WO2000057961A1 - Golf ball with multiple shell layers - Google Patents
Golf ball with multiple shell layers Download PDFInfo
- Publication number
- WO2000057961A1 WO2000057961A1 PCT/US1999/006715 US9906715W WO0057961A1 WO 2000057961 A1 WO2000057961 A1 WO 2000057961A1 US 9906715 W US9906715 W US 9906715W WO 0057961 A1 WO0057961 A1 WO 0057961A1
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- WIPO (PCT)
- Prior art keywords
- layer
- shell
- golf ball
- ball according
- hardness
- Prior art date
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Classifications
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0077—Physical properties
- A63B37/0092—Hardness distribution amongst different ball layers
- A63B37/00921—Hardness distribution amongst different ball layers whereby hardness of the cover is higher than hardness of the intermediate layers
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0029—Physical properties
- A63B37/0031—Hardness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0029—Physical properties
- A63B37/0033—Thickness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0029—Physical properties
- A63B37/0035—Density; Specific gravity
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
- A63B37/0039—Intermediate layers, e.g. inner cover, outer core, mantle characterised by the material
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
- A63B37/004—Physical properties
- A63B37/0043—Hardness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
- A63B37/004—Physical properties
- A63B37/0045—Thickness
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
- A63B37/004—Physical properties
- A63B37/0047—Density; Specific gravity
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/006—Physical properties
- A63B37/0061—Coefficient of restitution
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0077—Physical properties
- A63B37/0091—Density distribution amongst the different ball layers
Definitions
- the present invention generally relates to golf balls, and more particularly to a golf ball having a center formed from liquid or gel and a shell or cover which includes at least three layers.
- Conventional two-piece golf balls include a solid resilient core having a cover of a different type of material molded thereon.
- Solid cores of both two and three-piece balls often are made of polybutadiene and the molded covers generally are made of natural balata, synthetic balata, or ionomeric resins.
- Ionomeric resins are polymers containing interchain ionic bonding. As a result of their toughness, durability and flight characteristics, various ionomeric resins sold by E.I.
- Ionomeric resins are generally neutralized copolymers of an olefin, such as ethylene, and an unsaturated carboxylic acid, such as acrylic acid, methacrylic acid or maleic acid.
- Metal ions such as sodium or zinc, are used to neutralize some portion of the acidic group in the copolymer, resulting in a thermoplastic elastomer exhibiting enhanced properties, i.e., durability, etc., for golf ball cover construction over balata.
- One way to measure the COR of a golf ball is to propel the ball at a given speed against a hard massive surface, and to measure its incoming and outgoing velocity.
- the COR is the ratio of the outgoing velocity to the incoming velocity and is expressed as a decimal between zero and one.
- a golf ball that: has the "feel” and controllability of a balata covered three-piece ball; has a high initial velocity or initial coefficient of restitution, has a good "cut resistance” and durable cover; may be driven long distances in regulation play, hopefully by "average” golfers; and, importantly, may be uniformly and inexpensively manufactured by mass production techniques.
- the industry has sought to achieve this long recognized and desired objective by using a polymer or balata cover over a preformed core and by enhancing the ball's preformed core's capacity for transferring energy when the ball is struck by a golf club.
- U.S. Patent Nos. 4,431 ,193 and 4,919,434 disclose golf balls with multi-layer covers.
- U.S. Patent No. 4,431 ,193 discloses a multi-layer ball with a hard inner cover layer and a soft outer cover layer.
- U.S. Patent No. 4,919,434 discloses a golf ball with a 0.4 - 2.2 mm thick cover made from two thermoplastic cover layers.
- U.S. Patent No. 5,273,286 discloses a golf ball with a multi-layer core. The golf ball disclosed therein has an inner core, a shell surrounding the inner core, an outer core, and a cover. Summary of the Invention
- Multi-piece golf balls represent a completely novel approach as to how a commercially viable golf ball should be constructed and manufactured.
- a preformed spherical shell, rather than a preformed core, is the starting point for the golf ball, and the materials selected for the spherical shell may provide substantially all of the energy transfer contribution to the performance of the golf ball.
- the unique goif ball of the present invention (hereinafter sometimes the "Unique ball") relies primarily on the shell composition for transferring energy from the golf club to the ball when the ball is struck, and its core need not contribute anything to this energy transfer. Rather, the core's principal contribution is to give the ball the weight desired or needed to conform to U.S.G.A. rules.
- the golf ball of the present invention not only has a unique construction but also enjoys significant advantages over conventional multi-piece balls.
- the golf ball of the present invention has all the advantages that a conventional two-piece ball affords.
- the Unique ball enjoys the following advantages:
- the Unique ball distorts more and remains longer on the face of a golf club in a manner similar to balata covered, thread wound three-piece balls. This provides a "feel" and controllability very compatible to balata covered balls.
- the Unique ball has a significantly lower trajectory with long distance golf clubs (e.g. drivers) than conventional two-piece or three-piece balls made today. Skilled golfers, based on their choice of clubs and how the club head approaches the bail, can also easily and readily modify the trajectory of the present ball.
- the Unique ball can be driven farther (carry plus roll) than conventional two-piece and three-piece balls.
- Initial testing has shown that as the loft angle of long distance clubs increases, this increase in distance becomes more and more noticeable and that the roll of this Unique ball may approach twice that of a conventional two-piece ball.
- initial testing has also indicated that a golf ball, made in accordance with the present invention and having a coefficient of restitution of 0.745 to 0.765, may be driven farther than a conventional two-piece ball having a coefficient of restitution of 0.815. It is believed that less energy is lost because of the deformation and restoration of the Unique ball when it is struck by a club. Striking the ball deforms the cover and also the pre-formed core.
- This core deformation uses or wastes energy that does not occur with the Unique ball when using a liquid core. Further in the case of the Unique ball, the liquid core need not be put into rotation as is necessary in the case of conventional golf balls, thereby further conserving energy. Additionally, because of the lower trajectory of the ball, the ball will land at a more acute angle to the ground and this, too, lessens the energy expended on landing. Further, it is believed that some increase in distance is due to the lower spin rate of the Unique golf ball in flight, resulting in a significant increase in roll. (4) The Unique ball's increase in driving distance is surprisingly more noticeable with golfers who swing their club heads at speeds of 145 feet per second (f.p.s.) or below (that is, "average” or below average golfers). This will make the Unique ball especially attractive, from a commercial standpoint, since most golfers fall into these categories. In addition, the better golfers will not be penalized.
- the present invention may, as noted, be embodied in golf balls that conform to the initial velocity requirements of the U.S.G.A. and that may, in regulation play, be driven long distances, in terms of carry and roll. Such balls include those disclosed in U.S. Patent No. 5,273,287 and U.S. Patent No.
- the present invention also encompasses a number of methods of manufacturing or fabricating the Unique golf ball.
- One such method includes the steps of blow molding a hollow spherical shell or center from a parison of formable polymeric material, and filling the center of the shell with a core material which is a liquid (or at the time of the filling, can be handled as a liquid).
- Another method includes the steps of forming a hollow spherical shell from two hemispherical molded halves and introducing the liquid core material into the shell or center.
- the two hemispherical molded halves may be coupled together by a process selected from a group comprising spin welding, sonic welding, solvent welding, compression molding and adhesive bonding.
- the latter manufacturing or fabrication method also includes the introduction of the core material into the shell through a pre-drilled or preformed hole or holes and then plugging the hole or holes after the introduction of the core material.
- the exterior surface of the shell may constitute the outer surface of the ball's cover and conventional dimples may be formed thereon.
- another layer of cover material may be bonded to the outer surface of the shell and this outer layer functions as the ball's cover.
- the shell may also be referred to as a "center", but the term “shell” (as used herein and unless otherwise indicated) is generic to both situations— this is, where the shell serves as the outer part of the ball or where an additional overlayer is used as the outer cover of the ball.)
- the core material forms a homogeneous core that substantially fills the shell.
- the structural characteristics of the shell and core, made according to the contemplated methods, are such that the resulting golf ball has a high coefficient of restitution, conforms to the initial velocity requirements of the U.S.G.A., and may be driven long distances in regulation play.
- Another object of the invention is to provide a unique golf ball where the ball has a high coefficient of restitution, conforms to the initial velocity requirements of the U.S.G.A. and may, in regulation play, be driven long distances, in terms of carry and roll, as a result of being struck by a golf club; where the ball comprises a spherical shell and a core material that substantially fills the spherical shell; and where the spherical shell transmits substantially all of the energy from the golf club to the ball when the golf ball is struck by the club.
- a related object of the present invention is to provide a unique golf ball, of the type described, where the core material contributes to the overall weight of the golf ball, but contributes substantially nothing to the transfer of energy when the golf ball is struck by the golf club.
- Still another object of the present invention is to provide a uniquely constructed golf ball, of the type described, having a hollow, spherical shell of a deformable polymeric material and a unitary core of a material, which at the time of introduction into the shell, is a liquid or can be handled as a liquid and which forms a substantially homogeneous core substantially filling the hollow spherical shell; and where the outer surface of the shell preferably includes an outer, spherical layer of polymeric material which serves as the outer cover of the golf ball and which may or may not be the same as that used for the rest of the shell.
- a related object of the present invention is to provide such a golf ball where the thickness of the shell material is between about 0.060 inches and about 0.410 inches; where the shell is formed from a polymeric material selected from the group consisting of polyurethane resins, polyolefin resins or preferably ionic copolymers; where the core material is a member selected from a group consisting of a gel, a melt or preferably, a liquid; and where the polymeric material of the shell may be cellular and/or may comprise multiple layers.
- Yet another object of the present invention is to make or fabricate a golf ball by preforming a holiow preformed shell in the configuration of a sphere from a deformable polymeric material and by introducing into a shell a liquid core material which forms a homogenous core and which substantially fills the shell.
- a related object of the present invention is to preform the shell either by bonding together two hemispherical molded halves or preferably, by use of blow molding techniques.
- a further related object of the present invention is to reduce the cost of manufacturing multi-piece golf balls by injecting liquid core material into a preformed or forming spherical shell.
- a still further related object of this invention is to form a separate cover over and around ' the spherical shell containing the core material.
- a preferred form of the invention is a golf ball comprising a spherical shell which includes an inner first layer, a second layer and a third layer, the second layer being sandwiched between the first layer and the third layer, and a core which substantially fills the spherical shell, the core comprising at least one of a liquid and a gel.
- the convex outer surface of the third cover layer preferably is dimpled, while the convex outer surfaces of the first and second cover layers preferably are generally smooth.
- Each layer of the shell preferably has a thickness of at least 0.020 inches.
- the golf ball preferably further comprises a top coat layer formed over the spherical shell.
- the golf ball preferably also comprises a primer coat layer formed between the spherical shell and the top coat.
- the density of the second layer is less than the density of the first layer and/or the third layer.
- Each layer of the shell preferably has a different Shore D hardness than any adjacent shell layer. The difference in Shore D hardness of each layer and any adjacent layer preferably is at least three points and more preferably is at least five points.
- Each layer of the shell preferably is formed from at least one member selected from the group consisting of ionomers, vinyl resins, polyolefins, including metallocene catalyzed polyolefins, polyurethanes, polyamides, acrylic resins, blends of acrylic resins with polyvinyl chloride, blends of acrylic resins with elastomers, thermoplastic rubbers, polyphenylene oxide resins, blends of polyphenylene oxide with high impact polystyrene, thermoplastic polyesters, blends of polycarbonate with acrylonitrile butadiene styrene, polybutylene terephthalate, styrene maleic anhydride, polyethylene elastomers, blends of polyvinyl chloride with acrylonitrile butadiene styrene or ethylene vinyl acetate, and blends of thermoplastic rubbers with polyethylene, polypropylene, polyacetal, nylon, polyesters, or cellulose esters.
- the third layer of the shell preferably comprises ionomer.
- each layer of the shell is thermoplastic.
- each layer of the shell comprises ionomer.
- Each layer of the shell preferably has a different overall chemical composition.
- the shell is formed from a polyethylene-containing material.
- the core is a non- wound core. While the shell preferably has three layers, it can have four or more layers. All of the layers can have generally the same Shore D hardness.
- Another preferred form of the invention is a golf ball comprising a thermoplastic shell which includes a plurality of shell layers, and a non-wound core which comprises a liquid and which is positioned within the shell.
