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Title:
AZO DYESTUFFS
Document Type and Number:
WIPO Patent Application WO/2002/062902
Kind Code:
A1
Abstract:
Compounds of formula (I) wherein all substituents have the meanings as defined in Claim 1, their production and their use.

Inventors:
Geiwiz, Jürgen (Friedrichstrasse 2c, Lörrach-Hauingen, 79541, DE)
Oberholzer, Martin (Amselstrasse 5, Therwil, CH-4106, CH)
Application Number:
PCT/IB2002/000398
Publication Date:
August 15, 2002
Filing Date:
February 11, 2002
Export Citation:
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Assignee:
CLARIANT FINANCE (BVI) LIMITED (Citco Building, Wickhams Cay P.O. Box 66, Road Town Tortola, VG)
CLARIANT INTERNATIONAL LTD. (Rothausstrasse 61, Muttenz 1, CH-4132, CH)
Geiwiz, Jürgen (Friedrichstrasse 2c, Lörrach-Hauingen, 79541, DE)
Oberholzer, Martin (Amselstrasse 5, Therwil, CH-4106, CH)
International Classes:
B41J2/01; B41M5/00; C07C229/56; C09B29/16; C09B29/42; C09B35/023; C09B35/031; C09B35/378; C09B35/50; C09D11/00; D06P1/04; D06P1/06; D06P1/08; D21H17/07; D21H21/28; (IPC1-7): C09B35/50; C07C229/56; C09B35/378
Foreign References:
FR2147312A1
US3211717A
EP0855387A1
EP0955342A1
GB2190392A
Attorney, Agent or Firm:
Dünnwald, Dieter (Clariant International Ltd, Rothausstrasse 61, Muttenz 1, CH-4132, CH)
Kachholz, Traudel (Clariant international Ltd, Rothausstrasse 61, Muttenz 1, CH-4132, CH)
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Claims:
CLAIMS
1. A compound of formula (I) wherein each A is independently NH or O, B is a polyvalent group or atom, n'and n"are natural numbers and the sum of n'and n"is 2 2, m is a natural number 0, CC is a moiety of formula (a) wherein R, is H; C14alkyl; C14alkyl monosubstituted by hydroxy, halogen, cyano or C, 4alkoxy, X, and Xz independently of each other are halogen ; an aliphatic, cycloaliphatic, aromatic or heterocyclic amino group, said amino group comprising a protonatable nitrogen atom or a quaternary ammonium group, and being an aliphatic, cycloaliphatic, aromatic or heterocyclic mono (C, 4alkyl)amino group, the C14alkylgroup being unsubstituted or monosubstituted by halogen, C, 4alkoxy, C, 4alkyl, phenyl or hydroxy; an aliphatic, cycloaliphatic, aromatic or hetero cyclic di (C14alkyl)amino group, the C, 4alkylgroups being inde pendently unsubstituted or monosubstituted by halogen, C, 4alkyl, C, 4alkoxy, phenyl or hydroxy; a C56cycloalkylamino group, the cyclo alkyl group being unsubstituted or substituted by one or two C12alkyl groups; a phenylamino group, the phenyl ring being unsubstituted or substituted by one or two groups selected from halogen, C, 4alkyl, C, 4alkoxy, hydroxy and phenoxy; or a 5or 6membered ring con taining one or two hetero atoms, in addition to N, O or S, which heterocyclic ring is unsubstituted or substituted by one or two C14alkyl groups; or a group Z, where Z is independently selected from wherein p is 0 or an integer 1, 2 or 3, each Rg is independently hydrogen; unsubstituted C14alkyl or C14alkyl monosubstituted by hydroxy, halogen, cyano or C, 4alkoxy, each R2 and R3 is independently hydrogen; unsubstituted C16alkyl ; C26alkyl monosubstituted by hydroxy, amino or cyano; phenyl or phenylC, 4alkyl, where the phenyl ring of the latter two groups is unsubstituted or substituted by one to three groups selected from chlorine, C, 4alkyl, C14alkoxy, unsubstituted C56cycloalkyl or C56cycloalkyl substituted by one to three C14alkyl groups or a pyridinium ring, or R2 and R3 together with the nitrogen atom to which they are attached, form a 5or 6membered ring containing one to three hetero atoms (in addition to N, one or two further N, O or S), which heterocyclic ring is unsubstituted or substituted by one or two C14alkyl groups, each R4 and R5 has independently one of significances of R2 and R3, except hydrogen, R6 is C14alkyl or benzyl with the exception that R6 is not benzyl when R4 and R5 have one of the cyclic significations of R2 and R3, or R4, R5 and R6 together with the nitrogen atom to which they are attached, form a pyridinium ring which is unsubstituted or substituted by one or two methyl groups, Q1 is C28alkylene ; C36alkylene substituted by one or two hydroxy groups; Cl6alkylene1, 3 or 1,4phenylene, or*NHCOCH2, where * denotes the atom bound toNRg, Q2 is C28alkylene ; C36alkylene substituted by one or two hydroxy groups; C16alkylene1, 3or1, 4phenylene or 1,3 or 1,4phenylene, Q3 is C28alkylene, R7 is hydrogen; unsubstituted C16alkyl or C16alkyl monosubstituted by hydroxy, cyano, chlorine or phenyl, R8 is unsubstituted C16alkyl or C16alkyl monosubstituted by hydroxy, cyano or chlorine, and An3 is a nonchromophoric anion, Y is direct bond,COorCONH*, wherein the asterisk signifies the bond to the benzene ring and ois0 or1, or CC is a moiety of formula (b) wherein D is a basic groupNR,Q4NR2R3 or a cationic groupNR,Q4 N+R4R5R6, in which R1, R2, R3, R4, R5 and R6 have the same meanings as above and Q4 is C26alkylene, which may be interrupted by O, S or N (R1); C23alkylene substituted by one or two hydroxy groups; or *NHCOCH2, where * denotes the atom bound to theNR,radical, or CC is a moiety of formula (c,) or (c2) wherein each Rio independently of each other is H; C14alkyl ; C56cycloalkyl ; phenyl, benzyl or phenylethyl, each R, o independently of each other is H;OH or C14alkyl each T, independently of each other is H;CN ;COOR, 5 ; CONR16R17 ; SO2NR16R17; G is H ;R11NHR12 or R11NR13R14, wherein R11 signifies C16alkylene or C26alkenylene, R12 