JP2008161691A - Golf ball with improved feeling - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a golf ball which generates sound of a specific frequency and level on hitting. <P>SOLUTION: The golf ball comprises a polyurethane cover layer, a solid core, and one or more intermediate layers and has a sound pressure level lower than 81.5 dB. In another embodiment, the golf ball includes a polyurethane cover layer, a solid core and one or more intermediate layers and has a sound pressure level S lower than 81.5 dB, and S satisfies the following inequality: S<-0.032143F+189.5 (wherein F is a golf ball frequency in Hz). Further in another embodiment, the golf ball includes a polyurethane cover layer, a solid core and one or more intermediate layers and has a sound pressure level S lower than 81.5 dB, and S satisfies the following inequality: S<-0.01F+112 (wherein F is a golf ball frequency in Hz). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

Detailed Description of the Invention

FIELD OF THE INVENTION A multi-layer golf ball having a solid core, a multi-layer structure and a polyurethane cover that produces a sound of a specific frequency and loudness when hit by a golfer is disclosed.
BACKGROUND OF THE INVENTION The application of synthetic polymer chemistry to the field of sports equipment has revolutionized athlete performance in many sports. One sport where this is particularly true, especially with regard to improved golf ball performance and ease of manufacture, is golf. For example, the earliest golf balls consisted of a leather cover filled with wet feathers. These “feathered” golf balls have since been replaced by single part golf balls made from the natural rubber-like material “Gooda Percha”.

  More recently, wound balls generally have a solid rubber or liquid filled center around which a number of yards of stretched elastic yarn or yarn is wound to form a core. The wound core is then covered with a durable cover material such as an ionomer or other thermoplastic material or a softer cover such as balata or cast polyurethane. Wound balls are generally softer and more likely to rotate, allowing a skilled golfer to better control the flight of the ball. In particular, it is desirable for a golfer to be able to backspin a golf ball for the purpose of controlling the flight of the ball and controlling the movement of the ball upon landing. For example, significant backspin stops the ball instead of bouncing forward when it hits the landing. The hand for applying backspin to the golf ball is related to the degree to which the golf ball cover is deformed when the golf ball is hit with a golf club. It is easier to spin the wound ball because the wound ball is traditionally more deformable than the conventional two-part ball. However, the wound ball that rotates more generally has a shorter flight distance when hit compared to the two-part ball. Furthermore, because of the more complex structure, wound balls generally require more time and more money to manufacture than two-part balls.

Golf balls having a two-part construction are generally most popular with golfers for recreation because they are relatively durable and provide a long flight distance compared to typical wound balls having a balata cover. Two-part balls have a single solid core usually formed of crosslinked rubber, which is wrapped with a cover. In general, the solid core is made of polybutadiene, which is chemically crosslinked with a peroxide or sulfur compound together with a co-cross-linking agent such as zinc diacrylate. Such ball covers often include a tough and cut-resistant blend of one or more materials known as ionomers, which generally are ethylene / neutralized with some or all of the acid groups neutralized with a metal cation. Acrylic acid copolymer or ethylene / acrylic acid / acrylate terpolymer. Such ionomers are commercially available as SURLYN® (resin sold by EI DuPont de Nemours & Company, Wilmington, Del.) Or IOTEK® (sold by ExxonMobil, Irving, Texas). Available.
Overview In one aspect, a golf ball includes a polyurethane cover layer, a solid core, and one or more intermediate layers, and the ball has a sound pressure level S of less than 81.5 dB.

In another aspect, the golf ball includes a polyurethane cover layer, a solid core, and one or more intermediate layers, the ball has a sound pressure level S less than 81.5 dB, where S is the following inequality:
S <-0.032143F + 189.5
(Where F is the golf ball frequency in Hz)
Meet.

In another aspect, the golf ball includes a polyurethane cover layer, a solid core, and one or more intermediate layers, the ball has a sound pressure level S less than 81.5 dB, where S is the following inequality:
S <-0.01F + 112
(Where F is the golf ball frequency in Hz)
Meet.

In another aspect, the golf ball includes a polyurethane cover layer, a solid core, and one or more intermediate layers, the ball has a sound pressure level S less than 81.5 dB, where S is the following inequality:
S <-0.01F + 112
(Where F is the golf ball frequency in Hz)
And the polyurethane cover comprises a thermosetting polyurethane.

  In another aspect, the golf ball includes a cover layer, a core, and one or more intermediate layers, and the ball has a solid core; a cover that includes polyurethane, polyurea, or combinations thereof; and a sound pressure level S that is less than 81 dB.

  In another aspect, the golf ball includes a cover layer, a core, and one or more intermediate layers, the ball has a solid core; and a thermoset polyurethane cover; the golf ball frequency is ≦ 3360 Hz.

In another aspect, the golf ball includes a cover layer, a core, and one or more intermediate layers, the ball has a solid core; and a polyurethane cover or a polyurea cover; the golf ball frequency is <3360 Hz.
The following definitions are provided to assist in understanding the detailed description, but these are not intended to be narrower definitions than would be understood by those skilled in the art of golf ball composition and manufacturing.

  The numerical values listed here include all values from lower values to higher values. This clearly applies to all possible combinations of numbers between the minimum and maximum values listed here.

  “Bimodal polymer” refers to a polymer comprising two main fractions, and more particularly to the shape of the molecular weight distribution curve of the polymer, ie, the appearance of a graph of the polymer weight fraction as a function of molecular weight. When the molecular weight distribution curves from these fractions are superimposed on the molecular weight distribution curves of the total polymer product obtained, the curves show two maxima or are at least clearly broader compared to the individual fraction curves. Yes. Such polymer products are referred to as bimodal. The chemical composition of the two fractions may be different.

  A “chain extender” as used herein is a compound that is added to a polyurethane or polyurea prepolymer (or prepolymer starting material) at a level sufficiently low to maintain the thermoplastic properties of the final composition. There is an additional reaction.

  “Conjugated” refers to two or more sites of unsaturation separated by a single bond (eg, a site of unsaturation containing atoms other than carbon such as carbon-carbon double bonds, carbon-carbon triple bonds, and nitrogen). An organic compound containing

  A “curing agent” or “curing system” as may be used interchangeably herein is a compound that is added to a polyurethane or polyurea prepolymer (or prepolymer starting material), which adds additional crosslinking to the final composition. Use thermosetting resin.

  As used herein, “core” refers to the elastic center of a golf ball and may have a single structure. Alternatively, the core itself may have a layer structure, for example a layer structure with a spherical “center” and an additional “core layer”, such a layer being made of the same material as the core center or a different material.

  “Cover” means any layer of a golf ball that surrounds a core. Thus, the golf ball cover includes both the outermost layer, and also an intermediate layer disposed between the golf ball center and the outer cover. “Cover” can be used interchangeably with “cover layer”.

  “Fiber” is a general term and is described in A. Metalspark, Ohio, USA. S. M.M. Issued by International, Engineered Materials Handbook, Volume 2, “Engineering Plastics” defines a finite length (generally 0.10 to 0.13 mm (0.004 to 0.005 inches)) at least 100 times the diameter. It refers to the filament material that it has. The fibers may be continuous or of a specific short length (discontinuous), typically greater than 3.2 mm (1/8 inch). Although fibers according to this definition are preferred, fiber segments, i.e., fiber portions having a length less than the above, may also be used in the present invention. Embodiments of the golf ball components described herein include, by way of non-limiting example, glass fibers such as E fibers, Cem-Fil filament fibers, and 204 filament strand fibers; carbon fibers such as graphite fibers, high modulus carbon fibers, and high strength Carbon fibers; asbestos fibers such as warm and blue asbestos; cellulose fibers; aramid fibers such as Kevlar including types PRD29 and PRD49; metal fibers such as fibers such as copper, high strength steel and stainless steel. Further contemplated are single crystal fibers, potassium titanate fibers, calcium sulfate fibers, and one or more linear synthetic polymer fibers or filaments, such as nylon, including terylene, dacron, perlon, orion, type 242. Also contemplated are polypropylene fibers including monofilaments and fibrillated fibers. The golf balls of the present invention also include any combination of such fibers. Fibers used in golf ball components are described in further detail in Kim et al. US Pat. No. 6,012,991, incorporated herein by reference.

  In the case of a golf ball having two intermediate layers, “inner intermediate layer” can be used interchangeably with “inner mantle” or “inner mantle layer” and means the intermediate layer of the ball placed closest to the core.

  “Intermediate layer” can be used interchangeably with “mantle layer”, “inner cover layer” or “inner cover” and means any layer in the golf ball placed between the core and the outer cover layer To do.

“(Meth) acrylate” means an ester of methacrylic acid and / or acrylic acid.
“(Meth) acrylic acid copolymer” means a copolymer of methacrylic acid and / or acrylic acid.

  A “nanofiller” is defined as a substance having an aggregate structure with an aggregate particle size in the micron range and above. However, these agglomerates have a plate structure in which individual platelets with an approximate thickness of about 1 nanometer (nm) and an across of about 100 to about 1000 nm are stacked. As a result, the nanofiller has a very large surface area, resulting in high reinforcement efficiency for the material with low loading levels of particles. In general, such sub-micron sized particles increase the stiffness of the material without increasing weight or opacity and without reducing the low temperature toughness of the material. Inorganic nanofillers are generally manufactured from clays, and clay particles are described below to facilitate incorporation of nanofillers into the polymer material during the manufacture of nanocomposites or during the manufacture of polymer-based golf ball compositions. Such a suitable matching agent or coupling agent is generally coated or treated.

  A “nanocomposite” is defined as a polymer matrix having a nanofiller within the matrix. Nanocomposite materials and golf balls containing nanocomposite materials are described in US Pat. No. 6,794,447 to Kim et al. And US Patent Publication No. 2005/0059756 A1, and US Pat. No. 5,962,553 to Ellsworth, Maxfield et al., 5,385,776, and Okada et al., 4,894,411, all incorporated herein by reference. Examples of nanocomposite materials that have recently been sold are M1030D manufactured by Unitika, Inc., Osaka, Japan, and 1015C2, manufactured by UBE America, Inc., New York, NY.

  “External cover layer” means the outermost cover layer of a golf ball with indentation patterns, paint and written objects, symbols, and the like. In addition to the core, if the golf ball includes two or more cover layers, only the outermost layer is referred to as the outer cover layer. The remaining layers are called intermediate layers. The “external cover layer” can be used in place of the “external cover”.

  In the case of a ball with two intermediate layers, the “external intermediate layer” can be used interchangeably here with “external mantle” or “external mantle layer”, and the intermediate layer of the ball placed closest to the external cover layer Means.

  “Peptizers” have been used in rubber formulations to facilitate the processing of natural or synthetic rubbers and other high viscosity elastomers that are difficult to process during roll milling or mastication. A chemical or composition.

  “Polyalkenamer” can be used interchangeably with “polyalkenamer rubber” and includes one or more alkenes including cycloalkenes having 5-20, preferably 5-15, most preferably 5-12 ring carbon atoms. Means polymer. The polyalkenamer is one or more in the presence of an organometallic catalyst as described in US Pat. Nos. 3,492,245 and 3,804,803, both of which are hereby incorporated by reference in their entirety. It can be prepared by any suitable method including ring-opening metathesis polymerization of cycloalkene.

  “Prepolymer” refers to a final polymer material of a golf ball that is produced upon further processing, a material that can form a polymerized or partially polymerized material that can be further processed, such as, but not limited to, cross-linking.

“Polyurea” as used herein refers to a material produced by the reaction of a diisocyanate and a polyamine.
“Polyurethane” as used herein refers to a material produced by the reaction of a diisocyanate and a polyol.

  A "thermoplastic resin" is generally defined as a substance that can soften or melt when heated and can be cured again when cooled. Thermoplastic polymer chains are often not cross-linked or lightly cross-linked using chain extenders, but “thermoplastic resins” as used herein are initially used in, for example, the initial extrusion process or injection molding. During the process, it refers to a material that acts as a thermoplastic resin but can be crosslinked to form the final structure, for example, during the compression molding process.

  A “thermosetting resin” is generally defined as a substance that crosslinks or cures by interaction with a crosslinking or curing agent. Crosslinking can be caused by energy in the form of heat (generally above about 200 ° C.), either by chemical reaction (by reaction with a curing agent) or by irradiation. The resulting composition becomes hard when cured and does not soften upon heating. The thermosetting resin has this property because long chain polymer molecules are cross-linked to form a hard structure. Thermoset materials cannot be melted and reshaped after curing, and therefore thermoset materials are not recycled like thermoplastic materials that can be melted and reshaped.

“Thermoplastic polyurethane” refers to a material made by the reaction of a diisocyanate and a polyol, optionally with a chain extender.
“Thermoplastic polyurea” refers to a material made by the reaction of a diisocyanate and a polyamine, optionally with a chain extender.

“Thermosetting polyurethane” refers to a material made by the reaction of a diisocyanate with a polyol and a curing agent.
“Thermosetting polyurea” refers to a material made by reaction of a diisocyanate with a polyamine and a curing agent.

A “urethane prepolymer” is a reaction product of a diisocyanate and a polyol.
A “urea prepolymer” is a reaction product of a diisocyanate and a polyamine.

