DE2938766A1 - METHOD FOR PRINTING TEXTILE MATERIAL - Google Patents

Description

DR. BERG DIPL-ING STAPF DIPL-ING. SCHWABE CR. DR. S ^ NDMAIR

P.O. Box 860245 8000 Munich 86

Attorney's file: 30,383 September 25, 1979

CIBA-GEIGY AG Basel / Switzerland

Process for printing textile material

Case 1-12052 / '

r (0l ») 9« l272 Telegrams: 030015/0822 Bank accounts: Hypo-Bank Munich 4410122 «»

»« "BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM

Π "I" J ^ L " ⁸ ^" ^{1 association} »l» nk Munich 453100 (BLZ 700202 70)

* ·· "*" 05245 * 0 BERG d Postscheck Munich 65343-808 (BLZ 70010080)

ο-

CIBA-GEIGY AG 1-12052 / - *

Basel, Switzerland)

Process for printing textile material

The present invention relates to a method for printing textile material, in particular voluminous Material, as well as the printed material obtained by this process.

When printing on voluminous material, the Injection printing process used, in which the color paste through Nozzles is sprayed onto the material to be printed. While heavy quality textile material is satisfactory can be printed according to this process, with a weight under light quality 1000g / m often cause difficulties because the contours are blurred.

The present invention was therefore based on the object of developing a method for printing textile material, which can also be used for printing voluminous material of light quality using the injection printing process with sharp contours to be obtained. It is also intended to use this method synthetic thickener for all nozzles that are available on conventional injection printing machines.

According to the invention, this object is achieved in that the textile material is impregnated with an alkaline aqueous liquor and then with an acidic one Aqueous printing paste printed with a dye, a synthetic thickener that is neutral to alkaline pH range has a higher viscosity than in the acidic pH range, and optionally contains further additives.

Surprisingly, even with voluminous material, light quality of very sharp quality is obtained by this process

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Contours and there is no "frosting" effect. Since the Printing paste has an acidic pH value and thus a relatively low viscosity, can be all the usual Use nozzles. The inventive method has in addition, there is the unexpected advantage that the yield of the dyes and the brilliance of the coloring are better than when using a printing paste that contains a natural thickener. It also shows that the Electrolyte sensitivity of the synthetic thickeners when used according to the process according to the invention is lower, so that dyes with higher electrolyte contents can also be used, which were not previously possible could be used together with electrolyte-sensitive thickeners at neutral or alkaline pH.

Since the printing paste used in the process according to the invention is relatively thin due to its acidic pH value, it penetrates very well and evenly into the textile material one, even with bulky goods. However, the neutralization by the alkaline liquor on the goods then causes that the printing paste has a very high viscosity. This leads to the fact that you get a very good color penetration of the textile material and at the same time very sharp contours without a gray haze (frosting).

The alkaline one used in the process according to the invention aqueous liquor preferably has a pH value of greater " than 9, especially greater than 12. This pH value is determined by adding basic salts such as sodium carbonate or potassium carbonate or of bases, e.g.

Ammonia, triethanolamine, KOH or NaOH adjusted. NaOH is preferably used.

The amount of alkali must be such that it is sufficient to neutralize the acidic printing paste, see above that the textile material then has a neutral to alkaline pH value; depending on the substrate and

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Dye, this pH value can be between 7 and 11.

In addition, the aqueous alkaline liquor can contain auxiliaries such as antifoam agents, thickeners or, above all, wetting agents contain. A particularly preferred embodiment of the method according to the invention consists in that the aqueous alkaline liquor contains at least one dye or optical brightener, so that on the the entire material is given a basic color, on which a pattern is then printed.

The textile material is impregnated with this alkaline liquor in the usual way, for example by Immersion, spraying, pouring over or preferably by padding and then squeezing onto a Liquor pick-up of approx. 60 to 150%.

The textile material is then printed with an acidic aqueous printing paste containing a dye, a synthetic thickener and possibly other additives.

