DE2526688A1 - PRINT PASTE FOR PRINTING FIBER MATERIAL - Google Patents

Description

Our reference: OZ 31 392 Ks / St 6700 Ludwigshafen, June 13, 1975

Printing pastes for printing on fiber material

The invention relates to printing pastes, in addition to the usual ingredients a fully synthetic thickener and containing a disperse dye as dye, for printing on Fiber material made of polyester, cellulose acetate, or triacetate.

From DT-OS 1 619 660 printing pastes are known which, as essential constituents, a dye, a synthetic Contain thickener and a binder. Disperse dyes are also suitable as dyes. The printing pastes are used for printing textiles made of fiber materials of all kinds, such as cotton, linen, wool, polyacrylonitrile and polyethyleneterephthalate used.

The pH of the known printing pastes which contain disperse dyes is generally between 3 »5 and 6.5. Because of of the known state of the art, printing pastes containing disperse dyes were only printed in the acidic pH range, because the disperse dyes decompose in alkaline printing pastes.

The object of the invention is to show printing pastes which, in addition to the usual constituents, include a synthetic thickener and contain a disperse dye as dye, and when printing on fiber material made of polyester, cellulose acetate or triacetate give prints of better color strength and from which the thickener can be easily washed out.

The object is achieved according to the invention with the printing pastes described at the outset in that the pH of the printing pastes is greater than 7. The pH of the printing pastes is preferably adjusted to a value of 7.5 to 10.

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1000 parts by weight of the printing paste contain about 20 to 150 parts by weight of a disperse dye. Disperse dyes are those in the Color Index under this designation The printing pastes contain low-electrolyte to electrolyte-free formulations of disperse dyes. Preparations of the disperse dyes can be in either liquid or solid form are present. It is preferred to use preparations of disperse dyes which contain nonionic substances as dispersants contain ,, Suitable non-ionic dispersants are, for example, alkoxylation products of aliphatic, cycloaliphatic or aromatic optionally substituted ones Polyalcohols, phenols, amines or polyamines with ethylene oxide and / or propylene oxide “The derivatives of amines can also be quartered.

The usual constituents of the printing paste include, for example, dispersants, recrystallization inhibitors, water retention agents, Understand wetting agents, defoamers and pH regulating agents. 1000 parts by weight of the printing paste can contain about 10 to 120 parts by weight of one of the usual ingredients mentioned =

In addition to the nonionic products that are already contained in the dye preparations, dispersants are used can, also acting as electrolytes, ionogenic compounds in Consideration, for example, lignosulfonates, condensation products of formaldehyde with phenolic and / or naphthalenesulfonic acid, Sulfomethylation products of phenols and polyvinyl alcohol sulfates ο

Both nonionic and ionic dispersants can be used. However, nonionic dispersants are preferably used a.

Water-soluble alcohols, for example, are used as wetting agents and esters of C.

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Polyols into consideration. Under water retention agents should polyvalent aliphatic alcohols such as glycol or glycerine be understood.

Synthetic thickeners in the context of the present invention are polymers containing carboxyl groups or their alkali and ammonium salts. For example, are suitable

Homopolymers and copolymers of ethylenically 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 copolymerizable ethylenically unsaturated Monomers such as vinyl esters, acrylic acid esters, methacrylic acid esters, ethylene, styrene and vinyl ethers. Suitable thickeners is also obtained if the ethylenically unsaturated mono- and dicarboxylic acids mentioned, optionally in Presence of the other ethylenically unsaturated monomers mentioned, in the presence of monomers with two ethylenic polymerized unsaturated double bonds. Suitable monomers with two ethylenically unsaturated double bonds are, for example Divinyldioxane, butanediol diacrylate, butadiene and divinylbenzene. These monomers are approximately in the copolymer Contain 0.05 to 5 percent by weight. The carboxylic acid content of the thickeners is generally between 75 and 99.5 Weight percent.

Mixtures of a polymer containing carboxyl groups, an ^{organic water-immiscible liquid boiling above 130 °} C. and a nonionic or anionic emulsifier are also suitable as synthetic thickeners.

