|Publication number||US3118723 A|
|Publication date||Jan 21, 1964|
|Filing date||Feb 8, 1961|
|Priority date||Feb 8, 1961|
|Publication number||US 3118723 A, US 3118723A, US-A-3118723, US3118723 A, US3118723A|
|Inventors||Arthur J I Harding|
|Original Assignee||Arthur J I Harding|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (6), Referenced by (25), Classifications (29)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Bfllhfififi Patented Jan. El, 1954 "ice Spartanhurg, S.C. No Drawing. Filed Feb. 8, 1961, Ser. No. 87,786 Claims. (Cl. 8-14) This invention relates to a novel method of dyeing nylon, more particularly to a method of dyeing nylon to produce muiti-colored effects in a single dye bath, and to the nylon thus dyed.
According to this invention, multifilament nylon 1s dyed at an acid pH in a dye bath comprising at least one dyestulf and an aryl sulfonic acid condensation product, all as defined hereinafter, to produce a multi-colored dyeing thereof.
In British patent specification 680,862, there is disclosed and claimed by me a method of dyeing normal wool employing dyestuffs containing at least 2 sulforuc acid groups and certain aryl sulfonic acid condensation products to produce multi-colored dyeings in a single dye bath without resorting to mixtures of wools having different dyestuff affinities. This process takes advantage of ditferences in dyestuff affinity of various sites along the wool fibers, which differences are not observed in the usual dyeings. The process is believed to depend upon the heterogenous'nature of normal wool due to either the variety of amino groups making up its chemical structure or its nonuniform physical structure, or both.
Thus, it was believed that an analogous process would not be possible with synthetic fibers because of their uniform physical and chemical structure. This belief was found to be substantiated with, for example, the polyesters and the acrylics. However, it was found that with multifillament nylon an effect similar to that observed with wool could be produced. This was most surprising because there was nothing about the chemical or physical nature of nylon which would suggest that different dyestulf afiinities existed along the filament length. This effect is not due to the presence of mixtures of different types of nylon in the dye bath, e.g., a mixture of nylon 66 and nylon 6, although the difference in dyestu'lf atfinities between these two types of nylons can be markedly enhanced by the process of this invention to the extent that a reserve of nylon 66 can be achieved, if desired. 0n the contrary, nylon multifilament yarns that were believed to be substantially uniform in physical and chemical structure have sufficiently different dyeing characteristics along the filament length to enable the production of multi-colored elfects in a single dye bath when following the process of this invention.
It is an object of this invention to provide a process for obtaining multi-colored dyeing effects on multifilament nylon in a single dye bath without resorting to mixtures of different types of nylon.
it is another object of this invention to provide a process for dyeing nylon fabrics and piece goods to give multi-colored effects.
It is another object of this invention dyed multifilament nylon yarn, woven and ties, garments, and other piece goods.
Other objects will be apparent to those skilled in the art to which this invention pertains.
The term multi-colored when used herein means a mixture of any two or more colors, including white. Thus, nylon dyed a mixture of red and white or two shades of red is multi-colored according to this definition.
It is to be understood that the mulLi-colored dyeings obtained according to this process are those obtained as a result of non-solid dyeings along the length of filaments of one type of nylon. However, this efifect can be to provide novel knitted fabachieved concomitantly with the contrast dyeings that are obtained when dyeing two types of nylon, e.g., nylon 6 plus nylon 66.
Nylon which can be dyed according to this process are multi-filament nylon yarns and woven and knitted nylon garments prepared therefrom, e.g., socks, sweaters, sport shirts and blouses and fabrics and other yard goods, e.g., upholstery and carpet materials. While this invention is primarily directed to multi-filament nylon, i.e., continuous lengths of nylon, it will be apparent to those skilled in the art that an obvious equivalent thereto is nylon in which the length of nylon is cut into staple length and spun before being formed into yarn.
