US3467484A - Patterned application of benzyl alcohol with or without a resist on nylon fabrics and dyeing the patterned fabric - Google Patents

Patterned application of benzyl alcohol with or without a resist on nylon fabrics and dyeing the patterned fabric Download PDF

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US3467484A
US3467484A US532096A US3467484DA US3467484A US 3467484 A US3467484 A US 3467484A US 532096 A US532096 A US 532096A US 3467484D A US3467484D A US 3467484DA US 3467484 A US3467484 A US 3467484A
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benzyl alcohol
dye
treated
polyamide
polyamide material
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Julius Hermes
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CPFilms Inc
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Martin Processing Inc
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651Compounds without nitrogen
    • D06P1/65106Oxygen-containing compounds
    • D06P1/65118Compounds containing hydroxyl groups
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0096Multicolour dyeing
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/24Polyamides; Polyurethanes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92Synthetic fiber dyeing
    • Y10S8/924Polyamide fiber

Definitions

  • a polyamide textile material which is treated with benzyl alcohol over less than the entire surface of the polyamide material with a dye assisting agent, benzyl alcohol, so as to impart to the treated areas of the polyamide material enhanced dye acceptance characteristics.
  • the polyamide material is treated in localized areas by contacting the material with a bath containing benzyl alcohol and a solvent which is volatile at temperatures at less than 205 C. After the polyamide material is contacted with the bath, the excess solvent remaining on the treated surfaces of the textile material is removed by heating to a temperature less than 205 C. so that the benzyl alcohol remains entrapped in the polyamide material at the areas of contact so as to form a latent design in the so treated areas.
  • the polyamide material is subject to ready dyeing by standard polyamide dyeing procedures.
  • This invention relates to an improved method for forming a patterned dye effect on polyamide textile material, generally referred to as nylon.
  • This application is a continuation-in-part of my copending application Ser. No. 317,124, filed Oct. 18, 1963.
  • nylon types 6-, 66 and 610 Different types of polyamide materials are commercially available, such as nylon types 6-, 66 and 610, and, as a general rule, each of these has a different dye aflinity.
  • all types of polyamide materials are characterized by having a relatively low dyeing acceptance or aflinity.
  • a dyestufi in the dyeing of nylon, it has been necessary to mix a dyestufi in the form of a paste, apply it to the surface of the nylon material, and allow it to dry and thereafter, steam the treated material, wash it, and dry it; or, it was necessary in vat dyeing to subject the nylon material to elevated temperatures for a protracted period of time.
  • another method employed was to prepare a solution of dyestuif material, pass the nylon material therethrough at a relatively slow rate so that the dye could penetrate the material, and then subject the material to steaming, washing, and finally drying.
  • a nylon textile having a particular shaped design which is dyed with the remainder of the material remaining undyed.
  • Various configurations can be visualized, depending upon the use to which the material is to be put.
  • the prior art methods, as described above, cannot be efficiently employed to provide this patterned effect on a nylon textile material. Not only must extreme conditions be employed, but, more importantly, sharp colored definition is not readily obtainable with these processes.
  • Nylon textile materials are very often sold wherein the 3,467,484 Patented Sept. 16, 1969 Ice same pattern is reproduced in a number of color variations.
  • Another object of my invention is to provide a process for treating polyamide textile material having applied thereto at preselected portions thereof a dye assisting agent to form a latent design to which dye can be applied rapidly in a conventional manner.
  • Another object of my invention is to provide a process for treating polyamide textile material having applied thereto at preselected portions thereof a dye assisting agent and a dye modifying agent to form a latent design to which dye can be applied rapidly in a conventional manner.
  • a polyamide textile material can be treated with a dye assisting agent, more particularly benzyl alcohol, in a patterned configuration and the benzyl alcohol retained in the fibers until it is desired to introduce dye into the fabric.
  • a dye assisting agent more particularly benzyl alcohol
  • the fabric containing the latent design embodied by the retained benzyl alcohol can be stored for indefinite periods of time and then dyed in a facile manner which does not necessitate the extreme conditions described previously. While the indefinite storage is possible because of benzyl alcohols relatively high boiling point of about 205 C., the boiling point is low enough to permit removal of the latent design by simple heating steps without destroying the properties of polyamide fabric in which it has been retained.
  • the ability to remove the latent design without destroying the fabric is extremely desirable, for example, at the end of a seasons run when the dyer no longer wishes to manufacture the pattern of the previous season, but, obviously does not wish to lose the use of the fabric which he has already purchased.
  • the fabrics treated with the benzyl alcohol can then be heated, the fabric obtained from the heating step being essentially the same as a virgin material. This fabric can then be employed in any manner in which untreated fabrics are generally employed. In previous processes which produced a type of latent image on a fabric prior to dyeing, the ability to recover the fabric in an essentially untreated state was not present.
  • the benzyl alcohol employed according to the present invention is an organic swelling agent for the polyamide material and acts on the surface of the material to increase its afiinity for dyestuffs.
  • the benzyl alcohol can be called a dye assist agent.
  • the polyamide material to which the benzyl alcohol is applied can be in the form of a fiber, yarn, cloth, tow or film.
  • the benzyl alcohol is applied to the polyamide material prior to treatment of the material with the dyestulf. While the dyestuif can be applied to the polyamide material immediately after treatment with the benzyl alcohol, it, of course, can be even more advantageous to store the treated polyamide material for subsequent dyeing at some later time, at which time the latent pattern is developed.
  • a variety of methods can be utilized to apply the dye assist agent to the polyamide material.
  • application can be accomplished by passing the polyamide material through an aqueous solution, dispersion, suspension or the like, of the benzyl alcohol or applying slight pressure to the material in the preselected portions in the presence of the benzyl alcohol bath.
  • This slight pressure which is not sufficient to set the material, e.g., a polyamide fiber, can be applied using an applicating means, such as a roller, although other known applicating means may be employed, such as printing equipment or use of a calendar roller, provided, however, that extreme pressures are not encountered.
  • the roller can be actuated in a variety of ways to apply the slight pressure in selected areas, or a design may be imprinted on the calender roll employing sufiicient pressure to contact the polyamide material to the calender roll so as to transfer the benzyl alcohol to the predetermined portions of the polyamide material.
  • the pressure which is applied may be varied considerably.
  • the dye assist agent is applied to the polyamide material as a solution, dispersion, suspension, or the like.
  • the solvent or suspending medium is water, but in any event the boiling point of the solvent must be below about 205 C.
