Patent Application
20240316412
The present disclosure relates generally to color-shifting formulations and golf balls including color-shifting formulations. More specifically, the present disclosure relates to golf balls including color-shifting formulations that, when used in a layer disposed upon a subassembly, produces a golf ball that has a color appearance that differs from the color appearance of the color concentrate and subassembly. In addition, when used in a layer disposed upon a subassembly, the color-shifting formulations produce an angular color shift such that there is a different color appearance depending on the angle of incidence.
The performance of a golf ball is affected by a variety of factors including the materials, weight, size, dimple pattern, and external shape of the golf ball. Golf ball manufacturers are constantly improving or tweaking the performance of golf balls by adjusting the materials and construction of the ball as well as the dimple pattern and dimple shape. The appearance of a golf ball is also important to manufacturers and players. For example, color and color effects in a golf ball are visually appealing and may allow a player to identify his/her ball more easily by overall appearance (as opposed to a more careful and close inspection of the play number or unique markings on the ball).
Manufacturers, in choosing and defining overall golf ball color, have previously been limited by using the desired color on the outermost layer of the golf ball or the layer directly underneath a clear outermost layer of a golf ball. Such options present limitations for offering golf balls that are unique and attractive to players/consumers.
Toward this end, manufacturers have incorporated color effects such as optically variable pigments in golf balls. Examples include golf balls incorporating metal-oxide coated mica based pigments, metal-oxide coated aluminum oxide platelets and metal-oxide coated silica platelets involving interference, reflection and absorption phenomena. But there remains a need for a golf ball whose colors and color effects appear equally elegant, attractive and captivating to the human eye under the wide range of different lighting and/or weather conditions that occur on the green. The present invention addresses and solves this problem.
Accordingly, there is a need for a golf ball having an overall golf ball color that golfers will find visually interesting and/or more easily identifiable. In this aspect, it would be advantageous to identify color-shifting formulations for use in an outermost golf ball layer or the layer directly underneath a clear outermost layer that enhance or modify the color of the underlying golf ball subassembly. The present disclosure describes such color-shifting formulations, layers and golf balls including the color-shifting formulations, and methods of making the same.
The present disclosure relates to a golf ball, including:
In some embodiments, the plurality of incident angles include at least four angles that each differ by at least 10°. In other embodiments, both ao* for at least two incident angles within the plurality are different from each other by at least about 2, and wherein bo* for at least two incident angles within the plurality are different from each other by at least about 2. In still other embodiments, ao* for at least two incident angles within the plurality are different from each other by at least about 3, and wherein the bo* for at least two incident angles within the plurality are different from each other by at least about 3. In yet other embodiments, ao* for at least two incident angles within the plurality are different from each other by at least about 5, and wherein the bo* for at least two incident angles within the plurality are different from each other by at least about 5.
In some aspects, the color-shifting formulation includes reflective particulates. In other aspects, the reflective particulates include interference particulates, nanostructures, microstructures, or combinations thereof. In still other aspects, the base polymer includes a material selected from the group consisting of polyurethanes, polyureas, and hybrids, copolymers, and blends thereof. The base polymer may include an ionomer material.
The present disclosure also relates to a golf ball, including:
In some embodiments, the angular color shift is at least 5. In other embodiments, the angular color shift satisfies √((aθ1*−aθ2*)2)>2 and √((bθ1*−bθ2*)2)>2, wherein aθ1* represents a* at a first incident angle θ1 and aθ2* represents a* at a second incident angle θ2, and wherein bθ1* represents b* at the first incident angle θ1 and bθ2* represents b* at the second incident angle θ1. In still other embodiments, the golf ball has a plurality of color appearances, each color appearance in the plurality defined by CIELAB coordinates ao* and bo* obtained at from a distinct area of measurement and different from at least one other color appearance in the plurality by at least 5. In yet other embodiments, the base polymer includes a material selected from the group consisting of polyurethanes, polyureas, and hybrids, copolymers, and blends thereof. In other embodiments, the subassembly includes a core and a casing layer disposed on the core. The casing layer may include an ionomeric material.
The present disclosure also relates to a golf ball, including:
In some embodiments, the first angle of incidence is different from the second angle of incidence by at least 10°, wherein ao1* is different from ao2* by at least 2, or wherein bo1* is different from bo2* by at least 2. In other embodiments, the first angle of incidence is different from the second angle of incidence by at least 10°, wherein ao1* is different from ao2* by at least 2, and wherein bo1* is different from bo2* by at least 2. In still other embodiments, the golf ball has a fourth color appearance in the area of measurement and at a third angle of incidence characterized by CIELAB coordinates ao3* and bo3*, and wherein the fourth color appearance is different from the second and third color appearances.
The present disclosure relates to a golf ball, including:
In some embodiments, each incident angle θ differs by at least 10°.
The present disclosure also relates to a golf ball, including:
In some embodiments, the color-shifting formulation includes reflective particulates. The reflective particulates may include interference particulates, nanostructures, microstructures, or combinations thereof. In other embodiments, Lc* differs from Lo*, ac* differs from ao*, bc* differs from bo*, and hc° differs from ho°. In still other embodiments, the base polymer includes a material selected from the group consisting of polyurethanes, polyureas, and hybrids, copolymers, and blends thereof. In yet other embodiments, the base polymer includes an ionomer material.
The present disclosure also relates to a golf ball, including:
The present disclosure also relates to a golf ball, including:
In some embodiments, the base polymer includes a material selected from the group consisting of polyurethanes, polyureas, and hybrids, copolymers, and blends thereof. In other embodiments, the subassembly includes a core and a casing layer disposed on the core. In some other embodiments, the casing layer includes an ionomeric material. In yet other embodiments, at least three coordinates in the first set differ from corresponding coordinates in the second and third sets. In still other embodiments, the color-shifting formulation has a fourth color appearance defined by a fourth set of CIELAB coordinates Lc*, ac*, bc*, Cc*, and hc°. In some aspects, the fourth color appearance differs from the first, second, and third color appearances. In other aspects, at least three coordinates in the fourth set differ from corresponding coordinates in the first, second, and third sets. In still other aspects, at least four coordinates in the fourth set differ from corresponding coordinates in the first, second, and third sets.
The present disclosure also relates to a golf ball, including:
In some embodiments, the color-shifting formulation includes reflective particulates. In this aspect, the reflective particulates may include interference particulates, nanostructures, microstructures, or combinations thereof. In other embodiments, the base polymer includes a material selected from the group consisting of polyurethanes, polyureas, and hybrids, copolymers, and blends thereof. In still other embodiments, the base polymer includes an ionomer material.
The present disclosure further relates to a golf ball, including:
In some embodiments, the color-shifting formulation includes reflective particulates. In this aspect, the reflective particulates may include interference particulates, nanostructures, microstructures, or combinations thereof. In other embodiments, the base polymer includes a material selected from the group consisting of polyurethanes, polyureas, and hybrids, copolymers, and blends thereof. In still other embodiments, the base polymer includes an ionomer material.
Further features and advantages of the invention can be ascertained from the following detailed description that is provided in connection with the drawings described below:
The color-shifting formulations of the present disclosure include a base formulation and a color concentrate. The color-shifting formulations may be used to form one or more layers disposed over a subassembly. In this aspect, the golf balls of the present disclosure include a subassembly having a first color appearance (e.g., a first color, first effect, or combination thereof) and at least one layer disposed on the subassembly and formed from a color-shifting formulation of the present disclosure having an overall golf ball color appearance (e.g., an overall golf ball color, golf ball effect, or combination thereof) that a) differs from the first color appearance and/or b) depends on the angle of incidence and viewing angle. In other words, the overall golf ball color appearance not only has one or more different color properties than the subassembly (and the color-shifting formulation itself), the color-shifting formulation may also have an iridescent effect that causes the golf ball to appear to change color and/or provide a different appearance when viewed at different angles. In this aspect, the color-shifting layer is formed from a substantially optically transparent or translucent material, so that both the color-shifting layer and underlying subassembly contribute to the overall golf ball color appearance. Moreover, the overall golf ball appearance may have different color appearances at different angles of incidence. In this aspect, the golf balls of the present disclosure may exhibit high or low color shift depending on the angle of incidence and viewing angle.
The outermost layer of the subassembly may be white, colored, and/or may have a single- or multi-colored pattern.
The color of a tangible object is typically the result of molecular coloring agents or pigments. For example, the color of an orange is the result of molecular coloring agents on the surface of the orange. The color of a golf ball is typically the result of the pigment or pigments in the composition used to form the outermost, opaque or mostly translucent layer of the golf ball. Here, the present disclosure relates to formulations and constructions that provide golf balls that have a unique color and/or patterned appearance that are a function of both the color and/or pattern of the underlying subassembly and the color concentrate included in the color-shifting formulation used to form a layer disposed upon the subassembly such that the finished golf ball exhibits a color shift dependent on the angle of incidence and viewing angle.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art of this disclosure. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Well known functions or constructions may not be described in detail for brevity or clarity.
The terms “about” and “approximately” shall generally mean an acceptable degree of error or variation for the quantity measured given the nature or precision of the measurements. Numerical quantities given in this description are approximate unless stated otherwise, meaning that the term “about” or “approximately” can be inferred when not expressly stated.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well (i.e., at least one of whatever the article modifies), unless the context clearly indicates otherwise.
As used herein, the term “a*” refers to the red/green value in the CIE color scheme. As shown in
As used herein, the term “angle of incidence” or “incident angle” refers to angle of illumination relative to the viewing angle. As shown in
As used herein, the term “angular color shift” occurs when, for any given area of measurement, a* differs for each incident angle θ using the equation √((aθ1*−aθ2*)2), with aθ1* representing a* at a first incident angle and aθ2* representing a* at a second incident angle, b* differs for each incident angle using the equation √((bθ1*−bθ2*)2), with bθ1* representing b* at the first incident angle and bθ2* representing b* at the second incident angle, or both.
As used herein, the term “b*” refers to the blue/yellow value in the CIE color scheme. As shown in
As used herein, the term “chroma” or “C*” represents the intensity of the color, which may range from 0 (or neutral) to 81-95 or greater. Chroma may be calculated as follows: C*=√(a*2+b*2).
