GB2031469A

GB2031469A - Process for printing textile material

Info

Publication number: GB2031469A
Application number: GB7933358A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1978-09-27
Filing date: 1979-09-26
Publication date: 1980-04-23
Also published as: DE2938766A1; NZ191683A; DK403379A; FR2437462A1; AU5120579A; BE879023A; NL7907130A

Abstract

The textile material is firstly impregnated with an alkaline aqueous liquor, and subsequently printed with an acid aqueous printing paste containing a dye, a synthetic thickener having in the neutral to alkaline pH range a viscosity higher than it has in the acid pH range, and optionally further additives. The process renders possible the printing of voluminous material of light quality with the obtainment of designs having sharp contours.

Description

SPECIFICATION Process for printing textile material The present invention relates to a process for printing textile material, particularly voluminous material, and also to the material obtained by this process.

The process frequently used for printing voluminous material is the spray printing process, in which the colour paste is sprayed through nozzles onto the material to be printed. Whereas textile material of heavy quality can be satisfactorily printed by this process, difficulties are often experienced when a light quality material having a weight of below 1000 g/m2 is printed in that the contours are not sharp.

It was therefore the object of the present invention to develop a process for printing textile material, which process would be applicable also for printing voluminous material of light quality by the spray printing method, with sharp contours being obtained. Furthermore, this process would render possible the use of synthetic thickeners in the case of all types of nozzles employed on conventional spray printing machines.

This problem has been solved according to the invention by using a process in which the textile material is impregnated with an alkaline aqueous liquor, and subsequently printed with an acid aqueous printing paste containing a dye, a synthetic thickener having in the neutral to alkaline pH range a viscosity higher than it has in the acid pH range, and optionally further additives.

Surprisingly, there are obtained by this process, also on voluminous material of a light quality, very sharp contours, and no frosting effect occurs. Since the printing paste has an acid pH value, and hence a relatively low viscosity, all conventional nozzles can be used. The process according to the invention has in addition the unexpected advantage that the yield of the dyes and the brilliancy of the dyeings are better than those obtained using a printing paste which contains a natural thickener. Furthermore, it is shown that the electrolyte sensitivity of the synthetic thickeners when used in the process according to the invention is lower, so that it is possible to use dyes having higher electrolyte contents, which dyes were not able to be used hitherto together with electrolyte-sensitive thickeners with a neutral or alkaline pH value.

Because the printing paste used in the process according to the invention is relatively thinly liquid on account of its acid pH value, it penetrates very well and uniformly into the textile material, even in the case of voluminous material. The neutralisation occurring as a result of the alkaline liquor present on the material results then however in the printing paste acquiring a very high viscosity. The effect of this is that a very good dye penetration of the textile material is achieved, and simultaneously very sharp contours without frosting are obtained.

The alkaline aqueous liquor employed in the process according to the invention preferably has a pH value greater than 9, particularly greater than 1 2. This pH value is obtained by the addition of basic salts, for example sodium carbonate or potassium carbonate, or of bases, for example ammonia, triethanolanime, KOH or NaOH, with NaOH being preferably used.

The amount of alkali has to be such that it suffices to neutralise the acid printing paste, so that subsequently there exists on the textile material a neutral to alkaline pH value; and depending on the substrate and on the dye, this pH value can be between 7 and 11.

The aqueous alkaline liquor can additionally contain auxiliaries, for example antifoaming agents, thickeners or, in particular, wetting agents. In an especially preferred embodiment of the process according to the invention, the aqueous alkaline liquor contains at least one dye or optical brightener, so that there is obtained on the whole of the material a bottom dyeing, onto which a design can be subsequently printed.

The textile material is impregnated with the said alkaline liquor in the customary manner, for example by immersion, by spraying, by the liquor being poured over, or preferably by padding, and subsequent squeezing out to leave a liquor absorption of about 60 to 150%.

The textile material is subsequently printed with an acid aqueous printing paste containing 3 dye, a synthetic thickener and optionally further additives.

