Polyurethane cover compound for golf balls incorporating polyether polyol and polyphenylene ether polyol

Abstract

To provide a golf ball having a composition that improves shear durability without requiring additional materials or manufacturing processes. [Solution] The cover 16 is formed from a cover composition comprising an isocyanate-containing component, a first isocyanate-reactive component, a second isocyanate-reactive component, and a chain extender. The first isocyanate-reactive component may be a polyether polyol such as polytetramethylene ether glycol. The second isocyanate-reactive component may be a polyphenylene ether polyol such as poly(2,6-dimethyl-1,4-phenylene ether)diol. The ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 90:10 to about 99:1. The chain extender may be a chain extender with a hydroxyl terminal group or a chain extender with an amino terminal group.

Description

Technical Field

[0001] The present disclosure generally relates to polyurethane and hybrid polyurethane - polyurea compositions, methods of making such compositions, and golf balls including at least one layer formed from such compositions. The compositions of the present disclosure result in golf ball components having improved physical properties such as shear durability. A golf ball manufactured in accordance with the present disclosure can include a golf ball component formed from the compositions of the present disclosure. For example, in one embodiment, a golf ball formed in accordance with the present disclosure can include an inner ball surrounded by a cover formed from the polyurethane or hybrid polyurethane - polyurea composition of the present disclosure. In this aspect, a golf ball manufactured in accordance with the present disclosure can have many advantageous physical properties and play performance characteristics.

Background Art

[0002] The performance and / or durability of a golf ball are affected by various factors including the materials, weight, size, dimple pattern, and outer shape of the golf ball. Golf ball manufacturers are constantly improving the materials and structures of the balls to incrementally improve performance and / or durability. Modern multi - piece solid golf balls often include a core, a casing layer disposed around the core, and a cover layer disposed around the casing layer. As a result of favorable properties, polyurethanes and polyureas are utilized as structural and coating layers of such golf balls. In particular, the cover layer is generally formed from polyurethane, polyurea, or a polyurethane - polyurea hybrid. For example, a popular three - piece golf ball can include a rubber core surrounded by an ionomer - based casing layer and a cover layer formed from polyurethane or a polyurethane - polyurea hybrid.

[0003] Polyurethanes, polyureas, and polyurethane-polyurea hybrids used in the manufacture of golf balls, whether for structural or coating layers, are generally formed by the reaction of an isocyanate-containing component, which may be a polyfunctional isocyanate, with an isocyanate-reactive component, which may be a long-chain polyol or polyamine. Generally, polyurethanes are produced by the reaction of a polyfunctional isocyanate (NCO-R-NCO) with a long-chain polyol having terminal hydroxyl groups (OH-R'-OH) in the presence of a catalyst and other additives. The chain length of a polyurethane prepolymer can be extended by reacting the polyurethane prepolymer with a chain extender, which may be a short-chain diol (OH-R”-OH) for forming polyurethane or a short-chain diamine (NH2-R”-NH2) for forming a polyurethane-polyurea hybrid. Similarly, polyureas are produced by reacting a polyfunctional isocyanate (NCO-R-NCO) with a long-chain polyamine (NH2-R'-NH2) having terminal amino groups in the presence of a catalyst and other additives. The chain length of a polyurea prepolymer can be extended by reacting the polyurea prepolymer with a chain extender, which is a short-chain diamine (NH2-R'-NH2) for forming polyurea or a short-chain diol (OH-R'-OH) for forming a polyurea-polyurethane hybrid.

[0004] The resulting polyurethane, polyurea, or polyurethane-polyurea hybrid or polyurea-urethane hybrid possesses rubber-like elasticity due to the covalent bonding of "hard" and "soft" segments. This phase separation occurs primarily because the non-polar, low-melting-point soft segment is incompatible with the polar, high-melting-point hard segment. The hard segment (formed by the reaction of isocyanate-containing components and chain extenders) is relatively rigid and impede movement. The soft segment (formed by the reaction of isocyanate-containing components and isocyanate-reactive components) is relatively flexible and easily movable. Because the hard segment is covalently bonded to the soft segment, it suppresses the plastic flow of the polymer chain, creating the elastomer's elastomeric resiliency.

[0005] Thermoplastic and thermosetting polyurethanes, polyureas, or polyurethane-polyurea hybrids can be used to form golf ball covers. Thermoplastic compositions generally have minimal crosslinking, and the bonds within the polymer network are mainly due to hydrogen bonding or other physical mechanisms. Due to the low level of crosslinking, thermoplastic compositions are relatively flexible. In addition, the crosslinking bonds in thermoplastic compositions are reversibly broken by temperature increases, such as during molding or extrusion. In other words, thermoplastic materials soften when exposed to heat and return to their original state when cooled. On the other hand, the crosslinking bonds in thermosetting compositions are irreversibly fixed once the composition hardens and are not broken even when exposed to heat. Therefore, thermosetting compositions, which typically have a high level of crosslinking, are relatively rigid.

[0006] In this regard, one of the problems with multi-piece golf balls commonly used in modern play, which have cover layers made of polyurethane, polyurea, or polyurethane-polyurea hybrids, is that such golf balls tend to have low shear durability. Golf balls with low shear durability may delaminate more frequently when exposed to shear forces. Delamination is when the outer layer of a golf ball, such as the cover, becomes detached from the adjacent inner layer (such as the casing layer). Delamination generally occurs when a golf ball is struck with a high-angle club such as a wedge, or when a strong shear force is applied to the golf ball. As a result of the shear force, the outer and inner layers may move in different directions or at different speeds, causing them to detach from each other. Delamination may be visibly apparent as "bubbling" or air pockets between layers, or as a tear in the golf ball's cover. Delamination negatively affects not only the appearance of the golf ball but also its performance.

[0007] One way to improve the shear durability of multi-piece golf balls is to enhance the adhesion between the cover layer and the underlying casing or core layer. Currently, various types of adhesion-enhancing pretreatment processes exist to address the problems of cutting and shearing caused by insufficient adhesion between the casing and cover layers. Examples of pretreatment include surface roughening; surface energy modification such as corona treatment, plasma treatment, and flame treatment; adhesives; adhesion promoters; and combinations thereof. Adhesives are typically applied by spraying or dipping and usually require drying and post-curing steps. Certain adhesion promoters may be applied by dipping or spraying and then undergo washing and drying steps. In the case of golf balls with a cast urethane cover placed on a casing layer, the casing layer needs to be treated with a primer to enhance adhesion between the casing and cover and reduce the possibility of delamination. While these adhesion-enhancing processes increase the interlayer adhesion strength and the overall durability of the golf ball, they require expensive materials and additional steps in the manufacturing process, thereby increasing manufacturing time and cost. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Therefore, it is advantageous to have a composition for use in the cover layer of a golf ball that improves the shear durability of the golf ball without requiring additional materials or manufacturing processes, while providing desirable playing characteristics. This disclosure provides such a composition and a golf ball comprising components manufactured using such a composition. [Means for solving the problem]

[0009] (Summary of the invention) The problems detailed above and other problems are addressed by the following inventions, however, it should be understood that not all embodiments of the invention described herein address each of the above problems.

[0010] In some embodiments, the disclosure relates to a golf ball comprising a core and a cover disposed on the core and formed from a cover composition comprising an isocyanate-containing component, a first isocyanate-reactive component, a second isocyanate-reactive component comprising a polyphenylene ether polyol, and a chain extender reaction product. In another embodiment, the second isocyanate-reactive component comprises poly(2,6-dimethyl-1,4-phenylene ether)diol. In yet another embodiment, the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 70:30 to about 99:1. In yet another embodiment, the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 90:10 to about 99:1.

[0011] In further embodiments, the isocyanate-containing component comprises a first isocyanate-containing component and a second isocyanate-containing component. In yet another embodiment, the first and second isocyanate-containing components are aliphatic. In yet another embodiment, the chain extender is a chain extender with a hydroxyl-terminated group. In yet another embodiment, the chain extender is a chain extender with an amino-terminated group. In yet another embodiment, the ratio of the isocyanate-containing component to the first and second isocyanate-reactive components is about 1:0.95 to about 1.2:1. In yet another embodiment, the core comprises a rubber compound comprising a base rubber which is polybutadiene rubber, styrene-butadiene rubber, or a blend thereof. In yet another embodiment, the golf ball further comprises a casing layer disposed on the core and formed from a casing composition comprising an ionomer, and a cover disposed on the casing layer.

[0012] In some embodiments, the disclosure provides a golf ball comprising a core and a cover disposed on the core and formed from a cover composition, wherein the cover composition comprises a reaction product of an isocyanate-containing component, a first isocyanate-reactive component comprising a polyether polyol, a second isocyanate-reactive component comprising a polyphenylene ether polyol, and a chain extender, the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component being in the range of about 70:30 to about 99:1. In another embodiment, the first isocyanate-reactive component comprises polytetramethylene ether glycol. In yet another embodiment, the second isocyanate-reactive component comprises poly(2,6-dimethyl-1,4-phenylene ether)diol. In yet another embodiment, the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 90:10 to about 99:1.

[0013] In some embodiments, the disclosure provides a golf ball comprising a core and a cover disposed on the core and formed from a cover composition, wherein the cover composition comprises an isocyanate-containing component, a first isocyanate-reactive component comprising polytetramethylene ether glycol, a second isocyanate-reactive component comprising poly(2,6-dimethyl-1,4-phenylene ether)diol, and a reaction product of a chain extender. In yet another embodiment, the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 90:10 to about 99:1. In yet another embodiment, the isocyanate-containing component comprises a first isocyanate-containing component and a second isocyanate-containing component, wherein the first and second isocyanate-containing components are aliphatic. In yet another embodiment, the chain extender is a chain extender with a hydroxyl-terminated group. In yet another embodiment, the chain extender is a chain extender with an amino-terminated group.

[0014] Further features and advantages of this disclosure can be found in the following detailed description, provided in conjunction with the drawings below. [Brief explanation of the drawing]

[0015] [Figure 1] This is a cross-sectional view of a three-piece golf ball assembly according to one embodiment of the present disclosure. [Figure 2] This is a cross-sectional view of a four-piece golf ball according to one embodiment of the present disclosure. [Figure 3] This is a cross-sectional view of a five-piece golf ball according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0016] This disclosure relates to compositions that can be used to produce components of a golf ball. In some embodiments, the compositions of this disclosure can be used to form a cover layer of a golf ball. The compositions described herein can result in a golf ball with improved shear resistance (compared to a golf ball that does not contain components formed from the compositions of this disclosure). The compositions, components, and golf balls formed therefrom will be discussed in more detail below. composition The compositions of this disclosure may comprise a base polymer and one or more other components. The concentration of components is expressed as a weight percentage (weight%) unless otherwise specified. As used in this invention, the term “weight percent” (also known as “percent by weight” or “weight%”) is defined as the weight of a particular component present in a mixture relative to the total weight composition of the mixture. Mathematically, this can be expressed by dividing the weight of the component by the total weight of the mixture and multiplying by 100.