  “Unimodal polymer” refers to a polymer containing one major fraction, and more specifically, refers to the shape of the molecular weight distribution curve of the polymer, ie, the molecular weight distribution curve of the entire polymer product exhibits a single maximum.

  The combination of core and cover material provides a “hard” coated ball that is resistant to cutting and other damage caused by striking the ball with a golf club. Furthermore, such a combination results in a high initial velocity for the ball, resulting in a long flight distance. However, due to their hardness, these two-part balls have a relatively slow rotational speed, making control difficult, especially with relatively short approach shots. Therefore, these balls are generally considered to be “distance” balls. Because the material of the two-part ball is very hard, the ball generally has a hard “feel” when hit with a club. The feel of the golf ball is the result of recognizing how the batter perceives the club hitting the golf ball and means the combination of the hardness or softness of the ball and also the impact sound that the batter primarily experiences .

  The frequency is the “pitch” of the sound, and the true magnitude is measured at the decibel (db) level. The ball can be hit, that is, tested for sound and pitch with a 30 yard shot, which is then converted to the ball feel experienced by the golfer. Urethane is a soft material with a relatively low elastic repulsion, but the ball manufacturer has a high compression or stiffer, harder core combined with such a cover with a stiffer, harder mantle layer. I had to make up for this by combining. These mantle layers and cores maintain ball speed, but feel is enhanced. By plotting the db level versus frequency, the “feel” ratio is obtained. Earlier wound balata balls have a very low ratio and have a low or soft feel immediately after. Rigid two-part distance balls have a high ratio, i.e. they are very solid and have a loud feel. To date, multilayer balls with urethane covers and solid cores have not been made close to the feel ratio of previous tour balata balls. The present invention creates a golf ball having a softer ratio than existing ones and regains the feel of the wound ball using a urethane cover.

  More recently, many golf ball manufacturers have developed multi-layer golf balls, i.e., at least a core, mid layer or mantle to eliminate some of the undesirable aspects of conventional two-part balls, such as hard feel. , And balls having one or more cover layers. In an attempt to further adjust ball performance, particularly the distance traveled by the ball, and the feel transmitted to the golfer through the club when hitting the ball, the basic two-part ball structure is an additional layer between the core and the outer cover layer. Has been further adjusted by introducing. When one additional layer is introduced between the core and the outer cover layer, it becomes a so-called “three-part ball”, and similarly, when two additional layers are introduced between the core and the outer cover layer, This is a so-called “four-part ball” (the same applies hereinafter).

  Such a multilayer structure allows the introduction of new materials of varying hardness, and the property deficiencies in one layer are alleviated by further introducing different materials. Currently, SURLYN® is used as the primary source of cover material for most multi-layer, three-part golf balls. However, a problem with golf balls covered with SURLYN® is the lack of “click” and “feel” that golfers are accustomed to with balata. The “click” is a sound generated when a ball is hit with a golf club, and the “feel” is a general sense transmitted to a golfer when the ball is hit.

  However, unlike golf balls covered with SURLYN (R), golf balls covered with polyurethane should be made to have a balata "click" and "feel" and high durability. Can do. Polyurethanes or polyureas are generally produced by reaction of diisocyanates with polyols (in the case of polyurethanes) or polyamines (in the case of polyureas). The thermoplastic polyurethane or polyurea may consist solely of this initial mixture or may be further combined with a chain extender to alter properties such as the hardness of the thermoplastic material. Thermoset polyurethanes or polyureas are generally produced by reaction of diisocyanates with polyols or polyamines, respectively, and an additional crosslinker that crosslinks or cures the material to become a thermoset material. Multi-layer golf balls with solid cores and polyurethane covers have been used everywhere by professional golfers on a variety of professional world tours.

  However, since their introduction, the compression of the ball has increased with the investigation of increasing distance, and the overall short game feel has been sacrificed. Players have accepted this more solid feel to increase distance. Here, a solid core multilayer with a specific sound frequency and magnitude that has improved speed and distance over past wound balls and creates a softer overall sound / feel like past balata balls A polyurethane cover golf ball is disclosed.

  The present invention can be used to produce golf balls of any desired size. The USGA "Golf Rules" state that a competitive golf ball size must be at least 1.680 inches in diameter; however, any size golf ball can be used for leisure golf play. The preferred diameter of the golf ball is about 1.670 to about 1.800 inches. Extra large golf balls with diameters greater than about 1.760 inches to 2.75 inches are also within the scope of the present invention.

  Any diisocyanate available to those skilled in the art is suitable for use in the golf balls disclosed herein. Isocyanates include, but are not limited to, aliphatic, cycloaliphatic, aromatic aliphatic, aromatic, and derivatives thereof, and combinations of these compounds having two or more isocyanate (NCO) groups per molecule. included. As used herein, an aromatic aliphatic compound should be understood as a compound containing an aromatic ring in which the isocyanate group is not directly bonded to the ring. An example of an aromatic aliphatic compound is tetramethylene diisocyanate (TMXDI). The isocyanate may be an organic polyisocyanate terminated prepolymer, a low free isocyanate prepolymer, and mixtures thereof. Isocyanate-containing reactive components also include isocyanate functional monomers, dimers, trimers, or polymeric adducts, prepolymers, quasi-prepolymers, or mixtures thereof. Isocyanate functional compounds include monoisocyanates or polyisocyanates containing two or more isocyanate functional groups.

  Suitable isocyanate-containing components include the general structure: O = C = N-R-N = C = O, where R is preferably cyclic, aromatic or linear, containing from about 1 to about 50 carbon atoms. Diisocyanates having a branched hydrocarbon moiety). The isocyanate may contain one or more cyclic groups or one or more phenyl groups. When multiple cyclic or aromatic groups are present, linear and / or branched hydrocarbons containing from about 1 to about 10 carbon atoms can be present as spacers between the cyclic or aromatic groups. In some cases, the cyclic or aromatic group may be substituted in the 2,3- and / or 4-position, or in the ortho-, meta- and / or para-position, respectively. Substituents include, but are not limited to, halogens, first, second or third hydrocarbon groups, or combinations thereof.

Examples of isocyanates that can be used include, but are not limited to, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI); 3,3 -'- dimethyl-4,4'-biphenyl Toluene diisocyanate (TDI); high molecular weight MDI; carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate; para-phenylene diisocyanate (PPDI); meta-phenylene diisocyanate (MPDI); triphenylmethane-4, 4'- and triphenylmethane-4,4 "-triisocyanate;naphthylene-1,5-diisocyanate;2,4'-,4,4'- and 2,2-biphenyl diisocyanate; polyphenylene polymethylene polyisocyanate ( PMDI) ( Also known as high molecular weight PMDI); a mixture of MDI and PMDI; a mixture of PMDI and TDI; ethylene diisocyanate; propylene-1,2-diisocyanate; trimethylene diisocyanate; butylene diisocyanate; vitorylene diisocyanate; tolidine diisocyanate; Tetramethylene-1,3-diisocyanate; tetramethylene-1,4-diisocyanate; pentamethylene diisocyanate; 1,6-hexamethylene diisocyanate (HDI); octamethylene diisocyanate; decamethylene diisocyanate; 2 2,4,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1, 2-Diisocyanate; Dicyclohexylmethane diisocyanate; Cyclobutane-1,3-diisocyanate; Cyclohexane-1,2-diisocyanate; Cyclohexane-1,3-diisocyanate; Cyclohexane-1,4-diisocyanate; Diethylidene diisocyanate; Methylcyclohexylene diisocyanate (HTDI) 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; Cyanatoethylcyclohexane isocyanate; bis (isocyanatomethyl) -cyclohexane diisocyanate; 4,4′-bis (isocyanatomethyl) dicyclohexane; 2,4′-bis (isocyanatomethyl) dicyclohexane; isophorone diisocyanate (IPDI); Dimethyl diisocyanate, dodecane-1,12-diisocyanate, 1,10-decamethylene diisocyanate, cyclohexylene-1,2-diisocyanate, 1,10-decamethylene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, furfurylidene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3- Clopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,3-cyclobutane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 4,4'-methylene bis (phenyl isocyanate), 1-methyl -2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanato-methyl) cyclohexane, 1,6-diisocyanato-2,2,4,4-tetramethylhexane, , 6-Diisocyanato-2,4,4-tetratrimethylhexane, trans-cyclohexane-1,4-diisocyanate, 3-isocyanato-methyl-3,5,5-trimethylcyclohexyl isocyanate, 1 Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, cyclohexyl isocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, m-phenylene diisocyanate, m-xyl Range isocyanate, m-tetramethylxylylene diisocyanate, p-phenylene diisocyanate, p, p'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4 ' -Biphenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1 5-naphthalene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, metaxylene diisocyanate, 2,4-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4-chlorophenylene diisocyanate 4,4'-diphenylmethane diisocyanate, p, p'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2-diphenylpropane-4,4'-diisocyanate, 4,4 '-Toluidine diisocyanate, dianidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,3-xylylene diisocyanate, 1,4-naphthylene diisocyanate Azobenzene-4,4′-diisocyanate, diphenylsulfone-4,4′-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, isocyanatoethyl methacrylate, 3-isopropenyl-α, α -Substitution comprising dimethylbenzyl isocyanate, dichlorohexamethylene diisocyanate, ω, ω'-diisocyanato-1,4-diethylbenzene, polymethylene polyphenylene polyisocyanate, isocyanurate modified compounds of the above polyisocyanates, carbodiimide modified compounds, and biuret modified compounds And isomer mixtures. These isocyanates can be used alone or in combination. These combined isocyanates include triisocyanates such as biuret of hexamethylene diisocyanate and triphenylmethane triisocyanate, and polyisocyanates such as high molecular weight diphenylmethane diisocyanate; triisocyanate of HDI; 2,2,4-trimethyl-1 , 6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI); 2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate; 1,2-, 1,3- And 1,4-phenylene diisocyanates; aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylene diisocyanates; meta-tetramethylxylene Diisocyanate (m-TMXDI); para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurate of polyisocyanate, such as isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene diisocyanate, hexamethylene Isocyanurates of diisocyanates, and mixtures thereof, dimerized uretdiones of polyisocyanates, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; modified polyisocyanates derived from the above isocyanates and polyisocyanates Isocyanates; and mixtures thereof.

  Due to the advantages of injection molding over more complex injection molding processes, in some situations it has a formulation that can be cured as a thermosetting material only in a specific temperature range above the temperature of common injection molding processes This is advantageous. This allows parts such as golf ball cover layers to be injection molded first and then processed at higher temperatures and pressures to induce further cross-linking and curing to provide thermosetting to the final part. Is possible. Such initially injection moldable compositions are therefore referred to as post-curing urethane or urea compositions.

  If a post-curing, low yellowing urethane composition is required, a modified or blocked diisocyanate may be added to the diisocyanate starting material that is subsequently unblocked and induces further crosslinking after extrusion. Modified isocyanates used in the production of polyurethanes are defined as chemical compounds that contain isocyanate groups that are not reactive at room temperature but become reactive when a particular temperature is reached. The resulting isocyanate can act as a crosslinker or chain extender to form a crosslinked polyurethane. The degree of crosslinking depends on the type and concentration of modified isocyanate present in the composition. The modified isocyanate used in the composition is preferably one so that the urethane in the composition has a characteristic temperature that is high enough to maintain its thermoplastic behavior during initial processing (eg injection molding). Is selected. If the specific temperature is too low, crosslinking of the composition is completed before processing, which makes processing difficult. The modified isocyanate is preferably selected from the following group: isophorone diisocyanate (IPDI) based uretdione type crosslinker; combination of uretdione adduct of IPDI with IPDI partially modified with ε-caprolactam; ε-caprolactam and Combinations of isocyanate adducts modified with carboxylic acid functional groups; desmodur diisocyanates modified with caprolactam; desmodur diisocyanates with 3,5-dimethylpyrazole modified isocyanates; or mixtures thereof. Particularly preferred examples of modified isocyanates are those sold by Bayer under the registered trademark CRELAN. These examples include CRELAN TP LS 2147; CRELAN NI 2; isophorone diisocyanate (IPDI) based uretdione type crosslinkers such as CRELAN VP LS 2347; IPDI partially modified with ε-caprolactam and uretdione adducts of IPDI. In combination with, for example, CRELAN VP LS 2386; combinations of ε-caprolactam and isocyanate adducts modified with carboxylic acid functional groups, such as CRELAN VP LS 2181/1; caprolactam modified desmodurized diisocyanates, such as CRELAN NW5; 3 , 5-dimethylpyrazole-modified isocyanate and desmodular diisocyanates such as CRELAN XP 7180. These modified isocyanates can be used alone or in combination. Such modified isocyanates are described in further detail in US Pat. No. 6,939,924, which is hereby incorporated by reference in its entirety.

  Alternatively, if a post-curing polyurethane or polyurea composition is required, the diisocyanate may further comprise a reaction product of a nitroso compound and a diisocyanate or polyisocyanate. The reaction product has a characteristic temperature at which the reaction product decomposes to give nitroso compounds and diisocyanates or polyisocyanates which, by careful selection of the post-curing temperature, then the original thermoplastic composition. Further cross-linking is induced in the object, resulting in properties like a thermosetting material. Such nitroso compounds are described in further detail in US Pat. No. 7,037,985 B2, which is hereby incorporated by reference in its entirety.