  • the concentration of benzyl alcohol in the solvent may be varied; however, the benzyl alcohol should be in the range from about 3% to 9%, preferably about 5%, for best results when employing the teachings of this invention.
  • the polyamide material can be treated in a suspension of benzyl alcohol
  • a solution is preferable and, it is therefore preferred that the treating bath be slightly heated so as to insure that all of the benzyl alcohol in the bath is in solution.
  • the preferred temperature of the bath for application of the benzyl alcohol to the polyamide material is in the range from about 35 C. to 100 C., to insure solution of the benzyl alcohol without requiring extreme conditions of application.
  • the term bath as used hereinafter will be understood to include both solutions of benzyl alcohol and mixtures wherein the amounts of benzyl alcohol employed are beyond the solubility limitations of the solvent so that a suspension or dispersion is formed.
  • solvent includes both water and the indicated types or organic materials and mixtures thereof.
  • the treating bath should be in a pH range of about 3-7, but preferably the pH of the bath is approximately 3-4. This can be accomplished by the addition of an organic or mineral acid, such as sulfuric acid which may be in a concentration of about .01% although the concentration may be varied to achieve the proper pH in a given solution.
  • an organic or mineral acid such as sulfuric acid which may be in a concentration of about .01% although the concentration may be varied to achieve the proper pH in a given solution.
  • the excess benzyl alcohol solution remaining on the exterior of the polyamide material is removed in a conventional manner, for example, by passing the material through a water bath or by passing the material through a steam cabinet and hot water spray.
  • the temperature of the wash bath should not exceed 205 C. when treating the polyamide material to remove excess benzyl alcohol as such a temperature would also remove the benzyl alcohol entrapped or absorbed into the polyamide material.
  • the treated portions only of the polyamide material will have the benzyl alcohol solution or dispersion entrapped therein.
  • the solvent is then removed by heating the material to a temperature in excess of the boiling point of the solvent but lower than 205 C. At this stage, the benzyl alcohol alone is entrapped in the treated portions of the polyamide material.
  • the material can then be immediately dyed by subjecting it to normal dyeing opeartions or it can be stored for subsequent dyeing.
  • the poly-amide material may thereafter be dyed using conventional dyeing procedures, for polyamide material.
  • a dyed pattern will be formed in accordance with the latent design (i.e. the arrangement of the treated portions).
  • dyes which have an afiinity for polyamide such as acid colors, premetalized acid colors, dispersed colors and direct colors.
  • the preferred dyestuffs are the pre-metalized colors because of their dye fastness, wash and light fastness.
  • specific colors which may be employed, identified by their color index means and numbers are: premetalized acid colors, such as: C.I. acid blue 21, CI. No. 62,005, C.I. acid red 114 C1. No. 23,635, C.I. acid orange 64 pre-metalized, C.I. acid orange pre-metalized 590, C.I. acid milling blue R. C.I. Pr.
  • dispersed colors such as: C.I. dispersed yellow 3 OJ. No. 11,855, C.I. dispersed blue 7 Cl. No. 62,500, C.I. dispersed red 13 Cl. 11,115, C.I. dispersed orange 3 Cl. No. 11,005; and direct colors, such as C.I. direct yellow 44 Cl. 29,000, C.I. direct red 1 Cl. 11,110, 0.1. direct red 30 Cl. 23,630, C.I. direct blue 67 Cl. No. 27,925.
  • direct colors such as C.I. direct yellow 44 Cl. 29,000, C.I. direct red 1 Cl. 11,110, 0.1. direct red 30 Cl. 23,630, C.I. direct blue 67 Cl. No. 27,925.
  • the various dyes that may be used on the polyamide material treated with my dye assist agent may be applied by any of the commonly used methods for dyeing material used in the art today.
  • the dye when polyamide material treated in accordance with my invention is dyed, the dye is rapidly and efficiently transferred to the polyamide material employing non-extreme conditions.
  • the polyamide material will accept the dye in a relatively short time, for example, less than a minute so that vat dyeing may be employed; however, the material need not remain in the dye solution over extended periods of time as is commonly practiced today.
  • the material is washed and heated to a temperature in excess of 205 C. to remove the benzyl alcohol contained in the treated portions of the polyamide material.
  • This temperature is sufiicient to remove the benzyl alcohol without in any way affecting the polyamide or dyestuffs.
  • the resulting dyed material has pattern definition, is dyefast, wash and light fast and the dye is substantially uniformly distributed through the treated portions of the polyamide material where the benzyl alcohol had been previously applied.
  • the preselected portions of the polyamide material rather than being passed through only a single bath containing benzyl alcohol, may be passed through a plurality of baths in varying compositions and concentrations. Only a slight pressure is employed when the different baths are applied to these preselected portions of the polyamide material. One or more of the remaining baths contains a quantity of dye resist agents of varying concentrations.
  • a latent image or design which is readily dyed at a subsequent time, is formed thereon.
  • These various treated areas are such that all of the treated areas may be dyed either in a varying shade of a single color or varying shades of multi-color, or the dye may be excluded from the so treated zones or portions under proper conditions.
  • one of the baths may contain only a benzyl alcohol solution as the dye assist agent and active ingredient.
  • Other baths may contain dye resist agents of varying types and quantities.
  • Various dye resist agents may be employed which have an affinity for polyamide material.
  • sulfur-containing organic materials such as sulfurized phenols and naphthols and their substituted counterparts, sulfonated sulfurized phenols and naphthols and their substituted counterparts, and condensates of the above-described compounds with aldehydes and amino-aldehyde condensation products.
  • a solution formed of tannic acid and tartar emetic can be employed.
  • the treating baths which incorporate the various resists contain from about 3% to 9% of the benzyl alcohol, as previously described for the bath containing only benzyl alcohol, and amounts of resist present in the benzyl alcohol solution may vary in accordance with a specific resist agent. Concentrations of resists which have been found to be effective in forming a multi-color pattern or latent design effect, for example, a resist of the type having high molecular sulfur compounds may vary in concentration from about 3 to 8 grams/liter, whereas if a mixture of tannic acid and tartar emetic is employed, 16 grams of tannic acid to 4 grams of tartar emetic/ liter have been found to be suitable when employing the teachings of my invention.
  • the treated polyamide material may be dyed employing conventional techniques. However, after the treated polyamide material is dyed, the dye is set by heating the material in excess of 205 C. to remove the entrapped or retained benzyl alcohol from the treated portions.
