WO1998043711A1 - Perimeter weighted golf ball with visible weighting - Google Patents
Perimeter weighted golf ball with visible weighting Download PDFInfo
- Publication number
- WO1998043711A1 WO1998043711A1 PCT/US1998/006163 US9806163W WO9843711A1 WO 1998043711 A1 WO1998043711 A1 WO 1998043711A1 US 9806163 W US9806163 W US 9806163W WO 9843711 A1 WO9843711 A1 WO 9843711A1
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- WO
- WIPO (PCT)
- Prior art keywords
- golf ball
- weighting material
- ball
- weighting
- powder
- 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
- A63B37/005—Cores
- A63B37/006—Physical properties
- A63B37/0062—Hardness
- A63B37/00621—Centre 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
- A63B43/00—Balls with special arrangements
- A63B43/008—Balls with special arrangements with means for improving visibility, e.g. special markings or colours
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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
-
- 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
- A63B37/0062—Hardness
- A63B37/00622—Surface 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
- A63B45/00—Apparatus or methods for manufacturing balls
- A63B45/02—Marking of 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
- A63B37/005—Cores
- A63B37/0051—Materials other than polybutadienes; Constructional details
- A63B37/0054—Substantially rigid, e.g. metal
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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
- A63B37/005—Cores
- A63B37/006—Physical properties
- A63B37/0069—Flexural modulus; Bending stiffness
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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
- A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
- A63B37/0076—Multi-piece balls, i.e. having two or more intermediate layers
Definitions
- the present invention pertains to the construction of regulation golf balls including golf balls having enhanced distance and feel characteristics. More particularly, the invention relates to improved multi-layer golf balls having one or more
- weighting material may be incorporated in one
- the heavy weight filler particles are present in an outer cover layer.
- the golf balls of the invention have essentially the same "feel" characteristic of softer
- a golf ball can not weigh more than
- golf balls are manufactured today which by the Applicant are slightly larger (i.e., approximately 1.72 inches in diameter) while meeting the weight, velocity, distance and symmetry specifications set by the U.S.G.A.
- the initial velocity of the ball must not exceed 250 ft/sec. with a 2% maximum tolerance (i.e., 255 ft/sec.) when struck at a set club head speed on a U.S.G.A. machine.
- the overall distance of the ball must not exceed 280 yards with a 6% tolerance (296.8 yards)
- resilience and compression Two of the principal properties involved in a golf ball's performance are resilience and compression.
- Resilience is generally defined as the ability of a strained body, by virtue of high yield strength and low elastic modulus, to recover its size and form following deformation. Simply stated, resilience is a measure of energy retained to the energy lost when the ball is impacted with the club. In the field of golf ball production, resilience is determined by the coefficient of restitution (C.O.R.), the constant "e” which is the ratio of the relative velocity of an elastic sphere after direct impact to that before impact. As a result, the coefficient of restitution ("e”) can vary from 0 to 1 , with 1 being equivalent to a
- the distance a golf ball will travel when hit generally determines the distance a golf ball will travel when hit.
- the distance a golf ball will travel under controlled environmental conditions is a function of the speed and mass of the club and the size, density, composition and resilience (C.O.R.) of the ball and other factors.
- the initial velocity of the club, the mass of the club and the angle of the ball's departure are essentially provided by the golfer upon striking.
- club head, club head mass, the angle of trajectory and environmental conditions are not determinants controllable by golf ball producers and the ball size and weight are set by the U.S.G.A., these are not factors of concern among golf ball manufacturers.
- the factors or determinants of interest with respect to improved distance are generally the coefficient of restitution (C.O.R.), spin and the surface configuration (dimple pattern, ratio of land area to dimple area, etc.) of the ball.
- the coefficient of restitution (C.O.R.) in solid core balls is a function of the composition of the molded core and of the cover.
- the molded 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.
- center and cover of a wound core ball may also consist of one or more layers.
- the coefficient of restitution of a golf ball can be analyzed by determining the ratio of the outgoing velocity to the incoming velocity.
- the coefficient of restitution of a golf ball was measured by propelling a ball horizontally at a speed of 125 +/- 1 feet per second (fps) against a generally vertical, hard, flat steel plate and measuring the ball's incoming and outgoing velocity electronically.
- Speeds were measured with a pair of Oehler Mark 55 ballistic screens (available from Oehler Research Austin TX), which provide a timing pulse when an object passes through them. The screens are separated by 36" and are located 25.25" and 61.25" from the rebound wall.
- the ball speed was measured by timing the pulses from screen 1 to screen 2 on the way into the rebound wall (as the average speed of the ball over 36"), and then the exit speed was timed from screen 2 to screen 1 over the same distance.
- the rebound wall was tilted 2 degrees from a vertical plane to allow the ball to rebound slightly downward in order to miss the edge of the cannon that fired it.
- the incoming speed should be 125 +/- 1 fps. Furthermore, the correlation between C.O.R. and forward or incoming speed has been studied and a correction has been made over the +/- fps range so that the C.O.R. is reported as if the ball had an incoming speed of exactly 125.0 fps.
- the coefficient of restitution must be carefully controlled in all commercial golf balls if the ball is to be within the specifications regulated by the U.S.G.A. As mentioned to some degree above, the U.S.G.A. standards indicate that a "regulation" ball cannot have an initial velocity exceeding 255 feet per second in an atmosphere of 75°F when tested on a U.S.G.A. machine. Since the coefficient of restitution of a ball is related to the ball's initial velocity, it is highly desirable to
- the overall distance produced by a ball in actual play will vary depending on the specific abilities of the individual golfer.
- the surface configuration of a ball is also an important variable in affecting a ball's travel distance.