  Any polyol available to one of ordinary skill in the polyurethane art is suitable for use in the present invention. Polyols suitable for use in the low yellowing composition of the present invention include, but are not limited to, polyester polyols, polyether polyols, polycarbonate polyols and polydiene polyols such as polybutadiene polyols.

  Polyester polyols are made by condensation or step growth polymerization utilizing a diacid. The main diacids for the polyester polyols are adipic acid and isomeric phthalic acid. Adipic acid is used for materials that need flexibility, and phthalic anhydride is used for materials that need rigidity. Some examples of polyester polyols are poly (ethylene adipate) (PEA), poly (diethylene adipate) (PDA), poly (propylene adipate) (PPA), poly (tetramethylene adipate) (PBA), poly (hexamethylene) Adipate) (PHA), poly (neopentylene adipate) (PNA), polyol consisting of 3-methyl-1,5-pentanediol and adipic acid, random copolymer of PEA and PDA, random copolymer of PEA and PPA, PEA and Random copolymer of PBA, random copolymer of PHA and PNA, caprolactone polyol obtained by ring-opening polymerization of ε-caprolactone, and polyol obtained by ring-opening polymerization of β-methyl-d-valerolactone and ethylene glycol These can be used alone or in combination. Further, the polyester polyol may comprise a copolymer of at least one acid and at least one glycol as shown below. Acids include terephthalic acid, isophthalic acid, phthalic anhydride, oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, octanedioic acid, nonanedioic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid , Dimer acid (mixture), p-hydroxybenzoate, trimellitic anhydride, ε-caprolactone, and β-methyl-d-valerolactone. For glycol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylene glycol, polyethylene glycol, polytetramethylene glycol 1,4-cyclohexanedimethanol, pentaerythritol, and 3-methyl-1,5-pentanediol.

  Polyether polyols are produced by ring-opening addition polymerization of alkylene oxides (eg, ethylene oxide and propylene oxide) using an initiator of a polyhydric alcohol (eg, diethylene glycol) that is an active hydride. In particular, polypropylene glycol, (PPG), polyethylene glycol (PEG) or propylene oxide-ethylene oxide copolymers are obtained. Polytetramethylene ether glycol (PTMG) is produced by ring-opening polymerization of tetrahydrofuran produced by dehydration of 1,4-butanediol or hydrogenation of furan. Tetrahydrofuran can form copolymers with alkylene oxides. In particular, tetrahydrofuran-propylene oxide copolymers or tetrahydrofuran-ethylene oxide copolymers can be formed. The polyether polyols can be used alone or in combination.

  The polycarbonate polyol is obtained by condensation of a known polyol (polyhydric alcohol) with phosgene, chloroformate, dialkyl carbonate or diallyl carbonate. Particularly preferred polycarbonate polyols include polyol components using 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol or 1,5-pentanediol. Polycarbonate polyols can be used alone or in combination with other polyols.

  Polydiene polyols include liquid diene polymers containing hydroxyl groups having an average of at least 1.7 functional groups, including diene polymers or diene copolymers having 4 to 12 carbon atoms, or 2 to 2.2 Or a copolymer of such a diene added to a polymerizable α-olefin monomer having 5 carbon atoms. Specific examples include butadiene homopolymers, isoprene homopolymers, butadiene-styrene copolymers, butadiene-isoprene copolymers, butadiene-acrylonitrile copolymers, butadiene-2-ethylhexyl acrylate copolymers, and butadiene-n-octadecyl acrylate copolymers. These liquid diene polymers can be obtained, for example, by heating the conjugated diene monomer in the presence of hydrogen peroxide in the liquid reactant.

  Polybutadiene polyols include liquid diene polymers containing hydroxyl groups having an average of at least 1.7 functional groups, diene polymers or diene copolymers having 4 to 12 carbon atoms, or 2 to 2.2 It may consist of a copolymer of such a diene added to a polymerizable α-olefin monomer having a carbon atom. Specific examples include butadiene homopolymers, isoprene homopolymers, butadiene-styrene copolymers, butadiene-isoprene copolymers, butadiene-acrylonitrile copolymers, butadiene-2-ethylhexyl acrylate copolymers, and butadiene-n-octadecyl acrylate copolymers. These liquid diene polymers can be obtained, for example, by heating the conjugated diene monomer in the presence of hydrogen peroxide in the liquid reactant.

  Any polyamine available to those skilled in the polyurethane art is suitable for use in the present invention. Polyamines suitable for use in the low yellowing compositions of the present invention include, but are not limited to, amine-terminated hydrocarbons, amine-terminated polyethers, amine-terminated polyesters, amine-terminated polycaprolactones, amine-terminated polycarbonates, amine-terminated polyamides, And mixtures thereof. Amine-terminated compounds include polytetramethylene ether diamine, polyoxypropylene diamine, poly (ethylene oxide capped oxypropylene) ether diamine, triethylene glycol diamine, propylene oxide based triamine, trimethylolpropane based triamine, glycerin based It may also be a polyetheramine selected from triamines and mixtures thereof.

  The diisocyanate and polyol or polyamine component may be combined in advance to form a prepolymer prior to reaction with the chain extender or curing agent. Such prepolymer combinations are suitable for use in the present invention. Commercially available prepolymers include LFH580, LFH120, LFH710, LFH1570, LF930A, LF950A, LF601D, LF751D, LFG963A, LFG640D.

  One preferred prepolymer is a toluene diisocyanate prepolymer with polypropylene glycol. Such polypropylene glycol-terminated toluene diisocyanate prepolymers are available from Uniroyal Chemical Co., Middlebury, Conn. Under the registered trademark ADIPREN® LFG963A and LFG640D. The most preferred prepolymer is a polytetramethylene ether glycol terminated toluene diisocyanate prepolymer, for example, available from Uniroyal Chemical Company, Middlebury, Conn. Under the registered trademark ADIPREN® LF930A, LF950A, LF601D, and LF751D. .

  In one embodiment, the number of free NCO groups in the urethane or urea prepolymer may be less than about 14%. The urethane or urea prepolymer preferably has from about 3 to about 11%, more preferably from about 4 to about 9.5%, more preferably from about 3 to about 9% free NCO, based on the same weight.

  The polyol chain extender or curing agent is a first, second or third polyol. Examples of these polyol monomers include, but are not limited to, trimethylolpropane (TMP), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane. Diol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 2,5-hexanediol 2,4-hexanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, and 2-ethyl-2- (hydroxymethyl) -1,3-propanediol. Diamines can also act as chain extenders when added to the urethane prepolymer.

  Diamines and other suitable polyamines can act as chain extenders or curing agents when added to the composition. These include primary, secondary or tertiary amines having two or more amines as functional groups. Examples of these include aliphatic diamines such as tetramethylene diamine, pentamethylene diamine, hexamethylene diamine; alicyclic diamines such as 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane; or aromatic diamines. For example, diethyl-2,4-toluenediamine, 4,4 ″ -methylenebis- (3-chloro-2,6-diethyl) -aniline (LONZACURE registration from Air Products and Chemicals, Allentown, Pa.) 3,3′-dichlorobenzidene; 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA); N, N, N ′, N′-tetrakis (2-hydroxypropyl) ) Ethylenediamine, 3,5-dimethylthio-2,4-toluenediamine; 3,5 Dimethylthio-2,6-toluenediamine; N, N'-dialkyldiaminodiphenylmethane, trimethylene glycol-di-p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate, 4,4'-methylenebis-2- Chloroaniline, 2,2 ′, 3,3′-tetrachloro-4,4′-diaminophenylmethane, p, p′-methylenedianiline, p-phenylenediamine or 4,4′-diaminodiphenyl; and 2, 4,6-Tris (dimethylaminomethyl) phenol is included.

  Other examples include ethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine; 4,4′-bis (sec- Butylamino) -dicyclohexylmethane; 1,4-bis (sec-butylamino) -cyclohexane; 1,2-bis (sec-butylamino) -cyclohexane; 4,4′-bis (sec-butylamino) -dicyclohexylmethane 4,4'-dicyclohexylmethanediamine; 1,4-cyclohexane-bis (methylamine); 1,3-cyclohexane-bis (methylamine); diethylene glycol bis (aminopropyl) ether; 2-methylpentamethylene- Diamine; Diaminocyclohexane; Diethylenetriamine; Triethylenethe Tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido- (bis-propylamine); monoethanolamine, diethanolamine; triethanolamine; monoisopropanolamine; Isopropanolamine; isophoronediamine; and mixtures thereof.

Aromatic diamines tend to result in products that are more rigid (higher Mooney viscosity) than aliphatic or cycloaliphatic diamines.
As described in U.S. Patent Nos. 6,793,864, 6,719,646 and pending U.S. Patent Publication No. 2004 / 0201133A1, all of which are incorporated herein by reference, the curing agent may vary depending on the chemical structure. It can be a slow or fast polyamine or polyol. Slowly reacting polyamines are diamines having amine groups with sterically and / or electron-hindered electron withdrawing or bulky groups in positions very close to the amine reaction site. The distance between amine reaction sites also affects the reaction rate of the polyamine.

  Suitable curing agents include, but are not limited to, 3,5-dimethylthio-2,4-toluenediamine; 3,5-dimethylthio-2,6-toluenediamine; N, N'-dialkyldiaminodiphenylmethane; trimethylene glycol-di Selected from the group of slow reacting polyamines comprising: -p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; and mixtures thereof. Among these, 3,5-dimethylthio-2,4-toluenediamine and 3,5-dimethylthio-2,6-toluenediamine are isomers and are sold by Ethyl Corporation under the registered trademark ETHACURE (registered trademark) 300. Has been. Trimethylene glycol-di-p-aminobenzoate is sold by Polaroid under the registered trademark POLACURE 740M and polytetramethylene oxide-di-p-aminobenzoate is registered trademark of POLAMINES. N, N′-dialkyldiaminodiphenylmethane is sold by UOP under the registered trademark of UNILINK®.

  When a urethane elastomer is produced using a slow-reacting polyamine as a curing agent, a catalyst is generally required to promote the reaction between the urethane prepolymer and the curing agent. Particularly suitable catalysts include TEDA dissolved in dipropylene glycol, which can be added in an amount of 2-5% (eg, TEDA L33 available from Witco, Greenwich, Conn., And Air Products and DABCO 33LV available from Chemical Co.), more preferably TEDA dissolved in 1,4-butanediol which can be added in an amount of 2-5%. Another suitable catalyst includes a blend of 0.5% 33LV or TEDA L33 (above) and 0.1% dibutyltin dilaurate (available from Witco or Air Products and Chemical), This is added to a curing agent such as VIBRACURE® A250. Unfortunately, as is well known in the art, the use of a catalyst has a significant impact on the ability to control the reaction and thus the overall processability.

  To eliminate the need for a catalyst, a fast-acting curing agent that does not have electron-withdrawing groups or bulky groups that interfere with the reactive groups can be used. However, since the fast-acting curing agent is also relatively difficult to control, the problem with the lack of control associated with the use of the catalyst is not completely eliminated.

  In one embodiment, the use of dicyandiamide in a blend with a slower or faster curing agent can eliminate the problems associated with the use of either curing agent alone. The net result of such a combination is the realization of greater control and associated flexibility during the reaction used to produce the polyurethane or polyurea. Dicyandiamide is preferably used in combination with a faster-acting curing agent.

  Preferred hardener blends include fast-acting hardeners such as diethyl-2,4-toluenediamine, 4,4 ″ -methylenebis- (3-chloro-2,6-diethyl) -aniline (Allentown, Pa.). Available from Air Products and Chemicals under the registered trademark LONZACURE), 3,3'-dichlorobenzidene; 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA); N, N, This includes the use of N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine and Curalon L (registered trademark of aromatic diamine mixtures sold by Uniroyal), and any and all combinations thereof. A preferred fast-acting curing agent is diethyl-2,4-toluenediamine, which has two commercial grade names, Ethacure® 100 and Ethacure® 100LC, with coloring and by-products Few. That is, it is considered a cleaner product for those skilled in the art.

  Advantageously, the Ethacure® 100LC commercial grade results in a golf ball that is less susceptible to yellowing when exposed to UV light conditions. Although the player recognizes this desirable aesthetic effect, it should be noted that either of these two commercial greats can be used for the curing agent diethyl-2,4-toluenediamine.

  If a post-curing composition is required, the chain extender or curing agent can further comprise a peroxide or peroxide mixture. Before the composition is exposed to sufficient thermal energy to reach the activation temperature of the peroxide, the compositions of (a) and (b) behave as thermoplastics. Thus, it can be easily formed into a golf ball layer using injection molding. However, when sufficient thermal energy is applied to bring the composition to a temperature above the peroxide activation temperature, crosslinking occurs and the thermoplastic polyurethane turns into a crosslinked polyurethane.

  Examples of peroxides suitable for use in the compositions within the scope of the present invention include aliphatic peroxides, aromatic peroxides, cyclic peroxides, or mixtures thereof. First, second or third peroxides can be used, with the third peroxide being most preferred. Also peroxides containing one or more peroxy groups, for example 2,5-bis (t-butylperoxy) -2,5-dimethylhexane and 1,4-bis (t-butylperoxy-isopropyl) -benzene Can be used. Symmetric or asymmetric peroxides such as t-butyl perbenzoate and t-butyl cumyl peroxide can also be used. Furthermore, a peroxide having a carboxy group can also be used. Peroxides can be decomposed by thermal energy, shear forces, reaction with other chemical components, or combinations thereof.