and R13 independently of each other are H; unsubstituted C16alkyl ; C26alkyl substituted by OH, CN or halogen ; phenylCl3 alkyl, wherein the phenyl radical is optionally substituted from 1 to 3 times, by a substituent from the group of substituents comprising chlorine, C14alkyl or C14alkoxy ; unsubstituted C56cycloalkyl or C56cycloalkyl substituted from 1 to 3 times by C14alkyl groups, R, 4 signifies any of the meanings of R12 or Ri3 or hydrogen, R15 signifies a C16alkyl radical or phenylC13alkyl radical, R16 and R17 independently of each other are H or a 4alkyl radical, R, 8 independently of each other signifies H ; a C, 4alkyl radical ; NR16R17(CH2)24NR16R17 or CONR16R17, Rig signifies a C, 4alkyl radical or a hydroxyC, 4alkyl radical, R20 signifiesSorO, R2, signifies hydrogen or a C, 4alkyl radical and An~ is a nonchromophoric anion, with the provisos that (i) the sum of n', n"and m is smaller as or equal to the valencies of B, (ii) when the sum of n'and n"= 2 then m is > 1, (iii) when the sum of n'and n"= 3 and A=NH then m is 1 and their salts and mixtures thereof.
2. A compound according to Claim 1 characterized in that B is a linear or branched alkylen group.
3. A compound according to Claim 1 or 2 characterized in that B is a linear or branched alkylen group with 1 to 25 carbon atoms.
4. A compound according to Claim 1 characterized in that B is a linear or branched alkylen group containing 2 to 40 carbon atoms, which is interrupted by at least one heteroatom choosing from the group consisting of O, N and S.
5. A compound according to Claims 1,2 or 3 characterized in that B is a group B' C[(CH2)04]14.
6. A compound according to claims 1 or 4 characterized in that B signifies [(CH2), 4O(CH2), 4] 4C or [(CH2)13O(CH2)13O(CH2)13]4C or [(CH2012O(CH2)12O(CH2)12O(CH2)12]4C or [(CH2)14]2N(CH2)14N[(CH2)14]2.
7. A compound according to anyone of the preceding claims characterized in that A signifies0.
8. A compound according to anyone of the preceding claims characterized in that CC has the following formulae (c2) or (a,) wherein R, o signifies H ;CH3 or CH2CH3, T, signifies H;CN ;CONH2 ;CONCH3 ; Rio'signifies H ;CH3 orOH, G signifies H or (CH2)24NR13R14, wherein R, 3 and R, 4 are independently from each other H ;CH3 orCH2CH3, or wherein each R, is independently from each other H ;CH3,CH2CH3 or substituted C14alkyl, Xi and X2 are independently from each other halogen orNR2R3 wherein R2 and R3 are independently from each other H; C14alkyl; C24alkylenNH2 or C24alkylenOH, Y signifies a direct bond; wherein the asterisk signifies the bond to the benzene ring and o is 0 or 1.
9. Mixtures of compounds comprising at least one compound of formula (I).
10. Mixtures according to claim 9 comprising at least one compound according to formula (I) and at least one compound of the examples 1137 of the patent GB 2190392A and/or at least one C. I. Basic Red and/or at least one C. I. Basic Brown and/or at least one C. I. Basic Blue and/or at least one C. I. Basic Violet.
11. Mixtures according claims 9 or 10 comprising from 2 to 98 parts (by weight) of at least one compound of formula (I) as component one and at least one compound of the examples 1137 of the patent GB 2190392A and/or at least on C. I. Basic Brown 23 and/or C. I. Basic Red 12 and/or C. I. Basic Blue 1 and/or C. I. Basic Red 14 and/or C. I. Basic Violet 10 and/or C. I. Basic Blue 26 in an amount to have 100 parts in total as component two.
12. Use of compounds and/or mixtures according to anyone of the preceeding claims for dyeing or printing fiber material or dyeing or printing paper.
13. Materials dyed or printed with compounds and/or mixtures according to the claims 1 to 11.
14. Inkjet inks comprising a at least a compound according to claim 1 to 8 and/or mixtures according to claim 9 to 11.
15. Process for the preparation of inkjet inks, characterized in that a at least a compound according to claim 1 to 8 and/or mixtures according to claim 9 to 11 are used.
16. A process for the preparation of azo compounds of formula (I) comprising reacting the diazonium salt of a compound according to formula (II) or mixtures of such diazonium salts with a suitable coupling component com prising moieties of formula CC or with a mixture of suitable coupling components comprising moieties of formula CC wherein B and the moiety CC have the meaning as defined in claim 1.
17. A compound according to formula (II) wherein B signifies a linear or branched alkylen group, wherein the number of carbon atoms goes from 1 to 25 or a linear or branched alkylen group containing 2 to 40 carbon atoms, which is interrupted by at least one heteroatom choosing from the group of O, N and S, preferably O and/or S, A signifies independentlyNHorO m and n are natural numbers with the provisos that (i) the sum of n and m is smaller as or equal to the valencies of B, (ii) when n = 2 then m is 2 1, (iii) when n = 3 and X=NH then m is > 1, and their salts and/or mixtures thereof.
18. A compound according to claim 17 characterized in that B is a group B' C [(CH2) 04] 14.
19. A compound according to claim 17 characterized in that B signifies [(CH2)14O(CH2)14]4C or [(CH2)13O9CH2)13O(CH2)13]4C or [(CH2)12O(CH2)12O(CH2)12O(CH2)12]4C or [(CH2)14]2N(CH2)14N[(CH2)14]2.
20. Compounds according to claim 17,18, or19 characterized in that A signifies0.
Description:
AZO DYESTUFFS The present invention relates to novel azo or polyazo dyestuffs, their production, their use as well as to the novel amino compounds.