- the size and shape of the ball's dimples, as well as the overall dimple pattern and ratio of land area to dimpled area are important with respect to the ball's overall carrying distance.
- the dimples provide the lift and decrease the drag for sustaining the ball's initial velocity in flight as long as possible. This is done by displacing the air (i.e., displacing the air resistance produced by the ball from the front of the ball to the rear) in a uniform manner.
- the shape, size, depth and pattern of the dimple affect the ability to sustain a ball's initial velocity differently.
- compression is another property involved in the overall performance of a golf ball.
- the compression of a ball will influence the sound or "click" produced when the ball is properly hit.
- compression can affect the
- feel of the ball i.e., hard or soft responsive feel
- chipping and putting i.e., hard or soft responsive feel
- 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.
- two-piece and multilayer solid core balls exhibit much more consistent compression readings than balls having wound cores such as the thread wound three-piece balls.
- cover hardness and thickness are important in producing the distance, payability and durability properties of a golf ball. As mentioned above, cover hardness directly affects the resilience and thus distance characteristics of a ball. All things being equal, harder covers produce higher resilience. This is because soft materials detract from resilience by absorbing some of the impact energy as the material is compressed on striking.
- soft covered balls are preferred by the more skilled golfer because he or she can impact high spin rates that give him or her better control or workability of the ball.
- Spin rate is an important golf ball characteristic for both the skilled and unskilled golfer.
- high spin rates allow for the more skilled golfer, such as PGA and LPGA professionals and low handicap players, to maximize control of the golf ball. This is particularly beneficial to the more skilled golfer when hitting an approach shot to a green.
- back spin thereby stopping the ball quickly on the green, and/or “side spin” to draw or fade the ball, substantially improves the golfer's control over the ball.
- side spin to draw or fade the ball
- a high spin golf ball is not desirous by all golfers, particularly high handicap players who cannot intentionally control the spin of the ball.
- a high spinning ball will roll substantially less than a low spinning golf ball, a high spinning ball is generally short on distance.
- a more efficient ball for the less skilled player is a golf ball that exhibits low spin properties.
- the low spin ball reduces slicing and hooking and enhances distance.
- a high spinning ball is generally short on distance, such a ball is not universally desired by even the more skilled golfer.
- balata With respect to high spinning balls, up to approximately twenty years ago, most high spinning balls were comprised of balata or blends of balata with elastomeric or plastic materials.
- the traditional balata covers are relatively soft and flexible. Upon impact, the soft balata covers compress against the surface of the club producing high spin. Consequently, the soft and flexible balata covers provide an experienced golfer with the ability to apply a spin to control the ball in flight in order to produce a draw or a fade, or a backspin which causes the ball to "bite" or stop abruptly on contact with the green.
- the soft balata covers produce a soft "feel" to the low handicap player.
- payability properties workability, feel, etc.
- balata covered golf balls are easily cut and/or damaged if mis-hit. Golf balls produced with balata or balata- containing cover compositions therefore have a relatively short lifespan.
- soft balata covered balls are shorter in distance. While the softer materials will produce additional spin, this is frequently produced at the
- Ionomeric resins are polymers in which the molecular chains are cross- linked by ionic bonds.
- Ionomeric resins are generally ionic copolymers of an olefin, such as ethylene, and a metal salt of 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.
- the ionomeric resins were very durable, they initially tended to be very hard when utilized for golf ball cover construction, and thus lacked the degree of softness required to impart the spin necessary to control the ball in flight. Since the initial ionomeric resins were harder than balata, the ionomeric resin covers did not compress as much against the face of the club upon impact, thereby producing less spin.
- the initial, harder and more durable ionomeric resins lacked the "feel" characteristic associated with the softer balata related covers.
- the ionomer resins tended to produce a hard responsive "feel" when struck with a golf club such as a wood, iron, wedge or putter.
- multi-layered covers containing one or more ionomer resins have also been formulated in an attempt to produce a golf ball having the overall distance, payability and durability characteristics desired. For example, this was addressed by Spalding & Evenflo Companies, Inc., the assignee of the present invention, in U.S. Patent No. 4,431,193 where the construction of a multi-layered golf ball having two ionomer resin cover layers is disclosed.
- a multi-layer golf ball is produced by initially molding a first cover layer on a solid spherical core and then adding a second layer.
- the first layer is comprised of a hard, high flexural modulus resinous material such as type 1605 Surlyn® (now designated Surlyn® 8940).
- Type 1605 Surlyn® (Surlyn® 8940) is a sodium ion based low acid (less than or equal to 15 weight percent methacrylic acid) ionomer resin having a flexural modulus of about 51 ,000 psi.
- Type 1855 Surlyn® (Surlyn® 9020) is a zinc ion based low acid (10 weight percent methacrylic acid) ionomer resin having a flexural modulus of about 14,000 psi.
- the '193 patent teaches that the hard, high flexural modulus resin which comprises the first layer provides for a gain in coefficient of restitution over the coefficient of restitution of the core. The increase in the coefficient of restitution
- the relatively soft, low flexural modulus outer layer provides essentially no gain in the coefficient of restitution but provides for the advantageous "feel" and playing characteristics of a balata covered golf ball.
- the present invention is directed to new multi-layer golf ball compositions which provide for enhanced coefficient of restitution (i.e, improved travel distance) and/or durability properties when compared to the multi-layer balls found in the examples of the prior art.
- the travel distance of the balls of the invention is further improved by increasing the balls' moment of inertia and thereby reduce their overall spin rate.
- the balls of the invention have enhanced outer cover layer softness and feel.
- the improvements in distance, feel, etc. are produced without substantial sacrifices in controllability resulting from the loss of spin produced by the balls' increased moment of inertia.
- a low spin ball is generally preferred, particularly
- the present invention provides a remarkable and unique approach for readily increasing the moment of inertia of a golf ball.