  Homolytically decomposed peroxides, heterolyticly decomposed peroxides, or mixtures thereof can be used to promote the crosslinking reaction of the composition. Examples of suitable aliphatic and aromatic peroxides are diacetyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, dicumyl peroxide, 2,5-bis- (t-butylperoxy) -2, 5-dimethylhexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (butylperoxy) -3-hexyne, n-butyl-4, 4-bis- (t-butylperoxyl) valerate, 1,4-bis- (t-butylperoxyisopropyl) -benzene, t-butylperoxybenzoate, 1,1-bis- (t-butylperoxy) -3, 3,5-trimethylcyclohexane, and di- (2,4-dichlorobenzoyl). Peroxides are available from Akzo Nobel Polymer Chemical Company of Chicago, Illinois, Atofina Company of Philadelphia, Pennsylvania, and Acrochem Company of Akron, Ohio. Further details of this post cure system are disclosed in US Pat. No. 6,924,337, which is hereby incorporated by reference in its entirety.

  Polymer materials generally considered useful for the manufacture of golf balls are also included in the components of golf balls, including but not limited to synthetic and natural rubber, thermoset polymers such as other thermoset polyurethanes or heat Curable polyureas, and thermoplastic elastomers containing thermoplastic polymers such as metallocene catalyst polymers, unimodal ethylene / carboxylic acid copolymers, unimodal ethylene / carboxylic acid / carboxylate terpolymers, bimodal ethylene / carboxylic acid copolymers, bimodal ethylene / Carboxylic acid / Carboxylate terpolymer, Unimodal ionomer, Bimodal ionomer, Modified unimodal ionomer, Modified bimodal ionomer, Thermoplastic polyurethane, Thermoplastic polyurea, Polyamide, Copo Amides, polyesters, copolyesters, polycarbonates, polyolefins, halogenated (eg, chlorinated) polyolefins, halogenated polyalkylene compounds such as halogenated polyethylene [eg, chlorinated polyethylene (CPE)], polyalkenamers, polyphenylene oxide, polyphenylene sulfide, Diallyl phthalate polymer, polyimide, polyvinyl chloride, polyamide-ionomer, polyurethane-ionomer, polyvinyl alcohol, polyarylate, polyacrylate, polyphenylene ether, impact modified polyphenylene ether, polystyrene, impact polystyrene, acrylonitrile-butadiene-styrene copolymer , Styrene-acrylonitrile (SAN), Acrylonitrile-styrene -Acrylonitrile, styrene-maleic anhydride (S / MA) polymer, styrene copolymer, functionalized styrene copolymer, functionalized styrene terpolymer, styrene terpolymer, cellulose polymer, liquid crystal polymer (LCP), ethylene-propylene-diene terpolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), ethylene-propylene copolymer, ethylene vinyl acetate, polyurea, and polysiloxane, and any and all combinations thereof.

  Examples of copolyester thermoplastic elastomers include polyetherester block copolymers, polyactone ester block copolymers, and aliphatic and aromatic dicarboxylic acid copolyesters. A polyetherester block copolymer is a copolymer comprising a polyester hard segment polymerized from a dicarboxylic acid and a low molecular weight diol and a polyether soft segment polymerized from an alkylene glycol having 2 to 10 carbon atoms. A polylactone ester block copolymer is a copolymer having a polylactone chain in place of the polyether as the soft segment discussed above for the polyether ester block copolymer. Aliphatic and aromatic dicarboxylic acid copolyesters comprise an acid component selected from aromatic dicarboxylic acids, such as terephthalic acid and isophthalic acid, and aliphatic acids having 2 to 10 carbon atoms, and 2 to 10 It is a copolymer with at least one diol component selected from aliphatic and cycloaliphatic diols having carbon atoms. Blends of aromatic and aliphatic polyesters can also be used for these. Examples thereof include E.I. under the registered trademark of HYTREL. I. From DuPont de Nemours & Company and registered trademark of SKYPEL in Korea. K. Includes products sold by Chemical of Seoul.

  Examples of other thermoplastic elastomers are multi-block rubber-based copolymers, particularly those where the rubber block component is based on butadiene, isoprene or ethylene / butylene. The non-rubber repeating units of the copolymer may be derived from any suitable monomer including meth (acrylate) esters such as methyl methacrylate and cyclohexyl methacrylate, vinyl arylene such as styrene. The styrene block copolymer is a copolymer of styrene and butadiene, isoprene or a mixture of the two. If modification of the properties of the resulting SBC / urethane copolymer is required, additional unsaturated monomers may be added to the structure of the styrene block copolymer. The styrene block copolymer may be a diblock styrene polymer or a triblock styrene polymer. Examples of such styrene block copolymers are described, for example, in US Pat. No. 5,436,295 of Nishikawa et al., Which is incorporated herein by reference. Styrene block copolymers may have any molecular weight known to such polymers, and they may have a linear, branched, star, dendritic, or combined molecular structure. The styrene block copolymer may not be modified with functional groups, or may be modified with hydroxyl groups, carboxyl groups or other functional groups in its chain structure or at one or more ends. Styrene block copolymers can be obtained using any method common to the production of such polymers. Styrene block copolymers may also be hydrogenated using well known methods to obtain partially or fully saturated diene monomer blocks. Examples of styrene copolymers include, but are not limited to, registered trademark KRATON D (for styrene-butadiene-styrene and styrene-isoprene-styrene types), a resin manufactured by Kraton Polymer (formerly Shell Chemical), and KRATON G (for styrene-ethylene-butylene-styrene and styrene-ethylene-propylene-styrene types), as well as the registered trademark SEPTON, a resin manufactured by Kuraray. Examples of randomly distributed styrene polymers include paramethylstyrene-isobutylene (isobutene) copolymer developed by ExxonMobil Chemical and styrene-butadiene random copolymer developed by Chevron Phillips Chemical.

  Examples of other thermoplastic elastomers suitable as additional polymer components include those having functional groups such as carboxylic acid, maleic anhydride, glycidyl, norbornene, and hydroxyl functional groups. These examples include a block polymer having at least one polymer block A containing an aromatic vinyl compound and at least one polymer block B containing a conjugated diene compound and having a hydroxyl group in the terminal block copolymer, or its hydrogenation product Things are included. An example of this polymer is sold under the registered trademark SEPTON HG-252 from Kuraray Co., Kurashiki, Japan. Other examples of these include: a maleic anhydride functionalized triblock copolymer consisting of polystyrene endblocks and poly (ethylene / butylene) sold by Shell Chemical Company under the registered trademark KRATON FG1901X; E under the registered trademark FUSABOND . I. Maleic anhydride modified ethylene-vinyl acetate copolymer sold by DuPont de Nemours &Company; I. Ethylene-isobutyl acrylate-methacrylic acid terpolymer sold by DuPont de Nemours &Company; ethylene-ethyl acrylate-methacrylic anhydride terpolymer sold by Sumitomo Chemical Co., Ltd. under the registered trademarks BONDINE AX8390 and 8060; Brominated styrene-isobutylene copolymer sold by ExxonMobil Chemical Co. under the registered trademark BROMO XP-50; glycidyl or maleic anhydride functional groups sold by Elf Atochem of Puteaux, France under the registered trademark LOTADAR Resin.

The outer cover and / or one or more intermediate layers of the golf ball can include one or more ionomer resins. One group of such resins was found in E.D. I. Developed by DuPont de Nemours & Company and sold under the registered trademark SURLYN. The production of such ionomers is well known (see, eg, US Pat. No. 3,264,272). In general, the most commercial ionomers are unimodal and consist of polymers of monoolefins such as alkenes and unsaturated mono- or dicarboxylic acids having 3 to 12 carbon atoms. Additional monomers in the form of mono- or dicarboxylic esters can also be incorporated into the formulation as so-called “softening comonomers”. The incorporated carboxylic acid group is then neutralized with a basic metal ion salt to form an ionomer. Metal cations of basic metal ion salts used for neutralization include Li ⁺ , Na ⁺ , K ⁺ , Zn ²⁺ , Ca ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Pb ²⁺ , and Mg ^2+. Li ⁺ , Na ⁺ , Ca ²⁺ , Zn ²⁺ and Mg ²⁺ are preferred. Examples of basic metal ion salts include those of formic acid, acetic acid, nitric acid and carbonic acid, bicarbonates, oxides, hydroxides and alkoxides.

  At that time, it was well known that, as a general rule, the hardness of these cover materials increased with increasing acid content, but the first commercially available ionomer resins were acrylic or methacrylic up to 16% by weight. Contains acid. Thus, in Research Disclosure 29703, published in January 1989, DuPont announced ionomers based on ethylene / acrylic acid or ethylene / methacrylic acid with acid content above 15% by weight. In the same announcement, DuPont says that such so-called “high acid ionomers” are significantly improved in stiffness and hardness and are therefore advantageous for use in golf balls when used alone or in blends with other ionomers. I also taught.

  More recently, the high acid ionomer can be an ionomer resin having 16 to about 35 weight percent acrylic or methacrylic acid units in the polymer. Generally, such high acid ionomers have a flexural modulus of about 50,000 to about 125,000 psi.

  An ionomer resin further comprising from about 10 to about 50 weight percent softening comonomer in the polymer has a flexural modulus of from about 2,000 to about 10,000 psi, sometimes “soft” or “very low modulus”. Called ionomer. Common softening comonomers include n-butyl acrylate, iso-butyl acrylate, n-butyl methacrylate, methyl acrylate and methyl methacrylate.

Today there are a wide range of commercially available ionomer resins based on copolymers of ethylene and (meth) acrylic acid or terpolymers of ethylene and (meth) acrylic acid and (meth) acrylate, all of which as golf ball components Used. The properties of these ionomer resins can vary widely depending on the acid content, softening comonomer content, degree of neutralization, and the type of metal ion used for neutralization. Any commercially available product generally includes an ionomer of a polymer of the general formula E / X / Y, where E is ethylene and X is a C ₃ -C ₈ α, β-ethylene-based polymer. A saturated carboxylic acid such as acrylic acid or methacrylic acid, present in an amount of about 2 to about 30% by weight of the E / X / Y copolymer, and Y is an alkyl acrylate and alkyl methacrylate such as methyl acrylate or methyl methacrylate ( The alkyl group has 1 to 8 carbon atoms), and Y is present in the ionomer polymer in an amount of about 0 to about 50% by weight of the E / X / Y copolymer. The acid groups to be used are lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, and mixtures thereof It is partially neutralized with metal selected from.

  E / X / Y, where E is ethylene, X is a softening comonomer present, for example, in an amount of about 0 to about 50% by weight of the polymer, and Y is in an amount of about 5 to about 35% by weight of the polymer. Present and its acid moiety is neutralized from about 1 to about 100%, and a cation such as lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, or of such a cation An ionomer is formed with the combination.

  The ionomer may be a so-called bimodal ionomer as described in US Pat. No. 6,562,906. In addition to unimodal and bimodal ionomers, so-called “modified ionomers” are included, examples of which are US Pat. Nos. 6,100,321, 6,329,458 and 6,616,552, and It is described in US Patent Publication No. US2003 / 0158312A1.

  “Specialty propylene elastomers” include thermoplastic propylene-ethylene copolymers consisting of a majority amount of propylene and a small amount of ethylene. These copolymers have at least partial crystallinity due to adjacent isotactic prepolymer units. Without being bound by theory, it is believed that the crystalline segment is a physical cross-linking site at room temperature, physical cross-linking is removed at high temperatures (ie, near the melting point), and the copolymer is considered easy to process. In one embodiment, the specialty propylene elastomer comprises at least about 50 mole percent propylene comonomer. Specialty propylene elastomers can also contain functional groups such as maleic anhydride, glycidyl, hydroxyl and / or carboxylic acid. Suitable specialty propylene elastomers include propylene-ethylene copolymers made in the presence of a metallocene catalyst. More detailed examples of special propylene elastomers are shown below.

  An example of a special propylene elastomer is described in Kim et al. US Pat. No. 6,525,157, which is incorporated herein by reference in its entirety. Special propylene elastomers are commercially available from ExxonMobil Chemical Company under the registered trademark VISTAMAXX.

  In yet another aspect, a blend of ionomer and block copolymer can be included in a composition comprising a special propylene elastomer. An example of a block copolymer is a functionalized styrene block copolymer, where the block copolymer incorporates a first polymer block having an aromatic vinyl compound, a second polymer block having a conjugated diene compound, and a hydroxyl group located in the block copolymer. A copolymer, or a hydrogenated product thereof, wherein the ratio of block copolymer to ionomer is from 5:95 to 95: 5 (by weight), preferably from about 10:90 to about 90:10 (by weight), more preferably about 20: 80 to about 80:20 (weight), more preferably about 30:70 to about 70:30 (weight), and most preferably about 35:65 to about 65:35 (weight). A preferred block copolymer is SEPTON HG-252. Such blends are described in further detail in commonly assigned US Pat. No. 6,861,474 and US Patent Publication No. 2003/0224871, both of which are hereby incorporated by reference in their entirety.

