DE1248609B - Process for dyeing multi-strand polyamide yarn - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

D 06 ρ

German KL: 8 m -

1248 609
D38103IVc / 8m
February 8, 1962
August 31, 1967

The invention relates to a novel method for dyeing multifilament yarn and textiles made of synthetic polyamide (nylon), by means of which with the help of a a single dye liquor to achieve multi-colored effects.

in British Patent 860,862 is a Process for dyeing normal wool described in which dyes are used that at least contain two sulfonic acid groups and certain aryl sulfonic acid condensation products to produce a multicolored Achieve coloration with the aid of a single dye bath without the need for mixtures to use wool types that have a different affinity for dyes. This Method is based on the exploitation of differences that arise in terms of affinity for dyes at various points along the wool fibers and those in the usual dyeing processes are not observed. The process is probably based on the heterogeneous structure of normal Wool, which is based either on the diversity of the amino groups it contains or on a uneven physical structure or due to both factors.

It was therefore to be assumed that an analogous process would not be possible with textiles made of synthetic fibers, because these fibers are uniform in terms of their physical and chemical properties. This assumption was proven z. B. in the case of polyesters and acrylic plastics as correct. Surprisingly, however, it was found that in the case of multifilament nylon. no more than 7 g per denier can produce an effect similar to that observed with wool. This fact was all the more surprising given that nylon has no chemical or physical characteristics to indicate the existence of different affinities for dyes along the individual threads. The effect mentioned is not due to the presence of mixtures of * different types of nylon in the dye bath, e.g. B. on the fact that a mixture of nylon 66 and nylon 6 would be present, although it is possible to amplify the differences in affinity for dyes between these two types of nylon with the aid of the method according to the invention to such an extent that one, if necessary, a reserve on nylon 66 can achieve. In fact, multi-filament nylon yarns believed to have substantially uniform physical and chemical properties over the length of the individual multi-filament dyeing processes exist
Polyamide yarn

Applicant:.

Arthur Jacob Immins Harding,

Spartanburg, S. C. (V. St. A.)

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse
and Dr. E. Frhr. v. Pechmann, patent attorneys,
Munich 90, Schweigerstr. 2

Named as inventor:
Arthur Jacob Immins Harding,
Spartanburg, SC (V. St. A.)

Claimed priority:

V. St. v. America 8 February 1961 (87 786)

threads sufficiently large differences in terms of dyeing behavior that it can be with the help of the invention Method is possible with the help of a single dye bath to produce multicolored effects achieve.

The method according to the invention for dyeing perfect multi-filament yarn and manufactured therefrom Woven and knitted from synthetic polyamide (nylon) for the purpose of producing a multicolored effect using a single dye liquor is characterized in that one Nylon yarn of a tensile strength of less than grams per denier in a liquor that dyes a dye with at least two sulfonic acid groups and with zero to three reactive groups in the molecule contains, the sum of the sulfonic acid groups and the reactive groups being at least 3 and the pH is in the acidic range, in the presence of a water-soluble condensation product of an aryl sulfonic acid and an alde-

709 639/497

hyd or ketone in an amount of 0.1 to 5 percent by weight based on nylon, these The amount is insufficient to reserve the dye.

According to a particularly expedient embodiment of the dyeing process according to the invention the condensation product present is one of an arylsulfonic acid, in particular the Naphthalene sulfonic acid, with formaldehyde or from an aryl sulfonic acid with benzoin, which is in the form of his Sodium salt is present in the dye liquor.

If necessary, the liquor can also contain a dye with less than a total of two sulfonic acid and contain reactive groups in the molecule.

In the following, the term "multicolored" denotes a mixture of two or more arbitrary ones Colors including white. Thus, nylon is colored mixed red and white or two Having shades of red to be referred to as multicolored according to this definition.

It should be noted that the multicolored dyeings which can be achieved with the aid of the process according to the invention are those that show up as non-solid colorations over the length of the monofilaments of nylon of a certain type. However, this effect can be correspondingly achieved with the aid of contrast coloring achieve obtained by using two types of nylon, e.g. Nylon 6 and nylon 66 dye.