Synthetic thickeners are defined as synthetic thickeners Thickeners in question, which have a higher viscosity in the neutral to alkaline pH range than in the acidic pH range pH range. It is primarily a matter of polymers containing carboxyl groups. For example, are suitable Homopolymers and copolymers of unsaturated mono- and dicarboxylic acids with 3 to 5 carbon atoms, such as acrylic acid, Methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid and copolymers of the above Carboxylic acids with unsaturated monomers, such as vinyl esters, acrylic acid esters, methacrylic acid esters, ethylene, Styrene and vinyl ethers. Suitable thickeners are also obtained if the unsaturated mono- and dicarboxylic acids, optionally in the presence of the other unsaturated monomers mentioned, in the presence of mono-

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polymerized with two double bonds. Suitable ones Examples of monomers with two double bonds are divinyldioxane, butanediol diacrylate, butadiene and divinylbenzene. These About 0.05 to 5 percent by weight of monomers are contained in the copolymer. The carboxylic acid content of the thickeners is generally between 75 and 99.5 percent by weight.

Are particularly suitable for the method according to the invention Copolymers of ethylene and maleic anhydride or carboxyvinyl polymers, i.e., polymeric acrylic acids. Particularly suitable among these are a crosslinked carboxyvinyl polymer with a molecular weight of approx. 4,000,000 or a linear carboxyvinyl polymer with a molecular weight of approx. 1,000,000. A mixture of these two is preferably used.

These thickeners are used in the form of their acids. The amount of thickener is preferably chosen so that that the acidic printing paste has a viscosity of about 200-800 e-P *, in particular 400-600 © Pe, while the Viscosity of this printing paste in the neutral to alkaline range

»Ι ι? Λ S

Area preferably greater than 2000 © e, in particular larger than 10,000 & P6.

The type of in the printing paste and possibly also in the dyes contained in the aqueous alkaline liquor depends on the textile material to be printed. material from natural polyamides, such as wool, is made with anionic metal-free dyes, with metal complex, or reactive dyes printed. The same dyes and disperse dyes are used for synthetic polyamides into consideration. For printing on material made from natural or regenerated cellulose Reactive dyes and especially the so-called nouns, optionally heavy metal-containing dyes, are used and so-called disperse dyes are preferred for dyeing polyester materials. Textile material

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Polyacrylonitrile is preferred with disperse dyes or cationic dyes. These are dyes of different classes, for example Nitro, aminoketone, ketoneimine, methine, nitrodiphenylamine, quinoline, aminonaphthoquinone or coumarin dyes and especially about anthraquinone and azo dyes, such as Mcnazo- and disazo dyes.

Colorants are also to be understood as meaning optical brighteners. For example, brighteners from the following classes of compounds are possible: stilbenes, coumarins, benzocoumarins, Pyrenes, pyrazines, pyrazolines, oxazines, mono- or dibenzoxazolyl or -imidazolyl compounds, aryltriazole and v-Triazole derivatives and naphthalic acid imides.

In addition to water, thickener and dye, the printing paste can contain other additives, for example wetting agents, Antifoam agents or agents that influence the properties of the textile material, such as softeners, additives for flame retardant finishing as well as dirt, water and oil repellent Middle.

The printing paste can be applied to the textile material in the usual way, for example by film printing, rotary film printing > relief printing or by the so-called "polychromatic" or "TAK" process. Preferably, however, the printing paste is applied by injection printing, for example using the so-called “Millitron”, “Chromotronic”, “Mulitchromat ¹¹ ” or “Titan” process.

After printing, the textile material is finished in the usual way by first fixing the dye is, for example, by heating to over 100 ° C or by steaming. This is followed by rinsing, if necessary with the addition of small amounts of acids for neutralization, and dried. The use of synthetic thickeners and the good color yield in the process according to the invention

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possible a shortened wash or the use of smaller amounts of water than in the usual processes.

Woven fabrics and knitted fabrics of various types come into consideration as textile material for the method according to the invention. The method is particularly suitable for printing voluminous material, in particular velor or loop fabric or needle felt. The carpets are preferably carpets, in particular those made from synthetic polyamide. The advantages of the method according to the invention are particularly evident in the case of material with a weight of less than 1000 g / m 2, in particular less than 500 g / m 2.

