US3707344A

US3707344A - Differential-dyeing textiles

Info

Publication number: US3707344A
Application number: US28081A
Authority: US
Inventors: Guenter Becht; Joachim Kunde; Norman La France; Karl Robert Mueller
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1969-04-18
Filing date: 1970-04-13
Publication date: 1972-12-26
Anticipated expiration: 1989-12-26
Also published as: FR2045419A5; DE1919746A1; AT299874B; BE749092A; GB1296778A; NL7005347A

Abstract

TEXTILES OF AT LEAST TWO DIFFERENT POLYAMIDE YARNS WHEREIN FROM 10 TO 90% BY WEIGHT OF THE YARN IN THE TEXTILE IS YARN OF A POLYAMIDE WHICH CONTAINS FROM 1 TO 15% BY WEIGHT OF XYALKYLATED POLYAMIDE. THESE TEXTILES ARE DYED IN CONTRASTING SHADES IN A SINGLE-BATH PIECEDYEING PROCEDURE.

Description

United States Patent US. Cl. 821 B 8 Claims ABSTRACT OF THE DISCLOSURE Textiles of at least two different polyamide yarns wherein from to 90% by weight of the yarn in the textile is yarn of a polyamide which contains from 1 to by weight of oxyalkylated polyamide. These textiles are dyed in contrasting shades in a single-bath piecedyeing procedure.

The invention relates to differential-dyeing textiles comprising at least two different polyamide yarns.

It is known that yarn which have been dyed different colors may be processed into multicolored textiles. In order to obtain a certain range of multicolored textiles it is necessary to keep a large inventory of dyed yarns.

It is an object of this invention to provide differentialdyeing textiles of polyamide yarns which can be dyed in piece form. This and other objects which will appear hereinafter are achieved by the invention.

In accordance with this invention, textiles of at least two different yarns of filament-forming synthetic linear polyamides comprises from 10 to 90% by weight of yarn (A) of a polyamide which contains from 1 to 15% by weight of oxyalkylated polyamide.

Polyamides for the purposes of this invention are synthetic linear polyamides having recurring amide groups in the main chain.

The presence of yarn (A) of polyamide containing 1 to 15%, preferably 3 to 8%, by weight of oxyalkylated polyamide in the textiles is essential according to this invention. The production of polyamides modified with oxyalkylated polyamides may be carried out by conventional incorporation of the oxyalkylated polyamide, for example by fine distribution by kneading and homogenizing the melt, into filament-forming synthetic linear polyamides. Examples of such polyamides are polycondensates of lactams such as e-caprolactam, capryllactam, laurolactam or mixtures of these lactams, and the polycondensates of salts of diamines and dicarboxylic acids such as the salts of adipic acid. suberic acid or sebacic acid and hexamethylenediamine, octamethylenediamine or dodecamethylenediamine or cocondensates of the said polyamide-forming starting materials. It is possible to add the said oxyalkylated polyamide to the polyamide-forming starting materials prior to or during the production of the said polycondensates. Particularly favorable results are achieved when the modifying agent which is present in the filament-forming polyamide in a separate phase has a particle size of 0.01 to 0.5 micron.

The oxyalkylated polyamides may be prepared by known methods, for example according to Belgian Pat. No. 665,018 by reaction of a 1,2-alkylene oxide such as ethylene oxide and/or 1,2-propylene oxide with a polyamide under superatmospheric pressure at elevated temperature, particularly at temperatures of from 60 to 100 C. The reaction may be carried out in the absence or presence of organic solvents and/or reducing or oxidiz- 3,707,344 Patented Dec. 26, 1972 ice ing agents, the alkylene oxides preferably being reacted with the polyamides in the ratio by weight of 0.5:1 to 4:1.