Nylon products that can be dyed using the method of the present invention include multi-thread nylon yarns and woven and knitted fabrics made from them, including finished garments, z. B. stockings, sweaters, sports shirts and blouses, as well as yard goods such as upholstery and carpet fabrics. The multi-filament polyamide yarn can optionally be made from single filaments cut into staple fibers be crazy.

The method according to the invention is preferably used for nylon of type 6, since this material Has a greater affinity door dyes. In particular, light-colored polyamide yarn is preferred, with little or no pigments or fillers added. The multi-threaded one preferably used Yarn has a total denier weight of at least 100, while the denier weight per single thread between about 2 and. is at most 7 g. An example is carpet yarn with a total denier weight of 1000 or more, usually about 4000, and a denier weight of the monofilament of 7 g or fewer. In the case of structured polyamide, especially if the tenacity of the yarn during the Structuring has been brought to a high value, it makes somewhat greater difficulties, very pronounced to achieve multi-colored coloring effects. This difficulty occurs to a lesser extent on when the structured nylon is dyed in the form of knitwear, individual pieces or garments will.

According to the invention, dyes are used that dye nylon and at least two sulfonic acid groups, preferably three or more sulfonic acid groups, and between zero and three reactive ones Contain groups in the molecule, the sum of the sulfo groups and the reactive groups at least equals 3. The dyes which contain reactive groups, e.g. B. vinyl sulfo or cyanuric chloride groups, are referred to as so-called reactive dyes. To the dyes containing three or more sulfonic acid and reactive groups include acid dyes, fulled dyes, direct dyes and cotton dyes. These dyes are usually supplied by the manufacturer in the form of sodium salts. Of the The term "sulfonic acid group" excludes those groups in which the sulfonic acid group in Is in the form of an inner salt with a basic group. The for the inventive method

ίο preferred dyes are those with which the number of sulfonic acid groups contained therein is 3 or more.

The dye baths according to the invention are acidic; that is, they contain an organic or inorganic Acid or an acidic salt, e.g. B. acetic acid, formic acid, sulfuric acid, lactic acid, citric acid or another aliphatic acid or phosphoric acid or their acidic salts, e.g. B. the ammonium salts. The starting value of the pH of the liquor is preferably between about 2 and 5. If appropriate you can vary the pH during dyeing by using ammonium sulfate or phosphate is used to then allow the pH to slowly decrease during dyeing.

The amount of acid to be used depends on the affinity of the dye used Dye for nylon in the presence of condensation products, which are discussed below will. Since the condensation products used according to the invention retard the dyeing of nylon, In some cases it is necessary to use slightly larger amounts of the acid or a stronger acid than would normally be used with these dyes. The usual area is between 1 and 5% acetic acid or 1 to 5%, usually 1 to 3% formic acid, sulfuric acid or phosphoric acid, based on the weight of the nylon.

The condensation products used in accordance with the invention are generally called "retarders" or "Leveling agents" are known and are mostly used when dyeing wool. They are chemically as Condensation products of common carbocyclic aryl acids, sulfonic acids and one Aldons marked. The term »Aldon« here denotes an aldehydic or ketonic carbonyl compound, z. B. formaldehyde, acetaldehyde, benzaldehyde, benzoin, acetone, etc. This is it is a well-known and commonly used group of compounds in dyeing. All these Compounds have at least two sulfonic acid-substituted aryl groups in the molecule. The this Compounds corresponding to the definition are mono-, di- or trisulfonic acid-substituted benzenes or Naphthalenes which are further substituted with lower alkyl, hydroxy, nitro, amino, etc. groups and have been condensed with an Aldon in the manner described above to form a Create dimer, trimer, or polymer that is crosslinked through the aldoh; these reactions are as such known. According to US Pat. No. 2,623,806, in the condensation reaction also other connections, e.g. B. Dihydroxyphenylsulfon, can be used to create a mixed condenser

sationspr <j> duct to generate. These connections include the condensation products of naphthalene -! - or naphthalene-2-sulfonic acid or of naphthalene-2,7-disulfonic acid and formaldehyde, e.g. B. the-

those according to the formula
(HO ₃ S),

(SO ₃ H) ₁

CH-

CH ₂

(SO ₃ H) *

and the associated alkali metal salts when η ίο is O, 1, 2 or more (usually O or 1), while χ is 1 or 2. Other compounds include the condensation product of phenolic or cresol sulfonic acid and formaldehyde, which z. B. the formula