Various azo or polyazo dyestuffs as well as their production are already well known.

The variety of such compounds is enormous. Recent patents or patents application dealing with polyazo dyestuffs and its starting products are US 6,015,885, W097/24405.

Azo or polyazo compounds can be used for dyeing or printing all kinds of fiber material like cellulose, cotton, keratinous fibers, for example hair, or leather, but in particular paper or paper products or else bast fibers such as hemp, flax, sisal, jute, coir or straw.

The present invention relates to compounds of formula (I) wherein each A is independently-NH-or-0-, B is a polyvalent group or atom, n'and n"are natural numbers and the sum of n'and n"is : 2, m is a natural number > 0, CC is a moiety of formula (a)

wherein R, is H; C1 4alkyl ; C, 4alkyl monosubstituted by hydroxy, halogen, cyano or C, 4alkoxy, X, and X2 independently of each other are halogen; an aliphatic, cycloali- phatic, aromatic or heterocyclic amino group, said amino group comprising a protonatable nitrogen atom or a quaternary ammonium group, and being an aliphatic, cycloaliphatic, aromatic or heterocyclic mono (C1-4alkyl)-amino group, the C14alkyl-group being unsubstituted or monosubstituted by halogen, C14alkoxy, C1 4alkyl, phenyl or hydroxy; an aliphatic, cycloali- phatic, aromatic or heterocyclic di (C1 -4alkyl)-amino group, the C1-4alkyl- groups being independently unsubstituted or monosubstituted by halogen, C, 4alkyl, C, 4alkoxy, phenyl or hydroxy; a Ce-ecydoatkyjamino group, the cycloalkyl group being unsubstituted or substituted by one or two C1-2alkyl groups; a phenylamino group, the phenyl ring being unsubstituted or sub- stituted by one or two groups selected from halogen, C1 4alkyl, C14alkoxy, hydroxy and phenoxy; or a 5-or 6-membered ring containing one or two hetero atoms, in addition to N, 0 or S, which heterocyclic ring is unsub- stituted or substituted by one or two C14alkyl groups; or a group Z, where Z is independently selected from

wherein p is 0 or an integer 1,2 or 3, each Rg is independently hydrogen; unsubstituted C14alkyl or C1-4alkyl monosubstituted by hydroxy, halogen, cyano or C, 4alkoxy, each R2 and R3 is independently hydrogen; unsubstituted C1 6alkyl ; C2-6alkyl monosubstituted by hydroxy, amino or cyano; phenyl or phenyl-C1-4alkyl, where the phenyl ring of the latter two groups is unsubstituted or sub- stituted by one to three groups selected from chlorine, C1-4alkyl, C1-4alkoxy, unsubstituted C5. 6cyctoatky) or C5-6cycloalkyl substituted by one to three C1-4alkyl groups or a pyridinium ring, or R2 and R3 together with the nitrogen atom to which they are attached, form a 5-or 6-membered ring containing one to three hetero atoms (in addition to N, one or two further N, 0 or S), which heterocyclic ring is unsubstituted or substituted by one or two Chalky ! groups,

each R4 and R5 has independently one of significances of R2 and R3, except hydrogen, R6 is C1-4alkyl or benzyl with the exception that R6 is not benzyl when R4 and R5 have one of the cyclic significations of R2 and R3, or R4, R5 and R6 together with the nitrogen atom to which they are attached, form a pyridinium ring which is unsubstituted or substituted by one or two methyl groups, Q1 is C2-8alkylene ; C3-6alkylene substituted by one or two hydroxy groups; C1-6alkylene-1,3- or 1,4-phenylene, or-*NHCOCH2, where * denotes the atom bound to-NRg, Q2 is C2-8a) ky) ene ; C3-6alkylene substituted by one or two hydroxy groups; C1-6alkylene-1,3- or -1,4-phenylene or 1,3- or 1,4-phenylene, Q3 is C2-8alkylene, R7 is hydrogen; unsubstituted C, 6alkyl or C1 6alkyl monosubstituted by hydroxy, cyano, chlorine or phenyl, R8 is unsubstituted C1-6alkyl or C1-6alkyl monosubstituted by hydroxy, cyano or chlorine, and Ano is a non-chromophoric anion, Y is direct bond,-CO-or-CO-NH-*, wherein the asterisk signifies the bond to the benzene ring and ois0 or1, or CC is a moiety of formula (b)

wherein D is a basic group-NR,-Q4-NR2R3 or a cationic group -NR1-Q4-N+R4R5R6, in which R1, R2, R3, R4, R5 and R6 have the same meanings as above and Q4is C26alkylene, which may be interrupted by-O-,-S-or-N (R,)- ; C2-3alkylene substituted by one or two hydroxy groups; or-*NHCOCH2-, where * denotes the atom bound to the-NR1-radical, or CC is a moiety of formula (c1) or (c2) wherein each R10 independently of each other is H; C1-4alkyl ; C5 6cycloalkyl ; phenyl, benzyl or phenylethyl, each R, o' independently of each other is H;-OH or C1-4alkyl each T, independently of each other are H;-CN ; -COOR15 ; CONR16R17 ; SO2NR16R17 ;