- the plurality of shell layers preferably includes an inner first layer, a second layer, and a third layer, the second layer being sandwiched between the first layer and third layer.
- the density of the second layer preferably is less than the density of the first layer and/or the third layer.
- the third layer of the shell preferably is ionomeric. In a more preferred embodiment of the invention, all of the layers are ionomeric.
- Each of the layers of the shell preferably has a thickness of at least 0.020 inches.
- Yet another preferred form of the invention is a golf ball cover for use in forming a goif ball, the cover comprising a blow-molded thermoplastic shell which includes an inner first layer, a second layer, and a third layer, the second layer being sandwiched between the first layer and the third layer.
- At least one of the first layer and the second layer of the shell is foamed.
- the outer layer can be foamed as long as molding does not result in unacceptable surface imperfections on the ball.
- the invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others and the article possessing the features, properties, and the relation of elements exemplified in the following detailed disclosure.
- Fig. 1 is an elevational view, partly in section, showing a first embodiment of a golf ball in accordance with the principles of the present invention
- Fig. 2 is an elevational view, similar to that of Fig. 1, but illustrating an alternate core construction
- Fig. 3 is an elevational view, similar to Fig. 1 , but showing an alternate, thin wall shell construction
- Fig. 4 is an elevational view, similar to that of Fig. 3, but illustrating another alternate core construction
- Figs. 5 and 6 are sectional views of mold halves for forming the two mating, molded halves of a golf ball shell
- Fig. 7 is a sectional view of two hemispherical shell halves loaded in opposed fixtures of a spin welding machine prior to being coupled together to form a spherical shell;
- Figs. 8, 9 and 0 are fragmentary views of alternate ways molded shell halves can be formed and also show parts of the fixtures used to join such molded halves;
- Figs. 11 and 12 are sectional views of molded shell halves prior to being joined;
- Figs. 13, 14 and 15 are sectional views of a golf ball after the shell halves have been joined together and also illustrating the injection of liquid core material into the shell to fill the shell;
- Figs. 16, 17, 18 and 19 illustrate, in fragmentary sectional views, additional embodiments of shell construction where the shells are tailored to yield intended physical characteristics;
- Figs. 20, 21 , 22, 23 and 24 illustrate another method of golf ball manufacture or fabrication, and a golf ball constructed in accordance with that method
- Figs. 25A through 25E, 26A through 26E, 27A through 27E, 28A through 28E, 29A through 29E, and 30A through 30E illustrate steps utilized in the manufacture or fabrication of the various embodiments of the present invention, with each of Figs. 25E, 26E, 27E, 29E and 30E being an elevational view showing a golf ball made in accordance with the process illustrated in Figs. 25A through 25D, 26A through 26D, 27A through 27D, 28A through 28D, 29A through 29D, and 30A through 30D, respectively; and Figs.
- FIG. 31 A through 31 F, 32A through 32F, and 33A through 33F, 34A through 34F, 35A through 35F, 36A through 36E, 37A through 37G, 38A through 38G, and 39A through 39G illustrate the performance of golf balls fabricated in accordance with the principles of the present invention in comparison with the performance of conventional golf balls.
- Figs. 40 - 47 show sectional views of embodiments according to the invention having inner, intermediate and outer shell layers with various combinations of hardness.
- the shell is initially preformed in the shape of a hollow sphere.
- the shell is made from a synthetic polymeric material(s) and a variety of different manufacturing or fabricating methods may be utilized to preform the hollow spherical shell.
- the wall of the shell may be either solid or cellular.
- core material is introduced into the interior of the shell.
- the core material is a liquid or a unitary, non-cellular material which at the time of its introduction into the shell may be handled as a liquid.
- the core material may, in some embodiments, be introduced into the shell through a hole or holes in the shell or while the shell is being blow molded. After its introduction, the core material forms a homogeneous core which substantially fills and conforms to the inter surface of the shell.
- filling the shell constitutes substantially filling the shell since an "air" bubble should not materially detract from or adversely affect the intended performance of the golf ball.
- the shell is the principal transferring energy component of the golf ball, that is, for transferring energy from the golf club to the golf ball when the ball is struck by the club.
- the core need not contribute anything to this transfer of energy. Its primary function is to give the ball the weight desired and have the ball conform to the U.S.G.A. specifications. This does not mean, however, that the core could not be "tailored” to give the ball a particularly desired or better distortion characteristics on the club face, or in certain instances, could not be made to somewhat change the ball's performance characteristics.
- a material might be added to the core to increase the pressure within the shell or material-such as a suspension or solution, with free floating particles-could be added to the liquid core material to absorb some energy.
- the liquid core is also believed to contribute unique spin properties that cannot be achieved with a solid core, namely low initial spin rates and higher terminal spin than a comparable solid core ball.
- the golf ball according to one preferred embodiment of the invention has a shell which includes at least three layers.
- Each shell layer can be formed from a thermoplastic or thermoset material.
- the inner shell layer preferably is formed from a thermoplastic material.
- the intermediate shell layer also preferably is formed from a thermoplastic material.
- the outer shell layer preferably is formed from a thermoplastic material and more preferably is ionomeric.
- the inner and outer shell layers are hard and the intermediate shell layer is softer than the inner and outer shell layers.
- This type of construction results in a golf ball having relatively low spin rates for good distance and accuracy, and a relatively soft feel, the soft intermediate layer providing added flexibility to an otherwise very rigid cover.
- the inner and outer shell layers are soft and the intermediate shell layer is harder than the inner and outer shell layers. This type of golf ball is useful when high spin on short iron shots, but lower spin on tee shots is desired.
- This construction also gives the softest compression for a very soft feel
- the inner shell layer is hard, the outer shell layer is soft, and the intermediate shell layer has an intermediate hardness.
- the inner shell layer is soft, the outer shell layer is hard, and the intermediate shell layer has intermediate hardness. This embodiment is useful when a good balance of relatively low spin, yet soft feel is desirable.
- thermoplastic materials are generally preferred for use as materials for the shell.
- properties desirable for the synthetic polymeric resins are good flowability, moderate stiffness, high abrasion resistance, high tear strength, high resilience, and good mold release, among others.
- the shell layers each can contain 0.1 - 300 parts by weight, more preferably 20 - 200, and even more preferably 30 - 150 parts by weight of a filler based upon 100 parts by weight of resin composition. In this way, for example, a perimeter weighted ball can be formed. Suitable fillers are described below.
- Preferred polymeric materials for uses in accordance with this invention are ionic copolymers.
- Such copolymers include those which are available under the trademark SURLYN from E.I. DuPont De Nemours & Company of Wilmington, Del. (copolymers of ethylene and methacrylic acid partially neutralized with zinc, sodium or lithium); and those which are available and under the trademarks IOTEK or ESCOR from Exxon Chemical Company, Houston, Texas, (copoiymers of ethylene and acrylic acid partially neutralized with zinc or sodium).
- the shell is formed from mixtures or blends of zinc (“Zn”) and sodium (“Na”) ionic copolymers.
- Zn zinc
- Na sodium
- Other types of ionomers also can be used.
- Both "high acid” and “standard” IOTEK and SURLYN materials can be and have been used, for example, IOTEK 959 (Na) and IOTEK 960 (Zn) (50/50 weight/weight blend); IOTEK 8000
- Combinations of standard SURLYN (Na/Zn) materials and high acid IOTEK (Na/Zn) materials, and vice versa, may also be used.
- the shell is formed as center (e.g., with a diameter of about 1.50 inches) by blow molding
- the shell walls could comprise a single material or layers of different materials, as explained below, and the material(s) could be standard or high acid SURLYN (Na/Zn) materials and/or the IOTEK materials.
- the intermediate and outer cover layers which can be injection molded over this shell or center core, likewise can be made of standard or high acid SURLYN (Na/Zn) or IOTEK.
- Singular ionic copolymers can be used as shell materials in the subject invention. These singular materials are described in U.S. Pat. No. 3,454,280 issued Jul. 8, 1969. The present invention may likewise be used in conjunction with cellular polymeric golf ball shells as are described in U.S. Pat. No. 4,274,637 issued Jun. 23, 1981.
- the walls of the shells may have an overall thickness from about 0.060 inches to about 0.410 inches, preferably between about 0.075 inches and about 0.300 inches and even more preferred, between about 0.090 inches and about 0.190 inches.
- each layer has a thickness of 0.02 - 0.20 inches, preferably 0.03 - 0.15 inches, and more preferably 0.03 - 0.10 inches.
- Standard golf ball covers in use today generally have a thickness of about 0.090 inches.
- the specific gravity of the shell, as described above, is between about 0.75 and about 1.25, more preferably 0.92 - 1.02, and most preferably 0.96 - 0.98.
- Synthetic polymeric materials other than those described above, which may be used in accordance with this invention as shell materials include homopolymeric and copolymer materials which may be adapted for use in this invention as follows: (1) Vinyl resins formed by the polymerization of vinyl chloride, or by the copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride; (2) Polyolefins such as polyethylene, polypropylene, polybutylene, and copolymers such as polyethylene methylacrylate, polyethylene ethylacrylate, polyethylene vinyl acetate, polyethylene methacrylic or polyethylene acrylic acid or polypropylene acrylic acid or terpolymers made from these and acrylate esters and their metal ionomers, metallocene catalyzed polyolefins, polypropylene/EPDM grafted with acrylic acid as sold under the trademark POLYBOND by Reichhold Chemicals,
- Poiyurethanes such as are prepared from polyols and diisocyanates or polyisocya ⁇ ates, including reaction injection moldabie poiyurethanes, castable poiyurethanes and injection moldabie poiyurethanes;
- Polyamides such as poly (hexamethylene adipamide) and others prepared from diamines and dibasic acids, as well as those from amino acids such as poly (caprolactam), and blends of polyamides with ionomers, polyethylene, ethylene copolymers, EDPM, etc., (5) acrylic resins and blends of these resins with poly vinyl chloride, elastomers, etc.; (6) Thermoplastic elastomers such as urethanes, olefinic thermoplastic
- thermoplastic rubbers with polyethylene, polypropylene, polyacetal, nylon, polyesters, cellulose esters, etc.
- shorthand symbols are used to describe certain polymers. The symbols used above and their descriptions are as follows: ABS - Acrylonitrile butadiene styrene;
- PE Polyethylene
- PETG Polyethylene terephthalate/glycol modified
- EPDM Ethyl-propylene-non-conjugated diene terpolymer
- the white basic color of the golf ball shell may be formed by the pigmentation of one of the above-mentioned polymeric materials.
- Suitable pigments for use in accordance with this invention include the following: titanium dioxide, zinc oxide, zinc sulfide and barium sulfate.
- the amount of pigment used in conjunction with the polymeric shell composition naturally depends on the particular polymeric material utilized and the particular pigment utilized.
- concentration of the pigment in the polymeric shell composition can be from about 1 percent to about 25 percent as based on the weight of the polymeric material.
- a more preferred range is from about 1 percent to about 5 percent as based on the weight of the polymeric material.
- the most preferred range is from about 1 percent to about 3 percent as based on the weight of the polymeric material.
- the percent pigment utilized is in large part determined by the weight needed to provide a golf ball with the preferred physical characteristic. It is understood by one skilled in the art that the percent of pigment added must be balanced with the weight of the core material in order to attain the desired density of the resulting golf ball.
- Preferred shell compositions for use in accordance with this invention are the ionomers described above including SURLYN and IOTEK resins and they may be used in conjunction with fillers, pigments and other additives.
- the presently most preferred pigment for use in accordance with this invention is titanium dioxide.
- the concentration of titanium dioxide in the shell composition be from about 1 percent to about 10 percent as based on the weight of SURLYN resin utilized.
- a more preferred range for the concentration of titanium dioxide is from about 1 percent to about 5 percent as based on the SURLYN resin utilized.
- a most preferred concentration for the titanium dioxide is about 2 percent as based on the weight of the SURLYN or IOTEK resin utilized.
- the shell can be formed from multiple layers having different characteristics.
- a dual layer shell can be formed by blow molding and can be covered with a dimpled cover layer formed by injection molding, compression molding, casting, vacuum forming, powder coating, etc.
- a single layer can be blow molded and covered with a two-layer cover formed by injection molding, compression molding, casting, vacuum forming, powder coating, etc.
- a blow molded core is filled with liquid and plugged, and then two or more layers are molded over the blow molded core.
