US3819326A - Phosphonium salt assisted dyeing with anionic dyes on polyamide-polyester fibers - Google Patents

Abstract

A method of dyeing a textile fiber selected from the group consisting of the modified polyester, polyvinyl chloride, polyacrylonitrile and cellulose acetate fibers, such method comprising dyeing the fibers with an anionic dyestuff in the presence of at least one quaternary phosphonium salt of the formula
WHEREIN R, R1, R2 and R3 are each selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups of one to 18 carbon atoms and X is selected from the group consisting of halogens, alkoxy sulfate and OH group.

Description

United States Patent [191 Shimauchi et al.

[ June 25, 1974 PHOSPHONIUM SALT ASSISTED DYEING WITH ANIONIC DYES ON POLYAMIDE-POLYESTER FIBERS [751 Inventors: Shiro Shimauchi; Norihiro Minemura; Takeshi Matsui; Kenji Ito, all of Osaka; Takeo Shima, lwakuni; Shoji Kawase, lwakuni; Masataka Oshima, lwakuni, all of Japan [73] Assignee: Teiiin Limited, Osaka, Japan [22] Filed: Apr. 18, 1972 [21 I Appl. No.: 245,257

Related U.S. Application Data [62] Division of Ser. No. 804,294, March 4, 1970, Pat.

[30] Foreign Application Priority Data [51] 1 Int. Cl D06p 5/04 [58] Field of Search 8/168, 171, 164; 260/35 P [5 6] References Cited UNITED STATES PATENTS 2,746,836 5/l956 Rossin 8/171 2,989,360 6/1961 Mautner 8/84 X 3,584,074 6/1971 Shema et al 260/45.7 P

Primary Examiner-Donald Levy Attorney, Agent, or Firm-Sherman & Shalloway 5 7] ABSTRACT A method of dyeing a textile fiber selected from the group consisting of the modified polyester, polyvinyl chloride, polyacrylonitrile and cellulose acetate fibers, such method comprising dyeing the fibers with an anionic dyestuff in the presence of at least one quater- EiiiYlE SP'J J iPfl l of thef mvl wherein R, R R and R are each selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups of one to 18 carbon atoms and X is selected from the group consisting of halogens, alkoxy sulfate and OH group.

1 Claim, N0 Drawings Q 1 PHOSPHONIUM SALT ASSISTED DYEING WITH ANIONIC DYES N POLYAMIDE-POLYESTER FIBERS presence of at least one quaternary phosphonium salt of the formula wherein R, R R and R are eachselected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups of one 18 carbon atoms and X is selected from the group consisting of halogens, alkoxy sulfate and OH group.

Fibers manufactured from such synthetic polyesters as polyethylene terephthalate do not have any affinity at all for the ionic dyestuffs and, accordingly, they were previously dyed principally by means of disperse dyes. However, disperse dyes are costly and moreover the dyed products obtained by their use were not satisfactory with respect to brightness. Therefore, there was a strong demand in the trade for the modification of the polyester fibers so that they could be dyed by means of ionic dyestuffs, particularly acid dyes. It is, therefore, a primary object of this invention to provide a method by which modified polyesters can be dyed to deep shades.

Numerous methods of dyeing polyvinyl chloride fibers are known. For instance, there is a dy'eing method which comprises preparing an insoluble complex with an acid dye and a cationic surfactant and using this complex for dyeing the fiber; however, none of the conventional methods have been able to provide dyed products which are fullyv deep in shade. Therefore, a second object of the invention is to provide a dyeing method by which polyvinyl chloride fibers can be dyed to fully satisfactory deep shades.

Polyacrylonitrile fibers are usually dyed with cationic dyestuffs. However, in this case also, when expansion of the scope of color and when the case of dyeing of mixed spun products are considered, the impartation f dyeability of means of the acid dyes is desirable. A third object of the present invention is, therefore, to provide a dyeing method which expands the scope of color of the dyed products of polyacrylonitrile fibers as well as facilitates the dyeing of mixed spun products, especially mixed spun products with wool.

Cellulose acetate fibers are also dyed with disperse dyes as in the case with polyester fibers, but in this case also the shortcoming was noted that the brightness of the dyed product was not yet fully satisfactory. A fourth object is, therefore, to provide a dyeing method which can impart excellent dye-ability to cellulose acetate fibers and dye these fibers to bright shades.