G is H ; -R11NHR12 or -R11NR13R14, wherein R11 signifies C1-6alkylene or C2-6alkenylene, R12 and R13 independently of each other are H; unsubstituted C1-6alkyl ; C2-6alkyl substituted by OH, CN or halogen ; phenyl-C1 3 alkyl, wherein the phenyl radical is optionally substituted from 1 to 3 times, by a substituent from the group of substituents comprising chlorine, C1-4alkyl or C1-4alkoxy ; unsubstituted C5 6cycloalkyl or C5 6cycloalkyl substituted from 1 to 3 times by C1-4alkyl groups, R14 signifies any of the meanings of R, 2 or R, 3 or hydrogen, R15 signifies a C1 6alkyl radical or phenyl-C1 3alkyl radical, Pie and R17 independently of each other are H or a C, 4alkyl radical, R, 8 independently of each other signifies H; a C1-4alkyl radical; -NR16R17- (CH2)2-4-NR16R17 or -CONR16R17, R19 signifies a C14alkyl radical or a hydroxy-C, 4alkyl radical, R20 signifies-S-or-0-, R21 signifies hydrogen or a C1 4alkyl radical and An-is a non-chromophoric anion, with the provisos that (i) the sum of n', n"and m is smaller as or equal to the valencies of B, (ii) when the sum of n'and n"= 2 then m is 2 1, (iii) when the sum of n'and n"= 3 and A=NH then m is ! 1

and their salts and mixtures thereof.

In the compounds of formula (I) the anions An-can be any non-chromophoric anions such as those conventional in basic dyestuff chemistry. Suitable anions include chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleat, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate and benzoate as well as complex anions, for example zinc chloride double salts and anions of boric acid, citric acid, glycollic acid, diglycollic acid and adipic acid or addition products of ortho boric acids with polyalcohols with at least one cis diol group present. These anions can be exchanged for each other by ion exchange resins on reaction with acids or salts (for example via the hydroxide or bi- carbonate) or according to German Offenlegungsschrift 2,001,748 or 2,002,816.

In preferred compounds CC has the following formulae (c2) or (a,) wherein Rio signifies H ;-CH3 or-CH2CH3, T, signifies H;-CN ;-CONH2 ;-CONCH3 ; R10'signifies H ;-CH3 or-OH, G signifies H or-(CH2) 24NR13R14, wherein R13 and R14 are independently from each other H ;-CH3 or-CH2CH3, or

wherein each R, is independently from each other H ;-CH3,-CH2CH3 or substituted C1-4alkyl, X, and X2 are independently from each other halogen or-NR2R3, wherein R2 and R3 are independently from each other H; C1-4alkyl ; C2-4alkylen-NH2 or C2-4alkylen-OH, Y signifies a direct bond; wherein the asterisk signifies the bond to the benzene ring and o is 0 or 1.

If o is 0 then the NR,-triazine group is preferably attached to the naphthol group at position 6 or 7.

If o is 1 then the NR1-triazine group is preferably attached to the benzene ring at position 4'or 3'and to the naphthol group at position 6 or 7.

In further preferred compounds according to formula (I) B is a linear or branched alkylen group, wherein the number of carbon atoms goes from 1 to 25.

In further preferred compounds according to formula (I) B is a linear or branched alkylen group containing 2 to 40 carbon atoms, which is interrupted by at least one heteroatom choosing from the group of O, N and S, preferably O and/or S.

In more preferred compounds B is a group B'C [ (CH2) o-4] i-4.

In further more preferred compounds B is

[-(CH2) 14-O-(CH2), 434C or [-(CH2)1-3-O-(CH2)1-3-O-(CH2)1-3]4C or [-(CH2)1-2-O-(CH2)1-2-O-(CH2)1-2-O-(CH2)1-2]4C or [(-CH2)1-4]2N(CH2)1-4N[(-CH2)1-4]2.

Especially preferred compounds according to formula (I) have the formula (la), wherein CC is a moiety of formula (a,) or (c2), n"is 1,2,3 or 4, with the provisos that when n"is 1 then B"is C (CH20H) 3 when n"is 2 then B"is C (CH20H) z when n"is 3 then B"is; C (CH20H) when n"is 4 then B"is C; [-(CH2)1-4-O-(CH2)1-4]4C; [-(CH2)1-3-O-(CH2)1-3-O-(CH2)1-3]4C; [-(CH2)1-2-O-(CH2)1-2-O-(CH2)1-2-O-(CH2)1-2]4C or [(-CH2)1-4]2N(CH2)1-4N[(-CH2)1-4]2.

A further embodiment of the present invention relates to mixtures of compounds comprising at least one compound of formula (I).

Preferred mixtures comprise at least one compound of formula (la) wherein B"is C (CH20H) 3 and n"is 1 and at least one compound of formula (la) wherein B"is C (CH20H) 2 and n"is 2 and at least one compound of formula (la) wherein B"is C (CH20H) and n"is 3 and at least one compound of formula (la) wherein B"is C and n"is 4.

Further preferred mixtures comprise at least one compound according to formula (I) (preferably formula (la)) or a mixture of compounds as described above and at least one compound of the examples 1-137 of the patent GB 2190392A and/or at least one C. I. Basic Red and/or at least one C. I. Basic Brown and/or at least one C. I. Basic Blue and/or at least one C. I. Basic Violet.

These preferred mixtures comprise from 2 to 98 parts (by weight) of at least one compound according to formula (I) (preferably formula (la)) or a mixture of compounds as described above as component one and at least one compound of the examples 1- 137 of the patent GB 2190392A and/or at least one C. I. Basic Red and/or at least one C. I. Basic Brown and/or at least one C. I. Basic Blue and/or at least one C. I. Basic Violet in an amount to have 100 parts in total (e. g. from 98 to 2 parts) as component two. The mixtures may comprise component one and component two (component one/ component two) in a ratio (by weight) of 2.0/98.0; 2.5/97.5; 12.5/87.5; 22.5/77.5; 32. 5 / 67. 5; 42.5/57.5; 50.0/50.0; 57.5/42.5; 67.5/32.5; 77.5/22.5; 80. 0/20. 0; 87. 5 / 12. 5; 90.0/10.0; 95.0/5.0; 97.5/2.5; or 98.0/2.0.