OH

SO ₃ H

OH

OH

'5

20th

SO ₃ H Jn SO ₃ H

and the corresponding alkali metal salts when R is H or CH ₃ and η is 0 to 3 or 4. The condensation products of phenol-cresol or naphthalenesulfonic acid and benzoin or acetone and their alkali metal salts can also be used.

Specific examples of such condensation products are dinaphthylmethanedisulfonic acid, diphenylmethanedisulfonic acid, dihydroxyphenylmethanedisulfonic acid, Dicresylmethanedisulfonic acid, dihydroxynaphthylmethanedisulfonic acid ^ initronaphthylmethanedisulfonic acid, Dichloronaphthylmethanedisulfonic acid, diaminonaphthylmethanedisulfonic acid, dinaphthylmethane-2,7,2 ', 7'-tetrasulfonic acid and the sodium salts of all of these compounds.

The arylsulfonic acid condensation product is, based on the nylon, in an amount of 0.1 to 5 percent by weight used, which is not sufficient to bring about a reserve of the dye used. Usually an amount is used which is sufficient to increase the speed of the dyeing process "Effect" dye noticeably reduce, so that the condensation product acts as a retarder works. Usually the amount will range from about 0.25 to 3 percent.

In practicing the method of the present invention, the multi-filament nylon selected becomes common in the form of yarn or pieces made by weaving or knitting in one dyed in an acidic pH in a dye bath containing a nylon dyeing dye and contains the selected arylsulfonic acid condensation product as defined above. Here if the usual dyeing technique is used, d. that is, the nylon is usually put in the cold dye bath and the dye bath is then heated to the boil, dyeing continued until the dye bath has been depleted or an equilibrium state has been reached. Possibly you can rather the nylon with the arylsulfonic acid condensation product bring in contact than with the dye. However, for the sake of simplicity and convenience, the two are included Ingredients usually together in the dye bath.

When working with a single dye, the effects achieved vary between one coloration Tone on tone and one color on white, these effects being the definition given above for the Correspond to the designation »multicolored«. Particularly remarkable results are obtained when that Dye bath additionally contains at least one dye which comprises less than two sulfonic acid groups, and a dye which has at least one and preferably two more sulfonic acid groups than Contains dyes described above. With the help of such a mixture of dyes leaves Coloring in all colors of the rainbow can be achieved using a single dye bath.

The effects that can be achieved by means of the invention are described in particular when using one of the described Dye mixtures are often intensified when it comes to the material to be dyed are knitted or knitted goods or items of clothing or upholstery or pile carpets. Obviously, the uptake of the various dyes is due to the structure or build-up of the to coloring material affected. When using a dye with three sulfonic acid groups together with an overall color, d. H. a dye with less than two sulfonic acid groups, it shows z. B. that the higher sulfonic acid dyes concentrate at the base of the pile of tufts, where the Material is less accessible, although one should expect the opposite. As a result of this phenomenon completely new effects can be achieved if you use piece or flat goods, such as knitted goods and garments or carpets.

When a state of equilibrium or exhaustion has been reached, the nylon can be turned into Wash and dry in the usual way.

To make the process easier, you can add the usual dye additives to the dye bath, z. B. Glauber's salt or other substances, add as leveling agents or non-ionic wetting agents works. As with other dyeings, however, these additives can also produce the result achieved change something. Usually it is preferred to have minimal amounts of these other additives to add.

It has been found that the result obtained can be altered somewhat by removing the nylon subjected to a pre-treatment with formaldehyde or paraformaldehyde, e.g. B. by the Nylon is briefly heated or boiled in an aqueous solution containing up to about 2% formaldehyde or Contains paraformaldehyde based on the weight of the nylon. The nylon can then be used in the manner described here Way to be washed and dried. Alternatively, the formaldehyde can be added to the dye bath to add.