Other objects and advantages of this invention will become apparent from the following description.

Research was conducted both from the aspect of the modification of the polyester fiber and the method of dyeing the same. As a consequence, it was found that shaped articles of certain classes of modified polyesters could be dyed to exceedingly deep shades when dyed by the anionic dyestuffs in the presence of at least one compound selected from the quaternary phosphonium salts.

The quaternary phosphonium salts used in accordance with the present invention are those of the above st ls- $t s s amp es i sl d a.

[(OiHdaP-CHQIET' W Cl CHzCHnCHgOH Polyesters, as used herein, are principally intended to be polyethylene terephthalate. However, the expression polyester also refers to those polyesters which comprise at least 60 mol percent of ethylene terephthalate units and in which a part of the acid or dihydroxy component is substituted by one or more classes of either difunctional or hydroxy acids such as isophthalic acid, compounds having metal salts of sulfonic acid, betahydroxyethoxybenzoic acid, phydroxybenzoic acid, diphenyldicarboxylic acid, naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, adipic acid and sebacic acid, or the aliphatic, alicyclic and aromatic dihydroxy compounds such as diethylene glycol, trimethylene glycol, hexamethylene glycol, neopentylene glycol, 1,4- cyclohexanedimethanol, 2,2,4,4-tetramethylcyclobutanediol 1,3), 1,4-bishydroxyethoxybenzene, bisphenol A and compounds having the tertiary amino group [c.g. butyl-di(beta-hydroxyethyl)amine]. Further polyesters in which a minor proportion of a monofunctional compound such as benzoylbenzoic acid and- /or a polyfunctional compound of above trifunctional such as penta-erythritol and trimesic acid are copolymerized to a certain extent with substantial crosslinkings are applicable. In the preparation of these polyesters, the known catalysts and additives such as stabilizers, delustrants, etc., can be added with no trouble at all.

The term modified polyester compositions, as used herein, refers to the blended composition of a polyamide and a polyester obtained as hereinbefore described, the blended composition of a polyamide and a copolyester obtained by copolymerizing a polyalkylene glycol with a polyester, the blended composition of a polyester and a polyamide blend containing a polyalkylene glycol, and the blended composition of a polyester, polyamide and polyalkylene glycol. Modified polyester fibers which are paritcularly desirable include: (a) those obtained by melt-spinning a blended composition of 60 99.5 wt. percent of a polyester and 40 0.5 wt. percent of a polyamide and drawing the resulting filaments; (b) those obtained by melt-spinning a blended composition of 40-05 wt. percent of a polyamide with 60 99.5 wt. percent of a copolyester obtain by copolymerizing with a polyester 1 30 wt. percent, based on the overall weight of the composition, of a polyalkylene glycol and drawing the resulting filaments; (c) those obtained by melt-spinning a blended composition of 99.5 60 wt. percent of a polyester and 0.5 40 wt. percent of a polyamide blend containing, based on the overall weight of the composition, of l 30 wt. percent of a polyalkylene glycol, and drawing the resulting filaments; (d) those obtained by melt-spinning a blended composition consisting of 60 99.5 wt. percent of a polyester, 0.5 40 wt. percent of a polyamide and 0.6 30 wt. percent of a polyalkylene glycol and drawing the resulting filaments; (e) those obtained by meltspinning a blended composition of 60 99.5 wt. percent of a polyester and 40 0.5 wt. percent of a polyamide and drawing the resulting filaments, then shrinking the filaments by heat treating them and thereafter redrawing the filaments; (f) those obtained'by meltspinning a blended composition of 60 99.5 wt. percent of a polyester and 40 0.5 wt. percent of a polyamide, and drawing the resulting filaments, then shrinking the filaments 2 to 50 percent at a temperature ranging between 140C. and the melting temperature of the polyester fiber and thereafter redrawing the filaments; and (g) those obtained by melt-spinning a blended composition of 60 99.5 wt. percent of a polyester and 40 0.5 wt. percent of a polyamide and drawing the resulting filaments, followed by shrinking the filaments by heat treating them and thereafter redrawing the filaments at a temperature ranging between room temperature and 230C. and a draw ratio ranging from 2 percent to the point at which breakage of the polyester fiber takes place.

