Process for dyeing cellulose-containing fibre materials

Claim 2

A process for dyeing cellulosic fibers comprising the step of applying an aqueous dye liquor to the fibers in the presence of a cationic levelling agent and in the substantial absence of other electrolytes, wherein the aqueous dye liquor contains a cationic dye which is a planar molecule having at least one system of delocalized π-electrons of at least 9 conjugated doubled bonds.

Claim 3

A process according to claim 1, wherein the cationic dye is one containing at least 12 uninterruptedly conjugated double bonds lying in one plane.

Claim 4

A process according to claim 1 or 2, wherein the cationic dye contains 1 to 8 cationic groups.

Claim 5

A process according to claim 3, wherein the cationic dye contains 1 to 3 cationic groups.

Claim 6

A process according to claim 1, wherein the employed dye is a dye of the formula ##STR71## wherein R is hydrogen or an alkyl group having 1 to 4 C atoms; A is an optionally quaternised basic radical; n denotes the numbers 1 to 4 inclusive; m denotes the numbers from 1 to 4 inclusive; M is hydrogen or any chosen cation; and p denotes the numbers 0 to 2 inclusive, with the proviso that m is equally great as or greater than p, and wherein the benzene groups B and D can be identically or differently further mono- or polysubstituted.

Claim 7

A process according to claim 1, wherein the employed dye is a dye of the formula ##STR72## wherein Z is an optionally quaternised basic group; Y is an anionic group; X and X 1 independently of one another are identical or different substituents from the class: hydrogen, halogen, CN, substituted or unsubstituted alkyl (C 1 -C 4 ), substituted or unsubstituted phenyl, or NHCOR 1 , wherein R 1 is alkyl (C 1 -C 4 ), cycloalkyl, substituted or unsubstituted aryl, or a heterocyclic radical, or OCOR 2 , wherein R 2 is substituted or unsubstituted alkyl (C 1 -C 4 ) or cycloalkyl, or ##STR73## wherein R 4 and R 5 independently of one another are: hydrogen, substituted or unsubstituted alkyl (C 1 -C 4 ), cycloalkyl or aryl, or R 4 together with R 5 and including the N atom forms a heterocyclic ring, or X and X 1 are the group COOR 6 , wherein R 6 is hydrogen, substituted or unsubstituted alkyl or cycloalkyl; n denotes the numbers from 1 to 4 inclusive; m denotes the numbers 0 to 2 inclusive, with the proviso that the number m is smaller than n; and wherein the benzene groups A and A 1 can be identically or differently further mono- or polysubstituted.

Claim 8

A process according to claim 1, wherein the employed dye is a dye of the formula ##STR74## wherein X 1 and X 2 independently of one another are each a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, halogen, hydrogen, cyano, a phenylamino group which can be substituted in the phenyl group, or they are each the CONH 2 group, the CONH phenyl group which can be substituted in the phenyl group, or they are each a COO-alkyl(C 1 -C 4 ) group; Z is an optionally quaternised basic group; Y is an anionic group; and B's independently of one another are each a fused-on ring system having 2 to 4 carbocyclic and/or heterocyclic rings, which system can be further substituted, in addition to the substituents Z and Y; n denotes the numbers from 1 to 4 inclusive, and m the numbers from 0 to 2 inclusive, with the proviso that m is not greater than n.

Claim 9

A process according to any one of claims 1 inclusive, wherein the cationic levelling agent used is a polymeric compound.

Claim 10

A process according to claim 8, wherein the polymeric cationic levelling agent contains amine, ammonium, sulfonium or phosphonium groups.

Claim 11

A process according to claim 9, wherein the polymeric cationic levelling agent contains ammonium groups.

Claim 12

A process according to claim 10, wherein the polymeric levelling agent containing ammonium groups contains a copolymer from maleic anhydride and ethylene or styrene, which is reacted with an n-alkylamine having 2 or 3 carbon atoms, which is substituted in the terminal position on the alkyl group by alkylamino having 1 to 4 carbon atoms, or by a cyclic amine which contains 5 or 6 ring carbon atoms and optionally 1 oxygen atom; or it contains a homopolymer of a vinylpyridine which is unsubstituted or substituted by methyl or ethyl; the homo- or copolymer being quaternised with a halomethylnaphthalene or -diphenyl, with chloroacetamide or chloroacetonitrile, or with a benzyl halide which is unsubstituted or substituted by halogen, methyl or ethyl, and optionally with an alkyl or alkenyl halide having at most 4 carbon atoms.