Suitable polyamides from which the oxyalkylated polyamides (used as antistatic agents) may be prepared are for example polycondensates produced by conventional methods from lactams such as caprolactarn, capryllactam, laurolacta'm or mixtures of these lactams; salts of the type diamine/dicarboxylic acid, such as the salts of adipic acid, suberic acid or sebacic acid and hexamethylenediamine, octamethylenediamine or dodeca-methylenediamine, or copolyamides of the said polyamide-forming starting materials. Polyamides which have a low crystallinity such as copolyamides or polyamides which have been obtained by quenching the polymer melt, for example of molten polycaprolactam, are generally particularly suitable.

Yarns (B) which may be present in the textiles in addition to the yarn which is essential according to the invention are for example yarns of unmodified filament-forming synthetic linear polyamides such as the polycondensates of lactams such as e-caprolactam, capryllactam, laurolactam or mixtures of these lactams and the polycondensates of salts of diamines and dicarboxylic acids such as the salts of adipic acid, suberic acid or sebacic acid and hexamethylenediamine, octamethylenediamine or dodecamethylenedia-mine or cocondensates of the said polyamide-forming starting materials. Filament-forming polycaprolactam and polyhexamethylene adiparnide are particularly suitable as the unmodified polyamides. Products having a relative viscosity of from 2.2 to 2.8 have proved to be favorable.

Other yarns (C) which may be present in the textiles in addition to the yarn which is essential in accordance with the invention are those of conventional filamentforming synthetic linear polyamides having from 50 to- 130, particularly from 60 to 110, milliequivalents per kilogram of basic groups. The production of these polyamides may be carried out for example by using additional monofunctional or bifunctional primary amines such as hexamethylenediamine, in the production of the polyamides from the abovementioned lactams or dicarboxylic acid/diamine salts. It is also possible to introduce tertiary amine groups into the polyamides by using polyamide units bearing tertiary amine groups in the production of polyamides from the said lactams or dicarboxylic acid/diamine salts. It is also possible to activate basic groups for dyeing by using in the production of the polyamides in the said manner 0.01 to 0.3% by weight with reference to polyamide of phosphorus in the form of oxyacids of phosphorus or their esters.

Other yarns (D) which may be present in the textiles in addition to the yarn which is essential in accordance with this invention are those of polyamides which can be dyed full shades with basic dyes. Polyamides which contain from 50 to milliequivalents per kilogram of sulfonate groups in the form of alkali metal salts are suitable for the production of these yarns. Production of these polyamides may be carried out for example by using aliphatic, cyeloaliphatic or aromatic polyamide units bearing sulfonate groups in appropriate amounts in the production of the polyamides from the said lactams or dicarboxylic acid/diamine salts. For example the sodium or potassium salt of 5-sulfoisophthalic acid is suitable for the incorporation.

Textiles having the following yarn combinations are preferred:

(1) yarn (A) with yarn (B) (2) yarn (A) with yarn (C) (3) yarn (A) with yarn (D) or (4) yarn (A) with yarn (B) and with yarn (D).

The polyamide yarns which are essential according to the invention and the polyamide yarns used with them may contain conventional additives such as stabilizers or delustrants such as titanium dioxide. They may be processed smooth or textured into textiles. Examples of suitable texturing methods are gear crimping, stuffing box crimping or false twisting and air-texturing. The yarns may be composed of continuous filaments or staple fibers. Yarns and filament bundles are equivalent.

The term textiles in this specification includes hosiery, knitwear, woven and nonwoven goods and particularly carpets.

