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Publication numberUS3846069 A
Publication typeGrant
Publication dateNov 5, 1974
Filing dateMay 15, 1972
Priority dateJul 26, 1968
Publication numberUS 3846069 A, US 3846069A, US-A-3846069, US3846069 A, US3846069A
InventorsH Angliker, R Peter, K Artz
Original AssigneeCiba Geigy Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Sublimation transfer dyeing with styryl dyes
US 3846069 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 9 US. Cl. 8-2.5 6 Claims ABSTRACT OF THE DISCLOSURE A process for dyeing and printing textile materials made of acrylic fibres and/ or polyester fibres, wherein the textile material is printed by the transfer printing process with a styryl dyestuff.

This is a continuation of application Ser. No. 843,184, filed July 18, 1969, now abandoned.

It is known that prints on Woven or knitted textile fabrics can be produced by printing a support material, usually paper, With an aqueous dispersion of a water- 3,846,069 Patented Nov. 5, 1974 ice It is advantageous however, to use dyestuffs which sublime within a period of 15 to seconds, but at most 60 seconds, at 180 to 210 C.

Suitable styryl dyestuffs are for example the dyestuffs of general formula NC R1 wherein X is a sulphone, carboxylicacid ester, carboxylic acid amide or preferably, nitrile group, R and R each represents hydrogen or a substituted or unsubstituted alkyl residue and A denotes a para-phenylene residue which may be substituted.

The groups R and R may be identical or different and can denote hydrogen atoms, or alkyl groups or substituted alkyl groups, for example halogenated alkyl groups, for example fl-chloroethyl, 5,5,B-trifiuoroethyl or flyy-dichloropropyl groups, benzyl groups, fi-phenylethyl groups, fl-cyanoethyl groups, alkoxyalkyl groups for example fl-ethoxyethyl or a-methoxybutyl groups, hydroxyalkyl groups for example B-hydroxyethyl or 5,'y-dihydroxypropyl groups, acyloxyalkyl groups for example ,B-acetoxyethyl or 8,'ydiacetoxypropyl groups, B-alkylsulphonylalkyl insoluble dispersion dyestuff which can be sublimed, and rsubsequently pressing the printed paper against the woven or knitted textile fabric to be printed and heating to a temperature at which the dyestutf sublimes and passes over to the woven or knitted fabric so that the fabric is V dyed. Complicated patterns can be printed by means of this so-called transfer printing process without expensive printing machines being required at this stage.

Pure greenish-tinged yellow dyeings or prints have however not hitherto been obtained in this way and this invention is based on the surprising observation that styryl dyestuffs which can be sublimed are particularly suitable for transfer printing on acrylic fibres and especially polyester fibres and that particularly valuable greenish tinged yellow shades can thus be obtained.

The invention therefore provides a process for dyeing and printing textile materials of acrylic fibres and especially polyester fibres, wherein the textile material is printed according to the transfer printing process with styryl dyestuffs, with or without other dyestuffs.

Sublimable dyestuffs within the scope of the invention are those dyestuffs which according to the Process for the Determination of the Dry Fixing'and Pleating Fastness of Dyeings and Prints (Dry Heat) of the Swiss Standards Association, Standard Specification SNV 95 833/ 1961, produce a surface bleeding (surface dyeing) which is adequate for dyeing purposes. In Standard Specification SNV 95833/1961 a sample of the dyed material is heated at certain test temperatures for 30 seconds in intimate contact with an undyed material for which the dyestuff has good affinity according to conventional dyeing methods, and under a pressure of 40 g.il0 g. per cmfi.