Claim 13

A process according to claim 11, wherein the levelling agent contains cationic recurring units which correspond to one of the formulae ##STR75## wherein Q 1 is a substituent of one of the formulae ##STR76## wherein n is 5-19 inclusive, or Q 1 is a mixture of at least one substituent of any one of the given formulae with alkyl or alkenyl having at most 4 carbon atoms; and D is ethylene or n-propylene; E is hydrogen, methyl or phenyl; R 10 and R 11 are each methyl, ethyl, n-propyl or n-butyl, or together with the nitrogen atom to which they are bound they form a pyrrolidine, piperidine or morpholine group; A 1 is halogen; Y 1 and Y 2 are each hydrogen, methyl or ethyl; and Z 1 , Z 2 and Z 3 are each hydrogen, halogen, methyl or ethyl.

Claim 14

A process according to claim 12, wherein the levelling agent contains cationic recurring units of the formula ##STR77## wherein Q 2 is --CN, --CH 2 --CO--NH 2 or phenyl; D is ethylene or n-propylene; A 2 is chlorine or bromine; R 12 and R 13 are each methyl, ethyl or n-propyl, or together with the nitrogen atom to which they are bound they form a morpholine group.

Claim 15

A process according to claim 13, wherein the levelling agent contains cationic recurring units of the formula ##STR78## wherein D is ethylene or n-propylene; and R 14 and R 15 are each methyl or ethyl.

Claim 16

A process according to any one of claims 11 to 14 inclusive, wherein the levelling agent has a mean molecular weight of 1,500 to 1,000,000.

Claim 17

A process according to claim 10, wherein the polymeric levelling agent containing ammonium groups is a quaternary ammonium salt which contains cationic recurring units of the formula ##STR79## wherein R 16 , R 17 , R 18 and R 19 are identical to or different from one another, and are each substituted or unsubstituted alkyl, cycloalkyl or alkenyl having at most 20 carbon atoms, aryl or aralkyl; or (R 16 and R 17 ) and/or (R 18 and R 19 ) together with the nitrogen atom to which they can bound form a substituted or unsubstituted heterocyclic ring having 5 or 6 ring members; D is --(CH 2 ) m --, wherein m is a number from 1 to 20 inclusive, which groups can be interrupted by at least one --S--, ##STR80## or substituted by at least one hydroxyl, halogen, nitrile, alkyl, hydroxyalkyl, alkoxy, carboxyl or carbalkoxy group, or can be substituted by at least one substituted aryl or aralkyl group; or D 1 is polyoxyalkylene; or a radical of any one of the formulae ##STR81## or together with the nitrogen atom and at least one of the substituents bound to the nitrogen atoms it forms a radical of the formula ##STR82## in which formulae M 1 and M 2 are each hydrogen, alkyl, hydroxy- or haloalkyl having 1 to 4 carbon atoms, hydroxyl, halogen, carboxyl, carbalkoxy or phenyl; G is the direct bond, ##STR83## or substituted or unsubstituted alkylene; n is a number from 1 to 6 inclusive; p is a number from 1 to 3 inclusive, preferably 1 or 2; and D 2 is a radical of the formula ##STR84##