Suitable synthetic thickeners are, according to definition, those which have in the neutral to alkaline pH range a viscosity higher than in the acid pH range. They are in particular polymers containing carboxyl groups. Suitable polymers are for example homo- and copolymers of unsaturated mono- and dicarboxylic acids having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid, and also copolymers of the stated carboxylic acids with unsaturated monomers, such as vinyl esters, acrylic acid esters, methacrylic acid esters, ethylene, styrene and vinyl ethers. Suitable thickening agents are obtained also by polymerising the said unsaturated mono- and dicarboxylic acids, optionally together with the other unsaturated monomers mentioned, in the presence of monomers having two double bonds.Suitable such monomers having two double bonds are for example divinyldioxane, butanediol-diacrylate, butadiene and divinylbenzene. These monomers are contained in the copolymer to the extent of about 0.05 to 5 per cent by weight. The carboxylic acid content in the thickening agent is in general between 75 and 99.5 per cent by weight.

Particularly suitable for the process accord ing to the invention are copolymers from ethylene and maleic anhydride, or carboxyvi nyl polymers, that is to say, polymeric acrylic acids. An especially suitable copolymer among these is a crosslinked carboxyvinyl polymer having a molecular weight of about 4,000,000, or a linear carboxyvinyl polymer having a molecular weight of about 1,000,000. A mixture of these two is prefera bly used.

These thickeners are used in the form of their acids. The amount of thickener is preferably such that the acid printing paste has a viscosity of about 200-800 cPs, particularly 400-600 cPs, whilst the viscosity of this printing paste in the neutral to alkaline range is preferably greater than 2000 cPs, especially greater than 10,000 cPs.

The type of dyes contained in the printing paste and optionally also in the aqueous alkaline liquor is governed by the textile material to be printed. Material made from natural polyamides, for example wool, is printed with anionic metal-free dyes, with metal-complex dyes or with reactive dyes. For synthetic polyamides, the same dyes are suitable, and additionally also disperse dyes. For printing material made from natural or regenerated cellulose, there are used reactive dyes, and in particular the so-called substantive dyes optionally containing heavy metals; and for dyeing polyester materials are preferably used the so-called disperse dyes. Textile material made from polyacrylonitrile is printed preferably with disperse dyes or cationic dyes.They are dyes of various classes: for example nitro, aminoketone, ketoneimine, methine, nitrodiphenylamine, quinoline, aminonaphthoquinone or coumarin dyes, and particularly anthraquinone and azo dyes, such as monoazo and disazo dyes.

The term 'dyes' is to be understood as embracing also optical brighteners. These are for example brighteners of the following classes of compounds: stilbenes, coumarins, benzocoumarins, pyrenes, pyrazines, pyrazolines, oxazines, mono- or dibenzoxazolyl or imidazolyl compounds, aryltriazole and v-triazole derivatives, and also naphthalic acid imides.

In addition to water, thickener and dye, the printing paste can contain other additives, for example wetting agents, antifoaming agents, or agents influencing the properties of the textile material, for example softening agents and additives for imparting a flameproof finish, as well as agents rendering the material dirt-, water- and oil-repellent.

The printing' paste can be applied to the textile material in the customary manner, for example by screen printing, rotary screen printing or relief printing, or by the so-called "polychromatic" or "TAK" process. The printing paste is preferably applied however by means of spray printing, for example by the so-called "Millitrnn", "Chromotronic", "Mulitchromat" or "Titan" process.

After printing, the textile material is finished in the customary manner comprising firstly fixing the dye, for example by heating to above 1 00do or by steaming, subsequently rinsing, optionally with the addition of small amounts of acids for neutralising, and finally drying. The use of synthetic thickeners and the good dye yield in the process according to the invention render possible a shortened washing time and the use of amounts of water smaller than those needed in the customary processes.

Textile materials suitable for the process according to the invention are fabrics and knitted goods of a wide variety of types. The process is particularly suitable for printing voluminous material, especially velour or looped materials or needle felting. The preferred articles are carpets, particularly those made from synthetic polyamide. The advantages of the process according to the invention are demonstrated in particular in the case of material having a weight of below 1000 g/m2, especially below 500 g/m2.

