alkyl, alkoxy or halogen, or is tolyl, C5C6cycloalkyl or COR16; R 5 is C1C18alkyl, C_2C18alkenyl or phenyl, which may be monosubstituted to trisubstituted by alkyl, Ci alkoxy or halogen; in which R16 is or phenyl; R3, R4, R5 and Rg, independently of one another, are hydrogen, CiC^alkyl, Cι~C8alkoxy, C5C cycloalkyl, phenyl, phenylCιC alkyl or halogen; R7 is hydrogen, CrC18alkyl, C Cι8alkenyl, phenylCrC4alkyl, C3C24alkyl, which is interrupted by one or more O atoms, phenylCιC alkyl, phenyl, which may be monosubstituted to trisubstituted by CrC alkyl, CrC alkoxy or halogen, or is benzyl, a group of the formula CH2COOR23 or (CH2COO)kCH2CH(OR1)CH2R17; in which k is the number 0 or 1; m is a number from 1 to 17; R 7 is as defined for R2 or is a group of the formula 0(CH2COO) CH2CH(OR1)CH20(CH2) ; and R^ is CrC8alkyl; R8 is hydrogen, CrC 8alkyl or CH2R2; Ru is Si(Rn)(Ri2)(Rι3) or a group of the formula OO in which q is a number from 0 to 12; R25 is hydrogen or CιCι8alkyl; Xj is O, S, SO, SO2 or NRι8; in which RJ8 is hydrogen, C C18alkyl, CH2CH(OH)CH2O(CιC14alkyl) or COR19; in which R19 is C18alkyl; and X2 is CO, BR20, PR21 P(O)R22 SO or SO2; in which R2o_ R2ι and R^ are CιCι8alkyl or phenyl, which may be monosubstituted to trisubstituted by CιC alkyl, CιC4alkoxy or halogen; and R2ι and R^ may alternatively be phenoxy, which may be monosubstituted to trisubstituted by CιC4alkyl, CιC alkoxy or halogen; where, in the case of compounds of the formula (la) R2 may alternatively be a group of the formula .
6. A compound according to claim 5, where k is the number 0 or 1; p is a number from 2 to 12; R! is hydrogen; R2 is Cr8alkyl or OR14; in which RM is hydrogen, Cr8alkyl, C28alkenyl, C3C2 alkyl which is interrupted by one or more O atoms, phenyl, which may be monosubstituted to trisubstituted by CrC alkyl or CrC4alkoxy, or is tolyl or C5C6cycloalkyl; R3, R4, R5 and R6, independently of one another, are hydrogen, CiC^alkyl or CrC8alkoxy; R7 is C C 8alkyl, C28alkenyl, a group of the formula CH2COOR23 or (CH2COO)kCH2CH(OR1)CH2R17; in which k is the number 0 or 1; m is a number from 1 to 17; R 7 is as defined for R2 or is a group of the formula 0(CH2COO) CH2CH(OR1)CH20(CH2) — and R23 is CrC8alkyl; R8 is hydrogen, CrC8alkyl or CH2R2; R24 is Si(Rn)(R12)(R13) or a group of the formula 00' in which q is a number from 0 to 6; Rn, R12 and Ri3, independently of one another, are CιC6alkyl or phenyl; and R25 is hydrogen or C Cι8alkyl; Xi is O, S, SO, SO2 or NRι8; in which R18 is CH2CH(OH)CH2O(CιCι4alkyl); and X2 is CO, BR20, PR21 or P(O)R22; in which R2o, R21 and Rg are phenyl, which may be monosubstituted to trisubstituted by CιC alkyl or C C4alkoxy; and R2ι and R^ may alternatively be phenoxy, which may be monosubstituted to trisubstituted by CιC4alkyl or CιC4alkoxy; where, in the case of compounds of the formula (la), R2 may alternatively be a group of the formula .
7. A compound according to claim 5, where k is the number 0; p is a number from 2 to 12; Ri is hydrogen; R2 is ORι4; in which RJ4 is CiCgalkyl, C3C24alkyl which is interrupted by one or more O atoms, or phenyl; R3, R , R5 and Rg are hydrogen; R7 is CrC18alkyl or (CH2COO)kCH2CH(ORι)CH2R17; in which k is the number 0; and R17 is as defined for R2; R8 is hydrogen or CH2R2; R24 is a group of the formula (CH2) COO in which q is a number from 0 to 6; and R25 is hydrogen or Cr8alkyl; Xi is O or SO2; and X2 is P(O)R22; in which RM is phenyl or phenoxy.
8. A compound according to claim 5, of the formula (ja) or where k is the number 0; Ri is hydrogen; in which R1 is CιCι alkyl or phenyl; R3, R4, R5 and R6 are hydrogen; R7 is CrC18alkyl; R8 is hydrogen or CH2R2; Xi is O or SO2; and X2 is P(O)R22; in which R^ is phenyl or phenoxy.
9. A process for stabilizing magenta couplers and/or magenta dyes in colourphotographic materials, in which a stabilizer according to claim 1 is incorporated into the material.
10. The use of a compound according to claim 1 for stabilizing magenta couplers and/or magenta dyes in colourphotographic materials.
Description:
Colour-photographic recording material

The present invention relates to a novel colour-photographic recording material which contains a magenta coupler and, as stabilizer, an N-heterocyclylphenyl compound, and to novel N-heterocyclylphenyl compounds.

The alkylated hydroquinone ethers or diethers used hitherto as stabilizers in photographic materials exhibited inadequate activity, in particular in the case of lH-pyrazolo-[5,l-c][l,2,4]triazole magenta couplers (see also structure C-5).

A group of N-heterocyclylphenyl compounds has now been found which, surprisingly, has proved substantially free from such disadvantages. In addition, they are also suitable as coupler oils and thus facilitate a simplified incorporation of the couplers. In particular, this group of N-heterocyclylphenyl compounds is suitable for increasing the stability of magenta dyes in colour-photographic materials.

The novel stabilizers can be used for all types of photosensitive materials. 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, etc. They are preferably used, inter alia, for photosensitive colour material which contains a reversal substrate or forms positives.

Colour-photographic recording materials usually contain, on a support, a blue-sensitive and/or a green-sensitive and/or a red-sensitive silver-halide emulsion layer and, if desired, a protection layer, the stabilizer for the magenta dye being in the green-sensitive layer.

The present application thus relates to a colour-photographic recording material which contains a magenta coupler and, as stabilizer, at least one compound of the formula

0(CH 2 COO) CHj-CI-KOF-ψCHsF.a (fe),

where k is the number 0 or 1; p is a number from 1 to 18;

R ! is hydrogen, C r C 12 alkyl, C r C 12 alkoxy, -COR 9 , -COOR 10 or -Si(R n )(R 12 )(R 13 ); in which R 9 is C j .-Cgalkyl, or phenyl;

RJO is C 1 -C alkyl or benzyl; and

R π , R 12 and R 13 , independently of one another, are C j -Cβalkyl or phenyl; R 2 is hydrogen, C r C 18 alkyl, -OR 14 or -(CH 2 ) n COOR 15 ; in which n is a number from 0 to 17;

R 14 is hydrogen, C r C 18 alkyl, C 2 -C 18 alkenyl, phenyl-C 1 -C alkyl, C 3 -C 24 alkyl which is interrupted by one or more -O- atoms, C 2 -C 14 hydroxyalkyl, phenyl, which may be monosubstituted to trisubstituted by C 1 -C alkoxy or halogen, or is tolyl,

C 5 -C 6 cycloalkyl or -COR 16 ;

Ris is C 1 -C 1 galkyl, or phenyl, which may be monosubstituted to trisubstituted by C r C alkyl, C 1 -C 4 alkoxy or halogen; in which R 16 is Cj-Cjgalkyl, C 2 -C 1 galkenyl or phenyl; R 3 , R 4 , R 5 and R 6 , independently of one another, are hydrogen, -C^alkyl, C j -Cgalkoxy, C 5 -C 7 cycloalkyl, phenyl, phenyl-C 1 -C 4 alkyl or halogen;

R 7 is hydrogen, C j -Ci alkyl, C^-Cxgalkenyl, phenyl-Cj- alkyl, C3-C 24 alkyl, which is interrupted by one or more -O- atoms, phenyl-C 1 -C 4 alkyl, phenyl, which may be monosubstituted to trisubstituted by C-,-C 4 alkyl, Cj-C 4 alkoxy or halogen, or is benzyl, a group of the formula

-CH 2 COOR 23 or -(CH 2 COO) k CH 2 CH(OR 1 )CH 2 R 17 ; in which k is the number 0 or 1; m is a number from 1 to 17; R 17 is as defined for R or is a group of the formula

0(CH 2 COO) CH 2 CH(OR 1 )CH 2 0(CH 2 ) —

aanndd

R 23 i iss CC rr CC 88 aallkkyyll;; R 8 is hydrogen, C 1 -C 18 alkyl l o < r CH 2 R 2 ;