- the shell of the subject invention can utilize a wide variety of polymers.
- many of the polymers in question, and in particular SURLYN or IOTEK resins may not be glossy after injection molding.
- the average golfer prefers a glossy golf ball.
- the balls of this invention may be coated with a clear epoxy-urethane system subsequent to molding.
- the system can be, for example, a clear epoxy primer and/or water borne primer, followed by a clear urethane coat.
- Use of this clear coat system subsequent to the molding operation is not mandatory in order to achieve the desirable results of this invention; however, it is highly desirable.
- the above-mentioned system produces a golf ball which is durable and maintains its gloss during play. It will be understood by those skilled in the art that other clear coat systems can likewise be utilized. Further, it is understood by one skilled in the art that the golf balls of the invention can be painted with a pigmented paint in a conventional manner.
- a wide variety of materials could be utilized for a core including gels, hot-melts, liquids, and other materials which at the time of their introduction into a shell, can be handled as a liquid.
- suitable gels include water gelatin gels, hydrogels, and water/methyl cellulose gels. Golf ball embodiments with a gel or other solid core are shown in Figs. 2 and 4. Hot-melts are materials that are heated to become liquid and at or about normal room temperatures become solid. This property allows their easy injection into the shell to form the core.
- suitable liquids as shown in Figs. 1 and 3 include either solutions such as glycol/water, salt in water or oils or colloidal suspensions, such as clay, barytes, carbon black in water or other liquid, or salt in water/glycol mixtures.
- the presently preferred materials are liquids.
- a preferred example of a suitable liquid core material is a solution of inorganic salt in water.
- the inorganic salt is preferably calcium chloride.
- Other liquids that have been successfully used are conventional hydraulic oils of the type sold at, for example, gasoline stations and that are normally used in motor vehicles.
- the liquid material which is inserted in the shell in accordance with this invention to form the core, may also be reactive liquid systems that combine to form a solid.
- suitable reactive liquids are silicate gels, agar gels, peroxide cured polyester resins, two-part epoxy resin systems and peroxide cured liquid polybutadiene rubber compositions. It will be understood by those skilled in the art that other reactive liquid systems can likewise be utilized depending on the physical properties of the shell and the physical properties desired in the resulting finished golf balls.
- the core of all embodiments should be unitary, that is, of a substantially common material throughout its entire extent or cross-section, with its exterior surface in contact with substantially the entire interior surface of its shell. All cores are also essentially substantially homogenous throughout.
- the core material in order to provide a golf bail which has similar physical properties and functional characteristics to conventional golf balls, preferably the core material will have a specific gravity greater than that of the shell (and the outer cover when such a cover is molded over the shell).
- the core material may have a specific gravity of between about 0.8 and about 3.9, preferably at about 1.32.
- the specific gravity of the core material may be selected so that the golf ball will float in water.
- the specific gravity of the core may be varied depending on the physical dimensions and density of the outer shell and the diameter of the finished golf ball.
- the core (that is, the inner diameter of the shell) may have a diameter of between about 0.860 inches and about 1.62 inches, more preferably 1.20 - 1.55 inches, and most preferably about 1.30 inches.
- a golf ball 10 constructed in accordance with the principles of the present invention is shown in Fig. 1.
- the golf ball 10 maintains or improves the performance of presently known and utilized golf balls. It includes two major components: a core or internal portion 12; and a shell or external portion
- the shell 14 is formed in a substantially hollow spherical configuration, and the core 12 is a liquid material.
- the exterior surface of the liquid core 12 is and remains in contact with the interior surface of the shell which has a generally spherical shape.
- the outer, exterior surface of the shell 14 may be formed with conventional dimples 16 to provide improved flight characteristics and to create an appearance essentially identical with conventional, commercially available golf balls. The selection of the dimples and the dimple pattern is within the purview of those skilled in the golf ball art.
- the core 18 is of a solid material rather than a liquid material as is the core 12 of the Fig. 1 ball.
- this solid material is or can be handled as a liquid at the time this material is introduced into the shell.
- Figs. 3 and 4 illustrate further, alternate embodiments of the invention shown in Figs. 1 and 2, respectively, but where the thickness of the shell wall is thinner, that is, a thin wall shell 20 is shown with a liquid core 22 in the Fig. 3 embodiment, and a thin wall shell 20 with a solid core 24 is shown in the Fig. 4 embodiment.
- two hemispherically-shaped shell halves 28 and 30 are formed, preferably through injection molding, prior to being joined or coupled to form a completed spherical shell.
- Other techniques for forming the shell halves include conventional blow molding, injection blow molding and rotational casting.
- Figs. 5 and 6 illustrate mold halves 34 and 36 that include holes 38 and 40 for the introduction of the material, in fluid form, from which the shell is to be formed.
- These mold halves 34 and 36 may be identical in shape except at their equator where they are joined and where they may or may not be identical. As illustrated in Fig.
- the mold halves may be fully identical with flat, planar surfaces 42 and 44 at the equator of the ball, at the areas of joining illustrated in Fig. 8.
- Figs. 11 and 12 illustrate a tongue and groove arrangement with the tongue of a length H-1 slightly less than the length H-2 of the interior wall of the groove but slightly greater than the length H-3 of the exterior wall of the groove.
- Figs. 1 and 2. as well as Figs. 5, 6 and 7, also illustrate this alternative.
- Other configurations at the equator could also be utilized, such as mating undulations 50 and 52 of male and female segments across the thickness as shown in Fig. 9.
- the parting line 54 and 56 may take the form of a cylinder around the periphery of the ball, with the parting line in an orientation at an angle to the equator of the ball. This forms a triangular projection in the lower shell half and a mating triangular recess in the upper half. Additional surface area is thus provided for bonding purposes. Further, during spin welding, centrifugal forces acting with the shell edges and tooling wall urge together the mating halves for superior joining or coupling.
- the dimples 16 on the exterior surface of the shell halves may be formed during the injection molding of the halves.
- the ball may be molded with a smooth exterior surface and the dimples molded in after the joining of the halves and either before or after the injection of the core and plugging of the hole.
- the temperature for such subsequent dimple molding must be sufficiently low so as not to be detrimental to the core.
- the hemispherical halves may be joined together by any one of a wide variety of methods.
- a preferred method is the spin welding of the halves. This can be effected by fixedly supporting one of the halves 30 in a fixed fixture 60, shown as the lower half in Fig. 7, and supporting the other half 28, shown as the upper half, in a fixture 58 that is rapidly rotated about a vertical axis while moved axially toward the fixed half. Note the arrows included in Fig. 7. The frictional energy generated by the movement of one half with respect to the other, while being brought into contact, will generate sufficient heat to create a final cohesive bond between the melding and coalescing thermoplastic materials of the halves.
- the resulting structure is then a preformed, unitary hollow sphere that constitutes the shell of the ball.
- Spin welding techniques are conventional as described, for example, in U.S. Pat. No. 2,956,611 to Jendrisak.
- a commercially available spin welding machine, acceptable for performing this method, is Model No. SPW-1- EC manufactured by Olsen Manufacturing Company of Royal Oak, Mich.
- the hole 64 in the shell 14 is formed as for example, by drilling.
- the hole 64 could also be formed during molding.
- the hole is preferably tapered radially inwardly toward the center of the spherical shell 14 to facilitate its subsequent closure. It will be understood by those skilled in the art that two or more holes of the same or different sizes may be drilled or molded for the purposes associated with injecting the liquid material into the core 12 of the shell. Thereafter the core material may be injected through the hole 64 into the center of the shell, as through a hypodermic needle 66, or similar injection device, to substantially, totally fill the center of the shell for constituting the core 12.
- a conical plug 68 may be used for plugging of the hole 64.
- the material of the plug 68 is preferably the same as that of the remainder of the shell 14. Trimming the cylindrical radial outwardly extending end of the plug 68 completes the fabrication method unless, of course, the dimples are to be applied following these manufacturing steps.
- the plug 68 may be secured in the hole to seal the shell through any of the above described fabrication techniques, although spin welding is presently preferred. In certain embodiments, the core material may itself be relied upon to seal the hole.
- the shell 72 shown in Fig. 16, is formed from a first or inner layer 74 having radial thickness slightly less than the final golf ball. This shell layer 74 constitutes an internal layer of the final composite shell or laminate formed of plural shell layers.
- a final exterior shell layer 76 is applied to the exterior surface of the internal shell layer 74, preferably through conventional molding techniques, such as injection, compression, or rotational molding techniques. The exterior surface 76 of the shell is fabricated with dimples 16.
- the shell materials can be selected for tailoring the performance of the golf ball to a particular use or application.
- properties such as color, frictional bite, durability, and resistant to scuffs and cuts, may be built into the radial outer layer.
- the radial inner layer could simply provide desired resilience or energy transfer.
- the inner layer could be made of a polymeric material having . a relatively high modulus of elasticity for increased life and resilience while the outer layer could be formed of a polymeric material providing a lower modulus of elasticity for greater frictional contact with the face or ball striking surface of the golf club so as to achieve greater bite, payability and control.
- the shell 72 and its core may be manufactured or fabricated by any one of the techniques as described above.
- the shell 72 which, as noted, is formed of a plurality of bonded layers, could also be manufactured in a conventional shuttle method.
- the inner molded layer is first injected into the mold to form the inner layer.
- the outer layer of a different material tnan the inner layer, is injected over the first, inner layer. This may be effected through consecutive shootings into a common mold over a mold component in the fabrication of layered shell halves.
- This molding technique is common in the molding of typewriter keys wherein the different injected materials form the visible (contrasting colored) lettering on the keys. Figs.
- FIG. 17 illustrates a shell 88 having a central cellular stratum or layer
- non-cellular skins or layers 92 and 94 may be formed in situ by varying the process parameters wherein the shell 88 is molded.
- Skins 92 and 94 may be altered and formed by a plurality of techniques.
- the skins 92 and 94 may be formed by varying the temperature of the mold during the initial stages of the injection molding process and by varying other parameters, such as melt temperatures, injection time, injection speed, injection pressure, nozzle type, gating venting, holding pressure, holding time, shot weight, blowing agent concentration, nucleator concentration, polymeric composition, mold surface treatment and mold lubricant.
- U.S. Pat. No. 4,274,637 to Robert P. Molitor includes further details.
- Fig. 18 illustrates a shell 98 having an essentially uniform cellular structure.
- the shell 98 is shown molded over a hemispherical mold half.
- Fig. 19 illustrates still another shell 102 which has a central stratum or layer 104 sandwiched between a pair of strata or layers 106 and 108.
- the central stratum 104 has a density which is less than that of the strata 106 and 108.
- the strata 106 and 108 have a greater density than that of the central stratum 104.
- the density will vary.
- the respective densities of the strata can be varied by those skilled in the art by altering the process parameters as discussed above.
- Figs. 20 through 24 illustrate still further embodiments of the present invention.
- a shell 112 is fabricated from two hemispherical members 114 and 116 which are coupled together, for example, by spin welding.
- a hole 118 is formed in the hemispherical shell member 114 as shown in Fig. 20.
- the steps of fabricating the shell 112 are essentially the same as those described above. The most significant difference, is however, in the size of the shell wherein the exterior diameter is slightly less than that of the contemplated, completed golf ball.
- the filled shell that is, the shell and core
- the filled shell can, as noted above, be also referred to as a center or golf ball center.
- Figs. 21 and 22 illustrate methods of filling a shell similar to those previously discussed wherein the interior 122 of the shell or center 112 is filled with a liquid 124 through a drilled filling hole 118.
- a needle or similar device
- the filling hole 118 is closed through the use of a plug 126.
- the radially outer, exposed end of the plug 126 is next ground so its exterior surface is essentially coextensive with the exterior spherical surface of the remainder of the shell or center 112.
- Fig. 23 illustrates a two-piece injection mold 132 with the spherical, filled center 112 centrally located therein.
- the center 112 is held in position centrally within the mold 132 by pins 134 in a conventional manner.
- the mold 132 is then filled through an entrance port 136 to provide a layer of polymeric elastomeric material of an even thickness, completely around the previously formed center 112.
- the elastomeric layer is allowed to harden and bond to the center 112 and after trimming, forms a one-piece outer cover 140 for the final, finished golf ball 142.