- the approach of the present invention is economical and easily implemented in large scale commercial golf ball manufacturing processes.
- the present invention provides, in a first aspect, a golf ball comprising a core and an outer layer, the outer layer including at least one discrete region of a weighting material that serves to increase the moment of inertia of the golf ball.
- the weighting material or some indication thereof is visible at the ball's exterior surface.
- the present invention further provides a multi-layer golf ball having an increased moment of inertia, the golf ball comprising a core, an inner layer, and an outer layer.
- the inner layer comprises a relatively hard material having a flexural modulus of at least about 15,000 psi and a Shore D hardness of at least about 60.
- the outer layer comprises a relatively soft material having a flexural modulus of from about 1 ,000 psi to about 10,000 psi and a Shore D hardness of about 65 or less.
- the golf ball further comprises an effective amount of a weighting material disposed in either or both the inner layer or outer layer.
- the golf ball preferably further comprises at least one discrete region of a weighting material disposed in the outer layer. In a most preferred embodiment, the weighting material or some indication thereof, is visible along the ball's exterior.
- FIG. 1 is a cross-sectional view of a preferred embodiment golf ball embodying the invention illustrating a core 10 and a multi-layer cover 12 consisting of an inner layer 14 containing metal particles or other heavy filler materials 20 and an outer layer 16 having dimples 18;
- FIG. 2 is a diametrical cross-sectional view of a preferred embodiment golf ball of the invention having a core 10 and a cover 12 made of an inner layer 14 containing metal particles or other fragments 20 and an outer layer 16 having dimple 18;
- FIG. 3 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible star-shaped perimeter weighting system;
- FIG. 4 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible contoured-shaped perimeter weighting system;
- FIG. 5 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible pentagon-shaped perimeter weighting system
- FIG. 6 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible radiused pentagon-shaped perimeter weighting system
- FIG. 7 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible single stripe-shaped perimeter weighting system
- FIG. 8 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible double stripe-shaped perimeter weighting system
- FIG. 9 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible multi stripe-shaped perimeter weighting system
- FIG. 10 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible stripe and dimple-shaped perimeter weighting system
- FIG. 11 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible ring-shaped perimeter weighting system
- FIG. 12 is an elevational view of a preferred embodiment golf ball in accordance with the present invention utilizing a visible spiral-shaped perimeter weighting system.
- the present invention is directed to improved multi-layer golf ball compositions and the resulting regulation balls produced using those compositions.
- a smaller and lighter core is produced and metal particles, or other heavy weight filler materials, are included in the cover compositions.
- the particles are included in a relatively thick inner cover layer (or mantle) of a solid, three-piece multi-layered golf ball.
- the particles or other weighting material is disposed in an outer layer. Most preferably, the weighting material is viewable or otherwise visible along the ball's exterior. The size and weight of the core is reduced in order to produce an overall golf ball which meets, or is less than, the 1.62 ounce maximum weight limitation specified by the United States Golf Association.
- the multi-layer golf ball covers of the present invention include a first or inner layer or ply of a hard, high modulus material (i.e., flexural modulus of about 15,000, or greater psi (ASTM D-790) and a hardness of at least about 60 (more desirably 65 or more on the Shore D scale (ASTM D-2240)) such as a blend of one or more hard (high or low acid) ionomer resins.
- a second or outer layer or ply comprised of a comparatively softer, low modulus material i.e., flexural modulus of about 1 ,000 to
- the multi-layer golf balls of the invention can be of standard or enlarged size.
- the inner layer or ply of the golf ball of the invention includes a blend of high acid ionomer resins (greater than 16 weight percent acid) or a blend of high modulus low acid ionomers and has a Shore D hardness of 65 or greater.
- Various amounts of metallic particles or other heavy weight filler materials are included in the inner cover layer and the size and weight of the core is reduced in order to produce selective variations in the moment of inertia of the ball.
- the outer cover layer preferably comprises a blend of low modulus ionomer resins or is comprised of polyurethane and has a Shore D hardness of about 45 to 55 (i.e., Shore C hardness of about 65 to 75).
- multi-layer golf balls can be produced having inner and outer cover layers which exhibit improved C.O.R. values and have greater travel distance in comparison with balls made from a single cover layer.
- use of a softer outer layer adds to the desirable "feel" and a higher spin rate while maintaining respectable resiliency.
- the soft outer layer allows the cover to deform more during impact and increases the area of contact between the club face and the cover, thereby imparting additional spin on the ball.
- the soft cover provides a multi-layer ball with a balata-like feel and spin characteristics with improved distance and durability. It has now been determined that the travel distance of such multi-layer golf balls can be further improved without substantially sacrificing the feel and durability characteristics of the ball through the inclusion of metal particles or other heavy metal filler materials in the inner cover compositions.
- the metal particles or fragments increase the weight of the interior perimeter of a golf ball in comparison to the central core. Further, the core is also made smaller and lighter in order to conform with the weight requirements of the U.S.G.A.
- the moment of inertia of a golf ball (also known as rotational inertia) is the sum of the products formed by multiplying the mass (or sometimes the area) of each element of a figure by the square of its distance from a specified line such as the center of a golf ball.
- This property is directly related to the radius of gyration of a golf ball which is the square root of the ratio of the moment of inertia of a golf ball about a given axis to its mass. It has been found that the greater the moment of inertia (or the farther the radius of gyration is to the center of the ball) the lower the spin rate is of the ball.
- the present invention is directed, in part, to increasing the moment of inertia of a multi-layered golf ball by varying the weight arrangement of one or more of the cover, the inner layer, and the core components.
- the moment of inertia of a golf ball can be increased.
