CA1036756A - Transfer printing process - Google Patents

Abstract

Abstract The invention relates to the transfer printing hydrophobic fibre materials using paper supports which are printed with azo dyestuffs of the formula

Description

lrhe present invention relates to a process for printing hydrophobic fibre materials in accordance with the transfer printing principle, which is characterised in that sublimable azo dyestu~fs which are free from sulpho groups, of the formula (C~
~ ~=N ~ N~

are used, wherein Xl and X2 represent hydrogen or alkyl or cycloalkyl radicals which are optionally substituted by non-polar substituents and n represents 1-3, and the benzene ring A can contain non-ionic substituents which are customary in dyestuff chemistry, and the benzene ring B
can contain customary non-polar substituents, which do not significantly influence the sublimability of the base molecule.
In addition to hydrogen, suitable radicals Xl and X2 are Cl-C4-alkyl or C5-C7-cycloalkyl radicals which are optionally substituted by Cl-C2-alkoxy, halogen or phenyl.
Suitable non-ionic substituents, customary in dyestuff chemistry, in A are N02, CN, halogen, S02CH3, S02C2H5, Cl-C4-alkYl or Cl-c4-alkoxy~
Suitable non-polar substituents in B are Cl-C4-alkyl, Cl-C4-alkoxy, halogen, benzyloxy, phenoxy, optionally halogen-substituted Cl-C4-alkylcarbonylamino or formylamino.
"Halogen" preferably represents F, Cl and Br. Dyestuffs to be used preferentially correspond to the formula ;
Le A 15 466 - 2 -103~i756 ÇF~ p~
N=N ~ N ~ II
r~ ~
wherein Yl = H, N02, CN, CF3 or CH3, Y2 = Yl, Cl or Br, y3 = H or Cl, Rl and R2 = H, Cl-C4-alkyl, phenyl-Cl-C3-alkyl, cyclopentyl, cyclohexyl, methylcyclohexyl, Cl-C4-chloroalkyl or Cl-C2-alkoxy-Cl-C4-alkyl, R3 = H, Cl-C4-alkyl, Cl-C4-alkoxy, phenoxy or benzyloxy, R4 = H, CH3, CF3, C2H5, Cl, Br or NHCOR5 and R5 = H, Cl-C4-alkyl, Cl-C4-chloroalkyl, Cl-C4-bromo-alkyl or methoxy-C2-C4-alkyl.
Preferred types are those, within the scope of the formula II, wherein a) Yl = N02 and Y2 and y3 = H, b) Yl and Y2 = N02 and y3 = H, c) Yl = CN, Y2 = N02 and y3 = H, d) Yl and y3 = H and Y2 = CF3, as well as e) Yl = N02; Y2 = CF3 and y3 = H
wherein Rl-R4 have the indicated meaning.
Amongst these, in turn, preferred dyestuffs are those in which R3 = H, CH3, OCH3 or OC2H5 and R4 = H, CH3, C2Hs or Cl-The dyestuffs of the formula (I) are prepared according Le A 15 466 - 3 -to processes which are in themselves known, by diazotising an aniline of the formula (III) ~CF~)n III
~ N~

and combining the diazonium compound with a collpling component of the formula (IV).

IV
~ N \

Examples of possible diazo components of the formula (III) are: l-amino-2-trifluoromethylbenzene, 1-amino-4-tri-fluoromethylbenzene, l-amino-2-chloro-4-trifluoromethylbenz-ene, 1-amino-2-bromo-4-trifluoromethylbenzene, 1-amino-2-methyl-4-trifluoromethylbenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, l-amino-2-trifluoromethyl-4-methylbenzene, 1-amino-2,4-bis-trifluoromethylbenzene, 1-amino-2,6-bis-tri-fluoromethylbenzene, l-amino-2-chloro-5-trifluoromethylbenzene, 1-amino-2,5-bis-trifluoromethylbenzene, 1-amino-2,4,6-tris-trifluoromethylbenzene, l-amino-2-trifluoromethyl-4-nitro-benzene, l-amino-2-nitro-4-trifluoromethylbenzene, 1-amino-2-trifluoromethyl-4,6-dinitrobenzene, 1-amino-2,4-bis-trifluoro-methyl-6-nitrobenzene, 1-amino-2,6-bis-trifluoromethyl-4-nitro-benzene, 1-amino-4-trifluoromethyl-2,6-dinitrobenzene, l-amino-