- Dimples 138 are provided to the exterior surface of this cover 140 through the configuration of the mold or, in the alternative, the dimples may be formed separately in the finished golf ball 142.
- the core of the ball 124 is an injected liquid that is disposed within an intermediate center or shell 112 formed of mating, spin welded, hemispherical parts.
- the use of an exterior, one-piece cover 140 thereover provides additional stability to the ball 142 during play.
- the elastomeric components of the golf ball 142, including the intermediate two-part center or shell 112 and the exterior one-part cover 142, may be fabricated of any of the materials described above. It may be possible, however, to delete the color imparting, additional materials from the center or shell 112 since it cannot be seen after application of the cover 140.
- the entire radial thickness of the center 112 and cover 142, in combination, should be the same, as described above with respect to balls having shells, where the outer surface of the shell is the outer cover of the golf ball, and particularly, is between about 0.060 and about 0.300 inches.
- the center 112 should be of a thickness so that the final hemispheres may be properly handled during fabrication of the golf ball, that is, spin welded, drilled for the injection of the liquid for the core, filled with the core material, and having the drilled holes closed.
- a shell 152 is formed as a one-piece unit, preferably by blow molding, with the result that a golf ball 146 may be made relatively inexpensively.
- an extrudate or parison is extruded from a starting polymeric, elastomer material, preferably pellets.
- the extrudate 148 is a continuous tube fed into conventional clam shell mold halves of a blow molding machine.
- the extrudate is continuously cut to length and then captured in the mold halves.
- the mold halves preferably move in a step and repeat manner to receive the extrudate and then move to subsequent locations.
- the mold halves close and pressurized air is injected into the mold so as to force the extrudate into a desired spherical shaped shell.
- a core material liquid or fluid is injected into the shell through a filling hole, and then the filling hole is plugged or closed.
- the core material liquid 156 is used, in lieu of pressurized air, to mold the extrudate into a spherical shaped shell.
- the filling hole if there is one, is plugged or closed.
- the interior surfaces of the mold halves may include symmetric projections for directly forming dimples on the outer spherical surface of shell so that shell, with a liquid filled core, constitutes a final golf bail.
- the shell can be molded as a center (that is, where its outer diameter is less than that of a regulation golf ball) and a dimpled outer cover can thereafter be molded, as by the above noted conventional molding techniques, about the shell or center.
- a multi-layer parison that is, a parison of two or more layers of materials, can be extruded simultaneously to form a shell, that is either a center or a dimpled ball.
- the shell and the golf ball must, of course, be appropriately trimmed, particularly with regard to removing the excess extrudate, after the shell is molded.
- Figs. 25A through 25E generally illustrate the steps and/or stations of a fabrication or manufacturing method for the one-piece blow-molded golf ball 146.
- Fig. 25A shows the output of a conventional extrusion press — an extrudate or parison 148 — having enlarged side wails in its central extent or portion.
- Fig. 25B illustrates the parison or extrudate 148 disposed in the mold of the blow-molding machine at a step or station where the hollow spherical shell 152 is formed internally and dimples are formed on the external surface of the shell. Excessive extrudate material 154 is shown above and below the shell 152.
- FIG. 25C illustrates a station or step where the filling of the interior of the spherical shell 152 with core material liquid 156 occurs by means of a needle 158 that extends through a filling hole 160 in the upper extent of the shell.
- Fig. 25D shows the needle 158 removed and a plug 162 closing the filling hole 160.
- Fig. 25E illustrates the finished golf ball 146 after being trimmed of the excess material including that of the plug 162 above the surface of the ball 146.
- Figs. 26A through 26E illustrate the stations and/or steps of another blow molding fabrication method.
- Fig. 26A illustrates the same parison or extrudate 148 as used in the prior Figs. 25A - 25E embodiment.
- FIG. 26C show the same method steps or stations that are illustrated in Figs. 25B and 25C, respectively. However, in closing the filling hole step or station, as illustrated in Fig. 26D, no plug is utilized. Instead, after the removal of the needle 158, the molding machine is provided with mechanisms (not shown) to push extrudate material of the parison located adjacent the filling hole 160 so as to cover and fill the hole 160.
- Fig. 26E shows the finished golf ball 166, as trimmed, that constitutes the final product.
- Figs. 27A through 27E illustrate the steps 10 and/or stations of still another blow molding fabrication method.
- the parison 148 shown in Fig. 27A, is slightly smaller than the parison shown in Figs. 25A and 26A since in this embodiment, blow molding is utilized to fabricate only a golf ball center or shell 170 rather than an entire golf ball itself.
- the center 170 is about 1.50 inches in diameter, and is blow-molded as shown in Fig. 27B, in the same manner as the shell 152, except no dimples are formed on its external surface. It may be then filled with a fluid 156 and sealed, by and in the blow-molding machine, in a manner similar to the steps shown in Figs. 25D and 26D.
- the center 170 is provided with an outer or exterior cover 172, having dimples, through conventional techniques, such as injection molding techniques.
- the molded cover 172 is then trimmed to constitute the final golf ball 174 as shown in Fig. 27E.
- Figs. 28A through 28E illustrate the steps and/or stations of yet another method for fabricating a golf ball 178 with a blow-molded shell or center 180.
- Figs. 28A and 28B illustrate the five same method steps as shown in Figs. 27A and 27B.
- the center is filled with a core liquid 156 through a needle 158 and the filling hole is then plugged with a plug 184 and trimmed as described in the step illustrated in Fig. 25D. While the plug would generally be made from the same material as the shell, (e.g.. an ionic material), this is not necessary. Plugs of an elastomeric material (e.g...).
- the center 180 then receives an injection molded outer cover 186 having dimples thereon. Thereafter the exterior of the ball 178 is trimmed to constitute the final golf ball as shown in Fig. 28E.
- Figs. 29A through 29E illustrate the several steps and/or stations of a further golf ball fabrication method.
- Two shell halves 190 are conventionally injection molded and then bonded together as by spin welding as generally illustrated in Figs. 29A and 29B.
- Figs. 29C and 29D illustrate the steps or stations where the drilling of a filling hole 182 in the preformed shell or center occurs, where the shell is filled with core fluid 156 by means of a needle 158, and where the filling hole 182 is subsequently plugged, with a plug 184. Thereafter, a cover 186 is injection molded onto the shell or center, with dimples being formed on the exterior or outer surface of the shell.
- Fig. 29E illustrates the final golf ball 192 after trimming.
- Figs. 30A through 30E illustrate the steps and/or stations of a still further golf ball fabrication method.
- the shell halves 194 are formed through conventional injection molding techniques and have dimples molded in their outer spherical surfaces. The shell halves are then joined, by spin bonding techniques, to form a preformed shell as generally illustrated in Figs. 30A and 30B.
- the steps of drilling of the shell, the filling of the shell 196 with a core fluid 156, and thereafter, closing the fill hole in the shell, by a plug 184, are illustrated in Figs. 30C and 30D.
- the fill hole can also be closed by the use of mechanisms (not shown) which push material adjacent to the fill hole so as to cover and fill the hole.
- the finished golf ball 196 after being trimmed, is generally shown in Fig. 30E.
- a comparison of the shells made in accordance with the disclosed blow molding embodiments (e.g. the embodiments illustrated in Figs. 25 and 27) - vis-a-vis shells made from two injection molded half shells (e.g. the embodiments illustrated in Figs. 28 and 29) - reveals that there are differences.
- a parting line seam is formed across approximately 180 degrees of the periphery of a blow molded shell at the mold line and that in the remaining 180 degrees, there is no flash and effectively no seam. This is in contrast to the 360 degree seam in the spin bonded, two half shell shells.
- Even the seam formed throughout the 180 degrees span in the blow molded shells is superior to the seams where the shells are formed from two half shells that are spin welded together. It is believed that superior shell seams exist in shells made in accordance with the blow molding embodiments because those seams are created when the polymeric material is in a melt state.
- the cores of the three-piece wound balls are found to vary in density, in the tension under which the threads are wound onto the core and in the amount of material which is wound onto the core. All of these factors tend to create a golf ball which is less uniform than the Unique ball where the shell (center) is blow molded, filled with liquid and where a cover is injection molded onto the shell.
- the series of successive, high speed, stop action photographs which are included as Figs. 31 , 32 and 33, are of golf balls being hit by a 5-iron swung at 128 feet per second.
- the distortion of the Unique golf ball of the present invention shown in Fig. 32, is significantly greater than that of the conventional, two-piece TOP-FLITE II brand ball shown in Fig. 31.
- the impact distortion of the ball of the present invention is at least as great as the conventional, three-piece, TITLEIST DT brand ball shown in Fig. 33. From Figs. 31, 32 and 33, it can be seen that the Unique golf ball (Fig. 32) is on the club face of the iron longer than either the TOP-FLITE II or the TITLEIST DT brand balls of Figs. 31 and 33.
- the ability to stay on the face longer allows the golfer to impart greater control to the ball as well as giving more time for energy transfer. Further, it tends to give the golfer a superior, much desired "feel".
- Figs. 31-33, 34-36 and 37-39 further show that the Unique ball of the present invention has less back spin than either the TOP-FLITE II or the TITLEIST DT brand bails. Having less back spin when hit, for example, by a driver or a 5-iron is advantageous in obtaining greater distance by a optimized combination of launch angle and spin rate which results in greater roll. Further, the Unique golf ball is spinning less than a conventional ball and this causes the Unique ball to fly at a lower trajectory. Accordingly, the Unique ball is very efficient in terms of energy transfer, that is, a lower coefficient of restitution, and should travel further than a conventional two- or three-piece ball when hit under comparable circumstances.
- the Unique golf ball's improved performance may also be derived, at least in part, from the decreased moment of inertia which results from the novel construction of the balls.
- Moment of inertia is measured in ounce inch squared. Limited testing has shown that Unique balls, fabricated in accordance with the principles of the present invention, have a moment of inertia of about .240 ounce inch. In contrast, the moment of inertia of conventional golf balls varies from about .400 to about .445 ounce inch squared.
- the Unique golf ball of the present invention also shows a much greater gain in distance as the club head speed decreases and as the loft of the club head increases as compared with conventional TOP-FLITE brand golf balls or conventional three-piece balls. This leads to the belief that the Unique golf balls will be more playable and provide "longer" distances for all golfers including the average golfers.
- a golf ball according to another embodiment of the invention is shown and is designated as 208.
- the ball preferably has a diameter of at least 1.68 inches.
- the invention is also useful with golf balls having a diameter of 1.70 inches or more.
- the golf ball includes a central core 210 and a multi-layer shell 212.
- the multi-layer shell includes an inner layer 214, an intermediate layer 215, and an outer layer 216 with dimples 218.
- the inner layer 214 preferably has a Shore D hardness in the range of 60 - 80 and more preferably 62 - 78.
- the intermediate layer 215 preferably has a Shore D hardness in the range of 10 - 60, more preferably 30 - 60 and most preferably 55 - 60, the Shore hardness being at least three points softer, and more preferably at least five points softer than the Shore D hardness of the inner layer.
- the outer layer 216 preferably comprises an ionomer, but also or alternatively could include other materials, e.g.
- the outer layer 216 preferably has a Shore D hardness in the range of 60 - 80 and more preferably 62 - 78.
- a golf ball according to a further embodiment of the invention is shown and is designated as 308.
- the ball preferably has a diameter of at least 1.68 inches.
- the ball includes a central core 310 and a multi-layer shell 312.
- the multi-layer shell includes a soft inner layer 314 having a Shore D hardness which preferably is in the range of 10 - 60 and more preferably 30 - 50, a hard intermediate layer 315 which preferably has a Shore D hardness in the range of 60 - 80 and more preferably 62 - 78, and a soft outer layer 316 with dimples 318, the soft outer layer 316 preferably having a Shore D hardness in the range of 10 - 60 and more preferably 30 - 50.
- the inner and intermediate layers are preferably formed from an ionomeric or non-ionomeric polyolefin material.
- the outer layer preferably comprises ionomer.
- the golf ball includes a central core 410 and a multi-layer shell 412.
- the multi-layer shell includes a hard inner layer 414 preferably having a Shore D hardness of 60 - 80 and more preferably 62 - 78, an intermediate layer 415 preferably having a Shore D hardness of 50 - 65 and more preferably 55 - 60, and an outer layer 416 with dimples 418.
