DE3505018A1 - Aftertreatment process for dyed textile material - Google Patents

Abstract

Process for the aftertreatment of textile material dyed, slop-padded or printed with anionic dyestuffs or of hydroxy- or nitrogen group-containing textile material brightened with an anionic optical brightener with simultaneous or stepwise use A) of a polybasic compound, prepared by reaction of a mono- or polyfunctional primary and/or secondary and/or tertiary amino compound with cyanamide, dicyandiamide, guanidine or biguanidine, it being possible to replace up to 50 mol per cent of the cyanamide, dicyandiamide, guanidine or biguanidine by a dicarboxylic acid as long as the product A) contains at least one reactive hydrogen atom bonded to an N atom, and B) of a quaternary polyalkylenepolyamine. m

Description

POST-TREATMENT PROCESS FOR DYED TEXTILE MATERIAL

The invention relates to a method for the aftertreatment of dyed, padded or printed with anionic dyes or by with an anionic optical brightener containing lightened hydroxyl or nitrogen groups Textile material, such as natural or synthetic polyamide1, with simultaneous or gradual use A) a polybasic compound prepared by Implementation of a mono- or polyfunctional primary and / or secondary and / or tertiary amino compound with cyanamide, dicyandiamide, guanidine or bisguanidine, where up to 50 mole percent of the cyanamide, dicyandianiide, guanidine or bisguanidine can be replaced by a dicarboxylic acid or a mono- or diester of the dicarboxylic acid, as long as that ProductA) has at least one reactive hydrogen atom bonded to an N atom, and 8) a quaternary polyalkylenepolyamine Used as a suitable textile material one colored with substantive dyes or direct or reactive dyes, padded or printed, natural or regenerated cellulose, in particular Cotton, mixed with other natural and / or synthetic textile material, e.g. natural or synthetic polyamide, such as wool, silk, nylon, or such z.8. 2 1/2 acetate, triacetate, polyester, polyacrylonitrile or viscose, according to the invention can be post-treated.

A suitable method is characterized in that the Post-treatment carried out simultaneously with products A) and 8). In the gradual and the simultaneous use of products A) and B) occurs a synergistic one Effect a.

A particularly suitable post-treatment process is characterized by that one in an aqueous exhaust process at temperatures of about 30-700C during about 10 to 30 minutes and in a pH range from 4 to 7, advantageously between 4 to 4.5 works and on 100 parts Active ingredient of the compound B) 5 to 100 parts of active substance of a compound A) and preferably 10 to 30 parts Parts of the active substance of a compound A) used, the conditions in which Follow-up treatment, e.g. temperature, pH value, additional aids, must be adhered to are that the products A) + B) do not react chemically with one another.

Aids that are also used in post-treatment are those used in dyeing, padding or printing find, such as known plasticizers, handle agents, wetting agents, water repellants, products to improve sewability, etc.

The quantities of products A) and 8) to be used are essentially depending on the depth of coloration; in general, 0.5 to 6S is used based on dry weight. For a 1/1 standard depth, 3 0% to 4 are advantageous % used. The product A) is advantageously a water-soluble reaction product from an amine of the formula R - NH - R 1 or, advantageously, a polyamine of the formula RRN - (Z - X) n - Z - NRR II, wherein R independently of one another is hydrogen or one <1-10C) -alkyl radical optionally substituted by hydroxy, (I-4C) -alkoxy or cyano, n is a number from 0 to 100, Z independently of one another if n is> 0, (2-4C) -alkylene or -Hydroxyalkylen and X independently, if n> 1, -0-, -S- or -NR- mean, with the proviso that the amine of the formula II at least one Contains -NH- or -NH2 group, with cyanamide, dicyandiamide, guanidine or bisguanidine or a derivative thereof, or an addition salt of organic or inorganic Acids, such as mineral acids, the amines.

It is advantageous to use compounds of the formula II in which each R for hydrogen, (1-4C) -alkyl or hydroxyalkyl, in particular for hydrogen, n stands for a number from 0 to 30, especially 0 to 6 and especially 0 to 4, X is independent of each other for -NR-, especially for -NH- or -NCH3- and Z independently of one another for (2-4C) -alkylene, in particular 0, 2-ethylene, 13-propylene or 1,3- (2-hydroxy) -propylene stands.

Particularly suitable compounds of the formula II are diethylenetriamine, Triethylenetetramine, tetraethylenepentamine, 2-aminoethy1-3-aminopropylamine, dipropylenetriamine or N, N-bis (3-aminopropyl) methylamine and higher polyethylene polyamines, polypropylene polyamines or polyhydroxypropylene polyamines with up to 8 and advantageously up to 6 N atoms.

A good compound A) is a reaction product of dicyandiamide with diethylenetriamine or triethylenetetramine.

The products A) and the corresponding starting compounds are off of PCT Offenlegungsschrift 81/2423 known, or can according to the there mentioned Patents are produced; they are also used in this published application designated as products A).