[0017] The base polymer may contain organic units linked by a linkage formed by the reaction of an isocyanate-containing component having an isocyanate group (-N=C=O) with an isocyanate-reactive component having a terminal nucleophilic functional group such as a hydroxyl group (-OH) or an amino group (-NH2). The reaction between the isocyanate group (-N=C=O) of the isocyanate-containing component and the nucleophilic functional group of the isocyanate-reactive component results in at least one of the following linkages:

[0018] [ka]

[0019] The urethane bond (-NHCOO-) is obtained from the reaction between an isocyanate-containing component and an isocyanate-reactive component with a hydroxyl terminus. The urea bond (-HNCONH-) is obtained from the reaction between an isocyanate-containing component and an isocyanate-reactive component with an amino terminus. The base polymer of this disclosure is as follows (I): -(X - Y)- n (I) [Wherein, X represents a - soft segment formed from an isocyanate - reactive component discussed below, and Y represents a - hard segment formed from an isocyanate - containing component and a chain extender that extends the chain length of the polymer and increases the molecular weight.] As shown in, it alternately includes a multi - dispersion block of a soft segment and a hard segment. The soft segment imparts elasticity, toughness, and resiliency, and the hard segment contributes to strength, hardness, and high - temperature performance. In other words, the hard segment provides a physical and stable network formed by chemical bonds or hydrogen bonds or resulting from chain entanglement, and the soft segment provides rubbery deformability through a temporary network formed by crystalline, semi - crystalline or liquid - crystalline, or amorphous domains.

[0020] The base polymer can be produced by the reaction of a polyfunctional isocyanate (NCO - R - NCO) with a long - chain isocyanate - reactive component such as a long - chain polyol (OH - R’ - OH) or a polyamine (NH2 - R’ - NH2). For example, the base polymer of the cover can be formed from polyurethane, polyurea, or a hybrid of polyurethane and polyurea according to the desired properties and performance of the golf ball having a cover containing the base polymer.

[0021] The polyurethane or polyurethane-polyurea composition used to form the outer cover layer contains urethane bonds formed by the reaction of isocyanate groups (-N=C=O) and hydroxy groups (-OH). The polyurethane or polyurethane-polyurea composition can be produced by the reaction of an isocyanate-containing component and a component having a hydroxy group as a terminal group. In some embodiments, the polyurethane or polyurethane-polyurea composition is formed by reacting a polyfunctional isocyanate compound (NCO-R-NCO) with a long-chain polyol having terminal hydroxy groups (OH-R’-OH) in the presence of a catalyst and other additives to form a polyurethane prepolymer. As used herein, the term "prepolymer" means a polymer of relatively low to medium molecular weight, usually an intermediate material between the monomer and the final polymer, and can be further polymerized by reaction with a crosslinking agent or a chain extender. To form a polyurethane composition, the chain length of the polyurethane prepolymer is extended by reacting the polyurethane prepolymer with a short-chain diol (OH-R”-OH). To form a hybrid polyurethane-polyurea composition, the chain length of the polyurethane prepolymer is extended by reacting the polyurethane prepolymer with a short-chain diamine (NH2-R”-NH2).

[0022] Similarly, polyurea or polyurethane-polyurea compositions used to form the outer cover layer contain urea bonds formed by reacting an isocyanate group (-N=C=O) with an amino group (-NH2). Polyurea compositions can be produced by reacting an isocyanate-containing component with an amino-terminated component. In some embodiments, polyurea or polyurea-polyurethane compositions are produced by forming a polyurea prepolymer by reacting a polyfunctional isocyanate compound (NCO-R-NCO) with a long-chain polyamine (NH2-R'-NH2) having a terminal amino group in the presence of a catalyst and other additives. To form a polyurea composition, the chain length of the polyurea prepolymer is extended by reacting the polyurea prepolymer with a short-chain diamine (NH2-R”-NH2). To form a hybrid polyurethane-polyurea composition, the chain length of the polyurea prepolymer is extended by reacting the polyurea prepolymer with a short-chain diol (OH-R”-OH).

[0023] Isocyanate-containing ingredients The term "isocyanate-containing component" refers to any aliphatic or aromatic isocyanate having two or more isocyanate functional groups. Isocyanate-containing components may be monomers or monomeric units, because they can be polymerized to produce polymeric isocyanates containing two or more monomeric isocyanate repeating units. Isocyanate-containing components may have any suitable main chain structure, including saturated or unsaturated, and linear, branched, or cyclic. For example, suitable isocyanate-containing components include diisocyanates having the general structure: O=C=NRN=C=O (wherein R is preferably a cyclic, linear, or branched hydrocarbon portion containing about 1 to 20 carbon atoms). Isocyanate-containing components may be a single isocyanate-containing component or a blend of isocyanate-containing components. The term "isocyanate compound" may be used interchangeably with "isocyanate-containing component."

[0024] Any suitable isocyanate-containing component may be used to form a polyurethane or polyurethane-polyurea composition. Suitable isocyanate-containing components include isophorone diisocyanate (IPDI); 1,6-hexamethylene diisocyanate (HDI); 1,4-cyclohexyl diisocyanate (CHDI); 4,4'-diisocyanatodicyclohexylmethane diisocyanate (H12MDI); 4,4'-methylenediphenyl diisocyanate (MDI); 2,4'-methylenediphenyl diisocyanate (MDI); 2,4-toluene diisocyanate (TDI); 2,6-toluene diisocyanate (TDI); trimethylhexamethylene diisocyanate (TMDI); 3,3'-dimethyl This includes, but is not limited to, til-4,4'-biphenyl diisocyanate (TOD); p-phenylenediisocyanate (PPDI); dodecane diisocyanate (C12DI); m-tetramethylene xylene diisocyanate (TMXDI); 1,4-benzene diisocyanate; trans-cyclohexane-1,4-diisocyanate; 1,5-naphthalene diisocyanate (NDI); naphthalene-2,4-diisocyanate (NDI); 4,6-xylene diisocyanate (XDI); 1,4-bis(isocyanatomethyl)cyclohexane; or mixtures thereof.

[0025] In some embodiments, the isocyanate-containing component includes one or more cyclic groups. If multiple cyclic groups are present, linear and / or branched hydrocarbons containing about 1 to about 10 carbon atoms may be present as spacers between the cyclic groups. In some cases, the cyclic groups may be substituted at positions 2, 3, and / or 4. Substituents may include, but are not limited to, halogens, primary, secondary, or tertiary hydrocarbon groups, or mixtures thereof.

[0026] Suitable aromatic isocyanate-containing components that may be used in accordance with this disclosure include, for example, 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), 4,4'-methylenediphenyl diisocyanate (MDI), 2,4'-methylenediphenyl diisocyanate (MDI), polymer methylenediphenyl diisocyanate (PMDI), p-phenylenediisocyanate (PPDI), m-phenylenediisocyanate (PDI), 1,5-naphthalene diisocyanate (NDI), naphthalene 2,4-diisocyanate (NDI), p-xylenediisocyanate (XDI), and homopolymers, copolymers, and blends thereof.

[0027] Suitable aliphatic isocyanate-containing components that may be used in accordance with this disclosure include, for example, isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4'-diisocyanate ("H12MDI"), meta-tetramethylxylene diisocyanate (TMXDI), trans-cyclohexane diisocyanate (CHDI), 1,4-bis(isocyanatomethyl)cyclohexane (H6XDI), and homopolymers, copolymers, and blends thereof. Examples of suitable aliphatic isocyanate-containing components for use in this disclosure include Desomdur® N-3400 and Desomdur® W, available from Covestro AG in Leverkusen, Germany.

[0028] Isocyanate-reactive components The term "isocyanate-reactive component" refers to any aliphatic or aromatic compound having at least two primary or secondary hydroxyl or amino functional groups. In some embodiments, the isocyanate-reactive component is low-functionality, meaning it has two or fewer functional groups. In other embodiments, the isocyanate-reactive component is high-functionality, meaning it has more than two functional groups. While not bound by any particular theory, the use of low-functionality isocyanate-reactive components results in more flexible compositions, while the use of high-functionality isocyanate-reactive components results in more rigid compositions. The isocyanate-reactive component may be aliphatic, aromatic, or aliphatic-aromatic. The isocyanate-reactive component may be a single isocyanate-reactive component or a blend of isocyanate-reactive components.

[0029] In some embodiments, the isocyanate-reactive component may be a polyol. The polyol may be any aliphatic or aromatic compound containing two or more hydroxyl functional groups. The term "polyol" may be used interchangeably with components having a hydroxyl terminal group. Suitable polyols for use in accordance with this disclosure include, but are not limited to, polyether polyols, polyphenylene ether polyols, polybutadiene polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, polyamide polyols, and combinations or copolymers thereof. In any of the embodiments described below, the hydrocarbon chain may have saturated or unsaturated bonds, or substituted or unsubstituted aromatic and cyclic groups.

[0030] In one embodiment, the polyol includes polyether polyols. Suitable polyether polyols include, but are not limited to, polytetramethylene ether glycol (PTMEG); polyethylene glycol (PEG); polypropylene glycol (PPG); polyethylene propylene glycol; polyoxypropylene glycol; and mixtures thereof. The molecular weight of the polyether polyol can vary, but in some embodiments, the polybutadiene polyol has a molecular weight of about 1000 to about 5000 g / mol. In other embodiments, the polyether polyol has a molecular weight in the range of about 1200 to about 3000 g / mol. In yet another embodiment, the polyether polyol has a molecular weight in the range of about 1200 to about 2500 g / mol. In yet another embodiment, the polyether polyol has a molecular weight in the range of about 1200 to about 2000 g / mol.

[0031] In another embodiment, the polyol is a polyphenylene ether polyol. The molecular weight of the polyphenylene ether polyol can vary, but in some embodiments, the polyphenylene ether polyol has a molecular weight of about 1000 to about 4000 g / mol. In other embodiments, the polyphenylene ether polyol has a molecular weight in the range of about 1200 to about 3000 g / mol. In yet another embodiment, the polyphenylene ether polyol has a molecular weight in the range of about 1200 to about 2500 g / mol. In yet another embodiment, the polyphenylene ether polyol has a molecular weight in the range of about 1200 to about 2000 g / mol. Preferred examples of commercially available polyol blends containing polyphenylene ether polyol include, but are not limited to, those marketed under the trademark name Noryl®. For example, Noryl® AP2001G (containing poly(2,6-dimethyl-1,4-phenylene ether)diol) is available from SABIC in Riyadh, Saudi Arabia.

[0032] In yet another embodiment, the polyol includes polybutadiene polyols. As used in the present invention, the term “polybutadiene polyol” means a butadiene oligomer with hydroxyl functional groups at both ends, and may include partially hydrogenated / fully hydrogenated derivatives. Polybutadiene polyols may have 1,2-groups, 1,4-cis groups, and / or 1,4-trans groups in their skeleton. Depending on the synthesis method, the vinyl content and functional value may vary. In some embodiments, the polybutadiene polyol may have a 1,2-vinyl content of less than about 50 percent. In other embodiments, the polybutadiene polyol may have a 1,2-vinyl content of about 50 percent or more. For example, the 1,2-vinyl content may range from about 55 percent to about 70 percent. In one embodiment, the 1,2-vinyl content is in the range of about 62 to about 68 percent. In some embodiments, the functional value may be less than about 2. In other embodiments, the functional value may be about 2 to about 3. For example, the functional value may be about 2.3 to about 2.6. In one embodiment, a polybutadiene polyol for use as an isocyanate-reactive component has a functional value of about 1.9 and a 1,2-vinyl content of about 65 percent. One such commercially available polybutadiene polyol is Krasol® LBH2000, available from Cray Valley, Grand Junction, CO. The molecular weight of the polybutadiene polyol can vary, but in some embodiments, the polybutadiene polyol has a molecular weight of about 1000 to about 5000 g / mol. In other embodiments, the polybutadiene polyol has a molecular weight in the range of about 2000 to about 5000 g / mol.