- the outer layer preferably has a Shore D hardness of 10 - 60 and more preferably 30 - 50, with the hardness being at least three points lower than the Shore D hardness of the intermediate layer 415.
- the inner layer 414 and intermediate layer 415 preferably comprise ionomeric or non- ionomeric polyolefin materials.
- the outer layer 416 preferably comprises ionomer.
- a golf ball according to a further embodiment of the invention is shown and is designated as 508.
- the ball includes a central core 510 and a multi-layer shell 512.
- the multi-layer shell includes an inner layer 514 which preferably has a Shore D hardness of 10 - 60 and more preferably 30 - 50, an intermediate layer 515 which preferably has a Shore D hardness of 50 - 65 and more preferably 55 - 60, and an outer layer 516 with dimples 518.
- the outer layer has a Shore D hardness of 60 - 80 and more preferably 62 - 78.
- the inner and intermediate layers 514 and 515 preferably comprise ionomeric or non-ionomeric polyolefin materials.
- the outer layer 516 preferably comprises ionomer.
- the ball includes a central core 610 and a multi-layer shell 612.
- the multi-layer shell includes an inner layer 614 which preferably has a Shore D hardness of 60 - 80 and more preferably 62 - 78, an intermediate layer 615 which preferably has a Shore D hardness of 10 - 60 and more preferably 30 - 50, and an outer layer 616 with dimples 618.
- the outer layer preferably has a Shore D hardness of 50 - 65 and more preferably 55 - 60.
- the inner and intermediate layers 614 and 615 preferably comprise ionomeric or non-ionomeric polyolefin materials.
- the outer layer 616 preferably comprises ionomer.
- the ball includes a central core 710 and a multi-layer shell 712.
- the multi-layer shell includes an inner layer 714 which preferably has a Shore D hardness of 50 - 65 and more preferably 55 - 60, an intermediate layer 715 which preferably has a Shore D hardness of 10 - 60 and more preferably 30 - 50, and an outer layer 716 with dimples 718.
- the outer layer has a Shore D hardness of 60 - 80 and more preferably 62 - 78.
- the inner and intermediate layers 714 and 715 preferably comprise ionomeric or non-ionomeric polyolefin materials.
- the outer layer 716 preferably comprises ionomer.
- the ball includes a central core 810 and a multi-layer shell 812.
- the multi-layer shell includes an inner layer 814 which preferably has a Shore D hardness of 10 - 60 and more preferably 30 - 50, an intermediate layer 815 which preferably has a Shore D hardness of 60 - 80 and more preferably 62 - 78, and an outer layer 816 with dimples 818.
- the outer layer has a Shore D hardness of 50 - 65 and more preferably 55 - 60.
- the inner and intermediate layers 814 and 815 preferably comprise ionomeric or non-ionomeric polyolefin materials.
- the outer layer 816 preferably comprises ionomer.
- the ball includes a central core 910 and a multi-layer shell 912.
- the multi-layer shell includes an inner layer 914 which preferably has a Shore D hardness of 50 - 65 and more preferably 55 - 60, an intermediate layer 915 which preferably has a Shore D hardness of 60 - 80 and more preferably 62 - 78, and an outer layer 916 with dimples 918.
- the outer layer preferably has a Shore D hardness of 10 - 60 and more preferably 30 - 50.
- the inner and intermediate layers 914 and 915 preferably comprise ionomeric or non-ionomeric polyolefin materials.
- the outer layer 916 preferably comprises ionomer.
- each layer of the shell has the same Shore D hardness as the other layers.
- the Shore D hardness preferably is 50 - 80 and more preferably 55 - 70.
- Each layer can be formed from the generally same composition.
- the shell layers preferably are formed from ionomer.
- soft shell layers i.e. those with a Shore D hardness of 10 - 60 and preferably 30 - 50 comprise an ionomer with an average wt % acid content of about 15 or less which is at least 10% neutralized.
- the soft shell layers constitute a blend of two types of ionomers in which one component of the blend is an ethylene-acrylic acid or ethylene-methacryiic acid copolymer containing --15 wt% acid groups which are at least partially neutralized with a cation, and the other type of ionomer is a terpolymer of ethylene, acrylic acid or methacrylic acid and a softening termonomer such as butyl acrylate or methyl acrylate, resulting in an overall wt% acid content of about 15 or less.
- the blend preferably contains at least 75 wt% terpolymer type ionomer.
- suitable blends are described in U.S. Patent Nos. 4,884,814 and 5,120,791 , both of which are incorporated herein by reference.
- shell layers of intermediate hardness i.e. those with a Shore D hardness of 10 - 55
- shell layers of intermediate hardness i.e. those with a Shore D hardness of 10 - 55
- a blend of about 25 - 75 wt% copolymer ionomer and about 75 - 25 wt% terpolymer ionomer preferably is used.
- the hard ionomeric shell layer or layers can contain a single type of ionomer or a blend of two or more types of ionomers. Furthermore, a hardening and/or softening modifier can be added. In a particularly preferred form of the invention, the hard shell layer or layers contain one or more ionomers having at least 16 weight % acid groups, which are at least partially neutralized.
- Each of the three cover layers can be foamed or unfoamed. Preferably, each layer is unfoamed.
- a foamed layer has a lower density than an unfoamed layer, thereby affecting the weight distribution and moment of inertia.
- the melt index is increased by foaming.
- a foamed cover layer results in an increase in the weight of the core of the ball, thereby allowing for easier initiation of spin to a ball, particularly on short shots. This may partially compensate for a low spin rate on a hard covered ball, particularly in the case of a player who does not strike the bail at a fast swing speed.
- a foamed layer generally has a lower modulus and thus increased flexibility.
- a foamed layer is formed by adding a small amount of a chemical blowing agent to the cover material prior to molding. The blowing agent is selected such that it will release gas at the molding temperature for the cover layer.
- the outer cover layer of the golf ball preferably is made of ionomer, a metallocene catalyzed polyolefin such as EXACT, INSITE, AFFINITY, or ENGAGE which preferably is crosslinked, a polyamide, amide-ester elastomer, or graft copolymer of ionomer and polyamide such as CAPRON, ZYTEL, ZYTEL FN, a thermoplastic block polyamide such as PEBAX, which is a polyetheramide, etc., a crosslinked transpolyisoprene blend, a thermoplastic block polyester such as HYTREL, which is a polyetherester, or a thermoplastic or thermosetting polyurethane such as Estane® poiyurethanes, including Estane® X-4517.
- a metallocene catalyzed polyolefin such as EXACT, INSITE, AFFINITY, or ENGAGE which preferably is crosslinked,
- the inner and intermediate cover layers can be made of any of the materials listed in the previous paragraph as being useful for forming an outer cover layer. Furthermore, the inner and intermediate cover layers can be formed from a number of other non-ionomeric thermoplastics and thermosets. For example, lower cost polyolefins and thermoplastic elastomers can be used.
- Non-limiting examples of suitable non-ionomeric polyolefin materials include low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, rubber-toughened olefin polymers, acid copolymers which do not become part of an ionomeric copolymer when used in the inner cover layer, such as PRIMACOR, NUCREL, ESCOR and ATX, other plastomers and flexomers, thermoplastic elastomers such as styrene/butadiene/styre ⁇ e (SBS) or styrene/ethylene-butylene/styrene (SEBS) block copolymers, including Kraton® (Shell), dynamically vulcanized elastomers such as Santopre ⁇ e® (Monsanto), ethylene vinyl acetates such as Elvax® (DuPont), ethylene methyl acrylates such as Optema® (Exxon), polyvinyl chloride resins, and other e
- the non-ionomeric polyolefins can be mixed with ionomers.
- the inner, intermediate and outer cover layers optionally may include processing aids, release agents and/or diluents.
- Another useful material for a golf ball inner layer is a natural rubber latex (prevulcanized) which has a tensile strength of 4,000 - 5,000 psi, high resilience, good scuff resistance, a Shore D hardness of less than 15 and an elongation of >500%.
- a soft cover layer for use as an inner, intermediate or outer cover layer, one or more low modulus ionomers (i.e., soft ionomers), or a blend of one or more high modulus ionomers (i.e., hard ionomers) and one or more low modulus ionomers (i.e., soft ionomers) in a mixture can be used.
- a high modulus ionomer is one which has a flexural modulus of about 15,000 - 120,000 psi or more as measured under ASTM method D-790. The hardness of this type of ionomer is at least 50 on the
- Shore D scale as measured on a plaque in accordance with ASTM method D- 2240.
- hard ionomers are copoiymers with two types of monomers.
- a low modulus ionomer which can be blended with the high modulus ionomer to form the inner layer has a flexural modulus of about 1 ,000 to about 15,000 psi (ASTM D-790), and a plaque hardness of about 10 - 40 on the Shore D scale (ASTM D-2240).
- cover layers of intermediate hardness typically are blended in a ratio of 25 - 75 wt% hard (copolymer) ionomer and 75 - 25 wt% soft (terpolymer type) ionomer.
- cover layers of intermediate hardness as well as soft cover layers can be comprised of a single ionomer having a hardness that meets the requirements of Shore D hardness, i.e., a ball (not plaque) Shore D hardness of 10 - 60 for a soft cover layer and ball (not plaque) Shore D harness of 50 - 65 for a cover layer of intermediate hardness.
- one or more hard (high modulus) ionomers are used.
- low modulus ionomers can be blended with the high modulus ionomer or ionomers to improve compressing, toughness at low temperatures, enhanced feel, scuff resistance, etc., as long as the Shore D hardness requirements for the hard cover layer are met.
- the hard ionomer resins include ionic copolymers which are the e.g. sodium, zinc, magnesium, calcium, manganese, nickel, potassium or lithium, etc. salt, or blend thereof, of the reaction product of an olefin having from 2 to
- the carboxylic acid groups of the copolymer are partially neutralized by the metal ions, i.e., about 10 - 100%, typically about 10 - 75 % and more preferably about 30 - 70 % neutralized.
- the hard ionomeric resins typically are copolymers of ethylene with acrylic and/or methacrylic acid. Two or more hard ionomer resins can be blended.
- the metal cation salts utilized in the invention are those salts which provide the metal cations capable of neutralizing, to various extents, the carboxylic acid groups of the high acid copolymer. These include acetate, oxide or hydroxide salts of e.g. lithium, calcium, zinc, sodium, potassium, nickel, magnesium, and manganese, etc.
- lithium ion sources are lithium hydroxide monohydrate, lithium hydroxide, lithium oxide and lithium acetate.
- Sources for the calcium ion include calcium hydroxide, calcium acetate and calcium oxide.
- Suitable zinc ion sources are zinc acetate dihydrate and zinc acetate, a blend of zinc oxide and acetic acid.
- -Examples of sodium ion sources are sodium hydroxide and sodium acetate.
- Sources for the potassium ion include potassium hydroxide and potassium acetate.
- Suitable nickel ion sources are nickel acetate, nickel oxide and nickel hydroxide.
- Sources of magnesium include magnesium oxide, magnesium hydroxide and magnesium acetate.
- Sources of manganese include manganese acetate and manganese oxide.
- Non-limiting examples of commercially available hard ionomeric resins with intermediate acid levels which can be used in a blend to form the cover layers include the hard sodium ionic copolymer sold under the trademark Surlyn®8940 and the hard zinc ionic copolymer sold under the trademark Suriyn®9910.
- Surlyn®8940 is a copolymer of ethylene with methacrylic acid with about 15 weight % acid which is about 29 % neutralized with sodium ions. This resin has an average melt flow index of about 2.8.
- Surlyn®9910 is a copolymer of ethylene and methacrylic acid with about 15 weight % acid which is about 58 % neutralized with zinc ions. The average melt flow index of Surlyn®9910 is about 0.7.
- Hard cover layers and other cover layers containing hard-soft blends also can be made using high acid ionomer resins.
- High acid ionomer resins preferably contain more than 16 % by weight of a carboxylic acid, preferably 17 - 25 % by weight of a carboxylic acid, and most preferably about 18.5 - 21.5 % by weight of a carboxylic acid.
- Examples of a number of copolymers suitable for use to produce the high acid ionomers include, but are not limited to, high acid embodiments of an ethylene/acrylic acid copolymer, an ethyiene/methacrylic acid copolymer, an ethylene/itaconic acid copolymer, an ethylene/maleic acid copolymer, an ethyiene/methacrylic acid/vinyl acetate copolymer, an ethylene/acrylic acid/vinyl alcohol copolymer, etc.