R 24 is -Si(R n )(R 12 )(Ri 3 ) or a group of the formula

in which q is a number from 0 to 12; and

R 25 is hydrogen or C 1 -C 18 alkyl; X j is O, S, SO, SO 2 or NR 18 ; in which R 18 is hydrogen, C r C 18 alkyl, -CH 2 CH(OH)CH 2 O(C 1 -C 14 alkyl) or

-CO-R 19 ; in which R 1 is -C j galkyl; and X 2 is CO, BR 2 o_ PR 2 ι» P(0)R 22 , SO or SO 2 ; in which R 20 , R 2 ι and R 22 are -Cigalkyl or phenyl, which may be monosubstituted

to trisubstituted by C r C 4 alkyl, C r C 4 alkoxy or halogen; and

R 21 and R 22 may alternatively be phenoxy, which may be monosubstituted to trisubstituted by C r C 4 alkyl, C C 4 alkoxy or halogen;

where, in the case of compounds of the formula (la) R 2 may alternatively be a group of the formula

0(CH 2 COO) CH 2 CH(OR 1 )CH 2 0(CH 2 ) -

Any -C^alkyl substituents in the compounds according to the invention are radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl, and corresponding branched isomers.

C 5 -C 7 cycloalkyl radicals are, for example, cyclopentyl, cyclohexyl or cycloheptyl.

Alkyl radicals having 3 to 24 carbon atoms which are interrupted by oxygen are, for example, -(CH 2 CH 2 Oi 1 ^ r CH 3 ^ -(CT 2 CH 2 O- πr CH 2 CH 3 .

Alkenyl radicals having 2 to 18 carbon atoms may be monounsaturated or, from 4 carbon atoms, polyunsaturated, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl or radicals derived from the above alkyl radicals.

C r C 1 alkoxy radicals are, for example, methoxy, ethoxy, propoxy, butoxy or hexoxy and corresponding branched isomers.

Phenyl-C 1 -C 4 alkyl radicals are, for example, benzyl or cumyl.

C 2 -Cι 4 hydroxyalkyl radicals are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Halogen radicals are, for example, fluorine, chlorine, bromine or iodine. Preferably, halogen is chlorine.

Preferably, Rj is hydrogen.

Preferably, R 2 is C-i- galkyl or -OR 14 ; in which R 14 is hydrogen, C r C 18 alkyl, C 3 -C 2 alkych is interrupted by one or more -O- atoms, phenyl, which may be monosubstituted to trisubstituted by C C 4 alkyl or C 1 -C 4 alkoxy, or is tolyl or Cs- cycloalkyl; and, in the case of compounds of the formula (la), may alternatively be a group of the formula

Preferably, R 3 , R , R 5 and R 6 , independently of one another, are hydrogen, or Cj-Csalkoxy; and most preferably R 3 , R , R 5 and R 6 are hydrogen. Preferably, R 7 is Cx-C^aU yl, C 2 -C 18 alkenyl, a group of the formula

-CH 2 COOR 2 3 or -(CH 2 COO) k CH 2 CH(OR 1 )CH 2 Ri7; in which k is the number 0 or 1; m is a number from 1 to 17; R 17 is as defined for R or is a group of the formula

0(CH 2 COO) CH 2 CH(OR 1 )CH 2 0(CH 2 ) —

and

R 23 is C r C 8 alkyl. Preferably, R 8 is hydrogen, -Cgalkyl or CH 2 R 2 . Preferably, R 24 is -Si(Rn)(Rι 2 )(Ri 3 ) or a group of the formula

in which q is a number from 0 to 6;

Rn, Ri 2 and R i3 , independently of one another, are C C 6 alkyl or phenyl; and

R 25 is hydrogen or Cj-Cigalkyl. Preferably, Xi is O, S, SO, SO 2 or NR j g; in which R 18 is -CH 2 CH(OH)CH 2 O(C r 4 alkyl); and most preferably Xi is O or SO 2 . Preferably, X 2 is CO, BR 20 , PR 21 or P(O)R 22 ; in which R o, R 21 and R 22 re phenyl, which may be monosubstituted to trisubstituted by C^ alkyl, or C -C 4 alkoxy; and

R 2 ι and R 22 may alternatively be phenoxy, which may be monosubstituted to trisubstituted by Ci- alkyl or - alkoxy; and most preferably X 2 is P(O)R 22 in which R 22 is phenyl or phenoxy.

Preference is given to compounds of the formulae (la), (lb) or (II), where k is the number 0 or 1; p is a number from 2 to 12;

Ri is hydrogen;

R 2 is Cι-C 18 alkyl or -OR J4 ; in which R 14 is hydrogen, Ci-Ci alkyl, C^-C^alkenyl, C 3 -C alkyl which is interrupted by one or more -O- atoms, phenyl, which may be monosubstituted to trisubstituted by Cι-C alkyl or - alkoxy, or is tolyl or

R 3 , R , R 5 and R 6 , independently of one another, are hydrogen, C r Ci alkyl or

C C 8 alkoxy;

R 7 is C r 8 alkyl, C 2 -C 8 alkenyl, a group of the formula

-CH 2 COOR 23 or -(CH 2 COO) k CH 2 CH(ORi)CH 2 Ri 7 ; in which k is the number 0 or 1; m is a number from 1 to 17; . R is as defined for R 2 or is a group of the formula

0(CH 2 COO) CH 2 CH(OR- j )CH 2 0(CH 2 ) —

and

R- 23 is C r C 8 alkyl; R 8 is hydrogen, C r C 8 alkyl or CH 2 R 2 ;

(HgCJgC,

R 24 is -Si(Rn)(Ri 2 )(Ri 3 ) or a group of the formula H0 ) * CH 2> co °-

in which q is a number from 0 to 6;

Rn, R i2 and R 13 , independently of one another, are Ci- alkyl or phenyl; and

R 25 is hydrogen or Ci-Cigalkyl; X x is O, S, SO, SO 2 or NRι 8 ; in which R 18 is -CH 2 CH(OH)CH 2 O(C r 4 alkyl); and X 2 is CO, BR 20 , PR 21 or P(O)R 22 ; in which R 2 o, R 21 and R 2 2 are phenyl, which may be monosubstituted to trisubstituted by Cι-C 4 alkyl or C C 4 alkoxy; and

R 2 ι and R 22 may alternatively be phenoxy, which may be monosubstituted to trisubstituted by C r C 4 alkyl or Cι-C alkoxy;

where, in the case of compounds of the formula (la), R 2 may alternatively be a group of the formula

Particular preference is given to compounds of the formulae (la), (lb) and (II) which have a melting point of below 60°C or are liquid at room temperature. These compounds can be employed as photographic oil or partly replace the photographic oil.

Of particular importance are compounds of the formula (la), (lb) or (II), where k is the number 0; p is a number from 2 to 12;

Ri is hydrogen;

R 2 is -OR M ; in which R J4 is C -C 18 alkyl, C 3 -C 24 alkyl which is interrupted by one or more -O- atoms, or phenyl; R 3 , R , R 5 and R 6 are hydrogen; R 7 is C r 8 alkyl or -(CH 2 COO) k CH 2 CH(ORι)CH 2 Ri 7 ; in which k is the number 0; and

Ri 7 is as defined for R 2 ; R 8 is hydrogen or CH 2 R 2 ;

R 24 is a group of the formula OO-

in which q is a number from 0 to 6; and R- 25 is hydrogen or Cι-Cι 8 alkyl; Xi is O or SO 2 ; and

x 2 is P(O)R 22 ; in which R 22 is phenyl or phenoxy.

Very particular preference is given to compounds of the formula (la) or (II), where k is the number 0;

R ! is hydrogen;

R 2 is -OR 14 ; in which R w is Cι-Cι alkyl or phenyl; R 3 , R 4 , R 5 and R 6 are hydrogen; R 7 is C 1 -C lg alkyl; Rg is hydrogen or CH 2 R 2 ; Xi is O or SO 2 ; and X 2 is P(O)R 22 ; in which R 22 is phenyl or phenoxy.

The novel material preferably contains gelatin interlayers between the silver-halide emulsion layers.

Preference is given to photographic materials of this type in which the silver-hahde in the blue-sensitive and/or green-sensitive and/or red-sensitive layer is silver chloride bromide comprising at least 90 mol % of silver chloride.

Preference is furthermore given to photographic materials which contain the silver-halide emulsion layers in the sequence blue-sensitive, green-sensitive and red-sensitive layers.