2-cyano-4-trifluoromethylbenzene, 1-amino-2-trifluoromethyl-4-cyanobenzene, l-amino-4-trifluoromethyl-2,6-dicyanobenzene, l-amino-2-trifluoromethyl-4,6-dicyanobenzene, 1-amino-2,6-trifluoromethyl-4-cyanobenzene, 1-amino-4-trifluoromethyl-2-nitro-6-cyanobenzene, 1-amino-2-trifluoromethyl-4-cyano-6-Le A 15 466 - 4 _ nitrobenzelle~ l-amino-2-cllloro-4~(~-bis-tr.ifllloromethylbenzene, :I.-amino-2-fluoro-4-trifluoromethylbenzene, 1-amino-2-fluoro-4,~-bis-trifluoromethylbenzene, 1-alllino-2~(,-dichloro-4-tri-fl~oromethyl.aniline, :l-amino-2-trifluoromct~ly`l-5-.nitrobenzene, l-(N~N-diethylamino)-~-trifluoromethylbenzene, I.-(N-ethyl-N-benzy:Lamino)-~-trifluoromethy:lben2ene~ :1-am.ino-2-trifluoro-methyl-4-methylsulphonylbenzene, 1-amino-2-trifluoromethyl-4-ethylsulphonylbenzene~ l-amino-2,G-bis-trifluoromethyl-4-nitrobenzene and l-amino-2-methoxy-4-nitro-6-trifluoromethyl-benzene.
Examples of possible coupling components of the formula(IV) are: N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-propylaniline, N,N-diisopropylaniline, N,N-di-n-butyl-aniline, N-methyl-N-benzylaniline, N-ethyl-N-benzylaniline, N-n-propy`l-N-benzylaniline, N-methyl-N-~-phenylethylaniline, N-ethyl-N-~-phenylethylaniline, N-n-butyl-N-~-phenylethyl-aniline, N-methyl-N-cyclopentylaniline, N-ethyl-N-cyclopentyl-aniline, N-methyl-N-cyclohexylaniline, N-ethyl-N-cyclohexyl-aniline, N-n-butyl-N-cyclohexylaniline, N,N-di-benzylaniline, N-benzyl-N-cyclohexylaniline, N-~-phenethyl-N-cyclohexyl-aniline, N-m~thyl-N-~-chloroethylaniline, N-ethyl-N-~-chloro-ethylaniline, N-methyl-N-~-chloropropylaniline, N-ethyl-N-~-chloropropylaniline, N-ethyl-N-~-chloropropylaniline, N-ethyl-N-~-bromoethylaniline, N-n-propyl-N-~-chloroethylaniline, N-propyl-N-~-chloroethylaniline, N-benzyl-N-~-chloroethylaniline, N-cyclohexyl-N-~-chloroethylaniline, N,N-bis-~-chloroethyl-aniline, N-~-phenylethyl-N-~-chloroethylaniline, l-(N,N-dimethylamino)-3-methylbenzene, 1-(N,N-diethylamino)-3-methylbenzene, l-(N,N-di-n-propylamino)-3-methylbenzene, 1-(N,N-diisopropylamino)-3-methylbenzene, 1-(N,N-di-n-butyl-amino)-3-methylbenzene, 1-(N-methyl-N-benzylamino)-3-methyl-Le A 5 466 - 5 -~036756 benzene, l-(N-ethyl-N-benzylamino)-3-methylbenzene, l-(N-n-propyl-N-benzylamino)-3-methylbenzene, l-(N-methyl-N-~-phenyl-ethylamino)-3-methylbenzene, l-(N-ethyl-N-~-phenylethylamino)-