As used herein, the term “color appearance” constitutes one or more color properties such as hue, saturation, lightness, colorfulness, and/or chroma of a formulation, golf ball component, or finished golf ball, which may be represented in terms of tristimulus colorimetry. In this regard, the following CIELAB coordinates may be measured or calculated: lightness (L*), chroma (C*), hue angle from 0° to 360° (h°), the degree of redness (positive a*) and greenness (negative a*), and the degree of yellowness (positive b*), and/or blueness (negative b*). Such measurements may be taken with any suitable spectrophotometer, e.g., a multiangle colorimeter (such as from XRite). RGB values may also be measured: R represents red, G represents green, and B represents blue.
As used herein, the term “color shift” (angular or reference point) refers to a change in a* or b* or both, under the CIELAB colorimetry system. It should be understood that, unless otherwise noted, the L* coordinate of the layers, components, and golf balls described herein do not influence color shift.
As used herein, the term “copolymer” includes polymers having two or more types of monomers.
As used herein, the term “hue” or “h°” refers to the wavelength within the visible-light spectrum at which the energy output from a source is greatest and is represented based on the CIECAM color model as an angle from 0° to 360°. In this aspect, the diagram set forth in
As used herein, the term “L*” represents the lightness of a color and varies from 0 (or black) to 100 (or white). As shown in
As used herein, the terms “iridescent” and “iridescence” as used herein are each given its ordinary meaning in the art and generally refer to color appearance that changes as a function of light incidence and/or viewing angle.
As used herein, the term “saturation” refers to the relative bandwidth of the visible output from a light source. In this aspect, while hue refers to the color of the object itself, saturation describes the intensity (purity) of that hue. In other words, as saturation increases, colors appear more “pure” and as saturation decreases, colors appear more “washed out.”
The terms “first,” “second,” and the like are used to describe various features or elements, but these features or elements should not be limited by these terms. These terms are only used to distinguish one feature or element from another feature or element. Thus, a first feature or element discussed below could be termed a second feature or element, and similarly, a second feature or element discussed below could be termed a first feature or element without departing from the teachings of the disclosure. Likewise, terms like “top” and “bottom”; “front” and “back”; and “left” and “right” are used to distinguish certain features or elements from each other, but it is expressly contemplated that a top could be a bottom, and vice versa.
The color-shifting formulation of the present disclosure includes a color concentrate and a base formulation. Each of these constituents and properties of the formulation are discussed in more detail below.
The color concentrate may include at least one colorant and a plurality of reflective particulates. The colorant may be a pigment, a dye, or a combination thereof. As would be understood by those of ordinary skill in the art, while both pigments and dyes may be used to add color to a variety of materials, they are not the same. In particular, pigments are colored, usually inorganic compounds that are completely or nearly insoluble in the substrate whereas dyes are usually organic, soluble compounds. In other words, pigments may be finely ground particles of color that get suspended in a dispersing agent or vehicle. Dyes are chemicals that are dissolved in water or other liquid medium to create a colorant.
In some embodiments, the colorant is a pure pigment. In some aspects, the colorant may be a copper pigment, a chromium pigment, an aluminum pigment, a manganese pigment, a gold pigment, an arsenic pigment, a bismuth pigment, a cerium pigment, an iron pigment, a titanium pigment, a tin pigment, a zinc pigment, or a combination thereof. In other aspects, the pigment is a fluorescent pigment. In still other aspects, the pigment is a thermochromic pigment.
In one embodiment, the colorant may be a red pigment such as a quinacridone pigment, a blue pigment such as phthalocyanine pigment, a yellow pigment such as a complex oxide pigment, a violet pigment such as ultramarine violet, cobalt violet, manganese violet, dioxane violet and quinacridone violet, a black pigment such as carbon black, or combinations thereof.
In other embodiments, the colorant may be a dye.
Suitable reflective particulates for use in the color concentrate include, but are not limited to, interference particulates, nanostructures, and/or microstructures that cause light to undergo interference when reflected. In this regard, the color-shifting formulation (or color-shifting layer formed from the color-shifting formulation) changes hues with varying angles of light, dynamically shifting from one color to another as light reaches it. By changing the shape and/or size of the structures in the color concentrate, e.g., the width or depth, the slope of its sides, the color concentrates may be tailored to have differences in the reflection of light that result in further subtle changes in the color. The reflective particulate may include metal flake, iridescent glitter, metalized film, colored polyester foil, and combinations thereof to create the effect of iridescence, pearlescence, sparkle, and/or glitter.
In some aspects, the reflective particulates may include aluminum trihydrate (Al(OH)), barium sulfate (BaSO), zinc sulfide (ZnS), mica, ultramarine blue (PB 29), and combinations thereof. In other aspects, the color concentrate includes reflective particulates such as metallized polyester or coated aluminum metallized polyethylene terephthalate, polyester foil, highly polished aluminum foil, holographic film particles, and combinations thereof. In still other aspects, inorganic pigments that agglomerate are also suitable for use in the color concentrate. Non-limiting examples of such pigments include crystals of metal compounds such as metal oxides. In this aspect, metal oxides such as titanium dioxide, zinc oxide, copper oxide, tin oxide, iron oxide, silicon dioxide, aluminum oxide, zirconium dioxide, and other metal oxides commonly known are suitable for use in accordance with the present disclosure. For example, the reflective particulates may include metal oxide particles such as pigment yellow 53 (PY 53), red iron oxide (PR 101), black iron oxide (PBk 11), Chromium Green-Black Hematite (PG 17), cobalt aluminate (PB 28), and combinations thereof. In one embodiment, the reflective particulate may be a metal oxide coated mica, basic lead carbonate, bismuth oxychloride, natural pearl essence, or a combination thereof. With respect to the metal oxide coated mica, any of the metal oxides above may be useful to coat the mica. There are also several other types of substrates that can be oxide coated, such as glass flakes and alumina plates.
In some embodiments, the reflective particulates are platelets of mica coated with thin layers of titanium dioxide (TiO2) and/or iron oxide, or the like. The broad face of the platelets may range from 4 microns to 1,000 microns across and are about 0.25 to about 0.5 microns thick, although synthetic micas can achieve thicknesses of less than 0.25 microns.
In some aspects, the reflective particulates may comprise about 0.01 to about 10 weight percent based on the total weight of the color concentrate. In one embodiment, the color concentrate includes about 0.05 to about 8 weight percent reflective particulates based on the total weight of the color concentrate. In another embodiment, the reflective particulates are present in an amount of about 1 to about 7 weight percent based on the total weight of the color concentrate. In still another embodiment, the reflective particulates may comprise about 2 to about 6 weight percent based on the total weight of the color concentrate.
Suitable nanostructures may have a diameter (i.e., the largest cross-sectional dimension) of about 1 micron or less. In some embodiments, the diameter of the nanostructures in the color concentrate range from 1 nanometers to about 1000 nanometers. In some aspects, the nanostructures have a diameter of about 10 nanometers to about 900 nanometers. In other aspects, the nanostructures have a diameter of about 100 nanometers to about 700 nanometers. In still other aspects, the nanostructures have a diameter of about 50 nanometers to about 500 nanometers.
Suitable microstructures may have a diameter of about 250 microns or less. In some embodiments, the microstructures have a diameter of about 200 microns or less. For example, the microstructures may have an average diameter of about 5 μm to about 200 μm, about 100 μm to about 200 μm, about 50 μm to about 150 μm, or about 25 μm to about 175 μm. In still other embodiments, the microstructures have a diameter of about 100 microns or less, about 50 microns or less, about 25 microns or less, about 10 microns or less, about 5 microns or less, or about 2 microns or less. For example, in some aspects, the microstructures have an average diameter of about 10 μm to about 100 μm, 5 μm to about 50 μm, about 10 μm to about 50 μm, about 20 μm to about 100 μm, or about 15 μm to about 75 μm. In one embodiment, the color concentrate includes microstructures having an average diameter of less than about 50 μm, e.g., about 2 μm to about 49 μm. In another embodiment, the color concentrate includes microstructures having an average diameter of about 50 μm or more, e.g., about 50 μm to about 150 μm.
In some aspects, the color concentrate includes, but is not limited to, colorant-coated nanostructures, colorant-infused nanostructures, colorant-coated microspheres, colorant-infused microspheres, colorant-plated pigment flakes, or a combination thereof.
The color concentrate may be used in the color-shifting formulation in an amount of about 0.001 to about 20 percent by weight based on the total weight of the color-shifting formulation. In some embodiments, the color concentrate is present in the color-shifting formulation in an amount of about 0.003 to about 15 by weight of the total weight of the color-shifting formulation. In other embodiments, the color concentrate is present in the color-shifting formulation in an amount of about 0.005 to about 10 by weight of the total weight of the color-shifting formulation. In still other embodiments, the color concentrate is present in the color-shifting formulation in an amount of about 1 to about 7 by weight of the total weight of the color-shifting formulation. In yet another embodiment, the color concentrate is present in the color-shifting formulation in an amount of about 3 percent to about 6 percent by weight of the total weight of the color-shifting formulation.
The base formulation depends on the layer that the color-shifting formulation is to be used in, which is driven by the desired golf ball construction. For example, if the golf ball is a two-piece golf ball, e.g., a cover formed on a ball subassembly where the subassembly includes a solid spherical center, the base formulation in the color-shifting formulation used to form the cover may include any number of materials and compositions that are useful in a cover layer of a two-piece golf ball. In some embodiments, the base formulation in the color-shifting formulation used to form the cover of a two-piece golf ball includes a thermoplastic resin such as an ionomer. If the golf ball has three or more layers, e.g., a cover formed on a subassembly where the subassembly includes a dual core and a casing layer, the color-shifting formulation may be used in the cover. Similarly, if the golf ball includes a subassembly and a cover with a layer disposed between the subassembly and the cover, the layer may be formed from the color-shifting formulation. In this aspect, the base formulation may include thermoplastic or thermoset materials such as polyurethane, polyurea, a hybrid of polyurethane-polyurea, and ionomer resin.
Accordingly, a variety of materials may be used in the base formulation including, but not limited to, polyurethanes, polyureas, copolymers, blends and hybrids of polyurethane and polyurea, olefin-based copolymer ionomer resins, polyethylene (e.g., low density polyethylene, linear low density polyethylene, and high density polyethylene), polypropylene, rubber-toughened olefin polymers, acid copolymers (e.g., poly(meth)acrylic acid, which do not become part of an ionomeric copolymer); plastomers, flexomers, styrene/butadiene/styrene block copolymers, styrene/ethylene-butylene/styrene block copolymers, dynamically vulcanized elastomers, copolymers of ethylene and vinyl acetates, copolymers of ethylene and methyl acrylates, polyvinyl chloride resins, polyamides, poly(amide-ester) elastomers, and graft copolymers of ionomer and polyamide (Pebax®), thermoplastic polyether block amides, polyester-based thermoplastic elastomers (Hytrel®), polyurethane-based thermoplastic elastomers (Elastollan®), synthetic or natural vulcanized rubber, and combinations thereof.