- Such a change can occur in a multi-layered golf ball, including a ball containing one or more cover layers, to enhance distance due to the production of less side spin and improved roll.
- the present invention is directed to an improved multi-layer cover which produces, upon molding each layer around a core (preferably a smaller and lighter solid core) to formulate a multi-layer cover, a golf ball exhibiting enhanced distance (i.e., improved resilience, less side spin, improved roll) without adversely affecting, and in many instances, improving the ball's feel (hardness/softness) and/or durability (i.e., cut resistance, fatigue resistance, etc.) characteristics.
- a core preferably a smaller and lighter solid core
- This preferred embodiment golf ball comprises a multi-layered cover 12 disposed over a core 10, and method for making same.
- the core 10 is a solid core, although a wound core having the desired characteristics can also be used.
- the multi-layered cover 12 comprises two layers: a first or inner layer or ply 14 and a second or outer layer or ply 16.
- the inner layer 14 is comprised of a hard, high modulus (flexular modulus of 15,000 to 150,000), low or high acid (i.e. greater than 16 weight percent acid) ionomer resin or ionomer blend.
- the inner layer is comprised of a blend of two or more high acid (i.e. at least 16 weight percent acid) ionomer resins neutralized to various extents by different metal cations.
- the inner cover layer may or may not include a metal stearate (e.g., zinc stearate) or other metal fatty acid salt. The purpose of the metal stearate or other metal fatty acid salt is to lower the cost of production without affecting the overall performance of the finished golf ball.
- the inner layer compositions include the high acid ionomers such as those recently developed by E. I. DuPont de Nemours & Company under the trademark “Surlyn®” and by Exxon Corporation under the trademark “Escor®” or trade name “lotek”, or blends thereof.
- Examples of compositions which may be used as the inner layer herein are set forth in detail in copending U. S. Serial No. 07/776,803 filed October 15, 1991 , and Serial No. 07/901 ,660 filed June 19, 1992, both incorporated herein by reference.
- the inner layer high acid ionomer compositions are not limited in any way to those compositions set forth in said copending applications.
- the high acid ionomer resins recently developed by Spalding & Evenflo Companies, Inc., the assignee of the present invention, and disclosed in U.S. Serial No. 07/901 ,680, filed June 19, 1992, incorporated herein by reference, may also be utilized to produce the inner layer of the multi-layer cover used in the present invention.
- the high acid ionomers which may be suitable for use in formulating the inner layer compositions of the subject invention are ionic copolymers which are the metal, i.e., sodium, zinc, magnesium, etc., salts of the reaction product of an olefin having from about 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from about 3 to 8 carbon atoms.
- the ionomeric resins are the metal, i.e., sodium, zinc, magnesium, etc., salts of the reaction product of an olefin having from about 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from about 3 to 8 carbon atoms.
- the ionomeric resins are the metal, i.e., sodium, zinc, magnesium, etc., salts of the reaction product of an olefin having from about 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from about 3 to 8 carbon atoms.
- copolymers of ethylene and either acrylic or methacrylic acid can also be included to produce a softer terpolymer.
- an additional comonomer such as an acrylate ester (i.e., iso- or n- butylacrylate, etc.) can also be included to produce a softer terpolymer.
- the carboxylic acid groups of the copolymer are partially neutralized (i.e., approximately 10-75%, preferably 30-70%) by the metal ions.
- Each of the high acid ionomer resins which may be included in the inner layer cover compositions of the invention contains greater than about 16% by weight of a carboxylic acid, preferably from about 17% to about 25% by weight of a carboxylic acid, more preferably from about 18% to about 21.5 % by weight of a carboxylic acid.
- the inner layer cover composition preferably includes a high acid ionomeric resin and the scope of the patent embraces all known high acid ionomeric resins falling within the perimeters set forth above, only a relatively limited number of these high acid ionomeric resins have recently become commercially available.
- the high acid ionomeric resins available from Exxon under the designation "Escor®” and or “lotek”, are somewhat similar to the high acid ionomeric resins available under the "Surlyn®” trademark. However, since the Escor®/lotek ionomeric resins are sodium or zinc salts of poly(ethylene-acrylic acid) and the “Surlyn®” resins are zinc, sodium, magnesium, etc. salts of poly(ethylene-methacrylic acid), distinct differences in properties exist.
- Examples of the high acid methacrylic acid based ionomers found suitable for use in accordance with this 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
- Surlyn® AD-8422 is currently commercially available from DuPont in a number of different grades (i.e., AD-8422-2, AD-8422-3, AD-8422-5, etc.) based upon differences in melt index. According to DuPont, Surlyn® AD-8422 offers the following general properties when compared to Surlyn®8920, the stiffest, hardest of all on the low acid grades (referred to as "hard” ionomers in U.S. Patent No. 4,884,814):
- Surlyn® 8920 In comparing Surlyn® 8920 to Surlyn® 8422-2 and Surlyn® 8422-3, it is noted that the high acid Surlyn® 8422-2 and 8422-3 ionomers have a higher tensile yield, lower elongation, slightly higher Shore D hardness and much higher flexural
- Surlyn® 8920 contains 15 weight percent methacrylic acid and is 59% neutralized with sodium.
- Surlyn® SEP-503-1 (zinc cation) and Surlyn® SEP-503-2 (magnesium cation) are high acid zinc and magnesium versions of the Surlyn® AD
- the Surlyn SEP-503-1 and SEP-503-2 ionomers can be defined as follows:
- Surlyn® 8162 is a zinc cation ionomer resin containing approximately 20% by weight (i.e. 18.5-21.5% weight) methacrylic acid copolymer that has been 30-70% neutralized. Surlyn® 8162 is currently commercially available from DuPont.