[0033] In yet another embodiment, the polyol is a polyester polyol. Suitable polyester polyols include, but are not limited to, polyethylene adipate glycol; polybutylene adipate glycol; polyethylene propylene adipate glycol; o-phthalate-1,6-hexanediol; poly(hexamethylene adipate) glycol; and mixtures thereof. As will be understood by those skilled in the art, such polyester polyols may be synthesized by polycondensation reaction of ethylene / butylene / hexamethylene glycol with adipic acid.

[0034] In yet another embodiment, the polyol is a polycaprolactone polyol. Suitable polycaprolactone polyols include, but are not limited to, 1,6-hexanediol-started polycaprolactone, diethylene glycol-started polycaprolactone, trimethylolpropane-started polycaprolactone, neopentyl glycol-started polycaprolactone, 1,4-butanediol-started polycaprolactone, poly(δ-valerolactone), and mixtures thereof.

[0035] In yet another embodiment, the polyol is a polycarbonate polyol. Suitable polycarbonate polyols include, but are not limited to, polyphthalate carbonates; poly(hexamethylene carbonate) glycols; and mixtures thereof.

[0036] In another embodiment, the polyol is a polyamide polyol. Polyamide polyols are synthesized from secondary diamines, and the chain ends are functionalized to obtain primary or secondary alcohol end groups. In addition, polyamide polyols suitable for use in the cover compositions of this disclosure can be manufactured in accordance with U.S. Patent Publication No. 2008 / 0223519, the entire disclosure of which is incorporated herein by reference. In this embodiment, the polyamide polyol is of the formula T-[Z-(C=O)-R2-(C=O)] n -ZT [In the formula, n is at least 1, each T is independently selected and may be the same or different, and is X-R1-(C=O) (wherein each X is independently selected and may be the same or different, and is H or OH, each R1 is independently selected and may be the same or different, and is a hydrocarbon group having 2 to 54 carbon atoms), each R2 is independently selected and may be the same or different, and is a hydrocarbon group having 2 to 54 carbon atoms, and Z is NLN (wherein L represents a bond between a pair of nitrogen atoms connected by a hydrocarbon bond).] It may have a tertiary polyamide fragment. In some embodiments, L is an internitrogen hydrocarbon group. In other embodiments, L is a cyclic hydrocarbon group incorporating at least one nitrogen atom, and at least one but fewer than all Z groups comprise a polyoxyalkyl group. When the cover composition of this disclosure is prepared using a polyamide polyol as the isocyanate-reactive component, the soft segment may comprise a tertiary polyamide fragment.

[0037] In some embodiments, the isocyanate-reactive component may be a polyamine. The polyamine may be any aliphatic or aromatic compound containing two or more amino functional groups. The polyamine may be an amino-terminated component with a backbone of polycarbonate, polycaprolactone, polybutadiene, polyamide, or a combination thereof. In this embodiment, the amino-terminated component may include, but is not limited to, polycarbonate polyamines, polycaprolactone polyamines, polybutadiene polyamines, polyamide polyamines, polyester polyamines, and combinations or copolymers thereof. The hydrocarbon chain may have saturated or unsaturated bonds and substituted or unsubstituted aromatic and cyclic groups. The term "polyamine" may be used interchangeably with the amino-terminated component.

[0038] In one embodiment, the amino-terminated component includes polycarbonate polyamines such as poly(phthalate carbonate)diamine, poly(hexamethylene carbonate)diamine, (bisphenol A)-based polycarbonate diamine, and combinations thereof. In some embodiments, the polyamine may be an aromatic polycarbonate polyamine. In other embodiments, the polyamine may be an aliphatic polycarbonate polyamine.

[0039] In another embodiment, the amino-terminated component includes a polycaprolactone polyamine. Examples of polycaprolactone polyamines used in the cover compositions of this disclosure include, but are not limited to, (alkylene oxide)-started polycaprolactone polyamines, (ethylene glycol)-started polycaprolactone polyamines, (diethylene glycol)-started polycaprolactone polyamines, (propylene glycol)-started polycaprolactone polyamines, (dipropylene glycol)-started polycaprolactone polyamines, 1,4-butanediol-started polycaprolactone polyamines, trimethylolpropane-started polycaprolactone polyamines, (neopentyl glycol)-started polycaprolactone polyamines, 1,6-hexanediol-started polycaprolactone polyamines, (polytetramethylene ether glycol)-started polycaprolactone polyamines, and combinations thereof.

[0040] In yet another embodiment, the amino-terminated component may be a butadiene oligomer, with each terminus being an amino group. For example, the amino-terminated component may be a polybutadiene polyamine, a poly(hydrogenated butadiene) polyamine, or a combination thereof.

[0041] In yet another embodiment, the amino-terminated component includes a polyamide polyamine. The polyamide polyamine is synthesized from a secondary diamine, and the chain ends are functionalized to obtain a primary or secondary amino-terminated group.

[0042] In yet another embodiment, the amino-terminated component includes polyester polyamines, for example, poly(ethylene adipate)diamine, poly(butylene adipate)diamine, poly(hexamethylene adipate)diamine, poly(ethylenepropylene adipate)diamine, poly(ethylenebutylene adipate)diamine, poly(hexamethylenebutylene adipate)diamine, (o-phthalate-1,6-hexanediol)-based polyester polyamines, poly(ethylene terephthalate)-based polyester polyamines, and combinations thereof.

[0043] Other suitable polyamines for use in accordance with this disclosure include, but are not limited to, polyoxypropylene diamines, poly(ethylene oxide-capped oxypropylene) ether diamines, triethylene glycol diamines, propylene oxide-based triamines, trimethylolpropane-based triamines, glycerin-based triamines, and mixtures thereof.

[0044] In some embodiments, the cover composition may contain more than one type of isocyanate-reactive component; that is, the cover composition may contain a first isocyanate-reactive component at the concentration of the first isocyanate-reactive component and a second isocyanate-reactive component at the concentration of the second isocyanate-reactive component. In this embodiment, the ratio of the concentration (weight percent) of the first isocyanate-reactive component to the concentration (weight percent) of the second isocyanate-reactive component may be about 70:30 to about 99.5:0.5. In some embodiments, the ratio of the concentration of the first isocyanate-reactive component to the concentration of the second isocyanate-reactive component is approximately 70:30 to approximately 95:5 or approximately 75:25 to approximately 99:1 or approximately 70:30 to approximately 90:10 or approximately 75:25 to approximately 95:5 or approximately 80:20 to approximately 95:5 or approximately 85:15 to approximately 99:1 or approximately 70:30 to approximately 80:20 or approximately 75:25 to approximately 85:15 or approximately 80:20 It may also be approximately 90:10 or 85:15~95:5 or 90:10~99:1 or 70:30~75:25 or 75:25~80:20 or 80:20~85:5 or 82:18~87:13 or 85:15~90:10 or 87:13~92:8 or 90:10~95:5 or 92:8~97:3 or 95:5~99:1.

[0045] In some embodiments, the ratio of the concentration of the first isocyanate-reactive component to the concentration of the second isocyanate-reactive component may be about 80:20 to about 84:16, or about 82:18 to about 86:14, or about 84:16 to about 88:12, or about 86:14 to about 90:10, or about 88:12 to about 92:8, or about 80:20 to about 83:17, or about 82:18 to about 85:15, or about 84:16 to about 87:13, or about 86:14 to about 89:11, or about 88:12 to about 91:9. In other embodiments, the ratio of the concentration of the first isocyanate-reactive component to the concentration of the second isocyanate-reactive component may be about 90:10 to about 94:6, or about 92:8 to about 96:4, or about 94:6 to about 98:2, or about 90:10 to about 93:7, or about 92:8 to about 95:5, or about 94:6 to about 97:3, or about 96:4 to about 99:1. In further embodiments, the ratio of the concentration of the first isocyanate-reactive component to the concentration of the second isocyanate-reactive component may be approximately 80:20 to approximately 82:18, or approximately 81:19 to approximately 83:17, or approximately 82:18 to approximately 84:16, or approximately 83:17 to approximately 85:15, or approximately 84:16 to approximately 86:14, or approximately 85:15 to approximately 87:13, or approximately 86:14 to approximately 88:12, or approximately 87:13 to approximately 89:11, or approximately 88:12 to approximately 90:10, or approximately 89:11 to approximately 91:9. In further embodiments, the ratio of the concentration of the first isocyanate-reactive component to the concentration of the second isocyanate-reactive component may be approximately 90:10 to approximately 92:8, approximately 91:9 to approximately 93:7, approximately 92:8 to approximately 94:6, approximately 93:7 to approximately 95:5, approximately 94:6 to approximately 96:4, approximately 95:5 to approximately 97:3, approximately 96:4 to approximately 98:2, or approximately 97:3 to approximately 99:1.

[0046] In some embodiments, the isocyanate-reactive component may be formed from a blend of isocyanate-reactive compounds, or, in embodiments comprising a first isocyanate-reactive component and a second isocyanate-reactive component, either the first or second isocyanate-reactive component may comprise a blend of isocyanate-reactive compounds containing the isocyanate-reactive compound in the other isocyanate-reactive component. In such embodiments, it may be beneficial to determine the concentration of a particular isocyanate-reactive compound based on the total weight of the entire isocyanate-reactive component. The isocyanate-reactive compound may be a specific compound such as poly(2,6-dimethyl-1,4-phenylene ether)diol, or a compound of the type such as polyphenylene ether polyol.

[0047] For example, the isocyanate-reactive compound may be included in the cover composition at a concentration of about 0.1% to about 15.0% by weight of the total weight of the isocyanate-reactive components. In one embodiment, the isocyanate-reactive compound is included in the cover composition at a concentration of about 0.1% to about 10.0% by weight, or about 10.0% to about 12.0% by weight, or about 5.0% to about 15.0% by weight, or about 0.1% to about 8.0% by weight, or about 2.0% to about 10.0% by weight, or about 4.0% to about 12.0% by weight, or about 0.1% to about 5.0% by weight, or about 2.5% to about 7.5% by weight, or about 5.0% to about 10.0% by weight, or about 7.5% to about 12.5% ​​by weight, based on the total weight of the isocyanate-reactive components. In another embodiment, the isocyanate-reactive compound is present in the cover composition in an amount of about 0.1% to about 3.0% by weight, or about 2.0% to about 5.0% by weight, or about 4.0% to about 7.0% by weight, or about 6.0% to about 9.0% by weight, or about 8.0% to about 11.0%, or about 10.0% to about 12.0% by weight, or about 0.1% to about 2.0% by weight, or about 1.0% to about 3.0% by weight, based on the total weight of the isocyanate-reactive components. It is included in a concentration of weight percent or about 2.0 weight percent to about 4.0 weight percent or about 3.0 weight percent to about 5.0 weight percent or about 4.0 weight percent to about 6.0 weight percent or about 5.0 weight percent to about 7.0 weight percent or about 6.0 weight percent to about 8.0 weight percent or about 7.0 weight percent to about 9.0 weight percent or about 8.0 weight percent to about 11.0 or about 9.0 weight percent to about 11.0 weight percent or about 10.0 weight percent to about 12.0 weight percent. For example, in one embodiment, the cover composition may contain polyphenylene ether polyol in a concentration of about 2.5 weight percent to about 10 weight percent of the total weight of the isocyanate-reactive component.