- the base copolymer broadly contains greater than 16% by weight unsaturated carboxylic acid, from about 30 to about 83% by weight ethylene and from 0 to about 40% by weight of a softening comonomer.
- the copolymer contains about 20% by weight unsaturated carboxylic acid and about 80% by weight ethylene. Most preferably, the copolymer contains about 20% acrylic acid with the remainder being ethylene.
- Examples of commercially available high acid methacrylic acid-based ionomers which can be used in accordance with the invention include Surlyn® AD-8422 (sodium cation), Surlyn® 8162 (zinc cation), Surlyn® SEP-503-1 (zinc cation), and Surlyn® SEP-503-2 (magnesium cation). According to DuPont, all of these ionomers contain from about 18.5 to about 21 % by weight methacrylic acid.
- a cover layer with a particular Shore D hardness can be formed using a single ionomer, or more commonly, a blend of two or more ionomers.
- ionomers which can be used to form golf ball covers are as follows:
- ionomers which contain softening comonomers can be included in the cover layers.
- softening comonomer include vinyl esters of aliphatic carboxylic acids wherein the acids have 2 to 10 carbon atoms, vinyl ethers wherein the alkyl group contains 1 to 10 carbon atoms, and alkyl acrylates or methacrylates wherein the alkyl group contains 1 to 10 carbon atoms.
- Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or the like.
- Non-limiting examples of soft ionomers to be blended with the above- described hard ionomers to form the cover layers of the inventive golf ball comprise sodium, zinc magnesium, calcium, manganese, nickel, potassium or lithium, etc.
- the soft ionomer is preferably an ionomer made from an acrylic acid- based polymer and an unsaturated monomer of the acrylate ester class.
- the soft ionomers typically have an acid content of 3 - 12 wt% (including the weight percent of the softening comonomer).
- the cover layers optionally may include hardening or softening modifiers, non-limiting examples of which include a metal stearate, such as zinc stearate, or another fatty acid salt, as described in commonly assigned U.S. Patent Nos. 5,306,760 and 5,312,857.
- a metal stearate such as zinc stearate
- another fatty acid salt as described in commonly assigned U.S. Patent Nos. 5,306,760 and 5,312,857.
- One purpose of the metal stearate or other fatty acid salt is to reduce the cost of production of the ball without affecting overall performance of the finished ball.
- polar-group modified rubbers can be blended with ionomers as described, for example, in commonly assigned U.S. Patent Nos. 4,986,545, 5,098,105, 5,187,013, 5,330,837 and 5,338,610.
- Thermoplastic elastomers which act as hardening or softening agents including polyurethane, a polyester elastomer such as that sold by DuPont as HYTREL®, a polyester polyurethane such as B.F. Goodrich Company's ESTANE® polyester polyurethane X-4517, and a polyester amide such as that sold by Elf Atochem S.A. under the name PEBAX®, can be added.
- a plastomer such as that sold by Exxon under the name EXACTTM, e.g., EXACTTM 4049 can be included.
- EXACTTM e.g., EXACTTM 4049
- Various plasticizers and processing aids also can be used.
- the inner, outer and intermediate shell layers may contain plastomer.
- the plastomer may, but need not necessarily, be crosslinked or blended with ionomer or another compatible material.
- Plastomers are olefin copolymers with a uniform, narrow molecular weight distribution, a high comonomer content, and an even distribution of comonomers.
- the molecular weight distribution of the plastomers generally is about 1.5 - 4, preferably 1.5 - 3.5 and more preferably 1.5 - 2.4.
- the density is typically in the range of 0.85 - 0.97 if unfoamed and 0.10 - 0.90 if foamed.
- the comonomer content typically is in the range of 1 - 32%, and preferably 2 -
- composition distribution breadth index generally is greater than 30%, preferably is at least 45%, and more preferably is at least 50%.
- copolymer includes (1) copolymers having two types of monomers which are polymerized together, (2) terpolymers (which are formed by the polymerization of three types of monomers), and (3) copolymers which are formed by the polymerization of more than three types of monomers.
- the compositions further may include additives and fillers as well as a co-agent for use with a curing agent to aid in crosslinking the plastomer or to improve processability.
- composition distribution breadth index is defined as the weight percent of the copolymer molecules which have a comonomer content within 50 percent of the median total molar comonomer content.
- Plastomers are polyolefin copolymers developed using metallocene single-site catalyst technology. Plastomers exhibit both thermoplastic and elastomeric characteristics. Plastomers generally contain up to about 32 wt % comonomer. Plastomers which are useful in making golf balls include but are not limited to ethylene-butene copolymers, ethylene-octene copolymers, ethylene-hexe ⁇ e copolymers, and ethyle ⁇ e-hexene-bute ⁇ e terpolymers, as well as mixtures thereof.
- the plastomers employed in the invention preferably are formed by a single-site metallocene catalyst such as those disclosed in EP 29368, (JSP 4752597, USP 4808561 , and USP 4937299, the teachings of which are incorporated herein by reference.
- plastomers can be produced by metallocene catalysis using a high pressure process by polymerizing ethylene in combination with other monomers such as butene-1 , hexene-1 , octene-1 and 4-methyl-1 -pentene in the presence of catalyst system comprising a cyclopentadie ⁇ yl-transition metal compound and an alumoxane.
- EXACTTM plastomers (Exxon Chemical Co., Houston, Texas) are metallocene-cataiyzed polyolefins. This family of plastomers has a density of
- EXACTTM 4049 is a butene copolymer with a comonomer content of less than 28% and a polymer density of 0.873 g/cc. The properties of EXACTTM 4049 are shown on Table 8 below:
- This material has been found to be particularly useful in forming the inner and intermediate shell layers.
- E ⁇ XACT plastomers which are useful in the invention include linear ethylene-butene copolymers such as EXACT 3024 having a density of about 0.905 gms/cc (ASTM D-1505) and a melt flow index of about 4.5 g IOmi ⁇ . (ASTM D-2839); EXACT 3025 having a density of about 0.910 gms/cc (ASTM D-1505) and a melt fiow index of about 1.2 g/10min. (ASTM D-2839); E ⁇ XACT 3027 having a density of about 0.900 gms/cc (ASTM D-1505) and a melt flow index of about 3.5 gblOmi ⁇ .
- E ⁇ XACT plastomers are EXACT 4005 and EXACT 5010. Terpolymers of e.g. ethylene, butene and hexe ⁇ e also can be used. All of the above EXACT series plastomers are available from EXXON Chemical Co. Similar materials sold by Dow Chemical Co. as Insite® technology under the Affinity® and Engage® trademarks also can be used.
- E ⁇ XACT plastomers typically have a molecular weight distribution (MJMschreib) of about 1.5 to 2.4, where M w is weight average molecular weight and M ⁇ is number average molecular weight, a molecular weight of about 5,000 to about
- melt flow index above about 0.50 gblOmi ⁇ s, preferably about 1 - 10 g/ 0mins as determined by ASTM
- Plastomers which may be employed in the invention include copolymers of ethylene and at least one C 3 -C 20 -olefin, preferably a C 4 -C 8 ⁇ -olefin present in an amount of about 5 to about 32 mole %, preferably about 7 to about 22 mole %, more preferably about 9-18 mole %. These plastomers are believed to have a composition distribution breadth index of about 45% or more.
- Plastomers such as those sold by Dow Chemical Co. under the tradename ENGAGE are believed to be produced in accordance with USP 5,272,236, the teachings of which are incorporated herein in their entirety by reference.
- These plastomers are substantially linear polymers having a density of about 0.85 gms/cc to about 0.97 g/cc measured in accordance with ASTM D-792, a melt flow index ("Mi") of about 0.01 gms/10 minutes to about 1000 grams/10 minutes, a melt flow ratio (l 10 l 2 ) of about 7 to about 20, where l 10 is measured in accordance with ASTM D-1238 (190/10) and l 2 is measured in accordance with ASTM D-1238 (190/2.16), and a molecular weight distribution M ⁇ /M., which preferably is less than 5, and more preferably is less than about 3.5 and most preferably is from about 1.5 to about 2.5.
- These 5 plastomers include homopolymers of C 2 -C 20 olefins such as ethylene, propylene, 4-methyl-1-pente ⁇ e, and the like, or they can be interpolymers of ethylene with at least one C 3 -C 20 ⁇ -olefin and/or C 2 -C 20 acetylenically unsaturated monomer and/or C 4 -C 18 diolefins.
- These plastomers generally have a polymer backbone that is either unsubstituted or substituted with up to
- long chain branching means a chain length of at least about 6 carbons, above which the length cannot be distinguished using 13 C nuclear magnetic resonance spectroscopy.
- the preferred ENGAGE plastomers are characterized by a saturated ethylene- octene backbone, a narrow molecular weight distribution of about 2, and
- plastomers 15 a narrow level of crystallinity.
- These plastomers also are compatible with pigments, brightening agents, fillers such as those described above, as well as with plasticizers such as paraffinic process oil and naphthe ⁇ ic process oil.
- plasticizers such as paraffinic process oil and naphthe ⁇ ic process oil.
- Other commercially available plastomers may be useful in the invention, including those manufactured by Mitsui.
- the molecular weight distribution, (M ⁇ M,.), of plastomers made in accordance with USP 5,272,236 most preferably is about 2.0.
- Non-limiting examples of these plastomers include ENGAGE CL 8001 having a density of about 0.868 gms/cc, a melt flow index of about 0.5 g/10mins, and a Shore A hardness of about 75; ENGAGE CL 8002 having a density of about 0.87 5 gms/cc, a melt flow index of about 1 gms/1 Omin, Shore A hardness of about 75;
- ENGAGE CL 8003 having a density of about 0.885 gms/cc, a melt flow index of about 1.0 gms/1 Omin, and a Shore A hardness of about 86
- ENGAGE EG 8100 having a density of about 0.87 gms/cc, a melt flow index of about 1 gms/1 Omin., and a Shore A hardness of about 87
- ENGAGE 8150 having a density of about 0.868 gms/cc, a melt flow index of about 0.5gms/10min, and a Shore A hardness of about 75
- ENGAGE 8200 having a density of about 0.87 gms/cc, a melt flow index of about 5g/1 Omin., and a Shore A hardness of about 75
- ENGAGE EP 8500 having a density of about 0.87 gms/cc, a melt flow index of about 5g/10min., and a Shore A hardness of about 75.
- At least one layer of the golf ball contains at least 0.01 parts by weight of a filler.
- Fillers preferably are used to adjust the density, flex modulus, mold release, and/or melt flow index of a layer. More preferably, at least when the filler is for adjustment of density or flex modulus of a layer, it is present in an amount of at least five parts by weight based upon 100 parts by weight of the layer composition. With some fillers, up to about 200 parts by weight probably can be used.
- a density adjusting filler according to the invention preferably is a filler which has a specific gravity which is at least 0.05 and more preferably at least 0.1 higher or lower than the specific gravity of the layer composition. Particularly preferred density adjusting fillers have specific gravities which are higher than the specific gravity of the resin composition by 0.2 or more, even more preferably by 2.0 or more.
- a flex modulus adjusting filler according to the invention is a filler which, when used in an amount of e.g.
- a mold release adjusting filler is a filler which allows for the easier removal of a part from a mold, and eliminates or reduces the need for external release agents which otherwise could be applied to the mold.
- a mold release adjusting filler typically is used in an amount of up to about 2 wt% based upon the total weight of the layer.
- a melt flow index adjusting filler is a filler which increases or decreases the melt flow, or ease of processing of the composition.
- the layers may contain coupling agents that increase adhesion of materials within a particular layer e.g. to couple a filler to a resin composition, or between adjacent layers.
- Non-limiting examples of coupling agents include titanates, zirconates and silanes.
- Coupling agents typically are used in amounts of 0.1 - 2 wt% based upon the total weight of the composition in which the coupling agent is included.
- a density adjusting filler is used to control the moment of inertia, and thus the initial spin rate of the ball and spin decay.
- the addition in one or more layers, and particularly in the outer cover layer of a filler with a lower specific gravity than the resin composition results in a decrease in moment of inertia and a higher initial spin rate than would result if no filler were used.
- the addition in one or more of the cover layers, and particularly in the outer cover layer of a filler with a higher specific gravity than the resin composition results in an increase in moment of inertia and a lower initial spin rate.
