DE2244239A1 - Dyeing polyesters in multicolour effects - by treating or printing with aqs bath or paste containing carrier and dyeing with dispersion dyestuff without adding carrier - Google Patents

Abstract

Before dyeing, the material is treated with aq. bath or printed with aq. paste contg. cpds. (I) increasing the dye affinity of the polyester and then (in the case of treatment) dyed, together with untreated polyester material, with dispersion dyestuffs, without the addn. of carriers, at or below the b.pt.; or (in the case of printing) subjected to heat treatment (thermo-fixing) and then dyed in the same way. The method is esp. useful for dyeing aromatic polyesters, e.g. polyethylene terephthalate or polyclohexanedimethylene terephthalate and gives high contrast light and dark dyeing. (I) are dyeing accelerators (carriers) used in dyeing polyesters with dispersion dyestuffs, pref. aromatic cpds., aromatic carboxylic esters or phthalimide derivs.

Description

Process for the production of multicolor effects on fiber materials made of polyesters The invention relates to a method for producing multicolor effects on fiber materials made of polyester, which is characterized in that the Fiber materials treated with aqueous baths or printed with aqueous pastes before dyeing, which contain compounds which increase the dye uptake capacity of polyester and then - in the case of treatment - together with untreated polyester materials without the addition of carriers at or below boiling temperature with disperse dyes colors, or - in the case of printing - subjected to heat treatment and then without Addition of carriers at or below boiling temperature with disperse dyes colors.

As compounds increasing the dye uptake capacity of polyester are in the context of the claimed process when dyeing polyesters with Disperse dyes commonly used dye accelerators (carriers) understood.

Among these, the following have proven particularly useful: Aromatic compounds of the formula in which Rr is hydrogen, phenyl or chlorine, R2 is hydrogen, hydroxy or chlorine and R3 is hydrogen or chlorine, with the proviso that R1, R2 and R3 are not hydrogen at the same time and that R2 is only a hydroxyl group if R1 is a Is phenyl group; aromatic carboxylic acid esters of the formula In which RX is a C1-C4-alkyl radical, R2 is hydrogen or a C1-C2-alkyl group and R3 is a C1-C2-alkyl or C1-C2-alkoxy group; or phthalimide derivatives of the formula in which R1 is an alkyl radical optionally substituted by halogen, a hydroxy, alkoxy, acyloxy, carboxy or alkoxycarbonyl group, containing a total of 1 to 8 carbon atoms, the carbon chain of which can be interrupted by oxygen atoms, and R2 is hydrogen; Is halogen, a hydroxy, C1-C4-alkoxy, carboxy, C1-C4-alkoxycarbonyl or nitro group or a phenyl radical.

As representatives of the aromatic compounds to be used according to the invention of the formula I may be mentioned, for example: Diphenyl, o-oxydiphenyl, m-oxydiphenyl, p-Oxydiphenyl, sodium salt of o-Oxydipheny3s, dichlorobenzene and richlorobenzene.

As representatives of the aromatic carbonic acid esters of the formula II may be mentioned, for example: The ether esters of 2,3-dihydroxybenzoic acid, z. B. the esters of 2-hydroxy-3-methoxy-benzoic acid, of 2 3-dimethoxy-benzoic acid and 2-ethoxy-3-hydroxy-benzoic acid, such as methyl 2-hydroxy-3-methoxy-benzoate, 2-methoxy-3-hydroxy-benzoic acid methyl ester; the ether esters of 2,4-dihydroxybenzoic acid, z. B.

the esters of 2-hydroxy-4-ethoxybenzoic acid and 2,4-dimethoxybenzoic acid, like the 2-hydroxy-4-ethoxy-benzoic acid ethyl ester; the ether esters of 2,5-dihydroxybenzoic acid, z. B.

the esters of 2,5-dimethoxybenzoic acid and 2-hydroxy-5-methoxy-benzoic acid, such as methyl 2-hydroxy-5-methoxy-benzoate; di.e ether ester of 2,6-dihydroxybenzoic acid, z. B.

the esters of 2,6-dimethoxy-benzoic acid, 2-ethoxy-6-methoxy-benzoic acid and 2-hydroxy-6-methoxy-benzoic acid, such as methyl 2-hydroxy-6-methoxy-benzoate; the ether esters of 3,4-dihydroxybenzoic acid, e.g. B. the esters of 3-methoxy-4-hydroxy-benzoic acid, 3,4-dimethoxy-benzoic acid and 3-methoxy-4-ethoxy-benzoic acid, such as methyl 3-methoxy-4-hydroxy-benzoate, ethyl 3-methoxy-4-hydroxybenzoate and propyl 3-methoxy-4-hydroxy-benzoate; the Ether esters of 3,5-dihydroxybenzoic acid, e.g. B.

the esters of 3-methoxy-5-hydroxy-benzoic acid, of 3,5-dimethoxy-benzoic acid and 3, 5-diethoxybenzoic acid, such as 3-methoxy -5-hy droxy-benzoic acid emethy ester and methyl 3,5-dimethoxy-benzoate, 2-hydroxy-3-methyl-benzoic acid esters, like methyl 2-ltdroxy-5-methylbenzoate.