The Examples which follow serve to illustrate the invention. The term 'parts' denotes parts by weight, and the temperature values are given in degrees Centigrade.

EXAMPLE 1 Velvet pile carpeting made from polyamide 6 having a weight of 350-400 g/m2is impregnated on a padding machine with a padding liquor consisting of 988 parts of water, 10 parts of sodium hydroxide solution 36 Bé, and 2 parts of a wetting agent, and then squeezed out to a liquor absorption of 80%.

Onto the carpet pretreated in the manner described there is subsequently sprayed, by means of a nozzle, a printing paste of the following composition in the form of a design: 942 parts of water, 50 parts of thickener, 3 parts of antifoaming agent, and 3 parts of the yellow dye of the formula

1 part of the red dye of the formula

and 1 part of the blue dye of the formula

The thickener used has the following composition: 240 parts of white spirit, 50 parts of water-in-oil emulsifier, 20 parts of oil-in-water emulsifier, 20 parts of antifoaming agent, 50 parts of a crosslinked carboxyvinyl polymer having a molecular weight of about 4,000,000, 70 parts of a linear carboxyvinyl polymer having a molecular weight of about 1,000,000, and 550 parts of water of which the pH value has been adjusted to 4.5 with acetic acid.

The material sprayed with the printing paste is subsequently treated for 5 minutes with saturated steam at 101" in order to fix the dyes; the material is then rinsed, neutralised, rinsed again and dried.

There is obtained velvet pile carpeting which has a dark brown design with very sharp contours printed on it, and which displays excellent dye penetration with a complete absence of frosting.

Identically good results are obtained when, in place of the velvet pile carpeting, there is treated, exactly as described above, a polyamide 6 or polyamide 6.6 carpeting made from looped material having a weight of 300-350 g/m2, or from needle felting having a weight of 300-350 g/m2.

EXAMPLE 2 Carpeting made from polyamide 6 is impregnated on a padding machine with a padding liquor consisting of 987.25 parts of water, 10 parts of sodium hydroxide solution 36'B6, 2 parts of wetting agent, and 0.75 part of the pink dye of the formula

and is subsequently squeezed out to leave a liquor absorption of 80%.

There is then printed onto the above pretreated carpet, using a film screen, a printing paste of the following composition: 942 parts of water, 50 parts of the thickener from Example 1, 3 parts of antifoaming agent, and 5 parts of a brown dye mixture containing the 1:2 chrome complex of the following dyes:

the 1:2 chrome complex of the following dyes:

and the 1:2 cobalt complex of the first of these four dyes.

The printed carpet is subsequently treated for 5 minutes with saturated steam at 101" in order to fix the dyes; the carpet is then rinsed, neutralised, rinsed again and dried.

Carpeting displaying a very sharply outlined, dark brown printing on a pink background is obtained.

EXAMPLE 3 If the procedure is carried out as in Example 2 except that the padding liquor used for the pretreatment of the material consists in this case of 983 parts of water, 10 parts of sodium hydroxide solution 36 BQ, 2 parts of wetting agent, and 5 parts of the yellow 1:2 chrome complex of the dye of the formula

the process otherwise being performed as described in Example 2, carpeting displaying a very sharply outlined, dark brown printing on a yellow background is obtained.

EXAMPLE 4 A cotton-plush material ("Henkelpliisch, 370 g/m2) is pretreated as described in Example 1 with an alkaline padding liquor.

There is then printed onto this material, using a film screen, a printing paste of the following composition: 300 parts of cold water, 50 parts of the thickener from Example 1, 1 2 parts of the green dye of the formula

100 parts of urea, 300 parts of hot water, 3 parts of antifoaming agent, and 235 parts of cold water.

The dye is fixed by subsequent steaming for 12 minutes in saturated steam at 101 ; and the material is then rinsed and dried.

A green printing having sharp contours is obtained on the plush.