  • the treated portions will contain dye in varying color gradations. Under proper circumstances in which the selected dye Will not react with the dye resist agent employed, the dye will be repelled completely where the dye resist is in greatest concentration and will only dye in lighter color shades in varying gradations according to the amount of dye resist present in the treated portions.
  • various color gradations may be achieved over the entire treated portion of the fabric where the dye resist is present in varying concentrations.
  • a dye resist agent has a two-fold function, namely to resist certain dyes from the treated polyamide material or to accept certain dyes from the treated polyamide material.
  • the dyes employed will vary although the dyes mentioned previously in accordance with the benzyl alcohol treated portions are quite acceptable. Pre-metallized acid color dyes, dispersed dyes and direct dyes are quite suitable as set forth above.
  • the multi-color or gradation pattern effect may be obtained by passing the treated portions of the material through separate dye baths or a single dye bath may be employed containing various color dyes.
  • the treated polyamide material may be dyed in a single operation by incorporating into one dye bath solution selected dyestuffs. Due to the selectivity of the dyes, a specified dye will dye the benzyl alcohol treated portions and the other selected dyes which have an aflinity for the dye resist agent incorporated in selected portions of the polyamide material will dye those portions in shades according to the concentration of the resist present in the treated material.
  • the above solution is prepared by dissolving the named constituents in approximately 900 cc. of Water. After the constituents have been dissolved therein, the volume of the mixture is brought to one liter by adding a sufficient amount of water thereto.
  • the dye assist treating solution is heated to a temperature below 205 C., as for instance approximately C., and is conveniently placed in a tank fitted with a roller in which the roller is partially immersed therein so that as the treatment roller rotates, a film of the dye assist treating solution containing an aqueous solution of benzyl alcohol will be carried on the surface of the roller.
  • the polyamide material to be treated consists of a plurality of ends arranged substantially in side-by-side relationship to each other and extend longitudinally in the direction of the movement of the treating apparatus. In practice, the longitudinally extending ends of the polyamide material are passed over the treatment roller and are spaced a short distance therefrom.
  • a movable rotating bar or roller is positioned above the treatment roller and the polyamide material to be treated.
  • the movable roller is manipulated in a predetermined synchronized fashion so as to contact the upper surface of the polyamide material and to force the polyamide material against the treatment roller with a slight pressure sufficient enough to cause the film of treating solution carried on the surface thereof to be transferred to the polyamide material in the preselected portions.
  • the pressure is such that the polyamide material is not deformed or compressed so as to alter its original shape.
  • the film carried by the treatment roller is transferred to the material only in the portions in which the movable roller has pressed against the polyamide material and the treatment roller.
  • the contacting period for any portion of the polyamide material is a relatively short period of time of less than a second although depending upon the concentration of the treating solution, the period of time may vary.
  • the treated polyamide material is then passed through a heating zone at a temperature of less than 205 C. so as to set the treatment solution in the polyamide material. It is then washed to remove excess treatment solution but not the absorbed benzyl alcohol contained in the polyamide material in those areas where the movable roller has made contact with the material.
  • the material is then squeeze-dried and dried in the usual manner at a temperature in excess of the boiling point of the solvent and below 205 C. so as to remove the solvent and retain the absorbed benzyl alcohol therein.
  • the material may be dyed at once or stored for subsequent use for manufacture of textile products.
  • the treated greige goods are stored.
  • the so-treated material contains benzyl alcohol in the areas in which the movable roller has contacted the material on the treatment roller in predetermined areas and these treated areas are ready fo rapid dyeing in a conventional manner.
  • the treated ends of polyamide material contain predetermined zones having benzyl alcohol adsorbed or entrapped within the fibers of each end and each spool or end of polyamide material or the goods made therefrom may be dyed in a predetermined fashion so that zones of the yarn s dyed a given color and zones that have remained untreated will not be dyed at all, or the untreated zones may be dyed in the conventional manner.
  • the dyed polyamide material is then subjected to temperatures in excess of 205 C. to remove the entrapped or adsorbed benzyl alcohol in the treated zones so as to set the dye therein.
  • the dye is uniform and is fast to washing and light.
  • Example 2 Benzyl alcohol cc 50.00 Tannic acid cc 16.0 Tartar emetic gm 4.0 Oxalic acid gm 0.8 Sulfuric acid (l-) cc 0.8 Water, q.s. to 1 liter.
  • the temperature of the treatment, the pressure applied to the polyamide ends, the washing, drying and storing of the treated polyamide material is the same as in Example 1.
  • the polyamide material will be prepared having treated zones containing benzyl alcohol and tannic acid and tartar emetic adsorbed or entrapped within the fiber of the yarn.
  • the benzyl alcohol aids or assists the dye resist agent, i.e. to be adsorbed or entrapped in the polyamide fibers.
  • the treated polyamide material may be dyed in the manner indicated above.
  • Solutions A, B, and C are placed in treatment tanks A, B, and C of the same type and having the same temperature conditions as indicated in Example 1.
  • the polyamide material of Example 1 is passed over treatment tanks A, B, and C subjected to relatively the same contacting pressures as indicated in Example 1 in the following manner:
  • Each treatment tank is provided with a treatment roller to transfer the respective solutions to the polyamide material in a predetermined fashion.
  • a movable bar or roller is positioned over each treatment roller as described in Example 1.'
  • the polyamide material is treated by synchronizing the movable rollers to contact the polyamide material in successive zones whereby the solutions contained in tanks A, B, and C are applied in a predetermined fashion to form a latent design thereon. Also, solutions A, B, and C may be applied in space relationship to each other so that only preselected portions of the material may be untreated. Thereafter, the material is Washed and dried as described in Example 1 so that the dye assisting agent and dye resist are entrapped therein and the treated material is stored for subsequent use for manufacture of textile products.
  • the colors that may be applied to the material may vary greatly.
  • a dye solution may be prepared in which two different dyes may be used, namely C.I. dispersed blue 7 Cl. No. 62,500 and Cl. acid orange Cl. Pr. 590.
  • the polyamide material is treated with this dye mixture, the material will be dyed in the following manner:
  • Treated part C will remain a clear blue shade.
  • greige goods includes, for example, polyamide material in the form of filaments, yarns, tows, films and other textile products which may be woven, knitted or the like. These materials can be substituted for the ends of the polyamide material described in Examples 1 through 3.
  • the configurations of the so-treated zones may vary considerably.
  • the treatment roller may be provided with a design which is to be transferred to the particular polyamide material being treated. Obviously, many different types of treatment rollers may be made with variations in designs.