The preferred type of nylon to be used in the process is nylon 6, due to its greater dyestuff afiinity. Especially preferred is bright nylon, i.e., nylon which has little or no pigments or fillers added thereto. The preferred multi-filament nylon yarn has a. total denier of at least and a denier per filament of between about 2 and 10. An example of such yarns are carpet yarns having a total denier of at least 1,000 and a denier per filament of about 10 or less, usually 4,000 or more total denier and about 7 or less per filament. Very pronounced multicolored dyeings are somewhat more difficult to achieve with texturized nylon, particularly if the tenacity of the yarn is increased to a high level during the texturizing process. This dificulty is less pronounced when the texturized nylon is dyed in the form of knitted fabrics, piece goods, or garments. Low or medium tenacity nylon, i.e., having a tenacity of less than about 7 grams per denier, is preferred and should ordinarily be employed in the process of this invention.
The dyestuifs which are employed in the process of this invention are those which dye nylon and which contain at least 2 sulfonic acid groups, preferably 3 or more, and from 0 to 3 reactive groups in the molecule, the sum of the sulfonic groups and reactive groups being at least 3. The dyestuffs containing reactive groups, e.g., vinyl sulfone or cyanuric chloride groups, are referenced to in the dyeing art as reactive dyestuffs. Included in the dyestuifs containing 3 or more sulfonic acid and reactive groups are the acid dyestuffs, milling dyestuffs, di rect dyestuffs and cotton dyestuffs. These dyestuffs are ordinarily supplied by the manufacturer in the form of sodium salts. The term sulfonic acid group excludes those groups in which the sulfonic acid group is in the form of an inner salt with a basic group. The preferred dyestuffs for the process of this invention are those in which the number of sulfonic acid groups therein is 3 or more.
The dye baths of this invention are acid, i.e., they contain an organic or inorganic acid, or acidic salt, e.g., acetic acid, formic acid, sulfuric acid, lactic acid, citric acid or other aliphatic acid, or phosphoric acid, or acidic salts thereof, e.g., the ammonium salts. It is preferred that the starting pH of the dye bath be between about 2 and 5. If desired, the pH can be varied during the dyeing by employing ammonium sulfate or phosphate and then permit the pH to drift lower during the dyeing. The amount of acid to be employed will depend upon the affinity of the dyestuff employed in the dyeing to nylon in the presence of the condensation products as defined hereinafter. As the condensation products employed in the process of this invention are retarding agents for dyeing nylon, it is sometimes necessary to use somewhat greater amounts of acid or a stronger acid than would normally be employed with these dyestuffs. One percent to five percent acetic acid or 1% to 5%, usually 1% to 3% of formic, sulfuric, or pho phoric acid, calculated on the weight of the nylon, is the usual range.
The condensation products employed in the process of this invention are generally known as retarding or leveling agents, usually for dyeing wool. They are characterized chemically as condensation products of aryl, usually carbocyclie, sulfonic acids and an aldone. The term aldone as used herein means an aldehydic or ketonic carbonyl compound, e.g., formaldehyde, acetaldehyde, benzaldehyde, benzoin, acetone, etc. These are a well known and commonly employed class of compounds in the dyeing art. They each possess at least two sulfonic acid substituted aryl groups in the molecule. Compounds within this definition are mono, di, or trisulfonic acid substituted benzene or naphthalenes which can further be substituted with lower-alkyl, hydroxy, nitro, amino, etc., groups and which have been condensed with an aldone as described above to produce a dimer, trimer or polymer linked by the aldone by a reaction well known in the art. Compounds such as dihydroxy-phenyl sulfone can also be incorporated in the condensation reaction to produce a mixed condensation product. See US. 2,623,806. These compounds include the condensation products of naphthalene-1 or naphthalene-2 sulfonic acid, or naphthalene-2,7-
disnlfonic acid and formaldehyde, e.g., those of the formula Ho s):
and the alkali-metal salts thereof when n is 0, 1, 2 or more, usually or 1, and x is 1 or 2. Others include the condensation product of phenol or cresol sulfonic acid and formaldehyde, e.g., of the formula on on (1)11 (SOaIEDx /X 1 Jim.