  In another embodiment, the core, mantle and / or cover layer is blended together with at least three materials, components A, B and C, and these components are melt processed to in situ quasi-crosslinked polymer network A composition produced by forming a polymer blend composition comprising Such blends are described in further detail in Kim et al., Commonly assigned US Pat. No. 6,930,150, all incorporated herein by reference. Component A is a monomer, oligomer, prepolymer or polymer containing at least 5% by weight of at least one acidic functional group. Examples of such polymers suitable for use include, but are not limited to, ethylene / (meth) acrylic acid copolymers and ethylene / (meth) acrylic acid / alkyl (meth) acrylate terpolymers, or ethylene and / or propylene anhydride maleic Acid copolymers and terpolymers. Examples of such commercially available polymers include, but are not limited to, Escor® 5000, 5001, 5020, 5050, 5070, 5100, 5110 and 5200 series of ethylene-acrylic acid copolymers sold by Exxon, Michigan PRIMACOR® 1321, 1410, 1410-XT, 1420, 1430, 2912, 3150, 3330, 3340, 3440, 3460, 4311, 4608 and 5980 series of ethylene-acrylic acid copolymers sold by Dow Chemical Company, Midland, Canada And Nucrel 599, 699, 0903, 0910, 925, 960, 2806 and 2906 ethylene-methacrylic acid copolymers sold by DuPont.

Also included are bimodal ethylene / carboxylic acid polymers as described in US Pat. No. 6,562,906 (incorporated herein by reference). These polymers are ethylene / α, β-ethylenically unsaturated C _3-8 carboxylic acid high copolymers, especially ethylene (meth) acrylic acid copolymers, and ethylene / α, β-ethylenically unsaturated C _3-8 carboxylic acid copolymers. Ethylene, alkyl (meth) acrylates, (meth) having a molecular weight of about 80,000 to about 500,000, especially melt blended with an ethylene (meth) acrylic acid copolymer having a molecular weight of about 2,000 to about 30,000 Contains acrylic acid terpolymer.

  As discussed above, component B is preferably any monomer, oligomer, having a lower weight percent anionic functional group than that present in component A, most preferably not including such functional group. It may be a prepolymer or a polymer. Preferred materials for use as Component B are commercially available from ATOFINA Chemical Co., Philadelphia, Pennsylvania under the registered trademarks of PEBAX and LOTADAR; E.I. of Wilmington, Del. I. Sold by DuPont de Nimois &Company; registered trademark of SKYPEL and SKYTHANE, S. K. Sold by Chemical; sold by Kuraray of Kurashiki, Japan under the registered trademarks SEPTON and HYBRAR; sold by Noveon under the registered trademark of ESTHAN; and from Kraton Polymers under the registered trademark of KRATON Includes commercially available polyester elastomers. The most preferred material for use as Component B is SEPTON HG-252.

  Component C is a base capable of neutralizing the acidic functional group of component A, and is a base having a metal cation. These metals are those from groups IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB, VIIB and VIIIB of the periodic table. Examples of these metals include lithium, sodium, magnesium, aluminum, potassium, calcium, manganese, tungsten, titanium, iron, cobalt, nickel, hafnium, copper, zinc, barium, zirconium, and tin. Suitable metal compounds for use as component C source are, for example, metal salts, preferably metal hydroxides, metal oxides, metal carbonates or metal acetates. In addition to components A, B and C, other materials commonly used in polymer blend compositions may be incorporated into the composition produced using the method of the present invention. They include crosslinkers, co-crosslinkers, accelerators, activators, UV-active chemicals such as UV initiators, EB-active chemicals, colorants, UV stabilizers, optical brighteners, antioxidants, Processing aids, mold release agents, foaming agents, and organic, inorganic or metal fillers or fibers (including specific gravity adjusting fillers) are included.

  The composition is preferably made by thoroughly mixing the above materials with one another by using a dispersive mixing mechanism, a distributed mixing mechanism or a combination thereof. These mixing methods are well known in the production of polymer blends. As a result of this mixing, the anionic functional group of component A is uniformly dispersed throughout the mixture. Most preferably, components A and B are melt mixed with or without the above premixing and without component C to produce a two component molten mixture. Next, component C is separately mixed into a blend of components A and B. This mixture is melt-mixed to produce a reaction product. This two-stage mixing can be performed in a single process, such as, for example, an extrusion process using a suitable barrel length or screw configuration with multiple feed systems.

  Examples of polyamides used in the composition / golf ball according to the invention include (1) (a) dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, or 1,4-cyclohexane. Polycondensation of dicarboxylic acids with (b) diamines such as ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine or m-xylylenediamine; (2) cyclic lactams For example, ring-opening polycondensation of ε-caprolactam or ω-caprolactam; (3) polycondensation of aminocarboxylic acids such as 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, or 12-aminododecanoic acid; 4) Cyclic lactam and dicarboxylic acid and dia Copolymerization with min; or those obtained by any combination of (1) to (4) are included. In some examples, the dicarboxylic acid may be an aromatic dicarboxylic acid or an alicyclic dicarboxylic acid. In some examples, the diamine may be an aromatic diamine or an alicyclic diamine. Specific examples of suitable polyamides include polyamide 6; polyamide 11; polyamide 12; polyamide 4, 6; polyamide 6, 6; polyamide 6, 9; polyamide 6, 10; polyamide 6, 12; PA12, IT; PPA; PA6, IT; and PA6 / PPE.

  The polyamide may be a homopolyamide or a copolyamide. One example of a suitable group of polyamides are thermoplastic polyamide elastomers. The thermoplastic polyamide elastomer is generally a copolymer of polyamide and polyester or polyether. For example, the thermoplastic polyamide elastomer may include polyamide (nylon 6, nylon 66, nylon 11, nylon 12, etc.) as a hard segment and polyether or polyester as a soft segment. In one embodiment, the thermoplastic polyamide is an amorphous copolyamide based on polyamide (PA12).

One type of copolyamide elastomer is a polyetheramide elastomer. Examples of polyetheramide elastomers are those obtained from copolycondensation of polyamide blocks with reactive chain ends and polyether blocks with reactive chain ends and include the following:
(1) a diamine chain-terminated polyamide block having a polyoxyalkylene sequence of a dicarboxylic acid chain;
(2) a polyamide block at the end of a dicarboxylic acid chain having a polyoxyalkylene sequence at the end of a diamine chain obtained by cyanoethylation and hydrogenation of a polyoxyalkylene alpha-omega dihydroxylated aliphatic sequence known as a polyether diol; 3) Polyamide block at the end of the dicarboxylic acid chain with polyether diol, the product obtained in this particular case is a polyetheresteramide.

  More particularly, the polyamide elastomer comprises components (i) diamines and dicarboxylates, lactams or aminodicarboxylic acids (PA component), (ii) polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol (PG component). And (iii) can be prepared by polycondensation of dicarboxylic acids.

  Polyamide blocks at the end of dicarboxylic acid chains are obtained, for example, from the condensation of lactam alpha-omega amino carboxylic acids or of carboxylic diacids and diamines in the presence of carboxylic diacids which limit the chain length. The molecular weight of the polyamide sequence is preferably from about 300 to 15,000, more preferably from about 600 to 5,000. The molecular weight of the polyether sequence is preferably about 100 to 6,000, more preferably about 200 to 3,000.

  Amide block polyethers may also contain randomly distributed units. These polymers can be made by simultaneous reaction of polyether and polyamide block precursors. For example, polyether diols can react lactams (or alpha-omega amino acids) with diacids that limit chains in the presence of water. Polymers with very different lengths of predominantly polyether blocks and / or polyamide blocks but reacting randomly and also with different reactive groups distributed statistically along the polymer chain are obtained.

  Suitable amide block polyethers include U.S. Pat. Nos. 4,331,786, 4,115,475, 4,195,015, 4,839,441, 4,864,014. No. 4,230,848 and No. 4,332,920.

  The polyether may be, for example, polytetramethylene glycol (PTMG), also called polyethylene glycol (PEG), polypropylene glycol (PPG), or polytetrahydrofuran (PTHF). The polyether block is along the polymer chain in the form of a diol or diamine. However, for simplicity, they are called PEG blocks, or PPG blocks, or PTMG blocks.

The polyether block contains various units such as those derived from ethylene glycol, propylene glycol or tetramethylene glycol.
The amide block polyether comprises at least one polyamide block and one polyether block. Mixtures of two or more polymers with polyamide blocks and polyether blocks can also be used. The amide block polyether may contain any amide structure prepared by the above method.

  Preferably, the amide block polyether is the main component by weight, i.e. the amount of polyamide under the block form and statistically uniformly distributed in the chain is 50% by weight of the amide block polyether. That's it. It is advantageous if the amount of polyamide and the amount of polyether are in the ratio 1 / 1-3 / 1 (polyamide / polyether).

  One type of polyetherester elastomer is the Pebax system, which is available from Elf-Atchem. Preferably selected from Pebax 2533, 3533, 4033, 1205, 7033 and 7233. Also preferred are blends or combinations of Pebax 2533, 3533, 4033, 1205, 7033 and 7233. Pebax 2533 has a hardness of about 25 Shore D (according to ASTM D-2240), a flexural modulus of 2.1 kpsi (according to ASTM D-790), and a Bayshore resilience of about 62% (according to ASTM D-2632) It is. The hardness of Pebax 3533 is about 35 Shore D (according to ASTM D-2240), the flexural modulus is 2.8 kpsi (according to ASTM D-790), and the Bayshore resilience is about 59% (according to ASTM D-2632). Pebax 7033 has a hardness of about 69 Shore D (according to ASTM D-2240) and a flexural modulus of 67 kpsi (according to ASTM D-790). Pebax 7333 has a hardness of about 72 Shore D (according to ASTM D-2240) and a flexural modulus of 107 kpsi (according to ASTM D-790).

  Some examples of polyamides suitable for use are registered trademarks PEBAX, CRISTAMID and RILSAN, sold by Atfina Chemical Co., Philadelphia, Pennsylvania; Trademarks TROGAMID and VESTAMID for sale and E.I. in Wilmington, Delaware. I. It is a registered trademark ZYTEL sold by DuPont de Nemours & Company and is commercially available.

  Golf balls include traditional rubber components including natural and synthetic rubbers used for golf ball applications such as cis-1,4-polybutadiene, trans-1,4-polybutadiene, 1,2-polybutadiene, cis-polyisoprene, Trans-polyisoprene, polychloroprene, polybutylene, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer and partially and fully hydrogenated equivalents, styrene-isoprene-styrene block copolymer and partially and fully hydrogenated equivalents, nitrile rubber, Silicone rubber and polyurethane, and mixtures thereof can be included. Polybutadiene rubber, especially 1,4 containing at least 40 mol%, more preferably 80-100 mol% cis-1,4 bonds, due to its high resilience resilience, moldability and strength after vulcanization. -Polybutadiene rubber is preferred. The polybutadiene component may be synthesized by using rare earth based catalysts, nickel based catalysts or cobalt based catalysts commonly used in the field. The polybutadiene obtained by using a lanthanum rare earth-based catalyst uses a combination of lanthanum rare earth (atomic number 57 to 71) compounds, and particularly preferred are neodymium compounds.

The molecular weight distribution (Mw / Mn) of 1,4-polybutadiene rubber is about 1.2 to about 4.0, preferably about 1.7 to about 3.7, more preferably about 2.0 to about 3.5. Most preferably from about 2.2 to about 3.2. The Mooney viscosity (ML _{1 + 4} (100 ° C.)) of the polybutadiene rubber is about 20 to about 80, preferably about 30 to about 70, more preferably about 30 to about 60, and most preferably about 35 to about 50. As used herein, “Mooney-viscosity” refers to the industrial index of viscosity measured with a Mooney viscometer, which is a type of rotational plasticity meter (see JIS K6300). This value is represented by the symbol ML _{1 + 4} (100 ° C.), “M” represents Mooney viscosity, “L” represents a large rotor (L-type), “1 + 4” represents a preheating time of 1 minute, and a rotor rotation time of 4 minutes. “100 ° C.” indicates that the measurement was performed at a temperature of 100 ° C. As will be readily appreciated by those skilled in the art, blends of polybutadiene rubber may also be used in the golf balls of the present invention. Such blends can be made from materials having different molecular weights, molecular weight distributions, and Mooney viscosities, using mixtures of rare earth based catalysts, nickel based catalysts, or cobalt based catalyst derived materials.

  Golf ball cores and / or interlayers may also include 1,2-polybutadienes of different stereoregularities suitable for use in the compositions described herein as unsaturated polymers, which may include atactic 1, 2-polybutadiene, isotactic 1,2-polybutadiene, and syndiotactic 1,2-polybutadiene. Syndiotactic 1,2-polybutadiene having crystallinity suitable for use in the compositions described herein as an unsaturated polymer is polymerized from 1,2-addition of butadiene. The golf balls described herein have 1,2-bonds with crystallinity above about 70%, more preferably 1,2-bonds above about 80%, most preferably 1,2-bonds above about 90%. Syndiotactic 1,2-polybutadiene having a 2-bond may be included. The average molecular weight of 1,2-polybutadiene is about 10,000 to about 350,000, preferably about 50,000 to about 300,000, more preferably about 80,000 to about 200,000, most preferably about 10,000 to about 150,000. Suitable syndiotactic 1,2-polybutadiene having crystallinity suitable for golf balls is sold under the registered trademarks RB810, RB320 and RB830 by JSR Corporation of Tokyo, Japan. These 1,2-bonds are above 90%, the average molecular weight is about 120,000, and the crystallinity is about 15 to about 30%.