- High specific gravity fillers are preferred as less volume is used to achieve the desired inner cover total weight.
- Nonrei ⁇ forcing fillers are also preferred as they have minimal effect on COR.
- the filler does not chemically react with the resin composition to a substantial degree, although some reaction may occur when, for example, zinc oxide is used in a shell layer which contains some ionomer.
- the density-increasing fillers for use in the invention preferably have a specific gravity in the range of 1.0 - 20.
- the density-reducing fillers for use in the invention preferably have a specific gravity of 0.06 - 1.4, and more preferably 0.06 - 0.90.
- the flex modulus increasing fillers have a reinforcing or stiffening effect due to their morphology, their interaction with the resin, or their inherent physical properties.
- the flex modulus reducing fillers have an opposite effect due to their relatively flexible properties compared to the matrix resin.
- the melt flow index increasing fillers have a flow enhancing effect due to their relatively high melt flow versus the matrix.
- the melt flow index decreasing fillers have an opposite effect due to their relatively low melt flow index versus the matrix.
- Fillers which may be employed in layers other than the outer cover layer may be or are typically in a finely divided form, for example, in a size generally less than about 20 mesh, preferably less than about 100 mesh U.S. standard size, except for fibers and flock, which are generally elongated. Flock ' and finer sizes should be small enough to facilitate processing. Filler pa r tide size will depend upon desired effect, cost, ease of addition, and dusting considerations.
- the filler preferably is selected from the group consisting of precipitated hydrated silica, clay, talc, asbestos, giass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate, zinc sulfide, lithopone, silicates, silicon carbide, diatomaceous earth, polyvinyl chloride, carbonates, metals, metal alloys, tungsten carbide, metal oxides, metal stearates, particulate carbonaceous materials, micro balloons, and combinations thereof.
- suitable fillers, their densities, and their preferred uses are as follows: Table 9
- fillers except for metal stearates would be expected to reduce the melt flow index of the cover layer.
- the amount of filler employed is primarily a function of weight requirements and distribution.
- the golf balls of the invention preferably have a COR of at least .725, more preferably at least .730, and most preferably at least .740.
- the golf balls 5 of the invention preferably have an overall PGA compression of 50 - 120, more preferably 60 - 110, and most preferably 70 - 100.
- the intermediate and outer shell layers can be formed by compression molding or injection molding in the manner described above, by casting or using other conventional molding techniques. Furthermore, the layers can be
- any two adjacent layers can be molded from a single parison.
- all three layers are blow molded from a single parison.
- the golf bails of the present invention typically are coated with a thin, glossy, protective topcoat of polyurethane, epoxy, or another suitable topcoat material.
- the topcoat generally has a dry thickness in the range of 0.005 to 0.0030 inches, and more preferably 0.001 - 0.002 inches.
- a primer coat typically is 0 included between the outer cover layer and top coat.
- This primer coat generally also is made of polyurethane or epoxy, and typically has a dry thickness of 0.005 to 0.0030 inches, and more preferably 0.001 - 0.002 inches.
- topcoat and primer layers are applied over a dimpled outer cover layer.
- the 5 inner cover layer as defined in this application can be formed from two or more layers which, taken together, meet the requirements of hardness and thickness of the layer or layers which are defined herein as the inner cover layer.
- the intermediate cover layer can be formed from two or more layers which, taken together, meet the requirements of hardness and thickness of the layer or layers which are defined herein as the intermediate cover layer.
- the outer cover layer can be formed from two or more layers which, taken together, meet the requirements of hardness and thickness of the layer or layers which are defined herein as the outer cover layer.
- one or more additional, very thin ionomeric or non-ionomeric layers can be added on either side of the inner cover layer and intermediate cover layer as long as the objectives of the invention are achieved.
- the resilience or coefficient of restitution (COR) of a golf ball is the constant "e,” which is the ratio of the relative velocity of an elastic sphere after direct impact to that before impact.
- e the resilience or coefficient of restitution
- the COR can vary from 0 to 1 , with 1 being equivalent to a perfectly or completely elastic collision and 0 being equivalent to a perfectly or completely inelastic collision.
- COR COR
- club head speed club head mass
- ball weight ball size and density
- spin rate angle of trajectory and surface configuration
- environmental conditions e.g. temperature, moisture, atmospheric pressure, wind, etc.
- COR density and resilience
- the factors or determinants of interest with respect to improved distance are generally the coefficient of restitution (COR) and the surface configuration (dimple pattern, ratio of land area to dimple area, etc.) of the ball.
- the COR of solid core balls is a function of the composition of the core and of the cover.
- the core and/or cover may be comprised of one or more layers such as in multi-layered balls.
- the coefficient of restitution is a function of not only the composition of the center and cover, but also the composition and tension of the elastomeric windings.
- the center and cover of a wound core ball may also consist of one or more layers.
- the COR of the golf balls of the present invention is a function of the composition and physical properties of the core and cover layer materials such as flex modulus, hardness and particularly, their resilience, i.e. ability to quickly recover from a high impact deformation.
- the coefficient of restitution is the ratio of the outgoing velocity to the incoming velocity. In the examples of this application, the coefficient of restitution of a golf ball was measured by propelling a ball horizontally at a speed of 125 ⁇ 5 feet per second (fps) and corrected to 125 fps against a generally vertical, hard, flat steel plate and measuring the ball's incoming and outgoing velocity electronically.
- the incoming speed should be 125 ⁇ 5 fps but corrected to 125 fps.
- the correlation between COR and forward or incoming speed has been studied and a correction has been made over the ⁇ 5 fps range so that the COR is reported as if the ball had an incoming speed of exactly 125.0 fps.
- T e coefficient of restitution must be carefully controlled in all commercial golf balls if the ball is to be within the specifications regulated by the United
- PGA compression is another important property involved in the performance of a golf ball.
- the compression of the ball can affect the playability of the ball on striking and the sound or "click” produced.
- compression can affect the "feel” of the ball (i.e., hard or soft responsive feel), particularly in chipping and putting.
- compression utilized in the golf ball trade generally defines the overall deflection that a golf ball undergoes when subjected to a compressive load.
- PGA compression indicates the amount of change in golf ball's shape upon striking.
- PGA compression related to a scale of from 0 to 200 given to a golf ball. The lower the PGA compression value, the softer the feel of the ball upon striking.
- tournament quality balls have compression ratings around 70 - 110, preferably around 80 to 100.
- a standard force is applied to the external surface of the ball. A ball which exhibits no deflection (0.0 inches in deflection) is rated 200 and a ball which deflects 2/10th of an inch (0.2 inches) is rated 0. Every change of .001 of an inch in deflection represents a 1 point drop in compression. Consequently, a ball which deflects 0.1 inches (100 x .001 inches) has a PGA compression value of 100 (i.e., 200 -
- a ball which deflects 0.1 10 inches (110 x .001 inches) has a PGA compression of 90 (i.e., 200 - 1 10).
- PGA compression is determined by an apparatus fashioned in the form of a small press with an upper and lower anvil.
- the upper anvil is at rest against a 200-pound die spring, and the lower anvil is movable through 0.300 inches by means of a crank mechanism. In its open position the gap between the anvils is 1.780 inches allowing a clearance of 0.100 inches for insertion of the ball.
- the lower anvil is raised by the crank, it compresses the ball against the upper anvil, such compression occurring during the last 0.200 inches of stroke of the lower anvil, the ball then loading the upper anvil which in turn loads the spring.
- the equilibrium point of the upper anvil is measured by a dial micrometer if the anvil is deflected by the ball more than 0.100 inches (less deflection is simply regarded as zero compression) and the reading on the micrometer dial is referred to as the compression of the ball.
- tournament quality balls have compression ratings around 80 to 100 which means that the upper anvil was deflected a total of 0.120 to 0.100 inches.
- An example to determine PGA compression can be shown by utilizing a golf ball compression tester produced by Atti Engineering Corporation of Newark, N.J. The value obtained by this tester relates to an arbitrary value expressed by a number which may range from 0 to 100, although a value of 200 can be measured as indicated by two revolutions of the dial indicator on the apparatus.
- the value obtained defines the deflection that a golf ball undergoes when subjected to compressive loading.
- the Atti test apparatus consists of a lower movable platform and an upper movable spring-loaded anvil.
- the dial indicator is mounted such that it measures the upward movement of the springloaded anvil.
- the golf ball to be tested is placed in the lower platform, which is then raised a fixed distance.
- the upper portion of the golf ball comes in contact with and exerts a pressure on the springloaded anvil.
- the upper anvil is forced upward against the spring.
- Alternative devices have also been employed to determine compression.
- Applicant also utilizes a modified Riehle Compression Machine originally produced by Riehle Bros. Testing Machine Company, Phil., PA to evaluate compression of the various components (i.e., cores, mantle cover balls, finished balls, etc.) of the golf balls.
- the Riehle compression device determines deformation in thousandths of an inch under a fixed initialized load of 200 pounds. Using such a device, a Riehle compression of 61 corresponds to a deflection under load of 0.061 inches.
- Applicant's compression values are usually measured as Riehle compression and converted to PGA compression.
- additional compression devices may also be utilized to monitor golf ball compression so long as the correlation to PGA compression is know. These devices have been designed, such as a Whitney Tester, to correlate or correspond to PGA compression through a set relationship or formula.
- Shore D hardness of a cover is measured generally in accordance with ASTM D-2240, except the measurements are made on the curved surface of a molded cover, rather than on a plaque. Furthermore, the Shore D hardness of the cover is measured while the cover remains over the core. When a hardness measurement is made on a dimpled cover, Shore D hardness is measured at a land area of the dimpled cover. Durability is determined by firing the golf bails at 125 ft/sec (at 72 °F) into a five-sided steel pentagonal container, the walls of which are steel plates.
- the container has a 19 A inch long insert plate mounted therein, the central portion of which has horizontally extending square grooves on it which are intended to simulate a square-grooved face of a golf club.
- the grooves have a width 30 of 0.033 inches, a depth 32 of 0.100 inches, and are spaced apart form one another by land areas having a width of 0.130 inches.
- the five walls of the pentagonal container each have a length of 14 1 inches.
- the inlet wall is vertical and the insert plate is mounted such that it inclines upward 30° relative to a horizontal plane away from the opening in the container.
- the ball travels 15 1/2 - 15 3/4 inches horizontally from its point of entry into the container until it hits the square-grooved central portion of the insert plate.
- the angle between the line of trajectory of the ball and the insert plate is 30°.
- the balls are subjected to a number of blows (firings) and are inspected at regular intervals for breakage (i.e., any signs of cover cracking or delamination). If a microcrack forms in a ball, its speed will change and the operator is alerted. The operator then visually inspects the ball. If the microcrack cannot yet be observed, the ball is returned to the test until a crack can be visually detected.
- Balls are assigned a Durability rating according to the following scale. A sample of 10-12 balls of the same type are obtained and are tested using the durability test apparatus described in the previous paragraph. If less than all of the balls in the sample survive 70 blows each without cracking, the ball is assigned a Durability Rating of 1. if all of the balls survive 70 blows and one or more of the balls cracks before 120 blows, the ball is assigned a Durability Rating of 2. If all of the balls survive 120 blows and the average for the sample is up to 150 blows, the ball is assigned a Durability Rating of 3. If all of the balls survive 120 blows and the average for the sample is up to 200 blows, the ball is assigned a Durability Rating of 4.
- the ball is assigned a Durability Rating of 5. If all the balls survive 120 blows and the average for the sample is more than 240 blows, the ball is assigned a Durability Rating of 6.
- the term “spherical” is used in conjunction with the shell (center). It is understood by those skilled in the art that when referring to golf balls and their components, the term “spherical” includes surfaces and shapes which may have minor insubstantial deviations from the perfect ideal geometric spherical shape. In addition the inclusion of dimples on the exterior surface of the shell, to effect its aerodynamic properties, does not detract from its "spherical” shape for the purposes therein or in the art. Further the internal surface of the shell as well as the core may likewise incorporate intentionally designed patterns and still be considered “spherical” within the scope of this invention.
- the rotational moment of inertia of a golf ball is the resistance to change in spin of the ball and is conventionally measured using an "Inertia Dynamics Moment of Inertia Measuring Instrument".