  • the greige goods material formed in accordance with the invention herein is such that the treated portions have enhanced dyeing characteristics but the physical characteristics of the so-treated portions or zones, such as flexibility, resiliency and tensile strength are substantially unaffected and unaltered by the treatment with the benzyl alcohol and/or benzyl alcohol and dye resist agent.
  • a method of preparing fibrous polyamide greige goods in the form of filaments, yarns, woven and knitted textiles for subsequent dyeing in patterns of light and 9 10 dark areas in said goods without altering the fiexibility 2.
  • Polyamide fibrous greige goods made by the method areas substantially less than the entire surface area of claim 2. of the polyamide greige goods from about 3% to References Cited about 9% of benzyl alcohol in a liquid medium inert UNITED STATES PATENTS to said polyannde whlch serves as a carrier for said benzyl alcohol, said liquid medium having a boiling 3,083,069 3/1963 fllrsbrurmer et point lower than 205 C.

Description

United States Patent 3,467,484 PATTERNED APPLICATION OF BENZYL ALCOHOL WITH OR WITHOUT A RESIST ON NYLON FABRICS AND DYEING THE PATTERNED FABRIC Julius Hermes, Martinsville, Va., assignor to Martin Processing Co. Incorporated, Bassett, Va., a corporation of Virginia No Drawing. Continuation-impart of application Ser. No. 317,124, Oct. 18, 1963. This application Mar. 7, 1966, Ser. No. 532,096
Int. Cl. D06p 3/24 US. Cl. 8-15 3 Claims ABSTRACT OF THE DISCLOSURE A polyamide textile material which is treated with benzyl alcohol over less than the entire surface of the polyamide material with a dye assisting agent, benzyl alcohol, so as to impart to the treated areas of the polyamide material enhanced dye acceptance characteristics. The polyamide material is treated in localized areas by contacting the material with a bath containing benzyl alcohol and a solvent which is volatile at temperatures at less than 205 C. After the polyamide material is contacted with the bath, the excess solvent remaining on the treated surfaces of the textile material is removed by heating to a temperature less than 205 C. so that the benzyl alcohol remains entrapped in the polyamide material at the areas of contact so as to form a latent design in the so treated areas. The polyamide material is subject to ready dyeing by standard polyamide dyeing procedures.
This invention relates to an improved method for forming a patterned dye effect on polyamide textile material, generally referred to as nylon. This application is a continuation-in-part of my copending application Ser. No. 317,124, filed Oct. 18, 1963.
Different types of polyamide materials are commercially available, such as nylon types 6-, 66 and 610, and, as a general rule, each of these has a different dye aflinity. However, all types of polyamide materials are characterized by having a relatively low dyeing acceptance or aflinity. Heretofore, in the dyeing of nylon, it has been necessary to mix a dyestufi in the form of a paste, apply it to the surface of the nylon material, and allow it to dry and thereafter, steam the treated material, wash it, and dry it; or, it was necessary in vat dyeing to subject the nylon material to elevated temperatures for a protracted period of time. Alternatively, another method employed was to prepare a solution of dyestuif material, pass the nylon material therethrough at a relatively slow rate so that the dye could penetrate the material, and then subject the material to steaming, washing, and finally drying.
Often, in dyeing nylon textile material it is desirable to form a patterned effect, i.e., a pattern occupying substantially less than all of the area of the textile. For example, nylon textiles having a checkerboard pattern wherein alternate squares are dyed different colors or are dyed and undyed as frequently as desired. Similarly, it is often desirable to form a nylon textile having a particular shaped design which is dyed, with the remainder of the material remaining undyed. Various configurations can be visualized, depending upon the use to which the material is to be put. The prior art methods, as described above, cannot be efficiently employed to provide this patterned effect on a nylon textile material. Not only must extreme conditions be employed, but, more importantly, sharp colored definition is not readily obtainable with these processes.
Nylon textile materials are very often sold wherein the 3,467,484 Patented Sept. 16, 1969 Ice same pattern is reproduced in a number of color variations. With the prior art processes, it has been necessary to make each of the color patterns individually and, often, in uneconomical run sizes. It has not hitherto been possible for a dyer to obtain a polyamide textile material having a latent design, colorable in varying shades and hues, which can be easily and rapidly dyed at relatively low temperatures.
It is one object of my invention to provide a process for forming polyamide textile materials having a latent design to which dye can be applied to greige goods formed therefrom.
Another object of my invention is to provide a process for treating polyamide textile material having applied thereto at preselected portions thereof a dye assisting agent to form a latent design to which dye can be applied rapidly in a conventional manner.
Another object of my invention is to provide a process for treating polyamide textile material having applied thereto at preselected portions thereof a dye assisting agent and a dye modifying agent to form a latent design to which dye can be applied rapidly in a conventional manner.
It is a further object of my invention to provide treated polyamide textile material having a latent design which can be easily removed from the material without damaging it or interfering with further processing.
In accordance with the present invention, it has been unexpectedly discovered that a polyamide textile material can be treated with a dye assisting agent, more particularly benzyl alcohol, in a patterned configuration and the benzyl alcohol retained in the fibers until it is desired to introduce dye into the fabric. The fabric containing the latent design embodied by the retained benzyl alcohol can be stored for indefinite periods of time and then dyed in a facile manner which does not necessitate the extreme conditions described previously. While the indefinite storage is possible because of benzyl alcohols relatively high boiling point of about 205 C., the boiling point is low enough to permit removal of the latent design by simple heating steps without destroying the properties of polyamide fabric in which it has been retained. The ability to remove the latent design without destroying the fabric is extremely desirable, for example, at the end of a seasons run when the dyer no longer wishes to manufacture the pattern of the previous season, but, obviously does not wish to lose the use of the fabric which he has already purchased. The fabrics treated with the benzyl alcohol can then be heated, the fabric obtained from the heating step being essentially the same as a virgin material. This fabric can then be employed in any manner in which untreated fabrics are generally employed. In previous processes which produced a type of latent image on a fabric prior to dyeing, the ability to recover the fabric in an essentially untreated state was not present.
The benzyl alcohol employed according to the present invention is an organic swelling agent for the polyamide material and acts on the surface of the material to increase its afiinity for dyestuffs. Thus, the benzyl alcohol can be called a dye assist agent. When the polyamide material has been treated with benzyl alcohol, according to the present invention, dyes are rapidly accepted by the polyamide material and set into the material employing non-extreme conditions. The so-applied dyestuffs for a color which is not only fast, but uniform, in the areas where the fabric has been treated with benzyl alcohol.