More preferred mixtures comprise mixtures of 10 to 50 parts of component one and 90 to 50 parts of component two.

Especially preferred mixtures comprise mixtures of 15 to 30 parts of component one and 85 to 70 parts of component two.

Especially preferred mixtures comprise mixtures comprise at least one compound of formula (la) and at least on C. I. Basic Brown 23 and/or C. I. Basic Red 12 and/or C. I.

Basic Blue 1 and/or C. I. Basic Red 14 and/or C. I. Basic Violet 10 and/or C. I. Basic Blue 26.

A further embodiment of the present invention relates to novel amino compounds according to formula (II) wherein B signifies a linear or branched alkylen group, wherein the number of carbon atoms goes from 1 to 25 or a linear or branched alkylen group containing 2 to 40 carbon atoms, which is interrupted by at least one heteroatom choosing from the group of 0, N and S, preferably O and/or S, A signifies independently-NH-or-O- m and n are natural numbers with the provisos that (i) the sum of n and m is smaller as or equal to the valencies of B, (ii) when n = 2 then m is > 1, (iii) when n = 3 and A=NH then m is 2 1, as well as to their salts and/or mixtures thereof.

In especially preferred compounds of formula (II) B is a group B'C [ (CH2) 0-411-4.

In further especially preferred compounds of formula (II) B is [-(CH2)1-4-O-(CH2)1-4]4C or<BR> [-(CH2)1-3-O-(CH2)1-3-O-(CH2)1-3]4C or [- 1-2-O-(CH2)1-2-O-(CH2)1-2]4C or [(-CH2)1-4]2N(CH2)1-4N[(-CH2)1-4]2.

A further aspect of this invention is the synthesis of the novel compounds according to formula (II), wherein compounds of formula (III)

are reacted with a compound of formula (IVa) and/or a compound of formula (IVb) B(CH2OH)m+n (IVa) B (CH2NH2) n (CH20H) m (IVb) wherein B, m and n are defined as above to a compound according to formula (II).

Preferably the reaction takes place in a common polar solvent. Such solvents are e. g.

1-methyl-2-pyrrolidinone or N, N-dimethyl-acetamide.

The temperature for this reaction is preferably between 40°C and 70°C.

By the variation of the mole ratio between compound (III) and compound (IVa) and/or compound (IVb) and/or by the variation of the conditions of the reaction the value of n and m can be varied.

The compounds of formulae (III), (IVa) and (IVb) are known or may be produced in a manner familiar to the person skilled in the art.

Compounds according to formula (II) can be used as starting compounds in the production of compounds of formula (I).

The present process for the preparation of azo compounds (I) comprises reacting the diazonium salt of a compound according to formula (II) or mixtures of such diazonium salts with a suitable coupling component or with a mixture of suitable coupling components.

As coupling suitable component or as a mixture of suitable coupling components, any suitable coupling component and mixtures of suitable coupling components can be chosen. For example any suitable benzene, naphthalene or heterocyclic compound.

Examples of suitable coupling components are listed e. g. in DE 3625576, DE 2915323, GB 2303634 and US 5,929,215. Preferred coupling components comprise an optionally substituted pyridone group or a triazine group.

More preferred suitable coupling components comprise moieties of the formula CC wherein all substituents have the meanings as defined above. Even more preferred suitable coupling components comprise the formula (c2) or (a,).

Diazotization and coupling are effected by generally known processes.

The diazotization is carried out, for example using sodium nitrite in acid aqueous medium. The diazotization can also be carried out using other diazotization agents, for example nitrosulfuric acid. An additional acid may be present in the reaction medium during diazotization, for example phosphoric acid, sulfuric acid, acetic acid, propionic acid, hydrochloric acid or mixtures of these acids, e. g. mixtures of phosphoric acid and acetic acid. Diazotization is conveniently carried out in the temperature range of from - 10°C to 30°C, preferably from-10°C to 20°C.

Coupling of the diazotised compound of formula (II) to the suitable coupling compo- nent, more specifically those components comprising moieties of formula CC or even more specifically those of comprising moieties of formula (c2) or (a,) is carried out in known manner, for example in acid, aqueous or aqueous-organic medium, preferably in the temperature range from-10°C to 30°C, more preferably below 10°C. Acids used are, for example hydrochloric acid, acetic acid, sulfuric acid or phosphoric acid. Diazo- tization and coupling can for example be carried out in the same reaction medium.

Alkali metal nitrites, such as, for example, sodium nitrite, in solid form or as an aqueous, or in nitrosylsulfuric acid are employed as the nitrosating agents.

The preparation of the diazonium ion, typically through the reaction with excess nitrous acid or the like such as nitrosyl sulfuric at low temperature to form the electrophilic ion AN2+ is disclosed in the literature e. g. in"Advanced Organic Chemistry, Fieser &

Fieser, pages 736-740"or in"Organische Chemie, K. Peter C. Vollhardt, pages 1154- 1157, first edition (1. Auflage) 1988".

The coupling components comprising the moieties of formulae (c2) or (a,) are known or may be easily produced in a manner familiar to the person skilled in the art.

The compounds (or complexes) of formula (I) containing free basic groups may be converted wholly or in part into water-soluble salts by reacting with any one of the abovementioned inorganic or organic acids.

The azo dyes according to formula (1) and the mixtures of these dyes can be used to dye or print all kind of fiber materials.