[0048] To form a polyurethane or polyurea prepolymer, an isocyanate-reactive component (i.e., either a component with a hydroxyl group or a component with an amino group) is reacted with a stoichiometric excess of an isocyanate-containing component. This reaction produces an isocyanate-terminated prepolymer. The resulting isocyanate-terminated prepolymer can then be reacted with a curing agent blend, as will be discussed in more detail below.

[0049] Hardener blend Curing agent blends contain chain extenders (curing agents) to extend the chain length of the prepolymer and increase its molecular weight. Generally, thermoplastic polyurethane or polyurea compositions are typically formed by reacting an isocyanate blend with a chain extender in a 1:1 stoichiometric ratio. Thermosetting compositions, on the other hand, are crosslinked polymers and are typically produced by reacting an isocyanate blend with a chain extender in a stoichiometric ratio of approximately 1.05:1.

[0050] The chain extender may have a carbon chain skeleton having a hydroxyl-terminated group, an amino-terminated group, or a combination thereof. The skeleton may be branched or linear. In some embodiments, the chain extender may have an even number of carbon atoms between terminal groups. In other embodiments, the chain extender may have an odd number of carbon atoms between terminal groups. Generally, the chain extender has a low molecular weight (i.e., about 500 g / mol or less). In some embodiments, the chain extender has a molecular weight of about 400 g / mol or less. In other embodiments, the chain extender has a molecular weight of about 250 g / mol or less. The chain extender may be a single chain extender or a blend of multiple chain extenders.

[0051] Suitable hydroxyl-terminated chain extenders include: ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol (MPO); 2-methyl-1,4-butanediol; monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; dipropylene glycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol (BDO); ​​2,3-butanediol; 1,6-hexanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane (TMP); cyclohexyldimethylol; triisopropanolamine; N,N,N',N'-tetra-(2 (-hydroxypropyl)-ethylenediamine; diethylene glycol bis-(aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol; 1,3-bis-(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis-[2-(2-hydroxyethoxy)ethoxy]cyclohexane; 1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane; trimethylolpropane; polytetramethylene ether glycol (PTMEG) (preferably with a molecular weight of about 250 to about 500); hydroquinone bis(2-hydroxyethyl) ether (HQEE); 1,3-bis(2-hydroxyethyl)resorcinal (HER); and mixtures thereof.

[0052] Suitable amino-terminated chain extenders include unsaturated diamines, such as 4,4'-diamino-diphenylmethane (i.e., 4,4'-methylene-dianiline or "MDA"), m-phenylenediamine, p-phenylenediamine, 1,2- or 1,4-bis(sec-butylamino)benzene, 3,5-diethyl-(2,4- or 2,6-)toluenediamine (i.e., "DETDA"), and 3,5-dimethylthio-(2,4- or 2,6-)toluenediamine. -)toluenediamine, 3,5-diethylthio-(2,4- or 2,6-)toluenediamine, 3,3'-dimethyl-4,4'-diamino-diphenylmethane, 3,3'-diethyl-5,5'-dimethyl4,4'-diamino-diphenylmethane (i.e., 4,4'-methylene-bis(2-ethyl-6-methylbenzeneamine)), 3,3'-dichloro-4,4'-diamino-diphenylmethane (i.e., 4,4'-methylene-bis(2- Chloroaniline) or "MOCA"), 3,3',5,5'-tetraethyl-4,4'-diamino-diphenylmethane (i.e., 4,4'-methylene-bis(2,6-diethylaniline), 2,2'-dichloro-3,3',5,5'-tetraethyl-4,4'-diamino-diphenylmethane (i.e., 4,4'-methylene-bis(3-chloro-2,6-diethyleneaniline) or "MCDEA"), 3,3'-diethyl-5,5'-dichloro The amino-terminated chain extender may be 4,4'-diamino-diphenylmethane (or "MDEA"), 3,3'-dichloro-2,2',6,6'-tetraethyl-4,4'-diamino-diphenylmethane, 3,3'-dichloro-4,4'-diamino-diphenylmethane, 4,4'-methylene-bis(2,3-dichloroaniline) (i.e., 2,2',3,3'-tetrachloro-4,4'-diamino-diphenylmethane, or "MDCA"), or mixtures thereof. In some embodiments, the amino-terminated chain extender is diethyltoluenediamine. Examples of commercially available diethyltoluenediamines include, but are not limited to, Lonzacure® DETDA80LC, available from Arxada, Basel, Switzerland.

[0053] Multifunctional and highly branched chain extenders can be used to obtain a superbranched chain structure in the cover composition. In some embodiments, the chain extenders are trimethylolpropane, glycerol, triglyceride doricinolate, superbranched polyols, and combinations thereof.

[0054] The cover compositions of this disclosure may include a pigment dispersion. The pigment dispersion may be included in the curing agent blend together with a chain extender. The pigment dispersion may include a pigment and a dispersant and may be present in a carrier such as a hydroxyl-terminated carrier resin added to the curing agent blend. Examples of suitable pure pigments include, but are not limited to, copper pigments, chromium pigments, aluminum pigments, manganese pigments, gold pigments, arsenic pigments, bismuth pigments, cerium pigments, iron pigments, titanium pigments (i.e., titanium oxide of TiO2), tin pigments, zinc pigments, quinacridone pigments, phthalocyanine pigments, complex oxide pigments, ultramarine violet pigments, cobalt violet pigments, manganese violet pigments, dioxane violet pigments, quinacridone violet pigments, carbon black pigments, or combinations thereof. Examples of suitable dispersants include fatty acid-based wetting agents such as BYK®-W961; titanate-based additives such as Tytan CP-317; phosphate esters such as Chemphos TC-310S; or any other wetting dispersants. Examples of commercially available pigment dispersions include, but are not limited to, Stan-Tone HCC Vinyl Paste Dispersions from Avient Corporation in Avon Lake, Ohio, and Alkyd Dispersions from Penn Color Inc. in Doylestown, Pennsylvania. In other embodiments, the support for the pigment dispersion may be a non-reactive plasticizer, and the pigment dispersion may be added to a prepolymer blend or a curing agent blend.

[0055] The pigment dispersion may be included in the cover composition in varying amounts depending on the desired properties of the golf ball. In some embodiments, the pigment dispersion may be included in the cover composition at a concentration of about 0.1% to about 10.0% by weight. In one embodiment, the pigment dispersion is included in the cover composition at a concentration of about 0.1% to about 8.0% by weight, or about 0.01% to about 6.0% by weight, or about 0.01% to about 4.0% by weight, or about 2.0% to about 6.0% by weight, or about 4.0% to about 8.0% by weight, or about 6.0% to about 10.0% by weight. In another embodiment, the pigment dispersion is included in the cover composition at a concentration of about 0.1% to about 2.0% by weight, or about 1.0% to about 3.0% by weight, or about 2.0% to about 4.0% by weight, or about 3.0% to about 5.0% by weight, or about 4.0% to about 6.0% by weight, or about 5.0% to about 7.0% by weight, or about 6.0% to about 8.0% by weight, or about 2.0% to about 3.0% by weight, or about 3.0% to about 4.0% by weight, or about 3.5% to about 4.5% by weight, or about 4.0% to about 5.0% by weight, or about 5.0% to about 6.0% by weight, or about 6.0% to about 7.0% by weight, or about 7.0% to about 8.0% by weight.

[0056] Formation of composition The cover composition can be formed using a one-shot technique or a prepolymer technique. In some embodiments, the cover composition is formed using a one-shot technique in which an isocyanate-containing component, an isocyanate-reactive component, and a chain extender are reacted in a single step. In other embodiments, the cover composition is formed using a prepolymer technique in which a prepolymer is generated by an initial reaction between the isocyanate-containing component and the isocyanate-reactive component, and the cover composition is formed by a subsequent reaction between the prepolymer and the chain extender. To form a polyurethane or polyurea prepolymer, the isocyanate-reactive component (i.e., either a component with a hydroxyl-terminated group or a component with an amino-terminated group) is reacted with a stoichiometric excess of the isocyanate-containing component. In some embodiments, the ratio of the isocyanate-containing component to the isocyanate-reactive component is about 1:0.95 to about 1.2:1. This reaction generates a prepolymer with isocyanate-terminated groups.

[0057] As a result of the reaction between the isocyanate compound and the polyol or polyamine compound, a small amount of unreacted NCO groups are present in the prepolymer. The amount of unreacted NCO groups in the prepolymer should be about 15%, about 10%, or about 5% or less, based on the total weight of the prepolymer. In some embodiments, the prepolymer has about 12%, about 8%, or about 6% or less of unreacted NCO groups. In other embodiments, the prepolymer has about 1% to about 8%, or about 5% to about 7%, of NCO groups, based on the total weight of the prepolymer. As the weight percentage of unreacted isocyanate groups increases, the hardness of the composition also generally increases.

[0058] When the isocyanate-reactive component has a hydroxyl group as its terminal group, the resulting prepolymer contains urethane bonds and is referred to as a polyurethane prepolymer. When the isocyanate-reactive component has an amino group as its terminal group, the resulting prepolymer contains urea bonds and is referred to as a polyurea prepolymer. On the other hand, when polyurethane or polyurea prepolymer is reacted with a chain extender having an amino group as its terminal group or a chain extender having a hydroxyl group as its terminal group, the resulting composition contains urethane bonds and urea bonds and may be referred to as a polyurethane-polyurea hybrid or composition. The concentrations of urethane bonds and urea bonds in the hybrid composition can vary. Generally, the hybrid composition may contain a mixture of about 10 to 90 percent urethane bonds and about 90 to 10 percent urea bonds. In other embodiments, the cover composition may contain a mixture of about 20 to 80 percent urethane bonds and about 80 to 20 percent urea bonds. In other embodiments, the cover composition may contain a mixture of about 30 to 70 percent urethane bonds and about 70 to 30 percent urea bonds.

[0059] In some embodiments, the base polymer may be present in the cover composition in an amount of about 90 to about 100 weight percent. In one embodiment, the base polymer is present in the cover composition in an amount of about 90 to about 99.9 weight percent or about 92 to about 97 weight percent or about 90 to about 95 weight percent or about 93 to about 95 weight percent or about 90 to about 93 weight percent or about 92 to about 94 weight percent. In another embodiment, the base polymer is present in the cover composition in an amount of about 95 to about 99.9 weight percent or about 96 to about 99 weight percent or about 95 to about 98 weight percent or about 97 to about 99 weight percent. In a further embodiment, the base polymer may be included in the cover composition in an amount of about 96% to about 99.9% by weight, or about 97% to about 99.9% by weight, or about 98% to about 99.9% by weight, or about 99% to about 99.9% by weight, or about 98% to about 99.5% by weight, or about 98% to about 99% by weight, or about 98.5% to about 99.5% by weight.