The polyamide material to which the benzyl alcohol is applied can be in the form of a fiber, yarn, cloth, tow or film. To form the latent pattern, the benzyl alcohol is applied to the polyamide material prior to treatment of the material with the dyestulf. While the dyestuif can be applied to the polyamide material immediately after treatment with the benzyl alcohol, it, of course, can be even more advantageous to store the treated polyamide material for subsequent dyeing at some later time, at which time the latent pattern is developed.
A variety of methods can be utilized to apply the dye assist agent to the polyamide material. For example, application can be accomplished by passing the polyamide material through an aqueous solution, dispersion, suspension or the like, of the benzyl alcohol or applying slight pressure to the material in the preselected portions in the presence of the benzyl alcohol bath. This slight pressure, which is not sufficient to set the material, e.g., a polyamide fiber, can be applied using an applicating means, such as a roller, although other known applicating means may be employed, such as printing equipment or use of a calendar roller, provided, however, that extreme pressures are not encountered. The roller can be actuated in a variety of ways to apply the slight pressure in selected areas, or a design may be imprinted on the calender roll employing sufiicient pressure to contact the polyamide material to the calender roll so as to transfer the benzyl alcohol to the predetermined portions of the polyamide material. The pressure which is applied may be varied considerably.
The dye assist agent is applied to the polyamide material as a solution, dispersion, suspension, or the like. Preferably the solvent or suspending medium is water, but in any event the boiling point of the solvent must be below about 205 C. Other solvents which may be employed, for example, include methyl, ethyl, ketone, diacetone alcohol, or the like. The concentration of benzyl alcohol in the solvent may be varied; however, the benzyl alcohol should be in the range from about 3% to 9%, preferably about 5%, for best results when employing the teachings of this invention. Where concentrations of benzyl alcohol are employed below about 3%, insufficient benzyl alcohol is transferred to the polyamide material to provide adequate dye acceptance, but sufficient benzyl alcohol may be transferred to the polyamide material if the material is allowed to remain in contact with the benzyl alcohol solution for an extended period of time. In practicing the invention in accordance herewith when using benzyl alcohol solution in concentrations as set forth above, sufiicient benzyl alcohol is transferred to the polyamide material when it is contacted thereby for a period of time which should be less than 3 seconds. Concentrations above 9% may cause damage to the polyamide material due to the solvent action of the benzyl alcohol thereon. Benzyl alcohol has only a limited solubility in water at room temperature. While as previously mentioned, the polyamide material can be treated in a suspension of benzyl alcohol, a solution is preferable and, it is therefore preferred that the treating bath be slightly heated so as to insure that all of the benzyl alcohol in the bath is in solution. The preferred temperature of the bath for application of the benzyl alcohol to the polyamide material is in the range from about 35 C. to 100 C., to insure solution of the benzyl alcohol without requiring extreme conditions of application. The term bath as used hereinafter will be understood to include both solutions of benzyl alcohol and mixtures wherein the amounts of benzyl alcohol employed are beyond the solubility limitations of the solvent so that a suspension or dispersion is formed. The term solvent includes both water and the indicated types or organic materials and mixtures thereof.
The treating bath should be in a pH range of about 3-7, but preferably the pH of the bath is approximately 3-4. This can be accomplished by the addition of an organic or mineral acid, such as sulfuric acid which may be in a concentration of about .01% although the concentration may be varied to achieve the proper pH in a given solution.
After the polyamide material has been passed through the bath containing the benzyl alcohol, the excess benzyl alcohol solution remaining on the exterior of the polyamide material is removed in a conventional manner, for example, by passing the material through a water bath or by passing the material through a steam cabinet and hot water spray. In any event, the temperature of the wash bath should not exceed 205 C. when treating the polyamide material to remove excess benzyl alcohol as such a temperature would also remove the benzyl alcohol entrapped or absorbed into the polyamide material. After the excess benzyl alcohol has thus been removed, the treated portions only of the polyamide material will have the benzyl alcohol solution or dispersion entrapped therein. The solvent is then removed by heating the material to a temperature in excess of the boiling point of the solvent but lower than 205 C. At this stage, the benzyl alcohol alone is entrapped in the treated portions of the polyamide material. The material can then be immediately dyed by subjecting it to normal dyeing opeartions or it can be stored for subsequent dyeing.
The poly-amide material may thereafter be dyed using conventional dyeing procedures, for polyamide material. A dyed pattern will be formed in accordance with the latent design (i.e. the arrangement of the treated portions).
Many or various dyes may be employed in accordance with my invention, for example, dyes which have an afiinity for polyamide, such as acid colors, premetalized acid colors, dispersed colors and direct colors. Of these, the preferred dyestuffs are the pre-metalized colors because of their dye fastness, wash and light fastness. Examples of specific colors which may be employed, identified by their color index means and numbers are: premetalized acid colors, such as: C.I. acid blue 21, CI. No. 62,005, C.I. acid red 114 C1. No. 23,635, C.I. acid orange 64 pre-metalized, C.I. acid orange pre-metalized 590, C.I. acid milling blue R. C.I. Pr. 136; dispersed colors, such as: C.I. dispersed yellow 3 OJ. No. 11,855, C.I. dispersed blue 7 Cl. No. 62,500, C.I. dispersed red 13 Cl. 11,115, C.I. dispersed orange 3 Cl. No. 11,005; and direct colors, such as C.I. direct yellow 44 Cl. 29,000, C.I. direct red 1 Cl. 11,110, 0.1. direct red 30 Cl. 23,630, C.I. direct blue 67 Cl. No. 27,925. It should be understood that the above listing of dyes which can be utilized for dyeing the polyamide material treated in accordance with my invention is representative only, and is not to be considered as limiting in any way as to the full scope of the present invention.
The various dyes that may be used on the polyamide material treated with my dye assist agent may be applied by any of the commonly used methods for dyeing material used in the art today. In this connection, however, and as stated previously, when polyamide material treated in accordance with my invention is dyed, the dye is rapidly and efficiently transferred to the polyamide material employing non-extreme conditions. The polyamide material will accept the dye in a relatively short time, for example, less than a minute so that vat dyeing may be employed; however, the material need not remain in the dye solution over extended periods of time as is commonly practiced today. After the material is removed from the dye bath, the material is washed and heated to a temperature in excess of 205 C. to remove the benzyl alcohol contained in the treated portions of the polyamide material. This temperature is sufiicient to remove the benzyl alcohol without in any way affecting the polyamide or dyestuffs. The resulting dyed material has pattern definition, is dyefast, wash and light fast and the dye is substantially uniformly distributed through the treated portions of the polyamide material where the benzyl alcohol had been previously applied.
