US3564630A - Polyamide fibers and fiber blends of enhanced dyeability - Google Patents

Abstract

A PROCESS FOR INCREASING THE DEEP DYE CHARACTERISTICS OF POLYAMIDES, PARTICULARLY AROMATIC POLYAMIDES WHEN IN COMBINATION WITH KERATINOUS FIBERS AS BLENDS OF NYLON AND WOOL AND THE DYED PRODUCT PRODUCED THEREBY. THE PROCESS INVOLVES PRETREATING THE FIBER IN YARN OR FABRIC FORM WITH A LONG CHAIN ALKYL AROMATIC QUATERNARY AMMONIUM SALT AND SUBSEQUENTLY DYEING THE FIBER WITH AN ACID DYE, THE PRETREATMENT WITH THE QUATERNARY AMMONIUM SALT INCREASES THE AFFINITY FO THE POLYAMIDE FOR ACID DYESTUFFS WITHOUT GREATLY EFFECTING THE DYE AFFINITY OF THE KERATINOUS FIBER, THEREBY PROVIDING GREATLY IMPROVED DYE UNIFORMITY. THE DYE UNIFORMITY IN BLENDS OF BOTH ALIPHATIC AND AROMATIC POLYAMIDES IS INCREASED ACCORDING TO THE PRESENT PROCESS. WHEN THE POLYAMIDE IS AN AROMATIC POLYUAMIDE, IT IS PREFERRED TO USE A CARRIER IN THE DYEBATH TO AID IN THE DYEING OF THE FIBER.

Description

United States Patent C U.S. Cl. 8-21 12 Claims ABSTRACT OF THE DISCLOSURE A process for increasing the deep dye characteristics of polyamides, particularly aromatic polyamides when in combination with keratinous fibers as blends of nylon and wool and the dyed product produced thereby. The process involves pretreating the fiber in yarn or fabric form with a long chain alkyl aromatic quaternary ammonium salt and subsequently dyeing the fiber with an acid dye. The pretreatment with the quaternary ammonium salt increases the afiinity of the polyamide for acid dyestuffs Without greatly effecting the dye aflinity of the keratinous fiber, thereby providing greatly improved dye uniformity. The dye uniformity in blends of both aliphatic and aromatic polyamides is increased according to the present process. When the polyamide is an aromatic polyamide, it is preferred to use a carrier in the dyebath to aid in the dyeing of the fiber.

This invention relates to improving the dyeability of certain polyamides and more specifically aromatic polyamides and also to improving the union dyeing of keratinous fiber and polyamide fiber blends.

Aromatic polyamide fibers have recently been introduced to the textile industry. In general, the aromatic polyamide to which reference is made is a polymeric structure wherein an aromatic ring is introduced in either diamine or dibasic acid with the other monomer containing the aliphatic carbon chain component. When an aromatic diamine is employed, it is preferred that the amine groups be displaced from the aromatic ring by at least one carbon to prevent objectionable color formation. When an aromatic dibasic acid is employed, the placement of the carbonyl groups should be such that a stiff polymer will not result as a consequence of resonance. Representative of the preferred types of aromatic polyamides are polymetaxylylene adipamide, and polyhexamethylene terephthalamide:

0 o I n n THN-CHz-CHz-CHz-CHz-CHz-CHz-NHC-OCJ attempting to obtain a union dye in blends of aromatic polyamides and keratinous fibers, it is, therefore, not only necessary to increase the buildup of acid dyestuffs on the aromatic polyamide fiber but also to inhibit the buildup of acid dyestuffs on the keratinous fiber in order that the bath will not be exhausted prior to the aromatic polyamide being dyed.