As quaternary polyalkylene polyamines B) are advantageous a water-soluble reaction product of an N, N-Tetraalkyialkyiendiamins with a Dihaloalkane or a secondary alkylamine; with an EpiRalocenn, rin, advantageous of a di- (1-4C) -alkylamine with epichlorohydrin.

A particularly preferred compound B) has the repeating unit of the formula where R1 is independently a (1-4C) -alkyl radical, R2 is H or OH, R1, A- + 3 -CH2-, -CH2-CH2 - or -N - R4 -R1 R4 -CH2-CH2-O- CH2-CH2- or - (CH2) b-, m is a number between 7 to 75, b is a number between 1 to 5 and AO is an anion, e.g. an anion of inorganic or organic acids such as chloride, sulfate, acetate, formate, phosphate , Bisulfate mean.

A very particularly preferred component B) is characterized in that it is the repeating unit of the formula where R1 'is a (1-4C) -alkyl radical, especially methyl, a number between 20 and 30, advantageously an average value of about 25.

The structure of the products B) with the repeating unit of the formula IV advantageously corresponds to the formula where Rj, AE3 and m 'have the meanings given above, X0 stands for H, ClCH2CHOH-CH2- or OHCH2CHOH-CH2- and Y stands for H or -N + HR1'R1' A-.

The products B) and the corresponding starting compounds are off the DOS 31 37 404 known and can be prepared according to the method specified there will.

The textile material containing hydroxyl groups is made according to known methods dyed, padded or printed with the anionic dye. As an anionic Dyes are those in PCT laid-open specification 81/2423 or those in DOS 31 37 404 or 32 03 548 mentioned dyes. It is advantageous to use direct dyes, especially 1: 1 or 1: 2 metal complex-containing direct dyes or reactive dyes a.

The customary ones, in particular, are used as suitable anionic dyes Commercial dyes as they are known from the Color Index, e.g.

C.I. Direct Dyes, C.I. Reactive Dyes, especially those like her can be determined according to the test procedure described in DOS 32 03 548.

The reactive dyes carry, in addition to one to 4 sulfonic acid or Sulfonamide groups, in particular a mono-, di- or trihalopyrimidyl or mono- or dihalotriazinyl radical as reactive group. Containing anionic groups Direct dyes mostly belong to the azo series, such as the mono- or in particular Polyazo series or the anthraquinone or phthalocyanine series and have in the Usually one to four water-solubilizing groups, such as -S03H- or sulfonamide groups on. Suitable direct dyes are disclosed in U.S. Patent No. 4,443,223 knows.

The polyamide material, be it as a single substrate or as a mixture with textile material containing hydroxyl groups is likewise carried out according to known methods colored, padded or printed, e.g. also with reactive dyes.

The polyamide material is advantageously made with anionic mono- or poly-jifons Oil or nylon dyes with a molecular weight of 400-1000, optionally colored, padded or printed in metal complex form, especially with such anionic, at least disulfonated dyes with a molecular weight between 600-1000, optionally in metal complex form with a molecular weight of 800-1000, the dyes in double (2 x 1/1) standard strength in an aqueous BaXe with a liquor ratio of 1:30 in a pH range from 3 to 11 at temperatures between 30 to 980C after 60 min. cooking time on synthetic polyamide (nylon 6) an absorption quotient, the ratio between extracted dye and dye in the bath, from 50 to 100%.

Such dyes are known as C. .. Acid Oyes ".

Suitable such dyes are mentioned in DOS 3,326,952.

It is surprising that at the same time or gradually Use of the stated amounts of the known products A) and 8) in the aftertreatment of dyed textile material a synergistic effect occurs. This shows in a significant improvement in the fastness properties, in particular the wet fastness properties, also of the handle and the tensile strength, in the case of textile material containing hydroxyl groups, compared to post-treatment with the individual components A) and B). Besides that the aftertreated dyeings show no stiffening and do not result in any residual formaldehyde. The influence on light fastness and the change in nuance is also smaller than in comparison in the case of the commercially available formaldehyde-releasing fixatives.

For the simultaneous use of the middle of the hill1 it is advantageous to an aqueous dispersion mixture of products A) and B) as a stock solution with suitable Mix the ratio to a 20-50 with water before use %, advantageously 35-40 weight solution can be diluted.

In the following examples the parts mean parts by weight which Percent weight percent; the temperatures are given in degrees Celsius. the The percentages given are based on the dry weight of the goods.

PREPARATION OF THE AFTER-TREATMENT MIXTURE EXAMPLE a 80 parts of a aqueous 50% dispersion of the reaction product) of epichlorohydrin and dimethylamine, produced according to example 1 of English patent 1,396,195 are with LO parts of an approximately 50% aqueous solution of the reaction product (ht), prepared according to Example 1, Sections 1 and 2, of PCT Offenlegungsschrift 81/2423 (Implementation of diethylenetramine with dicyandiamide) mixed with constant stirring.