You can also change the results somewhat by removing the nylon before adding the condenser cation product and the dye with acid

acts or rather with the condensation product than brings into contact with the acid and the dye. These modifications allow the to achieve a wide variety of effects and shades and so increase the versatility of the process raise.

The invention is explained in more detail below with reference to several exemplary embodiments. All specified Percentages are based on the weight of the nylon to be dyed.

example 1

10

Multi-ply nylon yarn of 5000 denier with 816 monofilaments of Caprolan, which was light and of medium strength, was _{dyed in a dye bath, 5} , containing 2% acetic acid, 0.5% of a formaldehyde naphthalenesulfonic acid condensation product (Erional NW) and 0.5% Fastusol Blue LFFR, that is, a cotton dye with at least three sulfonic acid groups. The dye bath was brought to the boil in about 20 minutes and kept boiling for about 1 hour. The nylon was then washed and dried, showing that it was colored mixed blue and white similar to the dyeing of the piece.

Example 2

The procedure was exactly as in Example 1, but the dye was replaced by 0.5% Acilan Crocein F 9 B (Acid Red 47, C.]. 27300), d. H. a sulfonic acid dye with four sulfo groups. A coloration in candy red and white was achieved.

Example 3

The procedure was as in Example 1, but the dye Pyrazole Schnellrot 6 BL (Direktrot 79, C.I. 29065), d. H. a sulfonic acid dye having four sulfo groups is used. The nylon was made with colored a mixture of white and a moderately dark red.

Example 4

The procedure was exactly as in Example 1, but 0.5% Fastusol scarlet LGG was used as the dye (Direktrot 76, C. 1. 40270), d. H. a sulfonic acid dye having three sulfo groups is used. It happened a coloring of the nylon as a light mixture of white and orange.

Example 5

The procedure was exactly as in Example 1, but the dye used was 0.5% solantine gray BL (Direktschwarz 74, C.I. 34180), d. H. a sulfonic acid dye having five sulfo groups is used. It resulted the nylon is colored in a mixture of pastel blue and white.

Example 6

The procedure was as in Example I, but 0.5% Cibacron black BG, i.e. 0.5% cibacron black, was used as the dye. H. a Rcaklive dye with more than two sulfonic acid groups is used. Here the nylon was mixed in Colored blue-gray and white.

Example 7

Light nylon yarn of 5000 denier with 816 single threads was stained in a dye bath containing 0.5% Sun Yellow 3 LG, i.e. H. a cotton dye with at least four sulfonic acid groups, 0.1% Procion blue; HBS, d. H. a reactive dye with more than two sulfonic acid groups, 0.1% calcoideosin G (Acid Red 4, C.I. 14710), d. H. a sulfonic acid dye with a sulfonic acid group, 3% acetic acid and Q, 5% of a formaldehyde-naphthalenesulfonic acid-C condensation product (Erional NW) included. The dye bath was brought to the boil in about 30 minutes with occasional stirring and then kept boiling for about 1 hour. After washing and drying that was it Nylon thread dyed pink, this color being mixed with shades of blue-gray.

Example 8

The procedure was as in Example 7, but 0.1% Procion Brilliant Red H 3 B S, a reactive dye with more than two sulfonic acid groups, 0.15% milled yellow 5 G, a yellow sulfonic acid dye with a sulfonic acid group, and 0.12% Alpharazip FG (Acid Blue 9, C. 1. 42090), i.e. H. a Dye with two sulfonic acid groups was used. A multicolored pastel coloring was achieved Shades of pink ^ shades of lavender, shades of blue, shades of green, shades of orange and yellows included.

B e i s ρ i e 1 e 9 to 14

Examples 1 to 6 were repeated, but the nylon was used together with the acetic acid in Room temperature in the dye bath laipg stirred for a few minutes before the formaldehyde naphthalenesulfonic acid condensation product and the dye added. Essentially the same results were obtained.