Union dyeing of Wool-polyamide blends and especially wool-nylon blends is well known in the art. When dyeing mixtures of wool and nylon, however, a difficulty may arise especially with polysulfonated dyes owing to the low saturation value of nylon which contains basic groups only at the ends of the long chains. Hence, nylon quickly becomes saturated with dye except in the case of pale shades and when using a mixture of dyes this may result in one component being excluded altogether. With equalizing acid dyes, the nylon portion usually dyes darker than the Wool in pale shades and conversely with heavy shades. Equalizing acid dyes are commonly used for the preparation of pale shades by adding small quantities of colorless compounds possessing high affinity for nylon to the dyebath. These colorless compounds being compounds such as, for instance, Calsolene oil HS (leveling agent marketed by Imperial Chemical Industries) or Perminal BX (leveling agent marketed by Imperial Chemical Industries). These leveling agents act as a restraining agent for the nylon and thereby produced a solid shade in the wool-nylon blend. Where, however, dark shades are desired, equalizing acid dyes are usually replaced by neutral dyeing acid dyes which build up well on nylon in that these dyes contain the minimum number of sulfonic groups. While techniques such as the aforementioned technique are available for producing dark shades, wool dyers prefer, where possible, to use equalizing acid dyes because of the brightness and ease of application of this category of dyestuffs.

The most common form of union dyeing is one in which the component fibers require completely different but not compatible dyes, thus. enabling each fiber to be dyed without interference from the other. This ideal sitnation, however, is not often achieved. In most cases, one fiber is dyed while the other fiber is stained. As a result of this staining, the fabric must be scoured prior to being subjected to a second dyeing operation. Should the second dyeing operation stain the previously dyed fiber, still another scouring operation is required to remove this staining effect. It is readily apparent that in union dyeing, a single dyebath employing a single dyestuff is preferred to a process employing a plurality of dyebaths and a plurality of scouring operations.

It is, therefore, an object of this invention to provide a process for improving the dyeability of aromatic polyamides.

It is a further object of this invention to provide a deep dyed aromatic polyamide fiber.

It is an additional object of this invention to provide an improved union dyeing process for keratinous fiber, polyamide fiber blend.

It is another object of this invention to provide a keratinous fiber, polyamide fiber blend textile product union dyed with a single dyestuff.

It is still another object of this invention to provide a dark shade union dyeing process employing a single equalizing acid dye for keratinous fiber, polyamide fiber blends.

In accordance with this invention, it has now been discovered that in union dyeing operations on keratinous fiber, polyamide fiber blends wherein the dyeability of the polyamide component must be enhanced while the dyeability of the keratinous fiber component must be inhibited, a dyebath employing a single equalizing acid dye may be employed by pretreating the keratinous fiber, polyamide fiber blend, with a quaternary ammonium salt having the following general formula:

wherein R is a long chain alkyl group having a chain length of from C to C R and R are short chain alkyl groups independently selected from carbon chains of from C to C and X is a member selected from the group consisting of chloride, fluoride, bromide, sulfate and hydroxide. Preferably, R and R" are CH groups and X is a chloride. It is preferred that the dyebath also contain a carrier such as, for instance, Carolid (sodium salt of ortho phenyl phenol marketed by Tanatex Co.). Apparently, the carrier serves to promote the entry of dyestuffs into those new dyesites which have been provided by the presence of the quaternary ammonium salt. While the quaternary ammonium salt is suitable for obtaining improved dyeings of any polyamide, the process of the invention is especially suited for use with aromatic polyamide fibers, either alone or in the form of blends with keratinous fibers. The quaternary ammonium salt pretreatment of aromatic polyamides is found to produce products which are dyed to darker shades and to a deeper degree of penetration.

When the keratinous fiber, polyamide fiber blend being union dyed contains aromatic polyamide, the dyestuff employed may be of any shade. Where, however, the keratinous fiber polyamide fiber blend being union dyed contains aliphatic polyamide, preferred union dyeing results are obtained with dark shades of equalizing acid dyes. It is also found that with aliphatic polyamide blends, the presence of a carrier is not necessary.