As representatives of the phthalimide derivatives to be used according to the invention of the formula III are for example: N-ethyl-phthalimide, N-isopropyl-phthalimide, N-butyl-phthalimide, N-isobutyl-phthalimide, N- (2-ethyl-hexyl) -phthalimide, N-ethoxymethyl-phthalimide, N-propoxymethyl phthalimide, N- (3-hydroxypropyl) phthalimide, N- (3-methoxypropyl) phthalimide, N-acetoxyethyl-phthalimide, N- (3-propionyloxy-progyl) -phthalimide, 4-phthalimidobutyric acid methyl ester, 6-Phthalimidocaproic acid ethyl ester, also the corresponding N-derivatives of the 3- and 4-chlorophthalic acid imides, 3- and 4-nitrophthalic acid imides and 4-phenyl-4-hydroxy-, 4-methoxy-, 4-ethoxy-, 4-methoxy-carbony-1-lnd 4-ethoxy-carbony-phthalic acid imides.

The compounds of the formula I, II to be used according to the invention and III can be obtained by established methods.

The required amounts of the compounds to be used according to the invention of the formulas I, II and III can easily be determined by preliminary tests from case to skin determine. In general, amounts of 1 to 10 g per liter of treatment liquor have been found with the usual fouling ratios of 1: 2 to 1:50 or 1 to 20 g per kg Proven printing paste.

The compounds to be used according to the invention become expedient together with ionogenic and / or non-ionogenic.

Emulsifiers or dispersants used. The amounts of emulsifying or dispersants are expediently 5 to 20% of the weight of the dye absorption capacity the compound increasing polyester fiber materials.

The disperse dyes are those commonly used for dyeing polyesters disperse dyes used, as for example in Color Index, 3rd edition, (1971, Vol. 2 pp. 2479-2742 are described.

With the aid of the method according to the invention, it is possible to work on fiber materials of polyesters, especially aromatic polyesters such as polyethylene glycol terephthalates or polycyclohexanedimethylene terephthalates to produce attractive multicolor effects achieve. This is because fiber materials that have been pretreated according to the invention are dyed together with untreated polyester materials in continuous or discontinuous Work wisely without the addition of a carrier at or below the cooking temperature High-contrast light-dark colorations obtained because the pretreated fiber material has a much darker color than the non-pretreated fiber material.

The pretreatment of the fiber material, which z. B. in the form of threads, Ga.rn, woven, knitted or sliver can be present, is expedient in the way carried out that the material in an aqueous liquor heated to about 50 ° C, which contains the compounds to be used according to the invention, introduces and then the temperature of the treatment bath in the course of about 20 to 40 minutes to about 9A0 C increases in the bath 1o to. Keeps at this temperature for 60 minutes.

After separating the treatment liquor, the material with Esters rinsed warm and cold, dehydrated and, if necessary, dried and heat-set.

Another embodiment of the pretreatment consists in this.

that the polyester materials with aqueous pastes that according to the invention Compounds to be used and optionally wetting agents and thickeners contain, printed and then a heat treatment, preferably a 5- Heat treatment in steam atmosphere for up to 30 minutes.

The parts given in the following examples are parts by weight.

Example 1 Yarns made of polyethylene terephthalate are treated in one Yarn dyeing machine in a liquor ratio of 1:30 with a liquor per liter 4 g of oxydiphenyl (mixture of isomers) 1 g of diphenyl 1 g of a mixture A consisting of the same Parts of the obtained by the action of 5 to 7 moles of ethylene oxide on 1 mole of nonylphenol Phenol polyglycol ethers and the monoethanol ammonium salt of benzenesulfonic acid was, contains. The bath is heated from So OC to 980C in so minutes and then held at this temperature for 10 minutes. After thorough rinsing are gladly dehydrated and dried.

The pretreated yarn is with. woven with untreated polyester yarn. The fabric is dyed after thermosetting at approx. 2100C on a reel vat in a liquor ratio of 1:40 with a liquor that has been adjusted to a pH of 4.5 with sulfuric acid and 0.4 g of the dye of the formula per liter and contains 1 g of the sodium salt of dinaphthylmethanedisulfonic acid. The bath is heated from 60 ° C. to 98 ° C. within 45 minutes and held at this temperature for 120 minutes.

Then the fabric is rinsed and then with a liquor that in the liter 2 cc sodium hydroxide solution 380 Bé, 5 g sodium dithionite and 1 g sodium salt of a Contains prepafonic acid mixture with an average C-chain length of C15, after-treated, the bath being heated from 40 ° C to 70 ° C within 20 minutes. Then rinse the fabric is rinsed with fresh water, neutralized with formic acid and then rinsed several times with Afs Ester.