Claim 18

A process according to claim 16, wherein the levelling agent contains cationic recurring units of the formula ##STR85## wherein R 20 , R 21 , R 22 and R 23 are identical to or different from one another, and are cycloalkyl having 5 or 6 carbon atoms; alkyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkylthioalkyl and alkylcarbonylalkyl having 1 to 10 carbon atoms; arylcarbonylalkyl, alkylsulfonylalkyl and arylsulfonylalkyl having 1 to 4 carbon atoms in each alkyl part; carboxyalkyl having 1 to 4 carbon atoms in the alkyl part; carbalkoxyalkyl and di-(carbalkoxy)-alkyl having 1 to 4 carbon atoms in each alkoxy and alkyl part; carboxylic acid amidoalkyl which has 1 to 10 carbon atoms in the alkyl part and which can be N-substituted with lower alkyl or aryl; or they are phenyl or benzyl which can be substituted by hydroxyl, cyano, halogen and carboxyl, or by alkyl, hydroxyalkyl, cyanoalkyl, alkoxy and alkylthio having 1 to 4 carbon atoms; alkoxyalkyl, carbalkoxyalkyl and di-(carbalkoxy)alkyl having in each alkyl and alkoxy part 1 to 4 carbon atoms; or (R 20 and R 21 ) and/or (R 22 and R 23 ) together with the nitrogen atom to which they are bound for a substituted or unsubstituted heterocyclic ring having 5 or 6 ring members; D 3 is --(CH 2 ) m --, wherein m is a number from 1 to 20 inclusive, which groups can be interrupted by at least one ##STR86## or can be substituted by at least one hydroxyl, chlorine, nitrile or alkyl, alkoxy or hydroxyalkyl having 1 to 4 carbon atoms, carboxyl or carbalkoxy having 1 to 20, preferably 1 to 4, carbon atoms in the alkoxy part, or substituted or unsubstituted phenyl or benzyl groups; or D 3 is a radical of any one of the formulae ##STR87## or together with the nitrogen atoms and in each case at least one of the substituents bound to the nitrogen atoms D 3 is a radical of the formula ##STR88## in which formulae T is hydrogen or methyl; and x is at least 1; and D 2 , M 1 and M 2 and G have the meanings given in claim 16.

Claim 19

A process according to claim 17, wherein the levelling agent contains cationic recurring units of the formula ##STR89## wherein R 24 , R 25 , R 26 and R 27 are identical to or different from one another, and are alkyl or hydroxyalkyl having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms, CH 3 OOCCH 2 --C 2 H 5 OOCCH 2 -- or benzyl; or (R 24 and R 25 ) and/or (R 26 and R 27 ) together with the nitrogen atom to which they are bound form a piperidine or morpholine group; and D 4 is --(CH 2 ) m .sbsb.1, wherein m 1 is a number from 1 to 12 inclusive, or a radical of any one of the formulae ##STR90## or together with the nitrogen atoms and in each case at least one of the substituents bound to the nitrogen atoms D 4 is a radical of the formula ##STR91##

Claim 20

A process according to claim 18, wherein the levelling agent contains cationic recurring units of the formula ##STR92## wherein m 1 is 1 to 12 inclusive; and A 1 is halogen.

Claim 21

A process according to claim 18, wherein the levelling agent contains cationic recurring units of the formula ##STR93## wherein x is at least 1.

Claim 22

A process according to claim 10, wherein the polymeric levelling agent containing ammonium groups is a quaternary ammonium salt containing cationic recurring units of the formula ##STR94## wherein R 16 , R 17 , R 18 and R 19 have the meanings given in claim 13; D 5 and D 6 are each --C n H 2n --, wherein n is 1 to 12 inclusive; and the sum of the n's in D 5 and D 6 is at least 3, and for n equals 1 the bond to the bridge member X 1 does not occur by way of a nitrogen or oxygen atom; or D 5 and D 6 are an aromatic bridge member, and they are identical to or different from one another; D 7 is a radical of the formula ##STR95## wherein G 1 is straight-chain or branched-chain alkylene which has 2 to 12 carbon atoms and which can be substituted by halogen; G 2 is ethylene, isopropylene or n-butylene; m 2 is 2 to 12 inclusive; and p 1 is 2 to 15 inclusive; and X 1 is a bivalent bridge member of the formula ##STR96## wherein X 2 is the direct bond, alkylene, alkenylene, arylene or heteroarylene, diaminoalkylene, diaminoarylene, optionally halogen-substituted dioxyalkylene, polyoxyalkyleneoxy or dioxyarylene; X 3 is a diaminoalkylene, optionally halogen-substituted dioxyalkylene, polyoxyalkyleneoxy or optionally halogen-substituted dithioalkylene; X 4 is arylene; and X 5 is alkylene or arylene.

Claim 23

A process according to claim 21, wherein the levelling agent contains cationic recurring units of the formula ##STR97## wherein R 20 , R 21 , R 22 and R 23 have the meanings given in claim 14; X 6 is --C r H 2r --, wherein r is an integer from 1 to 12 inclusive, --(CH═CH--) s , wherein s is 1 or 2, a radical of the formula --NH(CH 2 ) m NH--, wherein m is 2 to 12 inclusive, ##STR98## wherein the aromatic rings can be substituted by halogen, alkyl and/or alkoxy; also of the formula ##STR99## wherein T 1 and T 2 are each hydrogen or methyl; and of the formula --OG 1 O--or --(OG 2 ) p .sbsb.1 O--, wherein G 1 , G 2 , p 1 and D 5 , D 6 and D 7 have the meanings given in claim 21; and q is 0 or 1.