EXAMPLE 5 A cotton-plush material ("HenkelplUsch", 370 g/m2) is impregnated on a padding machine with a padding liquor consisting of: 978 parts of water, 20 parts of sodium hydroxide solution 36 Bé, and 2 parts of wetting agent, and is then squeezed out to give a liquor absorption of 80%. There is then printed onto this material a printing paste consisting of 300 parts of cold water, 50 parts of the thickener from Example 1, 5 parts of the violet dye of the formula

R = mixture of C6 HsO- and -NH2 100 parts of urea, 300 parts of hot water, 3 parts of antifoaming agent, and 242 parts of cold water.

There is obtained after a steam treatment for 10 minutes in saturated steam at 101" a violet printing having sharply outlined contours and good print penetration.

EXAMPLE 6 A Dralon upholstery fabric ("Dralon-Plusch" with cotton backing, 465 g/m2) is pretreated as described in Example 1 with an alkaline liquor. There is then printed onto this material, using a film screen, a printing paste of the following composition: 300 parts of cold water, 50 parts of the thickener from Example 1, 3 parts of antifoaming agent, 1.5 parts of the dye of the formula

100 parts of lukewarm water, and 545.5 parts of cold water.

The dye is subsequently fixed as in Example 1, and the upholstery fabric is rinsed and dried.

A blue sharply outlined printing having good print penetration is obtained.

EXAMPLE 7 Dralon upholstery fabric ("Drnlon-Plu'sch" with cotton backing, 465 g/m2) is pretreated, in the manner described in Example 1, with a padding liquor consisting of 990 parts of water and 10 parts of sodium hydroxide solution (36 B6). There is then applied to this material a printing paste consisting of: 300 parts of cold water, 1.5 parts of wetting agent, 50 parts of the thickener from Example 1, 3 parts of the red dye of the formula

250 parts of hot water, and 395.5 parts of cold water.

The material is subsequently further treated as described in Example 1.

A sharply outlined red printing having good print penetration and a soft handle is obtained.

An equally good printing is obtained by proceeding as described above but using as the substrate a polyacrylonitrile tufted carpet (Acribel 370, 900 g/m2).

EXAMPLE 8 A tufted woollen carpet (looped material, 1 200 g/m2) is impregnated on a padding machine with a padding liquor consisting of 983 parts of water, 1 5 parts of triethanolamine, and 2 parts of wetting agent.

There is printed onto this carpet, using a film screen, the following printing paste: 300 parts of water, 30 parts of the thickener from Example 1, 3 parts of antifoaming agent, 5 parts of the red dye from Example 1, and 662 parts of water.

The material is subsequently steamed for 1 2 minutes in saturated stean at 101 ; it is then rinsed, neutralised, rinsed again and finally dried.

A red printing having sharp outlines is obtained.

EXAMPLE 9 A polyester velvet pile carpet (Du Pont Carrierless, 700 g/m2) is impregnated on a padding machine with the following padding liquor: 988 parts of water, 10 parts of sodium hydroxide solution 36 Bé, and 2 parts of wetting agent.

The material pretreated in this manner is printed with a printing paste consisting of 300 parts of water, 20 parts of the thickener from Example 1, 3 parts of antifoaming agent, 5 parts of the orange-coloured dye of the formula

in a virtually electrolyte-free formulation, and 672 parts of water.

Fixing is subsequently carried out for 1 2 minutes in saturated steam at 101 ; the material is then rinsed, neutralised, rinsed again and dried.

There is obtained a sharply outlined, orange-coloured printing having good print penetration.

EXAMPLE 10 A velvet pile carpet made from polyamide 6 having a weight of 350 g/m2 is impregnated on a padding machine with a padding liquor consisting of 988 parts of water, 10 parts of sodium hydroxide solution 36 Bé, and 2 parts of wetting agent, and is then squeezed out to give a liquor absorption of 80%.

There is then sprayed onto this pretreated material, by means of a nozzle, a printing paste of the following composition in the form of a design: 957 parts of water, 3 parts of antifoaming agent, 30 parts of thickener, 3 parts of the yellow dye from Example 1, 1 part of the red dye from Example 1, 1 part of the blue dye from Example 1, and 5 parts of 80% acetic acid.