A milky aqueous dispersion is obtained. This will be around Heated to 60 ° and until cleared up of the white, 35-40% dispersion with water offset.

A water-clear solution of the mixture of the two components is obtained example b 30 parts of a 50% strength aqueous dispersion of the reaction product from Example 2, Section 1 of PCT Offenlegungsschrift 81/2423 (reaction product as sulfate of triethylenetetramine with dicyandiamine) with 70 parts of a 50% aqueous Dispersion of the reaction product (al) of epichlorohydrin and dimethylamine (example 1) the English patent specification 1,396,195) and mixed cold with water to a water-clear 35-40% active product completed.

APPLICATION EXAMPLES Example 1 A cotton dye with 1.5% des Dye Direct Orange C.I. 107 using 15 ° S sodium sulfate known methods, is rinsed with water and then in a fresh aqueous Bath and a liquor ratio of 1:20 in the exhaust process with 1: of the fixative mixture 3 Aftertreated according to example a) for 20 minutes at 60-700, then with water rinsed cold and dried. In comparison to the untreated coloration stands out the aftertreated dyeing through improved washfastness, waterfastness and sweat resistance.

The fastness properties are better than the same dyeings with either 1 of the compound (a1) alone or with only 1% of the product (51) were aftertreated.

Example 2 If the aftertreatment according to Example 1 with the mixture (al) and and using a commercially available plasticizer based on a Reaction product of a higher molecular weight carboxylic acid with a polyalkylene polyamine, carried out, the same good wet fastness properties are obtained with slightly improved softness Handle, Example 3 A cotton dye with 1.75% of the Direct Scarlet dye C.I. 95, colored by known methods, is rinsed in a fresh Bath and a liquor ratio of 1:20 in the exhaust process and 2% of the fixative mixture aftertreated according to example b) for 30 minutes at 60 °. The wet fastness properties obtained are better than same colorations with either 2% of the compound (a1) alone or after-treated with only 2% of the product (ß2).

Example 4 If the aftertreatment according to Example 2 with the mixture (a1) and (2% each) using a commercially available cationic or non-ionic Plasticizer based on a reaction product of a higher molecular weight carboxylic acid carried out with a polyalkylene polyamide.

you get the same good wet fastness properties combined with a soft grip. Tabel E.g. No. Substrate dye. % of aftercare Fixative in the exhaust process Oauer in min. Temp. 5 cotton 1.5 to 3% v. 30 600 Direct Brown Ex. A) CI 113 6 Viscose 1.5% 1.5 X v. 30 70 ° Direct violet Ex. B) CI 66 7 cotton 0.8% 2% v. 30 70 ° Reactive Red Ex. A) CI 123 8 cotton 0.75 X 2 ov. 30 700 Reactive Yellow Ex. B) Ct 125 The cotton of Examples 7 and 3 dyed with the reactive dyes is intentionally not washed out sufficiently and not sufficiently soaped.

The aftertreated dyeings nevertheless result in improved wet fastness properties. The aftertreated colorations also show the same when a plasticizer is used good wet fastness properties and a pleasant, soft handle.

Claims (8)

REPAIR PROCESS FOR DYED TEXTILE MATERIAL Claims 1. Process for the aftertreatment of padded padded fabrics colored with anionic dyes or printed or whitened with an anionic optical brightener hydroxy- or nitrogen-containing textile material with simultaneous or gradual use A) a polybasic compound made by reacting a mono- or polyfunctional primary and / or secondary and / or tertiary Amino compound with cyanamide, dicyandiamide, guanidine or bisguanidine, whereby b1.szu 50 mole percent of the cyanamide, dicyandiamide, guanidine or biguanidine by a dicarboxylic acid or a mono- or diester of the dicarboxylic acid can be replaced, as long as that Product A) has at least one reactive hydrogen atom bonded to an N atom, and B) a quaternary polyalkylene polyamine. 2. The method according to claim 1, characterized in that the Post-treatment carried out simultaneously with products A) and B). 3. The method according to claim 1, characterized in that the Post-treatment is carried out in an aqueous solution based on 100 parts of active ingredient of compound B) 5 to 100 parts of active substance of a compound A) and preferably Contains 10 to 25 parts of active substance of a compound A). 4. The method according to claim 1, characterized in that the product A) a reaction product of dicyandiamide with diethylenetriamine or triethylenetetramine is. 5. The method according to claim 1, characterized in that the product B) a water-soluble reaction product of an N, N-tetraalkylalkylenediamine with a Is dihaloalkane or a secondary alkylamine with an epihalohydrin. 6. The method according to claim 1, characterized in that based on the dry weight of the substrate, 0.5 to 6% of the products A) + B) are used. 7. The textile material post-treated according to claim 1. 8. Textile auxiliaries containing the active ingredient per 100 parts Compound B) 5 to 100 parts of active substance of a compound A) and preferably 10 to 25 parts of active ingredient of a compound A).