- Examples of the high acid acrylic acid based ionomers suitable for use in the present invention also include the Escor® or lotek high acid ethyiene acrylic acid ionomers produced by Exxon.
- Escor® or lotek 959 is a sodium ion neutralized ethylene-acrylic neutralized ethylene-acrylic acid copolymer.
- loteks 959 and 960 contain from about 19.0 to about 21.0% by weight acrylic acid with approximately 30 to about 70 percent of the acid groups neutralized with sodium and zinc ions, respectively. The physical properties of these
- lotek 1002 is a sodium ion neutralized high acid ionomer (i.e., 18% by weight acid) and lotek 1003 is a zinc ion neutralized high acid ionomer (i.e., 18% by weight acid).
- the properties of these ionomers are set forth below:
- high acid ionomer blends produce inner cover layer compositions exhibiting enhanced hardness and resilience due to synergies which occur during processing.
- the metal cation neutralized high acid ionomer resins recently produced can be blended to produce substantially harder inner cover layers for multi- layered golf balls having higher C.O.R.'s than those produced by the low acid ionomer inner cover compositions presently commercially available.
- the base copolymer is made up of greater than 16% by weight of an alpha, beta-unsaturated carboxylic acid and an alpha-olefin.
- a softening comonomer can be included in the copolymer.
- the alpha-olefin has from 2 to 10 carbon atoms and is preferably ethylene
- the unsaturated carboxylic acid is a carboxylic acid having from about 3 to 8 carbons. Examples of such acids include acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, with acrylic acid being preferred.
- the softening comonomer that can be optionally included in the invention may be selected from the group consisting of vinyl esters of aliphatic
- carboxylic acids wherein the acids have 2 to 10 carbon atoms
- vinyl ethers wherein the alkyl groups contains 1 to 10 carbon atoms
- 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.
- examples of a number of copolymers suitable for use to produce the high acid ionomers included in the present invention include, but are not limited to, high acid embodiments of an ethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer, an ethylene/itaconic acid copolymer, an ethylene/maleic acid copolymer, an ethylene/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 the preferred high acid base copolymers which fulfill the criteria set forth above are a series of ethylene-acrylic copolymers which are commercially available from The Dow Chemical Company, Midland, Michigan, under the "Primacor" designation. These high acid base copolymers exhibit
- this copolymer is the more preferred grade utilized in the invention.
- 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 lithium, calcium, zinc, sodium, potassium, nickel, magnesium, and manganese.
- 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, magnesium acetate.
- Sources of manganese include manganese acetate and manganese oxide.
- the new metal cation neutralized high acid ionomer resins are produced by reacting the high acid base copolymer with various amounts of the metal cation
- salts above the crystalline melting point of the copolymer such as at a temperature from about 200° F to about 500° F, preferably from about 250° F to about 350° F under high shear conditions at a pressure of from about 10 psi to 10,000 psi.
- Other well known blending techniques may also be used.
- the new metal cation neutralized high acid based ionomer resins utilized to produce the new metal cation neutralized high acid based ionomer resins is the quantity which provides a sufficient amount of the metal cations to neutralize the desired percentage of the carboxylic acid groups in the high acid copolymer.
- the extent of neutralization is generally from about 10% to about 90%.
- Control for Formulations 23-26 is 50/50 lotek 8000/7030,
- the new metal cation neutralized high acid ionomer resins exhibit enhanced hardness, modulus and resilience characteristics. These are properties that are particularly desirable in a number of thermoplastic fields, including the field of golf ball manufacturing.
- the new acrylic acid based high acid ionomers extend the range of hardness beyond that previously obtainable while maintaining the beneficial properties (i.e. durability, click, feel, etc.) of the softer low acid ionomer covered balls, such as balls produced utilizing the low acid ionomers disclosed in U.S. Patent Nos. 4,884,814 and 4,911 ,451.
- an inner cover layer of a multi-layered golf ball By using these high acid ionomer resins, harder, stiffer inner cover layers having higher C.O.R.s, and thus longer
- the low acid ionomers which may be suitable for use in formulating the inner layer compositions of the subject invention are ionic copolymers which are the metal, i.e., sodium, zinc, magnesium, etc., salts of the reaction product of an olefin having from about 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from about 3 to 8 carbon atoms.
- the ionomeric resins are copolymers of ethylene and either acrylic or methacrylic acid.
- an additional comonomer such as an acrylate ester (i.e., iso- or n- butylacrylate, etc.) can also be included to produce a softer terpolymer.
- the carboxylic acid groups of the copolymer are partially neutralized (i.e., approximately
- each of the low acid ionomer resins which may be included in the inner layer cover compositions of the invention contains 16% by weight or less of a carboxylic acid.
- the outer cover layer 16 of the preferred embodiment multi- layered cover of the present invention is comparatively softer than the inner layer. The softness provides for the enhanced feel and playability characteristics typically associated with balata or balata-blend balls.
- the outer layer or ply is comprised of a relatively soft, low modulus (about 1 ,000 psi to about 10,000 psi) and low acid (less than 16 weight percent acid) ionomer, ionomer blend or a non-ionomeric elastomer such as, but not limited to, a polyurethane, a polyester
- elastomer such as that marketed by DuPont under the trademark Hytrel®, a polyurethane sold by BASF under the designation Baytec® or a polyester amide such
- the outer layer is fairly thin (i.e. from about 0.010 to about 0.110 in thickness, more desirably 0.03
- the outer layer includes a blend of hard and soft (low acid) ionomer resins such as those described in U. S. Patent Nos. 4,884,814 and 5,120,791 , both incorporated herein by reference.
- a desirable material for use in molding the outer layer comprises a blend of a high modulus (hard), low acid, ionomer with a low modulus (soft), low acid, ionomer to form a base ionomer mixture.