Those used to produce the thickening and setting of the alkaline The pH required base can either be added later when preparing the aqueous thickening or in advance the oily paste made from organic liquid, 100% synthetic Thickeners and emulsifiers with HLB values between about 2 and 17 can be incorporated. Instead of Free carboxylic acids can also be the finished alkali salts

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be incorporated into the oily medium or as Thickeners can be used. A customary aqueous thickening from such a mixture contains, for example 0.25 to 5 percent by weight, based on the printing paste, of a mixture of the following components:

a) 0.5 to 50 percent by weight, based on the mixture a), b), c) and d) of a copolymer of a carboxyl group-containing one Monomers such as acrylic acid, methacrylic acid, maleic anhydride and comonomers such as vinyl ethers, Vinyl esters, ethylene, butadiene or other copolymerizable monomers with 2 double bonds. The to achieve The slight crosslinking required because of a high molecular weight is achieved either primarily by direct polymerisation of monomers with at least 2 double bonds or secondary through subsequent crosslinking, e.g. at Maleic anhydride copolymers by reaction with Diamines.

b) 10 to 80 percent by weight, based on the mixture a), b), c) and d) of an organic liquid boiling above 130.degree. The chemical nature of the organic liquid does not play a significant role as long as it is in the printing paste, is especially inert to the copolymer. The organic liquid should be easily washable be. For example, aliphatic, cycloaliphatic and aromatic hydrocarbons are suitable, as well Alcohols, ketones, ethers and liquid esters of aromatic or aliphatic, branched or unbranched, saturated or unsaturated carboxylic acids having 10 to 20 carbon atoms and alcohols having 8 to 30 carbon atoms. It is preferable to use an odorless, oily liquid which, if necessary, can be easily washed out and may have a softening effect in the finished print.

c) 0.5 to 50 percent by weight, based on the mixture a), b), c) and d) of a nonionic or anionic emulsifier and

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d) a sufficient amount of a base around the carboxyl groups

of the copolymer and to neutralize the pH

of the printing paste to ^ 7 to 12, preferably 7 »5 to 10.

The base required to produce the thickener and to set the alkaline pH can either be incorporated into the oily paste of the thickener in advance during the preparation of the aqueous thickener. Suitable bases are derived from the alkali metals, ammonia and amines. Ammonia can be introduced into the mixture of components a), b) and c) in the form of an aqueous solution or in gaseous form. Aqueous solutions of amines, such as morpholine, or mixtures of the amines with aqueous ammonia can also advantageously be used. Aqueous amine solutions and aqueous ammonia solutions can also be added one after the other. In the last-mentioned cases, oily pastes are obtained which already contain the base and give a finished thickening directly when distributed in water. The pH can be adjusted to the desired degree nor later _o can other hand, the bases are also subsequently added in the preparation of the aqueous thickener. In order to obtain prints from which the synthetic thickener can be washed out particularly well, caustic soda or potassium hydroxide solution is used as the base, so that the thickener is in the form of sodium or potassium hydroxide. Potassium salt is present.

The synthetic thickeners used are preferably copolymers of 80 to 99.95 percent by weight of acrylic acid or Methacrylic acid with 0.05 to 5 percent by weight of the above monomers with 2 ethylenically unsaturated double bonds and Copolymers which contain 50 to 80 percent by weight maleic anhydride in addition to ethylene or vinyl acetate in copolymerized form. Even these copolymers can be crosslinked with monomers which have 2 ethylenically unsaturated double bonds. 1000 parts by weight of the aqueous printing paste contain 0.1 to 1, preferably 0.3 to 0.7 parts by weight of a synthetic thickener ο The printing pastes contain except those already mentioned

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Ingredients water, in an amount that the sum of the parts by weight is 1000 each.

For applying the printing paste to polyester, cellulose acetate and triacetate or mixtures of the fibers mentioned the printing processes customary for disperse dyes are suitable. For example, the fiber material is treated with a Printing ink containing the disperse dye and the synthetic thickener. The fiber material is then optionally dried and then applied, for example, with hot air, superheated steam, saturated steam or infrared light Temperatures between 100 and 220 ° C heated so that the prints are fixed. The printing color can also be considered on that upcoming fiber material can be applied by first applying it to paper, drying if necessary and then transferred to the textile substrate by means of thermal transfer printing. It is important in all cases that the pH of the printing paste is above 7.