While a two-color effect can be achieved by treating the polyamide material with the benzyl alcohol in preselected portions, multi-color effects may be achieved by only a slight variation in this process. For example, the preselected portions of the polyamide material, rather than being passed through only a single bath containing benzyl alcohol, may be passed through a plurality of baths in varying compositions and concentrations. Only a slight pressure is employed when the different baths are applied to these preselected portions of the polyamide material. One or more of the remaining baths contains a quantity of dye resist agents of varying concentrations. Thus, if the preselected portions of the polyamide material are passed through the baths containing benzyl alcohol and dye resist, a latent image or design, which is readily dyed at a subsequent time, is formed thereon. These various treated areas are such that all of the treated areas may be dyed either in a varying shade of a single color or varying shades of multi-color, or the dye may be excluded from the so treated zones or portions under proper conditions.
As stated above, one of the baths may contain only a benzyl alcohol solution as the dye assist agent and active ingredient. Other baths may contain dye resist agents of varying types and quantities. Various dye resist agents may be employed which have an affinity for polyamide material. For example, sulfur-containing organic materials, such as sulfurized phenols and naphthols and their substituted counterparts, sulfonated sulfurized phenols and naphthols and their substituted counterparts, and condensates of the above-described compounds with aldehydes and amino-aldehyde condensation products. Similarly, a solution formed of tannic acid and tartar emetic can be employed.
The list of resists quoted above is not meant to be limiting, nor does the use of a resist form any part of my invention, except as employed in conjuction with the benzyl alcohol treatment.
It has been unexpectedly found that not only is the benzyl alcohol retained in the polyamide material to aid in dye reception, but the benzyl alcohol also aids in insuring penetration of the various resists into the polyamide material for retention during storage, prior to subsequent use. For example, in the case of the tannic acid-tartar emetic resist, the benzyl alcohol has been found to dissolve the precipitate which is generally formed. When using this resist, a small quantity of oxalic acid should also be employed to prevent the formation of a blue solution which often forms when tannic acid is brought in contact with water, due to a reaction between the tannic acid and the small quantities of iron which are often found in water.
The treating baths which incorporate the various resists contain from about 3% to 9% of the benzyl alcohol, as previously described for the bath containing only benzyl alcohol, and amounts of resist present in the benzyl alcohol solution may vary in accordance with a specific resist agent. Concentrations of resists which have been found to be effective in forming a multi-color pattern or latent design effect, for example, a resist of the type having high molecular sulfur compounds may vary in concentration from about 3 to 8 grams/liter, whereas if a mixture of tannic acid and tartar emetic is employed, 16 grams of tannic acid to 4 grams of tartar emetic/ liter have been found to be suitable when employing the teachings of my invention.
As stated previously, the treated polyamide material may be dyed employing conventional techniques. However, after the treated polyamide material is dyed, the dye is set by heating the material in excess of 205 C. to remove the entrapped or retained benzyl alcohol from the treated portions. The treated portions will contain dye in varying color gradations. Under proper circumstances in which the selected dye Will not react with the dye resist agent employed, the dye will be repelled completely where the dye resist is in greatest concentration and will only dye in lighter color shades in varying gradations according to the amount of dye resist present in the treated portions. Alternatively, where the proper dye is selected, various color gradations may be achieved over the entire treated portion of the fabric where the dye resist is present in varying concentrations. Thus, a dye resist agent has a two-fold function, namely to resist certain dyes from the treated polyamide material or to accept certain dyes from the treated polyamide material. The dyes employed will vary although the dyes mentioned previously in accordance with the benzyl alcohol treated portions are quite acceptable. Pre-metallized acid color dyes, dispersed dyes and direct dyes are quite suitable as set forth above. When dyeing treated polyamide material having incorporated therein benzyl alcohol and a dye resist agent in varying concentrations, the multi-color or gradation pattern effect may be obtained by passing the treated portions of the material through separate dye baths or a single dye bath may be employed containing various color dyes. The treated polyamide material may be dyed in a single operation by incorporating into one dye bath solution selected dyestuffs. Due to the selectivity of the dyes, a specified dye will dye the benzyl alcohol treated portions and the other selected dyes which have an aflinity for the dye resist agent incorporated in selected portions of the polyamide material will dye those portions in shades according to the concentration of the resist present in the treated material.
EXAMPLES The following examples illustrate the treatment of polyamide materials so as to form latent images or designs to which dye may be subsequently applied thereto and also illustrate treatment with a dye modifying agent, in accordance with the invention herein.
Example 1 Ce. Sulfuric acid (1-10) 4.0 Benzyl alcohol 50.0 Water 946.0
The above solution is prepared by dissolving the named constituents in approximately 900 cc. of Water. After the constituents have been dissolved therein, the volume of the mixture is brought to one liter by adding a sufficient amount of water thereto.
The dye assist treating solution is heated to a temperature below 205 C., as for instance approximately C., and is conveniently placed in a tank fitted with a roller in which the roller is partially immersed therein so that as the treatment roller rotates, a film of the dye assist treating solution containing an aqueous solution of benzyl alcohol will be carried on the surface of the roller. The polyamide material to be treated consists of a plurality of ends arranged substantially in side-by-side relationship to each other and extend longitudinally in the direction of the movement of the treating apparatus. In practice, the longitudinally extending ends of the polyamide material are passed over the treatment roller and are spaced a short distance therefrom. A movable rotating bar or roller is positioned above the treatment roller and the polyamide material to be treated. The movable roller is manipulated in a predetermined synchronized fashion so as to contact the upper surface of the polyamide material and to force the polyamide material against the treatment roller with a slight pressure sufficient enough to cause the film of treating solution carried on the surface thereof to be transferred to the polyamide material in the preselected portions. The pressure is such that the polyamide material is not deformed or compressed so as to alter its original shape.