Suitable polyurethane materials are further disclosed in U.S. Pat. Nos. 5,334,673, 6,506,851, 6,756,436, and 7,105,623, the entire disclosures of which are hereby incorporated herein by reference. Suitable polyurea materials are further disclosed in U.S. Pat. Nos. 5,484,870, 6,835,794 and 7,378,483, and U.S. Patent Application Publication No. 2008/0064527, the entire disclosures of which are hereby incorporated herein by reference. Suitable polyurethane-urea materials include polyurethane/polyurea blends and copolymers comprising urethane and urea segments, as disclosed in U.S. Patent Application Publication No. 2007/0117923, the entire disclosure of which is hereby incorporated herein by reference.
Suitable ionomers for use in accordance with the present disclosure may include, but are not limited to, partially-neutralized ionomers and highly-neutralized ionomers (HNPs), including ionomers formed from blends of two or more partially-neutralized ionomers, blends of two or more highly-neutralized ionomers, and blends of one or more partially-neutralized ionomers with one or more highly-neutralized ionomers. For purposes of the present disclosure, “HNP” refers to an acid copolymer after at least 70 percent of all acid groups present in the composition are neutralized.
In some embodiments, the ionomers for use as the base formulation in the color-shifting formulation are salts of O/X- and O/X/Y-type acid copolymers, wherein O is an α-olefin, X is a C3-C8 α, β-ethylenically unsaturated carboxylic acid, and Y is a softening monomer. O may be ethylene or propylene. X may be methacrylic acid, acrylic acid, ethacrylic acid, crotonic acid, or itaconic acid. Y may be (meth) acrylate and alkyl (meth) acrylates wherein the alkyl groups have from 1 to 8 carbon atoms, including, but not limited to, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. In some aspects, O/X and O/X/Y-type acid copolymers include, without limitation, ethylene acid copolymers, such as ethylene/(meth)acrylic acid, ethylene/(meth)acrylic acid/maleic anhydride, ethylene/(meth)acrylic acid/maleic acid mono-ester, ethylene/maleic acid, ethylene/maleic acid mono-ester, ethylene/(meth)acrylic acid/n-butyl (meth)acrylate, ethylene/(meth)acrylic acid/iso-butyl (meth)acrylate, ethylene/(meth)acrylic acid/methyl (meth)acrylate, ethylene/(meth)acrylic acid/ethyl (meth)acrylate terpolymers, and the like. In some embodiments, α, B-ethylenically unsaturated mono- or dicarboxylic acids are (meth) acrylic acid, ethacrylic acid, maleic acid, crotonic acid, fumaric acid, itaconic acid.
In one embodiment, the ionomer is a highly neutralized E/X- and E/X/Y-type acid copolymer, wherein E is ethylene, X is a C3-C8 α, β-ethylenically unsaturated carboxylic acid, and Y is a softening monomer are used. X may be methacrylic acid, acrylic acid, ethacrylic acid, crotonic acid, or itaconic acid. Y may be an acrylate selected from alkyl acrylates and aryl acrylates and, in some embodiments, selected from (meth) acrylate and alkyl (meth) acrylates wherein the alkyl groups have from 1 to 8 carbon atoms, including, but not limited to, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. Nonlimiting examples of suitable E/X/Y-type copolymers are those wherein X is (meth) acrylic acid and/or Y is selected from (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, and ethyl (meth) acrylate. Additional examples of suitable E/X/Y-type copolymers are ethylene/(meth) acrylic acid/n-butyl acrylate, ethylene/(meth) acrylic acid/methyl acrylate, and ethylene/(meth) acrylic acid/ethyl acrylate.
The amount of ethylene in the acid copolymer may be at least about 15 weight percent, at least about 25 weight percent, at least about 40 weight percent, or at least about 60 weight percent, based on total weight of the copolymer. The amount of C3 to C8 α, β-ethylenically unsaturated mono- or dicarboxylic acid in the acid copolymer is typically from 1 weight percent to 35 weight percent, from 5 weight percent to 30 weight percent, from 5 weight percent to 25 weight percent, or from 10 weight percent to 20 weight percent, based on total weight of the copolymer. The amount of optional softening comonomer in the acid copolymer may be from 0 weight percent to 50 weight percent, from 5 weight percent to 40 weight percent, from 10 weight percent to 35 weight percent, or from 20 weight percent to 30 weight percent, based on total weight of the copolymer.
The various O/X, E/X, O/X/Y, and E/X/Y-type copolymers disclosed herein are at least partially neutralized with a cation source, optionally in the presence of a high molecular weight organic acid, such as those disclosed in U.S. Pat. No. 6,756,436, the entire disclosure of which is hereby incorporated herein by reference. The acid copolymer can be reacted with the optional high molecular weight organic acid and the cation source simultaneously, or prior to the addition of the cation source. Suitable cation sources include, but are not limited to, metal ion sources, such as compounds of alkali metals, alkaline earth metals, transition metals, and rare earth elements; ammonium salts and monoamine salts; and combinations thereof. In some embodiments, cation sources are compounds of magnesium, sodium, potassium, cesium, calcium, barium, manganese, copper, zinc, lead, tin, aluminum, nickel, chromium, lithium, and rare earth metals. The amount of cation used in the composition is readily determined based on desired level of neutralization. As discussed above, for HNP compositions, the acid groups are neutralized to 70 percent or greater, 70 to 100 percent, or 90 to 100 percent. In one embodiment, an excess amount of neutralizing agent, that is, an amount greater than the stoichiometric amount needed to neutralize the acid groups, may be used. In this aspect, the acid groups may be neutralized to 100 percent or greater, for example 110 percent or 120 percent or greater.
In other embodiments, partially-neutralized ionomeric compositions are prepared, wherein 10 percent or greater, normally 30 percent or greater of the acid groups are neutralized. When aluminum is used as the cation source, it may be used at low levels with another cation such as zinc, sodium, or lithium, since aluminum has a dramatic effect on melt flow reduction and cannot be used alone at high levels. For example, aluminum is used to neutralize about 10 percent of the acid groups and sodium is added to neutralize an additional 90 percent of the acid groups.
“Low acid” and “high acid” ionomeric polymers, as well as blends of such ionomers, may be used in the base formulation. In general, low acid ionomers are considered to be those containing 16 weight percent or less of acid moieties, whereas high acid ionomers are considered to be those containing greater than 16 weight percent of acid moieties. A suitable high acid ionomer is Surlyn® 8150, which is a copolymer of ethylene and methacrylic acid, having an acid content of 19 weight percent, 45 percent neutralized with sodium. In one embodiment, the base formulation may include a high acid ionomer and a maleic anhydride-grafted non-ionomeric polymer (e.g., Fusabond® 525D), which is a maleic anhydride-grafted, metallocene-catalyzed ethylene-butene copolymer having about 0.9 weight percent maleic anhydride grafted onto the copolymer. Blends of high acid ionomers with maleic anhydride-grafted polymers are further disclosed, for example, in U.S. Pat. Nos. 6,992,135 and 6,677,401, the entire disclosures of which are hereby incorporated herein by reference. In another embodiment, the base formulation includes a 50/45/5 blend of Surlyn® 8940/Surlyn® 9650/Nucrel® 960. In still another embodiment, the base formulation includes a 50/25/25 blend of Surlyn® 8940/Surlyn® 9650/Surlyn® 9910. In yet another embodiment, the base formulation includes a 50/50 blend of Surlyn® 8940/Surlyn® 9650. In still another embodiment, the base formulation includes a blend of Surlyn® 7940/Surlyn® 8940, optionally including a melt flow modifier. In still another embodiment, the base formulation includes a blend of a first high acid ionomer and a second high acid ionomer, wherein the first high acid ionomer is neutralized with a different cation than the second high acid ionomer (e.g., 50/50 blend of Surlyn® 8150 and Surlyn® 9150), optionally including one or more melt flow modifiers such as an ionomer, ethylene-acid copolymer or ester terpolymer. In yet another embodiment, the base formulation includes a blend of a first high acid ionomer and a second high acid ionomer, wherein the first high acid ionomer is neutralized with a different cation than the second high acid ionomer, and from 0 to 10 weight percent of an ethylene/acid/ester ionomer wherein the ethylene/acid/ester ionomer is neutralized with the same cation as either the first high acid ionomer or the second high acid ionomer or a different cation than the first and second high acid ionomers (e.g., a blend of 40-50 weight percent Surlyn® 8140, 40-50 weight percent Surlyn® 9120, and 0-10 weight percent Surlyn® 6320). Surlyn® ionomers, Fusabond® copolymers, and Nucrel® copolymers are commercially available from DuPont.
Ionomeric base formulations can be blended with non-ionic thermoplastic resins such as polyurethane, poly-ether-ester, poly-amide-ether, polyether-urea, thermoplastic polyether block amides (e.g., Pebax® block copolymers), styrene-butadiene-styrene block copolymers, styrene(ethylene-butylene)-styrene block copolymers, polyamides, polyesters, polyolefins (e.g., polyethylene, polypropylene, ethylene-propylene copolymers, polyethylene-(meth)acrylate, polyethylene-(meth)acrylic acid, functionalized polymers with maleic anhydride grafting, Fusabond® functionalized olefins commercially available from DuPont, functionalized polymers with epoxidation, elastomers (e.g., ethylene propylene diene monomer rubber, metallocene-catalyzed polyolefin) and ground powders of thermoset elastomers.
The color-shifting formulation may also contain a variety of fillers and additives to impart specific properties to the ball. For example, the color-shifting formulation may include metal fillers such as, particulate, powders, flakes, and fibers of copper, steel, brass, tungsten, titanium, aluminum, magnesium, molybdenum, cobalt, nickel, iron, lead, tin, zinc, barium, bismuth, bronze, silver, gold, and platinum, and alloys and combinations thereof may be used to adjust the specific gravity of the ball. Other additives and fillers that may be used in the color-shifting formulation include, but are not limited to, optical brighteners, coloring agents, toners, fluorescent agents, whitening agents, UV absorbers, light stabilizers, surfactants, processing aids, antioxidants, antistats, antiblocks, stabilizers, softening agents, foaming agents, fragrance components, plasticizers, impact modifiers, titanium dioxide, barium sulfate clay, mica, talc, glass flakes, milled glass, and mixtures thereof.