I R I 80313: SOaH and the corresponding alkali-metal salts thereof wherein R is H or CH and n is 0 to 3 or 4. Still others include the condensation products of phenol, cresol, or naphthalenesulfonic acid and benzoin or acetone and their alkalimetal salts.
Specific examples of such condensation products are dinaphthylmethanedisulfonic acid, diphenylmethanedisulfonic acid, dihydroxyphenylmethanedisulfonic acid, dicresylmethanedisulfonic acid. dihydroxynaphthylmethanedisulfonic acid, dinitronaphthylmethanedisulfonic acid, dichloronaphthylmethanedisulfonic acid, diaininonaphthylmethanedisulfonic acid, dinaphthylmethane-2,7,2',7'tetrasulfonic acid and the sodium salts of each.
The amount of aryl sulfonic acid condensation product employed is an amount, between 0.1 and 5% calculated on the weight of the nylon insuflicient to reserve the dyestulf employed. Usually an amount suflicient to noticeably reduce the dyeing rate of the effect dyestutf is employed, i.e., so that the condensation product acts as a retarding agent. Between about 0.25% and 3% is the usual range.
In carrying out the process of this invention, the selected multi-filament nylon, usually in the form of yarn or fabrics or piece goods woven or knitted therefrom, is dyed at an acid pH in a dye bath containing a dyestuff which will dye nylon and the selected aryl sulfonic acid condensation product as defined hereinbefore. The usual dyeing techniques are employed, i.e., the nylon is usually added to the cold dye bath and the temperature then raised to the boil, with the dyeing continued until exhaustion or equilibrium is achieved. If desired, the nylon can be contacted with the aryl sulfonic acid condensation product before the dyestuif. However, for convenience and simplicity sake, the two ingredients are usually incorporated together in the dye bath.
0 The nylon was washed, dried The effects obtained will, when using a single dyestuff,
6" of a formaldehyde naphthalenesulfonic vary from a tone on tone to a color on white, each of the above effects being within the term multi-colored as used herein. Spectacular effects are obtained if the dye bath additionally contains at least one of a dyestuff containing less than two sulfonic acid groups and a dyestutf which contains at least one more sulfonic acid group and preferably two more sulfonic acid groups, as compared with the dyestuffs as described hereinbefore. With such a mixture of dyestuffs, a rainbow of colors can be achieved from a single dye bath.
The effects produced by this invention, particularly when a mixture of dyestuifs as described above is employed, are frequently enhanced if the material to be dyed is knitted fabric or garments or material such as upholstery fabrics or tufted carpeting. The deposition of the various dyestuffs appears to be influenced by the type of construction of the material being dyed. Thus, it has been found that when employing a dyestuif having three sulfonic acid groups along with an all over color, i.e., a dyestuff having less than two sulfonic acid groups, the higher sulfonic acid dyestuff appears to concentrate itself at the base of the tufts where accessibility is more diffi- (SOsH);
cult, although the converse of this would be expected. Because of this phenomena, completely new effects can be obtained where dyeing piece and flat goods such as knitted fabric and garments and carpets.
When equilibirium or exhaustion has been achieved, the nylon can then be washed and dried in the usual fashion. The usual dyestulf additives, e.g., Glaubers salt or other materials used as leveling agents or nonionic wetting agents, may be added to the dye bath to facilitate the process. However, as with other dyeings, such additives may alter somewhat the result obtained. Usually, it is preferred to keep these other additives to a minimum.
It has been found that the effect obtained can be altered somewhat by pretreatment of the nylon with formaldehyde or paraformaldehyde, e.g., by heating or boiling the nylon for a short time in an aqueous solution containing up to about 2% formaldehyde or paraformaldehyde, calculated on the weight of the nylon. The nylon can then be washed and dried in the manner described herein. Alternatively, the formaldehyde can be incorporated in the dye bath.