The amount of the yarn (A) which is essential according to the invention and consists of polyamides having a content of oxyalkylated polyamides is to 90%, advantageously 20 to 80%, by weight and consequently the proportion of other polyamide yarns in the textiles is 90 to 10% and 80 to 20% by weight respectively. The ratio of the yarns to one another may vary within these limits. The textiles may contain one or more than one kind of yarn in addition to the yarn which is essential according to the invention. The ratio of the yarns present in the textiles in addition to the essential yarn may in turn vary Within wide limits. The yarn combination chosen is dictated by the desired color pattern and color effects in the textile. For a strong optical effect it may be advantageous for the various yarns to be present in about equal amounts, i.e. in a combination of two yarns the amount of each may be from 40 to 60% by weight and in a triple combination each may be present in an amount of 20 to 40% by weight, while in a combination of four yarns the amount of each may be from to 30% by weight. The distribution of color in the yarn blends in relation to the dyes to be used may easily be ascertained by simple preliminary experiments. The distribution of yarns in the textile may be varied markedly in weaving or tufting so that the zones of different coloration may be varied substantially.

The textiles are preferably piece-dyed. Generally it is advantageous to carry out the dyeing from an aqueous liquor by the one-bath method. When a tone-on-tone effect or a moulin dyeing having contrasting shades according to the content of different yarns is desired, acid dyes should be used exclusively. The pH has a certain influence on the degree of contrast, the contrast usually being better the higher the pH is. A pH of 4 to 9, particularly 7 to 9, has proved to be very favorable. When complementary colorations are to be obtained, it is advantageous to use disperse dyes in addition to the acid dyes.

For cross dyeing it is necessary for the textiles to contain yarns of basic-dyeable polyamides. Dyeing is carried out with acid dyes and basic dyes and if necessary with disperse dyes all at the same time to achieve cross dyeing. A pH of the dye liquor of 4 to 8, particularly 6 to 8, has proved to be favorable in this case.

In dyeing textiles in the presence of disperse dyes it is advantageous for the yarns from different polyamides to have the same affinity for the disperse dyes.

Conventional dyes are suitable. For example dyes of the anthraquinone or azo series having sulfonic groups are suitable as acid dyes. Acid dyes give a higher degree of contrast the higher the number of sulfonic groups present in the molecule. Thus three sulfonic groups produce a more marked contrast than two sulfonic groups or one sulfonic group. Examples of basic dyes are those having basic tertiary or quaternary nitrogenous groups.

Piece dyeing may be carried out batchwise or continuously, for example by drawing a length of carpet through the dye-bath. The one-bath method of piece dyeing differential-dyeing textiles according to the invention toneon-tone or multicolor effects constitutes an extremely efficient and economical procedure. The inventory is minimized. Moreover a variety of color styling patterns can be prepared because a great many variations are possible in the composition of the yarns, in the arrangement of these yarns in the textiles and in the choice of dyes.

Textiles according to this invention also have the valuable property of a decreased static electrification, particularly with an increasing content of the yarns which are essential according to the invention.

The following examples illustrate the invention. The parts and percentages specified in the examples are by weight.

EXAMPLE 1 (a) Production of an oxyalkylated polyamide: Ethylene oxide is forced onto 160 parts of powdered polycaprolactam (K value 66, internal viscosity determined according to the formula of H. Fikentscher, Cellulosechemie, 13, 58 (1932), so that a pressure of 5 to 10 atmospheres gauge prevails in the gas space and up to 560 parts of ethylene oxide react. The reaction temperature is to C. The reactor is vented and purged with nitrogen. 720 parts of oxyalkylated polyamide is obtained which has a K value (measured as a 1% solution in concentrated sulfuric acid) of 42.

(b) Dyeing yarn blends: To detect the differential dye takeup, 10 parts of yarn of polycaprolactam having a K value of 72 (total denier, 1200; 67 individual filaments) together with 10 parts of polycaprolactam yarn of the same denier and number of filaments to which during the polycondensation 7.5% of the oxyethylated polyamide prepared according to Example 1(a) has been added are dyed a liquor as follows:

In an aqueous dye liquor which contains 0.25% of the acid dye Acilan Fast Navy Blue R (with reference to the total weight of yarn) and 0.5 part per liter of an oxyalkylated emulsifying agent and which has been buffered to pH 7.2 with 0.3 part per liter of boric acid and 0.01 part per liter of borax, the yarn blend is dyed at the boil for one hour at a liquor ratio of 50:1 until the liquor is exhausted. The dye pickup of the two yarns is determined by extraction of the separated yarns with a 1:1 mixture of pyridine and water in a Soxhlet apparatus. The following percentage distribution of the dye in the yarns is obtained:

Yarn: Amount of dye taken up, percent Polycaprolactam 21.9 Modified olycaprolactam 78.1

The better dye absorption of the polyamide which has been modified with oxyalkylated polyamide may be clearly seen.

EXAMPLE 2 In accordance with Example 1(b), the yarn is dyed in a dye liquor at a liquor ratio of 50:1 which contains 0.5% of the acid dye Supranol Yellow 0 with reference to the Weight of yarn in all, and 0.5 part per liter of a conventional oxyalkylated emulsifier and which has been buffered to pH 8.0 with 0.4 part per liter of boric acid and 0.19 part per liter of borax. The following dye distribution is obtained:

Yarn: Amount of dye taken up, percent Polycaprolactam 31.4 Modified polylactam 68.6

EXAMPLE 3 A combination of equal parts of yarns of (I) polycaprolactam having a K value of 73;

(II) olycaprolactam having a K value of 74 which has 61 milliequivalents of basic groups per kilogram; and

(III) olycaprolactam having a K value of 67 which has been modified by 7.5% of the oxyethylated polyamide, prepared in Example 1(a) is dyed according to the conditions of 1(b) or 2. The following percentage dye distribution is found:

Acilan fast Supranol Yam navy blue R yellow I 4. 8 8. 1 II 64. 9 74. 4 III 30. 3 17.

The midposition of yarn III modified with the oxyalkylated polyamide according to the invention may be clearly seen,

EXAMPLE 4 A combination of equal parts of yarns of:

(I) polyhexamethylene adipamide having a K value of (II) polyhexamethylene adipamide having a K value of 70.4 which has 79 milliequivalents of basic groups per kilogram; and

(III) polycaprolactam having a K value of 67 which has been modified with 7.5% of the oxyethylated polyamide prepared in Example 1(a) is dyed under the conditions according to Example 1(b) or 2. The following percentage dye distribution are found:

Acilan fast Supranol Yarn navy blue R yellow 0 EXAMPLE 5 EXAMPLE 6 The two yarns specified in Example 1(b) are textured by the stuffing box method and twisted at the rate of 50 turns per meter. By tufting this material on a jute twill material, a piece of carpet is prepared which contains 550 g./m. of pile material. A sample piece of this carpet is dyed on the beck at pH 8 with 0.3% of Brilliant Alizarin Milling Blue FGL and 0.9% of Celliton Yellow 4 GE (with reference to the piece of carpet) at a liquor ratio of 80: 1. The sample exhibits a yellowish green moulin pattern after dyeing.

EXAMPLE 7 A knitted article is made up from equal parts of yarn of:

(I) polycaprolactam having a K value of 69 which has been modified with 5% by weight of the oxyalkylated polyamide prepared in Example 1(a); and

(II) polyhexamethylene adipamide having a K value of 71 which contains 1.5% by weight of sodium S-sulfoisophthalate and 0.4% by weight of hexamethylene diamine condensed therein.

The yarn has a denier of 1100 with 67 individual filaments. When the article is dyed in an aqueous dyebath having a pH of 7.1 which contains 0.5 by weight of the acid dye Acilan Fast Navy Blue R and 0.5% by weight of the basic dye Basacryl Yellow 7 GL (each with reference to the article) a pattern is obtained at a liquor ratio of 50:1 in which yarn (I) is dyed pure blue and yarn (II) is dyed pure yellow. Thus a cross dyeing having clearly separated color areas is obtained according to this example.

EXAMPLE 8 (I) A rnixture of 100 parts of olycaprolactam chips having a K value of 73 is melted and homogenized with 5 parts of the oxyalkylated polyamide chips prepared according to Example 1(a) in a twin shaft extruder.

(II) Polycaprolactam chips having a K value of 73 which contain 78 milliequivalents per kilogram of basic terminal groups are prepared by polycondensation of caprolactam with 0.3% by weight of hexamethylene diamine as regulator followed by annealing for twenty-four hours of the extracted chips at 160 C. in a stream of nitrogen.

Yarns having a drawn denier of 1100/67 are spun from both portions, textured by the edge drawing method and twisted at the rate of 50 turns per meter. By tufting this yarn on a jute twill material a piece of carpet is prepared having 600 g./m. of pile material. When this sample is dyed on the beck with 0.7% of Lanasyn Pure Red R with reference to the weight of the sample at a pH of 7.2 and a liquor ratio of 80:1, a pale red/dark red moulin pattern is obtained in which the paler fibers are those prepared according to (I) and the darker fibers are those prepared according to (II).

EXAMPLE 9 Three yarns having a drawn denier of 40/10 are spun from the following polyamides:

(I) a polyamide prepared according to Example 3(1);

(II) a polyamide prepared according to Example 8(I);

and

(III) a polyamide prepared according to Example 7(II).

Using these yarns in the ratio 1:1:1, stockings are knitted in shepherds check pattern. When these stockings are dyed with 1.5 of Lanapearl Red B and 0.5 of Sevron Blue B, with reference to the weight of the article, at a pH of 6.5 and a liquor ratio of 50:1, a blue/pale red/dark red shepherds check pattern is formed, yarn from (I) being pale red, yarn from (II) dark red and yarn from (III) blue.

We claim:

1. A difierential-dyeing textile which can be dyed in piece form and which is composed of at least two diiferent yarns of filament-forming synthetic linear polyamide having amide groups recurring in the main chain wherein from 10 to by weight of the yarns is a yarn A of a polyamide which contains from 3 to 8% by weight of an oxyalkylated polyamide which has been obtained by oxyalkylation with ethylene oxide or 1,2-propylene oxide in a ratio by weight of alkylene oxide: polyamide of about 0.5:1 to 4:1.

2. A differential-dyeing textile as claimed in claim 1 which comprises from 10 to 90% by weight of said yarn (A) and 90 to 10% by weight of at least one member of the group consisting of yarn (B) of unmodified polyamide and of yarn (C) of a polyamide having from 50 to milliequivalents per kilogram of basic groups and of yarn (D) of a polyamide having 50 to milliequivalents per kilogram of sulfonate groups.

3. A differential-dyeing textile as claimed in claim 1 which comprises from 10 to 90% by weight of said yarn (A) and 90 to 10% by weight of a yarn (B) of an unmodified polyamide.

4. A differential-dyeing textile as claimed in claim 1 which comprises 10 to 90% by weight of said yarn (A) and 90 to 10% by weight of a yarn (C) of a polyamide with 50 to 130 millequivalents of basic groups.

5. A differential-dyeing textile as claimed in claim 1 which comprises 10 to 90% by weight of said yarn (A) 7 and 90 to 10% by weight of a yarn (D) of a polyamide having to 150 milliequivalents per kilogram of sulfonate groups.

6. A differential-dyeing textile as claimed in claim 1 which comprises 10 to by weight of said yarn (A) and 90 to 10% by weight of yarn (C) of a polyamide having 50 to milliequivalents per kilogram of basic groups and of yarn (D) of a polyamide having 50 to milliequivalents per kilogram of sulfonate groups.

7. A textile as claimed in claim 1 which has been piecedyed in a single bath to provide a contrasting coloration.

8. A textile as claimed in claim 7 wherein at least one acid dye has been applied to the textile from a single bath.

References Cited UNITED STATES PATENTS 10 ROBERT F. BURNETT, Primary Examiner L. T. KENDELL, Assistant Examiner US. Cl. X.R.