The film carried by the treatment roller is transferred to the material only in the portions in which the movable roller has pressed against the polyamide material and the treatment roller. The contacting period for any portion of the polyamide material is a relatively short period of time of less than a second although depending upon the concentration of the treating solution, the period of time may vary. The treated polyamide material is then passed through a heating zone at a temperature of less than 205 C. so as to set the treatment solution in the polyamide material. It is then washed to remove excess treatment solution but not the absorbed benzyl alcohol contained in the polyamide material in those areas where the movable roller has made contact with the material. The material is then squeeze-dried and dried in the usual manner at a temperature in excess of the boiling point of the solvent and below 205 C. so as to remove the solvent and retain the absorbed benzyl alcohol therein. The material may be dyed at once or stored for subsequent use for manufacture of textile products. The treated greige goods are stored.
The so-treated material contains benzyl alcohol in the areas in which the movable roller has contacted the material on the treatment roller in predetermined areas and these treated areas are ready fo rapid dyeing in a conventional manner. It is to be noted that the treated ends of polyamide material contain predetermined zones having benzyl alcohol adsorbed or entrapped within the fibers of each end and each spool or end of polyamide material or the goods made therefrom may be dyed in a predetermined fashion so that zones of the yarn s dyed a given color and zones that have remained untreated will not be dyed at all, or the untreated zones may be dyed in the conventional manner. The dyed polyamide material is then subjected to temperatures in excess of 205 C. to remove the entrapped or adsorbed benzyl alcohol in the treated zones so as to set the dye therein. The dye is uniform and is fast to washing and light.
Example 2 Benzyl alcohol cc 50.00 Tannic acid cc 16.0 Tartar emetic gm 4.0 Oxalic acid gm 0.8 Sulfuric acid (l-) cc 0.8 Water, q.s. to 1 liter.
The above solution is prepared as in Example 1.
The temperature of the treatment, the pressure applied to the polyamide ends, the washing, drying and storing of the treated polyamide material is the same as in Example 1.
The polyamide material will be prepared having treated zones containing benzyl alcohol and tannic acid and tartar emetic adsorbed or entrapped within the fiber of the yarn. The benzyl alcohol aids or assists the dye resist agent, i.e. to be adsorbed or entrapped in the polyamide fibers. The treated polyamide material may be dyed in the manner indicated above.
Water, q.s. to 1 liter.
The above solutions are prepared as indicated in Example 1.
Solutions A, B, and C are placed in treatment tanks A, B, and C of the same type and having the same temperature conditions as indicated in Example 1. The polyamide material of Example 1 is passed over treatment tanks A, B, and C subjected to relatively the same contacting pressures as indicated in Example 1 in the following manner:
Each treatment tank is provided with a treatment roller to transfer the respective solutions to the polyamide material in a predetermined fashion. A movable bar or roller is positioned over each treatment roller as described in Example 1.'The polyamide material is treated by synchronizing the movable rollers to contact the polyamide material in successive zones whereby the solutions contained in tanks A, B, and C are applied in a predetermined fashion to form a latent design thereon. Also, solutions A, B, and C may be applied in space relationship to each other so that only preselected portions of the material may be untreated. Thereafter, the material is Washed and dried as described in Example 1 so that the dye assisting agent and dye resist are entrapped therein and the treated material is stored for subsequent use for manufacture of textile products.
Subsequently, when the polyamide material is to be dyed by the manufacturer, the colors that may be applied to the material may vary greatly. For instance, a dye solution may be prepared in which two different dyes may be used, namely C.I. dispersed blue 7 Cl. No. 62,500 and Cl. acid orange Cl. Pr. 590. When the polyamide material is treated with this dye mixture, the material will be dyed in the following manner:
(1) The material will dye a solid shade of blue before the dyes have been completely reacted.
(2) The treated parts A and B and the untreated part of the material will be dyed varying shades of green. Thus, part A will dye a dark Moss Green, part B will dye a light Moss Green and the untreated part will dye a Medium Green which is slightly darker than the light green of treated part B.
(3) Treated part C will remain a clear blue shade.
It is apparent by the proper selection of dyes, multicolored and/ or multi-shaded dye patterns and effects may be achieved. Further, other dyes that may be used have specific characteristics in which no reaction occurs. Where the portion of the material is described above, the dye used specifically reacts with my dye resist agent. Thus, a pattern having varying shades of dye adsorption will leave a portion of the material neutral, namely that portion which is treated with a heavy concentration of dye resist agent.
The foregoing examples illustrate the procedure for forming a treated greige goods material in the form of filaments or ends of polyamide material which has incorporated in the treated zones benzyl alcohol and/or benzyl alcohol and a dye resist agent. It is to be understood that the term greige goods includes, for example, polyamide material in the form of filaments, yarns, tows, films and other textile products which may be woven, knitted or the like. These materials can be substituted for the ends of the polyamide material described in Examples 1 through 3. The configurations of the so-treated zones may vary considerably. For example, the treatment roller may be provided with a design which is to be transferred to the particular polyamide material being treated. Obviously, many different types of treatment rollers may be made with variations in designs.
The greige goods material formed in accordance with the invention herein is such that the treated portions have enhanced dyeing characteristics but the physical characteristics of the so-treated portions or zones, such as flexibility, resiliency and tensile strength are substantially unaffected and unaltered by the treatment with the benzyl alcohol and/or benzyl alcohol and dye resist agent.
Many variations may be employed without departing from the spirit and scope of my invention as defined in the appended claims.
I claim:
1. A method of preparing fibrous polyamide greige goods in the form of filaments, yarns, woven and knitted textiles for subsequent dyeing in patterns of light and 9 10 dark areas in said goods without altering the fiexibility, 2. A method as claimed in claim 1, wherein said liquid resilience, tensile strength after dyeing consisting essenmedium contains, in addition to said benzyl alcohol, a tially of: dye resist agent.
applying, at a temperature of 35100 C., to localized 3. Polyamide fibrous greige goods made by the method areas substantially less than the entire surface area of claim 2. of the polyamide greige goods from about 3% to References Cited about 9% of benzyl alcohol in a liquid medium inert UNITED STATES PATENTS to said polyannde whlch serves as a carrier for said benzyl alcohol, said liquid medium having a boiling 3,083,069 3/1963 fllrsbrurmer et point lower than 205 C. whereby said benzyl alcohol 10 2,365,931 12/1944 Bengel' 8-4301 impregnates the fibers in said localized areas thereby 2,480,775 8/1949 Ryanentrapping small amounts therein; 2,734,001 2/1956 Mechlenburgh et a1. removing the excess of benzyl alcohol which is present at the surface of the impregnated areas by washing; OTHER REFERENCES and 15 Review of Textile Progress, 1960, page 389, pub. 1962 thereafter heating said greige goods to a temperature of by Butterworth and Co., London, England. TS 1300 R4. approximately 100 C. for a period of time to com- Schmidlin: Preparation and Dyeing of Synthetic Fibers,
pletely evaporate the washing medium, said temperapages 33, 153-155 and 232-233, pub. by Chapman and ture being less than that which will alter the resilience Hall, Ltd., London, England. T515485 S34.