Similarly, the results can be somewhat modified by treating the nylon with acid prior to the addition of the condensation product and dyestuff or contacted with the condensation product prior to the acid and dyestuif. By these modifications, a wide variety of effects and shades can be obtained, thus enhancing the versatility of the process.
The following examples are illustrative of the process of this invention but are not to be construed as limiting. All percents are based upon the weight of the nylon being dyed.
Example I Five thousand denier 816 filament, 1 /2 8 twist Caprolan brand bright, medium tenacity, multi-filament nylon yarn was dyed in a dye bath containing 2% acetic acid, 0.5 acid condensation product (Erional NW) and 0.5 of Fastusol Blue LFFR, a cotton dyestuif containing not less than 3 sulfonic acid groups. The dye bath was brought to a boil in about 20 minutes and boiling was continued for about one hour. and found to be dyed a mixture of blue and white, similar to a stock dyeing.
Example 11 The procedure of Example I was followed exactly except that 0.5% of Acilan Crocein F913 (Acid Red 47, Cl.
27300), a 4 sulfonic acid dyestufi, was substituted for the dyestuff. A peppermint stick red and white was obtained.
Example 111 The procedure of Example I was followed exactly except that Pyrazol Fast Red 6 BL (Direct Red 79, CI. 29065), a 4 sulfonic acid dyestulf, was substituted as the dyestuff. The nylon was dyed a mixture of white and moderately dark red.
Example IV The procedure of Example I was followed exactly ex cept that 0.5% Fastusol Scarlet LGG (Direct Red 76, CI. 40270), a 3 sulfonic acid dyestuif, was substituted as the dyestufi. The nylon was dyed a light mixture of white and orange.
Example V The procedure of Example I was followed exactly except that 0.5 of Solantine Gray BL (Direct Black 74, CI. 34180), a sulfonic acid dyestuff, was substituted as the dyestuff. The nylon was dyed a mixture of pastel blue and white.
Example VI The procedure of Example I was followed exactly except that 0.5% Cibacron Black BG, a reactive dyestulf containing more than 2 sulfonic acid groups, was substituted as the dyestufi. The nylon was dyed a mixture of blue-gray and white.
Example VII Five thousand denier, 816 filament, 1 /2 8 twist bright nylon yarn was dyed in a dyebath containing 0.5 Solar Yellow 3LG, a cotton dyestufi containing not less than 4 sulfonic acid groups, 0.1% Procion Blue I-IBS, a reactive dyestutf containing more than 2 sulfonic acid groups, 0.1% Calcoid Eosine G (Acid Red 4, Cl. 14710), a 1 sulfonic acid dyestuff, 3% acetic acid and 0.5% of a formaldehyde naphthalenesulfonic acid condensation product (Erional NN). The dye bath was brought to the boil with occasional stirring in about 30 minutes and then boiled for about an hour. The nylon yarn was washed and dried and found to be dyed a pink mingled with shades of blue-gray.
Example VIII The procedure of Example VII was followed, except that 0.1% rocion Brilliant Red H338, a reactive dyestuff containing more than 2 sulfonic acid groups, 0.15% of Milling Yellow 5G, a 1 sulfonic acid yellow dyestulf, and 0.12% of Alpharazine PG (Acid Blue 9, CI. 42090), a 2 sulfonic acid dyestuif, were employed as the dyestuffs. A pastel multi-colored dyeing was obtained containing pinks, lavenders, blues, greens, oranges and yellows.
xamples IXXIV Examples iVI were repeated except that the nylon and acetic acid were stirred together at room temperature for a few minutes in the dye bath before the formaldehyde naphthalene sulfonic acid condensation product and dyestuff were added to the dye oath. Substantially the same effects were produced.