Typical and prefeired stabilizers according to the invention are the following:

(100) OCH 2 CH(OH)CH 2 OC 8 H 17

(103) °2 S OCH 2 CH(OH)CH 2 OC 13 H 27 (i)

(104) O 2 S N OCH 2 CH(OH)CH 2 OC(CH 3 ) 3

(105) O 2 S N (* — OCH 2 CH(OH)CH 2 OC 8 H 17 (i)

(106) °2 S N — OCH 2 CH(OH)CH 2 OC 9 H 19

(108) 0 2 S N ft OCH 2 CH(OH)CH 2 OC 12 H 25 (i)

(109) ° 2 S N OCH 2 CH(OH)CH 2 OC 12 H 25 /C 13 H 27 /C 14 H

(110) ° 2 S N y OCH 2 CH(OH)CH 2 OC 6 H 5

(111) ° 2 S N OCH 2 CH(OH)CH 2 OCOC(CH 3 ) 2 C 6 H 13

(112)

In the above compounds, "Ph" is a phenyl radical and "C 12 H 25 /C 13 H 27 /C 14 H 29 *" stands for a mixture of dodecyl, tridecyl and tetradecyl radicals..

In general, the novel stabilizers are used in from 0.1 to 4 times, preferably from 0.2 to 2 times, the amount by weight relative to the colour coupler used together with them.

The magenta couplers in the colour-photographic recording material can be, for example, simple l-aryl-5-pyrazolones or pyrazole derivatives which are fused to 5-membered heterocyclic rings, eg. imidazopyrazoles, pyrazolopyrazoles, pyrazolotriazoles or pyrazolotetrazoles.

A group of magenta couplers comprises 5-pyrazolones of the formula C

as described in British Patent 2003 473. In this formula, R !6 is hydrogen, alkyl, aryl, alkenyl or a heterocyclic group. R is hydrogen, alkyl, aryl, a heterocyclic group, an ester group, an alkoxy group, an alkylthio group, a carboxyl group, an arylamino group, an acylamino group, a (thio)urea group, a (thio)carbamoyl group, a guanidino group or a sulfonamido group.

R i7 is preferably a " R ιβ - ~ v y R2 ° group, in which R J8 is imino, acylamino or

R 19 ureido, R 1 9 is hydrogen, halogen, alkyl or alkoxy, R 2 o is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group.

If Q' is hydrogen, the magenta coupler is tetraequivalent with respect to the silver halide.

Preferred examples of magenta couplers of this type are compounds of the formula

in which R 2 o is as defined 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 tetraequivalent magenta couplers of this type are given in US-A 2983 608, 3 061 432, 3 062 653, 3 127 269, 3 152 896, 3 311 476, 3 419 391, 3 519429, 3 558 319, 3 582 322, 3 615 506, 3 684514, 3 834908, 3 888 680, 3 891 445, 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 O, S or N. Diequivalent couplers of this type give greater colour density and are more reactive towards the oxidized developer than are the corresponding tetraequivalent magenta couplers.

Examples of diequivalent magenta couplers are described in US-A 3 006 579, 3 419 391, 3 311 476, 3 432 521, 3 214437, 4 032 346, 3 701 783, 4 351 897, 3 227 554, in

EP-A 133 503, DE-A 2944601, JP-A 78/34044, 74/53 435, 74/53 436, 75/53 372 and 75/122 935.

Typical and preferred magenta couplers conform to the formulae:

It is possible for 2 pyrazolone rings to be linked via a divalent Q', giving so-called bis-couplers. These are described, for example, in US-A 2 632702, US-A 2 618 864, GB-A 968461, GB-A 786 859, JP-A 76/37 646, 59/4086, 69/16 110, 69/26589, 74/37 854 and 74/29 638. Y is preferably an O-alkoxyarylthio group.

As mentioned above, the magenta couplers used can also be pyrazoles fused to 5-membered heterocyclic rings, known as pyrazoloazoles. Their advantages over simple pyrazoles are that they give dyes of greater formalin resistance and have purer absorption spectra.

Magenta couplers of the pyrazoloazole type, which are likewise preferred, may be represented by the formula

in which R t 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 compounds, preference is given to magenta couplers of the formulae

(C-3) (C-4) (C-5)

(C-6)

Rn, R i2 and Rι 3 , independently of one another, are, for example, hydrogen, halogen, -CR 3 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, sulfonyl, alkoxycarbonyl, heterocyclyloxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, imido, heterocyclylthio, sulfinyl, phosphonyl, aryloxycarbonyl, acyl or azolyl, preferably hydrogen, halogen (for example chlorine or bromine), -CR 3 in which the radicals R 3 , 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)dodecan- amido)phenyl)propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3-(2,4-di-t-amyl- phenoxy)propyl; aryl (for example phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl or 4-tetra- decanamidophenyl); heterocyclyl (for example 2-furyl, 2-thienyl, 2-pyrimidinyl or 2-benzothiazolyl); cyano; hydroxyl, nitro; carboxyl; amino; alkoxy (for example methoxy, ethoxy, 2-methoxyethoxy; 2-dodecylethoxy, 2-methanesulfonylethoxy); aryloxy (for example phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxy- carbamoylphenoxy or 3-methoxycarbamoyl); acylamino (for example acetamido, benzamido, tetradecanamido, 2-(2,4-di-t-amylphenoxy)butanamido, 4-(3-t-butyl- 4-hydroxyphenoxy)butanamido, 2-(4-(4-hydroxyphenylsulfonyl)phenoxy)decanamido or methylbutylamino); anilino (for example phenylamino, 2-chloroanilino, 2-chloro-5- tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylaniUno, N-acetylanilino, 2-chloro-5-(alpha-(3-t-butyl-4-hydroxyphenoxy)dodecanamidoan ilino); ureido (for

example phenylureido, methylureido or N,N-dibutylureido); sulfamoylamino (for example N,N-dipropylsulfamoylamino or N-methyl-N-decylsulfamoylamino); alkylthio (for example methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio or 3-(4-t-butylphenoxy)propylthio); arylthio (for example phenylthio, 2-butoxy-5-t-octyl- phenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio or 4-tetradecanamido- phenylthio); alkoxycarbonylamino ' (for example methoxycarbonylamino or tetradecyl- oxycarbonylamino); sulfonamido (for example methanesulfonamido, hexadecanesulfon- amido, benzenesulfonamido, p-toluenesulfonamido, octadecanesulfonamido or 2-meth- oxy-5-t-butylbenzenesulfonamido); carbamoyl (for example N-ethylcarbamoyl, N,N-di- butylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl or N-(3-(2,4-di-t-amylphenoxy)propyl)carbamoyl); sulfamoyl (for example N-ethyl- sulfamoyl, N,N-dipropylsulfamoyl, 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 l-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 trimethyl- silyloxy or dibutylmethylsilyloxy); aryloxycarbonylamino (for example phenoxy- carbonylamino); imido (for example N-succinimido, N-phthalimido or 3-octadecenyl- succinimido); heterocyclylthio (for example 2-benzothiazolylthio, 2,4-diphenyloxy- l,3,5-triazole-6-thio or 2-pyridylthio); sulfinyl (for example dodecanesulfinyl, 3-pentadecylphenylsulfinyl or 3-phenoxypropylsulfinyl); phosphonyl (for example phenoxyphosphonyl, octyloxyphosphonyl or phenylphosphonyl); aryloxycarbonyl (for example phenoxycarbonyl); acyl (for example acetyl, 3-phenylpropanoyl, benzoyl or 4-dodecyloxybenzoyl); or azolyl (for example imidazolyl, pyrazolyl or 3-chloro- pyrazol-1-yl).

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

Preferred groups Rn are alkyl, aryl, alkoxy, aryloxy, alkylthio, ureido, urethane and acylamino groups.

R 12 may be as defined for Rn and is preferably hydrogen, alkyl, aryl, a heterocyclic ring, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acyl or cyano.

Ri 3 may be as defined for R and is preferably hydrogen, alkyl, aryl, a heterocyclic ring, alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl, carbamoyl or acyl, in particular alkyl, aryl, a heterocyclic ring, alkylthio or arylthio.

Q is hydrogen or a leaving group, such as halogen, alkoxy, aryloxy, acyloxy, alkyl- or arylsulfonyloxy, acylamino, alkyl- or arylsulfonamido, alkoxycarbonyloxy, aryloxy- carbonyloxy, alkyl-, aryl- or heterocyclyl-S-carbamoylamino, a 5- or 6-membered, nitrogen-containing heterocyclic radical, imido or arylazo. These groups may be further substituted as indicated for Rn.