In one embodiment, the color-shifting formulation includes one or more matting agents to induce diffuse reflection of light irradiated to the golf ball. Non-limiting examples of suitable matting agents include amorphous silica, fuming silica, silica gel, alumina, titania, zirconia, zircon, tin oxide, magnesia, polypropylene, polyethylene, polytetrafluoroethylene, Al-stearate, latex, Zn-stearate, Ca-stearate, Mg-stearate, finely divided polypropylene waxes, urea-formaldehyde condensates, and combinations thereof. In one embodiment, the matting agent is amorphous silica, fumed silica, silica gel, or a combination thereof. In this aspect, the matting agent may be included in an amount of about 0.5 to about 10 percent by weight based on the total weight of the color-shifting formulation. In one embodiment, the matting agent is included in an amount of about 1 percent to about 8 percent by weight based on the total weight of the color-shifting formulation. In another embodiment, the color-shifting formulation includes about 2 percent to about 5 percent by weight matting agent based on the total weight of the color-shifting formulation.
As generally discussed above, the color-shifting formulation has a degree of transparency. In this aspect, a color-shifting formulation of the present disclosure may have an average transmittance of visible light (e.g., between about 380 nm and about 770 nm or alternately between about 400 nm and about 700 nm) of at least about 40 percent. The average transmittance referred to herein is typically measured for incident light normal (i.e., at approximately 90°) to the plane of the object and can be measured using any known light transmission apparatus and method, e.g., a UV-Vis spectrophotometer. In some embodiments, the formulation has a transparency of about 60 percent or greater. In other embodiments, the formulation is about 80 percent or more transparent. In still other embodiments, the formulation has a transparency of about 90 percent or more.
The color-shifting formulation has a color appearance that differs from the color appearance of the subassembly and the color appearance of the golf ball (at any one angle of incidence). In one embodiment, the color-shifting formulation may be defined by its own CIELAB coordinates (Lc*, ac*, bc*, Cc*, and/or hc°). As discussed in more detail below, one or more of the CIELAB coordinates for the color-shifting formulation differs from one or more of the CIELAB coordinates of the subassembly and one or more of the CIELAB coordinates of the golf ball (at any one angle of incidence). For example, the Lc*, ac*, bc* values may differ from the corresponding Ls*, as*, bs* values for the subassembly. In some embodiments, each CIELAB coordinate of the color-shifting formulation differs from the corresponding CIELAB coordinate of the subassembly and the corresponding CIELAB coordinate of the golf ball (at any one angle of incidence).
In some embodiments, the color appearance of the color-shifting formulation may be defined by its own RGB values (RC, GC, BC). As discussed in more detail below, one or more of the RGB values for the color-shifting formulation differs from one or more of the RGB values for the subassembly and one or more of the RGB values of the golf ball (at any one angle of incidence). In some aspects, each RGB value of the color-shifting formulation differs from the corresponding RGB value of the subassembly and corresponding RGB value of the golf ball (at any one angle of incidence).
As briefly discussed in the preceding section, golf balls formed in accordance with the present disclosure may have a construction that includes a subassembly and a color-shifting layer disposed on the subassembly. For the purposes of this disclosure, the subassembly may be any single layer or multi-layered golf ball component disposed beneath the color-shifting layer. For example, a golf ball formed in accordance with the present disclosure may include a subassembly that consists of a solid spherical core and a color-shifting layer disposed on the subassembly. In some embodiments, as shown in
In other embodiments, one or more layers may be disposed on the color-shifting layer. In this regard, the color-shifting layer may have an additional layer formed thereon, such as a coating or clear paint layer. For example, the cross-sectional view of a ball in
In another embodiment shown in the cross-sectional view of a ball in
Regardless of the terms used above, the outermost structural layer of the subassembly may be considered an outer core layer, an intermediate layer, a casing or mantle layer, or inner cover layer, or any other layer disposed directly beneath the color-shifting layer of the golf ball. Additional details related to the subassembly (and components thereof), color-shifting layer, and any additional layer(s) disposed on the color-shifting layer are provided below.
Conventional and non-conventional materials may be used for forming the layers of the subassembly including, for instance, polybutadiene, butyl rubber, and other rubber-based core formulations, ionomer resins, highly neutralized polymers, and the like. In particular, the material selected for use in a solid spherical center and layers surrounding the center to form the subassembly depends on the desired performance properties, e.g., hardness and compression of the subassembly. The diameter of the components of the subassembly may vary, but if the subassembly includes a center and at least one additional layer, the diameter of the center may be between about 50 percent and 90 percent of the diameter of the subassembly.
The subassembly itself may range from about 1.50 inch to about 1.66 inch. In one embodiment, the subassembly has a diameter of about 1.52 inch to about 1.64 inch. In another embodiment, the core assemblage diameter ranges from about 1.54 inch to about 1.62 inch.
In one embodiment, the subassembly (or its components) is formed form a thermoset rubber formulation that includes a base rubber in an amount of about 5 percent to about 100 percent by weight based on the total weight of the rubber formulation. In some aspects, the center of the subassembly and any layers disposed thereon are formed from a thermoplastic or thermoset composition, such as thermoset rubber. The compositions used to form the subassembly components may be the same or different for each layer/component. For example, in one embodiment, the center is formed from a thermoset rubber and the outer core layer is formed from a thermoplastic composition. In another embodiment, the center and the outer core layer are both formed from thermoset rubber compositions.
In one embodiment, the rubber formulation includes about 55 percent to about 95 percent base rubber based on the total weight of the formulation. The rubber formulation may also include a reactive cross-linking co-agent, radical scavengers, fillers, and other additives. The rubber formulation may be cured using suitable curing processes including, but not limited to, peroxide-curing, sulfur-curing, high-energy radiation, and combinations thereof. In this regard, the rubber formulation may include free-radical initiators such an organic peroxides.
The base rubber may be polybutadiene, polyisoprene, ethylene propylene rubber, ethylene-propylene-diene rubber, styrene-butadiene rubber, styrenic block copolymer rubbers, polyalkenamers such as, for example, polyoctenamer, butyl rubber, halobutyl rubber, polystyrene elastomers, polyethylene elastomers, polyurethane elastomers, polyurea elastomers, metallocene-catalyzed elastomers and plastomers, copolymers of isobutylene and p-alkylstyrene, halogenated copolymers of isobutylene and p-alkylstyrene, copolymers of butadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, and blends of two or more thereof. In one embodiment, the rubber formulation includes polybutadiene rubber, butyl rubber, or a blend thereof as the base rubber. If the base rubber is polybutadiene, any suitable catalyst may be used to synthesize the polybutadiene rubber depending upon the desired properties. In one embodiment, a transition metal complex (for example, neodymium, nickel, or cobalt) or an alkyl metal such as alkyl lithium is used as a catalyst. Other catalysts include, but are not limited to, aluminum, boron, lithium, titanium, and combinations thereof. The polybutadiene may be cis- or trans- and may have a high (e.g., about 80 to about 130) or low (e.g., about 30 to about 75) Mooney viscosity, or be a blend of high and low Mooney viscosity polybutadiene rubbers.
Suitable reactive cross-linking co-agents include, but are not limited to, metal salts of unsaturated carboxylic acids having from 3 to 8 carbon atoms; unsaturated vinyl compounds and polyfunctional monomers (e.g., trimethylolpropane trimethacrylate); phenylene bismaleimide; and combinations thereof. As would be understood by those of ordinary skill in the art, the co-agent may be included in the rubber formulation in varying amounts depending on the specific core component for which the rubber formulation is intended.
Suitable radical scavengers include, but are not limited to, halogenated organosulfur, organic disulfide, and inorganic disulfide compounds such as pentachlorothiophenol (PCTP) and salts thereof, ditolyl disulfide, diphenyl disulfide, dixylyl disulfide, and 2-nitroresorcinol. Examples of suitable fillers include, but are not limited to metal fillers, carbon black, clay and nanoclay particles, talc, glass (e.g., glass flake, milled glass, and microglass), and combinations thereof. Fillers may be used in the core formulations in an amount of about 1 percent to about 20 percent by weight based on total weight of rubber formulation. Antioxidants, processing aids, accelerators (for example, tetra methylthiuram), dyes and pigments, wetting agents, surfactants, plasticizers, coloring agents, fluorescent agents, chemical blowing and foaming agents, defoaming agents, stabilizers, softening agents, impact modifiers, antiozonants, as well as other additives known in the art, may also be added to the rubber formulation.
As discussed above, single and multi-layered subassemblies can be made in accordance with this invention. In multi-layered subassemblies, a thermoset material such as, for example, thermoset rubber, can be used to make the outer core layer and a thermoplastic material such as, for example, ethylene acid copolymer containing acid groups that are at least partially or fully neutralized can be used to make a casing layer that is disposed upon the outer core layer. In this aspect, suitable ionomer compositions include partially-neutralized ionomers and highly-neutralized ionomers (HNPs), including ionomers formed from blends of two or more partially-neutralized ionomers, blends of two or more highly-neutralized ionomers, and blends of one or more partially-neutralized ionomers with one or more highly-neutralized ionomers may be used to form the casing layer. Suitable ethylene acid copolymer ionomers and other thermoplastics that can be used to form the casing layer are the same materials that can be used to make a cover layer of a two-piece golf ball, i.e., a golf ball that includes a center and a cover.
Regardless of the components/layers of the subassembly, the subassembly has at least a first color appearance associated therewith. The subassembly (or regions thereof) may be defined by CIELAB coordinates (Ls*, as*, bs*, Cs*, and/or hs°) and/or RGB values. As discussed in more detail below, one or more of the CIELAB coordinates for the subassembly differs from one or more of the CIELAB coordinates of the golf ball (and one or more of the CIELAB coordinates of the color-shifting formulation). Similarly, one or more of the RGB values for the subassembly differs from one or more of the RGB values of the golf ball (and one or more of the RGB values of the color-shifting formulation).
The subassembly may be a single color or be multi-colored, e.g., have two differently colored hemispheres or multiple differently colored regions. For example, in some embodiments, a subassembly may be a single, solid color defined by one set of CIELAB coordinates (Ls*, as*, bs*, Cs*, and/or hs°) and/or RGB values (Rs, Gs, Bs). In other embodiments, a subassembly may be divided into first and second regions where a first color is used in a first region of the subassembly and a second color is used in the second region of the subassembly. In this aspect, the first region may be defined by one set of CIELAB coordinates (Ls1*, as1*, bs1*, Cs1*, and/or hs1°) and/or RGB values (R1, G1, B1) and the second region may be defined by another set of CIELAB coordinates (Ls2*, as2*, bs2*, Cs2*, and/or hs2°) and/or RGB values (R2, G2, B2). However, as discussed in more detail below with respect to the angular color shift of the color-shifting layer, the subassembly does not possess an angular color shift of at least 2 for any single area of measurement on the subassembly.