When aromatic polyamide fibers in unblended form are being dyed for purposes of obtaining darker shades, it is preferred that a carrier be present and that the dyestuff be a monosulfonated acid dye. The monosulfonated acid dyes are found to give good penetration, light fastness and color build-up, and to have good resistance to sublimation and crocking. The following dyestuffs have been found to be especially suitable for use with unblended aromatic polyamide fibers pretreated with a quaternary amine salt: Dimacide Red 2B; Nylanthrene Yellow FLW; Nylanthrene Orange SLF; Supernylite Yellow 3G; Nylomine Red 2B3 (C.I. Acid Red 266); Nylomine Brown B; Nylomine Scarlet B; Nylomine Orange GS (C.I. Acid Yellow 64); Nylomine Blue GS (C.I. Acid Blue 14); Dimacide Blue J S; Cibalan Yellow F-GL (C.I. Acid Yel- W 128) Irgalan Grey BL (C.I. Acid Black 58); Cibalan Red 2GL (Cl. Acid Red 211).

It should be understood that the term keratinous fiber as employed herein is meant to include any of the fibers containing major quantities of any of the various sulfur-containing fibrous proteins such as, for instance, wool, vicuna, llama, alpaca, cashmere, angora, camel hair, regenerated keratin and the like.

The term polyamide as employed herein is meant to include any polymeric material containing the characteristic amide type component whether aliphatic or aromatic such as, for instance, polyhexamethylene adiparnide, polymetaxylylene adipamide, polyhexamethylene terephthalamide and the like.

The term carrier as employed herein is meant to include any organic compound which loosens the tight bonding between the long fiber molecules thus facilitating entry of dye molecules. Specific carriers which may be deemed to be included in this category are phenols, aromatic esters, chlorinated aromatic hydrocarbons and the like. The preferred carrier of this invention is ortho phenyl phenol which is introduced into a dyebath in the form of a sodium salt.

In general, it is preferred that the pretreatment be such as to result in a pickup of .1 percent by weight to about 5 percent by weight of quaternary ammonium salt based on the dry weight of the fabric, the most preferred amount being about 2 percent by weight. When a carrier is included in the dyebath, it is preferred that the carrier be present in amounts of from about .1 percent by weight to about 20 percent by weight and most preferably about 5 percent by weight.

The following specific examples are given for purposes of illustration and should not be considered as limiting the spirit or scope of this invention.

EXAMPLE 1 A polyhexamethylene terephthalamide yarn is treated in a bath containing 2% by weight of dimethyl benzyl (myristyl-cetyl) ammonium bromide plus 5 grams per liter of Carolid (sodium salt of ortho phenyl phenol marketed by Tanatex Co.), the bath being maintained at about 98 C. The yarn is then washed and placed in a dyebath for about three minutes at a temperature of about 170 F., the bath containing 6.5 grams per liter of solvent FT (a polyethoxyether of a fatty alcohol in a low boiling solvent) (carrier marketed by Francaise des Matieres Coloromtes, S.A., France), 2% by Weight of Eric Fast Scarlet B (CI. No. 14710) maintained at a pH of about 4. The same procedure is repeated with a sample of polyhexamethylene terephthalamide yam which is not given the pretreatment with dimethyl benzyl (myristyl-cetyl) ammonium chloride. The yarn which has been pretreated with the quaternary amine is found to dye a much darker shade and to a deeper degree of penetration than the sample which was not pretreated.

EXAMPLE 2 A challis fabric prepared from polymetaxylylene adipamide yarn is placed in an aqueous bath maintained at C. containing 2% by weight BTC 824 fatty alkyl dimethylbenzyl ammonium chloride (quaternary ammonium salt marketed by Onyx Chemical Corp.) for a period of about 15 minutes. The fabric is then rinsed and placed in an aqueous bath maintained at 50 C. and containing 3% Tinegal NA condensation product of ethyleneoxide with a fatty alcohol (surfactant marketed by Geigy Chem.- ical C0.) and 2% CH COOH. After a mild agitation 2% by weight of Nylomine Orange GS added and the bath agitated for two minutes and then raised to the boil, 1% of H 50, is added and the bath boiled for an additional 50 minutes. The dyed fabric is then given a cold rinse and cured at 385 F. for 3 minutes. The dyeing procedure is repeated on an identical challis fabric which has not been given the quaternary ammonium salt pretreatment. The quaternary ammonium salt treated fabric is found to dye a much darker shade and to deeper degree of penetration than the untreated sample.