Q is preferably halogen (for example fluorine, chlorine or bromine); alkoxy (for example ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropoxy, methylsulfonyl- ethoxy or ethoxycarbonylmethoxy); aryloxy (for example 4-methylphenoxy, 4-chloro- phenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy or 2-carboxyphenoxy); acyloxy (for example acetoxy, tetradecanoyloxy or benzoyloxy); alkyl- or arylsulfonyloxy (for example methane- sulfonyloxy or toluenesulfonyloxy); acylamino (for example dichloroacetylamino or heptafluorobutyrylamino); alkyl- or arylsulfonamido (for example methanesulfonamido, trifluoromethanesulfonamido or p-toluenesulfonamido); alkoxycarbonyloxy (for example ethoxycarbonyloxy or benzyloxycarbonyloxy); aryloxycarbonyloxy (for example phenoxycarbonyloxy); alkyl-, aryl- or heterocyclyl-S- (for example dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio or tetrazolylthio); carbamoylamino (for example N-methylcarbamoylamino or N-phenylcarbamoylamino); a 5- or 6-membered, nitrogen-containing ring (for example imidazolyl, pyrazolyl, triazolyl, tetrazolyl or l,2-dihydro-2-oxo-l-pyridyl); imido (for example succinimido or hydantoinyl); or arylazo (for example phenylazo or 4-methoxyphenylazo).

Q may alternatively form corresponding bis-compounds by condensation of 4 equivalents of coupler with an aldehyde or ketone. Furthermore, Q may contain photographically active groups, such as development inhibitors or development accelerators. Q is preferably halogen, alkoxy, aryloxy, alkyl- or 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 JP-A 85/33 552; pyrazolopyrazoles in JP-A 85/43 695; pyrazoloimidazoles in JP-A 85/35 732, JP-A 86/18 949 and US-A 4500 630; pyrazolotriazoles in JP-A 85/186567, JP-A 86/47957, JP-A 85/215 687,

JP-A 85/197 688, JP-A 85/172982, EP-A 119 860, EP-A 173 256, EP-A 178 789, EP-A 178 788 and in Research Disclosure 84/24624.

Further pyrazoloazole magenta couplers are described in: JP-A 86/28 947,

JP-A 85/140241, JP-A 85/262 160, JP-A 85/213 937, JP-A 87/278 552,

JP-A 87/279 340, JP-A 88/100457, EP-A 177765, EP-A 176804, EP-A 170 164, EP-A

164 130, EP-A 178 794, DE-A 3 516996, DE-A 3 508 766 and Research Disclosure 81/20

919, 84/24531 and 85/25758.

Examples of suitable couplers of this type are:

CH 2 -CH 2 -CH 2 -S0 2 -C- | 2 H 2 5

C 10 H 21

CsH d)

2 S0 2 C. j8 Hg

CH 3

CH, H NH-CO

Cς 5H π 11 (t)

15cH π ;31

(i)C 3

CH,

Yellow couplers which can be used in the material according to the invention are preferably compounds of the formula A

R r CO-CH-CO-NHR 2 (A),

in which R j is alkyl or aryl, R 2 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 the compounds of the formula A in which R ! is t-butyl and R 2 is a group of the formula

in which R 3 is hydrogen, halogen, alkyl or alkoxy, and R 4 , R 5 and R 6 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, carbamoyl, sulfonyl, sulfamoyl, alkylsulfonamido, acylamino, ureido or amino.

Preferably, R 3 is chlorine, R and R 5 are hydrogen and R 6 is an acylamino group. This group also includes the compounds of the formula

in which x is 0-4, R 7 is hydrogen or alkyl, and R 8 and R 9 are alkyl.

Another group of yellow couplers conforms to the formula B

in which R 10 is hydrogen, halogen or alkoxy, Rn, R^ and R 13 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, carbamoyl, sulfonyl, sulfamoyl,

sulfonamido, acylamino, ureido or amino, and Rj and Q are as defined above.

This group includes compounds of the formula B in which R^ is t-butyl, RJO is chlorine, R n and R 13 are hydrogen, and R 12 is alkoxycarbonyl.

In the compounds of the formulae A and B, leaving group Q may be hydrogen or a heterocyclic group

in which R 1 is a divalent organic group which supplements the ring to make up a 4-7-membered ring, or Q is an -OR 15 group in which R 15 is alkyl, aryl, acyl or a heterocyclic radical.

Typical examples of customary yellow couplers are the compounds of the formulae below:

a) Q = SO, OCH jj CgHc

O

d) Q = - ..A. N.

COOCH3

(CH 3 ) 3 C-CO-CH-CONH

Furtherexamples ofyellowcouplers aregiveninUS-A 2407210, 2778658, 2875057,

2908513, 2908573, 3227155, 3227550, 3253924, 3265506, 3277155, 3408194,

3341331, 3369895, 3384657, 3415652, 3447928, 3551155, 3582322, 3725072, 3891445, 3933501, 4115121,4401752and4022620,inDE-A 1547868, 2057941,

2 162 899, 2 163 813, 2 213 461, 2 219917, 2 261 361, 2 261 362, 2 263 875, 2 329 587, 2 414006 and 2 422 812, in GB-A 1 425 020 and 1 077 874 and in JP-A 88/123 047 and in EP-A 447 969.

Typical and preferred yellow couplers conform to the formulae:

H 2 S0 2 C 12 H 25

Cyan couplers may be, for example, derivatives of phenol, of 1-naphthol or of pyrazoloquinazolone. Preference is given to structures of the formula E

in which R 2 ι, R 2 - -^ 23 an( * *^ 24 are hydrogen, halogen, alkyl, carbamoyl, amino, sulfonamido, phosphoramido or ureido. R 2 ι is preferably H or Cl, R 22 is preferably an alkyl or amino group. R 23 is preferably an amino group and R 24 is preferably hydrogen. Q" is hydrogen or a leaving group which is eliminated during the reaction with the oxidized developer. A detailed list of cyan couplers is given in US-A 4 456 681.

Fuπher examples of cyan couplers are given in the following: US-A 2 369929, 2423730,

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, 3 227 550, 3 253 294, 3 311 476, 3 386 301,

3 419 390, 3 458 315, 3 476560, 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 652286, 3 737 326, 3 758 308, 3 839 044, 3 880 661, 4

004 929, 4 124 396, 4 333 999, 4463 086, 4456 681, 4 873 183 and 4923 791 and in EP-A 354549 and EP-A 398 664.

The red-sensitive silver-halide emulsion layer of the material according to the invention preferably contains a cyan coupler of the formula

and/or of the formula

in which Z-, is alkyl or aryl, Z 2 is alkyl, cycloalkyl, aryl, a heterocyclic group or a ballast group, Z 3 is hydrogen or halogen, Zj and Z 3 together can form a ring, and Z 4 is hydrogen or a leaving group, and Z 5 is a ballast group, Z 6 is hydrogen or a leaving group and Z 7 is alkyl.

Examples of customary cyan couplers are the following:

(E-3)

(E-8) t-C, : H 11

The colour developers usually used for colour-photographic materials are p-dialkylaminoanilines. Examples of these are 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-hydroxyethyl- aniline, 3-methyl-4-amino-N-ethyl-N-α-methanesulfonamidoethylaniline , 3-methyl- 4-amino-N-ethyl-N-α-methoxyethylaniline, 3-α-methanesulfonamidoethyl-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-aminoanilin e, and the salts of these compounds, for example sulfates, hydrochlorides or toluene- sulfonates.

The compounds of the formulae (la), (lb) and (II) according to the invention, the magenta couplers and other colour couplers can be incorporated into the colour-photographic material in a known manner, for example into silver-halide emulsions which contain gelatin and/or other binders. They are used, for example, in silver-bromide, silver-chloride or silver-iodide emulsions or in emulsions which contain mixtures of silver halides, such as silver bromide/iodide or silver-chloride/bromide emulsions.

The compounds of the formulae (la), (lb) and (II) according to the invention can be incorporated into the colour-photographic material together with the magenta coupler and if desired further additives by predissolving them in high-boiling organic solvents. Preference is given to solvents which boil higher than 160°C. Typical examples of these solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or 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, and amides, for example dimethylformamide. If the additives are themselves liquid, they can also be incorporated into the photographic material without the assistance of solvents.

The compounds according to the invention may if desired be dispersed in the gelatin layer as oil.

Further details on high-boiling solvents which can be used are given in the publications below:

Phosphates: GB-A 791 219, BE-A 755 248, JP-A 76/76739, 78/27 449, 78/218 252,

78/97 573, 79/148 133, 82/216 177, 82/93 323 and 83/216 177 and EP-A 265 296.

Phthalates: GB-A 791 219, JP-A 77/98 050, 82/93 322, 82/216 176, 82/218 251,

83/24 321, 83/45 699 and 84/79 888.

Amides: GB-A 791 129, JP-A 76/105 043, 77/13 600, 77/61 089, 84/189 556, 87/239 149,

EP-A 270341 and WO 88/00723.

Phenols: GB-A 820 329, FR-A 1 220 657, JP-A 69/69946, 70/3818, 75/123 026,

75/82 078, 78/17 914, 78/21 166, 82/212 114 and 83/45 699.