- the moment of inertia is relatively low because the liquid center of the ball does not immediately rotate when the outside of the ball begins to spin. If an increased moment of inertia is desired, this may be achieved by adding high density materials to the cover and reducing the density of the liquid core to maintain the desired ball weight.
- Formulation 514-92-1 was injection molded into half shells, approximately 1.68 inches in diameter and 0.190 inches thick.
- Formulation 514-92-1 is as follows:
- the pole height was greater than the equator radius by 0.007 inches to allow for material flow during spin welding of the two half shells to form the hollow spheres.
- the two half shells had a tongue and groove configuration.
- the two half shells were spin bonded together to produce a hollow sphere at 4100 revolutions per minute (rpm) and 15 second dwell.
- the grooved half shell had a molded tapered hole 0.0125 inches in diameter at the exterior ball surface and 0.0625 inches in diameter at the interior ball surface.
- Specific gravity of the cover material can range from .95 to 1.25. The preferred range is .97 5 to 1.0.
- the flex modulus expressed in psi at 73 degrees Fahrenheit has a range of 30,000 to 60,000. The preferred range is 45,000 to 60,000. Flex modulus is measured in accordance with A.S.T.M. Test D 790. Samples to date using ionomer compounds as listed below have the following average data:
- the estimated volume of the cover is .979 cubic inches, or 16.04 cubic centimeters.
- Formulation A A liquid core material, Formulation A, was introduced using a hypodermic syringe to completely fill the interior void.
- Formulation A is: Formulation A Parts by Weight
- a molded plug in the shape as shown in Figs. 12 and 15 of the same material as the shell was spin bonded into the hole to seal the contents.
- Spin bonding conditions were 3150 rpm and 15 seconds dwell.
- Example 1 The procedure of Example 1 was followed, except that the filling material was glycerine.
- the resulting product after defiashi ⁇ g had the following properties:
- Example 2 The procedure of Example 1 was followed, except that the filling material was hydraulic oil, "Mobil Etna 26" which is a trademark of Mobile Oil Corp. of New York City, New York.
- the resulting product after deflashing had the following properties:
- Example 3 As is described in Example 1 above, the tests of Example 3 were repeated and 12 balls manufactured.
- the resulting products after deflashing had the following properties:
- Example 2 The procedure of Example 1 was followed, except that the filling material was gelatin sugar water solution, Formulation B.
- Formulation B is as follows: Formulation B Parts by Weight
- Gelatin 45 ("Royal" Gelatin dessert, manufactured by Nabisco Brands,
- Example 1 The procedure of Example 1 was followed, except that the shell material 514-93-3, was as follows:
- Escor 900 50 (“Escor" is a Trademark of Exxon
- Example 1 As is described above in Example 1 , the tests of Example 1 were repeated and 12 goif balls formed. The resulting products after deflashing had the following physical properties:
- a number of blow molded inner shells were obtained which had an outer diameter of 1.510 inches and an inner shell layer thickness of 0.110 inches.
- the inner shells contained a solution, which had a specific gravity of about 1.3, of calcium chloride and water.
- the liquid filled inner shells were made from a pre-extruded blend of 50 parts by weight lotek 1002 and 50 parts by weight lotek 1003. The liquid filled inner shells were media tumbled for an hour and allowed to dry before additional layers were formed thereon.
- Intermediate shell layers were injection molded over the inner shell layers using a laboratory 1.62 inch injection mold to form a number of inner balls.
- the inner balls were centerless ground to a diameter of 1.59 inches.
- Dimpled outer shell layers were then injection molded over the intermediate shell layers.
- the balls were primed with a polyurethane primer and then coated with a polyurethane top coat.
- the primer coat had a dry thickness of about 0.0005 inches and the top coat had a thickness of about 0.0015 inches.
- the properties of the golf balls and shell layer formulations are shown on Table 10 below.
- the "whitener package” on Tables 10 - 12 has the following formulation: 2.3 phr titanium dioxide (Unitane 0-110), 0.025 phr optical brightener
- Example 6 The procedure of Example 6 was repeated using different combinations of shell layer formulations.
- the properties of the golf balls and the shell layer formulations are shown below on Table 10.
- Example 6 A number of the blow molded cores of Example 6 were covered with a single dimpled shell layer of ionomer.
- the properties of the golf balls and the shell layer formulations are shown on Table 10 below.
- a comparison of the balls of Examples 6 - 9 with those of Comparative Examples 1 - 3 shows that the inclusion of an intermediate layer between the inner shell layer and the outer shell layer generally results in an increase in spin rate. This is evident from a comparison of Example 6 with Comparative Example 1 and a comparison of Example 7 with Comparative Example 2.
- Examples 8 and 9 are compared with Comparative Example 3, Examples 8 and 9 have a significantly higher coefficient of restitution than Comparative -Example 3 at the same spin rate.
- a number of blow molded inner shells were obtained having an outer diameter of 1.410 inches an inner shell layer thickness of 0.065 inches.
- the inner shells contain a solution of calcium chloride and water, which had a specific gravity of about 1.41.
- the liquid filled inner shells were made from a pre-extruded blend of 50 parts by weight IOTEK 1002 and 50 parts by weight
- the inner shells were blow molded at a melt temperature of 320 - 350°F.
- the liquid filled inner shells were media tumbled for an hour and allowed to dry before additional layers were formed thereon.
- An intermediate shell layer having an outer diameter of about 1.550 inches and a wall thickness of about 0.070 inches was formed over the inner shell layer to form an inner ball.
- the inner shells were made from a pre- extruded blend of 50 parts by weight IOTEK 1002 and 50 parts by weight IOTEK 1003.
- the inner balls were media tumbled for one hour.
- outer shell layers were then injection molded over the intermediate shell layers.
- the outer shell layers had an outer diameter of
- the outer shell layers were made of a pre-extruded blend of IOTEK 1002, IOTEK 1003, and white masterbatch.
- the bails were primed with a polyurethane primer and then coated with a polyurethane top coat.
- the primer coat had a dry thickness of about 0.0005 inches and the top coat had a dry thickness of about 0.0015 inches.
- Table 11 The properties of the golf balls and shell layer formulations are shown on Table 11 below. As shown by the data on Table 11, golf balls having three shell/cover layers with intermediate wall thicknesses have a good COR in combination with favorable durability.
- Example 11 The procedure of Example 10 was repeated with the exception that different intermediate shell layer and/or outer shell layer formulations were used. The results are shown below on Table 11. The durability values shown on Table 11 are average number of blows to failure for a set of six balls of each type. The balls were shot in a barrel test at 125 ft/sec.
- Example 16 The procedure of Example 10 was repeated using a number of different cover layer formulations and a different set of wall thicknesses.
- the inner shells had a theoretical outer diameter of 1.490 inches and a wall thickness of 0.110 inches.
- the intermediate shell layers had a theoretical outer diameter of 1.596 inches and a theoretical wall thickness of 0.053 inches.
- the outer shell layers had a theoretical outer diameter of 1.681 inches and a theoretical wall thickness of 0.043 inches, resulting in an overall theoretical wall thickness of 0.196 inches.
- the cover formulations and golf ball properties are shown below on Table 12.
- Example 20 The cover formulations and golf ball properties are shown below on Table 12.
- Example 10 The procedure of Example 10 was repeated using a different set of shell wall thicknesses.
- the inner shell had an actual outer diameter of 1.41 inches.
- the intermediate shell layer had an actual outer diameter of 1.550 inches.
- the outer shell layer had an outer diameter of about 1.684 inches.
- the cover formulation and ball properties are shown on Table 12.
- Example 20 The procedure of Example 20 was repeated with the exception that the inner shells were blow molded at a melt temperature of 400°F. This increase in temperature resulted in substantially improved durability of the resulting balls.
- the use of a three layer shell allows one to more finely tailor the properties of a golf ball, including spin, compression, COR, etc., to better meet the needs of players having a wide variety of skill levels, particularly more highly skilled players.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/006715 WO2000057961A1 (en) | 1999-03-29 | 1999-03-29 | Golf ball with multiple shell layers |
GB0122982A GB2363728A (en) | 1999-03-29 | 1999-03-29 | Golf ball with multiple shell layers |
JP2000607708A JP2003520619A (en) | 1999-03-29 | 1999-03-29 | Golf ball with multiple shell layers |
CA002366729A CA2366729A1 (en) | 1999-03-29 | 1999-03-29 | Golf ball with multiple shell layers |
AU33670/99A AU771494B2 (en) | 1999-03-29 | 1999-03-29 | Golf ball with multiple shell layers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1999/006715 WO2000057961A1 (en) | 1999-03-29 | 1999-03-29 | Golf ball with multiple shell layers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000057961A1 true WO2000057961A1 (en) | 2000-10-05 |
Family
ID=22272450
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/006715 WO2000057961A1 (en) | 1999-03-29 | 1999-03-29 | Golf ball with multiple shell layers |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP2003520619A (en) |
AU (1) | AU771494B2 (en) |
CA (1) | CA2366729A1 (en) |
GB (1) | GB2363728A (en) |
WO (1) | WO2000057961A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU740245B2 (en) * | 1995-10-03 | 2001-11-01 | Callaway Golf Company | Multi-piece golf balls |
US7131915B2 (en) | 2001-04-10 | 2006-11-07 | Acushnet Company | Three-layer-cover golf ball |
EP2226356A1 (en) * | 2007-09-30 | 2010-09-08 | Jiangmen Proudly Water-soluble Plastic Co., Ltd | A golf ball-forming composition, golf balls prepared from the composition and the process for preparing thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5547162B2 (en) * | 2011-11-04 | 2014-07-09 | ダンロップスポーツ株式会社 | Golf ball |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US715295A (en) * | 1902-10-18 | 1902-12-09 | Kempshall Mfg Co | Playing-ball. |
US5480155A (en) * | 1989-03-10 | 1996-01-02 | Lisco, Inc. | Golf ball |
US5683312A (en) * | 1996-03-11 | 1997-11-04 | Acushnet Company | Fluid or liquid filled non-wound golf ball |
US5861937A (en) * | 1997-05-30 | 1999-01-19 | Nidek Co., Ltd. | Ophthalmic apparatus |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5816937A (en) * | 1996-01-12 | 1998-10-06 | Bridgestone Sports Co., Ltd. | Golf ball having a multilayer cover |
-
1999
- 1999-03-29 AU AU33670/99A patent/AU771494B2/en not_active Ceased
- 1999-03-29 GB GB0122982A patent/GB2363728A/en not_active Withdrawn
- 1999-03-29 CA CA002366729A patent/CA2366729A1/en not_active Abandoned
- 1999-03-29 JP JP2000607708A patent/JP2003520619A/en active Pending
- 1999-03-29 WO PCT/US1999/006715 patent/WO2000057961A1/en active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US715295A (en) * | 1902-10-18 | 1902-12-09 | Kempshall Mfg Co | Playing-ball. |
US5480155A (en) * | 1989-03-10 | 1996-01-02 | Lisco, Inc. | Golf ball |
US5683312A (en) * | 1996-03-11 | 1997-11-04 | Acushnet Company | Fluid or liquid filled non-wound golf ball |
US5861937A (en) * | 1997-05-30 | 1999-01-19 | Nidek Co., Ltd. | Ophthalmic apparatus |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU740245B2 (en) * | 1995-10-03 | 2001-11-01 | Callaway Golf Company | Multi-piece golf balls |
US7131915B2 (en) | 2001-04-10 | 2006-11-07 | Acushnet Company | Three-layer-cover golf ball |
EP2226356A1 (en) * | 2007-09-30 | 2010-09-08 | Jiangmen Proudly Water-soluble Plastic Co., Ltd | A golf ball-forming composition, golf balls prepared from the composition and the process for preparing thereof |
EP2226356A4 (en) * | 2007-09-30 | 2011-01-12 | Proudly Eco Friendly Products Co Ltd | A golf ball-forming composition, golf balls prepared from the composition and the process for preparing thereof |
CN101396600B (en) * | 2007-09-30 | 2012-11-07 | 江门市宝德利水溶性塑料有限公司 | Water soluble biological degradation type golf balls and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
GB0122982D0 (en) | 2001-11-14 |
JP2003520619A (en) | 2003-07-08 |
CA2366729A1 (en) | 2000-10-05 |
AU771494B2 (en) | 2004-03-25 |
GB2363728A (en) | 2002-01-09 |
AU3367099A (en) | 2000-10-16 |
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