  The core and / or intermediate layer of the golf ball may also include a polyalkenamer. Examples of suitable polyalkenamer rubbers include polypentenamer rubber, polyheptenamer rubber, polyoctenamer rubber, polydecenamer rubber and polydodecenamer rubber. For further details on polyalkenamer rubber, see Rubber Chem. & Tech. 47, p. 511-596, 1974, incorporated herein by reference. Polyoctenamer rubber is commercially available from Huls AG, Mar, Germany, and U.S. in Somerset, New Jersey. S. It is commercially available through Creanova distributors and is sold under the VESTENAMER trademark. Two grades of VESTENAMER® trans-polyoctenamer are commercially available: VESTENAMER 8012 represents a material with a melting point of about 54 ° C. and a trans-content of about 80% (and a cis-content of 20%); Indicates a material with a trans-content of about 60% (and a cis-content of 40%) with a melting point of about 30 ° C. All of these polymers have a double bond for every 8th carbon atom in the ring.

  The polyalkenamer rubbers used in the present invention exhibit excellent melt processability above their sharp melting temperature, and various rubber additions as main components without adversely affecting the crystallinity that facilitates injection molding It is highly miscible with the product. Thus, unlike synthetic rubbers commonly used in golf ball production, it is possible to produce injection-moldable polyalkenamer-based compounds. This is disclosed in Hyun Kim et al., Co-pending US application Ser. No. 11 / 335,070 dated Jan. 18, 2006, all incorporated herein by reference.

As used herein, “injectable” as applied to polyalkenamer rubber or polyalkenamer / polyamide compositions refers to materials that are easy to handle in injection molding equipment designed for use with common thermoplastic resins. . In one example, the term injection moldable composition applied to uncrosslinked polyalkenamer rubber as used herein was measured using a dynamic mechanical analyzer (DMA) and ASTM D4440 at 200 ° C. The viscosity is less than about 5,000 Pa-sec, preferably less than about 3,000 Pa-sec, more preferably less than about 2,000 Pa-sec, most preferably less than about 1,000 Pa-sec, and at 25 ° C. Storage modulus (G ′) at 1 Hz measured using analyzer (DMA) and ASTM D4065 and ASTM D4440 is above about 1 × 10 ⁷ dyn / cm ² , preferably about 1.5 × 10 ⁷ dyn / cm Above ² , more preferably above about 1 × 10 ⁸ dyn / cm ² , most preferred Or a composition above about 2 × 10 ⁸ dyn / cm ² .

  More preferred compositions for use in golf balls, preferably golf ball cores or interlayers, are co-pending US application Ser. No. 11 / 335,070 dated Jan. 18, 2006 to Hyun Kim et al. (All hereby incorporated by reference). Blends of polyalkenamers and polyamides as disclosed in US Pat. The polyalkenamer / polyamide composition used to make the golf ball is about 2 to about 90% by weight, preferably about 5 to about 80% by weight, more preferably about 7 to about 70% by weight, even more preferably about 10 to 10%. About 60% by weight (based on the final weight of the injection molding composition) of one or more polyalkenamer polymers, especially cycloalkenes having 5-20, preferably 5-15, most preferably 5-12 ring carbon atoms Of polyalkenamers. Polyalkenamers can be prepared in the presence of an organometallic catalyst as described in US Pat. Nos. 3,492,245 and 3,804,803, both of which are hereby incorporated by reference in their entirety. It can be prepared by ring-opening metathesis polymerization of cycloalkene.

  The polyalkenamer / polyamide composition used in the manufacture of golf balls is about 10 to about 98% by weight, preferably about 20 to about 95% by weight, more preferably about 30 to about 93% by weight, even more preferably about 40 to about About 90% by weight (based on the final weight of the injection molding composition) of one or more polyamide polymers.

  In some embodiments, the polyalkenamer / polyamide composition is at least about 60 wt%, preferably at least about 70 wt%, more preferably at least about at least, based on the total amount of polymer in the layer or core made from the polyalkenamer / polyamide composition. 80% by weight of at least one polyamide. In another aspect, the polyamide component of the polyalkenamer / polyamide composition is a major component of the material used to form at least one component (eg, core or inner cover layer) of the golf ball. As used herein, “major component” means that the polyamide is present in an amount of at least about 50% by weight, based on the total weight of all components in the material.

  When synthetic rubbers such as the above polybutadienes or polyalkenamers and blends thereof are used in golf balls, they are additional materials commonly used in rubber formulations, such as crosslinkers, cocrosslinkers, peptizers and accelerators. May be included.

  Suitable crosslinkers for use in golf balls include peroxides, sulfur compounds, or other known chemical crosslinkers, as well as mixtures thereof. Non-limiting examples of suitable cross-linking agents include first, second or third aliphatic or aromatic organic peroxides. Peroxides containing one or more peroxy groups such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,4-di- (2-t-butylperoxyisopropyl) benzene. Can be used. Symmetric and asymmetric peroxides such as t-butyl perbenzoate and t-butyl cumyl peroxide can be used. Peroxides incorporating carboxyl groups are also suitable. The peroxide used as the cross-linking agent can be decomposed by thermal energy, shear force, irradiation, reaction with other chemical components, or combinations thereof. Homolytic and heterolytic peroxides may be used. Non-limiting examples of suitable peroxides include diacetyl peroxide; di-t-butyl peroxide; dibenzoyl peroxide: dicumyl peroxide; 2,5-dimethyl-2,5-di (benzoylperoxy) hexane; 1,4-bis- (t-butylperoxyisopropyl) -benzene; t-butylperoxybenzoate; 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, such as Acrochem, Akron, Ohio Trigonox 145-45B for sale; 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, for example R.D., Norwalk, Conn. T.A. Varox231-XL sold by Vanderbilt; and di- (2,4-dichlorobenzoyl) peroxide. The crosslinker is about 0.05 to about 5 parts by weight, more preferably about 0.2 to about 3 parts by weight, most preferably about 0.2 to about 2 parts by weight per 100 parts by weight of unsaturated polymer. Can be blended.

Each crosslinker has a specific decomposition temperature, which is the temperature at which 50% of the crosslinker decomposes at this temperature for a specific time (t _1/2 ). For example, the decomposition temperature of 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane at t _1/2 = 0.1 hour is 138 ° C., and t _1/2 = 0. The decomposition temperature of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 in 1 hour is 182 ° C. Two or more crosslinkers having different specific decomposition temperatures at the same t _1/2 may be blended into the composition. For example, if at least one crosslinker has a first specific decomposition temperature less than 150 ° C. and at least one crosslinker has a second specific decomposition temperature above 150 ° C., it has a first specific decomposition temperature The weight ratio of at least one crosslinker to the at least one crosslinker composition having a second characteristic decomposition temperature is from 5:95 to 95: 5, more preferably from 10:90 to 50:50.

  In addition to the use of chemical crosslinkers, exposure of the composition to radiation acts like a crosslinker. The unsaturated polymer mixture may be irradiated by known methods such as using microwave or gamma radiation, or an electron beam device. Additives may be used to improve the radiation curing of the diene polymer.

  The rubber and crosslinking agent may be blended with a co-crosslinking agent, and the co-crosslinking agent may be a metal salt of an unsaturated carboxylic acid. Examples of these include unsaturated fatty acids having 3 to 8 carbon atoms, such as zinc and magnesium salts of acrylic acid, methacrylic acid, maleic acid and fumaric acid, zinc of palmitic acid and acrylic acid and methacrylic acid Most preferred are salts. Unsaturated carboxylic acid metal salts can be prepared as preformed metal salts or by introducing α, β-unsaturated carboxylic acid and metal oxide or hydroxide into the rubber composition and reacting them in the rubber composition. Can be blended into the rubber by forming a metal salt. The unsaturated carboxylic acid metal salt can be blended in any desired amount, but is preferably blended in an amount of about 10 to about 60 parts by weight unsaturated carboxylic acid per 100 parts by weight synthetic rubber.

The core composition may contain one or more so-called “peptizers”.
The peptizer preferably comprises an organic sulfur compound and / or a metal or non-metal salt thereof. Examples of such organosulfur compounds include thiophenols such as pentachlorothiophenol, 4-butyl-o-thiocresol, 4-t-butyl-p-thiocresol, and 2-benzamidothiophenol; thiocarboxylic acid, For example, thiobenzoic acid; 4,4'-dithiodimorpholine; and sulfides such as dixylyl disulfide, dibenzoyl disulfide; dibenzothiazyl disulfide; di (pentachlorophenyl) disulfide; dibenzamido diphenyl disulfide (DBDD), and alkylated phenol Sulfides such as VULTAC sold by Atfina Chemical Co., Philadelphia, Pennsylvania are included. Preferred organic sulfur compounds include pentachlorothiophenol and dibenzamide diphenyl disulfide.

  Examples of metal salts of organic sulfur compounds include sodium, potassium, lithium, magnesium, calcium, barium, cesium and zinc salts of the above thiophenols and thiocarboxylic acids, with zinc salts of pentachlorothiophenol being most preferred.

Examples of non-metallic salts of organic sulfur compounds include the ammonium salts of the above thiophenols and thiocarboxylic acids, where the ammonium cation has the general formula [NR ¹ R ² R ³ R ⁴ ] ⁺ , where R ¹ , R ² , R ³ and R ⁴ are selected from the group consisting of hydrogen, C ₁ -C ₂₀ aliphatic, alicyclic or aromatic moieties, and any or all combinations thereof, most preferably NH ₄ ⁺ salt of pentachlorothiophenol.

  Additional peptizers include aromatic or conjugated peptizers containing one or more heteroatoms such as nitrogen, oxygen and / or sulfur. More commonly, such peptizers are heteroaryl or heterocyclic compounds having at least one (or more) heteroatoms, which may be the same or different. Such peptizers include indole peptizer, quinoline peptizer, isoquinoline peptizer, pyridine peptizer, purine peptizer, pyrimidine peptizer, diazine peptizer, pyrazine peptizer, triazine. A peptizer, a carbazole peptizer, or a combination of such peptizers is included.

Suitable peptizers include one or more additional functional groups such as halogen, in particular chlorine; sulfur-containing moieties such as thiols (when the functional group is sulfohydryl (-SH)), thioethers (when the functional group is -SR). ), Disulfide, (R ₁ S-SR ₂ ) and the like; and combinations of functional groups. Such peptizers are disclosed in further detail in Hyun Kim et al., Co-pending US application 60 / 752,475 dated 20 December 2005, which is hereby incorporated by reference in its entirety.

  When used in the golf ball of the present invention, the peptizer is about 10 parts by weight or less, about 0.01 to about 10 parts by weight, preferably about 0.10 to about 7 parts by weight per 100 parts by weight of the synthetic rubber component. More preferably in an amount of about 0.15 to about 5 parts by weight.

The core composition may also contain one or more accelerators. When added to the unsaturated polymer, the accelerator increases the vulcanization rate and / or decreases the vulcanization temperature.
The polymer composition used to make the golf ball may also contain one or more fillers. Such fillers are generally other than elongate fibers and flocs, eg, U.S., generally less than about 20 mesh, preferably less than about 100 mesh. S. It is a standard size fine shape. Filler particle size depends on desired results, cost, ease of addition, and dusting considerations. The appropriate amount of filler required will vary depending on the application, but can generally be readily determined without undue experimentation.

  Fillers are precipitated hydrated silica, limestone, clay, talc, asbestos, barite, glass fiber, aramid fiber, mica, calcium metasilicate, barium sulfate, zinc sulfide, lithopone, silicate, silicon carbide, diatomaceous earth, carbonate, Eg calcium carbonate or magnesium or barium, sulfates such as calcium sulfate or magnesium or barium, metals such as tungsten, steel, copper, cobalt or iron, metal alloys, tungsten carbide, metal oxides, metal stearates, and other It is preferably selected from the group consisting of granular carbonaceous materials, as well as any or all combinations thereof. Preferred examples of fillers include metal oxides such as zinc oxide and magnesium oxide. In another preferred embodiment, the filler comprises continuous or discontinuous fibers. In another preferred embodiment, the filler is US Pat. No. 6,794,447 and co-pending US patent application Ser. No. 10 / 670,090 dated September 24, 2003 and co-pending US patent dated August 25, 2004. It includes one or more so-called nanofillers as described in application Ser. No. 10 / 926,509, all incorporated herein by reference.