The thickener used has the following composition: 65 parts of oleic acid, 25 parts of a linear carboxylvinyl polymer having a molecular weight of about 1,000,000, 5 parts of a crosslinked carboxylvinyl polymer having a molecular weight of about 4,000,000, 3 parts of an oil-in-water emulsifier, and 2 parts of a water-in-oil emulsifier.

The material sprayed with the printing paste is subsequently treated for 5 minutes with saturated steam at 101 to fix the dyes; the material is then rinsed, neutralised, rinsed again and dried.

There is obtained velvet pile carpeting which has a dark-brown design having very sharp outlines printed on it, and which exhibits very good penetration with a complete absence of frosting.

EXAMPLE ii A carpet material made from polyamide 6.6 is impregnated on a padding machine with a padding liquor consisting of 989 parts of water, 10 parts of sodium hydroxide solution 36 Bé, and 1 part of wetting agent, and is squeezed out to give a liquor absorption of 80%.

There is then printed onto this pretreated material, using a film screen, a printing paste of the following composition: 961 parts of water, 3 parts of antifoaming agent, 30 parts of the thickener from Example 10, 5 parts of the blue dye from Example 1, and 1 part of 80% acetic acid.

The printed material is subsequently treated for 5 minutes with saturated steam as 101" to fix the dye which has been applied; the material is then rinsed, neutralised, rinsed again and dried.

The carpet material displays a sharply outlined blue printing with good penetration and without frosting.

Claims

1. A process for printing textile material, in which process the textile material is impregnated with an alkaline aqueous liquor, and subsequently printed with an acid aqueous printing paste containing a dye, a synthetic thickener having in the neutral to alkaline pH range a viscosity higher than it has in the acid pH range, and optionally further additives.

2. A process according to Claim 1, wherein the textile material printed is voluminous material.

3. A process according to claim 1 or claim 2, wherein the textile material printed is velours or looped material or needle felting.

4. A process according to any of the preceding claims wherein the textile material printed is carpet material.

5. A process according to claim 4 wherein the carpet material is made from synthetic polyamide.

6. A process according to any one of the preceding claims, wherein the textile material used is one having a weight of below 1000 g/m2, preferably below 500 g/m2.

7. A process according to any one of the preceding claims, wherein textile material made from synthetic polyamide is printed with anionic dyes.

8. A process according to any of the preceding claims, wherein the alkaline aqueous liquor has a pH value greater than

9.

10. A process according to any of the preceding claims, wherein the aqueous alkaline liquor has a pH value greater than 1 2.

11. A process according to any of the preceding claims, wherein the textile material is impregnated with an alkaline aqueous liquor in an amount sufficient to ensure that after the printing of the material with an acid aqueous printing paste there exists on the textile material a neutral to alkaline pH value.

1 2. A process according to any of the preceding claims, wherein printing is performed with an acid aqueous printing paste containing a carboxyvinyl polymer as the synthetic thickener.

1 3. A process according to any of the preceding claims, wherein the synthetic thickener used is a crosslinked carboxyvinyl polymer having a molecular weight of about 4,000,000, or a linear carboxyvinyl polymer having a molecular weight of about 1 ,000,000, or a mixture of these two.

1 4. A process according to any of claims 1 to 11, wherein printing is performed with an acid aqueous printing paste containing as the synthetic thickener a copolymer formed from ethylene and maleic anhydride.

1 5. A process according to any of the preceding claims, wherein the acid aqueous printing paste has a viscosity of 200-800 cPs.

16. A process according to any of the preceding claims wherein the acid aqueous printing paste has a viscosity of 400-600 cPs.

1 7. A process according to any of the preceding claims, wherein printing is performed with an acid aqueous printing paste containing a synthetic thickener as defined in such an amount that the viscosity in the neutral to alkaline range is greater than 2,000 cPs.

1 8. A process according to any of the preceding claims wherein printing is performed with an acid aqueous printing paste containing a synthetic thickener as defined in such an amount that the viscosity in the neutral to alkaline range is greater than 10,000 cPs.

1 9. A process according to any of the preceding claims, wherein the printing paste is applied by spray printing.

20. A process according to claim 1 substantially as described in any of Examples 1 to 11.

21. The printed textile material obtained by the process according to any of the preceding claims.