3-methylbenzene, 1-(N,n-butyl-N-~-phenylethylamino)-3-methyl-benzene, 1-(N-methyl-N-cyclopentylamino)-3-methylbenzene, 1-(N-ethyl-N-cyclopentylamino)-3-methylbenzene, l-(N-methyl-N-cyclohexylamino)-3-methylbenzene, ].-(N-ethyl-N-cyclohexyl-amino)-3-methylbenzene, 1-~N,N-dibenzylamino)-3-methylbenzene, l-(N-benzyl-N-cyclohexylamino)-3-methylbenzene, l-(N-~-phenyl-ethyl-N-cyclohexylamino)-3-methylbenzene, l-(N-methyl-N-~-chloroethylamino)-3-methylbenzene, l-(N-ethyl-N-~-chloroethyl-amino)-3-methylbenzene, 1-(N-methyl-N-~-chloropropylamino)-3-methylbenzene, l-(N-ethyl-N-~-chloropropylamino)-3-methylbenz-ene, l-(N-ethyl-N-~-chloropropylamino)-3-methylbenzene, l-(N-ethyl-N-~-bromoethylamino)-3-methylbenzene, l-(N-benzyl-N-~-chloroethylamino)-3-methylbenzene, l-(N-cyclohexyl-N-~-chloro-ethylamino)-3-methylbenzene, l-(N-~-phenylethyl-N-~-chloro-ethylamino)-3-methylbenzene, 1-(N,N-bis-~-chloroethylamino)-3-methylbenzene, l-(N,N-dimethylamino)-3-chlorobenzene, l-(N,N-diethylamino)-3-chlorobenzene, 1-(N-ethyl-N-benzylamino)-3-chlorobenzene, l-(N-ethyl-N-~-phenylethylamino)-3-chlorobenz-ene, l-(N-ethyl-N-cyclohexylamino)-3-chlorobenzene, l-(N-ethyl-N-~-chloroethylamino)-3-chlorobenzene, l-(N,N-diethyl-amino)-3-bromobenzene, 1-(N-ethyl-N-benzylamino)-3-bromobenz-ene, 1-(N-ethyl-N-~-chloroethylamino)-3-bromobenzene, l-(N,N-dimethylamino)-3-acetylaminobenzene, 1-(N,N-dimethylamino)-3-propionylaminobenzene, 1-(N,N-dimethylamino)-3-formylamino-benzene, l-(N,N-dimethylamino)-3-chloroacetylaminobenzene, l-(N,N-dimethylamino)-3-~-chloropropionylaminobenzene, 1-(N,N-diethylamino)-3-formylaminobenzene, l-(N,N-diethylamino)-3-acetylaminobenzene, 1-(N,N-diethylamino)-3-butyrylamino-Le A 15 466 - 6 -10;~67S6 benzene, l-(N,N-diethylamino)-3-chloroacetylaminobenzene, 1-(N,N-ethylbenzylamino)-3-acetylaminobenzene, l-(N-ethyl-N-benzylamino)-3-chloroacetylaminobenzene, l-(N-ethyl-N-benzyl-amino)-3-formylaminobenzene, 1-(N,N-dibutylamino)-3-formyl-aminobenzene, l-(N,N-dibutylamino)-~-chloroacetylaminobenzene, l-(N,N-dimethylamino)-2-methoxy-5-formylaminobenzene, l-(N,N-dimethylamino)-2-methoxy-5-acetylaminobenzene, l-(N,N-diethyl-amino)-2-methoxy-5-acetylaminobenzene, 1-(N,N-diethylamino)-2-ethoxy-5-acetylaminobenzene, 1-(N,N-diethylamino)-2-phenoxy-5-acetylaminobenzene, 1-(N,N-diethylamino)-2-benzyloxy-5-acetylaminobenzene, l-(N,N-diethylamino)-2-methyl-5-acetyl-aminobenzene, l-(N,N-diethylamino)-2-methyl-5-chlorobenzene, l-(N,N-diethylamino)-2,5-dimethylbenzene, l-(N,N-diethylamino)-2-ethyl-5-formylaminobenzene, 1-(N,N-diethylamino)-2-propoxy-5-acetylaminobenzene~ 1-(N,N-diethylamino)-2-methoxy-5-chloroacetylaminobenzene, l-(N-ethyl-N-benzylamino)-2-methoxy-5-acetylamin~obenzene, 1-(N-ethyl-N-cyclohexylamino)-2-methoxy-5-acetylaminobenzene, 1-(N-ethyl-N-~-chloroethylamino)-2-methoxy-5-acetylaminobenzene, 1-(N,N-ethylamino)-2-methoxy-5-methylbenzene, 1-(N,N-diethylamino)-2-methoxy-5-chlorobenzene, l-(N-benzyl-N-n-butylamino)-2-methoxy-5-acetylaminobenzene and l-(N,N-dibenzylamino)-2-phenoxy-5-chloroacetylaminobenzene.
The transfer printing process is generally known and has been described, for example, in French Patent Specifica-tions 1,223,330 and 1,334,829. The dyestuffs, for example in the form of so-called printing inks, such as are described, for example, in French Patent Specification 1,573,698, or in the form of pastes, are applied to temporary supports (paper, other cellulosic materials, such as cotton or cellophane, metal foils and the like, such as are known, for example, from French Patent Specification 1,575,069). These Le A 15 466 - 7 _ printing inks are dyestuff solutions, also containing syn-thetic resin, in suitable organic solvents, such as benzene, toluene, xylene, chlorobenzene, chloroform, dichloroethane, trichloroethylene, perchloroethylene, ethanol, iso-propanol, benzyl alcohol, cyclohexanone, ethyl acetate or their mixtures.
However, the printing inks and printing pastes can also be formulated on an aqueous basis and are thus dispersions of the dyestuffs in water, which in addition con~k customary dis-persing agents and thickeners (compare French Patent Specifi-cation 1,223,330) and US Patent Specification 3,647,503).