Example 15

A men's stocking knitted from spun nylon 6 (staple fibers) was placed in a dye bath colored, the 5% acetic acid, 0.5% of a formaldehyde naphthalenesulfonic acid - condensation product (Irgasol DA), 0.15% Solway Ultra Blue B 150% (acid blue 78, C.I. 62105), a sulfonic acid dye, 0.12% polar brilliant red G, a dye with two sulfonic acid groups, and 0.3% Cibacrongclb G,

a reactive dye with at least three sulfonic acid groups, the dye bath for Brought to the boil and kept in the boiling state for at least 1/2 hour. This resulted in one Coloration in three tones, the blue and green

(lovat) 'and some red included.

Example 16

270 g of a multi-layer pile carpet material made of structured semi-matt nylon 6 (DuPont 501) was washed: 1 with a non-ionic cleaning agent (Tergi: ol NPX), rinsed and then in a small, narrow Beck-type dyeing vessel hanging from the ceiling with a liquid ratio of approx 40: 1 colored. While the material was circulating, 3% orthophosphoric acid was added to the cold bath, whereupon the bath was heated ^{to about 55 ° C.} After 5 minutes, 1% paraformaldehyde and then 1% of a formaldehyde naphthalenesulfonic acid condensation product (Erional NW) and then a mixture was added that contained 0.2% Neopilatbraun GR, a premetallized dye with 0 to 1 sulfonic acid groups, 0.2% Solophenyl yellow UP , a tree-

wool dye with three or more sulfonic acid groups, and 0.105% cibacron orange 2 E, a reactive dye with at least two sulfonic acid groups. The strip shaped carpet material was agitated in the dye bath while the temperature until it was raised to the boiling point. The bath was boiled for 1 hour. The coloring effect showed a mixture of gold and light brown.

Example 17

The procedure was exactly as in Example 16, but the paraformaldehyde was omitted. Here a similar but slightly softer effect was achieved. Orthophosphoric acid can be used accordingly replace with acetic acid.

Example 18

It was worked exactly according to example 16, with 0.2% xylene light yellow 2 GP, a colorant Dye with a sulfonic acid group, 0.4% Cibacron - brilliant orange G, a reactive dye with at least two sulfonic acid groups, and 0.2% pontamine BT, a cotton dye with at least three Sulfonic acid groups. The carpet material was brownish in two tones Colored orange.

Example 19

The carpet of Example 16 was dyed in the same manner using of 5% acetic acid, 1% of a formaldehyde naphthalenesulfonic acid condensation product (Erional NW), 0.25% anthraquinone blue SWF (acidic BaIu 25, C.I. 62055), a dye with a sulfonic acid group, 0.12% polar brilliant red G (acid red 122) of a fulling dye with two sulfonic acid groups, and 0.3% Pyracol Red 7 BSW (Direktrot 80, C.I. 35780), a cotton dye with six sulfonic acid groups. The carpet material was dyed in a mixture of red, blue and purple.

10

Example 20

A nylon fabric made of Capralan (light nylon 6) of 5000 denier with 816 monofilaments was in a Brought warm dye bath containing 3% acetic acid and 0.5% of a condensation product of aromatic Aryl sulfonic acid and benzoin (Albetex W.S.). The dye bath was brought to the boil and kept boiling for about 15 minutes. This gave the material a color between copper and gold.

Claims (2)

Patent claims: 1. Process for dyeing perfect multifilament yarn and fabrics made therefrom and knitted from synthetic polyamide for the purpose of producing a multicolor Effect using a single dye liquor, characterized in that the polyamide yarn has a tensile strength of less than 7 g per denier of the monofilament in a liquor that dyes a dye with at least two sulfonic acid groups and with zero to contains three reactive groups in the molecule, the sum of the sulfonic acid groups and of the reactive groups is at least 3 and the pH is in the acidic range, and although in the presence of a water-soluble condensation product of an aryl sulfonic acid and an aldehyde or ketone in an amount of 0.1 to 5 percent by weight, based on polyamide, this amount is not sufficient to reserve the dye. 2. The method according to claim 1, characterized in that a liquor is used which in addition, a dye with less than a total of two sulfonic acid and reactive groups contains in the molecule. Considered publications:
British Patent No. 680,862;
At the. Dyest. Rep., 1950, pp. 389/390;
Journ. of the Soc. of Dyess and CoI., 1960, p. 104.