Example XV A mens stocking knit from spun nylon 6 staple was dyed in a dye bath containing 5% acetic acid, 0.5 of a formaldehyde naphthalenesulfonic acid condensation product (Irgasol DA), 0.15% Solway Ultra Blue B 150% (Acid Blue 78, O1. 62105), a one sulfonic acid dyestuif, 0.12% Polar Brilliant Red G, a two sulfonic acid dyestulf and 0.3% Cibacron Yellow G, a reactive dyestuif containing at least 3 sulfonic acid groups, the dye bath was brought to the boil and maintained at the boil for at least one-half hour. The resulting dyeing was a threetone blue and green lovat type shade containing a little red.
6 Example XVI Two hundred seventy g. of tufted multi-level carpet made from Du Pont 501 textured semi-dull nylon 6 was scoured with a nonionic detergent (Tergitol NPX), rinsed and then dyed in a miniature strip overhead Beck Dyeing Kettle with a liquor ratio of about 40:1. While the fabric circulated, 3% of orthophosphoric acid was added to the cold bath which was then warmed to F. After 5 minutes, 1% of paraformaldehyde was added followed by 1% of a formaldehyde naphthalenesulfonic acid condensation product (Erional NW) and then by a mixture of 0.2% Neopilate Brown GR, a premetallized dyestuff containing 0-1 sulfonic acid groups, 0.2% of Solophenyl Yellow AUF, a cotton dyestuif containing 3 or more sulfonic acid groups and 0.05% of Cibacron Orange 2E, a reactive dyestufi containing at least 2 sulfonic acid groups. The carpet strip was circulated in the dye bath while the temperature thereof was brought to the boil. Boiling continued for one hour. The dyed effect was a mixture of gold and light brown.
Example XVII The procedure of Example XVI was followed exactly except that the paraformaldehyde was eliminated. The effect obtained was similar but somewhat softer. Similarly, the ortho-phosphoric acid can be substituted by acetic acid.
Example XVII The procedure of Example XVI was followed exactly employing 0.2% of Xylene Light Yellow 26?, a 1 sulfonic acid dyestuff, 0.4% of Cibacron Brilliant Orange G, a reactive dyestuif containing at least 2 sulfonic acid groups, 0.2% of Pontamine BT, a cotton dyestuff containing at least 3 sulfonic acid groups, as the dyestuffs. The carpet was dyed 2-tone burnt orange.
Example XIX The carpet described in Example XVI was dyed in the same manner employing 5% acetic acid, 1% of formaldehyde naphthalene-sulphonic acid condensation product (Erional NW), 0.25% of Anthraquinone Blue SWF (Acid Blue 25, CI. 62055), a 1 sulfonic acid dyestuflf, 0.12% Polar Brilliant Red G (Acid Red 122), a 2 sulfonic acid milling dyestuff, and 0.3% of Pyrazol Red 7BSW (Direct Red 80, Cl. 35780), a 6 sulfonic acid cotton dyestuff. The carpet was dyed a mixture of red, blue and purple.
Example XX Nylon fabric woven from 5,000 denier, 816 filament, 1 /2 5 twist Capralan bright nylon 6 was added to a warm dye oath containing 3% acetic acid, 0.5 of a condensation product of aryl aromatic sulfonic acid and benzoin (Albetex W.S.). The dyebath was brought to a boil and boiling was continued for about 15 minutes. The fabric was dyed a mixture of copper and gold.
What is claimed is:
1. A process for dyeing multifilament and spun staple nylon yarns and fabrics, garments and piece goods formed therefrom to produce multi-colored dyeings in a single dyebath which comprises dyeing said nylon in a dyebath containing a dyestulf containing at least 2 sulfonic acid groups and from 0-3 reactive groups in the molecule, the sum of the sulfonic acid groups and reactive groups being at least 3, at an acid pH, in the presence of a Water soluble condensation product of an aryl sulfonic acid and an aldone in an amount, between 0.1% and 5% calculated on the weight of the nylon, insufiicient to reserve said dyestuif, thereby producing multicolored dyed nylon without the necessity of any special treatment of the nylon.