[0060] additives The cover compositions of this disclosure may also include fillers, additives, and other components that do not impair (and possibly improve) the properties of the final coating composition. These additional materials include, but are not limited to, wetting agents, colorants, fluorescent whitening agents, hindered amine light stabilizers, rheology modifiers, catalysts, fluorosurfactants, non-fluorescent and fluorescent whitening agents such as titanium dioxide and zinc oxide, ultraviolet (UV) absorbers, leveling agents, slip agents, processing aids, surfactants, defoamers, crosslinking agents, and other conventional additives, such as antioxidants, stabilizers, softeners, plasticizers, impact modifiers, foaming agents, density-modifying fillers, reinforcing agents, and compatibilizers.

[0061] In some embodiments, a catalyst is used to facilitate the reaction between an isocyanate-containing component and an isocyanate-reactive component to produce a prepolymer, or to facilitate the reaction between the prepolymer and a chain extender during the chain extension step. Catalysts may be particularly useful when an aliphatic isocyanate-containing component is used and / or when the reaction is carried out at low temperatures. In this embodiment, preferred catalysts include amino catalysts and organometallic catalysts. Preferred amine catalysts include, but are not limited to, triethylenediamine (TEDA), triethylamine, tributylamine, dimethylethanolamine (DMEA), dimethylcyclohexylamine (DMCHA), and combinations thereof. Suitable organometallic catalysts include, but are not limited to, bismuth catalysts; zinc octanoate; stannous octanoate; tin catalysts, such as bis-butyltin dilaurate, bis-butyltin diacetate, stannous octanoate; tin(II) chloride, tin(IV) chloride, bis-butyltin dimethoxide, dimethylbis[(1-oxoneodecyl)oxy]stannane, di-n-octyltin bis-isooctyl mercaptoacetate, and combinations thereof. Organic acids such as oleic acid and acetic acid, as well as retarding catalysts, may also be used. When a catalyst is used, it may be added in an amount sufficient to catalyze the reaction of the components in the reaction mixture. In some embodiments, the catalyst is present in an amount of about 0.001 to about 1 weight percent of the reaction mixture. In other embodiments, the catalyst is present in an amount of about 0.1 to about 0.5 weight percent of the reaction mixture.

[0062] golf ball A golf ball formed according to this disclosure includes at least a core and a cover. While not bound by any particular theory, a golf ball manufactured using the cover composition of this disclosure may be more durable than a conventional golf ball without sacrificing performance or processability. In some embodiments, a golf ball formed according to this disclosure has a cover layer formed from the cover composition of this disclosure.

[0063] Referring to Figure 1, in one version, a three-piece golf ball 10 may be manufactured according to this disclosure. The ball 10 includes a core 12, a cover 16, and a casing layer 14 positioned between the core 12 and the cover 16. Referring to Figure 2, in one version, a four-piece golf ball 20 may be manufactured according to this disclosure. The ball 20 includes a center 22, an outer core layer 24, a cover 28, and a casing layer 26 positioned between the outer core layer 24 and the cover 28. Referring to Figure 3, in another version, a five-piece golf ball 30 includes a core 32 including a center 32a, an outer core layer 32c, and an inner core layer 32b positioned between the center 32a and the outer core layer 32c, a cover 36, and a casing layer 34 positioned between the core 32 and the cover 36. In any of these embodiments, the casing layers 14, 26, and 34 may be considered or referred to as an intermediate layer, a mantle layer, an inner cover layer, or any other layer positioned between the core assembly of the ball and the outer cover. In any of these embodiments, the cover 16, 28, or 36 may be formed from the cover composition of the present disclosure.

[0064] While golf balls manufactured according to this disclosure can be of any size, the USGA requires that golf balls used in competition have a diameter of at least 1.68 inches. According to this disclosure, the weight, diameter, and thickness of the core and cover layers can be adjusted as needed so that the ball meets the USGA specifications of a maximum weight of 1.62 ounces and a minimum diameter of 1.68 inches or more. Since there is no upper limit, many golf balls have an overall diameter in the range of approximately 1.68 inches to approximately 1.80 inches. In this regard, the diameter of golf balls manufactured according to this disclosure is in the range of approximately 1.68 inches to approximately 1.80 inches. In another embodiment, the diameter of the golf ball is approximately 1.68 inches to approximately 1.74 inches. In yet another embodiment, the diameter of the golf ball is approximately 1.68 inches to approximately 1.70 inches. When playing outside the rules of the United States Golf Association (USGA), golf balls can be smaller in size. In one embodiment, the diameter of a golf ball manufactured according to this disclosure is approximately 1.68 inches or less, for example, in the range of 1.55 inches to approximately 1.68 inches.

[0065] While each of the above-described cover compositions is suitable for use as a cover layer in a golf ball, it is intended that cover compositions formed according to this disclosure may also be used to form one or more other layers in any of the above-described one-piece, two-piece, three-piece, four-piece, five-piece, or more-piece (laminated) balls. That is, the core layer, the intermediate layer, and / or the cover layer may all be formed from the cover compositions of this disclosure.

[0066] The core of a golf ball formed according to this disclosure may be a single-layer core including a solid ball, or a multi-layer core including a center and at least one core layer positioned above it. The core component may be formed from a rubber compound, which may also be referred to herein as a core composition. In one embodiment, the rubber compound includes a base rubber in an amount of about 5 to 100 weight percent based on the total weight of the compound. In one embodiment, the base rubber is included in the rubber compound in an amount ranging from a lower limit of about 5 percent or 10 percent or 20 percent or 30 percent or 40 percent or 50 percent to an upper limit of about 55 percent or 60 percent or 70 percent or 80 percent or 90 percent or 95 percent or 100 percent. For example, the base rubber may be present in the rubber compound in an amount of about 40 to 95 weight percent based on the total weight of the compound. In one embodiment, the rubber compound includes a base rubber in an amount of about 55 to 95 weight percent based on the total weight of the compound.

[0067] The base rubber may be polybutadiene, polyisoprene, ethylene propylene rubber, ethylene-propylene diene rubber, styrene-butadiene rubber, styrene block copolymer rubber, polyalkenamer (e.g., polyoctenamer), butyl rubber, halobutyl rubber, polystyrene elastomer, polyethylene elastomer, polyurethane elastomer, polyurea elastomer, metallocene catalyst elastomer and plastomer, copolymer of isobutylene and p-alkylstyrene, halogenated copolymer of isobutylene and p-alkylstyrene, copolymer of butadiene and acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, and blends of two or more of these. In one embodiment, the rubber compound includes polybutadiene rubber, butyl rubber, or a blend thereof as the base rubber. Examples of commercially available polybutadiene rubbers that can be used as a base rubber in accordance with this disclosure include, but are not limited to, CB1221 available from ARLANXEO Performance Polymers in Maastricht, Netherlands. Examples of commercially available styrene-butadiene rubbers that can be used in rubber formulations in accordance with this disclosure include, but are not limited to, Plioflex® 1502 available from Goodyear, Inc. in Akron, Ohio.

[0068] The rubber compound further comprises a reactive crosslinking agent. Preferred agents include, but are not limited to, metal salts of unsaturated carboxylic acids having 3 to 8 carbon atoms; unsaturated vinyl compounds and polyfunctional monomers (e.g., trimethylolpropane trimethacrylate); phenylene bismaleimide; and combinations thereof. In one embodiment, the agent is one or more metal salts of acrylate, diacrylate, methacrylate, and dimethacrylate, where the metal is selected from magnesium, calcium, zinc, aluminum, lithium, and nickel. In another embodiment, the agent comprises one or more zinc salts of acrylate, diacrylate, methacrylate, and dimethacrylate. For example, the agent may be zinc diacrylate (ZDA). In yet another embodiment, the agent may be zinc dimethacrylate (ZDMA).

[0069] The additives may be included in the rubber compound in varying amounts, depending on the specific core component to which the rubber compound is intended. In one embodiment, the amount of additives used in the rubber compound increases with each outer component of the core assembly. In other words, the additives in the rubber compound for the center are included in a first amount, and the additives in the rubber compound for the outer core layer are included in a second amount. The second amount may be greater than the first amount. In this embodiment, the first amount may be about 25 percent to about 90 percent of the second amount. For example, the first amount may be about 40 percent to about 80 percent of the second amount. In one embodiment, the first amount is about 60 percent to about 75 percent of the second amount.

[0070] Radical scavengers such as halogenated organic sulfurs, organic disulfides, or inorganic disulfide compounds may also be added to the rubber formulation. In some embodiments, halogenated organic sulfur compounds for use according to this disclosure include, but are not limited to, pentachlorothiophenol (PCTP) and salts of PCTP, such as zinc pentachlorothiophenol (ZnPCTP). In other embodiments, dityl disulfide, diphenyl disulfide, dixyl disulfide, 2-nitroresorcinol, and combinations thereof are added to the rubber formulation.

[0071] Rubber formulations may also contain fillers. Suitable non-limiting examples of fillers include carbon black, clay and nanoclay particles, talc, glass (e.g., glass flakes, milled glass, and microglass), mica and mica-based pigments (e.g., Iriodin® pearlescent pigments from Merck Group), and combinations thereof. Metal oxide and metal sulfate fillers are also intended to be included in rubber formulations. Suitable metal fillers include, for example, particles, 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, as well as alloys and combinations thereof. Suitable metal oxide fillers include, for example, zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, and zirconium oxide. Suitable metal sulfate fillers include, for example, barium sulfate and strontium sulfate. Rubber regrind, a crushed recycled rubber material obtained from discarded rubber golf ball cores, can also be used as a filler.

[0072] If a filler is included, the amount of the filler may be about 1 to about 40 parts by weight per 100 parts by weight of the total rubber. In one embodiment, the rubber compound contains at least one filler in an amount of about 1 to about 20 parts by weight, or about 1 to about 15 parts by weight, or about 15 to about 20 parts by weight, per 100 parts by weight of the total rubber. In another embodiment, the rubber compound contains at least one filler in an amount of about 1 to about 10 parts by weight, or about 3 to about 8 parts by weight, or about 4 to about 6 parts by weight, per 100 parts by weight of the total rubber. For example, the rubber compound may contain any of these amounts of metal oxide. In a further embodiment, the rubber compound contains at least one filler in an amount of about 1 to about 30 parts by weight, or about 5 to about 15 parts by weight, or about 10 to about 20 parts by weight, or about 15 to about 25 parts by weight, per 100 parts by weight of the total rubber. In yet another embodiment, the rubber compound contains at least one filler in an amount of about 12 to about 22 parts by weight, or about 15 to about 20 parts by weight, or about 16 to about 18 parts by weight per 100 parts by weight of the total rubber. For example, the rubber compound may contain any of these amounts of metal sulfate.