The azo compounds according to formula (I) or mixtures thereof, especially those comprising coupling components comprising the moieties of formula (c2) or (a,) are used in particular as dyes for dyeing and printing cationically dyeable substrates, such as wool, hair, silk, leather, acid-modified nylon materials, polyacrylonitrile materials, basically dyeable, modified polyester materials, natural and regenerated cellulose materials, such as cotton, hemp, flax, sisal, jute, coir or straw and viscose, on which these compounds have good affinity.

A preferred use of the azo dyes according to formula (I) and of mixtures of these dyes, especially those comprising coupling components comprising the formula (c2) or (a,) lies in the dyeing of paper of all kinds, especially bleached, unsized and sized lignin- free paper as well as wood containing paper or lignin containing paper.

A more preferred use of the azo dyes according to formula (I) and of mixtures of these dyes, especially those comprising coupling components of formula (c2) or (a,) lies in the dyeing of wood containing paper or lignin containing paper.

The novel dyes can be applied by a wide range of different processes to the paper material, e. g. in pulp dyeing, in the size press and from aqueous inks by the Ink Jet method.

Concentrated aqueous solutions of dyes of formula (I) can be prepared by filtering the dye suspension obtained in the synthesis of the dye, if appropriate effecting deionisa-

tion, conveniently by a membrane separation method, and stabilizing the solution by the addition of auxiliaries such as urea, E-caprolactam or polyethylene glycol. It is, however, also possible to suspend the isolated dye in hydrochloric acid, to filter the dye suspension once more and to mix the filter cake with lithium hydroxide or a suitable amine, typically an alkanolamine, and the requisite amount of water. Finally, it is also possible to carry out the coupling in the presence of lithium hydroxide, ammonia or alkanolamine, and to deionise the synthesis solution.

For the preparation of inks for printing processes suitable organic solvents or mixtures thereof are used. E. g. alcohols, ethers, esters, nitriles, carbonacidamides, cyclic amides, urea, sulfones and sulfone oxides.

Furthermore additional auxiliaries such as e. g. buffers, viscosity improvers, surface tension improvers, fixation accelerants, biocides, corrosion inhibitors, leveling agents, drying agents, humefactants, ink penetration additives, light stabilizers, UV absorbers, optical brighteners, coagulation reducers, ionic or nonionic surfactants and conducting salts, may be added to the ink composition.

The fractions of the individual components of the ink compositions are 1-35 parts of a dye of the formula (I) and/or its salt or mixtures of various dyes of the formula (I), 65-99 parts of water or a medium including a mixture of water and an organic solvent, an an- hydrous organic solvent or a solid having a low melting point and optionally and 0-5 parts of one or more additives. The total sum of all the parts of a composition according to the invention is 100 parts.

A further embodiment of the present invention are materials printed or dyed with compounds of formula (I) or mixtures thereof.

A further embodiment of the present invention are ink-jet inks comprising compounds according to formula (I) (preferably formula (la)) and/or mixtures comprising at least one compound according to formula (I) (preferably formula (la)) or a mixture of com- pounds as described above and at least one compound of the examples 1-137 of the patent GB 2190392A and/or at least one C. I. Basic Red and/or at least one C. I. Basic Brown and/or at least one C. I. Basic Blue and/or at least one C. I. Basic Violet, as well as a process for the preparation of this ink-jet inks by using this compounds and/or this mixtures.

The following examples further serve to illustrate the invention. In the Examples all parts and all percentages are by weight, and the temperatures given are in degrees Celsius, unless indicated to the contrary.

SYNTHESES OF BRIDGED ANTHRANILIC ACID ESTERS: EXAMPLE 1 65.3 parts isatoic anhydride are added slowly to a mixture of 13.6 parts pentaerytrite and 1.0 parts potassium carbonate in 50 parts 1-methyl-2-pyrrolidone at 50°C. The suspension is stirred for 2 hours and than diluted with 500 parts water. The resulting slurry is filtered, and the collected solid washed with water and dried in vacuum at 60°C to obtain a white powder, having the formula (V) Example 1 could be also used for dyestuff synthesis without isolation.

EXAMPLE 2 49 parts isatoic anhydride are added slowly to a mixture of 13.6 parts pentaerytrite and 1.0 parts potassiumcarbonate in 50 parts N, N-dimethyl-acetamide at 50°C. The sus- pension is stirred for 2 hours and diluted with 500 parts water. The resulting slurry is filtered, and the obtained solid washed thoroughly with water and dried in vacuum at 60°C to obtain a white powder, which is a mixture containing compounds having the formula (Via, Vlb, Vlc, V)

Further compounds of the general formula (Ila) may be produced analogously to the procedure given in Example 1 and 2.

TABLE 1/EXAMPLES 3-7 Ex. B n 3 (-CH2-O-CH2) 4C 4 4 (-CH2-O-CH2CH2-O-CH2CH2-O-CH2) 4C 4 5 -(CH2CH2-O-CH2)4C 4 6 (-CH2CH2) 2NCH2CH2N (CH2CH2-) 2 4 zu - i-CH2CH3

SYNTHESES OF THE AZO-DYESTUFFS: EXAMPLE 8 60 parts of the amino-compound of Example 1 are dissolved in a mixture of 50 parts water, 120 parts 30 % HCI and 60 parts acetic acid and diazotized at 0°C-5°C with 28 parts of a 4 N solution of sodium nitrite. 392 parts of a 20 % solution of 6-hydroxy-4- methyl-1- (3'-methylamino)-propylpyridone- (2) in sulfuric acid are added to the diazo- solution. By the addition of 20 parts 30 % sodium hydroxide solution and 150 parts ice the pH is adjusted to 2 at a temperature of 10°C-20°C. After 1 hour stirring the pH is adjusted to 10 with 30 % sodium hydroxide and the precipitated dyestuff is filtered off.