2. The process of claim 1 wherein the condensation product is that of an aryl sulfonic acid and formaldehyde.
3. The process of claim 1 wherein the condensation product is that of an aryl sulfonic acid and benzoin.
4. The process of claim 1 wherein the nylon has a tenacity of less than about 7 grams per denier, the dyebath additionally contains a dyestuif containing less than a total of 2 sulfonic acid groups and reactive groups in the molecule.
5; A process for dyeing multifilarnent nylon having a tenacity of less than about 7 grams per denier to produce multi-colored dyeings in a single dyebath which comprises dyeing said nylon in a dyebath containing a dyestuff containing at least 3 sulfonic acid groups in the molecule, an acid and a water soluble condensation product of an aryl sulfonic acid and an aldone in an amount, between 0.1% and 5% calculated on the weight of the nylon, insufiicient to reserve said dyestuff, thereby producing multicolored dyed nylon Without the necessity of any special treatment of the nylon.
6. The process of claim 5 wherein the condensation product is that of an aryl sulfonic acid and formaldehyde.
7. The process of claim 5 wherein the condensation product is that of an aryl sulfonic acid and benzoin.
8. The process of claim 5 wherein the nylon is type 6 bright nylon.
9. A process for dyeing yarns, garments and flat goods prepared from multifilament type 6 nylon multifilament nylon of a total denier of at least 100 and a denier per filament of between about 2 and 10 and a tenacity of acid and an aldone in an amount, between 0.1% and 5 calculated on the weight of the nylon, sufficient to retard but insutficient to reserve said dyestufi containing at least 3 sulfonic acid groups in the molecule, thereby producing multicolored dyed nylon without the necessity of any special treatment of the nylon.
10. The process of claim 9 wherein the nylon is sernidull nylon in the form of tufted carpet.
References Cited in the file of this patent UNITED STATES PATENTS 2,199,233 Williams Apr. 30, 1940 2,289,232 Babcock July 7, 1942 2,480,775 Ryan Aug. 30, 1949 2,900,218 Gray Aug. 18, 1954 FOREIGN PATENTS 680,862 Great Britain Oct. 15, 1952 218,920 Australia Dec. 3, 1958
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|US2289232 *||Jul 14, 1939||Jul 7, 1942||Du Pont||Method and apparatus for producing filamentary structures|
|US2480775 *||Jul 3, 1948||Aug 30, 1949||Du Pont||Dyeing nylon hosiery|
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|AU218920B *||Title not available|
|GB680862A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
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|US3298774 *||Jul 19, 1963||Jan 17, 1967||j||Dyeing poly amide fibers|
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|US5182154 *||Dec 26, 1989||Jan 26, 1993||Monsanto Company||Stain resistant nylon carpets|
|US5230708 *||Jun 1, 1989||Jul 27, 1993||Allied-Signal Inc.||Methods and compositions to enhance stain resistance of nylon carpet fibers: thlocyanate to reduce yellowing|
|USRE33365 *||Aug 21, 1989||Oct 2, 1990||Monsanto Company||Stain resistant nylon fibers|
|EP0028756A2 *||Oct 25, 1980||May 20, 1981||Bayer Ag||Process for dyeing polyamide fibres|
|EP0235989A1 *||Feb 13, 1987||Sep 9, 1987||E.I. Du Pont De Nemours And Company||Method for producing stain resistant polyamide fibers|
|U.S. Classification||8/478, 8/589, 8/549, 8/587, 8/DIG.210, 8/924, 8/930, 8/929|
|International Classification||D06P3/10, D06M15/41, D06P3/24, D06P3/82, D06P1/62|
|Cooperative Classification||D06P3/248, D06P3/10, Y10S8/924, Y10S8/929, D06P1/625, D06M15/412, D06P3/241, Y10S8/21, Y10S8/93, D06P3/8209|
|European Classification||D06P3/10, D06P1/62B2D, D06P3/24A, D06M15/41B, D06P3/82V2, D06P3/24R|