The definition according to the present invention however, also further includes dyestuffs which after a heating time of up to 2 minutes and/or at a lesser contact pressure have adequately surface-bled on to (or surfacedyed) the undyed textile material. It is immaterial whether the dyestuff sublimes in the physical sense provided it only passes in the gaseous state from one substrate to the other. A similar test to that in Standard Specification SNV 96855/ 1961 is described in the Standard Specification of the American Association of Textile Chemists and Colourists AATCC 117-1966T. In each case the direct contact of the material carrying the dyestuff with the undyed material is important.

groups for example B-methanesulphonylethyl or B-ethaneulphonylethyl groups, alkylcarbamoyloxyalkyl or arylcarbamoyloxyalkyl groups for example fi-methylcarbamyloxyethyl groups, alkyloxycarbonyloxyalkyl groups for ex ample ,B-(methoxy, ethoxy or isopropoxy)-carbonyloxyethyl groups, B-benzoyloxyethyl groups or fi-(p-alkoxyor phenoxybenzoyl-oxy)-ethyl groups. The groups R and R in general should not contain more than eight, and preferably not more than five carbon atoms.

Styryl dyestuffs which either possess an alkyl substituent on the phenylene ring and/or in which the group X represents a nitrile residue are particularly preferred.

As examples, the following dyestuffs may be mentioned:

Homologous series of dyestuffs with increasing fastness to sublimation are for example represented by the fatty acid esters of the monoor di-(B-hydroxyethyl) derivatives. Dyestuffs with the desired sublimation properties can be obtained by varying the number of carbon atoms in the fatty acid residue.

In multi-colour printing by the transfer process the styryl dyestuffs to be used according to the invention can be used together with other dyestuffs which sublime in the same temperature range.

The printing ink carriers required for the transfer printing can be of any desired structure based on cellulose, preferably non-textile, and preferably two-dimensional, which is printed in the desired pattern with an aqueous or preferably at least partially organic printing ink; practically anhydrous organic printing inks are preferred. Paper is principally used as the printing ink carrier. The printing inks usually contain the dyestuff partially dissolved and partially as a fine dispersion. Esters, ketones or alcohols, for example butyl acetate, acetone, methyl ethyl ketone, ethanol, isopropanol or butanol are preferably used as solvents. The printing inks may contain thickeners. In aqueous inks water-soluble thickeners are used, for example polyvinyl alcohol, carob bean flour, methylcellulose or water-soluble polyacrylates.

In the case of the preferred organic inks, easily soluble high molecular weight resins are used which have a softening point so high that the resins are not tacky during transfer printing; as resins, cellulose derivatives, for example the acetates or the ethyl, hydroxyethyl and/or hydroxypropyl ethers may be particularly mentioned.

In order to manufacture the printing inks, dyestuff preparations may be used which contain the above mentioned styryl dyestuffs and a resin which can be identical with the above mentioned thickeners or different therefrom. When it is different, it can also be a low molecular weight resin which does not cause any thickening effect and only serves to prevent agglomeration of the finely ground dyestuff. Preferably, the above mentioned cellulose derivatives are used as the resin.

A series of further resins, solvents and other suitable additives is mentioned in Patent Application Ser. No. 743,287, filed July 9, 1968 by Guenther Zwahlen, now abandoned in favor of US. Ser. No. 99,678, filed Dec. 18, 1970 as a continuation-in-part thereof, now abandoned in favor of US. Ser. No. 354,978, a continuation of the latter application, filed April 27, 1973. In addition to the above-disclosed, preferred cellulose derivative resins, U.S. Ser. No. 743,287 discloses the following eligibles resins:

(a) Colophony, and the derivative thereof in all forms, for example, hydrogenated, dimerized or polymerized, esterified with monohydric or polyhydric alcohols, with resin-formers, for example, acrylic acid and butanediol or maleic acid and pentaerythritol, modified colophony, calcium or zinc salts of colophony, abietic acid and the esters thereof. Soluble phenol resins modified with colo phony and resins based on acrylic compounds, and also other natural resins, for example, linseed oil varnish, shellac and other copals,

(b) Maleic resins, oil-free alkyd resins, styrolized alkyd resins, vinyltoluene-modified alkyd resins with synthetic fatty acids, linseed oil-alkyd resins, dehydrated castor oilalkyd resins, castor oil-alkyd resins, soybean oil-alkyd resins, coconut oil-alkyd resins, tall oil-alkyd resins, fish oil-alkyd resins and acrylic acid-modified alkyd resins,

(c) Terpene resins,

(d) Polyvinyl resins, for example, polyvinylacetate, polyvinyl chloride and polyvinylidene chloride, polyvinylacetals, polyvinyl alcohol, polyvinyl ether, copolymers and graft polymers with different vinyl monomers, polyacrylic acid resins, for example, acrylic acid esters and methacrylic acid esters and the copolymers thereof,.

(e) Styrene polymers and copolymers,

(f) Polyolefines, for example, polyethylene and polyethylene wax, polypropylene and polypropylene wax, polybutylene, polyisobutylene, polyisoprene, substituted polyolefines, halogenated polyolefines and the copolymers thereof, for example, ethylene and vinyl acetate copolymers, and other synthetic resins based on unsaturated hydrocarbons.

(g) Coumarone resins, indene resins and Coumaroneindene resins,

(l1) Aminoplasts, for example, urea and melamine resins, phenol resins, for example, novolaks (non-plasticized resols, resols modified with fatty acids or water-soluble resols); alkylphenol and arylphenol resins, terpenephenol resins, naphthaleneformaldehyde resins, carbamic acid and sulphatoamide resins, furan resins, ketone resins and aldehyde resins.

Also suitable are soluble polycondensation precursors, for example, phenol cresol, urea or melamine formaldehyde resins etherified with higher alcohols, especially butyl alcohol, linseed oil-stand oil and wool oil-stand oil ester resins,

(i) Polyamide and polyester resins, for example, linear or branched polyester based on phthalic acid, adipic acid, sebacic acid and diols or diol/triol mixtures and nylon 6, nylon 66 and isocyanate homopolymers,

(k) Cellulose derivatives of all kinds, for example, cellulose ethers, for example, methyl cellulose, hydroxyalkyl cellulose and alkylhydroxyalkyl cellulose, for example, hydroxyethyl cellulose or hydroxypropyl cellulose, cyanoethyl cellulose, ethyl cellulose and benzyl cellulose in commercial form, and also nitrocellulose, which may also be hyponitrated. The corresponding derivatives of other polysaccharides may also be used, for example, derivatives of starch;

(1) Unvulcanized caoutchouc and derivatives thereof, for example, cyclocaoutchouc or chlorocaoutchouc and so forth,

(m) Non-cross-linked silicone resins,

(n) Polyurethanes (especially urethane primary products that do not harden until subjected to an elevated temmerature (o) Epoxy resins (especially resin-hardener mixtures and pre condensates thereof that do not harden until subjected to an elevated temperature), especially those based on bis-phenyl-A-diglycidyl ethers, and finally,

(p) Precursors of unsaturated polyester resins and dialkylphthalate prepolymers.

Suitable textile materials are particularly woven and knitted fabrics but also fleeces, consisting of acrylic or acrylonitrile fibres, polyacrylonitrile fibres and copolymers of acrylonitrile and other vinyl compounds for example acrylic esters, vinyl chloride or vinylidene chloride, copolymers of dicyanethylene and vinyl acetate, as well as of acrylonitrile block copolymers and especially of aromatic polyester fibres, for example those consisting of terephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane, and copolymers of terphthalic and isophthalic acid and ethylene glycol, as well as mixtures of these fibres.

In the Example which follows, the parts denote parts by weight unless otherwise specified.

EXAMPLE 20 Parts of the styryl dyestuff of formula (synthesized according to British Patent Specification No. 458,405) are ground in a laboratory sandmill with 20 parts of hydroxypropylcellulose (trade name Klucel J; Hercules) and 360 parts of water for 24 hours while cool ing. A loose yellow powder is obtained by spray drying.

2.5 Parts of the resulting powder, 2.5 parts of hydroxypropylcellulose and 10 parts of isopropanol are stirred until the resin has completely dissolved and the dyestuff, to the extent that it does not dissolve, is uniformly distributed.

Paper is printed in a pattern with the resulting ink by the gravure printing process, and is dried.

(NC)2C=CHO-N(CH3)2 (Ber. 35, 1320 (1920).)

ON CzH O O CC=CH (J. Chem. Eng. Data, 8, 597-599 (1963).)

We claim:

1. In the process of sublimation transfer printing for coloring textile materials containing acrylic fiber, polyester fiber, or mixtures thereof, the improvement of using a styryl dyestulf which sublimes within a period of 60 seconds at 180 to 200 C. and which has the formula NC R1 wherein R and R each is hydrogen, an unsubstituted alkyl group of 1 to 8 carbon atoms, or an alkyl group of 1 to 8 carbon atoms substituted with halogen, phenyl, cyano, alkoxy, hydroxy, acyloxy, alkylsulphonyl, alkylcarbamoyloxy, phenylcarbamoyloxy, or alkyloxycarbonyloxy, and Y is hydrogen or methyl.

2. The process of claim 1 wherein R and R each is hydrogen, methyl, ethyl, chloroethyl, cyanoethyl, hydroxyethyl, or acetoxyethyl.

3. The sublimation transfer printing process of claim 1 wherein the sublimable dyestutf is applied to a cellulosic transfer sheet and contacted with the textile material under conditions of time, temperature, and pressure sufficient to cause the transfer of the dyestuff to the textile.

4. The process of claim 3 wherein the'transfer sheet is paper.

5. A transfer sheet for use in the sublimation transfer process which comprises a cellulosic support printed with at least one styryl dyestuif of the formula NC R1 wherein R and R each is hydrogen, an unsubstituted alkyl group of 1 to 8 carbon atoms, or an alkyl group of 1 to 8 carbon atoms substituted with halogen, phenyl, cyano, alkoxy, hydroxy, carbalkoxy, acylamino, acyloxy, alkylsulphonyl, alkylcarbamoyloxy, phenylcarbamoyloxy, or alkyloxycarbonyloxy, and Y is hydrogen or methyl.

6. A transfer sheet according to claim 5 in which the styryl dyestuff is in admixture with a cellulose ether or ester.

References Cited FOREIGN PATENTS 1,223,330 10/1958 France 8-2.5

OTHER REFERENCES Colour Index, 2nd edition, pp. 3401-3402. Pub. by Soc. Dyers & Col., Parkshere, England, March 1970.

AATCC Manual, p. 122, Test Method 1171967.

Kellett: Textile Mercury & Argus, Aug. 22, 1958, pp. 267, 269, and 275.

DONALD LEVY, Primary Examiner US. Cl. X.R. 8176, 177, 179

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3925273 *Aug 5, 1974Dec 9, 1975Sandoz AgOil-in-water transfer printing emulsions and method
US5139997 *Feb 4, 1991Aug 18, 1992Basf AktiengesellschaftThermal printing on plastic-coated paper
US5580410 *Dec 14, 1994Dec 3, 1996Delta Technology, Inc.Pre-conditioning a substrate for accelerated dispersed dye sublimation printing
DE2918685A1 *May 7, 1979Nov 15, 1979Minnesota Mining & MfgWaermeumdruckfarbstoffe
U.S. Classification8/471, 8/562, 8/922, 8/933, 8/636
International ClassificationD06P5/28, C09B23/14, B41M5/385, C09D11/02
Cooperative ClassificationB41M5/3854, Y10S8/933, C09D11/037, D06P5/006, Y10S8/922, C07C255/00, C09B23/143
European ClassificationC07C255/00, C09D11/037, C09B23/14D, D06P5/00T2Z, B41M5/385C