A dyestuff of the following formula (VII) is obtained.

The dyestuff is very soluble in diluted acids, particularly organic acids such as formic acid, lactic acid, acetic acid and methoxyacetic acid. The solution dyes paper in brilliant yellow shades. The obtained dye shows excellent wet fastness (against water, alcohol, milk, soapy water, sodium chloride solution, urine, etc.).

Further dyestuffs of the general formula (lb) may be produced analogously to the procedure given in Example 8.

TABLE 2/EXAMPLES 9-34 Ex. B n"CC Shade CH3 zu 9 1 4 1 yellow O N OH H H CH3 10 4, Nv I yellow C OH O N-OH H Ex. B n"CC Shade CH3 ci 0 nui I \ CI 4 H3c, N OH yellow H. CH2 L ; H3 CH3 CH3 zu ci- j j! cF 12 4 O ? NIOH yellow HJ CL, UH3 CH3 0 N OH 13--4 yellow H3CuN L ; H3 CH3 CON 0 N OH O OH 14--4 yellow CH3 L ; H3 Ex. B n"CC Shade CONH2 XI O N'% _OH 15--4 yellow H. CH2 ut-13 /CH3 + CH3 /nez CL 16 4 0 N OH yellow H3c, N 1 UN3 17 4 yellow HO N 0 H 17-c-4"fL "° HOO CH3 CN 18 4 yellow HO N O H CH3 CONHZ 19 4 yellow HO N 0 H CH3 \ - 4 HO N O Y2OW 'cl3 ,--r NA Ex. B n"CC Shade CH 3 CN 21 4 HO N 0 yellow kCH, NH2 CH 3 CH3 ACONH2 22 4 HO N 0 yellow WCH3 NH2 NHZ OH NHCH2C i I \ \ N i 23--4 orange H CH3 CH3N+ I CH, Cl- ! t! ci 24 (-CH2-O-CH2) 4C 4 o N OH yellow H. CH2 CL, UH 3 Ho /nez In cri 25 (-CH2-0-CH2) 4C 4 o OH yellow HJ Cl, CH3 H NHCH 2c I \ \ NI 26 (-CH2-0-CH2) 4C 4 Ho s NNN °ange Ho 3s Ex. B n"CC Shade H3 H3 CI (-CH2-O-CH2CH2-O-OANXOH Y 27 CH2CHz-O-CHZ) 4C 4 ellow CH2CH2-0-CHz) 4C CH3 CHUG CH3 CH3 CH3 N+ 1 , NJ (-CH2-O-CH2CH2-O- 28 4 O N OH yellow OH 4C HJ CH, OHNHCHC (-CH2-O-CH2CH2-O-+> N 29 4 . kA. orange 29 CH2CH2-0-CH2) 4C 4 HO3S) <H N Nk orange g3 ___.. __ CH3 CH3 , nu 30- (CH2CH2-0-CH2) 4C 4 0 N OH yellow HJ CL, UH3 CH3 31-(CH2CH2-O-CH2) 4C 4 yellow 1 UN3 Ex. B n"CC Shade OH NHCH2C I \ \ NI 32- (CH2CH2-0-CH2) 4C4HO-6aN'ill, NNF orange H03S H-_N'-N CH3 j CH, 33 (-CH2) 2NCH2CH2N (CH2-) 2 4 ooh Con 0 N OH CH3 CN l Cl- ! cF 0 N OH 34 (-CH2) 2NCH2CH2N (CH2-) 24 yellow UT3 CHg CH3 EXAMPLE 35 To a mixture of 200 parts of ice, 90 parts of 30% HCI, 80 parts of acetic acid and 30 parts of N, N-dimethyl-acetamide 50 parts of the amino compounds of Example 2 are added and diazotised with 21 parts of 4N solution of sodium nitrite. The temperature is maintained at 0°C-5°C by the addition of 100 parts of ice. To the diazo solution 378 parts of an approx. 20% aqueous solution of 6-hydroxy-4-methyl-pyridonyl- (3)-3'- methylpyridinium chloride are added. By the addition of 15 parts of 30% solution of sodium hydroxide the pH value is adjusted to 3 at a temperature of 10°C-20°C. After 1 hour stirring the pH value is adjusted to 10 with 30 % solution of sodium hydroxide and the precipitated dyestuff is filtered off, washed with 10 % solution of sodium carbonate and dried at 60°C in vacuum to obtain a yellow powder which is a mixture containing compounds having the formula (Vllla, Vlilb, Vlllc, Vllld)

The mixture of these dyestuffs is very soluble in diluted acids, particularly organic acids such as formic acid, lactic acid, acetic acid and methoxyacetic acid. The solution dyes paper in brilliant yellow shade. The obtained dyeing shows excellent wet fastness (against water, alcohol, milk, soapy water, sodium chloride solution, urine, etc.).

Further mixtures of dyestuffs of the general formulae (iXa), (IXb), (IXc) and (IXd) may be produced analogously to the procedure given in Example 35.