The subassembly color may be a primary color such as red, yellow and blue, a secondary color such as orange, violet, and green, or a tertiary color such as yellow-orange, red-orange, red-violet, blue-violet, blue-green, and yellow-green, white, or black. In some embodiments, a colorant may be sprayed onto the outermost layer of the subassembly such that the subassembly has the color appearance of the colorant. In other embodiments, the subassembly has the color appearance of the composition used to form the outermost layer of the subassembly.
The color of the outermost cover of the subassembly may be achieved using one or more coloring agents. In this aspect, the coloring agent may be a pigment, a dye, or a combination thereof. In some embodiments, the coloring agent is a pure pigment. In some aspects, the pure pigment is a copper pigment, a chromium pigment, an aluminum pigment, a manganese pigment, a gold pigment, an arsenic pigment, a bismuth pigment, a cerium pigment, an iron pigment, a titanium pigment, a tin pigment, a zinc pigment, or a combination thereof. The pigment may also be a fluorescent pigment. Mineral-based pigments such as talc may also be used as the coloring agent.
The color-shifting layer is formed from the color-shifting formulation. As discussed above, the base formulation of the color-shifting formulation depends on where the color-shifting layer is placed in the golf ball. Accordingly, the properties and dimensions of the color-shifting layer also depend on where the color-shifting layer is located in a golf ball formed in accordance with the present disclosure. For example, when the color-shifting layer is the outermost layer of a golf ball, it may have a material hardness that is less than if the color-shifting layer forms the inner cover layer of the golf ball. Similarly, when the color-shifting layer forms the outermost layer of a golf ball, the thickness may be less than if the color-shifting layer forms an inner cover layer of a golf ball.
As discussed above, once the color-shifting formulation is used to form a color-shifting layer, the plaque, golf ball component, or finished golf ball has a color appearance (at any one angle of incidence at a single area of measurement) that differs from the color appearance of the subassembly and the color appearance of the color-shifting formulation. In some embodiments, once the color-shifting formulation is used to form the color-shifting layer, the plaque, golf ball component, or finished golf ball has a plurality of color appearances (at one or more angles of incidence at a single area of measurement) where each differ from each other and from the color appearance of the subassembly and the color appearance of the color-shifting formulation. In other embodiments, once the color-shifting formulation is used to form the color-shifting layer, the plaque, golf ball component, or finished golf ball has a plurality of color appearances (at one or more angles of incidence at a first area of measurement and at one or more angles of incidence at a second area of measurement) where each differ from each other and from the color appearance of the subassembly and the color appearance of the color-shifting formulation.
In addition, once the color-shifting formulation is applied to a substrate to form a color-shifting layer, at a single area of measurement (e.g., a 2 mm area), the color-shifting layer has a plurality of color appearances depending on the angle of incidence. In this aspect, the color-shifting layer has an angular color shift. In other words, for a single area of measurement, the color-shifting layer may have a first color appearance at a first angle of incidence and a second color appearance different from the first color appearance at a second angle of incidence. For example, for a single area of measurement, a color-shifting layer may have an ac* value at one incident angle that varies from the ac* value at another incident angle by at least about 2.
In some aspects, in a single area of measurement, a color-shifting layer may have an ac* value at one incident angle that varies from the ac* value at another incident angle by at least about 3. In other aspects, in a single area of measurement, a color-shifting layer may have an ac* value at one incident angle that varies from the ac* value at another angle of incidence by at least about 5. In yet aspects, in a single area of measurement, a color-shifting layer may have an ac* value at one incident angle that varies from the ac* value at another angle of incidence by at least about 7. In still other aspects, in single area of measurement, a color-shifting layer may have an ac* value at one incident angle that varies from the ac* value at another angle of incidence by at least about 10.
Similarly, for a single area of measurement, a color-shifting layer may have an bc* value at one incident angle that varies from the bc* value at another angle of incidence by at least about 2. In some aspects, in a single area of measurement, a color-shifting layer may have an bc* value at one incident angle that varies from the bc* value at another angle of incidence by at least about 3. In other aspects, in a single area of measurement, a color-shifting layer may have an bc* value at one incident angle that varies from the bc* value at another angle of incidence by at least about 5. In yet other aspects, in a single area of measurement, a color-shifting layer may have an bc* value at one incident angle that varies from the bc* value at another angle of incidence by at least about 7. In still other aspects, in a single area of measurement, a color-shifting layer may have an bc* value at one incident angle that varies from the bc* value at another incident angle by at least about 10.
In some aspects, the angular color shift of the color-shifting layer occurs at a plurality of single areas of measurement on the color-shifting layer. In this regard, the plurality may be at least 3, 5, 7, 10, 15, or more. For example, once the color-shifting formulation is applied to a substrate to form a color-shifting layer, the color-shifting layer has a plurality of color appearances depending on the angle of incidence at a plurality of single areas of measurement (e.g., each 2 mm area in multiple locations on the color-shifting layer). In other words, for a plurality of single areas of measurement, the color-shifting layer may have a first color appearance at a first angle of incidence and a second color appearance different from the first color appearance at a second angle of incidence. In some aspects, for a plurality of single areas of measurement, each ac*, bc*, or both at one incident angle differs from the corresponding coordinate(s) (ac*, bc*, or both) at any other angle of incidence for the single area of measurement by at least about 2. In other aspects, for a plurality of single areas of measurement, each ac*, bc*, or both at one incident angle differs from the corresponding coordinate(s) (ac*, bc*, or both) at any other angle of incidence for the single area of measurement by at least about 3, 5, 7, or 10.
In comparison, in any single area of measurement of the subassembly, as* at one incident angle is substantially the same as as* at any other angle of incidence in the area of measurement. In other words, the subassembly has no angular color shift. Similarly, for any single area of measurement, bs* of the subassembly at one incident angle is substantially the same as bs* at any other angle of incidence in the area of measurement. In this context, “substantially the same” means that the difference between the a* or b* value (as applicable) at a first incident angle and the corresponding a* or b* value at a second incident angle is less than 2. In some embodiments, for any single area of measurement on the subassembly, the average difference of as* between adjacent incident angles is less than 2. Similarly, for any single area of measurement, the subassembly may have an average difference of bs* between adjacent incident angles of less than 2.
In other embodiments, for a single area of measurement (e.g., a 2 mm area), ac15°* (value of ac* at 15° incident angle) of a color-shifting layer may vary from ac75°* (value of ac* at 75° incident angle) by at least about 5. In some embodiments, for a single area of measurement, ac15°* (value of ac* at 15° incident angle) of a color-shifting layer may vary from ac75°* (value of ac* at 75° incident angle) by at least about 8. In other embodiments, for a single area of measurement, ac15°* (value of ac* at 15° incident angle) of a color-shifting layer may vary from ac75°* (value of ac* at 75° incident angle) by at least about 10.
In other embodiments, for a single area of measurement, bc15°* (value of bo* at 15° incident angle) of a color-shifting layer may vary from bc75°* (value of bc* at 75° incident angle) by at least about 5. In some embodiments, for a single area of measurement, bc15°* (value of bc* at 15° incident angle) of a color-shifting layer may vary from bc75°* (value of bc* at 75° incident angle) by at least about 8. In other embodiments, for a single area of measurement, bc15°* (value of bc* at 15° incident angle) of a color-shifting layer may vary from bc75°* (value of bc* at 75° incident angle) by at least about 10.
In comparison, in any single area of measurement of the subassembly, as15°* (value of as* at 15° incident angle) may vary from as75°* (value of as* at 75° incident angle) by less than 2. In this aspect, as15* of the subassembly is substantially the same as as75* at any other incident angle in the area of measurement. Similarly, bs15* of the subassembly is substantially the same as bs75* in the area of measurement.
Different colors generated by the color-shifting layers of the present disclosure may span the entire color palette from red, orange, yellow, green, blue, to purple. In some embodiments, the colors across the plaque, golf ball component, or finished golf ball may shift with angle across multiple colors. In other embodiments, the color in a defined area will be bounded in a certain range in a* and b* but the a* and b* values independently vary with angle of incidence. For example, an iridescent green color-shifting layer disposed on a white subassembly may have a* ranging from about −16 to 2 for incident angles from −15° to 110°, but an average difference between each adjacent incident angle of about 2 to about 4. Similarly, this same color-shifting layer disposed on a white subassembly may have a b* ranging from about 2 to about 10 and an average difference in a* between each adjacent incident angle of about 1 to 3.
A purple color-shifting layer disposed on a white subassembly may have a* ranging from about 30 to −10 for incident angles from −15° to 110°, but an average difference in a* between each adjacent incident angle of about 5 to about 10 (depending on particle size). Similarly, this same color-shifting layer disposed on a white subassembly may have a b* ranging from about −12 to about 12 and an average difference between each adjacent incident angle of about 6 to 12.
When this same purple color-shifting layer is disposed on a green subassembly, the a* may range from about 40 to −10 for incident angles from −15° to 110°, but the average difference between each adjacent incident angle still ranges from about 5 to about 10 (depending on particle size). Similarly, this same color-shifting layer disposed on a green subassembly may have a b* ranging from about −15 to about 20 and an average difference between each adjacent incident angle still ranging from about 6 to 12.
Without being bound by any particular theory, the particle size of the color-shifting formulation may have effect on the differences between the a* and b* values across the incident angles for any single area of measurement. For example, when a purple color-shifting layer with an average particle size of less than 50 μm is disposed on a yellow subassembly, the a* may range from about 25 to −2.5 for incident angles from −15° to 110° and the average difference in a* between each adjacent incident angle is less than 7. The b* ranges from about −20 to about 15 and an average difference of b* between each adjacent incident angle is less than 9.
When a purple color-shifting layer with an average particle size of about 50 μm or greater is disposed on a yellow subassembly, the a* may range from about 40 to −4 for incident angles from −15° to 110° and the average difference in a* between each adjacent incident angle is greater than 7. The b* ranges from about −25 to about 20 and an average difference of b* between each adjacent incident angle is greater than 9.
In other aspects, when a color-shifting layer is disposed upon a subassembly, at least one of ac* or bc* have an average color shift over all adjacent pair of incident angles of greater than 2 at a single area of measurement. In other embodiments, when a color-shifting layer is disposed upon a subassembly, at least one of ac* or bc* have an average color shift over all adjacent pair of incident angles of greater than 3 at a single area of measurement. In still other embodiments, when a color-shifting layer is disposed upon a subassembly, both ac* and bc* have an average color shift over all adjacent pair of incident angles of greater than 3 at a single area of measurement. In still other embodiments, when a color-shifting layer is disposed upon a subassembly, both ac* and bc* have an average color shift over all adjacent pair of incident angles of greater than 5 at a single area of measurement. In yet other embodiments, when a color-shifting layer is disposed upon a subassembly, both ac* and bc* have an average color shift over all adjacent pair of incident angles of greater than 6 at a single area of measurement.
The golf balls of the present disclosure may be formed using a variety of application techniques. For example, thermoset materials can be formed into golf ball layers by conventional casting, liquid injection molding, or reaction injection molding techniques. Thermoplastic materials can be formed into golf ball layers by conventional compression or injection molding techniques. In other words, a layer may be formed using any suitable technique that is associated with the material used to form the layer. In this aspect, depending on the material used to the form the component or layer, compression molding, flip molding, injection molding, retractable pin injection molding, reaction injection molding (RIM), liquid injection molding (LIM), casting, vacuum forming, powder coating, flow coating, spin coating, dipping, spraying, and the like may be used. In some embodiments, each layer is separately formed. For example, an ethylene acid copolymer ionomer composition may be injection-molded to produce half-shells over a core assemblage. Alternatively, the ionomer composition can be placed into a compression mold and molded under sufficient pressure, temperature, and time to produce the hemispherical shells, which may then be placed around the core assemblage in a compression mold. An outer cover layer including a polyurethane or polyurea composition over the ball subassembly may be formed by using a casting process.
With respect to the color-shifting layer, as discussed above, the base formulation used to form the layer dictates the method by which the layer is formed. For example, when the base formulation of the color-shifting formulation is polyurethane- or polyurea-based, the color-shifting layer may be formed by casting. When the base formulation of the color-shifting formulation is ionomeric, the color-shifting layer may be injection molded or compression molded. The use of certain molding processes allows for, in some aspects, the color-shifting formulation to be applied to only a portion of the color-shifting layer. For example, the color-shifting formulation may be used on only one hemisphere of the color-shifting layer if injection molding or compression molding are used to form the color-shifting layer since these molding processes involve the joining of two hemispheres at an equator.
Golf balls made in accordance with the present disclosure may be subjected to finishing steps such as flash-trimming, surface-treatment, marking, coating, and the like using techniques known in the art. In one embodiment, a white-pigmented cover may be surface-treated using a suitable method such as, for example, corona, plasma, or ultraviolet (UV) light-treatment. Indicia such as trademarks, symbols, logos, letters, and the like may be printed on the cover using pad-printing, ink-jet printing, dye-sublimation, or other suitable printing methods. Clear surface coatings (for example, primer and top-coats), which may contain a fluorescent whitening agent, may be applied to the cover. Golf balls may also be painted with one or more paint coatings in a variety of colors. In one embodiment, white primer paint is applied first to the surface of the ball and then a white top-coat of paint may be applied over the primer.
Golf balls made in accordance with this invention can be of any size, although the USGA requires that golf balls used in competition have a diameter of at least 1.68 inches. For play outside of United States Golf Association (USGA) rules, the golf balls can be of a smaller size. In one embodiment, golf balls made in accordance with this invention have a diameter in the range of about 1.68 to about 1.80 inches.
Dimensions of golf ball components, i.e., thickness and diameter, may vary depending on the desired properties. For the purposes of the invention, any layer thickness may be employed. Non-limiting examples of the various embodiments outlined above are provided here with respect to layer dimensions.
In solid core embodiments, the core may have a diameter ranging from about 1.39 inches to about 1.64 inches. In some embodiments, the solid core may have a diameter of about 1.45 inches to about 1.62 inches. In still further embodiments, the solid core may have a diameter of about 1.50 inches to about 1.60 inches.
In dual core embodiments, the inner core (center) may have a diameter of about 0.25 inches to about 1.51 inches. In other embodiments, the inner core (center) may have a diameter of about 0.30 inches to about 1.45 inches. In still other embodiments, the inner core (center) may have a diameter of about 0.50 inches to about 1.30 inches. In further embodiments, the inner core (center) may have a diameter of about 0.75 inches to about 1.15 inches. In still further embodiments, the inner core (center) may have a diameter of about 0.90 inches to about 1.05 inches. For example, the inner core (center) may have a diameter of about 1.01 inches. The dual core, including the center and the outer core layer, may have a diameter of about 1.39 inches to about 1.64 inches. In some embodiments, the dual core has a diameter of about 1.45 inches to about 1.62 inches. In still further embodiments, the dual core has a diameter of about 1.50 inches to about 1.60 inches.
The outer cover of a golf ball formed in accordance with the present disclosure may have a thickness to provide sufficient strength, good performance characteristics, and durability. In some embodiments, the cover thickness is from about 0.02 inches to about 0.35 inches. In other embodiments, the cover has a thickness of about 0.02 inches to about 0.12 inches. For example, the outer cover may have a thickness of about 0.02 inches to about 0.1 inches. In one embodiment, the outer cover has a thickness from about 0.02 inches to about 0.07 inches. In another embodiment, the outer cover thickness is about 0.05 inches or less, preferably from about 0.02 inches to about 0.05 inches. In yet another embodiment, the outer cover layer of such a golf ball is between about 0.02 inches and about 0.045 inches. In still another embodiment, the outer cover layer is about 0.025 to about 0.04 inches thick.
The range of thicknesses for an intermediate or casing layer of a golf ball is large because of the vast possibilities when using an intermediate layer, e.g., as an outer core layer or an inner cover layer. When used in a golf ball formed in accordance with the present disclosure, the intermediate layer or casing layer may have a thickness about 0.3 inches or less. In one embodiment, the thickness of the intermediate layer is from about 0.002 inches to about 0.1 inches, preferably about 0.01 inches or greater. In one embodiment, the thickness of the intermediate layer is about 0.09 inches or less, preferably about 0.06 inches or less. In another embodiment, the intermediate layer thickness is about 0.05 inches or less. In yet another embodiment, the intermediate layer thickness is about 0.02 inches to about 0.04 inches.
Varying combinations of these ranges of thickness for the intermediate and outer cover layers may be used in combination with other embodiments described herein. For example, when the golf ball has a dual cover, the inner cover layer may have a thickness of about 0.01 inches to about 0.12 inches, about 0.015 inches to about 0.08 inches, or about 0.02 inches to about 0.045 inches. The outer cover layer may have a thickness of about 0.01 inches to about 0.08 inches, about 0.015 inches to about 0.055 inches, or about 0.025 inches to about 0.04 inches. In some embodiments, the cover may be a single layer having a thickness of about 0.010 inches to about 0.040 inches. In other embodiments, the cover may be a single layer having a thickness of about 0.020 inches to about 0.035 inches. In still further embodiments, the cover may be a single layer having a thickness of about 0.025 inches to about 0.030 inches.
The hardness of the components of the golf ball may vary depending on the particular material used to form the component. It should be understood, especially to one of ordinary skill in the art, that there is a fundamental difference between “material hardness” and “hardness, as measured directly on a golf ball.” Material hardness is defined by the procedure set forth in ASTM-D2240 and generally involves measuring the hardness of a flat “slab” or “button” formed of the material of which the hardness is to be measured. Hardness, when measured directly on a golf ball (or other spherical surface) is a completely different measurement and, therefore, results in a different hardness value. This difference results from a number of factors including, but not limited to, ball construction (i.e., core type, number of core and/or cover layers, etc.), ball (or sphere) diameter, and the material composition of adjacent layers. It should also be understood that the two measurement techniques are not linearly related and, therefore, one hardness value cannot easily be correlated to the other.
The core of golf balls made according to the present disclosure may have varying hardnesses depending on the particular golf ball construction. In one embodiment, the core hardness is about 50 Shore C to about 105 Shore C, as measured on a formed sphere. In another embodiment, the hardness of the core is about 60 Shore C to about 100 Shore C. In still another embodiment, the core has a hardness of about 70 Shore D to about 95 Shore C.
Intermediate layer(s) of the present invention may also vary in hardness depending on the specific construction of the ball. In one embodiment, the hardness of the intermediate layer is about 30 Shore D or greater. In another embodiment, the hardness of the intermediate layer is about 90 Shore D or less, preferably about 80 Shore D or less, and more preferably about 70 Shore D or less. In yet another embodiment, the hardness of the intermediate layer is about 50 Shore D or greater. In one embodiment, the intermediate layer hardness is from about 50 Shore D to about 75 Shore D.
As with the core and intermediate layers, the hardness of the cover may vary depending on the construction and desired characteristics of the golf ball. For example, when the intermediate layer is intended to be the hardest point in the ball, e.g., about 50 Shore D to about 75 Shore D, the cover material may have a hardness of about 20 Shore D or greater, as measured on the slab. In another embodiment, the cover hardness is from about 30 Shore D to about 65 Shore D. In one embodiment, the cover has a hardness of about 40 Shore D to about 65 Shore D. In another embodiment, the cover has a hardness of less than about 60 Shore D. In other embodiments, the cover and intermediate layer materials have hardnesses that are substantially the same. When the hardness differential between the cover layer and the intermediate layer is not intended to be as significant, the ratio of the Shore D hardness of the outer cover to the intermediate layer is about 1.0 or less, preferably about 0.8 to 1.0 or less. In still other embodiments, the cover layer is harder than any underlying intermediate layer(s). In this aspect, the ratio of Shore D hardness of the cover layer to the intermediate layer is about 1.33 or less, preferably from about 1.14 or less.
As previously described, in some embodiments, golf balls made in accordance with the present disclosure may include a subassembly as described herein and a color-shifting layer disposed on the subassembly to form a finished golf ball. In other embodiments, the golf balls made in accordance with the present disclosure include a subassembly as described herein, a color-shifting (inner cover) layer disposed on the subassembly, and a clear outermost cover layer to form a finished golf ball. In this aspect, the outer cover layer may have a hardness that is less than that of the color-shifting (inner cover) layer. For example, the color-shifting (inner cover) layer may have a hardness of greater than about 60 Shore D and the clear outermost cover layer may have a hardness of less than about 60 Shore D. In one embodiment, the inner cover may have a hardness of about 40 to about 65 Shore D and the outer cover may have a hardness of about 30 to about 55 Shore D. In this embodiment, the color-shifting layer may be formed from an ionomeric material, and the outermost cover layer may be formed from a polyurethane, polyurea, or hybrid polyurethane-polyurea material.
In an alternative embodiment, the color-shifting (inner cover) layer may have a hardness of less than about 60 Shore D and the outer cover layer may have a hardness of greater than about 55 Shore D and the inner cover layer hardness is less than the outer cover layer hardness. In this alternative embodiment, the color-shifting (inner cover) layer may be formed of a partially or fully neutralized ionomer, a thermoplastic polyester elastomer, a thermoplastic polyether block amide, or a thermoplastic or thermosetting polyurethane or polyurea, and the outermost cover layer may include an ionomeric material.
A finished golf ball in accordance with the present disclosure has a different color appearance than either of the subassembly or the color-shifting formulation. In particular, when the color-shifting formulation is used in a layer disposed on the subassembly, a unique visual presence is achieved under visible light (between about 380 nm and about 770 nm or between about 400 nm and about 700 nm). For example, the subassembly may have a black color that appears bluish-green once the color-shifting layer is applied thereon. In addition, a finished golf ball in accordance with the present disclosure has a plurality of different color appearances depending on the angle of incidence.
In this regard, the differences in the color appearance between the subassembly, the color-shifting formulation, and golf ball (at any angle of incidence) according to the invention may be measured by a difference in hue, saturation, lightness, colorfulness, and/or chroma. In some embodiments, the color appearance of the subassembly and overall color appearance may differ by hue but be the same in another color measurement such as Chroma, lightness, etc. In other embodiments, the color appearance of the subassembly and overall color appearance have the same hue but differ in another color measurement such as Chroma, lightness, etc.
Accordingly, in certain embodiments, the subassembly may have a first color appearance defined by a first set of CIELAB coordinates (Ls*, as*, bs*, Cs*, and/or hs°) and an overall ball appearance at a plurality of incident angles defined by a plurality of second sets of CIELAB coordinates (Lo*, ao*, bo*, Co*, and/or ho°). At least one of the first set of CIELAB coordinates differ from its corresponding coordinate in the second set of CIELAB coordinates. For example, the subassembly may have a first hue hs° and the ball may have a second hue ho° that differs from first hue hs°. By way of further example, the subassembly may have a hue hs° of 25° and the ball may have a hue ho° that is between about 25 percent and about 60 percent of hs°. In some aspects, at least two of the first set of CIELAB coordinates differ from their respective coordinates in the second set of CIELAB coordinates. In some embodiments, at least three of the first set of CIELAB coordinates differ from the corresponding coordinates in the second set of CIELAB coordinates. In other embodiments, at least four of the first set of CIELAB coordinates differ from the corresponding coordinates in the second set of CIELAB coordinates. In still other embodiments, each of the first set of CIELAB coordinates differ from the corresponding coordinates in the second set of CIELAB coordinates. For example, in one aspect, each of the subassembly's CIELAB coordinates Ls*, as*, bs*, Cs*, and hs° differ from the ball's corresponding CIELAB coordinates Lo*, ao*, bo*, Co*, and ho°.
In other embodiments, the subassembly may have a first color appearance defined by a first set of RGB values (Rs, Gs, Bs) and an overall ball appearance at a particular angle of incidence defined by a second set of RGB values (Ro, Go, Bo). As would be understood by those of ordinary skill in the art, each RGB value (red, green, and blue) defines the intensity of the color with a value between 0 and 255. At least one of the first set of RGB values differ from its corresponding coordinate in the second set of RGB values. For example, RS and Ro may differ. In some aspects, at least two of the first set of RGB values differ from their respective coordinates in the second set of RGB values. In some embodiments, all three RGB values in the first set differ from the corresponding coordinates in the second set of RGB values. For example, in one aspect, each of the subassembly's RGB values Rs, Gs, Bs differ from the ball's corresponding RGB values Ro, Go, Bo.
As briefly discussed above, the color-shifting formulation is also defined by its own CIELAB coordinates or RGB values. In this regard, the color-shifting formulation may be represented by a third set of CIELAB coordinates (Lc*, ac*, bc*, Cc*, and/or hc°) and/or RGB values (Rc, Gc, Bc) where at least one of the third set of CIELAB coordinates and/or RGB values differ from the corresponding coordinates in each of the first and second set of CIELAB coordinates and/or RGB values.
Accordingly, in certain embodiments, the subassembly may have a first color appearance defined by a first set of CIELAB coordinates (Ls*, as*, bs*, Cs*, and/or hs°), an overall ball appearance at a particular angle of incidence defined by a second set of CIELAB coordinates (Lo*, ao*, bo*, Co*, and/or ho°), and the color-shifting formulation defined by a third set of CIELAB coordinates (Lc*, ac*, bc*, Cc*, and/or hc°). At least one of the first set of CIELAB coordinates differ from its corresponding coordinate in the second and third sets of CIELAB coordinates. For example, the subassembly may have a first hue hs°, the ball may have a second hue ho° that differs from first hue hs°, and the color-shifting formulation may have a third hue hc° that differs from both hs° and ho°. By way of further example, the subassembly may have a hue hs° of 25°, the ball may have a hue ho° that is between about 25 percent and about 60 percent of hs°, and the color-shifting formulation may have a hue hc° that differs from both hs° and ho°. In some embodiments, at least two of the third set of CIELAB coordinates differ from the corresponding coordinates in each of the first and second set of CIELAB coordinates. In other embodiments, at least three of the third set of CIELAB coordinates differ from the corresponding coordinates in each of the first and second set of CIELAB coordinates. In other embodiments, at least four of the third set of CIELAB coordinates differ from the corresponding coordinates in each of the first and second set of CIELAB coordinates. In still other embodiments, each of the third set of CIELAB coordinates differ from the corresponding coordinates in both the first and second set of CIELAB coordinates. For example, in one aspect, each of the subassembly's CIELAB coordinates Ls*, as*, bs*, Cs*, and hs° differ from the ball's corresponding CIELAB coordinates Lo*, ao*, bo*, Co*, and ho°, which differ from the color-shifting formulation's corresponding CIELAB coordinates Lc*, ac*, bc*, Cc*, and hc°.
In other embodiments, the subassembly may have a first color appearance defined by a first set of RGB values (Rs, Gs, Bs), an overall ball appearance at a particular angle of incidence defined by a second set of RGB values (Ro, Go, Bo), and the color-shifting formulation defined by a third set of RGB values (Rc, Gc, Bc). At least one of the first set of RGB values differ from its corresponding coordinate in the second and third sets of RGB values. For example, Rs, Ro, and Rc may all differ. In some embodiments, at least two of the third set of RGB values differ from the corresponding coordinates in each of the first and second set of RGB values. In other embodiments, each of the third set of RGB values differ from the corresponding coordinates in both the first and second set of RGB values.
When the subassembly is multi-colored, e.g., the subassembly is divided into regions where each region has its own set of CIELAB coordinates (Ls1*, as1*, bs1*, Cs1*, and hs1°; Ls2*, as2*, bs2*, Cs2*, and hs2°, etc.) and/or RGB values (Rs1, Gs1, Bs1), at least one of each region's CIELAB coordinates and/or RGB values differ from the corresponding coordinate/value in the CIELAB coordinates and/or RGB values for the golf ball (Lo*, ao*, bo*, Co*, and/or ho° and/or Ro, Go, Bo) and the CIELAB coordinates and/or RGB values for the color-shifting formulation (Lc*, ac*, bc*, Cc*, and/or hc° and/or Rc, Gc, Bc). In some embodiments, at least two of each region's CIELAB coordinates and/or RGB values differ from the corresponding coordinate/value in the CIELAB coordinates and/or RGB values for the golf ball (Lo*, ao*, bo*, Co*, and/or ho° and/or Ro, Go, Bo) and the CIELAB coordinates for the color-shifting formulation (Lc*, ac*, bc*, Cc*, and/or hc° and/or Rc, Gc, Bc). In other embodiments, at least three of each region's CIELAB coordinates and/or each of the RGB values differ from the corresponding coordinate/value in the CIELAB coordinates and/or each of the RGB values for the golf ball (Lo*, ao*, bo*, Co*, and/or ho° and/or Ro, Go, Bo) and the CIELAB coordinates and/or RGB values for the color-shifting formulation (Lc*, ac*, bc*, Cc*, and/or hc° and/or Rc, Gc, Bc). In still other embodiments, at least four of each region's CIELAB coordinates differ from the corresponding coordinate in the CIELAB coordinates for the golf ball (Lo*, ao*, bo*, Co*, and/or ho°) and the CIELAB coordinates for the color-shifting formulation (Lc*, ac*, bc*, Cc*, and/or hc°). In yet other embodiments, all of each region's CIELAB coordinates differ from the corresponding coordinate in the CIELAB coordinates for the golf ball (Lo*, ao*, bo*, Co*, and/or ho°) and the CIELAB coordinates for the color-shifting formulation (Lc*, ac*, bc*, Cc*, and/or hc°).
In some embodiments, the color-shifting layer creates an interference pattern (e.g., structural color) upon reflection of incident electromagnetic radiation. Without being bound by any particular theory, it is contemplated that, at least in some embodiments, the overall color appearance of the golf ball results from light interacting with the geometrical structures in the color-shifting formulation in a way that causes light interference and not only presents an overall color appearance that differs from the color appearance of the subassembly and the color appearance of the color-shifting formulation, but also causes the color observed when viewing the surface of the golf ball to be dependent upon the angle of the viewer as well as the angle of the light incident to the surface.
In this aspect, a golf ball formed with an outer color-shifting layer may have a first color appearance in a single area of measurement at one angle of incidence that differs from a second color appearance in the single area of measurement at another angle of incidence. In some embodiments, for any single area of measurement on the golf ball, this golf ball may have n color appearances at θn angles of incidence (where n indicates a color appearance associated with a particular angle of incidence (θ)), each of which differ from each other and differ from the color appearances of the subassembly and the color-shifting formulation. Each angle θ may differ from each other by at least about 10°. In some embodiments, θn may range from −15° to 110°.
In other embodiments, the golf ball has a plurality of color appearances where each color appearance has a particular angle θ of incidence associated therewith. For example, the color appearance of the golf ball in a single area of measurement at various angles of incidence θ may be described as follows:
In some aspects, Lo1*, Lo2*, Lo3*, Lo4*, Lo5*, and Lo6* each differ from each other. Similarly, the other CIELAB coordinates ao*, bo*, Co*, and ho° For each angle of incidence θ may differ from each other. In one embodiment, each CIELAB coordinate Lo*, ao*, bo*, Co*, and ho° for a particular angle of incidence differs from each corresponding CIELAB coordinates for the other angles of incidence and the corresponding CIELAB coordinates for the subassembly and color-shifting formulation.
In some embodiments, the color appearance of a golf ball made in accordance with the present disclosure may be defined by a subset of the CIELAB coordinates above. For example, the color appearance of a golf ball in a single area of measurement at various angles of incidence θ may be characterized by Lo*, ao*, and bo*.
In other embodiments, the color appearance of a golf ball in a single area of measurement at various angles of incidence θ may be characterized by ao* and bo*. For example, for a single area of measurement, the golf ball may have an ao* value at one incident angle that varies from the ao* value at another incident angle by at least about 2. In some aspects, in any single area of measurement, the golf ball may have an ao* value at one incident angle that varies from the ao* value at another incident angle by at least about 3. In other aspects, in any single area of measurement, the golf ball may have an ao* value at one incident angle that varies from the ao* value at another incident angle by at least about 5. In yet other aspects, in any single area of measurement, the golf ball may have an ao* value at one incident angle that varies from the ao* value at another incident angle by at least about 7. In still other aspects, in any single area of measurement, a color-shifting layer may have an ao* value at one incident angle that varies from the ac* value at another incident angle by at least about 10. In yet other aspects, in any single area of measurement, a color-shifting layer may have an ao* value at one incident angle that varies from the ac* value at another incident angle by at least about 15.
Similarly, for any single area of measurement, a golf ball may have an bo* value at one incident angle that varies from the bo* value at another incident angle by at least about 2. In some aspects, in any single area of measurement, a golf ball may have an bo* value at one incident angle that varies from the bo* value at another incident angle by at least about 3. In other aspects, in any single area of measurement, a color-shifting layer may have an bo* value at one incident angle that varies from the bo* value at another incident angle by at least about 5. In yet other aspects, in any single area of measurement, a color-shifting layer may have an bo* value at one incident angle that varies from the bo* value at another incident angle by at least about 7. In still other aspects, in any single area of measurement, a color-shifting layer may have an bo* value at one incident angle that varies from the bo* value at another incident angle by at least about 10. In yet other aspects, in any single area of measurement, a color-shifting layer may have an bo* value at one incident angle that varies from the bo* value at another incident angle by at least about 15.
In other embodiments, for any single area of measurement (e.g., a 2 mm area), ao15°* (value of ao* at 15° incident angle) of a golf ball may vary from ao75°* (value of ao* at 75° incident angle) by at least about 5. In some embodiments, for any single area of measurement, ao15°* of a golf ball may vary from ao75°* by at least about 8. In other embodiments, for any single area of measurement, ac75°* of a golf ball may vary from ao75°* by at least about 10.
In other embodiments, for any single area of measurement, bo15°* (value of bo* at 15° incident angle) of a golf ball may vary from bo75°* (value of bo* at 75° incident angle) by at least about 5. In some embodiments, for any single area of measurement, bo15°* of a golf ball may vary from bc75°* (value of bo* at 75° incident angle) by at least about 8. In other embodiments, for any single area of measurement, bo15°* of a golf ball may vary from bo75°* by at least about 10.
In some embodiments, the colors across the golf ball may shift. In this aspect, ao*, bo*, or both for at least one incident angle from −15 degrees to 110 degrees may exhibit a color shift of more than about 5 from a reference (first) point on the surface of the golf ball (within a selected aperture area) (ao1*, bo1) to a different (second) point on the surface of the golf ball (within the selected aperture area) (ao2*, bo1) and defined by
In some aspects, the color shift is more than about 10 in at least two different areas of measurement on the golf ball. For example, using a 12 mm area of a finished golf ball (“the analyzed area”) having a color-shifting layer over a solid subassembly, a* may shift by at least about 10 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. In some embodiments, a* may shift by at least about 15 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. In other embodiments, a* may shift by at least about from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. Similarly, b* may shift by at least about 10 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. In some embodiments, b* may shift by at least 15 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. In other embodiments, b* may shift by at least about 20 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. In still other embodiments, both a* and b* may shift by at least about 10 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. In yet other embodiments, both a and b* may shift by at least about 15 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. In other embodiments, both a* and b* may shift by at least about 20 from a first 2 mm area within the analyzed area to a second 2 mm area within the analyzed area. While the discussion above relates to two distinct areas on the golf ball surface, the disclosure is not limited to the “reference point” color shift in just two areas of the golf ball. Rather, the reference point color shift may occur at a plurality of areas on the surface of a golf ball. In this aspect, the plurality of areas may be at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, and at least 10. In some aspects, a golf ball formed with a color-shifting layer in accordance with the present disclosure has a color shift across more than 10 distinct areas of measurements on the golf ball.
In other embodiments, the color appearance of the golf ball at various angles of incidence θ may be described as follows:
In some embodiments, Ro1, Ro2, and Ro3 each differ from each other. Similarly, Go1, Go2, and Go3 and/or Bo1, Bo2, and Bo3 may each differ from each other. In one embodiment, each RGB value Ro, Go, Bo for a particular angle of incidence differs from each corresponding RGB value for the other angles of incidence and the corresponding RGB values for the subassembly and color-shifting formulation. In fact, golf balls formed in accordance with the present disclosure have RGB values that change, at least relative to one another, from one angle of incidence to another. In this aspect, at least two of the RGB values may “flop” depending on the angle of incidence. For example, at a high angle illumination (e.g., about 70° to about 90°), the color appearance as defined in RGB values may be dominated by red (R) and green (G) and blue (B) may be only a minor component of the color appearance, whereas at low angle illumination (e.g., less than about 20°), the color appearance may be dominated by R and B and G now has only a minor role in the color appearance.
In some embodiments, the color appearance of the golf ball may be defined as follows:
The following example describes golf balls that can be made in accordance with this invention.
CIELAB coordinates and/or RGB values are ascertainable for each of the subassembly, color-shifting formulation, and golf ball (at a single angle of incidence or a plurality of angles of incidence. Thus, the differences between the subassemblies and the finished golf balls may be characterized by the set of color properties (and the differences therebetween).
As such, in addition to any qualitative color appearance assessment, color appearance in CIELAB coordinates and/or RGB values may be ascertained for the subassemblies, plaques and finished golfs using, in the case of CIELAB coordinates, a multiangle colorimeter or other suitable instrument (such as a BYK-mac i multiangle spectrophotometer from BYK-Gardner or a MetaVue™ spectrophotometer from X-Rite) or, in the case of RGB values, using a stereomicroscope (such as the Olympus SZ-61 trinocular stereomicroscope), a camera (such as the Olympus UC-30 mounted on the stereomicroscope), and software (such as Olympus Stream Essentials).
In the case of the CIE values, plaques and ball/sphere samples may analyzed with a 5-angle color measurement: 15°/25°/45°/75°/110° relative to the camera aperture. For example, using the X-rite spectrophotometer, a 2 mm-12 mm area may be designated anywhere on the ball, and the CIE coordinates may be measured over this area. In one specific trial, a golf ball with a green iridescent color-shifting formulation disposed over a mint-green subassembly was analyzed. As shown in
In the case of the RGB values, ball samples may be illuminated from low angle (≤20°) and/or high angle (about 70 to about 90°) relative to the camera aperture (“angle of incidence”). Using the ‘Line Profile’ in the software, a rectangular area may be designated on the ball, stretching from the “high angle illumination” portion to the “low angle illumination” portion of the ball, and the RGB values may be measured over this area. In one specific example, the ball sample includes a mint green subassembly covered by an iridescent purple color-shifting layer. As shown in
Different color-shifting formulations of the present disclosure were analyzed over a white plaque (Examples A-D), a yellow plaque (Examples E-F), and a green plaque (Examples G-H) using a BYK-mac i 23 mm (catalog number 6340) at D65/10°.
Details regarding the color-shifting formulations and underlying plaques are provided in Table 2 below. The subscripts SP and LP denote an average particle size of <50 μm and ≥50 μm, respectively. The color-shifting formulation includes a color concentrate present in an amount of 5 percent by weight of the total formulation. The base formulation is ionomeric.
As set forth in Tables 3-5 below and graphically illustrated in
Each L*, a*, and b* value in the tables below represent the average of three measurements. The control data in Table 3 below reflects a standard white plaque.
The angular color shift of Example A is shown in
The angular color shift of Example E is shown in
The angular color shift of Example G is shown in
As shown in Table 6 below, the difference between a* for each adjacent pair of incident angles, i.e., −15° and 15°, 15° and 25°, 25° and 45°, 45° and 75°, and 75° and 110°, was first calculated and then the average of all the individual adjacent pair differences was obtained to determine the average a* color shift at a single area of measurement. This similar exercise was performed for b*. For all example plaques made with a color-shifting layer in accordance with the present disclosure, at least one of a* or b* have an average color shift for adjacent pair of incident angles greater than 2. For example, with the exception of Ex. B, the average a* color shift for each adjacent pair of incident angles is at least 3. Similarly, the average b* color shift for each adjacent pair of incident angles is at least 2. In this aspect, all but Ex. B have an average a* and b* color shift for each adjacent pair of incident angles at a single area of measurement of at least 2.
In contrast, the average difference between either the a* or b* values for each adjacent pair of incident angles for any of the solid color plaques is less than 2. And, for each of the Examples C-H, the average a* color shift for each adjacent pair of incident angles is at least 6 and the average b* color shift for each adjacent pair of incident angles is at least 7. With respect to Example B, while the average a* color shift is less than 2, the average b* color shift is the highest of the examples and greater than 12.
The golf balls described and claimed herein are not to be limited in scope by the specific embodiments herein disclosed since these embodiments are intended as illustrations of several aspects of the disclosure. Methods and materials are described herein for use in the present invention; other, suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and not intended to be limiting. Any equivalent embodiments are intended to be within the scope of this disclosure. Indeed, various modifications of the device in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. Any section headings herein are provided only for consistency with the suggestions of 37 C.F.R. § 1.77 or otherwise to provide organizational queues. These headings shall not limit or characterize the invention(s) set forth herein.
This application claims priority to U.S. Prov. Pat. App. No. 63/450,438, filed Mar. 7, 2023, the entire disclosure of which is incorporated by reference herein.
| Number | Date | Country | |
|---|---|---|---|
| 63450438 | Mar 2023 | US |