It was not foreseeable that obtained with alkaline printing pastes prints of excellent Parbtiefe because the disperse dyes decompose in the known printing pastes with natural thickeners carbohydrate in the alkaline range, even with the usual addition of oxidizing _agents%. In the case of the printing pastes according to the invention, it is not necessary to add oxidizing agents. It has also been shown that prints with synthetic thickeners that have been subjected to hot air or superheated steam treatment in an alkaline medium to fix the dyes can be washed out better or faster than those produced in the acidic or neutral range.

The invention is explained in more detail with the aid of the following examples » The parts given in the examples are parts by weight.

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example 1

A polyester fabric is printed on a film printing machine with a printing paste adjusted to pH 8.5 and composed of HO parts of the dye

and 960 parts of a 3 strength solution of 52 parts of white oil, ¹ I parts of oleic acid diethanolamide, 12 parts of a copolymer of 99.5% acrylic acid and 0 ^ 5% divinyldioxane, 12 parts of a maleic anhydride-ethylene copolymer in a molar ratio of 1: 1, 10 Parts of a mixture of morpholine and water in the ratio 8: 2 and 10 parts of ammonia 25 / Sig in water.

The printed material is dried at a temperature of 110 ° C., treated with superheated steam at 180 ° C. for 6 minutes, then Rinsed cold and warm the reductive wash usual for prints with disperse dyes (with sodium dithionite and caustic soda) subjected and then dried »

A strongly colored red print on a white ground is obtained, the print which is produced in the usual manner with an acid (pH 5 »5) set printing paste is reached, far exceeds the strength of the ink.

Example 2

A polyester knitted fabric is printed on a roller printing machine with a print paste adjusted to pH 8 and composed of 60 parts of the dye of the formula

O ₀ / r * -OCH, ^ C ₅ H ₁₁ CN

-N = N- C / ^ - N ^d

r NHCOCH ₃ ^ CglfyOH

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and 940 parts of a 356 solution of 52 parts white oil, 4 parts of oleic acid diethanolamide, 12 parts of a copolymer of 99> 5 / £ acrylic acid and 0.5 $ divinyldioxane, 12 parts of a Maleic anhydride-ethylene copolymer in a molar ratio of 1: 1 and 20 parts of NaOH (25%) in water.

The print is dried at a temperature of 120 ^° C., treated with superheated steam for 7 minutes at 170 ^° C. and then washed as described in example 1 and finished.

A blue print on a white background with excellent Color depth. It differs from a print that is made in the usual way with an acidic printing ink is achieved by the much better color strength.

Example 3

With the printing paste described in Example 1 (pH 8.5), but instead of the dye mentioned there, 50 parts of the blue, electrolyte-free dye of the formula

N- (CH ₀ ) ^ - OCH,

if you print a Triacetatge fabric on a film printing machine. Treating the getrockenten pressure 7 minutes at 190 ⁰ C with superheated steam and makes it available as described in Example 1 finished. A deeply colored, bright blue print on a white background is obtained.

Example 4

A paper is printed with a printing paste adjusted to pH 7-5 and composed of 30 parts of the electrolyte-free dye the formula

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co

H,

OCH.

NHo

and 970 parts of a 3% aqueous solution of 40 parts White oil, 4 parts of oleic acid diethanolamide, 13 parts of the im Example 1 specified polyacrylic acid copolymer, 9 parts of the maleic anhydride copolymer according to Example 1, 6 parts of a maleic anhydride-vinyl isobutyl ether copolymer (1: 1), 10 parts of a mixture of morpholine and water in the ratio 8: 2 and 17.0 parts of ammonia 25 # ig in Water and dry the print at a temperature of 115 ° C.

The paper is left with the printed side lying on a polyester fabric, together with this run through a calender ^{at 20O 0 C for 30 seconds.} The dye is transferred to the fabric. A red print is obtained on a white background which, by virtue of its thickness, advantageously differs from one which is achieved with an acidic printing paste.

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Claims (1)

- io - ο.ζ. 31 392 claims Printing pastes which contain a synthetic thickener and a disperse dye as the dye, for printing fiber material made of polyester, cellulose acetate or triacetate, characterized in that the pH of the printing pastes is greater than 7 Printing pastes according to claim 1, characterized in that the pH is 7.5 to 12. Printing pastes according to claims 1 and 2, characterized in that they contain low-electrolyte to electrolyte-free disperse dyes. Printing pastes according to claims 1 to 3, characterized in that the synthetic thickener is present as a sodium or potassium salt. BASF Aktiengesellschaft 609882/1110