The manufacture of a fiber by melt-spinning and drawing a blended composition of a polyester and some amount of polyamide is known (British Pat. Specification No. 610,140). However, the fiber which has been merely melt-spun and drawn in this manner does not demonstrate desirable dyeability when the usual 4 method of dyeing it with anionic dyestuffs is employed. It is only when the fiber is dyed by the dyeing method of the present invention that it is possible to provide products dyed to bright and deep shades so as to be very useful.

As a result of further research with a view to improving the dyeability of the fiber itself obtained from the polyester polyamide composition, it was found that when one of the methods of the present invention, i.e.,

that wherein the fiber formed by melt-spinning and drawing the aforementioned polyester composition is y then shrunk 2 50 percent at a temperature ranging between 140C. and the melting temperature of the polyester fiber, and thereafter it is again drawn at a temperature between room temperature and 230C. and a draw ratio ranging between 2 percent and the point at which its breakage takes place is employed and the so obtained fiber is used in combination with an anionic dye and at least one quaternary phosphonium salt as defined above, dyed products which are of greater 2. 2-hydroxybenzophenone series, for example, those of the following formulae:

wherein R is H, C H (wherein n is 1-18),

(where R is alkyl or aryl); and

wherein R is H or -SO H.

(where R is alkyl or aryl).

. 3. 2,2'-dihydroxybenzophenone series, for example, those of the formula wherein R is H, C,,H2,, (where n ll8),

4. Phenylsalicylic acid series, for example, those of the formula wherein R is H, c,.ii2,,; (wherein n 1-18),

(where R is alkyl or aryl).

5. Substituted acrylonitrile series, for example, those of the formulae polycaproamide, polyenanthamide, polyundecamide, polyhexamethylene adipamide and polymetaxylene adipamide, or copolymers of these with other amidefomiing substances. These polyamidescan be used either alone or in combinations of two or more thereof. Of these polyamides, the aromatic polyamides such, for example, as those which have copolymerized therewith the hexamethylene-diammonium terephthalate component give especially desirable results with respect to compatibility. These polyamides are incorporated in the polyester in an amount of 0.5 40 percent by weight, and preferably 5 to percent by weight. If the content of polyamide is less than 0.5 percent by weight, the affinity of the resulting fiber for ionic dyestuffs is inadequate. On the other hand, if the content of the polyamide exceeds percent by weight, the proper ties as a polyester fiber are lost. Accordingly, it is undesirable for the content of the polyamide to be outside the range indicated above.

lnaddition, the dyeability of the fiber can be further enhanced by incorporating in'the foregoing polyesters and/or polyamides in an amount not exceeding 30 percent by weight, based on the overall weight of the fiber, a polyoxyalkylene glycol. As the polyoxyalkylene glycol, mention can be made of such, for example, as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene-oxypropylene glycol block or random copolymer methoxypolyoxyethylene glycol, phenoxypolyoxyethylene glycol and octylphenoxypolyoxyethylene glycol. These polyoxyalkylene glycols may be present in either the polyester or the polyamide, or

s in both components. It may be added either during the wherein R is alkyl or aryl.

While the amount of these ultraviolet absorbents used will vary depending upon the class of the material to be dyed, the class of the dyestuff and the concentration and bath ratio, etc., the use of about 1 10 percent (o.w.f.) based on the material to be dyed will do. It is also possible to achieve the result desired by imparting the ultraviolet absorbent to the fiber using a separate bath.

Again, the modified polyester composition of the present invention not only possesses excellent affinity for anionic dyestuffs, as noted hereinbefore, but also demonstrates satisfactory affinity for disperse dyes. In addition, it can also be dyed satisfactorily by means of the basic dyes in the presence of anionic substances. As anionic substances, included are inorganic acids such as sulfuric and acetic acids and the salts thereof; and benzenesulfonic acid, toluene-sulfonic acid, higher alkylbenzenesulfonic acid, and sulfuric esters of higher alcohols and the salts thereof; and phenols.

There are no particular restrictions as to the polyamides to be used in the present invention. as long as they are serviceable with respect to their thermal resistance, etc. Mention can be made of such, for example, as

early stages of the manufacture of the polyester or during the blending of the components.

It does not matter whether the polyvinyl chloride fiber used in the present invention is a homopolymer, a copolymer or an after-chlorinated product.