EXAMPLE 3 A tropical fabric composed of 55 percent by Weight polyhexamethylene terephthalarnide and 45 percent by weight wool is scoured with a nonionic detergent. The fabric is pretreated in a bath maintained at about 98 C. with a 10 percent solution of a quaternary ammonium salt having the following formula:

The fabric is then washed and placed in a dyebath for about three minutes at a temperature of about F., the bath being composed of 2 percent by weight Nylomine Blue GS, 3 percent by weight Penigal NA, 3 percent by weight ammonium acetate and 2 percent by weight acetic acid. The dyed fabric is then scoured in a common scour bath. A uniform color build-up on both the Wool and the aromatic polyamide components is found to take place.

The procedure is again repeated with the exception that the pretreatment with the quaternary ammonium salt is omitted. The resultant fabric is found to be deeply dyed on the wool component and only lightly dyed on the aromatic polyamide component.

EXAMPLE 4 A knit stocking fabric composed of 50 percent nylon 6,6 and 50 percent wool is scoured in a nonionic detergent. The fabric is pretreated in a bath maintained at about 98 C., the bath being a percent aqueous solution of a quaternary ammonium salt having the following The fabric is then washed and placed in a dyebath for about three minutes at a temperature of about 170 F., the bath being composed of 3 percent by weight Polar Brilliant Blue RAW (C.I. Acid Blue 80), the bath being adjusted to a pH of about 5 by the addition of sufficient acetic acid. The dyed fabric is then scoured in a common scour bath. A uniform color build-up on both the wool and nylon 6,6 components is found to take place.

The procedure is again repeated with the exception that the pretreatment with the quaternary ammonium salt is omitted. The resultant fabric is found to be deeply dyed on the wool component and only lightly dyed on the nylon component.

Having thus disclosed the invention, what is claimed 1. A process for union dyeing a keratinous fiber polyamide fiber blended textile material with a single dyestuif, said process comprising pretreating said textile material with a quaternary ammonium salt having the following general formula:

wherein R is a long chain alkyl group having a chain length of from C to C R and R are short chain alkyl groups independently selected from carbon chains of from C to C and X is a member selected from the group consisting of chloride, fluoride, bromide and sulfate, contacting said textile material with a hot aqueons acidic dyebath containing an acid dye, dyeing said material and subsequently rinsing said dyed material thereby obtaining a dyed material of improved uniformity.

2. The dyed textile product produced by the process of claim 1.

3. The process of claim 1 wherein the keratinous fiber is wool.

4. The process of claim 1 wherein the quaternary ammonium salt is dimethyl benzyl (myristybcetyl) ammonium chloride.

5. The process of claim 1 wherein the dyestuff is a monosulfonated acid dye.

6. The process of claim 1 wherein a dye carrier is used in the dyebath.

7. The process of claim 1 wherein the quaternary ammonium salt is added to the fiber in an amount of 0.1 to 5 weight percent.

8. The process of claim 1 wherein R and R" are both CH groups and X is chloride.

9. The process of claim 1 wherein said polyamide is an aromatic polyamide and wherein said single dyestuff is applied in the presence of a carrier.

10. The process of claim 1 wherein said polyamide is an aliphatic polyamide and wherein said dyestuff is a dark shade dyestuif.

11. The process of claim 1 wherein R and R are both CH groups and X is chloride and wherein said polyamide is polyhexamethylene terephthalamide and said dyestuff is applied in the presence of a carrier.

12. The process of claim 1 wherein said aromatic polyamide fiber is a fiber selected from the group consisting of polymetaxylylene adipamide and polyhexamethylene terephthalamide.

References Cited UNITED STATES PATENTS 2,371,536 3/1945 MacGregor 8-21 3,380,969 4/1968 Hill et al 8-55 3,338,660 8/1967 Biedermann 821 OTHER REFERENCES H. C. Speel: Textile Chemicals and Auxiliaries, Reinhold Pub. Co., 1952, pp. 334, 335, 350, 351, 359, 360.

NORMAN G. TORCHIN, Primary Examiner J. E. CALLAGHAN, Assistant Examiner US. Cl. X.R. 884, I72, 178