  Inorganic nanofiller materials are generally made of clay, such as hydrotalcite, phyllosilicate, saponite, hectorite, beidellite, stevensite, vermiculite, halloysite, mica, montmorillonite, micafluoride, or octosilicate . To facilitate incorporation of the nanofiller into the polymer material during the manufacture of the nanocomposite or during the manufacture of the polymer-based golf ball composition, the clay particles are generally coated or treated with a suitable compatibility agent. The compatibilizer can make the bond between inorganic and organic materials better, which can make the inorganic nanofiller hydrophilic and the polymer optionally hydrophobic. The compatibilizer can exhibit various structures depending on the nature of the inorganic nanofiller and the target matrix polymer. Examples include, but are not limited to, compounds, oligomers or polymers containing hydroxy-, thiol-, amino-, epoxy-, carboxylic acid-, ester-, amide-, and siloxy-groups. Nanofillers can be incorporated into the polymer by dispersion into individual monomers or oligomers prior to polymerization, or by melt blending of the particles into the matrix polymer. Examples of commercial nanofillers are 1. Cloisite grades including 10A, 15A, 20A, 25A, 30B and NA + from Southern Clay Products, Inc. (Gonzalez, TX) and 1. from Nanocall, Inc. (Arlington Heights, Ill.). 24TL and C.I. Nanomer grade including 30 EVA.

  When added to a matrix polymer such as a polyalkenamer rubber, the nanofiller can be mixed in three ways. One type of mixing is to disperse the aggregate structure into the matrix polymer, but there is no interaction between the matrix polymer and the aggregate platelet structure during mixing, and thus the stacked platelet structure is essentially maintained. Is done. Here, this mixing type is defined as an “undispersed” mixing type.

  However, if the nanofiller is selected correctly, the matrix polymer chains will enter the aggregates and separate the platelets, so that when examined by transmission electron microscopy or X-ray diffraction, the platelet aggregates expand. Yes. At this point, the nanofiller is said to be substantially uniformly dispersed in the matrix polymer structure and acting on the matrix polymer structure. This expansion level occurs to varying degrees. If a small amount of matrix polymer is layered between individual platelets, this mixing type is known as an “intercalation” mixing type.

  In certain situations, further penetration of the matrix polymer chain into the aggregate structure separates the platelets, leading to complete collapse of the platelet stack in the aggregate. Thus, when examined with a transmission electron microscope (TEM), the individual platelets are well mixed throughout the matrix polymer. As used herein, this mixing type is known as an “exfoliated” mixing type. The exfoliated nanofiller has platelets well dispersed throughout the matrix polymer; the platelet distribution may not be uniform, but is preferably uniformly dispersed.

  While not wishing to be limited to any theory, the expected explanation for varying degrees of dispersion within the matrix polymer structure of such nanofillers is the nanofiller platelet structure of the conformer surface coating. It is an influence on the interaction between the matrix polymer. By carefully selecting the nanofiller, it is possible to change the penetration of the matrix polymer into the nanofiller platelet structure during mixing. Thus, the degree of interaction and penetration of the matrix polymer into the nanofiller controls the separation and dispersion of individual nanofiller platelets within the polymer matrix. The interaction between the polymer matrix and the nanofiller platelet structure is defined here as the “reaction to the polymer structure” of the nanofiller, and the subsequent dispersion of the platelets within the polymer matrix is now within the structure of the polymer matrix. Defined as “substantially uniform dispersion” of the nanofiller.

  If the compatibility agent is not present on the surface of a filler such as clay, or if the clay coating is performed after its addition to the polymer matrix, then penetration of the matrix polymer into the nanofiller is sufficient. Far away, the individual clay platelets hardly separate and disperse within the matrix polymer.

  The physical properties of the polymer change with the addition of nanofillers. The physical properties of the polymer are expected to be further improved as the nanofiller is dispersed into the polymer matrix to form the nanocomposite.

  Nanofiller encapsulated materials improve these properties at a much lower density than conventional filler encapsulated materials. For example, a nylon-6 nanocomposite manufactured by RTP in Wichita, Kansas uses 3-5% clay loading, has a tensile strength of 11,800 psi, a specific gravity of 1.14, 30% of the conventional The mineral filler material has a tensile strength of 8,000 psi and a specific gravity of 1.36. The properties of nanocomposites with fewer inorganic materials than conventional fillers are the same, which allows products that contain nanocomposite fillers that are lighter than conventional fillers but retain these same properties To do.

  Nanocomposites react to the structure of organic materials such as polymers and are well dispersed by intercalation or exfoliation to improve the strength, temperature resilience and other properties of the resulting composite The material is up to about 20%, from about 0.1% to about 20%, preferably from about 0.1% to about 15%, most preferably from about 0.1% to about 10%. For individual nanocomposites and their manufacture, see Ellsworth US Pat. No. 5,962,553, Maxfield et al. US Pat. No. 5,385,776, and Okada et al. US Pat. No. 4,894,411. It is described in. Examples of recently sold nanocomposites include M1030D manufactured by Unitika Ltd., Osaka, Japan, and 1015C2 manufactured by UBE America Inc., New York, NY.

  When the nanocomposite is blended with other polymer systems, the nanocomposite can be considered a type of nanofiller concentrate. However, the nanocomposite concentrate can be a more general polymer in which the nanofiller is mixed; the nanofiller concentrate does not require the nanofiller to react and / or uniformly disperse into the support polymer. .

  In the case of polyalkenamers, the nanofiller reacts to the structure of the core polymer matrix and is well dispersed by intercalation or exfoliation into the nanofiller, up to about 20% by weight, up to about 0.1 to about 20% by weight. %, Preferably from about 0.1 to about 15% by weight, most preferably from about 0.1 to about 10% by weight (based on the final weight of the polymer matrix material).

  If desired, the various polymer compositions used in the manufacture of golf balls may contain other common additives such as plasticizers, pigments, antioxidants, U.S.A. V. It may further contain absorbers, optical brighteners, or other additives commonly used in the manufacture of plastic formulations or golf balls.

Another particularly suitable additive includes the general formula:
_{(R 2 N) m -R'- (} X (O) n OR y) m
Wherein R is hydrogen or a C ₁ -C ₂₀ aliphatic, alicyclic or aromatic system; R ′ is one or more C ₁ -C ₂₀ linear or branched aliphatic or alicyclic A formula group, or a substituted linear or branched aliphatic or alicyclic group, or an aromatic group, or an oligomer of 12 or fewer repeating units, such as, but not limited to, a polypeptide derived from an amino acid sequence of up to 12 amino acids, And X is C or S or P, provided that when X = C, n = 1 and y = 1, when X = S, n = 2 and y = 1, X = (When P, n = 2 and y = 2, and m = 1 to 3)
Are included. These materials are described in further detail in co-pending US patent application Ser. No. 11 / 182,170 dated July 14, 2005, which is hereby incorporated by reference in its entirety. These materials include but are not limited to caprolactam, enantolactam, decanolactam, undecanolactam, dodecanolactam, capron 6-amino acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, adipic acid, azelaic acid, sebacic acid And diamine hexamethylene salt of 1,12-dodecanoic acid and diamine nonamethylene salt of adipic acid, 2-aminocinnamic acid, L-aspartic acid, 5-aminosalicylic acid, aminobutyric acid; aminocaproic acid; aminocaprylic acid; (Aminocarbonyl) -1-cyclopropanecarboxylic acid; aminocephalosporanic acid; aminobenzoic acid; aminochlorobenzoic acid; 2- (3-amino-4-chlorobenzoyl) benzoic acid; aminonaphthoic acid; aminonicotinic acid; Norbornane Carvone Aminopenicillic acid; aminopentenonic acid; (aminophenyl) butyric acid; aminophenylpropionic acid; aminophthalic acid; aminofolic acid; aminopyrazinecarboxylic acid; aminopyrazolecarboxylic acid; aminosalicylic acid; aminoterephthalic acid; Valeric acid; ammonium hydrogen citrate; anthranilic acid; aminobenzophenone carboxylic acid; aminosuccinamic acid, ε-caprolactam; ω-caprolactam, (carbamoylphenoxy) acetic acid, sodium salt; carbobenzyloxyaspartic acid; carbobenzylglutamine; Benzyloxyglycine; 2-aminoethyl hydrogen sulfate; aminonaphthalenesulfonic acid; aminotoluenesulfonic acid; 4,4'-methylene-bis- (cyclohexylamine) carbamate It includes fine ammonium carbamate.

  Most preferably, the material is 4,4′-methylene-bis- (cyclohexylamine) carbamate (available from RT Vanderbilt, Inc., Norwalk, Conn., Diak® 4), 11-aminoundecane Selected from the group consisting of acids, 12-aminododecanoic acid, ε-caprolactam; ω-caprolactam, and any and all combinations thereof.

In a particularly preferred embodiment, the nanofiller additive component in the golf ball has the general formula:
_{(R 2 N) m -R'- (} X (O) n OR y) m
Surface-modified with a compatibilizing agent comprising said compound having

  The most preferred embodiment is a filler comprising a nanofiller clay material surface modified with an amino acid comprising 12-aminododecanoic acid. Such fillers are available from Nanonocol Corporation under the registered trademark Nanomer 1.24TL.

  The filler can be blended in various effective amounts, for example, from above 0 to at least about 80 parts by weight, more typically from about 10 to about 80 parts by weight per 100 parts by weight of the base rubber. If desired, the rubber composition may further include an effective amount of a plasticizer, an antioxidant, and other additives commonly used in golf ball manufacture.

Various compositions used as components of golf balls can include monomeric amide modifiers, such as monomeric aliphatic and / or aromatic amide polymer modifiers. Amides are organic compounds that contain the group —CONR _{2, where} R is hydrogen; aliphatic groups such as alkyl, alkenyl or alkynyl groups; aromatic groups; and combinations thereof. Amides useful in the present invention are primary amides, secondary amides or tertiary amides, and combinations thereof. That is, an individual compound may have more than one amide moiety, one of which is a first, second or third amide and the other amide is a first amide moiety. With different degrees of substitution. For example, if the first amide is a first amide, the second amide moiety is a second amide or a third amide.

  The amide may be saturated or unsaturated. Further, the unsaturated amide may have one or more sites of unsaturation including aromatic amides. Alkenamides can have cis or trans double bonds. In the case of compounds having multiple sites of unsaturation, such double bonds can be all cis, all trans, or a combination of cis and trans double bonds. Certain compounds are better as polymer modifiers if the olefin is all or predominantly cis, or all or predominantly trans. Furthermore, the position of the double bond in the compound can affect the usefulness of the compound in modifying the polymer composition.

  The polymer composition includes an amount of amide modifier effective to modify the composition as desired. For example, with amide modifiers, more desirable rheological properties than non-modified polymer compositions, more desirable mechanical properties than non-modified polymer compositions, and rheological and mechanical properties Can result in a combination. For example, it is surprising that useful polymer compositions modified with suitable (one or more) amides can be compositions that can advantageously modify rheological properties, such as melt flow index (MFI). Also found. At the same time, mechanical properties such as hardness, flexural modulus and COR can be essentially maintained, and in some formulations improved compared to the same composition without monomeric amide (s). It is particularly surprising that increasing the useful amount of modifier to a relatively high concentration, eg, 1% by weight or more, can advantageously modify certain polymer properties while maintaining a suitable COR value. It was.

  For example, without limitation, the amide modifier is about 0.1 to about 50 pph (parts per hundred parts), more typically about 0.1 to about 20 pph, based on the weight of the polymer portion of the composition. It is generally believed that it can be added in an amount of from about 0.5 to about 15 pph, most commonly from about 1 to about 10 pph.

  The golf ball can also include a suitable amount of one or more additional ingredients commonly used in golf ball compositions. Agents that provide specific effects, such as additives and stabilizers, can be present. Examples of suitable ingredients include colorants, antioxidants, dispersants, mold release agents, processing aids, fillers, and any and all combinations thereof. Although not required, the use of UV stabilizers, i.e. light stabilizers such as substituted hydroxyphenylbenzothiazoles, can increase the UV stability of the final composition. Examples of commercially available UV stabilizers are those sold by Ciba Geigy under the registered trademark TINUVIN.

  Generally, a golf ball core is manufactured by mixing various components and other additives with or without melting. The composition can be mixed using a dry blender, such as a tumble mixer, V-blender, ribbon blender, or two roll mill. The golf ball composition can also be mixed using a mill, an internal mixer, such as a Banbury or Farrell continuous mixer, an extruder, or combinations thereof, with or without the application of thermal energy to melt. The viscous core component may be mixed with the cross-linking agent or each additive may be added to the kneaded unsaturated polymer in an appropriate order. In another manufacturing method, the crosslinker and other components may be added to the unsaturated polymer as a concentrate portion using dry blending, roll milling or melt mixing. If the radiation is a cross-linking agent, the mixture containing the unsaturated polymer and other additives may be irradiated after mixing and during or after forming into a part such as the core of the ball.

  When the resulting mixture is compressed or injection molded, for example, solid spheres for the core are obtained. The polymer mixture is sent to a molding cycle where heat and pressure are applied while the mixture is placed in a mold. The shape of the cavity depends on the part of the golf ball that is molded. By compression and heat, one or more peroxides decompose to release free radicals and initiate crosslinking. The temperature and time of the molding cycle depends on the type of peroxide and peptizer selected. The molding cycle may be a single process in which the mixture is molded at a single temperature for a fixed time.

  For example, the preferred method of core production is to first mix the core components on a two roll mill to form about 30-40 g slug, then compression molding in a single step at a temperature of 150-180 ° C. for 5-12 minutes. To do.