Good results can naturally be expected even if this method is applied to the mixed woven products of polyvinyl chloride fiber and other classes of fibers. Moreover, in the case of a mixed spun product of polyvinyl chloride fiber with wool, there is a great advantage in that the two fibers can be dyed with the same acid dye in a single bath.

As the polyacrylonitrile fibers to be used in the present invention, acrylic fibers that do not possess dye receptive sites are usable. Included are the Orlon (trademark of DuPont Company) type, Dynel (trademark of Union Carbide and Chemical Company) type, and the acrylic conjugated fiber. Again, it goes without saying that the present invention also has applicability to the mixed textile products of the foregoing fibers with other classes of fibers.

As the cellulose acetate fibers to be used in the present invention, included are the usual diacetate to triacetate fibers. Again, the present invention can also be applied to the cellulose acetate fibers obtained by the after acetylation technique. Again, the invention can, of course, be applied to the mixed textile products of the foregoing fibers with other classes of fibers. The

' method of the present invention is especially effective in the case of a mixed product of acetate fibers with polyamide fibers, since both fibers are dyeable with acid dyes.

The modified polyester fibers that can be dyed by means of the method of the present invention are the so-called readily dyeable polyester fibers whose dyeability by means of disperse dyes has been improved, as hereinbefore described, by either an elevated temperature treatment or the introduction (blending or copolymerizing) of a third component, The term readily dyeable polyester fibers, as used herein, denote those fibers having a dye adsorption of at least 60 percent as determined by the method of measurement of the rate of dye adsorption as defined below.

The rate of dye adsorption is determined in the following manner. The specimen is washed in a 100-fold amount of distilled water (70C.) for 30 minutes with stirring, followed by air drying and thorough opening of the fiber. One gram of the so standardized specimen is weighed and dyed under the following conditions:

After completion of the dyeing and cooling to room temperature, a suitable amount of the remaining dye liquor is taken and combined with an equal amount of CF. acetone (reagent), following which this acetonewater lzl) mixture is diluted 25 times and the optical density is measured using a spectrophotometer. Next, the before-dyeing dye liquor diluted in a similar manner is measured for its optical density. The rate of dye adsorption is then obtained by the following equation, the average of three measurements rounded to whole numbers being used.

Dye adsorption (l -d/d,,) X 100 wherein d the optical density of the before-dyeing dye liquor and d the optical density of the after-dyeing remaining liquor.

Polyester fibers having a dye adsorption of below 60 percent cannot provide satisfactory dyed products even though the method of the present invention is used.

If the present invention is applied to polyamide fibers (e.g. nylon) the results are negative. This is believed to be due to the fact that the dye is not dissociated as a result of the anionic dye forming a complex, with the consequence that in the case of the polyamide fibers having dye receptive sites the results are negative as a result in the decline in the dye adsorption.

Further, the anionic dyestuffs, as referred to herein, denote all of those dyes having an anionic group, i.e., the acid dyes, direct dyes, metal complex dyes, reactive dyes and acid mordant dyes.

In practicing the present invention, the dyeing methods that can be used include the various conventional methods such as the dip, padding and printing techniques.

The dyeing conditions will vary depending upon the class and form of the textile to be dyed and the class of dyeing method to be employed. For instance, in the case of the most widely practiced dip method, the dyeing conditions will be as indicated below.

In the case of the dyeing the modified polyester fiber, the aforementioned compounds are added to the dye bath in a concentration of 1 I percent o.w.f. A dyeing temperature of below 100C. does not result in a satisfactory dye adsorption, therefore a temperature exceeding 100C. is required. Usually, the dyeing is carried out at a temperature of 1 l30C. until the intended color deepness is obtained. Again, carrier dyeing can also be carried out effectively using known carriers conjointly. In addition, it is also possible to make conjoint use of the organic and inorganic acids or salts in carrying out the dyeing operation.

On the other hand, in the case of the method of dip dyeing polyvinyl chloride fibers, the dyeing may be carried out at 50 C. using the aforesaid compounds in a concentration of about l-50 percent o.w.f. (percentage based on the weight of the material to be dyed), though varying depending upon the dyestuff used. Again, carrier dyeing can also be carried out effectively using known carriers conjointly.

Further, in the case of the cellulose acetate and polyacrylonitrile fibers, the amount of the compounds used will differ depending upon the concentration of the dyestuif used, but usually the amount ranges from I to I00 percent. A dyeing temperature in the range of 80 C. is convenient and, if possible, the higher, the better. Again, carrier dyeing is also effectively carried out by conjointly using known carriers.