- a high modulus ionomer herein is one which measures from about 15,000 to about 70,000 psi as measured in accordance with ASTM method D-790.
- the hardness may be defined as at least 50 on the Shore D scale as measured in accordance with ASTM method D-2240.
- a low modulus ionomer suitable for use in the outer layer blend has a flexural modulus measuring from about 1 ,000 to about 10,000 psi, with a hardness of about 20 to about 40 on the Shore D scale.
- the hard ionomer resins utilized to produce the outer cover layer composition hard/soft blends include ionic copolymers which are the sodium, zinc, magnesium or lithium salts of the reaction product of an olefin having from 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from 3 to 8 carbon atoms.
- the carboxylic acid groups of the copolymer may be totally or partially (i.e. approximately 15-75 percent) neutralized.
- the hard ionomeric resins are likely copolymers of ethylene and either acrylic and/or methacrylic acid, with copolymers of ethylene and acrylic acid being the
- Two or more types of hard ionomeric resins may be blended into the outer cover layer compositions in order to produce the desired properties of the resulting golf balls.
- the hard ionomeric resins introduced under the designation Escor® and sold under the designation "lotek” are somewhat similar to the hard ionomeric resins sold under the Surlyn® trademark.
- the "lotek” ionomeric resins are sodium or zinc salts of poly(ethylene-acrylic acid) and the Surlyn® resins are zinc or sodium salts of poly(ethylene-methacrylic acid) some distinct differences in properties exist.
- the hard "lotek” resins i.e., the acrylic acid based hard ionomer resins
- various blends of "lotek” and Surlyn® hard ionomeric resins, as well as other available ionomeric resins, may be utilized in the present invention in a similar manner.
- Examples of commercially available hard ionomeric resins which may be used in the present invention in formulating the inner and outer cover blends S O n c include the hard sodium ionic copolymer sold under the tradem m o ao i e — rk Surlyn®8940 and the hard zinc ionic copolymer sold under the trademark Surlyn®9910.
- Surlyn®8940 is a copolymer of ethylene with methacrylic acid and about 15 weight percent acid
- Surlyn®9910 is a copolymer of ethylene and methacrylic acid with about 15 weight percent acid which is about 58 percent neutralized with zinc ions.
- the average melt flow index of Surlyn®9910 is about 0.7.
- lotek tradename by the Exxon Corporation include lotek 4000, lotek 4010, lotek
- soft ionomers are used in formulating the hard/soft blends of the inner and outer cover compositions.
- These ionomers include acrylic acid based soft ionomers. They are generally characterized as comprising sodium or zinc salts of a terpolymer of an olefin having from about 2 to 8 carbon atoms, acrylic acid, and an unsaturated monomer of the acrylate ester class having from 1 to 21 carbon atoms.
- the soft ionomer is preferably a zinc based ionomer made from an acrylic acid base polymer in an unsaturated monomer of the acrylate ester class.
- the soft (low modulus) ionomers have a hardness from about 20 to about 40 as measured on the Shore D scale and a flexural modulus from about 1 ,000 to about 10,000, as measured in accordance with ASTM method D-790.
- ethylene-acrylic acid based soft ionomer resins developed by the Exxon Corporation under the designation "lotek 7520" may be combined with known hard ionomers such as those indicated above to produce the inner and outer cover layers.
- the combination produces higher C.O.R.s at equal or softer hardness, higher melt flow (which corresponds to improved, more efficient molding, i.e., fewer rejects) as well as significant cost savings versus the inner and outer layers of multi-layer balls produced by other known hard-soft
- Exxon's experimental product data sheet lists the following physical properties of the ethylene acrylic acid zinc ionomer developed by Exxon: TABLE 5
- test data collected by the inventor indicates that lotek 7520 resins have Shore D hardnesses of about 32 to 36 (per ASTM D-2240), melt flow indexes of 3 ⁇ 0.5 g/10 min (at 190°C. per ASTM D-1288), and a flexural modulus of about 2500-3500 psi (per ASTM D-790). Furthermore, testing by an independent testing laboratory by pyrolysis mass spectrometry indicates that lotek 7520 resins are
- lotek 7510 has the advantages (i.e. improved flow, higher C.O.R. values at equal hardness, increased clarity, etc.) produced by the lotek 7520 resin when compared to the methacrylic acid base soft ionomers known in the art (such as the Surlyn 8625 and the Surlyn 8629 combinations disclosed in U.S. Patent No.
- lotek 7510 when compared to lotek 7520, produces slightly higher C.O.R. valves at equal softness/hardness due to the lotek 7510's higher hardness and neutralization. Similarly, lotek 7510 produces better release properties (from the mold cavities) due to its slightly higher stiffness and lower flow rate than lotek 7520. This is important in production where the soft covered balls tend to have lower yields caused by sticking in the molds and subsequent punched pin marks from the knockouts. According to Exxon, lotek 7510 is of similar chemical composition as lotek 7520 (i.e. a zinc salt of a terpolymer of ethylene, acrylic acid, and methyl acrylate) but is more highly neutralized. Based upon FTIR analysis, lotek 7520 is estimated to be about 30-40 wt.-% neutralized and lotek 7510 is estimated to be about 40-60 wt.-% neutralized. The typical properties of lotek 7510 in comparison of
- IOTEK 7520 IOTEK 7510 Ml, g/10 min 2.0 0.8 IOTEK 7520 IOTEK 7510
- the outer cover layer formulation may also comprise a soft, low modulus non-ionomeric thermoplastic elastomer
- estane® X-4517 has the following properties:
- thermoplastic polyurethanes such as: Texin thermoplastic polyurethanes from Mobay Chemical Co. and the Pellethane thermoplastic polyurethanes from Dow Chemical Co.; lonomer/rubber blends such as those in Spalding U.S. Patents 4,986,545; 5,098,105 and 5,187,013; and, Hytrel polyester elastomers from DuPont and pebax polyesteramides from Elf Atochem S.A.