[0073] Other additives and fillers include, but are not limited to, fluorescent whitening agents, fluorescent agents, whitening agents, UV absorbers, light stabilizers, surfactants, processing aids, antioxidants, stabilizers, softeners, chemical blowing and foaming agents, defoaming agents, fragrance components, plasticizers, wetting agents, impact modifiers, ozone degradation inhibitors, titanium dioxide, clay, mica, talc, glass flakes, milled glass, colorants, such as pigments, pigment dispersions, and dyes, and mixtures thereof.

[0074] The rubber compound may be cured using a conventional curing process. Non-limiting examples of curing processes suitable for use in accordance with this disclosure include peroxide curing, sulfur curing, high-energy radiation curing, and combinations thereof. In one embodiment, the rubber compound comprises a free radical initiator selected from an organic peroxide, a high-energy radiation source capable of generating free radicals, and a combination thereof. Suitable organic peroxides include, but are not limited to, dicumyl peroxides, n-butyl-4,4-di(t-butylperoxy)valerate; 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane; 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; di-t-butyl peroxide; di-t-amyl peroxide; t-butyl peroxide; t-butylcumyl peroxide; 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3; di(2-t-butylperoxyisopropyl)benzene; dilauroyl peroxide; dibenzoyl peroxide; t-butyl hydroperoxide; and combinations thereof. In certain embodiments, the free radical initiator is dicumyl peroxide, including, but is not limited to, Perkadox® BC, commercially available from Akzo Nobel. Peroxide-based free radical initiators may be present in the rubber compound in an amount of at least 0.05 parts by weight per 100 parts by weight of total rubber, or in an amount within the range where the lower limit is 0.05 parts by weight, 0.1 parts by weight, 1 part by weight, 1.25 parts by weight, 1.5 parts by weight, 2.5 parts by weight, or 5 parts by weight per 100 parts by weight of total rubber, and the upper limit is within the range where 2.5 parts by weight, 3 parts by weight, 5 parts by weight, 6 parts by weight, 10 parts by weight, or 15 parts by weight per 100 parts by weight of total rubber. Unless otherwise specified, concentrations are in units of percentage (phr). As used in this invention, the term "percentage" (also known as "phr" or "pph") is defined as the number of parts by weight of a particular component present in the mixture relative to 100 parts by weight of the polymer component. Mathematically, this can be expressed by dividing the weight of the component by the total weight of the polymer and multiplying by 100.

[0075] The core diameter may range from approximately 1.50 inches to approximately 1.60 inches. In one embodiment, the core has a diameter of approximately 1.52 inches to approximately 1.58 inches. In another embodiment, the core has a diameter of approximately 1.52 inches to approximately 1.56 inches.

[0076] If the cover layer of a golf ball formed in accordance with this disclosure is not formed from the cover composition of this disclosure, such layer may be formed from any of the base polymers described above with respect to the cover composition, e.g., polyurethane; polyurea; copolymers, blends, and hybrids of polyurethane and polyurea; olefin copolymer ionomer resins; polyethylene, e.g., including low-density polyethylene, linear low-density polyethylene, and high-density polyethylene; polypropylene; rubber-reinforced olefin polymers; acid copolymers, e.g., poly(meth)acrylic acid that is not part of an ionomer copolymer; plastomers; flexomers; styrene / butadiene / styrene block copolymers; styrene / ethylene-butylene / styrene block copolymers; dynamically vulcanized elastomers; copolymers of ethylene and vinyl acetate; copolymers of ethylene and methyl acrylate; polyvinyl chloride resins; polyamides, poly(amide ester) elastomers, and ionomer graft copolymers; crosslinked trans-polyisoprene and its blends; polyester thermoplastic elastomers; polyurethane thermoplastic elastomers; synthetic or natural vulcanized rubber; and combinations thereof.

[0077] Similarly, if the layer positioned between the core and the cover (if any) is not formed from the thermoplastic elastomer composition of the Disclosure, conventional and non-conventional materials may be used to form such a layer of the ball, including, for example, ionomer resins, highly neutralized polymers, polybutadiene, butyl rubber, and other rubber-based core formulations. In this embodiment, ionsomers suitable for use in accordance with the Disclosure may include partially neutralized ionsomers and highly neutralized ionsomers (HNPs), which include blends of two or more partially neutralized ionsomers, blends of two or more highly neutralized ionsomers, and ionsomers formed from blends of one or more partially neutralized ionsomers and one or more highly neutralized ionsomers. For the purposes of the Disclosure, “HNP” means an acid copolymer after at least 70 percent of the total acid groups present in the composition have been neutralized.

[0078] Suitable ionomers may be salts of O / X and O / X / Y type acid copolymers, where O is an α-olefin, X is a C3-C8 α,β-ethylenically unsaturated carboxylic acid, and Y is a softening monomer. O is preferably selected from ethylene and propylene. X may be selected from methacrylic acid, acrylic acid, ethacrylic acid, crotonic acid, and itaconic acid, and Y can be selected from (meth)acrylates and alkyl(meth)acrylates having an alkyl group with 1 to 8 carbon atoms, including, but not limited to, n-butyl(meth)acrylate, isobutyl(meth)acrylate, methyl(meth)acrylate, and ethyl(meth)acrylate. Non-limiting examples of O / X and O / X / Y type copolymers include ethylene acid copolymers, such as ethylene / (meth)acrylic acid, ethylene / (meth)acrylic acid / maleic anhydride, ethylene / (meth)acrylic acid / maleic acid monoester, ethylene / maleic acid, ethylene / maleic acid monoester, ethylene / (meth)acrylic acid / n-butyl (meth)acrylate, ethylene / (meth)acrylic acid / iso-butyl (meth)acrylate, ethylene / (meth)acrylic acid / methyl (meth)acrylate, and ethylene / (meth)acrylic acid / ethyl (meth)acrylate copolymers.

[0079] Low-acid and high-acid ionomer polymers, as well as blends of such ionomers, may be used. Generally, low-acid ionomers are considered to contain an acidic portion of 16 weight percent or less, while high-acid ionomers (e.g., Surlyn® 8150) are considered to contain an acidic portion of more than 16 weight percent. In one embodiment, the inner cover layer is formed from a composition comprising a high-acid ionomer. In another embodiment, the inner cover layer is formed from a composition comprising a high-acid ionomer and a maleic anhydride-grafted non-ionomer (e.g., Fusabond® 525D (DuPont)). Blends of high-acid ionomers and maleic anhydride-grafted polymers are further disclosed, for example, in U.S. Patents 6,992,135 and 6,677,401, which are incorporated herein by reference.

[0080] The layer positioned between the core and the cover (if any) may also be formed from a composition comprising a 50 / 45 / 5 blend of Surlyn® 8940 / Surlyn® 9150 / Nucrel® 960. In this embodiment, the composition may have a material hardness of 80–85 Shore C. In another embodiment, the inner cover layer is formed from a composition comprising a 50 / 25 / 25 blend of Surlyn® 8940 / Surlyn® 9150 / Surlyn® 9910, with a material hardness of approximately 85–95 Shore C. In yet another embodiment, the inner cover layer is formed from a composition comprising a 50 / 50 blend of Surlyn® 8940 / Surlyn® 9150, with a material hardness of approximately 82–90 Shore C. A composition comprising a 50 / 50 blend of Surlyn® 8150 and Surlyn® 9120 may also be used.

[0081] The outermost cover layer preferably has a material hardness of 85 Shore C or less. The thickness of the outermost cover layer preferably has a lower limit of 0.010, 0.015, or 0.025 inches and an upper limit of 0.035, 0.040, 0.055, or 0.080 inches. Methods for measuring the hardness of each layer of the golf ball are described in more detail herein. If an inner cover layer is included, the inner cover layer preferably has a material hardness of a lower limit of 70, 75, 80, or 82 Shore C and an upper limit of 85, 86, 90, or 92 Shore C. The thickness of the intermediate layer preferably has a lower limit of 0.010, 0.015, 0.020, or 0.030 inches and an upper limit of 0.035, 0.045, 0.080, or 0.120 inches.

[0082] In one embodiment, a golf ball manufactured according to the Disclosure comprises a core as described herein, a casing layer disposed on the core, and a cover formed from the cover composition of the Disclosure, wherein the cover has a hardness lower than that of the casing layer. For example, the casing layer disposed between the core and the cover may have a hardness greater than about 60 Shore D, while the cover may have a hardness less than about 60 Shore D.

[0083] In some embodiments, if the layer positioned between the core and the cover is intended to be the hardest part of the ball, for example, about 45 Shore D to about 75 Shore D, the cover may have a hardness of about 20 Shore D or more, preferably about 25 Shore D or more, and more preferably about 30 Shore D or more, as measured on the slab. In another embodiment, the cover itself has a hardness of about 30 Shore D or more. In particular, the cover may have a hardness of about 30 Shore D to about 70 Shore D. In one embodiment, the cover has a hardness of about 40 Shore D to about 65 Shore D, and in another embodiment, about 40 Shore D to about 55 Shore D. In another embodiment of the present disclosure, the cover has a hardness of less than about 55 Shore D, preferably less than about 50 Shore D, and more preferably about 35 Shore D to about 50 Shore D. In one embodiment, the cover has a hardness of about 40 Shore D to about 50 Shore D.

[0084] If a double cover is placed around the core, the casing layer may have a thickness of approximately 0.01 inches to 0.1 inches, approximately 0.015 inches to 0.08 inches, or approximately 0.02 inches to 0.05 inches. The cover may have a thickness of approximately 0.015 inches to 0.055 inches, approximately 0.02 inches to 0.04 inches, or approximately 0.025 inches to 0.035 inches.

[0085] The core of a golf ball formed according to this disclosure may have a coefficient of restitution (CoR) of at least about 0.760, and more preferably at least about 0.780, about 0.790, or about 0.800. The casing layer of a golf ball formed according to this disclosure may have a coefficient of restitution (CoR) of at least about 0.780, more preferably at least about 0.800, about 0.810, or about 0.820. Such a CoR allows the player to generate higher ball speeds from the tee and achieve longer distances on drives. At the same time, a golf ball including a cover formed from the cover composition of this disclosure means that the player will have a more comfortable and natural feel when striking the ball with the club.

[0086] The compressibility of a core manufactured from the rubber compound of this disclosure may be in the range of about 20 to about 120 DCM, or more preferably about 50 to about 120 DCM. For example, the compressibility of the core may be about 50 to about 85 DCM, or about 60 to 80 DCM, or about 65 to about 75 DCM. In another example, the core compressibility is about 40 to about 90 DCM, or about 50 to about 80 DCM, or about 60 to about 70 DCM, or about 65 to about 70 DCM. The compressibility of a casing layer manufactured from the casing composition of this disclosure may be in the range of about 40 to about 140 DCM, or about 70 to about 105 DCM, or about 80 to 100 DCM, or about 85 to about 95 DCM. In another example, the compressibility of the casing layer may be about 60 to about 110 DCM, or about 70 to about 100 DCM, or about 800 to about 90 DCM, or about 85 to about 90 DCM.

[0087] The shear durability of the golf balls of this disclosure manifests as the ability of the golf ball to maintain its mechanical stability and integrity when shear stress acts upon it, preferably being equal to or greater than that of golf balls formed with conventional covers. As shown in Table 1 below, “shear durability score” is a qualitative or relative measure that incorporates and weights shear modes (i.e., cover cutting / damage, wear-type damage, and / or paint damage) and severity, thereby enabling the score to be averaged and reducing the impact of errors in the overall score taken into the measure.

[0088] [Table 1] TIFF2026100794000004.tif166168

[0089] In other words, a higher shear endurance score indicates higher shear endurance of the material. The above shear endurance scores can be determined by using a mechanical golf swing machine to strike each of approximately 6 to 12 substantially identical golf balls of substantially the same composition at least once with either a sand wedge or a pitching wedge. After a suitable calibration procedure, each experimental golf ball may be tested and assigned a score based on visible signs of damage after being struck. The shear endurance score for a golf ball with a particular cover represents the numerical average of all substantially identical golf balls tested. An alternative method for testing the shear resistance of a golf ball cover involves using a player test to evaluate the results after the ball has been struck multiple times with a wedge or short iron.

[0090] Exposing golf balls to high-humidity environments, such as by immersing them in water or storing them in high humidity for extended periods, can reduce their durability. Therefore, in some test procedures, to simulate the durability of golf balls over long periods or under extreme conditions, each golf ball may be immersed in water or stored in high humidity for extended periods before being tested.

[0091] In one embodiment, a golf ball formed according to this disclosure, i.e., a golf ball having a cover formed from the cover composition disclosed herein, has a shear strength score of at least 6. In another embodiment, the shear strength score of a golf ball formed according to this disclosure is at least 7. In yet another embodiment, a golf ball formed according to this disclosure, i.e., a golf ball having a cover formed from the cover composition disclosed herein, has a shear strength score of at least 8.

[0092] Another test commonly used to measure the shear durability of golf balls is the repeated ball impact test. The repeated ball impact test involves repeatedly impacting a finished golf ball and visually inspecting whether the coating film has peeled off. To make the repeated ball impact test reproducible, the test may be carried out by using a pneumatic cannon or similar device to launch the ball towards a rigid wall at a 45-degree angle to the wall at 125 feet per second. The ball may thus be subjected to 100, 200, or 300 or more impacts, depending on the desired level of testing.

[0093] When a golf ball is formed using the casing and cover composition of this disclosure, it is preferable that there are no cracks or fissures after approximately 100 or more blows. In one embodiment, the casing and cover composition of this disclosure prevents cracks or fissures up to approximately 200 or more blows. In yet another embodiment, a golf ball formed using the casing and cover composition of this disclosure is completely free of cracks or fissures up to approximately 300 or more blows. In yet another embodiment, a golf ball formed using the casing and cover composition of this disclosure is completely free of cracks or fissures up to approximately 600 or more blows.

[0094] In some embodiments, the shear durability of a golf ball formed according to this disclosure, i.e., a golf ball having a cover formed from the cover composition disclosed herein, is equal to or better than that of a golf ball having a conventional cover (while keeping all other components of the ball constant). In one embodiment, the shear durability of a golf ball formed according to this disclosure, i.e., a golf ball having a cover formed from the cover composition disclosed herein, is about 102 percent or more of the shear durability of a golf ball having a conventional cover (while keeping all other components of the ball constant). In another embodiment, the shear durability of a golf ball formed according to this disclosure, i.e., a golf ball having a cover formed from the cover composition disclosed herein, is about 105 percent or more of the shear durability of a golf ball having a conventional cover (while keeping all other components of the ball constant). In yet another embodiment, the shear durability of a golf ball formed according to this disclosure, i.e., a golf ball having a cover formed from the cover composition disclosed herein, is about 110 percent or more of the shear durability of a golf ball having a conventional cover (while keeping all other components of the ball constant).

[0095] In some embodiments having a first isocyanate-reactive component and a second isocyanate-reactive component, the shear durability of the golf ball formed according to this disclosure is given by formula I:

[0096]

number

[0097]

number

[0098] In yet another embodiment,

[0099]

number

[0100] Golf ball components, such as covers, formed from the compositions of the present disclosure can provide golf balls with improved concentricity. In this embodiment, a golf ball having a cover formed from the cover composition of the present disclosure may enable better concentricity of the core or the case-covered core within the cover. As will be understood by those skilled in the art of golf ball manufacturing (and typical players), more precise centering of the core within the golf ball leads to greater consistency in results and improved game. While not bound by any particular theory, it is believed that the higher viscosity and / or increased reactivity (i.e., shorter gelation time) of the cover composition of the present disclosure will enable more concentric placement of the core within the cover.

[0101] In some embodiments, the midpoint of the core formed within a golf ball having a cover formed from the cover composition of the Disclosure is typically about 0.02 inches or less from the midpoint of the golf ball center. In other words, the core of a golf ball having a cover formed from the cover composition of the Disclosure may have a deviation from concentricity of about 0.02 inches or less. In another embodiment, the core of a golf ball having a cover formed from the cover composition of the Disclosure may have a deviation from concentricity of about 0.015 inches or less. In yet another embodiment, the core of a golf ball having a cover formed from the cover composition of the Disclosure may have a deviation from concentricity of about 0.010 inches or less. In yet another embodiment, the core of a golf ball having a cover formed from the cover composition of the Disclosure may have a deviation from concentricity of about 0.005 inches or less.

[0102] The concentricity measurement may be expressed alternatively as a percentage of the center deviation relative to the cover thickness. For example, in one embodiment, the core of a golf ball having a cover formed from the cover composition of the present disclosure has a center deviation of about 8 percent or less relative to the cover thickness. In another embodiment, the core of a golf ball having a cover formed from the cover composition of the present disclosure has a center deviation of about 7 percent or less relative to the cover thickness. In yet another embodiment, the core of a golf ball having a cover formed from the cover composition of the present disclosure has a center deviation of about 6 percent or less relative to the cover thickness. In yet another embodiment, the core of a golf ball having a cover formed from the cover composition of the present disclosure has a center deviation of about 5 percent or less relative to the cover thickness. In yet another embodiment, the core of a golf ball having a cover formed from the cover composition of the present disclosure has a center deviation of about 4 percent or less relative to the cover thickness. For example, the core of a golf ball having a cover formed from the cover composition of the present disclosure has a center deviation of about 3.5 percent or less relative to the cover thickness.

[0103] Golf balls having covers formed from the cover compositions of this disclosure exhibit many improved properties because the concentricity of the golf ball components is improved. For example, the resulting golf ball exhibits uniform shot dispersion due to the improved concentricity. Shot dispersion refers to the distance a golf ball unintentionally flies to the right or left. Golf balls formed according to this disclosure may have reduced shot dispersion due to the improved concentricity. Furthermore, the resulting golf balls also exhibit improved shear durability. In fact, golf balls having covers formed from the cover compositions of this disclosure may be significantly more durable than golf balls having covers formed from conventional cover compositions, as described above.

[0104] The golf balls of this disclosure can be formed using a variety of coating techniques. For example, the golf ball layers may be formed using 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, spray coating, etc. Conventionally, compression molding and injection molding are applied to thermoplastic materials, while RIM, liquid injection molding, and casting are used for thermosetting materials. In this embodiment, the cover layer can be formed on the core assembly using any suitable technique relating to the material used to form the layer. For example, the cover composition of this disclosure can be formed into one or more layers of a golf ball using casting or injection molding techniques.

[0105] Golf balls manufactured in accordance with this disclosure can be subjected to finishing processes such as flash trimming, surface treatment (e.g., buffing of parting lines and surface treatment by vibrating medium tumble), marking, and coating using techniques known in the art. In one embodiment, a cover colored with a white pigment can be surface-treated using a preferred method such as corona treatment, plasma treatment, or ultraviolet (UV) treatment. Markings such as trademarks, symbols, logos, and letters can be printed on the cover using pad printing, inkjet printing, dye sublimation, or other preferred printing methods. A transparent surface coating (e.g., a primer coat and a topcoat) which may contain a fluorescent whitening agent can be applied to the cover. Golf balls can also be painted with one or more paint coatings of various colors. In one embodiment, a white primer paint can be applied to the surface of the ball first, and then a white topcoat paint can be applied over the primer. [Examples]

[0106] The present invention is further illustrated by the following embodiments. It should be understood that these embodiments are for illustrative purposes only and should not be construed as limiting the scope of the present disclosure.

[0107] Example 1 The following examples describe a golf ball having a core layer, a casing layer positioned around the core, and a cover layer positioned around the casing layer. The cover layer in these examples is formed from a cover composition formed according to this disclosure. The casing layer and core layer are also formed according to this disclosure. Table 2 below provides the components in the cover composition. The components of the cover composition are divided into prepolymers and curing agent blends, but it is understood that the prepolymers and curing agent blends, when mixed, form a single cover composition. The concentration of each component is given as a weight percentage based on the total weight of the cover composition. The concentration of a component is defined as a weight percentage (weight %) of the weight of a particular component present in the cover composition relative to the total weight of the cover composition.

[0108] The cover compositions shown in Table 2 below include a polyurethane-based polymer formed from a polyurethane prepolymer and a polyurea curing agent blend. The polyurethane prepolymer includes an isocyanate-containing compound, a blend of Desomdur® N-3400 and 4,4'-diisocyanatodicyclohexylmethanediisocyanate (H12MDI), and an isocyanate-reactive compound, a blend of PTMEG2000 (polytetramethylene ether glycol 2000) and Noryl® AP2001G. The polyurea curing agent blend includes diethyltoluenediamine, an amino-terminated chain extender; a titanium dioxide (TiO2) pigment dispersion; and acetic acid, a catalyst.

[0109] [Table 2]

[0110] The casing layer and core layer of this embodiment are also formed in accordance with the present disclosure. Table 3 below provides the components in the rubber compound of the core layer and the components in the casing composition of the casing layer. The concentration of each component in the core rubber compound is given in percentage (phr). As used in the present invention, the term “percentage” (also known as “phr” or “pph”) is defined as the number of parts by weight of a particular component present in a mixture relative to 100 parts by weight of the polymer component. Mathematically, this can be expressed by dividing the weight of the component by the total weight of the polymer and multiplying by 100. The concentration of each component in the casing composition is defined as a weight percentage (p%) of the casing composition relative to the total weight of the casing composition. Mathematically, this can be expressed by dividing the weight of the component by the total weight of the mixture and multiplying by 100.

[0111] The core rubber formulations shown in Table 3 below include a blend of base rubbers, Buna® CB1221 and Plioflex® 1502; a zinc diacrylate additive; a hardened rubber regrind as the first filler; PolyWate® 325 (barium sulfate) as the second filler; zinc oxide (ZnO) as the third filler; Perkadox® BC (dicumyl peroxide) as the initiator; and a blend of a radical scavenger (zinc pentachlorothiophenol (Zn-PCTP)). The casing composition shown in Table 3 includes a blend of two ionomers, Surlyn® 8150 and Surlyn® 9120.

[0112] [Table 3]

[0113] Example 2 The following examples describe a golf ball having a core layer, a casing layer positioned around the core, and a cover layer positioned around the casing layer. The cover layer in these examples is formed from a cover composition formed according to this disclosure. The casing layer and core layer are also formed according to this disclosure. Table 4 below provides some properties of prepolymers used in cover compositions and properties of covers formed from such cover compositions.