Claim 24

A process according to claim 19, wherein the levelling agent contains cationic recurring units of the formula ##STR100## wherein R 28 is alkyl having 1 to 4 carbon atoms; D 8 is --C m .sbsb.3 H 2m .sbsb.3 --, ##STR101## m 2 is 2 to 12 inclusive; and m 3 is 2 to 6 inclusive.

Claim 25

A process according to claim 21, wherein the levelling agent contains cationic recurring units of the formula ##STR102## wherein X 7 is --OG 1 O--, --(OG 2 ) p .sbsb.1 O--, --S(CH 2 ) m .sbsb.2 S-- or --NH(CH 2 ) m .sbsb.2 NH--; and G 1 , G 2 , m 2 , p 1 , D 5 , D 6 , D 7 , R 20 , R 21 , R 22 and R 23 have the meanings given in claims 17 and 21.

Claim 26

A process according to claim 21, wherein the levelling agent contains cationic recurring units of the formula ##STR103## wherein X 8 is --CONH--, --OCONH-- or --COO--, and D 5 , D 6 , D 7 and R 20 , R 21 , R 22 and R 23 have the meanings given in claims 17 and 21.

Claim 27

A process according to claim 25, wherein the levelling agent contains cationic recurring units of the formula ##STR104## wherein D 9 is alkylene having 1 to 4 carbon atoms, or phenylene; and D 10 is alkylene having 2 to 6 carbon atoms, or phenylene.

Claim 28

A process according to claim 21, wherein the levelling agent contains cationic recurring units of the formula ##STR105## wherein X 9 is a radical of the formula ##STR106## and m 2 , D 5 , D 6 , D 7 , R 20 , R 21 , R 22 and R 23 have the meanings given in claims 17 and 21.

Claim 29

A process according to claim 21, wherein the levelling agent contains cationic recurring units of the formula ##STR107## wherein m 3 is 2 to 6 inclusive; and D 7 , R 20 , R 21 , R 22 and R 23 have the meanings given in claims 17 and 21.

Claim 30

A process according to claim 28, wherein the levelling agent contains cationic recurring units of the formula ##STR108## wherein D 7 and m 3 have the meanings given in claims 18 and 20.

Claim 31

A process according to claim 1, wherein the levelling agent has a mean molecular weight of 1,000 to 100,000.

Claim 32

A process according to claim 1, wherein the cationic levelling agent is used in amounts of 0.01-5 percent by weight, relative to the cellulose material.

Claim 33

A process according to claim 31, wherein the cationic levelling agent is used in amounts of 0.1-0.5 percent by weight, relative to the cellulose material.

Claim 34

A process according to claim 1, wherein the aqueous dye liquor contains at least 2 cationic or basic dyes.

Claim 35

A process according to claim 1, wherein the aqueous dye liquor contains at least 3 cationic dyes.

Claim 36

A process according to claim 1, wherein the cellulose-containing fibre material is pretreated with an aqueous liquor containing at least one cationic levelling agent.

Claim 37

A process according to claim 35, wherein the celulose-containing fibre material is pretreated at a temperature of 10° C. to 130° C.

Claim 38

A process according to claim 36, wherein the cellulose-containing fibre material is pretreated at a temperature of 20° C. to 50° C.

Claim 39

A process according to claim 1, wherein the pH value of the pretreatment liquor and/or dye liquor is between 3 and 11 inclusive.

Claim 40

A process according to claim 38, wherein the pH value of the pretreatment liquor and/or dye liquor is between 4 and 7 inclusive.

Claim 41

A process according to claim 1, wherein the cellulose material is treated in the exhaust process.

Claim 42

A process according to claim 1, wherein textile cellulose material or paper is treated.

Claim 43

A process according to claim 41, wherein cotton, viscose, linen or rayon is treated.

Claim 44

A dye liquor for performing the process according to claim 1, which dye liquor comprises at least one cationic dye which (a) has available at least one system of delocalised π-electrons, which system consists of at least 9 conjugated double bonds lying in one plane, and (b) possesses a planar molecular structure, as well as at least one cationic levelling agent.

Claim 45

The cellulose-containing fibre material dyed by the process according to claim 1.