- Baytec® (such as Baytec® RE 832), relates to a
- Component A is a modified diphenylmethane di isocyanate ( DI) prepolymer and component B is a polyether polyol blend.
- DI diphenylmethane di isocyanate
- the weight of the cover layers is increased in the present invention by making the cover layers thicker and through the inclusion of about 1 to about 100 parts per 100 parts resin of metal particles and other heavy weight filler materials.
- the term “heavy weight filler materials” is defined as any material having a specific gravity greater than 1.0. This term “heavy weight filler materials” is used interchangeably with the term “weighting material” as also used herein.
- the particles (or flakes, fragments, fibers, etc.) of heavy filler are added to the inner cover layer as opposed to the outer cover, in order to increase the
- weighting materials or heavy filler in the outer cover. This is particularly the case when producing a golf ball having a visible weighting system as described herein.
- the inner layer is filled with one or more of a variety of reinforcing or non-reinforcing heavy weight fillers or fibers such as metal (or metal alloy) powders, carbonaceous materials (i.e., graphite, carbon black, cotton flock, leather fiber, etc.), glass, Kevlar® fibers (trademarked material of Du Pont for an aromatic polyamide fiber of high tensile strength and greater resistance of elongation than steel), etc.
- These heavy weight filler materials range in size from about 10 mesh to about 325 mesh, preferably about 20 mesh to about 325 mesh and most preferably about 100 mesh to about 325 mesh.
- metal (or metal alloy) powders include but are not limited to, bismuth powder, boron powder, brass powder, bronze powder, cobalt powder, copper powder, inconel metal powder, iron metal powder, molybdenum powder, nickel powder, stainless steel powder, titanium metal powder, zirconium oxide powder, aluminum flakes, and aluminum tadpoles. It will be understood that the foregoing materials may be in other forms besides powders.
- the amount and type of heavy weight filler material utilized is dependent upon the overall characteristics of the low spinning multi-layered golf ball desired. Generally, lesser amounts of high specific gravity materials are necessary to produce an increase in the moment of inertia in comparison to low specific gravity materials. Furthermore, handling and processing conditions can also affect the type of heavy weight filler material incorporated into cover layers. In this regard, Applicant has found that the inclusion of approximately 10 phr brass powder into an inner cover layer produces the desired increase in the moment of inertia without involving substantial processing changes. Thus, 10 phr brass powder is generally, the most preferred heavy filler material at the time of this writing.
- cover compositions both inner and outer cover layer
- dyes for example,
- cover compositions of the present invention may also contain softening agents, such as plasticizers, processing aids, etc., as long as
- the desired properties produced by the golf ball covers are not impaired.
- the present invention also provides particular patterns of weighting materials disposed proximate or generally within the outer periphery of a golf ball.
- the use of a weighted perimeter has been found to increase a ball's moment of inertia and reduce the overall spin rate.
- golf balls with weighted perimeters utilize a visible pattern of weighting material disposed along a portion of the outer periphery of the ball.
- characteristics and properties of a weighted perimeter ball in accordance with the present invention are affected, or at least influenced by, the shape or configuration of the pattern of weighting material along the ball's outer periphery.
- the shape of such pattern can also serve as a unique identifier of the ball.
- a consumer may readily determine whether a particular golf ball comprises a weighting system.
- FIG. 3 illustrates a preferred embodiment golf ball 30 in accordance with the present invention utilizing a visible star-shaped perimeter
- weighting system 32 This system comprises a first pattern preferably centered about a dimple, and having a plurality, namely five (5), radially extending arms extending outward from the center of the pattern or dimple. The sides of each radially extending arm intersect with the sides of adjacent radially extending arms. The distal end of each radially extending arm is preferably rounded.
- the golf ball 30 further comprises a second visible star-shaped perimeter weighting system pattern located
- This second pattern is most preferably directly opposite from the first pattern and is of equal size and mass as the first pattern.
- FIG. 4 is an elevational view of a preferred embodiment golf ball 40 in accordance with the present invention utilizing a contoured-shaped perimeter weighting system 42.
- This system comprises patterns similar to the star-shaped pattern depicted in FIG. 3 except that generally continuous arcuate sections extend between and connect the sides of adjacent radially extending arms.
- the golf ball 40 further comprises a second visible contoured-shaped perimeter weighting system pattern located on the opposite side of the ball 40. This second pattern is most preferably directly opposite from the first pattern and is of equal size and mass as the first pattern.
- FIG. 5 illustrates a preferred embodiment golf ball 50 in accordance with the present invention utilizing a pentagon-shaped perimeter weighting system 52. It can be seen that the pentagon shape is symmetrically disposed about a center dimple and five (5) adjacent or surrounding dimples. Additionally, each side of the pentagon is slightly curved inward so as to not extend over a neighboring dimple.
- the golf ball 50 further comprises a second visible pentagon-shaped perimeter
- the weighting system pattern located on the opposite side of the ball 50.
- the second pattern is most preferably directly opposite from the first pattern and is of equal size
- FIG. 6 illustrates a preferred embodiment golf ball 60 in accordance with the present invention utilizing a visible radiused pentagon-shaped perimeter weighting
- This pattern is also symmetrically disposed over a center dimple and the five (5) perimeter dimples, like the pentagon pattern depicted in FIG. 5. This pattern
- the golf ball 60 further comprises a second visible radiused pentagon-shaped perimeter weighting
- FIG. 7 is an elevational view of a preferred embodiment golf ball 70 in accordance with the present invention utilizing a visible single stripe perimeter weighting system 72. It can be seen in FIG. 7 that the stripe is approximately slightly larger in width than the diameter of a typical dimple on the golf ball 70. The stripe preferably extends around the circumference of the ball 70.