  Golf balls may be formed by injection molding methods in combination with various core components, which are well known to those skilled in the art. The cure time depends on the various materials selected and those skilled in the art can easily adjust the length of the cure time based on the particular material used and the discussion herein.

Generally, the golf ball cover and intermediate layer are placed on a core or other intermediate layer using one of three methods (injection, injection molding or compression molding).
Please refer to FIG. FIG. 2 shows a three-part golf ball 1 that includes a core 2, an intermediate layer 3, and an outer cover layer 4. The golf ball also has a plurality of indentations formed in the outer cover layer 4 and arranged in various desired patterns.

The diameter of the core of the multi-part golf ball is about 0.5 to about 1.62 inches, preferably about 0.7 to about 1.60 inches, and more preferably about 1 to about 1.58 inches.
The PGA compression of the core of the multi-part golf ball is from about 10 to about 100, preferably from about 35 to about 90, more preferably from about 40 to about 80.

  The core of the golf ball may also include a center and one or more core layers disposed about the center. These core layers may be made of the same rubber used for the central portion, or may be different thermoplastic elastomers. The various core layers (including the center) each exhibit a different hardness. The difference in hardness between the center hardness and the next adjacent layer, as well as the difference in hardness between the various core layers, is above 2 units of Shore D, preferably above 5 units and most preferably above 10 units.

In a preferred embodiment, the hardness of the center and each continuous layer increases as it goes out of the center to the outer core layer.
In another preferred embodiment, the hardness of the center and each continuous layer decreases as it goes inward from the outer core layer.

  The thickness of the intermediate layer of the multi-part golf ball is about 0.01 to about 0.50 inch, preferably about 0.02 to about 0.30 inch, more preferably about 0.03 to about 0.20 inch. Most preferably from about 0.03 to about 0.10 inches.

  The hardness of the intermediate layer of the multi-part golf ball is measured on the ball above about 25, preferably above about 30, more preferably above about 40, most preferably above about 50 Shore D units. It is.

  The flexural modulus of the intermediate layer of the multi-part golf ball is about 5 to about 500 kpsi, preferably about 15 to about 400 kpsi, more preferably about 20 to about 300 kpsi, even more preferably about 25 to about 200 kpsi, most preferably About 30 to about 150 kpsi.

  The cover of the multi-part golf ball has a thickness of about 0.01 to about 0.20 inches, preferably about 0.02 to about 0.15 inches, more preferably about 0.03 to about 0.10 inches. Most preferably from about 0.03 to about 0.07 inches.

The hardness of the cover of the multi-part golf ball is about 25 to about 80, more preferably about 30 to about 70, even more preferably about 40 to about 60 Shore D.
In some embodiments, the polyurethane, polyurea or combinations thereof constitute the major (eg, greater than 50%, especially greater than 75%, and more particularly greater than 90%) polymer present in the cover. In some embodiments, the cover is substantially free of ionomers.

The PGA ball compression of the multi-part golf ball is above about 30, preferably above about 40, more preferably above about 50, and most preferably above about 60.
1 and 2 show only two and three-part golf ball structures, the golf ball has from 0 to at least 5 intermediate layers, preferably 0 to 3 intermediate layers, more preferably 1 to 3 intermediate layers, most preferably May include one to two intermediate layers.

In certain illustrated aspects, the multi-part golf ball also has a sound pressure level S of less than 81.5 dB, preferably less than 81 dB, more preferably less than 80.5 dB.
In certain illustrated embodiments, the multi-part golf ball of the present invention also has the following inequality:
S <−0.032143F + 189.5;
Preferably the following inequality:
S <-0.01000F + 112.0
(Where F is the golf ball frequency in Hz)
A sound pressure level S satisfying

  The COR of a multi-part golf ball has an inbound velocity of 125 feet / second and is greater than about 0.760, preferably greater than about 0.780, more preferably greater than about 0.790, and most preferably about 0.795. Greater than, and most preferably greater than about 0.800.

  The COR of a multi-part golf ball is also greater than about 0.760, preferably greater than about 0.780, more preferably greater than about 0.790, and most preferably about 0.00 at an inbound velocity of 143 feet / second. Greater than 795, most preferably greater than about 0.800.

In the illustrated embodiment, the golf ball is:
A low PGA compression core (eg, 40-80 PGA compression, more preferably less than 60 PGA compression) (preferably the core comprises at least one nanocomposite and / or nanofiller);
At least one intermediate layer comprising a polyalkenamer, preferably a cross-linked polyalkenamer; and a polyurethane cover, preferably an injection molded polyurethane cover.
Examples The following examples are presented to illustrate certain features of the disclosed golf ball embodiments. One skilled in the art will appreciate that the invention is not limited to the features illustrated by these examples. PGA compression, C.I. O. R. And Shore D hardness was measured using the test methods defined below for materials and / or golf balls made according to the present disclosure.

  Shore D hardness was measured according to ASTM D2240. The hardness of the layer was measured perpendicular to the flat part between the indentations in the ball. The diameter of the core or ball was measured using a standard linear caliper or standard size gauge.

  Compression was measured by applying a spring-loaded force to the ball to be tested with a manual device ("Atti gauge") manufactured by Atti Engineering, Union City, NJ. This machine, equipped with a Federal Dial Gauge, Model D81-C, uses a pre-calibrated spring under a known load. The sphere to be tested is pressed a distance of 0.2 inches (5 mm) against this spring. If the spring compresses 0.2 inches, the compression value is considered 100; if the spring compresses 0.1 inches, the compression value is considered 0. A more compressible and softer material has a lower Atti gauge value than a harder and less compressible material. The value is obtained immediately after applying the force, preferably within at least 5 seconds. The compression measured with this device is also called PGA compression.

The approximate relationship between Atti or PGA compression and Riehle compression can be expressed as:
(Atti or PGA compression) = (160-Riele compression)
Thus, 100 Riehle compression would be the same as 60 Atti compression.

  The initial velocity of a golf ball after hitting a golf club is determined by the United States Golf Association ("USGA"). The USGA requires that the initial velocity of a formal golf ball be 250 feet / second ± 2% or less than 255 feet / second. USGA's initial speed limit is related to the ultimate distance that the ball can fly (280 yards ± 6%) and also to the recovery factor (“COR”). The recovery factor is the ratio of the relative speed between two objects after direct impact to the relative speed before impact. As a result, the COR can vary from 0 to 1, with 1 corresponding to a fully elastic collision and 0 corresponding to a completely inelastic collision. Golf ball manufacturers are interested in this property for golf ball design and testing because the COR of a ball directly affects the initial velocity and flight distance of the ball after a club impact.

The golf ball sound pressure level S in decibels (dB) and frequency (Hz) is a marble ("Starnet Crystal Pink") platform with a ball from 113 inches high to 4.25 inches thick and at least 12 inches square. It was measured by dropping it on the surface. The resulting impulsive sound was captured from the impact position by a microphone placed at a 30 ° angle from the horizontal at a fixed position close to 12 inches, and converted by software conversion into an intensity in dB and a frequency in Hz. Data was collected as follows:
Microphone data is collected using a laptop PC with a sound card. A weight filler is applied to the analog signal from the microphone. This signal is then digitally collected at 44.1 KHz by a laptop data acquisition system for further processing and analysis. Data analysis was performed as follows:
Data analysis is divided into two processes:
a. Time series analysis that produces a root mean square (rms) sound pressure level (SPL) for each ball impact sound.

i. The rmsSPL from the control calibration signal is generated in the same way as the ball data.
ii. The total SPL (decibel) is calculated from the reference signal for each ball impact sound.
iii. The median SPL is recorded based on three impact tests.
b. Spectral analysis for each ball impact sound i. An output spectrum is formed using Fourier and auto-regressive spectrum evaluation techniques.
ii. Identify the frequency (cycles / second-Hz) from the highest level peak that shows the most active sound producing the vibration mode of each ball.
Example 1 Ball Production A 1.510 inch diameter solid core incorporating cis-1,4-polybutadiene produced with a rare earth catalyst as a base rubber was produced. The core was also blended with rubber grade zinc oxide purchased from Acrochem (Akron, Ohio), zinc diacrylate “ZDA”, commercially available from Sartomer, and a peroxide crosslinking initiator. The core component was mixed with a two-roll mill to form about 34.5 g of slug, and compression molded at 170 ° C. for 7 minutes. The resulting core had a PGA compression of 60 as measured after aging for 1 day at room temperature.

  The mantle material was manufactured from a blend of two copolymer ionomers each having an acid content greater than 16% by weight, injection molded around the core at a thickness of 0.055 inches, and Shore D hardness measured on a curved surface Got a 66D Manturer. The final golf ball was made by casting a thermoset urethane cover around the manteller to produce a 1.680 inch diameter golf ball with a recessed surface having the ball structure and properties shown in Table 1. A thermoset polyurethane cover was made from Chemtura LF950A (toluene diisocyanate urethane prepolymer) and ETHACURE E100LC diamine.

                      Table 1 Structure of Example 1

        Table 2-Sound level and frequency of Example 1 and comparative commercial ball (Comp Ex)

＊ＴＰＵ＝熱可塑性ポリウレタン

* TPU = thermoplastic polyurethane

A three-part golf ball 1 is shown that includes a solid center or core 2, an intermediate layer 3, and an outer cover layer 4. 4 shows a four-part golf ball including a core 2, an outer cover layer 5, an inner intermediate layer 3 and an outer intermediate layer 4. 1 and 2 only show three-part and four-part golf ball structures, the golf ball has from 1 to at least 5 intermediate layers, preferably from 1 to 3 intermediate layers, more preferably from 1 to 2 intermediate layers. May be included.

Explanation of symbols

1 golf ball 2 core 3 intermediate layer 4 outer cover layer or outer intermediate layer 5 outer cover layer

Claims (24)

A golf ball comprising a cover layer, a core and one or more intermediate layers,
1) solid core;
2) a cover comprising polyurethane, polyurea or a combination thereof; and 3) a sound pressure level S of less than 81 dB
Golf ball having. S is the following inequality:
S <-0.032143F + 189.5
(Where F is the golf ball frequency in Hz)
The golf ball according to claim 1, wherein: S is the following inequality:
S <-0.01F + 112
(Where F is the golf ball frequency in Hz)
The golf ball according to claim 1, wherein:   The golf ball of claim 3, wherein the cover comprises a thermosetting polyurethane.   The golf ball of claim 1, wherein the cover comprises a polyurethane made from a polypropylene glycol-terminated toluene diisocyanate prepolymer.   The golf ball of claim 1, wherein the cover comprises a polyurethane made from a reaction product of a polypropylene glycol-terminated toluene diisocyanate prepolymer and a diamine.   The golf ball of claim 1, wherein the golf ball has an S less than 80.5 dB.   The golf ball according to claim 1, wherein the cover does not include an ionomer.   The golf ball of claim 1, wherein the cover consists essentially of polyurethane.   The golf ball of claim 1, wherein the core comprises at least one nanocomposite or nanofiller, the intermediate layer comprises a polyalkenamer, and the cover layer comprises polyurethane. A golf ball comprising a cover layer, a core and one or more intermediate layers,
1) solid core;
2) polyurethane cover or polyurea cover; and 3) S is the following inequality:
S <-0.032143F + 189.5
(Where F is the golf ball frequency in Hz)
Satisfying the sound pressure level S of less than 81.5 dB
Golf ball having.   The golf ball of claim 11, wherein the polyurethane cover comprises a thermosetting polyurethane.   The golf ball of claim 11, wherein the golf ball includes a polyurethane cover.   The golf ball of claim 12, wherein the cover comprises a polyurethane made from a polypropylene glycol-terminated toluene diisocyanate prepolymer.   The golf ball of claim 11, wherein the core comprises at least one nanocomposite or nanofiller, the intermediate layer comprises a polyalkenamer, and the cover layer comprises polyurethane. A golf ball comprising a cover layer, a core and one or more intermediate layers,
1) solid core;
2) polyurethane cover or polyurea cover; and 3) a sound pressure level S of less than 81.5 dB, where S is the following inequality:
S <-0.01F + 112
(Where F is the golf ball frequency in Hz)
Meet,
Golf ball having.   The golf ball of claim 16, wherein the polyurethane cover comprises a thermosetting polyurethane.   The golf ball of claim 16, wherein the golf ball includes a polyurethane cover.   The golf ball of claim 16, wherein the core comprises at least one nanocomposite or nanofiller, the intermediate layer comprises a polyalkenamer, and the cover layer comprises polyurethane. A golf ball comprising a cover layer, a core and one or more intermediate layers,
1) solid core; and 2) with thermosetting polyurethane cover; golf ball frequency ≦ 3360 Hz
Is a golf ball. Golf ball frequency <3360Hz
The golf ball according to claim 20, wherein   The golf ball of claim 20, wherein the cover comprises a polyurethane made from a polypropylene glycol-terminated toluene diisocyanate prepolymer.   21. A golf ball according to claim 20, wherein the core comprises at least one nanocomposite or nanofiller and the intermediate layer comprises a polyalkenamer. A golf ball comprising a cover layer, a core and one or more intermediate layers,
1) solid core; and 2) with polyurethane or polyurea cover; golf ball frequency <3360 Hz
Is a golf ball.

Images