The printing inks can be printed by the customary printing processes (relief printing, gravure printing, offset printing, film printing or screen printing).
Suitable substrates for transfer printing with dye-stuffs of the formula I are textile materials which consistwholly or predominantly of polyesters, such as polyethylene glycol tereph~halate, poly-1,4-bis-hydroxymethylcyclohexane terephthalate or cellulose triacetate and cellulose 2~-acetate or of polyamides or polyacrylonitrile, but also non-textile plastics articles, such as films, tapes or blocks of commercially available polymerisation or polycondensation plastics.
Particularly suitable dyestuffs I sublime in the range from 140-250C, preferably from 160-220C.
Example 1 A) 75 g of the dyestuff of the formula ~F~
0~ N~N=N~N~C~ C~ ~:1 C~
50 g of an anionic dispersing agent, for example a lignin-Le A 15 466 - 8 -sulphonate or a condensation product of naphthalenesulphonic acid and formaldehyde, and 100 ml of water are mixed and converted to a finely divided form by grinding for 10 hours in a ball mill.
The dispersion thus obtained, which contains approx.
30% of crude colourant, is stable on storage.
B) The aqueous dispersion obtained according to A) can be converted to a printing paste as follows: 50 to 200 g are worked into a paste with 400 g of a 10% strength carob bean flour ether thickener and 550 to 400 ml of water.
C) A paper is printed with this printing paste by the gravure printing process. If this paper is pressed against a textile of polyester fibres for 15 to 60 seconds at 200C, a clear, deep red print with good fastness properties is obtained.
Example 2 A) 40 to 50 g of the dyestuff used in Example 1 are worked into a paste with 5 to 10 g of an emulsifier mixture of ethoxylated nonylphenol (4 to 12 mols of ethylene oxide) in water. 10 g of ethylcellulose N4 (Hercules Powder) and 30 to 40 parts of a maleate resin which has been prepared by condensation of colophony with maleic acid are added. The mixture is kneaded at 80 to 100C for approx. 2 hours and is then ground on one of the customary mills. A finely granular dyestuff powder is obtained.
B) 200 g of the dyestuff powder obtained according to A) are introduced into a mixture of 730 g of ethanol, 50 g of ethylene glycol and 20 g of ethylcellulose N22 (Hercules Powder), whilst stirring.
C) Papers can be printed with the printing ink thus obtained by the gravure printing process. Textiles of Le A 15 466 - 9 -~0367S6 cellulose triacetate or polyamide, for example knitted fabrics, can be printed with these printed papers by the transfer process, and deep red prints are obtained.
The dyestuff of Example 1 was prepared as follows:
~0 parts of finely powdered 1-amino-2-trifluoromethyl-4-~itrobenzene were dissolved in 300 parts of concentrated sulphuric acid whilst stirring; during this time the tempera-ture should not exceed 20C. The solution is then cooled to 0C and nitrosylsulphuric acid prepared by dissolving 20 parts of sodium nitrite in 80 parts of concentrated sulphuric acid is gradually added dropwise at the same temperature.
The mixture is stirred for approx. 2 hours longer at 0C.
The diazonium salt solution thus prepared is now added gradually at 0-5C, whilst stirring well, to a solution of 58 parts of 1-(N-ethyl-N-~-chloroethylamino)-3-methylbenzene in 2,000 parts of water and 50 parts of concentrated hydro-chloric acid, to which 10 parts of amidosulphonic acid have been added. The coupling reaction starts immediately.
It can be accelerated by buffering with a solution to pH 4-5 by means of sodium acetate. After completion of coupling, the azo dyestuff formed is filtered off, washed with water until free of salt and dried. 116 parts of a red dyestuff powder are obtained.
The table which follows lists further dyestuffs which are obtained when the diazo component of column 2 is diazo-tised and combined with the coupling component of column 3 to give the azo dyestuff, and also lists the shades obtainable therewith in accordance with the process indicated in Example 1.