A very high-contrast light red-dark red coloration is obtained, there the pretreated yarn has a much darker red color than the untreated yarn.

Example 2 Yarns made from polycyclohexanedimethylene terephthalate are used in the Liquor ratio of 1: so introduced into a 50 0C warm bath that in the liter 5 g of methyl 2-hydroxy-3-methyl-benzoate and 1 g of that described in Example 1 Mixture A contains. The bath will reach 980C within 30 minutes warmed up and then held at this temperature for 15 minutes. After thorough flushing with waeeer the yarns are dewatered and dried.

The pretreated yarn is processed with untreated polyester yarn into a Mouliné yarn, which is then dyed in a dyeing machine in a liquor ratio of 1:30 with a liquor that has been adjusted to a pH of 4.5 with sulfuric acid and 0.33 g per liter of the dye of the formula and contains 1 g of the sodium salt of iinaphthylmethanedisulfonic acid. The bed is heated to So0C within 30 minutes and kept at this temperature for 90 minutes. After rinsing, the yarns are subjected to the alkali-odor-reductive aftertreatment with sodium hydroxide solution / sodium dithionite described in Example 1, rinsed, neutralized and rinsed again.

A high-contrast, luminous light blue-dark blue coloration is obtained, because the pretreated yarn has a much darker blue color than the non-pretreated yarn.

EXAMPLE 3 Fabric made of polyethylene terephthalate is imprinted with a paste containing 10 g of diphenyl, 2 g of the mixture A described in Example 1 and 18 g of alginate (dry matter) per kilogram. The fabric is then steamed at approx. 100 ° C. for 15 minutes. After rinsing, drying and heat setting it is dyed in a liquor ratio of 1:40 with a liquor containing 0.1 g of the dye Color Indes No. 12790, 2nd edition (1956 and 3, 0.25 g des Dye of the formula and contains 1 g of the sodium salt of dinaphthylmethanedisulfonic acid. Then proceed as described in Example 1.

A very nice green print is obtained, with the printed areas have a significantly darker green color than the unprinted areas.

Example 4 Yarns made from polycyclohexanedimethylene terephthalate are used in the 1: 30 liquor ratio in a 50 ° C bath brings, 6 g of N-butylphthalimide and 1 g of the mixture described in Example 1 per liter A contains. The bath is heated to 98 ° C within 3n minutes and 30 minutes kept at this temperature. After thorough rinsing with water, the yarns will dehydrated and dried.

The pretreated yarn is knitted with untreated PolyeBter yarn. The knitted piece is made in a liquor ratio of 1:25 with a liquor as in the example 1 described dyed, washed, post-treated with alkaline-reductive means, rinsed and acidified.

A very high-contrast light red-dark red coloration is obtained, there the pretreated yarn has a much darker red color than it does not pretreated.

Claims (4)

Claims. 1.) Process for the production of multicolor effects on fiber materials made of polyesters, characterized in that the fiber materials are made before dyeing Treated with aqueous baths or printed with aqueous pastes that increase the dye absorption capacity contain increasing compounds of polyester, and then - in the case of Treating - together with untreated polyester fiber materials without the addition of Carrier at or below boiling temperature with disperse dyes, or - in the case of printing - subjected to a heat treatment and then without any additive of carriers at or below boiling temperature with disperse dyes. 2.) The method according to claim 1, characterized in that as the dye absorption capacity of polyester increasing compounds for dyeing Polyesters used with disperse dyes usable dye accelerators (carriers). 3.) Process according to Claim 1 and 2, characterized in that the compounds which increase the dye uptake capacity of polyester are aromatic compounds of the formula in which R1 is hydrogen, phenyl or chlorine, R2 i3r is hydrogen, hydroxy or chlorine, and R3 is hydrogen or chlorine, with the proviso that R1, R2 and R3 are not hydrogen at the same time and that R2 is only a hydroxy group if R1 is a phenyl group; aromatic carboxylic acid esters of the formula in which R1 is a C1-C4-alkyl radical, R2 is hydrogen or a C1-C2-alkyl group and R3 is a C1-C2-alkyl or C1-C2-alkoxy group; or phthalimide derivatives of the formula in which R1 stands for an alkyl radical which is optionally substituted by halogen, a hydroxy, alkoxy, acyloxy, carboxy or alkoxy carbonyl group and contains a total of 1 to 8 carbon atoms, the carbon chain of which can be interrupted by oxygen atoms, and R2 is hydrogen, halogen , a hydroxy, C1-C4-alkoxy-4-carboxy, C1-C1-alkoxycarbonyl or nitro group or 1 denotes a phenyl radical; used. 4.) Polyester materials multicolour-colored according to claim 1 to 3.