Other oxygen-containing compounds: US-A 3 748 141, 3 779765, JP-A 73 75 126, 74/101 114, 74/10 115, 75/101 625, 76/76740, 77/61 089, EP-A 304 810 and BE-A 826 039.

Other compounds: JP-A 72/115 369, 72/130 258, 73/127 521, 73/76 592, 77/13 193, 77/36 294, 79/95 233, 91/2748, 83/105 147 and Research Disclosure 82/21 918.

The amount of high-boiling solvent is, for example, in the range from 50 mg to 2 g per m 2 of base, preferably from 200 mg to 1 g per m 2 .

The photographic layers may furthermore contain colour cast inhibitors. These prevent colour casts being formed, due, for example, to reaction of the coupler with unintentionally oxidized developer or with by-products of the colour-formation process. Colour cast inhibitors of this type are usually hydroquinine derivatives, but may also be derivatives of aminophenols, of gallic acid or of ascorbic acid. Typical examples of these inhibitors are given in the publications below: US-A 2 360290, 2 336 327, 2403 721, 2 418 613, 2 675 314, 2701 197, 2704713, 2728 659, 2732300, 2735 365; EP-A 124 877, EP-A 277 589, EP-A 338 785; JP-A 75/92 988, 75/92989, 75/93 928, 75/110 337, 84/5247 and 77/146235.

Photographic layers may also contain DIR couplers (DIR denotes Development Inhibition Release), which forni colourless compounds with the oxidized developer. They are added to improve the sharpness and grain of the colour prints.

The photographic layers in the material according to the invention may also contain UV absorbers. These filter out the UV light and thus protect the dyes, the couplers and other components against photodegradation. Examples of such UV absorbers are 2-(2-hydroxyphenyl)benzotriazoles, 2-hydroxyphenyl-l ,3,5-triazines,

2-hydroxybenzophenones, salicylic acid esters, acrylonitrile derivatives or thiazolines. UV absorbers of this type are described in greater detail, for example, in the following publications: US-A 3 314794, 3 352681, 3705 805, 3 707 375, 4045 229, 3 700455, 3 533 794, 3 698 907, 3705 805, 3738 837 and JP-A 71/2784. Preferred UV absorbers are the 2-(2-*hydroxyphenyl)benzotriazoles (HBTs) of the formula

in which T ls T 2 and T 3 , independently of one another, are hydrogen, halogen, alkyl, alkyl which is substituted by a carboxylate group, alkoxy, aryloxy, hydroxyl or acyloxy, and T is hydrogen, alkoxy, aryloxy or acyloxy.

Particular preference is given to HBT compounds which are liquid at room temperature.

Examples of preferred HBT compounds are:

HBT No.

HBT-1 H CH 3 H HBT-2 H C(CH 3 ) 3 H HBT-3 C(CH 3 ) 3 CH 3 Cl HBT-4 C(CH 3 ) 3 C(CH 3 ) 3 Cl HBT-5 C(CH 3 ) 2 C 2 H 5 C(CH 3 ) 2 C 2 H 5 H HBT-6 CH(CH 3 )C 2 H 5 C(CH 3 ) 3 H

HBT-7 C(CH 3 ) 2 - C(CH 3 ) 2 -^> H

HBT-8 C(CH 3 ) 3 CH 2 CH 2 COOC 8 H 17 Cl

(isomers)

HBT-9 C(CH 3 ) 3 CH 2 CH 2 COOC 8 H 17 H

(isomers)

HBT- 10 C 12 H 2 5 (isomers)* CH 3 H

* Principal product

Other preferred UV absorbers are 2-hydroxyphenyl-l,3,5-triazines of the formula

in which R x is a group of the formula , where R 4 , R 5 and R 5 ,

independently of one another, are hydrogen, Cι-C 12 alkyl or halogen, or R j is a group of

the formula , and

R 2 , R 3 and R 7 , independently of one another, are monovalent organic radicals. R , R 3 and R 7 are preferably, independently of one another, a radical CH 2 CH(OR 8 )CH 2 OR9, where R 8 is hydrogen or acetyl, and R 9 is -C-^alkyl.

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 light-sensitive layer (colour layer) or in an intermediate layer, alone or together with other additives. Such compounds are described in greater detail, for example, in the publications below: US-A 3 700455, 3 591 381, 3 573 052, 4030 931, 4 174 220, 4 178 184, 4 228 235, 4 279990, 4 346 165, 4 366226, 4447 523, 4 528 264, 4 581 326, 4 562 146, 4 559 297, GB-A 1 309 277, 1 547 302, 2023 862, 2 135 788, 2 139 370, 2 156 091;

DE-A 2 301 060, 2 347 708, 2 526468, 2 621 203, 3 323 448; DD-A 200 691, 214 468; EP-A 106799, 113 124, 125 522, 159 912, 161 577, 164 030, 167 762, 176 845, 246766, 320 776; JP-A 74/134 326, 76/127 730, 76/30462, 77/3822, 77/154 632, 78/10 842, 79/48 535, 79/70 830, 79/73 032, 79/147 038, 79/154 325, 79/155 836, 82/142 638, 83/224 353, 84/5246, 84/72443, 84/87 456, 84/192 246, 84/192 247, 84/204 039, 84/204040, 84/212 837, 84/220733, 84/222 836, 84/228 249, 86/2540, 86/8843, 86/18 835, 86/18 836, 87/11 456, 87/42 245, 87/62 157, 86/6652, 89/137 258 and in Research Disclosure 79/17 804.

The photographic layers may also contain certain phosphorus(III) compounds, in particular phosphites and phosphonites. These act 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. Phosphorus(III) compounds of this type are described in greater detail, for example, in the publications below: US-A 4407 935, US-A 4436 811, US-A 4 956406, EP-A 181 289, JP-A 73/32728, JP-A 76/1420 and JP-A 55/66741.

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 publications below: US-A 4050938, 4 239 843, 4 241 154, 4 242429, 4 241 155, 4 242430, 4273 854, 4 246 329, 4 271 253, 4 242431, 4248 949, 4 245 195, 4 268 605, 4 246330, 4 269 926, 4 245 018, 4 301 223, 4 343 886, 4 346 165, 4 590 153; JP-A 81/167 138, 81/168 652, 82/30 834, 82/161 744; EP-A 137 271, 161 577, 185 506; DE-A 2 853 865.

The photographic layers may also contain hydroquinone compounds. These act as light stabilizers for the colour couplers and for the colour images and as scavengers of oxidized developer in the intermediate layers. They are used in particular in the magenta layer. Hydroquinone compounds of this type and combinations thereof with other additives are described in greater detail, for example, in the publications below: US-A 2 360 290, 2 336 327, 2403 721, 2 418 613, 2 675 314, 2 701 197, 2 710 801, 2 732 300, 2728 659,

2 735 765, 2704713, 2 937 086, 2 816028, 3 582333, 3 637 393, 3 700453, 3 960570,

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, 4429 031, 4 346 165, 4 360 589, 4 346 167, 4 385 111,

4 416978, 4430425, 4 277 558, 4489 155, 4 504 572, 4 559 297, FR-A 885 982; GB-A 891 158, 1 156 167, 1 363 921, 2022 274, 2066 975, 2071 348, 2 081 463,

2 117 526, 2 156091; DE-A 2408 168, 2726 283, 2 639 930, 2901 520, 3 308 766,

3 320483, 3 323 699; DD-A 216 476, 214468, 214469, EP-A 84 290, 110 214, 115 305, 124 915, 124 877, 144 288, 147 747, 178 165, 161 577; JP-A 75/33 733, 75/21 249, 77/128 130, 77/146 234, 79/70036, 79/133 131, 81/83 742, 81/87 040, 81/109 345, 83/134 628, 82/22 237, 82/112749, 83/17 431, 83/21 249, 84/75 249, 84/149 348, 84/182 785, 84/180 557, 84/189 342, 84/228 249, 84/101 650, 79/24 019, 79/25 823, 86/48 856, 86/48 857, 86/27 539, 86/6652, 86 72 040, 87/11 455, 87/62 157, and in Research Disclosure 79/17 901, 79/17 905, 79/18 813, 83/22 827 and 84/24014.