The following examples serve to illustrate the invention. In this, parts mean parts by weight and the Temperatures are given in degrees Celsius.

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example 1

A velor carpet made of polyamide 6 with a weight

2
from 350-400 g / m is applied with a padding liquor consisting of

988 parts of water,
10 parts of sodium hydroxide solution 36 ° Be and

2 parts wetting agent,

impregnated on a padder and squeezed to a liquor pick-up of 80%.

Using a nozzle, a color paste of the following composition in the form of a Pattern sprayed on:

942 parts of water,
50 parts thickener

3 parts antifoam agent,

3 parts of the yellow dye of the formula

/ ^0CH 3

• • - • ν •• "" • ν •• "• ν

SO ₃ H

1 part of the red dye of the formula

, 's

SO-H
3

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as

1 part of the blue dye of the formula

NH-

SO ₃ H

O NH- · ^) ^# " ^CH 3

^X CH ₃

The thickener used has the following composition:

240 parts of mineral spirits,
50 parts of water-in-oil emulsifier, 20 parts of oil-in-water emulsifier, 20 parts of antifoam agent, 50 parts of crosslinked carboxyvinyl polymer

a molecular weight of about 4,000,000, 70 parts of linear carboxyvinyl polymer

a molecular weight of approximately 1,000,000

and
550 parts of water, whose pH value with acetic acid

was set to 4.5.

The material sprayed with the color paste is then Treated with saturated steam at 101 ° for 5 minutes to fix the dyes, rinsed, neutralized, again rinsed and dried.

A velor carpet is obtained with a dark brown pattern with very sharp contours, which is a very good one Has penetration and no "frosting" whatsoever.

Equally good results are achieved if instead of the velor carpet you use a polyamide-6 or polyamide-6,6

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Carpet made of loops with a weight of 300-350 g / m or made of needle felt with a weight of

300-350 g / m treated exactly as described above.

Example 2

A carpet made of polyamide 6 is made with a padding liquor consisting of

987.25 parts of water, 10 parts of sodium hydroxide solution 36 ⁰ Be,

2 parts wetting agent and

0.75 parts of the pink dye of the formula

0 NH

MJ OCH ₂ CH ₂ OH

ν \ / ν

Il I 0 OH

impregnated on a padder and squeezed to a liquor pick-up of 80%.

A printing paste of the following composition is printed onto the carpet that has been pretreated in this way using a film printing stencil:

942 parts of water, 50 parts of the thickener from Example 1,

3 parts antifoam agent and

Containing 5 parts of a brown dye mixture the 1: 2 chromium complex of the following dyes:

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OH

HO

^SO 2 ^CH 3

Cl

COOCH.

the 1: 2 chromium complex of the following dyes:

OH

OH

OH

so

OH

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

The printed carpet is then treated with saturated steam at 101 ° for 5 minutes to fix the dyes, rinsed, neutralized, rinsed again and dried.

A carpet is obtained which has a very sharp dark brown print on a pink background.

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Example 3

If you work as in Example 2, but used for pretreatment a log fleet consisting of

983 parts of water, 10 parts of sodium hydroxide solution 36 ° Be, 2 parts of wetting agent and 5 parts of the yellow 1: 2 chromium complex of the dye of the formula COOH

HO ⁷ V

HO ⁷ V

.K

I Il

and if the rest of the procedure is as described in Example 2, a carpet with a very sharp position is obtained dark brown print on yellow background.

Example 4

A cotton plush material (handle plush, 370 g / m) is used pretreated as described in Example 1 with an alkaline padding liquor.

A color paste of the following composition is applied to this material with a film printing stencil printed:

300 parts of cold water, 50 parts of the thickener from Example 1, 12 parts of the green dye of the formula

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ςΟΟΗ

0Η- _χ ^ - N = N - _χ ρ - N = N - VSOH

N C - O - Cu-O-CO

I Il

CH ₃

100 parts urea,

300 parts of hot water,

3 parts antifoam and 235 parts cold water.

To fix the dye, it is then steamed for 12 minutes in saturated steam at 101 °, then rinsed and dried.

