Colorants in Nylon Fiber

This application claims the benefit of U.S. provisional application Ser. No. 63/567,889 filed Mar. 20, 2024, the disclosure of which is hereby incorporated in its entirety by reference herein.

The present disclosure relates to the use of colorants in nylon fiber.

Nylon is widely used across many fields. When coloring nylon resin for use in fiber applications, for example, the physical and chemical properties of pigment compositions may affect end use properties of the fiber such as mechanical properties, wash fastness, color fastness, and heat resistance.

In various aspects, a pigment composition is provided. The pigment composition may comprise a single pigment component comprising i) a cobalt titanium oxide complex or ii) a tin titanium zinc oxide complex; one or more additives having compatibilizer, adhesion promoting, and/or dispersion aiding capabilities; and a carrier resin.

In other aspects, a fiber is provided. The fiber may comprise a single pigment component comprising a i) cobalt titanium oxide complex or ii) a tin titanium zinc oxide complex; one or more additives having compatibilizer, adhesion promoting, and/or dispersion aiding capabilities; and a carrier resin.

Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present disclosure, which constitute the best modes of practicing the disclosure presently known to the disclosure. The Figures are not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the disclosure that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the disclosure and/or as a representative basis for teaching one skilled in the art to variously employ the present disclosure.

Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the disclosure. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: all R groups (e.g. Rwhere i is an integer) include hydrogen, alkyl, lower alkyl, Calkyl, Caryl, Cheteroaryl, alylaryl (e.g., Calkyl Caryl), —NO, —NH, —N(R′R″), —N(R′R″R′″)L, Cl, F, Br, —CF, —CCl, —CN, —SOH, —POH, —COOH, —COR′, —COR′, —CHO, —OH, —OR′, —OM, —SOM, —POM, —COOM, —CFH, —CFR′, —CFH, and —CFR′R″ where R′, R″ and R′″ are Calkyl or Caryl groups, Mis a metal ion, and Lis a negatively charged counter ion; R groups on adjacent carbon atoms can be combined as —OCHO—; single letters (e.g., “n” or “o”) are 1, 2, 3, 4, or 5; in the compounds disclosed herein a CH bond can be substituted with alkyl, lower alkyl, Calkyl, Caryl, Cheteroaryl, —NO, —NH, —N(R′R″), —N(R′R″R′″)L, Cl, F, Br, —CF, —CCl, —CN, —SOH, —POH, —COOH, —COR′, —COR′, —CHO, —OH, —OR′, —OM, —SOM, —POM, —COOM, —CFH, —CFR′, —CFH, and —CFR′R″ where R′, R″ and R′″ are Calkyl or Caryl groups, Mis a metal ion, and Lis a negatively charged counter ion; hydrogen atoms on adjacent carbon atoms can be substituted as —OCHO—; when a given chemical structure includes a substituent on a chemical moiety (e.g., on an aryl, alkyl, etc.) that substituent is imputed to a more general chemical structure encompassing the given structure; percent, “parts of,” and ratio values are by weight; the term “polymer” includes “oligomer,” “copolymer,” “terpolymer,” and the like; molecular weights provided for any polymers refers to weight average molecular weight unless otherwise indicated; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the disclosure implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.

It must also be noted that, as used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.

As used herein, the term “about” means that the amount or value in question may be the specific value designated or some other value in its neighborhood. Generally, the term “about” denoting a certain value is intended to denote a range within +/−5% of the value. As one example, the phrase “about 100” denotes a range of 100+/−5, i.e. the range from 95 to 105. Generally, when the term “about” is used, it can be expected that similar results or effects according to the disclosure can be obtained within a range of +/−5% of the indicated value.

As used herein, the term “and/or” means that either all or only one of the elements of said group may be present For example, “A and/or B” shall mean “only A, or only B, or both A and B”. In the case of “only A”, the term also covers the possibility that B is absent, i.e. “only A, but not B”

It is also to be understood that this disclosure is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present disclosure and is not intended to be limiting in any way.

The term “comprising” is synonymous with “including,” “having,” “containing,” or “characterized by.” These terms are inclusive and open-ended and do not exclude additional, unrecited elements or method steps.

The phrase “consisting of” excludes any element, step, or ingredient not specified in the claim. When this phrase appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

The phrase “consisting essentially of” limits the scope of a claim to the specified materials or steps, plus those that do not materially affect the basic and novel characteristic(s) of the claimed subject matter.

The phrase “composed of”' means “including” or “consisting of.” Typically, this phrase is used to denote that an object is formed from a material.

With respect to the terms “comprising,” “consisting of,” and “consisting essentially of,” where one of these three terms is used herein, the presently disclosed subject matter can include the use of either of the other two terms.

The term “one or more” means “at least one” and the term “at least one” means “one or more.” The terms “one or more” and “at least one” include “plurality” and “multiple” as a subset. In a refinement, “one or more” includes “two or more.”

The term “substantially,” “generally,” or “about” may be used herein to describe disclosed or claimed embodiments. The term “substantially” may modify a value or relative characteristic disclosed or claimed in the present disclosure. In such instances, “substantially” may signify that the value or relative characteristic it modifies is within ±0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or 10% of the value or relative characteristic.

It should also be appreciated that integer ranges explicitly include all intervening integers. For example, the integer range 1-10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Similarly, the range 1 to 100 includes 1, 2, 3, 4 . . . 97, 98, 99, 100. Similarly, when any range is called for, intervening numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be taken as alternative upper or lower limits. For example, if the range is 1.1. to 2.1 the following numbers 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 can be selected as lower or upper limits.

When referring to a numeral quantity, in a refinement, the term “less than” includes a lower non-included limit that is 5 percent of the number indicated after “less than.” For example, “less than 20” includes a lower non-included limit of 1 in a refinement. Therefore, this refinement of “less than 20” includes a range between 1 and 20. In another refinement, the term “less than” includes a lower non-included limit that is, in increasing order of preference, 20 percent, 10 percent, 5 percent, or 1 percent of the number indicated after “less than.”

In the examples set forth herein, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples. In a refinement, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples. In another refinement, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 10 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.

For all compounds expressed as an empirical chemical formula with a plurality of letters and numeric subscripts (e.g., CHO), values of the subscripts can be plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures. For example, if CHO is indicated, a compound of formula CHO. In a refinement, values of the subscripts can be plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures. In still another refinement, values of the subscripts can be plus or minus 20 percent of the values indicated rounded to or truncated to two significant figures.

Throughout this application, where publications are referenced, the disclosures of these publications in their entireties are hereby incorporated by reference into this application to more fully describe the state of the art to which this disclosure pertains.

The following examples illustrate the various embodiments of the present disclosure. Those skilled in the art will recognize many variations that are within the spirit of the present disclosure and scope of the claims.

Nylon is a family of synthetic polyamide thermoplastic fibers. Nylon was developed in the 1930's, with the first nylon, nylon 66, being synthesized in 1935 at a DuPont research facility. Initially, the majority of the nylon made was used to manufacture women's stockings. Nylon was later used in military applications, including rope, parachutes, airplane fuel tanks, and mosquito netting. Now, nylon is fairly ubiquitous, being found in clothing, sheets, tubes, pipes, bolts, screws, plastic fittings, plastic machine parts, circuit board hardware, and other applications.

Color masterbatches, also referred to as color concentrates, are used to color thermoplastic polymers such as nylon (polyamide). Color masterbatches often include pigments in the form of organic or inorganic particles that will confer a specific color to the polymers, and a carrier resin. The masterbatches also often include various additive ingredients designed to interact on a chemical level with the pigments and carrier resin to fine tune or enhance end use properties such as colorfastness, crocking, or heat resistance. The particular combination of pigments, carrier resin, and additives gives rise to distinct chemical and physical properties which in turn affect the chemical and physical properties of the sheets, tapes, films, parts, or fibers generated using the color masterbatch.

The present disclosure provides pigment compositions that may be color masterbatches for nylon. The pigment compositions may comprise a pigment, a carrier resin, and one or more additives. The additives may improve end use properties including but not limited to mechanical properties, washfastness, color fastness, and heat resistance. The pigment compositions may also be used as color masterbatches in other resins such as polyethylene resins, or polyethylene terephthalate.

The pigment compositions may include a single pigment component. The pigment may be organic or inorganic pigment. Organic pigments may be one pigment or a combination of pigments, such as for instance Pigment Yellow Numbers 12, 13, 14, 17, 74, 83, 114, 126, 127, 174, 188; Pigment Red Numbers 2, 22, 23, 48:1, 48:2, 52, 52:1, 53, 57:1, 112, 122, 166, 170, 184, 202, 266, 269; Pigment Orange Numbers 5, 16, 34, 36; Pigment Blue Numbers 15, 15:3, 15:4; Pigment Violet Numbers 3, 23, 27; and/or Pigment Green Number 7. Inorganic pigments may be one of the following non-limiting pigments: iron oxides, titanium dioxides, chromium oxides, ferric ammonium ferrocyanides, ferric oxide blacks, Pigment Black Number 7 and/or Pigment White Numbers 6 and 7. Other organic and inorganic pigments and dyes can also be employed, as well as combinations that achieve the colors desired.

Pigments that may be used in the pigment compositions may include but are not limited to pigments including cobalt titanium oxide, such as Sicopal® Turquoise K 8215 FK (PG 50) provided by SunChemical of Parsippany, New Jersey, or tin titanium zinc oxide, such as Sicopal® Orange K 2430 (PO 82) also from SunChemical. In various embodiments, the pigments may be included in the pigment compositions in an amount from about 15 to about 40, or from about 20 to about 30, or about 25 weight percent, based on the total weight of the pigment composition. In other embodiments, the pigments may be included in pigment compositions in an amount from 1 to about 40 weight percent based on the total weight of the pigment composition. Some pigments may not be used in the pigment compositions. For example, pigments including dioxazine, such as Cromophtal® Violet K 5700 provided by SunChemical may not be used in the pigment compositions. Such pigments may not provide the heat stability required for desired applications. Additionally, pigments including anthraquinone such as solvent red 52 provided by SunChemical may not produce the desired level of colorfastness, weathering, or heat stability for example.

Carrier resins that may be used in the pigment compositions may include polyamide resins such as nylon resins. Polyethylene and polyethylene terephthalate (PET) may also be used. Examples of nylon resins that may be used in the pigment compositions include but are not limited to Nylon 6 for fiber applications. The nylon resins may have a higher relative viscosity (RV). For example, the nylon resins may have an RV of from about 2.5 to 3.0, or about 2.7 for fiber applications, and an RV of about 3.5-4.0 for film applications. In various embodiments, the carrier resin may be included in the pigment compositions in an amount from about 40 to about 75, or from about 45-70, or from about 50-60 weight percent, based on the total weight of the pigment composition. The carrier resin may be added as two separate components. For example, carrier resin in the form of pellets may be added in an amount of from about 40 to about 75, or from about 45-70, or from about 50-60 weight percent, based on the total weight of the pigment composition. In other embodiments, carrier resin in the form of pellets may be added in an amount from about 40 to 99 weight percent based on the total weight of the pigment composition. Carrier resin may also be crushed and added in powder form, or if available in flake form, and may be added directly in powder or flake form in an amount from about 7 to 12, or 9 to 11, or 10 weight percent, based on the total weight of the pigment composition.

In addition to the pigments and carrier resins, the pigment compositions may also include additives that may fine tune or enhance end use properties such as colorfastness, crocking, or heat resistance for example. The additives that may be included with the pigments may include:

Antioxidants: Antioxidants used in the pigment compositions may be hindered phenolic antioxidants. The antioxidants may be N, N′-bis(3-(3,5-ditertbutyl-4-hydroxphenyl or Tris-(2,4-di-tert-butyl-phenyl)-phosphite or a blend of both, for example, such as Irganox® B 1171 provided by BASF which is a blend of BX AO 1098 (N, N′-bis(3-(3,5-ditertbutyl-4-hydroxphenyl) propionyl)hexanediamine) and BX AO 168 (Tris-(2,4-di-tert-butyl-phenyl)-phosphite), CAS NUMBER (BX AO 1098) 23128-74-7; CAS NUMBER (BX AO 168) 31570-04-4. (BASF). Both a primary and a secondary antioxidant may be used in the pigment compositions. Hindered phenolic antioxidants may be used as primary antioxidants for example, and organo-phosphite antioxidants may be used as secondary antioxidants. Tris (2,4-di-tert-butylphenyl) phosphite such as that provided in RIANOX 168 from Rianlon of Tianjin, China may be used as a secondary antioxidant for example. Primary antioxidants may be included in the pigment compositions in an amount from 0.05 to 0.15 or from 0.075 to 0.125, or about 0.1 weight percent, based on the total weight of the pigment composition. The primary and secondary antioxidants may be used together and/or individually.

Components having compatibilizer or adhesion promoting capabilities may also be used in the pigment compositions. Compatibilizer/adhesion promoters may be low density polyethylene homopolymers for example such as AC®6A from Honeywell of Morris Plains, New Jersey. Compatibilizer/adhesion promoters may additionally be an ethylene maleic anhydride copolymer such as AC®573 or AC®573A from Honeywell of Morris Plains, New Jersey. Compatibilizer/adhesion promoters may be included in the pigment compositions in an amount from about 2 to 6, or 2.5 to 5.5, or 3 to 5 weight percent, based on the total weight of the pigment composition. The compatibilizer/adhesion promoters may additionally have dispersion aiding capabilities. The compatibilizer/adhesion promoters may be provided in powder form.

Dispersion aids: Dispersion aids may be used in the pigment compositions to improve stability and dispersion. Examples of dispersion aids that may be used in the pigment compositions include Solsperse™ 21000. Dispersion aids may be included in the pigment compositions in an amount from about 1 to 4, or about 1.5 to 3.5, or about 2 to 3 weight percent, based on the total weight of the pigment composition.

The pigment compositions may be masterbatch compositions. When added to a clear base resin at a letdown ratio of from about 2 to 10 weight percent, with the final pigment amount in the end product being about 0.5 weight percent. The pigment compositions may improve end properties of fibers including colorfastness, weathering, washfastness, and heat stability in nylon fibers. End use properties may be measured using the tests described in the Examples below. Desirable end use properties may be as follows: DE less than or equal to 2.00 in weathering at 200 hours; gray scale 4.00 or above for Rotowash 2A Test Cycle; gray scale 4.00 or above for wet & dry crock; and gray scale 4.00 or above for heat stability in Nylon.

The pigment compositions according to various embodiments may expand the color space beyond what traditional colorants choices may achieve. The pigment compositions according to various embodiments may produce sustainable solutions for the fiber market. The pigment compositions may be used with a variety of non-limiting indoor and outdoor textile applications including fine denier apparel, upholstery, artificial turf, outdoor woven fabrics including boat covers, chairs, umbrellas, and other similar fabrics, and carpet and rugs. The pigment compositions according to various embodiments may provide benefits including a wider color space, high strength, high chroma, color consistency, lot-to-lot control, improved color fastness, and improved physicals.

illustrate examples of fibers manufactured using the pigment compositions according to various embodiments.illustrates an example of a turquoise fiber.illustrates an example of an orange fiber. The pigment compositions used to manufacture the illustrated fibers may be used in Nylon and PET applications. The illustrated fibers may be used in all indoor & outdoor textiles including fine denier apparel, carpet, artificial turf, woven fabrics, and/or upholstery.illustrates an example of a yellow fiber manufactured using the pigment compositions according to an embodiment. The illustrated fiber may be used in Nylon applications. The illustrated fiber may be used in all indoor textiles including fine denier apparel, upholstery, and/or carpet.illustrates an example of a black fiber manufactured using the pigment compositions according to an embodiment. The illustrated fiber may be used in Nylon applications. The illustrated fiber may be used in indoor textiles.illustrates an example of a black fiber manufactured using the pigment compositions according to an embodiment. The illustrated fiber may be used in PET applications. The illustrated fiber may be used in indoor and/or outdoor textiles.illustrate examples of fibers manufactured using the pigment compositions according to various embodiments.illustrates an example of a red fiber.illustrate examples of two different orange fibers. The illustrated fibers may be used in Nylon applications. The illustrated fibers may be used in indoor textiles.

The test methods for Color, physical, weathering, crocking and washing are as follows:

CMC Lab, 10° observer, D65 Illuminant Da, Db, DL, DE color data along with gray scale is recorded from a Datacolor 1050 Spectrophotometer.

The purpose of this test is to determine the colorfastness to light of textile materials. Equipment used for testing is an Atlas Xenotest 440 Xenon-Arc Accelerated weathering per AATCC 16E. Textile filament specimens are wound onto specimen holders and placed in the Xenon-Arc machine for the specified amount of exposure time (200 hrs., 250 hrs., 400 hrs., 500 hrs., 750 hrs., and 1000 hrs.). Specimens are removed at designated exposure times and then tested for physical property retention using a Tensile Testing Machine. Textile filament specimens that have not been exposed (0 hrs.) in the Xenon-Arc are tested using a Tensile Testing Machine and used as standards for retention of physical property calculations.

The purpose of this test is to determine the degree of color transfer from the surface of textile floor coverings to other surfaces by rubbing. Both gray scale for color change, and gray scale for staining are measured. Equipment used for testing include Taber 5750 Line Abraser, color spectrophotometer, test specimen and test cloth.

A colored fabric sock Fiber line: Filteco JOB438/1 or Sock Knitter: Lawson Hemphill FAK/S is secured in place, while an unexposed white test cloth is attached to the clear test cylinder of the linear abrasion tester. The number of cycles the clear test cylinder with test cloth will rub the fabric sock is set to 60 cycles per minute for a total of 10 cycles. Once the testing cycles are complete, the test cloth is read using the spectrophotometer. An unexposed white test cloth is used as standard. Color data for gray scale for color change, and gray scale for staining is recorded from the spectrophotometer. The same procedure is used for wet crocking. The only difference is a wet test cloth (wet with water) is used instead of a dry test cloth and the rubbed cloth specimen is allowed to dry before spectrophotometer measurement.

This is a test for accelerated laundering. The purpose of this test method is to evaluate colorfastness to laundering of textiles which are expected to withstand frequent laundering. Equipment used for testing include SDLAtlas Rotawash, an accelerated laundering machine equipped with stainless steel rotating (38-42 rpm) closed canisters in a thermostatically controlled water bath, stainless steel balls, AATCC standard reference detergent, distilled or deionized water, color spectrophotometer, and test specimens.

A non-washed colored fabric specimen is read on the spectrophotometer as standard. This same fabric specimen is placed in the stainless-steel canister along with the specified amount of AATCC standard reference detergent, deionized water, and steel balls. The stainless steel canisters are placed inside the accelerated laundering machine, where the water is already at the specified temperature. The test is started and runs for approximately 45 minutes for 2A and 3A test methods. The fabric sample is removed from the stainless steel canister and hung to dry. The fabric specimen is then read on the spectrophotometer using the original reading as standard.

Chips are molded in a temperature range of 500-600° F., at 1, 5, & 15 minutes for each temperature. Overall color change (DE) and gray scale for color change are measured on those chips. The chips are formulated with 1% final organic pigment or 2% final inorganic pigment; 5% final TiO2 pigment; and Resin PA 6/6.

For the weathering, rotowash, and crocking tests, the compositions were first made into masterbatches and subsequently made into fibers using the following processes:

Desired results were: DE less than or equal to 2.00 in weathering at 200 hours; gray scale 4.00 or above for Rotowash 2A Test Cycle; gray scale 4.00 or above for wet & dry crock; and gray scale 4.00 or above for heat stability in Nylon.