TABLE 3/EXAMPLES 36-54 Ex. CC Shade CH3 Ho neo 'il 36 yellow HN CL, r-H3 CN CON 'inc HN 37 yel low HAN I CH3 CONH2 CONH2 'ILL Ho N 0 han CHEZ I CH3 Ex. CC Shade CH3 yellow Ho N 0 HO N-'O H CH3 ni HO N''O I 40 yellow CH3 CL3 CH3 YY N cH3 J 41 HO N 0 ci-yellow H3c, N I CH3 CH3 A HO NEO 42 yellow H3c, N I ( ; H3 CH3 CN I HO N O 43 yellow I CHEZ CH3 Ex. CC Shade CH3 CONHZ HO N 0 HO N O 44 yellow H, c, J H'CN CHEZ PH3 CH3 N + N ci 45 HO N 0 yellow H3c, N I CH3 CH3 46 1 yellow Ho N 0 H CH3 CN 47 mellow yellow H CL3 CONH2 CONHZ 48 yellow HO N O H CH3 \ i 49 Ho N 0 yellow Y NH2 NH2 Ex. CC Shade CH 3 CN 50 Ho N 0 yellow kCH, NH2 CH 3 CONH2 CONHZ 51 Ho N 0 yellow WNHCH3 NH2 CH3 OH HAN Y N 52 \ NII _NI orange HO H N HX 3 NHZ NH OH'HNN CH3 < NAIN CL 53 I '^ orange HO, H N HN CH cl, OU OH HN OH HN"- 54 N"'N orange Oh H H EXAMPLE 55 12.5 parts of Exp. 35 and 87.5 parts of C. I. Basic Brown 23 are mixed. This dye composition is useful to add to ground cellulose and will give paper made thereof a brown hue.

The parts relates to the total amount of dyestuff, which is 100. Furthermore additional auxiliaries may be added to this dye composition e. g. buffers, viscosity improvers, surface tension improvers, biocides, light stabilizers, UV absorbers, optical brighteners and ionic or nonionic surfactants.

Further mixtures of dyestuffs may be produced analogously to the procedure given in Example 55.

TABLE 4/EXAMPLES 56-66 Exp Component one Component two Wt-% of Dye I Wt-% of Dye II 56 Exp. 26 C. I. Basic Brown 23 27. 5 72. 5 59 Exp. 28 C. I. Basic Red 12 40 60 60 Exp. 34 C. l. Basic Blue 1 37. 5 62. 5 61 Exp. 35 C. I. Basic Brown 23 22.5 77.5 62 Exp. 35 C. I. Basic Red 14 97. 5 2. 5 63 Exp. 35 C. l. Basic Violet 10 90 10 64 Exp. 35 C. I. Basic Red 12 80 20 65 Exp. 35 C. I. Basic Blue 26 22. 5 77. 5 66 Exp. 35 C. I. Basic Blue 1 95 5 67 Exp. 39 C. I. Basic Red 12 50 50 The use examples, which follow, serve to illustrate the invention. In the examples, parts are weight percent, unless otherwise stated; the temperatures are reported in degrees Celsius.

USE EXAMPLE A A hollander is used to grind 70 parts of chemically bleached sulfite softwood cellulose and 30 parts of chemically bleached sulfite birchwood cellulose into 2000 parts of water. 0.2 part of the dye from Example 8 is sprinkled in. After a mixing time of 20 minutes paper is made from the stuff. The thusly obtained absorbent paper has a yellow color. The wastewater is colorless.

USE EXAMPLE B 0.5 part of the dye solution of Example 35 is poured into 100 parts of bleached sulfite cellulose ground with 2000 parts of water in a hollande. Mixing for 15 minutes was followed by sizing. Paper made from this material has a yellow hue.

USE EXAMPLE C An absorbent web of unsized paper is pulled at 40°C-50°C through a dye solution of the following composition: 0.5 part of the dye of Example 8, 0.5 part of starch and 99.0 parts of water Excess dye solution is squeezed off by two rolls. The dry paper web has a yellow color.

The method of Use Examples A to C is also suitable for dyeing with the dyes of tables 2 and 3.

USE EXAMPLE D 15 kg of wastepaper (woody), 25 kg of bleached groundwood and 10 kg of unbleached sulfate pulp were beaten in a pulper to form a 3% aqueous pulp suspension. The pulp suspension was diluted to 2% in a dyeing vat. This suspension was then admixed in succession with 5% of kaolin and 1.25 kg of a 5% acetic acid solution of the dye of Example 8, reckoned on dry total fiber, by stirring. After 20 minutes the pulp in the mixing vat is admixed with 1% (based on absolutely dry fiber) of a resin size dispersion.

The homogeneous pulp suspension was adjusted with alum to pH 5 on the paper machine just upstream of the headbox.

The paper machine was used to produce 80 g/m2 of yellow bag paper with a machine finish.

USE EXAMPLE E A dry stock consisting of 60% groundwood and 40% unbleached sulfite pulp is beaten with sufficient water and ground to 40 SR freeness in a hollander for the dry content to be just above 2.5% and then adjusted with water to a dry content of exactly 2.5% for the high-density pulp.

200 parts of this high-density pulp are admixed with 5 parts of a 0.25% aqueous solution of the dye of Example 8, stirred for about 5 min., admixed with 2% of resin size and 4% of alum, based on dry stock, and again stirred for some minutes until homo- geneous. The material is diluted with 500 parts of water to 700 parts by volume and used in a known manner to prepare sheets of paper by drainage on a sheet-former.

These sheets of paper have a deep yellow color.

The method of Use Examples D and E is also suitable for dyeing with the dyes of tables 2 and 3.

USE EXAMPLE F 15 kg of wastepaper (woody), 25 kg of bleached groundwood and 10 kg of unbleached sulfate pulp were beaten in a pulper to form a 3% aqueous pulp suspension. The pulp suspension was diluted to 2% in a dyeing vat. This suspension was then admixed in succession with 5% of kaolin and 1.25 kg of a 5% acetic acid solution of the dye composition of Example 59, reckoned on dry total fiber, by stirring. After 20 minutes the pulp in the mixing vat is admixed with 1% (based on absolutely dry fiber) of a resin size dispersion. The homogeneous pulp suspension was adjusted with alum to pH 5 on the paper machine just upstream of the headbox.

The paper machine was used to produce 80 g/m2 of brown bag paper with a machine finish.

USE EXAMPLE G A ink composition for ink jet printing consists of 6 parts of a dye of the Example 22, 20 parts of glycerol and 74 parts of water.

This ink composition is used for printing papers, papery substrates, textile fiber materials and plastic films and plastic transparencies.