The photographic layers may also contain further derivatives of hydroquinone ethers. These compounds act 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 publications below: US-A 3 285 937, 3 432 300, 3 519429, 3 476772, 3 591 381, 3 573 052, 3 574 627, 3 573 050, 3 698 909,

3 764337, 3 930 866, 4 113488, 4015 990, 4 113495, 4 120723, 4 155765, 4 159910,

4 178 184, 4 138 259, 4.174220, 4 148 656, 4207 111, 4254216, 4 134011, 4273 864, 4264720, 4279990, 4332 886, 4436 165, 4360589, 4416978, 4 385 111, 4459015, 4 559297, 4 631 252, 4 616082; GB-A 1 347 556, 1 366441, 1 547 392, 1 557 237,

2 135788; DE-A 3 214567, 4008 785, 4 012305; DD-214469, EP-A 161 577, 167 762, 164 130, 176 845; JP-A 76/123 642, 77/35 633, 77/147 433, 78/126, 78/10 430, 78/53 321, 79/24019, 7925 823, 79/48 537, 79/44521, 79/56 833, 79/70036, 79/70 830, 79/73 032, 79/95 233, 79/145 530, 80/21 004, 80/50 244, 80/52057, 80/70 840, 80/139 383, 81/30 125, 81/151 936, 82/34552, 82/68 833, 82/204306, 82/204037, 83/134634, 83/207 039, 84/60 434, 84/101 650, 84/87450, 84/149 348, 84/182785, 86/72040, 87/11 455, 87/62 157, 87/63 149, 86/2151, 86/6652, 86/48 855, 89/309 058 and in Research Disclosure 78/17 051.

Preferred costabilizers are those of the formulae P, S A, SB, HQ and RE below.

Compounds of the formula P

in which

R_ and R , independently of one another, are hydrogen, acyl or alkyl;

R a , R b and R c , independently of one another, are H, alkyl, cycloalkyl, aryl, halogen, alkoxy, aroxy, acyloxy, alkylthio, arylthio, acyl, sulfonyl, sulfamoyl, acylamino, sulfonylamino or nitro;

A is a bond, S =£ O] m , alkylene or -NR d -;

R d is alkyl or acyl; and m is 0, 1 or 2.

Examples of compounds of the formula P are:

3 H 7 _C-0 fl P _ 0 -C-C 3 H 7 P10

Compounds of the formula SA

in which R j is hydrogen; R 2 is phenyl or R] and R are methyl; q is 0, 1 or 2; and

X is a divalent radical which supplements the ring of the formula SA to form a tetrahydrothiopyran ring.

Examples of compounds of the formula S A are those given in US 4 993 271 and

Compounds of the formula SB

R 3 -S-(C p H 2p )-Z-R

in which

R 3 is alkyl, aryl or a (C p H 2p )-Z-R 4 group; p is 1-12;

Z is -CO-O- or -O-CO-; and

R 4 is a univalent, divalent, trivalent or tetravalent group.

Examples of compounds of the formula SB are:

C 12 H 25 -S-CH 2 CH 2 CO-O-C 4 H 9 SB 1 S(CH 2 CH 2 CO-OC 4 H 9 ) 2 SB 2

Compounds of the formula HQ

in which

R e and R < j, independently of one another, are alkyl or cycloalkyl; and

R f and R g , independently of one another, are as defined for R a , R b and R c

Examples of compounds of the formula HQ are:

[-C 8 H 17 -t= -C(CH 3 ) 2 CH 2 C(CH 3 ) 3 ]

Compounds of the formula RE

in which

Rjand R^, independently of one another, are H, acyl or alkyl; or R_ and R m are bonded together to a P-O-aryl radical; and

R h , R;, R j and R k , independently of one another, are as defined for R a , R b and R < ., with the proviso that at least one of the radicals R_ and R: is not alkyl.

Examples of compounds of the formula RE are:

Silver-halide emulsions which can be used are conventional silver-chloride, silver-bromide or silver-iodide emulsions or mixtures thereof, such as silver-chlorobromide and silver-chloroiodide emulsions, in which the silver halides may have any known crystal form. The use of silver-chloride emulsions is particularly important in the material according to the invention. 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 materials according to the invention. The same applies to the bases 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. For this purpose, it is possible to use cyanine pigments, merocyanine pigments, holopolar pigments, hemicyanine pigments, styryl pigments or hemioxanol pigments.

The photographic layers may furthermore contain conventional plasticizers, such as glycerol. The emulsions may also be cured by means of curing agents which are customary for gelatin. Finally, the emulsions may also contain customary coating auxiliaries.

The present invention thus furthermore relates to colour-photographic recording materials according to claim 1, which contain further organic stabilizers, UV absorbers, optical brighteners, light stabilizers, colour cast inhibitors and/or plasticizers.

The present invention also relates to compounds of the formula

where k is the number 0 or 1; p is a number from 1 to 18;

Rj is hydrogen, C r C 12 alkyl, C r C 12 alkoxy, -COR 9 , -COOR 10 or -Si(R n )(R 12 )(R 13 ); in which R 9 is Cj-Csalkyl, C -C 18 alkenyl or phenyl;

R 10 is C 1 -C 4 alkyl or benzyl; and

R π , R 12 and R 13 , independently of one another, are -Cgalkyl or phenyl; R 2 is hydrogen, C r C 18 alkyl, -OR 14 or -(CH 2 ) n COOR 15 ; in which n is a number from 0 to 17;

R 14 is hydrogen, C r C 18 alkyl, C 2 -C 18 alkenyl, phenyl-C r C 4 alkyl, C 3 -C 24 alkyl which is interrupted by one or more -O- atoms, C 2 -C 1 hydroxyalkyl, phenyl, which may be monosubstituted to trisubstituted by C r C 4 alkyl, C 1 -C 4 alkoxy or halogen, or is tolyl,

C 5 -C 6 cycloalkyl or -COR 16 ;

R 15 is C r C 18 alkyl, C 2 -C 1 galkenyl or phenyl, which may be monosubstituted to trisubstitut by C r C alkyl, C r C 4 alkoxy or halogen; in which R^ is Cx-C^alkyl, C^-C j galkenyl or phenyl; R 3 , R 4 , R 5 and R 6 , independently of one another, are hydrogen, C r C 12 alkyl, C r C 8 alkoxy,

C 5 -C 7 cycloalkyl, phenyl, phenyl-C r C 4 alkyl or halogen;

R 7 is hydrogen, C r C 18 alkyl, C 2 -C 18 alkenyl, phenyl-C r C 4 alkyl, C 3 -C 24 alkyl, which is interrupted by one or more -O- atoms, phenyl- - alkyl, phenyl, which may be monosubstituted to trisubstituted by C r C alkyl, C r C 4 alkoxy or halogen, or is benzyl, a group of the formula

-CH 2 COOR 23 or -(CH 2 COO) k CH 2 CH(OR 1 )CH 2 R 17 ; in which k is the number 0 or 1; m is a number from 1 to 17; R 17 is as defined for R 2 or is a group of the formula

and

R 23 is C r C 8 alkyl; R 8 is hydrogen, C r C 18 alkyl or CH 2 R 2 ;

R 2 is -Si(R n )(R 12 )(R 13 ) or a group of the formula OO-

in which q is a number from 0 to 12; R 25 is hydrogen or C r 8 alkyl;

X- is O, S, SO, SO 2 or NR 18 ; in which R l8 is hydrogen, C r C 18 alkyl, -CH 2 CH(OH)CH 2 O(C r C 14 alkyl) or

-CO-R 19 ; in which R 19 is C r C 18 alkyl; and X 2 is CO, BR 20 , PR 21 - P(0)R 22 - SO or SO 2 ; in which R o, R 21 and R 22 arc or phenyl, which may be monosubstituted to trisubstituted by C C alkyl, C j - alkoxy or halogen; and

R 2 ι and R 22 may alternatively be phenoxy, which may be monosubstituted to trisubstituted by C C 4 alkyl, C r C 4 alkoxy or halogen;

where, in the case of compounds of the formula (la) R 2 may alternatively be a group of the formula

Preference is given to compounds of the formulae (la), (lb) or (II), where k is the number 0 or 1; p is a number from 2 to 12;

Rj is hydrogen;

R 2 is C j -C 18 alkyl or -OR 14 ; in which R 14 is hydrogen, C r C 18 alkyl, C 2 -C 18 alkenyl, C 3 -C 4 alkyl which is interrupted by one or more -O- atoms, phenyl, which may be monosubstituted to trisubstituted by C -C 4 alkyl or Cj-C alkoxy, or is tolyl or C 5 -C 6 cycloalkyl;

R 3 , R , R 5 and R 6 , independently of one another, are hydrogen, C j -C 12 alkyl or

Cj-C 8 alkoxy;

R 7 is C j -C 18 alkyl, C 2 -C 18 alkenyl, a group of the formula

-CH 2 COOR 23 or -(CH 2 COO) k CH 2 CH(OR 1 )CH 2 R 17 ; in which k is the number 0 or 1; m is a number from 1 to 17; R 17 is as defined for R 2 or is a group of the formula

0(CH 2 COO) CH 2 CH(OR 1 )CH 2 0(CH 2 ) —

and

R 23 is C r C 8 alkyl; R 8 is hydrogen, Cj-Csalkyl or CH R 2 ;

R 24 is -Si(Ru)(Ri 2 )(Ri 3 ) or a group of the formula OO-

in which q is a number from 0 to 6;

R π , R 12 and R 13 , independently of one another, are C 1 -C 6 alkyl or phenyl; and

R 25 is hydrogen or Cj-C 18 alkyl; X_ is O, S, SO 2 or NR 18 ; in which R 18 is -CH 2 CH(OH)CH 2 O(C r C 14 alkyl); and X 2 is CO, BR 20 . PR 21 or P(O)R 22 ; in which R 2 o_ 21 and R 22 are phenyl, which may be monosubstituted to trisubstituted by C r C alkyl, or - alkoxy; and

R 21 and R 22 may alternatively be phenoxy, which may be monosubstituted to trisubstituted by C r C 4 alkyl or C j - alkoxy;

where, in the case of compounds of the formula (la), R 2 may alternatively be a group of the formula

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

The novel compounds can be prepared by methods known per se, for example by reacting a compound of the formula

o / \

H 2 C - CH-CH 2 OR 14 _ w here X 3 is O or SO 2 and the radicals R 3 , R 4 , R 5 , R 6 and R 14 are as defined in claim 1.