of the localized treated areas of said goods, whereby the entire mass of greige goods in benzyl alcohol DONALD LEVY, Primary Examiner treated and untreated areas has the same and uniform characteristics of flexibility, tensile strength and re- US. Cl. X.R.
siliency and the treated areas dye to a darker shade than the untreated areas. 25
US532096A 1966-03-07 1966-03-07 Patterned application of benzyl alcohol with or without a resist on nylon fabrics and dyeing the patterned fabric Expired - Lifetime US3467484A (en)

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US3653798A (en) * 1967-01-07 1972-04-04 Geigy Ag J R Process for the dyeings of blends of spandex fibers and polyamide fibers
US3860390A (en) * 1972-04-17 1975-01-14 Wolfgang Lindemann Dye composition of benzyl alcohol, phenyl glycol ether and octylphenyl pentaglycol ether
US3957434A (en) * 1974-12-16 1976-05-18 Ciba-Geigy Corporation Coloring synthetic fibers with diphenylcarbinol dyeing assistants
US3961881A (en) * 1973-08-21 1976-06-08 Imperial Chemical Industries Limited Coloration process
US3999940A (en) * 1975-01-02 1976-12-28 Congoleum Corporation Multicolored pile materials and processes for making the same
US4105403A (en) * 1976-05-07 1978-08-08 The United States Of America As Represented By The Secretary Of Agriculture Knitted cotton fabric durably patterned by differential shrinkage
US4172702A (en) * 1974-08-28 1979-10-30 Textron Inc. Method of producing dyed polymer-coated articles
US4229177A (en) * 1978-06-05 1980-10-21 Velsicol Chemical Corporation Dye compositions
US4238191A (en) * 1979-11-26 1980-12-09 Burlington Industries, Inc. Bulking of polycarbonamides: qiana
US4251582A (en) * 1974-08-28 1981-02-17 Textron Inc. Dyeable and dyed polymer-coated articles
US4308025A (en) * 1979-11-26 1981-12-29 Burlington Industries, Inc. Simultaneous bulking and dyeing process
US4500319A (en) * 1979-02-26 1985-02-19 Congoleum Corporation Textured pile fabrics
US4550579A (en) * 1984-04-13 1985-11-05 Frank Clifford G Apparatus for the dyeing of shaped articles
US4653295A (en) * 1984-04-13 1987-03-31 Frank Clifford G Apparatus for the dyeing of shaped articles
US4799935A (en) * 1987-04-21 1989-01-24 Burlington Industries, Inc. Method for dyeing in high-boiling nonionic solvents
US6117192A (en) * 1999-05-24 2000-09-12 Tatecraft Industries, Inc. Dye composition, dyeing apparatus and dyeing method
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US2480775A (en) * 1948-07-03 1949-08-30 Du Pont Dyeing nylon hosiery
US2734001A (en) * 1956-02-07 Setting and stiffening fabrics
US3083069A (en) * 1959-09-02 1963-03-26 Geigy Ag J R Process for the dyeing of polypeptide fibres

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US2734001A (en) * 1956-02-07 Setting and stiffening fabrics
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US2480775A (en) * 1948-07-03 1949-08-30 Du Pont Dyeing nylon hosiery
US3083069A (en) * 1959-09-02 1963-03-26 Geigy Ag J R Process for the dyeing of polypeptide fibres

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3653798A (en) * 1967-01-07 1972-04-04 Geigy Ag J R Process for the dyeings of blends of spandex fibers and polyamide fibers
US3860390A (en) * 1972-04-17 1975-01-14 Wolfgang Lindemann Dye composition of benzyl alcohol, phenyl glycol ether and octylphenyl pentaglycol ether
US3961881A (en) * 1973-08-21 1976-06-08 Imperial Chemical Industries Limited Coloration process
US4172702A (en) * 1974-08-28 1979-10-30 Textron Inc. Method of producing dyed polymer-coated articles
US4251582A (en) * 1974-08-28 1981-02-17 Textron Inc. Dyeable and dyed polymer-coated articles
US3957434A (en) * 1974-12-16 1976-05-18 Ciba-Geigy Corporation Coloring synthetic fibers with diphenylcarbinol dyeing assistants
US3999940A (en) * 1975-01-02 1976-12-28 Congoleum Corporation Multicolored pile materials and processes for making the same
US4105403A (en) * 1976-05-07 1978-08-08 The United States Of America As Represented By The Secretary Of Agriculture Knitted cotton fabric durably patterned by differential shrinkage
US4229177A (en) * 1978-06-05 1980-10-21 Velsicol Chemical Corporation Dye compositions
US4500319A (en) * 1979-02-26 1985-02-19 Congoleum Corporation Textured pile fabrics
US4238191A (en) * 1979-11-26 1980-12-09 Burlington Industries, Inc. Bulking of polycarbonamides: qiana
US4308025A (en) * 1979-11-26 1981-12-29 Burlington Industries, Inc. Simultaneous bulking and dyeing process
US4550579A (en) * 1984-04-13 1985-11-05 Frank Clifford G Apparatus for the dyeing of shaped articles
US4653295A (en) * 1984-04-13 1987-03-31 Frank Clifford G Apparatus for the dyeing of shaped articles
US4799935A (en) * 1987-04-21 1989-01-24 Burlington Industries, Inc. Method for dyeing in high-boiling nonionic solvents
US6117192A (en) * 1999-05-24 2000-09-12 Tatecraft Industries, Inc. Dye composition, dyeing apparatus and dyeing method
IT201700040825A1 (en) * 2017-04-12 2018-10-12 Biella Fancy Yarns S R L Process for preparing a textile material for a dyeing process

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CH319767A4 (en) 1971-10-15
DE1619120C3 (en) 1981-03-12
JPS5113796B1 (en) 1976-05-04
GB1141427A (en) 1969-01-29
CH518399A (en) 1971-10-15
DE1619120B2 (en) 1973-09-27
DE1619120A1 (en) 1970-11-05
BE694970A (en) 1967-09-04
NL6703503A (en) 1967-09-08
FR1513095A (en) 1968-02-09

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