As such known carriers, mention can be made of the phenolic compounds such as oand p-phenylphenol, the chlorobenzene type compounds such as monochlorobenzene, o-dichlorobenzene and trichlorobenzene, benzoic acid and benzoic acid type compounds such as benzoic acid, and the naphthlenic compounds such as methyl naphthalene. These carriers are added, for example, to the dye bath as an aqueous solution in the case of those which are watersoluble and as either a dispersion or emulsion in the case of those which are water-insoluble.

For carrying out level dyeing by dispersing the dyestuff thoroughly and for preventing the formation of tar, it is preferred to use a suitable nonionic surfactant in the method of the present invention. Surfactants such as indicated are those which are usually widely used as dispersants. Included are, for example, the polyethylene glycol type surfactants such as polyethylene glycol alkylamines, polyethylene glycol alkyl ethers and polyethylene glycol aliphatic acid esters, and the ether or ester type surfactants which contain the polyhydric alcohols such as sorbitan aliphatic acid esters and aliphatic acid monoglycerides as the hydrophilic group.

The textile which has been dyed in accordance with the method of the present invention is thoroughly soaped after its dyeing and thereafter submitted to reduction clearing, if necessary. The textile dyed by such method still retains adequate fastness even after it has undergone these after treatments.

While the particulars of the principle underlying the present invention are not yet determined, it is believed that the water dissolved or dispersed dyestuff forms a complex with the quaternary phosphonium compound, thereby becoming compatible and having affinity with respect to the hydrophobic fibers and simultaneously to function at times as carrier at elevated temperature to become diffused into the interior of the fiber and result in the adsorption of the dye. Accordingly, the balance of the affinity between the dyestuff and the phosphonium compound becomes an important factor that determines the dye adsorption. The effects contemplated by the present invention cannot be achieved by just the insolubilization of the dye but can only be attained, as hereinbefore indicated, in only those cases where the specific phosphonium compounds are used.

With respect to the dyeing of polyvinyl chloride and polyacrylonitrile fibers, particularly preferred phosphonium salts include tributylbenzylphosphonium salts, tetrabutylphosphonium salts and triphenylphosphonium salts. With respect to the dyeing of cellulose 9- acetate fibers, tributylallylphosphonium salts and triphenylbutylphosphonium salts are preferred. Still further in connection with the dyeing of modified polyester fibers, it is preferred in accordance with the present invention to employ such phosphonium salts as tributylbenzylphosphonium salts, tetrabutylphosphonium salts, triphenylbenzylphosphonium salts, triphenylbutylphosphonium salts and tributylarylphosphonium salts.

Also, better dye adsorption is obtained when the pH of the dye bath is on the acid side.

Next, examples will be given for further illustration of the present invention in detail. in the examples asp/c indicates the specific viscosity measured at 35C. using orthochlorophenol as the solvent and intrinsic viscosity is defined as sp/c in which c is concentration in grams of polymer per 100 cc of solution. Also all parts are on a weight basis. Dyeability was indicated by the rate of dye absorption in the case of disperse dyes, and in the case of ionic dyes it was indicated by a qualitative indication, rate of dye adsorption and classification into grades ranging from 1 to 10. Grade 1 denotes that no dyeing at all took place, while Grades 2 and higher denote that as the grade becomes higher, the dyeing becomes better. Dyeings which are of practical use are those having ratings of Grade or higher.

Example 1 Twenty parts of polymethoxylylene adipamide (mp/c 0.59) were blended with 180 parts of 3 mol percent isophthalic componentcopolymerized polyethylene terephthalate (nsp/c 1.05), after which the resulting blend was melt-spun at a spinning temperature of280C. in customary manner. The freshly spun filaments were then drawn 4.42 X by means of an 85C. pin, followed by shrinking. 22 percent at 205C. and thereafteragain being drawn percent at 160C.

The fibers obtained were dyed using a dye bath composed of 4 percent (o.w.f.) of an acid dye Nylomin Blue GS-4, 5 percent (o.w.f.) of acetic acid, 4 percent (o.w.f.) of nonylphenoxypolyoxyethylene glycol and 10 percent (o.w.f.) of tetrabutylphosphonium bromide, and under the conditions of a bath ratio of 1:100 and 120C. X 60 minutes. A dyed product of deep blue shade (Grade 8-9) was'obtained.