Novel compounds in which Rj is not hydrogen can be prepared by further reaction with an acylating agent or silylating agent.

Compounds of the formula II can be prepared, for example, by reacting a compound of the formula

which is then reacted with R 22 P(O)Cl 2 , giving

R 22 (0)P , where the substituents are as defined in

claim 1.

The dimeric compounds of the formula (la) or (II) can be prepared, for example, by reacting a compound of the formula (1°) or the analogous compound (11°) with a

O O bisglycidyl compound of the formula H 2 C - CH-CH 2 -(CH 2 V * CH 2 -CH — CH 2

The examples below illustrate the invention in greater detail. In the examples and in the remainder of the description, parts are parts by weight, percentages are percent by weight and " " is a tert-butyl radical [an analogous situation also applies to the other alkyl radicals], unless otherwise stated.

Example 1 : Preparation of l-morpholino-4-[2'hydroxy-3'-(2"ethylhexyloxy)]propyloxy- phenyl

A mixture of 3 g (16.8 mmol) of 4-morpholinophenol, 3.75 g (20 mmol) of 2-ethylhexyl glycidyl ether and 124 mg (0.33 mmol) of ethyltriphenylphosphonium bromide is heated at 130°C for 4 hours under nitrogen. The crude product is chromatographed over silica gel

(ethyl acetate/hexane 6:4), giving 4.7 g (76 %) of the compound as a colourless oil

(m.p. <30°C).

Elemental analysis:C 2 ιH 35 NO 4 Calculated: C 69.01; H 9.65; N 3.83 %

Found: C 68.79; H 9.79; N 3.89 %

Example 2. Preparation of l-(2-dodecyloxy-tetradecyloxy)-3-(4-morpholin-4-yl-phenoxy)- propan-2-ol (101) 4-Morpholinyl-phenol (12.5 g, 70 mmol), mixture of dodecyl and tetradecyl glycidyl ether (19.7 g, 77 mmol) and ethyltriphenylphosphonium bromide (1.3 g, 3.5 mmol) are reacted as described for compound 100 and the crude product is crystalised from hexane to obtain a white solid 13.4 g (44 %) m.p. 49-52°C.

Example 3. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(2-ethyl- hexyloxy)-propan-2-ol (102 " )

4-(l,l-dioxo-thiomorphoUn-4-yl)phenol (4.1 g, 18 mmol), 2-ethylhexyl glycidyl ether (4.4 g, 23,6 mmol) and ethyltriphenylphosphonium bromide (0.37 g) are heated under nitrogen for 5 h at 145°C and the crude product is chromatographed over silica gel (hexane/ethylacetate 1:1) to afford a colourless liquid 5.2 g (70 %).

Anal, calcd. for C 2 iH 35 NO 5 S C 60.99 H 8.53 N 3.39

C 61.00 H 8.61 N 3.45

Example 4. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(isotri- decyloxy)-propan-2-ol (103)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), isotridecylglycidyl ether (2.6 g, 10 mmol) and ethyltriphenylphosphonium bromide (0.1 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 2.4 g (50 %).

Anal, calcd. for C 26 H 45 NO 5 S C 64.56 H 9.38 N 2.90

C 64.50 H 9.27 N 2.95

Example 5. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy " l-3-(t-butyloxy)- propan-2-ol (104)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), t-butylglycidyl ether (1.56 g, 12 mmol) and ethyltriphenylphosphonium bromide (0.1 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 2.8 g (78 %).

Example 6. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(isooctyl- oxy)-propan-2-ol (105)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), isooctylglycidyl ether (1.9 g,

10 mmol) and ethyltriphenylphosphonium bromide (0.2 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 2.85 g (69 %).

Example 7. Preparation of l-[4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(3,5,5- trimeth ylhexyloxy)-propan-2-ol ( 106)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), 3,5,5-trimethylhexylglycidyl ether (2 g, 10 mmol) and ethyltriphenylphosphonium bromide (0.1 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 2.8 g (65 %).

Example 8. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxyl-3-(isodecylox)- propan-2-ol (107)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), isodecylglycidyl ether (2.15 g, 10 mmol) and ethyltriphenylphosphonium bromide (0.2 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 2.3 g (52 %).

Anal, calcd. for C^Hy^OsS C 62.55 H 8.90 N 3.17

C 62.58 H 8.86 N 3.24

Example 9. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy.-3-(isododecyl- oxy)-propan-2-ol (108)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), isododecylglycidyl ether (2.4 g, 10 mmol) and ethyltriphenylphosphonium bromide (0.2 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 1.4 g (30 ).

Anal, calcd. for C 25 H 43 NO 5 S C 63.93 H 9.23 N 2.98

C 63.97 H 9.06 N 2.99

Example 10. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(dodecyl- oxy-tetradecyloxy)-propan-2-ol (109)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), a mixture of dodecyl/tridecyl/tetradecylglycidyl ether (2.6 g, 10 mmol) and ethyltriphenylphosphonium bromide (0.1 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 2.14 g (45 %).

Example 11. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy " l-3-.phenoxy)- propan-2-ol (110)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), phenylglycidyl ether (1.5 g,

10 mmol) and ethyltriphenylphosphonium bromide (0.1 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 2.2 g (58 %).

Example 12. Preparation of l-r4-(l;l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(2,2-dimethyl hexanol)-propan-2-ol (111) 4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), 2,2-dimethyl-hexanoylglycidyl ether (2.3 g, 10 mmol) and ethyltriphenylphosphonium bromide (0.2 g) are reacted and purified (dioxane/hexane 1:1, eluent) as described for compound 102 to afford a light yellow liquid 3.6 g (79 %).

Example 13. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(nonyl)- propan-2-ol (112)

4-(l,l-dioxo-thiomorpholin-4-yl)phenol (2.3 g, 10 mmol), 2-(decyl)-oxirane (1.9 g,

10 mmol) and ethyltriphenylphosphonium bromide (0.2 g) are reacted and purified as described for compound 102 to afford a light browm solid 1.6 g (38 %), m.p. 84°C.

Example 14. Preparation of l-r4-(l,l-dioxo-thiomorpholin-4-yl)-phenoxy1-3-(2,2,4-tri- methyl-3-hvdroxy-pentyloxy)-propan-2-ol (114) 4-(l,l-dioxo-thiomorphoUn-4-yl)phenol (1.13 g, 5 mmol), 2,2,4-trimethyl-3-hydroxy-pentyloxyglycidyl ether (1.0 g, 5 mmol) and ethyltriphenylphosphonium bromide (0.1 g) are reacted and purified as described for compound 102 to afford a light yellow liquid 0.86 g (40 %).

Example 15. Preparation of l-r3-(3,5-di t-butyl-4-hvdroxy-phenyl)-propane- carboxy)-2-(4-morpholin-4-yl phenoxy)-ethane (118) 2-(4-Morpholinyl-phenoxy)-ethanol (1.12 g, 5 mmol), methyl 3,5-di t-butyl-4-hydroxyphenyl propionic acid (1.38 g, 5 mmol) and dibutyltinoxide (0.12 g, 0,5 mmol in xylene (30 ml)) are heated at 140°C under nitrogen for 5h and the crude product is chromatographed over silicagel (ethyl acetate/hexane, 3:7) to obtain a white solid 0.5 g (21 %) m.p. 105-109°C.

Example 16. Preparation of l-r3-(3-t-butyl-5-methyl-4-hvdroxy-phenyl)-propane- carboxy)-2-(4-morpholin-4-yl phenoxy)-ethane (119) 2-(4-Morpholinyl-phenoxy)-ethanol (1.12 g, 5 mmol), methyl

3-t-butyl-5-methyl-4-hydroxyphenyl propionic acid (1.25 g, 5 mmol) and dibutyltinoxide (0.12 g, 0,5 mmol in xylene (30 ml)) are heated at 140°C under nitrogen and the product is purified as described for compound 118 to obtain a light yellow oil 1.72 g (78 %).