[0114] The cover compositions shown in Table 4 below include a polyurethane-based polymer formed from a polyurethane prepolymer and a polyurea curing agent blend. In compositions 1, 2, and 3, the polyurethane prepolymer includes an isocyanate-containing component, a blend of Desomdur® N-3400 and 4,4'-diisocyanatodicyclohexylmethanediisocyanate (H12MDI), and an isocyanate-reactive compound, a blend of PTMEG2000 (polytetramethylene ether glycol 2000) and Noryl® AP2001G, formed from a blend of PTMEG and polyphenylene ether polyol in a 60:40 ratio. The concentration of Noryl® AP2001G, and thus the polyphenylene ether polyol, was varied among compositions 1, 2, and 3. The concentrations of Noryl® AP2001G and polyphenylene ether polyol are provided as weight percentages based on the total weight of the isocyanate-reactive component. In control composition C, the polyurethane prepolymer comprises a blend of isocyanate-containing compounds, Desomdur® N-3400 and 4,4'-diisocyanatodicyclohexylmethanediisocyanate (H12MDI), and a blend of isocyanate-reactive compounds, PTMEG2000 (polytetramethylene ether glycol 2000). The prepolymers of compositions 1, 2, and 3, as well as the control composition, were prepared using a stoichiometric excess of the isocyanate-containing component so that the prepolymers contained 5.5% unreacted NCO groups. The polyurea curing agent blends of all compositions shown contain Lonzacure® DETDA80LC (diethyltoluenediamine), an amino-terminated chain extender; a titanium dioxide (TiO2) white pigment dispersion; and acetic acid, a catalyst.

[0115] [Table 4]

[0116] As shown in Table 4, the hardness of the covers formed according to this disclosure increases with increasing concentrations of Noryl® AP2001G and, consequently, polyphenylene ether polyol, but the shear durability decreases when the concentrations of Noryl® AP2001G and polyphenylene ether polyol exceed 25% and 10%, respectively. Table 4 also shows that compositions 1, 2, and 3 exhibit a decrease in gelation time as the concentration of Noryl® AP2001G and, consequently, polyphenylene ether polyol increases, and that the gelation time is shorter compared to the control composition, indicating increased reactivity of the cover compositions. Table 4 also shows that compositions 1, 2, and 3 exhibit improved concentricity of the case-covered core within the cover, as there was no visible displacement of the case-covered core in compositions 1, 2, and 3, in contrast to the case-covered core which exhibited a typical amount of displacement. While not bound by any particular theory, it is believed that the improved reactivity of compositions 1, 2, and 3 (i.e., the reduction in gelation time) will lead to greater concentricity within the cover of the case-covered core.

[0117] Example 3 The following examples describe a golf ball having a core layer, a casing layer positioned around the core, and a cover layer positioned around the casing layer. The cover layer in these examples is formed from a cover composition formed according to this disclosure. The casing layer and core layer are also formed according to this disclosure. Table 5 below provides some properties of prepolymers used in cover compositions and properties of covers formed from such cover compositions.

[0118] The cover compositions shown in Table 5 below include a polyurethane-based polymer formed from a polyurethane prepolymer and a polyurea curing agent blend. In compositions 1 to 6, the polyurethane prepolymer includes an isocyanate-containing component, a blend of Desomdur® N-3400 and 4,4'-diisocyanatodicyclohexylmethanediisocyanate (H12MDI), and an isocyanate-reactive compound, a blend of PTMEG2000 (polytetramethylene ether glycol 2000) and Noryl® AP2001G, formed from a blend of PTMEG and polyphenylene ether polyol in a 60:40 ratio. The concentration of Noryl® AP2001G, and thus the polyphenylene ether polyol, was varied among compositions 1 to 6. The concentrations of Noryl® AP2001G and polyphenylene ether polyol are provided as weight percentages based on the total weight of the isocyanate-reactive component. In control compositions C1 and C2, the polyurethane prepolymer comprises a blend of isocyanate-containing compounds, Desomdur® N-3400 and 4,4'-diisocyanatodicyclohexylmethanediisocyanate (H12MDI), and a blend of isocyanate-reactive compounds, PTMEG2000 (polytetramethylene ether glycol 2000). The prepolymers of compositions 1, 2, 3 and C1 were prepared using a stoichiometric excess of the isocyanate-containing component so that the prepolymer had 5.5% unreacted NCO groups. The prepolymers of compositions 4, 5, 6 and C2 were prepared using a stoichiometric excess of the isocyanate-containing component so that the prepolymer had 8.25% unreacted NCO groups. The polyurea curing agent blends of all compositions shown contain Lonzacure® DETDA80LC (diethyltoluenediamine), an amino-terminated chain extender; a titanium dioxide (TiO2) white pigment dispersion; and acetic acid, a catalyst.

[0119] [Table 5]

[0120] Table 5 shows that an increase in unreacted NCO groups in the polymer generally leads to an increase in the hardness, tensile strength, and fracture energy of the cover, all other equal. Tensile strength, elongation, and fracture energy were measured according to test method ASTMD412-06a. As also shown in Table 4, Table 5 shows that the hardness of the cover formed according to this disclosure increases with increasing concentration of Noryl® AP2001G and, consequently, polyphenylene ether polyol, while the relative increase is approximately the same whether the prepolymer has 5.5% or 8.25% unreacted NCO groups. In particular, Table 5 shows that when the prepolymer has 5.5% unreacted NCO groups, tensile strength and fracture energy generally increase with increasing concentration of Noryl® AP2001G and polyphenylene ether polyol, but elongation remains approximately the same or slightly decreases. When the unreacted NCO group content of the prepolymer is 8.25%, increasing the concentrations of Noryl® AP2001G and polyphenylene ether polyol slightly mitigates the effects on tensile strength and elongation, but increases the effect on elongation.

[0121] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art in the field of this disclosure. Furthermore, terms such as those defined in commonly used dictionaries should be construed to have the meaning consistent with their meaning in the context of this specification, and should not be construed in an idealized or overly formal sense unless expressly defined herein. Well-known functions or structures may not be described in detail for the sake of brevity or clarity.

[0122] The terms “approximately” and “nearly” generally mean an acceptable degree of error or variation in the measured quantity, taking into account the nature or precision of the measurement. The numerical values ​​given herein are approximations unless otherwise specified, and the terms “approximately” or “nearly” mean that they can be inferred unless explicitly stated.

[0123] The technical terms used herein are intended solely to describe specific embodiments and are not intended to limit them. Where used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms (i.e., at least one of the articles being modified) unless the context clearly indicates otherwise.

[0124] Terms such as “first,” “second,” etc., are used to describe various features or elements, but these features or elements should not be limited by these terms. These terms are used solely to distinguish one feature or element from another. Thus, the first feature or element described below may be called the second feature or element, and similarly, the second feature or element described below may be called the first feature or element without departing from the teachings of this disclosure. Similarly, terms such as “top” and “bottom,” “front” and “rear,” and “left” and “right” are used to distinguish certain features or elements from one another, but it is expressly intended that the top may also be the bottom, and vice versa.

[0125] The golf balls described and claimed herein are not limited in scope by the specific embodiments disclosed herein, for these embodiments are intended to illustrate some aspects of the disclosure. Any equivalent embodiments are intended to fall within the scope of the disclosure. Indeed, various modifications of the apparatus, in addition to those shown and described herein, will be apparent to those skilled in the art from the above description. Such modifications will also be construed to fall within the scope of the appended claims. All patents and patent applications cited herein are expressly incorporated herein by reference in their entirety. Any section headings herein are provided solely to conform to the implication of 37 C. FR § 1.77, or otherwise solely to provide an organizational list. These headings are not intended to limit or characterize the inventions described herein. [Explanation of symbols]

[0126] 10 3-piece golf balls 12 cores 14. Casing layer 16 Cover 20 4-piece golf balls 22 Center 24 Outer core layer 26 Casing layer 28 Cover 30 5-piece golf balls 32 cores 32a Center 32b Inner core layer 32c outer core layer 34 Casing layer 36 Cover

Claims

1. It's a golf ball, core, and A cover disposed on a core and formed from a cover composition, the cover composition is Isocyanate-containing ingredients, The first isocyanate-reactive component, A second isocyanate-reactive component, comprising a polyphenylene ether polyol, and Chain extender The reaction product includes the cover Golf balls, including...

2. The golf ball according to claim 1, wherein the second isocyanate-reactive component comprises poly(2,6-dimethyl-1,4-phenylene ether)diol.

3. The golf ball according to claim 2, wherein the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 70:30 to about 99:

1.

4. The golf ball according to claim 2, wherein the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 90:10 to about 99:

1.

5. The golf ball according to claim 1, wherein the isocyanate-containing component comprises a first isocyanate-containing component and a second isocyanate-containing component.

6. The golf ball according to claim 5, wherein the first isocyanate-containing component and the second isocyanate-containing component are aliphatic.

7. The golf ball according to claim 1, wherein the chain extender is a chain extender having a hydroxyl group as its terminal group.

8. The golf ball according to claim 1, wherein the chain extender is a chain extender having an amino as a terminal group.

9. The golf ball according to claim 1, wherein the ratio of the isocyanate-containing component to the first and second isocyanate-reactive components is about 1:0.95 to about 1.2:

1.

10. The golf ball according to claim 1, wherein the core comprises a rubber compound including a base rubber, the base rubber being polybutadiene rubber, styrene-butadiene rubber, or a blend thereof.

11. The golf ball according to claim 1, further comprising a casing layer disposed on the core, wherein the casing layer is formed from a casing composition containing an ionomer, and the cover is disposed on the casing layer.

12. It's a golf ball, core, and A cover disposed on a core and formed from a cover composition, the cover composition is Isocyanate-containing ingredients, A first isocyanate-reactive component containing a polyether polyol, A second isocyanate-reactive component containing a polyphenylene ether polyol, wherein the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of approximately 70:30 to approximately 99:1, and Chain extender The reaction product includes the cover Golf balls, including...

13. The golf ball according to claim 12, wherein the first isocyanate-reactive component comprises polytetramethylene ether glycol.

14. The golf ball according to claim 12, wherein the second isocyanate-reactive component comprises poly(2,6-dimethyl-1,4-phenylene ether)diol.

15. The golf ball according to claim 12, wherein the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 90:10 to about 99:

1.

16. It's a golf ball, core, and A cover disposed on a core and formed from a cover composition, the cover composition is Isocyanate-containing ingredients, A first isocyanate-reactive component containing polytetramethylene ether glycol, A second isocyanate-reactive component containing poly(2,6-dimethyl-1,4-phenylene ether)diol, and Chain extender The reaction product includes the cover Golf balls, including...

17. The golf ball according to claim 16, wherein the ratio of the first isocyanate-reactive component to the second isocyanate-reactive component is in the range of about 90:10 to about 99:

1.

18. The golf ball according to claim 16, wherein the isocyanate-containing component comprises a first isocyanate-containing component and a second isocyanate-containing component, and the first and second isocyanate-containing components are aliphatic.

19. The golf ball according to claim 16, wherein the chain extender is a chain extender having a hydroxyl group as its terminal group.

20. The golf ball according to claim 16, wherein the chain extender is a chain extender having an amino as a terminal group.

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