Example 2 Twenty parts of a copolyamide ("asp/c 0.54) consisting of 70 mol percent of caprolactam and 30 mol percent of hexamethylenediammonium terephthalate were melt-blended with 80 parts of polyethylene terephthalate (nsp/c= 1.05) at 285C. for 10 minutes, after which the resulting blend was spun at a spinning speed of 285C. in customary manner. The freshly spun filaments were drawn 4.3 X by means of an 85C. pin, then shrunk 25 percent at a temperature of 230C. and thereafter again drawn 10 percent at a temperature of 150C. A dye bath composed of 4 percent (o.w.f.) of Nylomin Blue OS, 5 percent (o.w.f.) of acetic acid, 4 percent (o.w.f.) of nonylphenoxypolyoxyethylene glycol and 4 percent (o.w.f.) of triphenylbutylphosphonium chloride was used and the fibers obtained were dyed under the conditions of a bath ratio of 1:100 and 120C. X 60 minutes, with the consequence that Example 3 Thirteen parts of polyhexamethylene adipamide (nsp/c=0.63) and 87 parts of polyethylene terephthalate (nsp/c 1.05) were melt-blended as in Example 2, and the resulting blend was melt-spun at a spinning temperature of 285C. in customary manner. The freshly spun filaments were drawn 4.25 X by means of an 87C. pin, then shrunk 30 percent at 215C. and thereafter again drawn 15 percent at a temperature of 160C.

When the fibers obtained were dyed with the acid dye Nylomin Blue GS as in Example 2, they were dyed to a deep blue shade (Grade 8). On the other hand, they were dyed to a deep green shade (Grade 7 8) by means of the basic dye Malachite Green.

Example 4 Twenty parts of polymethaxylene adipamide ('nsp/c 0.59). were melt-blended with 180 parts of 3 mol percent isophthalate componentcopolymerized polyethylene terephthalate (nsp/c 1.05), as in Example 2, after which the resulting blend was melt-spun at a spinning temperature of 280C. in customary manner. The freshly spun filaments were drawn 4.42 X by means of an 85C. pin, then shrunk 22 percent at 205C., and thereafter again drawn 10 percent at 160C.

When the fibers obtained were dyed as in Example 2 with the acid dye Nylomin Blue GS, they were dyed to a deep blue shade (Grade 8 9). On the other hand, when they were dyed with the basic dye Malachite Green, they were dyed to a deep green shade.

Example 5 In preparing a copolyamide consisting of mol percent of caprolactam and 30 mol percent of hexamethylenediammonium terephthalate, polyoxyethylene glycol (molecular weight about 4,000) was blended therewith in such an amount that the content of the latter in the copolyamide would be 20 percent by weight. Forty parts of the blend and 160 parts of polyethylene terephthalate ("asp/c 1.05) were then blended as in Example 2 (nsp/c of the blend 0.45). This blend was spun in customary manner at a spinning temperature of 285C. The freshly spun filaments were then drawn 4.14 X by'means of an C. pin, then shrunk 20 percent at 200C. and thereafter again drawn 17 percent at C. When this fiber was dyed as in Example 2, it was dyed to a deep blue shade (Grade 9) by means of the acid dye Nylomin Blue GS and was dyed to a deep green shade (Grade 9) by means of the basic dye Mala chite Green.

Example 6 Example 2. They were dyed to a deep blue shade (Grade 8) by means of acid dye Nylomin Blue GS and to a deep green shade (Grade 7) by means of the basic dye Malachite Green.

Example 7 The polyvinyl chloride fiber Valren (trademark of Teijin Limited) was dipped in a dye bath of the following composition where it was dyed at 100C. for 60 minutes to obtain a dyed product of a deep blue shade.

Suminol Fast Blue PR (C. 1. Acid Blue I29) Tributylbenzylphosphonium bromide 10 (o w.f.) Univadine W 3 70 (o w.f.) Acetic acid 3 (o w.f.) Bath ratio 1:50

Example 8 The polyvinyl chloride fiber Tevilon was dipped in a dye bath of the following composition:

Suminol Fast Red B conc. Triphenylbutylphosphonium bromide Methyl naphthalene (carrier) Univadine W Sulfuric acid Bath ratio When the dyeing was carried out at 50C. for 90 minutes, a product dyed to a deep shade of red was obtained.