You get a green print with sharp on the plush Contours.

Example 5

A cotton plush material (handle plush, 370 g / m 2) is made with a padding liquor consisting of

978 parts of water,
20 parts caustic soda 36 ° Be and 2 parts wetting agent,

impregnated on a padder and squeezed to a liquor pick-up of 80%. On this material is then printed 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

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η γ ^Μ ~ τ N / A NH •
Il
• ν. T
• SO ₃ Na > / Sun ₃ R. • = · -N = SO ₃ Na

R = mixture of C, H _n O- and -

NH

100 parts of urea,

300 parts of hot water,

3 parts antifoam and 242 parts cold water.

After steaming for 10 minutes in saturated steam at 101 °, a violet print is obtained sharp contours and good print through.

Example 6

A Dralon upholstery fabric (Dralon plush with cotton stock, 465 g / m) is pretreated as described in Example 1 with an alkaline liquor. On this material will a color paste of the following composition is printed using a film printing stencil:

300 parts of cold water, 50 parts of the thickener from Example 1, 3 parts of antifoam agent, 1.5 parts of the dye of the formula

NHC ₂ H ₄ OH
·

I Il Il ·. · ·

ö NHC ₂ H ₄ OH

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* MJt

100 parts lukewarm water, 545.5 parts cold water.

The dye is then fixed as in Example 1, and the furniture fabric is rinsed and dried.

A clear blue print with good quality is obtained Penetration.

Example 7

Dralon upholstery fabric (Dralon plush with cotton stock, 465 g / m 2) is pretreated as described in Example 1 with a padding liquor consisting of 990 parts of water and 10 parts of 36 ° Be sodium hydroxide solution. A printing paste is then applied to this material, consisting of

300 parts of cold water,

1.5 parts wetting agent,

50 parts of the thickener from Example 1, 3 parts of the red dye of the formula

• -C-

-N II II N CN = NS

Cl

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

It is then treated further as described in Example 1

A sharp red print with good quality is obtained

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Penetration and soft grip.

A print that is just as good is obtained by proceeding as described above, but using a polyacrylonitrile tufted carpet as the substrate (Acribel 370, 900 g / m) was used.

Example 8

A tufted wool carpet (loop fabric, 1200 g / m) is made with a padding liquor consisting of

983 parts of water, 15 parts of triethanolamine and

2 parts wetting agent,

impregnated on the foulard.

The following printing paste is printed on this carpet with a film printing stencil:

300 parts of water, 30 parts of the thickener from Example 1,

3 parts antifoam agent,

5 parts of the red dye from Example 1, 662 parts of water.

The goods are then steamed for 12 minutes in saturated steam at 101 ° C. , then rinsed, neutralized, rinsed and dried.

A red, sharp print is obtained. Example 9

A polyester velor carpet (Du Pont Carrierless, 700 g / m) is impregnated on a foulard with the following padding liquor:

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988 parts of water,
IO parts caustic soda 36 ⁰ Be,

2 parts wetting agent.

The goods pretreated in this way are printed with a printing paste consisting of

300 parts of water,
20 parts of the thickener from Example 1,

3 parts antifoam agent,

5 parts of the orange dye of the formula

/ ν "" ^ \ "/ 2 4 2 4

«-N = N- · / * ~ ^N \ = ^X. =. ^X ^ CHCN

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

It is then fixed, rinsed, neutralized, rinsed again and again in saturated steam for 12 minutes dried.

A sharp orange-colored print also results good penetration.

Example 10

A velor carpet made of polyamide 6 with a weight

2
of 350 g / m is used with a padding liquor consisting of

988 parts of water,
10 parts caustic soda 36 ° Be and 2 parts wetting agent,

impregnated on a padder and squeezed to a liquor pick-up of 80%.

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Using a nozzle, a color paste of the following composition in the form of a Pattern sprayed on:

957 parts of water,

3 parts antifoam agent, 30 parts 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, 5 parts of 80% acetic acid.

The thickener used has the following composition:

65 parts of oleic acid

25 parts of linear carboxylic vinyl polymer with a

Molecular weight of about 1,000,000, 5 parts of crosslinked carboxyl vinyl polymer with

a molecular weight of approx. 4,000,000 3 parts oil-in-water emulsifier

2 parts water-in-oil emulsifier

The material sprayed with the color paste is then Treated with saturated steam at 101 ° C for 5 minutes to fix the dyes, rinsed, neutralized, rinsed and dried again.

A velor carpet is obtained with a dark brown pattern with very sharp contours, which is a very good penetration and no frosting whatsoever.

Example 11

A carpet material made of polyamide 6.6 is made with a padding liquor consisting of

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989 parts of water,
10 parts caustic soda 36 ° Be and 1 part wetting agent,

impregnated on a padder and squeezed to a liquor pick-up of 80%.

A printing paste of the following composition is applied to the carpet material pretreated in this way using a printing stencil imprinted:

961 parts of water,

3 parts of antifoam agent, 30 parts of the thickener from Example 10, 5 parts of the blue dye from Example 1, 1 part of 80% acetic acid.

The printed material is then ^{treated with saturated steam at 101 °} C. for 5 minutes to fix the printed dye, rinsed, neutralized, rinsed again and dried.

The carpet material has a sharp blue print, with good penetration and without "frosting".

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Claims (15)

DR. Hü P. C CIP : ..- I No. ?. STAPP To you·.'.?. Sr-Hi-VA!, · = C:?. ^. SANDMAIB 8 MUNICH ÜO · MA U t. H K IH C H ERSTR. Claims Ii method for printing textile material, characterized in that that the textile material is impregnated with an alkaline aqueous liquor and then printed with an acidic aqueous printing paste containing a dye, a synthetic thickener, the has a higher viscosity in the neutral to alkaline pH range than in the acidic pH range, as well as possibly contains further additives. 2. The method according to claim 1, characterized in that that printed as a textile material voluminous material, in particular velor or loop fabric or needle felt will. 3. The method according to claims 1 and 2, characterized in that that as a textile material carpets, especially those made of synthetic polyamide, are printed will. 4. The method according to one of claims 1 to 3, characterized in that a textile material 2 such with a weight below 1000 g / m, preferably 2
less than 500 g / m is used. 5. The method according to any one of claims 1 to 4, characterized in that textile material made of synthetic Polyamide is printed with anionic dyes. 6. The method according to claim 1, characterized in that that the textile material is impregnated with an alkaline aqueous liquor, which at least one Contains dye or optical brightener. 7. The method according to claims 1 to 6, characterized in that that the textile material is impregnated with an alkaline aqueous liquor whose pH value 030015/0822 ORIGINAL! NSPECTED is greater than 9, preferably greater than 12. 8. The method according to claims 1 to 7, characterized
characterized in that one uses the textile material
an alkaline aqueous liquor in such an amount
impregnated that after printing with an acidic
aqueous printing paste has a neutral to alkaline pH value on the textile material. 9. The method according to claim 1, characterized in that one with an acidic aqueous printing paste
printed, which as a synthetic thickener
Contains carboxy vinyl polymer. 10. The method according to claim 9, characterized in that a cross-linked thickener is used as the synthetic thickener Carboxyvinyl polymer with a molecular weight of about 4,000,000 or a linear carboxyvinyl polymer with a molecular weight of about 1,000,000 or, preferably, a mixture of these two is used. 11. The method according to claim 1, characterized in that printing is carried out with an acidic aqueous printing paste, which as a synthetic thickener contains a copolymer of ethylene and maleic anhydride. 12. The method according to claim 1, characterized in that printing is carried out with an acidic aqueous printing paste which has a viscosity of 200-800 bPe, preferably 400-600 e4? E. 13. The method according to claim 1, characterized in that printing is carried out with an acidic, aqueous printing paste which, according to the definition, is synthetic
Contains thickener in such an amount that the viscosity in the neutral to alkaline range is greater than
2,000 «Pe, preferably greater than 10,000 ef> e. 030015/0822 14. The method according to claim 1, characterized in that that the printing paste is applied by injection printing. 15. The printed textile material obtained according to the method of claims 1 to 14. 030015/0822