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Claims (7)

Patent Claims

1) Process for printing hydrophobic fibre materials in accordance with the transfer printing principle, characterised in that sublimable azo dyestuffs which are free from sulpho groups, of the formula I
are used, wherein X1 and X2 represent hydrogen or alkyl or cycloalkyl radicals which are optionally substituted by non-polar substituents and n represents 1-3, and the benzene ring A can contain non-ionic substituents which are customary in distaff chemistry, and the benzene ring B can contain customary non-polar substituents, which do not significantly influence the sublimability of the base molecule.

2) Process according to Claim 1, characterised in that dyestuffs of the formula II
are used, wherein y1 = H, N02, CN, CF3 or CH3, y2 = y1, Cl or Br, y3 = H or Cl, R1 and R2 = H, C1-C4-alkyl, phenyl-C1-C3-alkyl, cyclopentyl, cyclohexyl, methylcyclohexylj C1-C4-chloroalkyl or Cl-C2-alkoxy-Cl-C4-alkyl, R3 = H, C1-C4-alkyl, C1-C4-alkoxy, phenoxyorbenzyloxy, R4 - H, CH3, CF3, C2H5, Cl, Br or NHCOR5 and R5 = H, C1-C4-alkyl, C1-C4-chloroalkyl, C1-C4-bromoalkyl or methoxy-C2-C4-alkyl.

3. Process according to claim 1, characterised in that a dyestuff of the formula is used.

4. Process according to claim 1, characterised in that a dyestuff of the formula is used.

5. Process according to claim 1, characterised in that a dyestuff of the formula is used.

6. Process according to claim 1, characterized in that a dyestuff of the formula is used.

7. Process according to claim 1, characterized in that a dyestuff of the formula is used.