Example 17. Preparation of 4,8-bis-butoxymethyl-6-(4-dodecyloxy-phenyl)-2-phenyl- ri,3,6,21dioxazaphosphocane-2-oxide (200)

To a solution of 4-dodecyloxy-N,N-di(2-hydroxy-3-butoxy)-propyl aniline (5.38 g,

10 mmol), pyridine (3 g, 30 mmol) and dimethylammopyridine (0.2 g) in dichloromethane

(20 ml) is added a solution of phenylphosphonous dichloride (2.14 g, 11 mmol) in dichloromethane (5 ml) at 0°C and then stirred at room temperature for 6 h. After treating with water, the crude product is purified over silicagel (ethyl acetate/hexane, 1:1) to afford a light yellow solid 1.2 g (18 %, compound 200) and a white solid 1.3 g (20 %, another isomer).

Example 18. Preparation of 4,8-bis-butoxymethyl-6-(4-dodecyloxy-phenyl)-2-phenoxy- T 1 ,3 ,6,21 dioxazaphosphocane-2-oxide (201 )

It is prepared from 4-dodecyloxy-N,N-di(2-hydroxy-3-butoxy)-propyl aniline (5.38 g, 10 mmol), pyridine (3 g, 30 mmol), dimethylaminopyridine (0.2 g) and phenylphosphonic dichloride (2.32 g, 11 mmol) in dichloromethane as described for compound 200 to obtain a white solid 1.44 g (21 %) and its isomer 1.4 g (20 % a white solid).

Example 19. Preparation of 6-(4-dodecyloxy-phenyl)-2-phenyl-

T 1 ,3 ,6,21 dioxazaphosphocane-2-oxide (202)

It is prepared from 4-dodecyloxy-N,N-di(2-hydroxy)ethyl aniline (3.66 g, 10 mmol), pyridine (2 g, 25 mmol), dimethylaminopyridine (0.2 g) and phenylphosphonous dichloride (2.15 g, 11 mmol) in dichloromethane as described for compound 200 to obtain a white solid 1 g (21 %).

Example 20. Preparation of 6-(4-dodecyloxy-phenyl)-2-phenoxy- f 1 ,3,6,21dioxazaphosphocane-2-oxide (203)

It is prepared from 4-dodecyloxy-N,N-di(2-hydroxy)-ethyl aniline (3.66 g, 10 mmol), pyridine (2 g, 25 mmol), dimethylaminopyridine (0.2 g) and phenylphosphonic dichloride

(2.11 g, 10 mmol) in dichloromethane as described for compound 200 to obtain a white solid 1.3 g (25 %).

Example 21. Preparation of 6-(4-methoxy-phenyl)-2-phenoxy- f 1 ,3,6,2]dioxazaphosphocane-2-oxide (204)

It is prepared from 4-methoxy-N,N-di(2-hydroxy)-ethyl aniline (2.1 g, 10 mmol), pyridine

(2 g, 25 mmol), dimethylaminopyridine (0.2 g) and phenylphosphonic dichloride (2.11 g,

10 mmol) in dichloromethane as described for compound 200 to obtain a white solid 1.2 g

(34 %); m.p. 124-126°C.

Example 22. Preparation of 4,8-bis-butoxymethyl-6-(4-methoxy-phenyl)-2-phenoxy- f 1 ,3,6,21dioxazaphosphocane-2-oxide (205)

It is prepared from 4-methoxy-N,N-di(2-hydroxy-3-butoxy)-propyl aniline (1.91 g,

5 mmol), pyridine (1,2 g, 15 mmol), dimethylaminopyridine (0.2 g) and phenylphosphonic dichloride (1.1 g, 5.1 mmol) in dichloromethane as described for compound 200 to obtain a pale yellow liquid 0.4 g (16 %) and its isomer 0.5 g (19 % a pale yellow liquid).

Example 23. Preparation of 4,8-bis-butoxymethyl-6-(4-methoxy-phenyl)-2-phenyl-

T 1 ,3,6,2 ,dioxazaphosphocane-2-oxide (206)

It is prepared from 4-methoxy-N,N-di(2-hydroxy-3-butoxy)-propyl aniline (1.91 g,

5 mmol), pyridine (1,2 g, 15 mmol), dimethylaminopyridine (0.2 g) and phenylphosphonous dichloride (1 g, 5.1 mmol) in dichloromethane as described for compound 200 to obtain a colourless liquid 0.6 g (24 %) and its isomer 0.6 g (24 % a colourless liquid).

Example 24. Preparation of

4,8-bis-(2-ethyl-hexyloxymethyl)-6-(4-dodecyloxy-phenyl)- 2-phenyl- T 1 ,3,6,21dioxazaphosphocane-2-oxide (207)

It is prepared from 4-methoxy-N,N-di(2-hydroxy-3-ethyl-hexyloxy)-propyl aniline (2 g, 4 mmol), pyridine (0,8 g, 10 mmol), dimethylaminopyridine (0.2 g) and phenylphosphonous dichloride (0.8 g, 4 mmol) in dichloromethane as described for compound 200 to obtain a pale yellow liquid 0.8 g (32 %) and its isomer 0.85 g (34 %, a pale yellow liquid).

Example 25. Preparation of 6-(4-dodecyloxy-phenyl)-ri,3,6,21dioxthiazocane-2-oxide

(208)

It is prepared from 4-dodecyloxy-N,N-di(2-hydroxy)-etiιyl aniline (1.8 g, 5 mmol), pyridine (0,95 g, 6 mmol), dimethylaminopyridine (0.2 g) and thionyl chloride (0.72 g,

6 mmol) in dichloromethane as described for compound 200 to obtain a white solid 1.1 g (53 %).

Anal, calcd. for C 22 H 37 NO 4 S C 64.20 H 9.06 N 3.40 S 7.79

C 63.99 H 9.07 N 3.30 S 7.85

Example 26: A polyethylene-coated base material is coated with a gelatin layer containing

silver bromide, magenta coupler (M-l 1) and a stabilizer.

The gelatin layer contains the following components (per m 2 of base material):

Table 1

The stabilizer is used either alone or as a mixture with a costabilizer, in which case the stabilizeπcostabilizer ratio is 4.5:3.5; the total amount of stabilizer remains constant.

The curing agent used is 2,4-dichloro-6-hydroxytriazine, and the wetting agent used is the sodium salt of diisobutylnaphthalenesulfonic acid.

A step wedge having a density difference of 0.15 logE per step is exposed onto each of the resultant samples, which are subsequently processed in accordance with the manufacturer's instructions by the Kodak EP2 process for colour negative papers.

After exposure and processing, the remission density in green for the magenta step is measured at a density between 0.9 and 1.1 of the wedge. The wedge is then exposed behind a UV absorber filter in an Atlas exposure unit with 15 kJ/cm 2 , and the remission density is re-measured. The drop in magenta dye density (-ΔD) is greatly reduced in the presence of the stabilizers compared with a sample containing no stabilizer (Table la to lc).

Table la:

% dye loss with costabilizer stabilizer alone PI P2 no

100

101

102

103

104

105

106

107

108

109

111

112

114

118

119

Table lb:

% dye loss with costabilizer stabilizer alone PI P2

Table lc:

% dye loss with costabilizer stabilizer alone SA1 SB3 HQ6 RE9

no stabilizer 57

100 13

102 9

203 19

Example 27: A polyethylene-coated base material is coated with a gelatin layer containing silver bromide, magenta coupler (M-5) and a stabilizer.

The gelatin layer contains the following components (per m 2 of base material):

Table 2

The stabilizer is used either alone or as a mixture with a costabilizer, in which case the stabilizeπcostabilizer ratio is 1:1; the total amount of stabilizer remains constant.

The curing agent used is 2,4-dichloro-6-hydroxytriazine, and the wetting agent used is the sodium salt of diisobutylnaphthalenesulfonic acid.

A step wedge having a density difference of 0.15 logE per step is exposed onto each of the resultant samples, which are subsequently processed in accordance with the manufacturer's instructions by the Kodak EP2 process for colour negative papers.

After exposure and processing, the remission density in green for the magenta step is measured at a density between 0.9 and 1.1 of the wedge. The wedge is then exposed behind a UV absorber filter in an Atlas exposure unit with 30 kJ/cm 2 , and the remission density is re-measured. The drop in magenta dye density (-ΔD) is greatly reduced in the presence of the stabilizers compared with a sample containing no stabilizer Table 2a and 2b).

Table 2a:

% dye loss with costabilizer stabilizer alone PI P2 no

100

101

102

103

104

105

106

107

108

109

110

111

112

114

118

119

Table 2b:

% dye loss with costabilizer stabilizer alone PI P2 no

200

201

202

203

204

205

206

207

208




 
Previous Patent: PROJECTOR

Next Patent: PHOTOMASK BLANKS