Example 9 The polyvinyl chloride fiber Valren was dipped in a dye bath of the following composition:

Kayanol Millin Yellow 3 GW Tributylbenzylphosphonium bromide Methyl naphthalene (carrier) Acetic acid Bath ratio 1:

ases When the dyeing was carried out at 100C. for 60 minutes, a product dyed to a deep shade of yellow was obtained.

Example 10 The polyacrylonitrile fiber Kanekalon was dipped in a dye bath of the same composition as that of Example 7. When the dyeing was carried out at 100C. for 60 minutes, a product dyed to a deep shade of blue was 7 obtained.

Example 1 l Example 12 Using as a cellulose acetate textile a crepe de chine fabric composed of diacetate fiber, this fabric. was dipped in a dye bath of the following composition:

Kayacyl Sky Blue R 4 (o.w.f.) Tributylbenzylphosphonium bromide 10 (o.w.f.) Univadine W 4 (o,w.f.) Sulfuric acid 3 (o.w.f.) Bath ratio 1:50

The dyeing was carried out at C. for 90 minutes and a product dyed to a deep shade of blue was obtained.

Example 13 The polyester fiber Tetoron" T-89 was dipped in a dye bath of identical composition as that of Example 12, wherein it was dyed at 120C. for 90 minutes to yield a product dyed to a deep shade of blue.

Example 14 As a modified polyester fiber, Tetoron T-89 (dye adsorption of 85 percent) was used, and this fiber was dipped in a dye bath of the following composition:

Polar Yellow 5 GN 4 (o.w.f.) (C. 1. Acid Yellow Triphenylethylphosphonium bromide 10 (o.w.f.) Univadine W 4 (o.w.f.) Orthophenylphenol 4 (o.w.f.) Acetic acid 2 (o.w.f.)

When the fiber was dyed at C. for 90 minutes, a product dyed to a deep shade (Grade 6) of yellow was obtained.

What is claimed is:

1. A method of dyeing a modified polyester textile fiber having a dye adsorption of at least 60 percent and which is selected from the group consisting of:

a. that obtained by melt-spinning a blended composition of 60 99.5 percent by weight of polyester and 40 0.5 percent by weight of polyamide and drawing the resulting filaments;

b. that obtained by melt-spinning a blended composition of 40 0.5 percent by weight of polyamide with 60 99.5 percent by weight of a copolyester obtained by copolymerizing with a polyester 1 30 percent by weight, based on the overall weight of the composition, of a polyoxyalkylene glycol, and drawing the resulting filaments;

. that obtained by melt-spinning a blended composition of 99.5 60 percent by weight of polyester and 0.5 40 percent by weight of a polyamide blend containing, based on the overall weight of the composition, 1 30 percent by weight of a polyoxyalkylene glycol, and drawing the resulting filaments;

d. that obtained by melt-spinning a blended composition of 60 99.5 percent by weight of polyester, 0.5 40 percent by weight of polyamide and 0.6 30 percent by weight of polyoxyalkylene glycol and drawing the resulting filaments;

-. that obtained by meltspinning a blended composition of 60 99.5 percent by weight of polyester and 40 0.5 percent by weight of polyamide, drawing the resulting filaments, followed by heat treating and shrinking the filaments, and thereafter again drawing the filaments;

f. that obtained by melt-spinning a blended composition of 60 99.5 percent by weight of polyester and 40 0.5 percent by weight of polyamide, drawing the resulting filaments, followed by shrinking the filaments 2 percent to 50 percent of their initial length by heating the filaments at a temperature of between 140C. and the melting point of said polyester filaments, and thereafter redrawing the filaments; and

. that obtained by melt-spinning a blended composiof at least one quaternary phosphonium salt of the formula wherein R, R R and R are each selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and aralkyl groups of one to 18 carbon atoms and X is selected from the group consisting of halogens, alkoxy sulfate and OH group.

h UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTIUN Pate t 34819326 I Dated June 25; 1974 Inventor(s) I Shiro SHIMAUCHI ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

. 'In the Headingunder "Foreign Application Priority Data",

line 7 thereof: cancel "43-61638" and substitute therefor Signed and sealed this 12th day of Nonember 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents