This application claims the benefit of priority to U.S. Patent Application No. 62/890,253 filed August 22, 2019, the disclosure of which is hereby incorporated by reference in its entirety.

FIELD

The present disclosure generally relates to polyester or nylon fiber compositions, masterbatches for producing such fibers, articles produced from such fibers, and methods of preparing such masterbatches, fibers, and articles, wherein the fibers and articles have a delustered appearance, even when little to no titanium dioxide is present in the fiber composition.

BACKGROUND

In some applications, it is desirable for fiber materials, such as fibers utilized to produce clothing, carpeting, furniture, and other technical and industrial textiles, to exhibit a low degree of luster. In general, luster can be reduced through the use of delustering agents that scatter light. One of the most common fiber delustering agents is titanium dioxide (T1O2), an inorganic mineral- based pigment available in anatase and rutile grades. Anatase T1O2 has a softer crystal structure than rutile T1O2, and is therefore less abrasive than rutile. However, both grades of T1O2 are considered undesirably abrasive in fiber fabrication processing. The anatase form is almost exclusively used over the rutile form in fiber and textile applications because of its lesser abrasiveness, even though rutile T1O2 tends to provide fiber with a more desirable blue shade appearance than is typically achieved through the use of the anatase form.

Blue shades, and color in general, can be described mathematically. For example, the CIELAB L*, a*, b* color space mathematically describes all perceivable colors in three dimensions: L* for lightness, a* for green -red, and b* for blue-yellow. See Hunter Lab, Applications Note, “Insight on Color,” Vol. 8, No. 7 (2008). In the CIELAB color space, the L* axis runs from top to bottom. The maximum L* value is 100, which indicates a perfect reflecting diffuser (i.e., the lightest white). The minimum L* value is 0, which indicates a perfect absorber (i.e., the darkest black). Positive a* is red. Negative a* is green. Positive b* is yellow. Negative b* is blue. CIELAB a* or b* values equal to 0 indicate no red-green or blue-yellow color appearance, in which case the article would appear pure white. In contrast, a* or b* values that deviate far from 0 indicate that light is non-uniformly absorbed or reflected. As a* or b* values deviate from 0, the color may no longer appear as bright white. One of the most important attributes of the CIELAB model is device independence, which means that the colors are defined independent of their nature of creation or the device they are displayed on.

The L*, a*, and b* values of the CIELAB color scale can be obtained using any CIELAB color measurement instrument and are calculated from known formulas. See Hunter Lab, Applications Note, “Insight on Color,” Vol. 8, No. 7 (2008). With the b* value, the CIELAB model permits the quantification of how blue a product is; with the L* value, the CIELAB model permits the quantification of how light a product is. Lightness is typically achieved by adding highly reflective and minimally absorbing components, such as TiCh.

Because TiCL-containing fiber compositions are generally abrasive, they are detrimental to the equipment used in fiber production processes, including polyester and nylon spinning processes such as partially oriented yam (POY), fully drawn yarn (FDY), bulk continuous filament (BCF), Drawn Texturized Yarn (DTY), and staple fiber production processes. Such compositions abrade the equipment as the TiCh-containing fiber composition comes into contact with various equipment surfaces (e.g., metal and ceramic surfaces) as well as other fibers. Accordingly, abrasion and wear caused by T1O2 can cause significant problems in both the manufacturing process and the finished goods.

For example, in the manufacturing of yam fibers, processes such as high speed melt spinning and texturizing cause fibers to pass through metal godets, ceramic guides and rollers, deleteriously abrading such equipment components in the process. TiCh-containing polyester or nylon compositions tend to abrade processing equipment more rapidly than virgin polyester or nylon compositions that do not contain TiCh. Similarly, there is a correlation between T1O2 loading and equipment abrasion whereby fibers with higher T1O2 content correspond to a higher rate of abrasion over time. Manufacturing abrasive yarn fibers can thus require frequent replacement of machine parts, such as needles and yarn guides, which increases spare part consumption as well as manufacturing costs.

Subsequent textile manufacturing processes, such as knitting, weaving, and tufting, can also suffer from abrasiveness caused by T1O2 because, in addition to TiCh-containing fibers contacting the equipment (e.g., metal needles employed during knitting), the fibers also contact each other (e.g., in the warp and weft direction during weaving), causing further unwanted wear and abrasion. To help improve wear resistance of clothing fabrics, finishings and coatings have been applied, but such additional processing requires added material and increased manufacturing costs.

Furthermore, disadvantages of TiC extend beyond abrasiveness. For instance, in polyester fibers, mineral fillers such as TiC in polyester fibers can lead to degradation of the polyester that can change processing characteristics and negatively impact physical properties, causing yellowness and/or reduced tensile strength. Mineral filler particles can also agglomerate and cause stress concentration points, leading to a loss of structural integrity, and causing filtration buildup that creates problems in recycling processes. Mineral fillers also add weight and increase density, which in turn increases cost. Further, TiCh has specifically come under scrutiny with respect to its potential carcinogenicity. Manufacturing fibers using a masterbatch that includes mineral filler may also result in uneven distribution of the mineral filler, causing an inconsistent color appearance. Further, mineral fillers are prone to release degradation components, such as ethylacrolein and other non-intentionally added substances (NIAS), and can also can have an adverse impact on weathering characteristics of the article.

Thus, there is a need for improved fiber compositions for forming articles with a delustered appearance that is achieved with little to no T1O2, and/or reduction or elimination of one or more of the above disadvantages (e.g., abrasiveness) associated with mineral fillers such as T1O2,. There is also a need for improved delustered fiber compositions and articles having an improved blue- shade white appearance.

SUMMARY

In one aspect, the disclosed technology relates to an oriented, delustered fiber composition, including, based on the total weight of the composition: about 92.0 wt% to about 99.99 wt% matrix polymer; about 0.01 wt% to about 3.0 wt% incompatible polymer; and 0 wt% to about 5.0 wt% light scattering pigment; wherein the fiber composition is oriented and has a visual luster that is less than or equal to a visual luster of a comparable oriented fiber composition, wherein the comparable oriented fiber composition contains more titanium dioxide (T1O2) than the fiber composition and contains the same matrix polymer as the fiber composition in an amount that is within 5 wt% of the amount in the fiber composition. In some embodiments, the comparable oriented fiber composition contains no incompatible polymer. In some embodiments, the fiber composition has an L* value that is greater than or equal to an L* value of the comparable oriented fiber composition.

In some embodiments, the matrix polymer includes polyethylene terephthalate (PET). In some embodiments, the matrix polymer includes nylon. In some embodiments, the incompatible polymer includes polymethylpentene (PMP). In some embodiments, the incompatible polymer includes COC. In some embodiments, the incompatible polymer includes a hydrogenated styrenic polymer. In some embodiments, the light scattering pigment is present and is selected from anatase titanium dioxide, zinc sulfide, and rutile titanium dioxide. In some embodiments, the light scattering pigment is present and is anatase TiCh. In some embodiments, the composition does not contain TiCk. In some embodiments, the composition further includes an additive or colorant.

In some embodiments, the composition further includes an additive selected from anti block agents, anti -oxidants, anti-statics, slip agents, chain extenders, cross linking agents, flame retardants, IV reducers, laser marking additives, mold releasers, optical brighteners, flow aids, plasticizers, nucleating agents, oxygen scavengers, anti-microbials, UV stabilizers, acetaldehyde scavengers, coupling agents, compatibilizers, non-mineral fillers, mineral fillers other than TiCk, stain repellants, lubricants, and combinations thereof. In some embodiments, the additive is selected from anti -oxidants, anti-statics, chain extenders, flame retardants, optical brighteners, anti-microbials, UV stabilizers, stain repellants, and combinations thereof. In some embodiments, the composition further includes a colorant selected from dyes, organic pigments, inorganic pigments, effect pigments, and combinations thereof.

In some embodiments, the composition has a lower CIELAB b* value than the comparable oriented fiber composition. In some embodiments, the composition is less abrasive than the comparable oriented fiber composition. In some embodiments, the oriented fiber composition is texturized.

In another aspect, the disclosed technology relates to an article including any of the fiber compositions disclosed herein. In some embodiments, the article is a garment or floor covering.

In another aspect, the disclosed technology relates to a masterbatch composition for use in combination with polyester or nylon to manufacture an oriented, delustered fiber composition, wherein the masterbatch composition includes incompatible polymer and light scattering pigment. In some embodiments, the masterbatch composition includes 5 wt% to 100 wt% incompatible polymer, and 0 wt% to 70 wt% light scattering pigment, based on the total weight of the masterbatch composition. In some embodiments, the masterbatch composition includes 30 wt% to 70 wt% incompatible polymer, and includes 70% to 30% light scattering pigment, based on the total weight of the masterbatch composition. In some embodiments, the masterbatch composition further includes an additive or colorant. In some embodiments, the masterbatch composition further includes an additive selected from anti-block agents, anti -oxidants, anti-statics, slip agents, chain extenders, cross linking agents, flame retardants, IV reducers, laser marking additives, mold releasers, optical brighteners, flow aids, plasticizers, nucleating agents, oxygen scavengers, anti microbials, UV stabilizers, acetaldehyde scavengers, coupling agents, compatibilizers, non mineral fillers, mineral fillers other than TiCk, stain repellants, lubricants, and combinations thereof. In some embodiments, the masterbatch composition further includes a colorant selected from dyes, organic pigments, inorganic pigments, effect pigments, and combinations thereof.

In another aspect, the disclosed technology relates to a method of manufacturing an oriented, delustered article, including subjecting any of the fiber compositions disclosed herein to a fiber spinning process to form an article.

DETAILED DESCRIPTION

The present disclosure relates delustered fiber compositions containing little to no T1O2, articles (finished goods) produced from such delustered fiber compositions, masterbatches for producing such fiber compositions, and manufacturing methods thereof.

The following discussion includes various embodiments that do not limit the scope of the appended claims. Any examples set forth herein are intended to be non-limiting and merely illustrate some of the many possible embodiments of the disclosure. Further, particular features described herein can be used in combination with other described features in each of the various possible combinations and permutations. Unless otherwise specifically defined herein, all terms are to be given their broadest reasonable interpretation including meanings implied from the specification as well as meanings understood by those skilled in the art and/or as defined in dictionaries, treatises, etc. It must also be noted that, as used in the specification and claims, the singular forms "a," "an," and "the" include plural referents unless otherwise specified, and that the terms "includes" and/or "including," when used in this specification, specify the presence of stated features, steps, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, elements, components, and/or combinations thereof. As used herein, the term “deluster” means to reduce, subdue or dull the natural luster of a material. Delustering can be achieved through chemical and/or physical processing. Delustering improves soil-hiding characteristics, as it limits the soil magnification that would occur with clear or shiny fiber. Delustered fibers may include, for example, synthetic fibers containing polymer additives and/or having cross-sectional design modifications that limit the natural brightness or reflectivity of the fibers.

The disclosed articles are made from delustered, oriented, optionally texturized fiber compositions containing at least one matrix polymer and at least one incompatible polymer. In general, the incompatible polymer is a minor component that is added to the matrix polymer, which makes up the majority of the fiber composition. Optionally, the delustered fiber compositions may also include at least one light scattering pigment. The fiber compositions are subjected to orientation stress to become delustered and suitable for use in a process for fabricating an article. For example, the fiber composition may be a yam that has been subjected to orientation stress to become suitable for knitting or weaving to produce clothing or other textiles having a delustered appearance. In some embodiments, the fiber composition is both oriented and texturized.

The disclosed fiber compositions and/or articles have reduced luster. In some embodiments, the fiber compositions and/or articles also have a blue-shade white appearance. In some embodiments, the fiber compositions also have reduced abrasiveness.

Matrix Polymer

The disclosed fiber compositions include a matrix polymer, which may be any grade of polyester or nylon suitable for fiber spinning. Non-limiting examples of suitable polyesters include: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid (PLA), poly trimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene furanoate (PEF), polycyclohexylene dimethylene terephthalate (PCT), sulfonated polyesters, polycaprolactone (PCL), polyhydroxyalkanoate (PHA), copolymers of any of the foregoing, and combinations thereof. Non-limiting examples of suitable nylons (polyamides) include: polycaprolactam (PA6 or nylon 6), nylon 6/6 (PA6/6), nylon 5/10 (PA5/10), nylon 1/6 (PA1/6), nylon 4/6 (PA4/6), nylon 10 (PA10), nylon 4/10 (PA4/10), nylon 6/10 (PA6/10), nylon 11 (PA11), nylon 12 (PA12), nylon 6/12 (PA6/12), copolymers of any of the foregoing, and combinations thereof. The matrix polymer comprises the majority of the fiber composition. In some embodiments, the composition includes matrix polymer in an amount of about 97.0 wt% to about 99.99 wt%, about 98.0 wt% to about 99.99 wt%, about 99.0 wt% to about 99.99 wt%, about 97.0 wt% to about 99.7 wt%, about 98.0 wt% to about 99.7 wt%, about 99.0 wt% to about 99.7 wt%, about 97.0 wt% to about 99.5 wt%, about 98.0 wt% to about 99.5 wt%, or about 99.0 wt% to about 99.5 wt%, based on the total weight of the composition.

Incompatible Polymer

The disclosed fiber compositions include an incompatible polymer that is immiscible with the matrix polymer. In general, the incompatible polymer is added into the matrix polymer. In some embodiments, the incompatible polymer is added to the matrix polymer by pellet mixing or matsterbatch.

Non-limiting examples of suitable incompatible polymers include: polymethylpentene (PMP), cyclic olefin copolymers, cyclic olefin polymers, partially or fully hydrogenated styrenic polymers (e.g., hydrogenated polystyrene), polydimethylsiloxane, polypropylene, polyethylene, polyethersulfone, and combinations thereof. As used herein, the term “COC” refers to both cyclic olefin copolymers and cyclic olefin polymers. Cyclic olefin copolymers include, but are not limited to, copolymers of ethylene and norbornene or ethylene and tetracyclodecene. For example, some COC are commercially available from Polyplastics as TOPAS® (COC), Zeonex as ZEONOR® (COC), and Mitsui as APEL™ (COC). The grades available from Zeonex are referred to as cyclic olefin polymers due to the difference in polymerization and a subsequent hydrogenation process.

The incompatible polymer comprises the minority of the fiber composition. In some embodiments, the composition includes incompatible polymer in an amount of about 0.01 wt% to about 3.0 wt%, about 0.1 wt% to about 3.0 wt%, about 0.5 wt% to about 3.0 wt%, about 1.0 wt% to about 3.0 wt%, about 1.5 wt% to about 3.0 wt%, about 2.0 wt% to about 3.0 wt%, about 2.5 wt% to about 3.0 wt%, 0.01 wt% to about 2.0 wt%, about 0.1 wt% to about 2.0 wt%, about 0.5 wt% to about 2.0 wt%, about 1.0 wt% to about 2.0 wt%, or about 1.5 wt% to about 2.0 wt%, based on the total weight of the composition. Producing articles with a relatively low amount of incompatible polymer can lead to density reduction of the article, advantageously lowering the overall weight and cost of the article. Light Scattering Pigment

As used herein, a “light scattering pigment” refers to a delustering agent that scatters and/or absorbs light to reduce or eliminate light transmitted through or reflected out of the fiber or the article made therefrom. In some embodiments, when a light scattering pigment is present in the fiber composition, the light scattering pigment may be combined with other pigments and/or dyes that are incorporated into the fiber composition during fiber production (e.g., in a masterbatch or during a melt spinning process).

Non-limiting examples of suitable light scattering pigments include: titanium dioxide (anatase or rutile grade) (e.g., PW 6), zinc sulfide (e.g., PW 7), barium sulfate (e.g., PW 21), iron oxide pigments such as red iron oxide (e.g., PR 101), black iron oxide (e.g., PBLK 11), chromium green-black hematite (e.g., PG 17), chrome green oxide (e.g., PG 17), carbon black (e.g., PBLK 7), complex inorganic colored pigments such as titanium buff rutile brown (e.g., PBR 24), nickel antimony (e.g., PY 53), zinc ferrite (e.g., PY 119, PBR 11, PBR 33), chromium tungsten titanium buff rutile (e.g., PY 163), manganese antimony titanium buff rutile (e.g., PY 164), bismuth vanadate (e.g., PY 184), organic reds such as quinacridone red (e.g., PV 19, PR 122), perylene red (e.g., pr 178, pr 179), red diketo-pyrrolo-pyrol (e.g., PR 254), disazo red (e.g., PR 144, PR 214), phthalocyanine pigments (e.g., PB 15:1, PB 15:3, PG 7), cobalt pigments (e.g., PB 36, PB 28), organic yellow pigments (e.g., PY 147, PY 150, PY 155), and effect pigments such as aluminum pigments (e.g., Pigment Metal 1).

In some embodiments, the fiber composition contains little to no light scattering pigment. For example, the fiber composition may contain a light scattering pigment (e.g., TiCk) in an amount of about 4 wt% or less, about 3 wt% or less, about 2 wt% or less, about 1.5 wt% or less, about 1 wt% or less, about 0.5 wt% or less, or 0 wt%, based on the total weight of the composition.

Additional Components

One or more additional components (e.g., additives, colorants) may optionally be included in the disclosed fiber compositions.

Non-limiting examples of suitable additives include anti-block agents (e.g., silica), anti oxidants (e.g., primary phenolic anti-oxidant IRGANOX® 1010), anti-statics (e.g., glycerol monostearate), slip agents (e.g., erucamide), chain extenders (e.g., carbonyl biscaprolactam), cross linking agents (e.g., pyromellitic dianhydride), flame retardants (e.g., alumina trihydrate), IV reducers (e.g., AMP-95™), laser marking additives (e.g., IRIOTEC® 8835), mold releasers (e.g., calcium stearate), optical brighteners (e.g., Optical Brightener OB-1), flow aids (e.g., DAIKIN PPA DA-310ST), plasticizers (e.g., polyester copolymers), nucleating agents (e.g., talc), oxygen scavengers (e.g., OXYCLEAR®), anti-microbials (e.g., triclosan), UV stabilizers (e.g., TINUVIN 234), acetaldehyde scavengers (e.g., anthranilamide), coupling agents (e.g., OREVAC® 18507), compatibilizers (e.g., OREVAC® CA 100), non-mineral fillers such as cross linked silicone (e.g., TOSPEARL 1110A), cross linked polystyrene (TECHPOLYMER SBX-8) or cross linked PMMA (GANZPEARL GMX-0610), mineral fillers (other than TiCb), stain repellants, lubricants, and combinations thereof.

Non-limiting examples of suitable colorants include: dyes (e.g., solvent red 135), organic pigments (pigment blue 15:1), inorganic pigments (e.g., iron oxide pigment red 101), effect pigments (e.g., aluminum flake), and combinations thereof. The Colour Index system is an internationally recognized colorant classification system. The prime descriptor most commonly used by colorant users is the Colour Index Generic Name (CIGN), which describes a commercial product by its recognized usage class, its hue, and a serial number that reflects the chronological order in which related colorant types have been registered with the Colour Index - e.g., Cl Acid Blue 52 (AB 52), Cl Direct Red 122 (DR 122), Cl Pigment Yellow 176 (PY 176), Cl Solvent Black 34 (SBlk 34), Cl solvent red 135 (SR 135), solvent red 195 (SR 195), solvent yellow 114 (SY 114), solvent yellow 93 (SY 93), solvent yellow 179 (SY 179), disperse yellow 241 (DY 241), solvent yellow 133 (SY 133), solvent blue 104 (SB 104), solvent green 3 (SG 3), solvent violet 13 (SV 13), solvent orange 60 (SO 60), disperse orange 47 (DO 47), disperse violet 26 (DV 26), and the like, all of which may be used in manufacturing delustered fiber compositions and articles disclosed herein. In some embodiments, the fiber composition includes a plurality of colorants.

Masterbatch Compositions, Fiber Compositions, and Articles

As used herein, the term “masterbatch” or “masterbatch composition” refers to a concentrate for use in combination with a matrix polymer to manufacture an oriented, delustered fiber composition disclosed herein. In general, the masterbatch includes an incompatible polymer and, optionally, a light scattering pigment. The amount of incompatible polymer in the masterbatch may be in the range of about 5 wt% to about 100 wt%, about 20 wt% to about 90 wt%, about 30 wt% to about 80 wt%, about 50 wt% to about 80 wt%, about 30 wt% to about 70 wt%, or about 50 wt% to about 70 wt%, based on the total weight of the masterbatch. The amount of light scattering pigment in the masterbatch may be in the range of 0 wt% to about 80 wt%, such as about 5 wt% to about 60 wt%, about 10 wt% to about 40 wt%, or about 30 wt% to about 70 wt%, based on the total weight of the masterbatch. In some embodiments, the masterbatch further includes one or more additives and/or colorants as disclosed herein.

As used herein, the term “fiber composition” (or “composition” when used in reference to a fiber) refers to a delustered, oriented fiber material comprising at least one matrix polymer and at least one incompatible polymer, and little to no titanium dioxide, as discussed above. Optionally, the fiber composition may be texturized. Non-limiting examples of fiber compositions include partially oriented yam (POY), fully drawn yarn (FDY), other types of yarn, bulk continuous filament (BCF), Drawn Texturized Yam (DTY), and staple fiber.

As used herein, the term "article" refers to a finished good made from a fiber composition disclosed herein. Non-limiting examples of articles include: textiles, garments, fabrics (e.g., knits, wovens, non-wovens), yarns, floor coverings (e.g., carpeting, mgs), linens, draperies, curtains, upholsteries, non-textiles, and the like. In some embodiments, an article is a finished good in which a disclosed fiber composition is present in only a portion of the finished good - e.g., a shirt having sections made from different materials to satisfy varying requirements for performance and consumer comfort. Accordingly, weight percentages of components included in the disclosed fiber compositions are described as being based on the total weight of the composition (i.e., the fiber material), which is the same as being based on the total weight of the portion of the article in which the fiber composition is present, rather than being based on the total weight of the whole article (unless, of course, the whole article is formed of a disclosed fiber composition).

In some embodiments, the disclosed articles are made from fiber compositions having an advantageously lighter weight and reduced density. For example, in one embodiment, the disclosed fiber composition includes a matrix polymer of PET, which has a density of 1.38 g/cm ³ , and an incompatible polymer of PMP, which has a density of 0.833 g/cm ³ . By combining PMP with PET, the final density of the polymer blend is reduced as compared to a fiber composition that does not contain incompatible polymer, thereby reducing the density of the composition and articles made therefrom. Reduced Luster

Luster can be measured by visual means using a scale of 1-5. According to this visual assessment, a fiber composition (or an article made therefrom) exhibiting a high visual luster would be assigned a value of 5 (bright), and a fiber composition (or an article made therefrom) exhibiting a low visual luster would be assigned a value of 1 (dull). Gradations of intermediate luster would be assigned a value of 2, 3, or 4. This type of measurement is referred to herein as “visual luster.”

In some embodiments, the disclosed fiber compositions and articles made therefrom, have a visual luster that is less than or equal to the visual luster of a comparable fiber containing more TiC>2 (e.g., 20-50% more TiC ). For example, in some embodiments, a disclosed fiber composition containing 1.0 wt% TiC will have the same or less visual luster as compared to a comparable fiber containing 1.2 wt% - 1.5 wt% TiC . A comparable fiber may be a fiber having the same matrix polymer in an amount that is within 5 wt% of the amount in the disclosed composition, but having more (e.g., 20-50% more) T1O2 than the disclosed composition. Alternatively, a comparable fiber may be a fiber having the same matrix polymer in an amount that is within 5 wt% of the amount in the disclosed composition, but having more (e.g., 20-50% more) T1O2 than the disclosed composition and no incompatible polymer.

In some embodiments, “an amount that is within 5 wt%” is an amount that is within 0.5 wt%, within 1 wt%, within 2 wt%, within 3 wt%, within 4 wt%, or within 5 wt%. The amount of matrix polymer in the comparable fiber may be more than or less than the amount of matrix polymer in the disclosed fiber composition.

Luster can also be measured by preparing a woven, knitted or card winding sample of an oriented, delustered fiber, and then measuring gloss with a multi-angle gloss meter, such as the BYK gloss meter micro-TRI-gloss, using one or more incident angles of 20, 45, 60, and/or 85 degrees in accordance with the method of ASTM D523 or ASTM D2457.

In some embodiments, the disclosed fiber compositions and articles made therefrom, have a gloss (measured at 60 degrees) that is less than or equal to the gloss of a comparable fiber containing more T1O2 (e.g., 20-50% more T1O2). For example, in some embodiments, a disclosed fiber composition containing 1.0 wt% T1O2 will have the same or less luster (degree of gloss) as compared to a comparable fiber containing 1.2 wt% - 1.5 wt% TiCh. A comparable fiber may be as described above. Luster can also be measured by using a handheld x-ray fluorescence analyzer, such as an X-MET8000 manufactured by Hitachi High-Tech Global. This device works by measuring the level of titanium in the fiber, and then assumes the fiber has achieved a certain level of luster based on the content of titanium and assuming that all titanium is in the form of TiCL. For example, a fiber composition containing 0-0.1 wt% T1O2 is presumed to be bright or lustrous, a fiber composition containing 0.35-0.50 wt% T1O2 is presumed to be semi-dull, and a fiber composition containing higher amounts of T1O2 (1.0 wt% or more) is presumed to be dull or fully delustered.

Blue-Shade White Appearance / Brightness

An article made from a fiber composition containing anatase T1O2 is generally yellower than a comparable article made from a fiber composition containing rutile T1O2, sometimes by as much as 4.0 b* units. A difference of just 0.5 b* units (where a lower b* value on the CIELAB color scale corresponds to a desirably bluer appearance) is significant, particularly when comparing white articles (e.g., garments, carpet, wovens, knits, other textiles), because white articles can appear whiter simply by having a lower b* value, which can be highly desirable. Hence, being able to achieve a blue-shade white appearance without the unwanted problems associated with anatase and/or rutile T1O2 provides the disclosed fiber compositions and articles with a superior advantage.

Additionally, an improved L* value that shifts upward by 0.5 units or more is also considered significant and corresponds to a desirably brighter appearance. Hence, being able to achieve a brighter appearance without the unwanted problems associated with anatase and/or rutile T1O2 provides some embodiments of the disclosed fiber compositions and articles with a superior advantage.

In some embodiments, the disclosed fiber compositions, and articles made therefrom, have a b* value that is lower than the b* value of a comparable fiber containing more T1O2, or a comparable fiber containing more T1O2 and no incompatible polymer - e.g., a b* value of at least 0.5 units lower, at least 1.0 units lower, at least 1.3 units lower, at least 1.5 units lower, at least 1.8 units lower, or at least 2.0 units lower than the b* value of the comparable fiber. A comparable fiber may be as described above.

Furthermore, not only do some embodiments of the disclosed fiber compositions exhibit a more blue-shade white appearance that comparable fibers, but such disclosed fiber compositions also provide light scattering and delustering effects similar to those achieved with anatase TiC without sacrificing physical properties of the composition, such as tensile strength and/or elongation. This advantageous result is demonstrated in Example 1 below (compare Sample 2 with Comparative Sample 1).

Reduced Abrasiveness

An abrasion tester, such as the Lawson Hemphill CTT-E Abrasion Tester, can predict fiber abrasion behavior over time. For example, to test yarn abrasion behavior with an abrasion tester, the yarn is run over a standard abrasion wire made of copper or similar material. A standard test tension is applied to the yam depending on the denier. When the wire breaks, the tests stops. The length of yam that runs before the wire breaks corresponds to the abrasiveness of the yarn, whereby a longer length indicates a less abrasive yam. For example, a yarn that runs for 5000 m before breaking is less abrasive than the same denier yarn than runs for 2500 m before breaking under the same test conditions.

In some embodiments, a fiber composition of the present disclosure is less abrasive than a comparable fiber, as described above, when subjected to the same test conditions.

Manufacturing Methods

The present disclosure also relates to methods of manufacturing the fiber compositions and articles disclosed herein. These methods include mixing the components (i.e., the matrix and incompatible polymers as well as any light scattering pigment(s) and/or additional components that may be present) to achieve uniformity of the blend. The blended batch of ingredients is referred to as a premix, which can be used to make masterbatch pellets.

In general, masterbatch pellets contain matrix polymer(s), incompatible polymer(s), optional light scattering pigment(s), optional colorant(s), optional additive(s), and optional dispersant(s). The masterbatch pellets may be manufactured by one of several methods. In some embodiments, the method includes premixing, extruding, and pelletizing steps. For example, one method of making masterbatch pellets includes combining the ingredients in a high intensity mixer, such as a Henschel mixer, which includes a mixing bowl with a center shaft that contains one or more mixing blades in a stacked configuration. The premix is then transferred from the mixer to a feeder (e.g., a volumetric feeder), which directs the premix (e.g., via feed auger) into the feed throat of an extruder (e.g., a twin screw co-rotating extruder). The extruder melt processes the premix using high and low shear dispersing screw elements that disperse any pigments, additives or other components into the polymers. The molten polymer mixture may be conveyed down the length of the extruder, passed through a breaker plate with screens, and through a die head containing holes, thereby forming strands. The strands cool as they pass through a water bath where they solidify. The solid strands may then continue to a pelletizer, which cuts the strands into uniform pellets to form masterbatch pellets.

In a non-limiting illustrative example, melt spun fibers may be manufactured from pre dispersed masterbatch pellets, which are accurately dosed along with matrix polymer (e.g., PET) pellets using a mechanical gravimetric dosing unit into the hopper of a fiber spinning extruder. The pellet mixture is then fed into the feed throat of an extruder to form a molten mixture. The molten mixture is conveyed by the extruder through a transition piece to a melt pump, which pumps the molten mixture through one or more spinerettes to form individual fiber filaments. These filaments pass through a quench box that cools the filaments. The filaments are then drawn over godet rolls, which orient the polymer. The incompatible polymer domains along with any light scattering pigments reflect, scatter and absorb light, which provides for the desired color and luster of the resulting fiber (e.g., yam).

In another non-limiting illustrative example, to manufacture a yam composition, matrix and incompatible polymers may be extruded together and then processed through a spinneret to form a spun partially oriented yam (POY). As the matrix and incompatible polymers are processed and formed into spun yarn, the incompatible polymer disperses into small domains within the matrix polymer. Without being limited to any particular theory, it is believed that these domains act as light scattering sites due to differences in refractive index. Spun POY may then be oriented in a secondary process, such as texturizing, to form a delustered fiber composition (i.e., a final yam) suitable for knitting, weaving and/or further fabrication. As the spun yam is texturized by mechanical or other means, the yarn is further stretched or oriented, causing the scattering sites to elongate and increase the degree of scattering, leading to higher scattering and greater yam delustering. The resulting delustered yarn can then be further processed to form a variety of articles (e.g., clothing, carpeting, furniture, or other technical or industrial textiles) while reducing abrasion on textile spinning and texturizing equipment, therefore extending the life of the equipment and components thereof (e.g., guides, godet rolls, etc.). Similar methods may be used to manufacture other delustered fiber compositions, such as fully drawn yam (FDY), bulk continuous filament (BCF), Drawn Texturized Yarn (DTY), and staple fibers, in both texturized and non-texturized forms. For example, carpet may be manufactured by subjecting the disclosed fiber compositions to any one or more tufting, dyeing, and/or finishing processes.

In a non-limiting illustrative example, spun fiber is wound onto fiber spools or bobbins called packages. Yarn packages are used in tufting, which is a process of weaving synthetic or staple fiber into a primary backing material. The primary backing material may be made of woven polypropylene, and its main value is to provide a base cloth to hold the yam in place during the tufting process. A tufting machine can perform loop pile construction using needles that work in concert to penetrate and pull the yarn through the primary backing material, and a small hook called a looper that grabs the yarn and holds it in place. A subsequent step of carpet manufacturing involves dyeing processes. For example, in yam dyeing, sometimes called pre-dyeing, color is applied to the yarn prior to tufting. Advantages of yarn dyeing methods include good side-by-side color consistency, large lot sizes, and uniformity. Another dyeing process is carpet dyeing, in which color is applied to the yarn after the carpet has been tufted. Suitable carpet dyeing techniques include Beck or batch dyeing, which involves stitching the ends of the carpet together, and then running the tufted carpet loop through large vats of dye and water for several hours. The Beck process is ideal for smaller production runs, and heavier face weight products. Continuous dyeing is similar to Beck dyeing, but involves running the carpet through several processes in addition to the dye application. Continuous dyeing applies color directly to the carpet face, such as by spraying or printing.

The disclosed fiber compositions can also be used to manufacture various types of garments, including athletic wear such as exercise shorts, leggings, and shirts for all sporting activities. In some embodiments, these articles are made primarily from polyester with blends of other polymers like spandex, cotton, and nylon woven or knitted into the garment to provide flexibility and comfort. Suitable processes for making garments generally include fiber spinning and fabric weaving or knitting. EXAMPLES

The disclosed technology is next described by means of the following examples. The use of these and other examples anywhere in the specification is illustrative only, and in no way limits the scope and meaning of the disclosure or of any exemplified form. Likewise, the disclosure is not limited to any particular preferred embodiments described herein. Indeed, modifications and variations of the disclosure may be apparent to those skilled in the art upon reading this specification, and can be made without departing from its spirit and scope. The disclosure is therefore to be limited only by the terms of the claims, along with the full scope of equivalents to which the claims are entitled. All yams described in the following examples are considered representative fiber compositions.

For purposes of the present disclosure and the following examples, various parameters (e.g., visual luster and whiteness / color values) are measured as described below.

Visual Luster: Visual assessments of luster were performed and recorded on a scale of 1- 5. According to this visual assessment, an oriented fiber exhibiting a high visual luster was assigned a value of 5 (bright), and an oriented fiber exhibiting a low visual luster was assigned a value of 1 (dull). Gradations of intermediate luster were assigned a value of 2, 3, or 4, with the lower values indicating correspondingly lower degrees of luster.

Whiteness / L*, a*, b*: Color values were measured using an X-Rite spectrophotometer in reflectance. L*, a*, and b* values were calculated, assuming a D65 illuminant and a 10° standard observer.

Example 1

Representative fiber compositions containing matrix polymer, incompatible polymer, and light scattering pigment. In the prepared samples, the matrix polymer (major phase) was dried polyethylene terephthalate (PET) having an intrinsic viscosity (IV) about 0.80 dl/g and a glass transition temperature (Tg) of 70°C - 80°C; the incompatible polymer (minor phase) was polymethylpentene (PMP) (TPX RT-31 manufactured by Mitsui Chemical); and the light scattering pigment was anatase titanium dioxide (TiCh). Masterbatch pellets of PET, PMP, and T1O2, were prepared on a twin screw extruder. Masterbatch (MB) Compositions: Samples 1 and 2 were prepared from a masterbatch comprising 40 wt% polyester (a blend of PET and PBT), 5 wt% PMP, and 55 wt% anatase T1O2, based on the total weight of the masterbatch. Samples 3 and 4 were prepared from a masterbatch comprising no matrix polymer, 35 wt% PMP, and 65 wt% anatase T1O2, based on the total weight of the masterbatch. Comparative Sample 1 was prepared from a masterbatch comprising 40 wt% polyester, no incompatible polymer, and 60 wt% anatase T1O2, based on the total weight of the masterbatch. The compositions of the masterbatch pellets are shown in Table 1.

Fiber Compositions: For each of Samples 1-4 and Comparative Sample 1, the masterbatch pellets were mixed with PET pellets, and the mixture was fed into an extruder of a VB fiber spinning machine set at 285 °C, passed through a spinnerette, stretch oriented, and wound onto a Barmag winder at a rate of 3150 m/min to produce a POY package of yarn. The POY was then texturized on a mechanical texturizing machine, and drawn an additional 1.7x the length of the original POY to produce the oriented, texturized final fiber. The compositions of the final fibers of Samples 1-4 and Comparative Sample 1 are shown in Table 1.

Table 1: Compositions of Masterbatches and Final Fibers

Processing conditions for the preparation of Samples 1-4 and Comparative Sample 1 are shown in Table 2. Winding speed refers to the speed of the winder for the fiber spinning line. The temperature is the setting of the extruder barrel temperature on the fiber spinning line. Since the polymer materials have a long residence time in the extruder, the temperature setting is often at or close to the melting point of the polymers. Texturizing draw ratio refers to the amount of draw the fiber is subjected to during texturizing. This is a separate process from fiber spinning, in which fiber (here, POY) was wound onto a bobbin. Subsequent to fiber spinning, the fiber on the bobbin was processed through a texturizer and subjected to additional orientation of about 1.7x. Table 2: Processing Conditions

Visual luster, whiteness / color values, denier, tenacity, and break force of the oriented, texturized fibers was assessed, and the results are shown in Table 3. Dynafil measurements reflect the draw force of the fiber, and Dynafil CV is a coefficient of variation of the draw force, expressed as a percentage. Elongation reflects the total elongation of the fiber at its breaking pointed, as measured on a tensile tester and expressed as a percentage. Elongation CV is a coefficient of variation of the elongation, expressed as a percentage. Tenacity reflects the peak strength of the fiber divided by its denier. Break force reflects the break strength of the fiber and is measured in grams, Tenacity, denier, and break force are related in accordance with the following formula: [Tenacity] x [Denier] = [Break Force]

Table 3: Results

Samples 1-3 showed surprisingly advantageous results, including a more desirable blue- shade white appearance (i.e., lower b* value) with less TiC content as compared to Comparative Sample 1. Sample 2 showed further surprisingly advantageous results, including a more delustered visual appearance with less TiC content as compared to Comparative Sample 1. Also, the beneficial properties of Sample 2 were shown to be achieved without sacrificing physical properties of the composition, such as tensile strength and/or elongation (compare Sample 2 with Comparative Sample 1).

Sample 4 showed surprisingly advantageous results, including a significantly more blue- shade white in appearance (i.e., having a b* value that was 1.15 units lower) with a similar T1O2 content as compared to Comparative Sample 1.

Thus, the representative fiber compositions of Samples 1-4 provided benefits of anatase T1O2 from a delustering perspective, benefits of an otherwise unachievable blue color appearance, and/or benefits of reduced mineral concentration from an abrasion, wear and recycling perspective. Additionally, the representative fiber compositions of Samples 1-4 pose less of a risk of carcinogenicity than a fiber composition containing a higher weight percentage of T1O2.

Example 2

Representative fiber compositions containing matrix polymer, an incompatible polymer, and optionally TiCk were prepared. In the prepared samples, the matrix polymer was dried PET having an intrinsic viscosity (IV) about 0.80 dl/g and a glass transition temperature (Tg) of 70°C - 80°C; the incompatible polymer (minor phase) was COC (grade TOPAS® 5013F) or PMP (grade TPX RT-31 manufactured by Mitsui Chemical); and the light scattering pigment was anatase TiCk.

Samples 5-9 were prepared by adding the incompatible polymer (COC) as the minor phase to the matrix polymer (PET), and then forming oriented, texturized fiber compositions in the same manner as Example 1.

For Samples 10-11, masterbatch pellets comprising 57 wt% incompatible polymer (COC) and 43 wt% anatase T1O2 were prepared using a twin screw extruder. The masterbatch pellets were then mixed with PET pellets to form oriented, texturized fiber compositions in the same manner as Example 1.

For Sample 12, masterbatch pellets comprising 53 wt% incompatible polymer (PMP) and 47 wt% anatase T1O2 were prepared using a twin screw extruder. The masterbatch pellets were then mixed with PET pellets to form oriented, texturized fiber compositions in the same manner as Example 1. For Comparative Sample 2 (the same as Comparative Sample 1), masterbatch pellets comprising 40 wt% polyester (a blend of PET and PBT) and 60 wt% anatase T1O2 (and no incompatible polymer) were prepared using a twin screw extruder. The masterbatch pellets were then mixed with PET pellets to form oriented, texturized fiber compositions in the same manner as Example 1.

The compositions of the masterbatch pellets and final fibers of Samples 5-12 and Comparative Sample 2 are shown in Table 4.

Table 4: Compositions of Masterbatches and Final Fibers

The final fibers of Samples 5-12 and Comparative Sample 2 were subjected to texturizing under the following processing conditions: winding speed (3150 ft/min); temperature (285°C); and texturizing draw ratio (1.7x). Whiteness / color values, denier, and/or tenacity of the pre-texturized and post-texturized fibers was assessed, and the results are shown in Table 5. Table 5: Results

Samples 5-12 showed surprisingly advantageous results, including a substantially more blue-shade white appearance (i.e., lower b* value). Such a desirable effect was achieved with no TiCk (Samples 5-8), less TiCk (Samples 9, 10, and 12), or only slightly more TiCk (Sample 11) content as compared to Comparative Sample 2. Without being bound by any particular theory, it is believed that the presence of the incompatible polymer in Samples 5-12 was instrumental in achieving these advantageous results. These results also show that physical properties of TiCk- containing fibers can likewise be achieved by fibers containing an incompatible polymer and less TiCk content - i.e., the incompatible polymer can essentially replace TiCk and still result in a fiber having desirable physical properties, such as fiber tenacity and elongation.

Samples 5-10 and 12 may further have added advantages as these samples would all be expected to be more delustered and also less abrasive than Comparative Sample 2 due to their lower TiCk content.

Example 3

This example relates to an assessment of the pressure rise generated during a process of manufacturing fiber compositions using the masterbatches of Samples 1 and 3. The test is designed to replicate a fiber spinning process that cannot tolerate large particles having a diameter approaching the diameter of a single fiber strand. In the case of apparel POY yam, a suitable manufacturing denier per filament (dpf) range is 0.50 to 10.0. In this process, the screen pack was designed by stacking a variety of screens to achieve a small screen hole opening of approximately 15 microns. A maximum pressure rise of 50 bar/kg is acceptable; a maximum pressure rise of 40 bar/kg is preferred. A pressure rise in excess of 200 bar/kg indicates that the screen is getting blocked, and thus the material is not suitable for the process.

The pressure rise generated by each of Samples 1 and 3 is shown in Table 6.

Table 6: Pressure Rise

Samples 1 and 3 showed advantageous results, including demonstrating that physical properties of TiCh-containing fibers can likewise be achieved by fibers containing an incompatible polymer and less TiCh content - i.e., that the incompatible polymer can essentially replace T1O2 and still achieve desirable physical properties, such as a low pressure rise during processing. All references cited and/or discussed in this specification are incorporated herein by reference in their entireties and to the same extent as if each reference was individually incorporated by reference.