- FIG. 8 illustrates a preferred embodiment golf ball 80 in accordance with the present invention utilizing a double striped perimeter weighting system 82.
- each stripe preferably intersects one another at right angles, and that the width of each stripe is approximately only slightly greater than the diameter of a typical dimple on the ball 80.
- Each stripe preferably extends around the circumference of the ball 80. It is also preferred that the stripes are equal in width, or approximately so.
- FIG. 9 is an elevational view of a preferred embodiment golf ball 90 in
- the multi stripe perimeter weighting system 92 comprises preferably four (4) stripes, intersecting one another at a common point of intersection. Again, the width of each stripe is preferably approximately slightly
- FIG. 10 illustrates a preferred embodiment golf ball 100 in accordance with the present invention utilizing a visible stripe and dimple perimeter weighting system.
- the system comprises a plurality of stripes 104 and a plurality of dimples 102. Each of the stripes preferably extends around the circumference of the ball 100.
- the system comprises two (2) intersecting stripes 104, disposed at right angles to one another, and a total of eight (8) dimples 102 as shown in FIG. 10. It will be understood that the other four (4) weighted dimples 102 are located on the other side of the ball 100.
- the stripes preferably are of equal width.
- FIG. 11 illustrates a preferred embodiment golf ball 110 in accordance with the present invention utilizing a ring-shaped perimeter weighting system as shown in FIG. 11.
- the system comprises a plurality of rings 114 and 116 and a center weighted dimple or spot 118.
- the rings 114 and 116 are concentrically arranged about the center spot 118.
- Two (2) identical concentrically arranged rings are located on the other side of the ball 110. Most preferably, these rings are directly opposite from the rings 114 and 116, and are of equivalent size and mass as the rings 114 and 116.
- FIG. 12 is an elevational view of a preferred embodiment golf ball 120 in accordance with the present invention utilizing a first spiral-shaped perimeter
- weighting system 122 It will be understood that an identical second spiral-shaped pattern is located on the other side of the ball 120. Most preferably, the second spiral pattern is of equivalent size and mass as the first pattern and is directly opposite from the first pattern.
- a hard, relatively heavy, inner cover layer is molded (by injection molding or by compression molding) about a relatively light core (preferably a lighter and smaller solid core).
- a comparatively softer outer cover layer is molded over the inner cover layer.
- the core (preferably a solid core) is about 1.28 inches to 1.570 inches in diameter, preferably about 1.37 to about 1.54 inches, and most preferably 1.42 inches.
- the cores weigh about 18 to 39 grams, desirably 25 to 30, and most preferably 29.7-29.8 grams.
- the solid cores are typically compression molded from a slug of uncured or lightly cured elastomer composition comprising a high cis content polybutadiene and a metal salt of an ⁇ , ⁇ , ethylenically unsaturated carboxylic acid such as zinc mono or diacrylate or methacrylate.
- the manufacturer may include fillers such as small amounts of a metal oxide such as zinc oxide.
- lesser amounts of metal oxide can be included in order to lighten the core weight so that the finished ball more closely approaches the U.S.G.A. upper weight limit of 1.620 ounces.
- core composition including compatible rubbers or ionomers, and low molecular weight fatty acids such as stearic acid.
- Free radical initiators such as peroxides are admixed with the core composition so that on the application of heat and pressure, a complex curing cross-linking reaction takes place.
- cores disclosed in U.S. Patent Nos. 5,645,597; 5,480,155; 5,387,637; 5,150,906; 5,588,924; 5,507,493; 5,503,397; 5,482,286; 5,018,740; 4,852,884; 4,844,471 ; 4,838,556; 4,726,590; and 4,650,193; all of which are hereby incorporated by reference, may be utilized in whole or in part.
- the core compositions of the invention may be based on polybutadiene, and mixtures of polybutadiene with other elastomers. It is preferred that the base elastomer have a relatively high molecular weight.
- the broad range for the molecular weight of suitable base elastomers is from about 50,000 to about 500,000. A more preferred range for the molecular weight of the base elastomer is from about 100,000 to about 500,000.
- cis-polybutadiene is preferably employed, or a blend of cis-polybutadiene with other elastomers may
- cis-polybutadiene having a weight-average molecular weight of from about 100,000 to about 500,000 is employed.
- the high cis-polybutadiene manufactured and sold by Shell Chemical Co., Houston, Texas, under the tradename Cariflex BR-1220, the high cis- polybutadiene sold by Bayer Corp. under the designation Taktene 220, and the polyisoprene available from Muehlstein, H & Co., Greenwich, Connecticut under the designation "SKI 35" are particularly well suited.
- the unsaturated carboxylic acid component of the core composition is the reaction product of the selected carboxylic acid or acids and an oxide or carbonate of a metal such as zinc, magnesium, barium, calcium, lithium, sodium, potassium, cadmium, lead, tin, and the like.
- a metal such as zinc, magnesium, barium, calcium, lithium, sodium, potassium, cadmium, lead, tin, and the like.
- the oxides of polyvalent metals such as zinc, magnesium and cadmium are used, and most preferably, the oxide is zinc oxide.
- Exemplary of the unsaturated carboxylic acids which find utility in the present core compositions are acrylic acid, methacrylic acid, itaconic acid, crotonic acid, sorbic acid, and the like, and mixtures thereof.
- the acid component is either acrylic or methacrylic acid.
- the carboxylic acid salt such as zinc diacrylate
- the unsaturated carboxylic acids and metal salts thereof are generally soluble in the elastomeric base, or are readily dispersible.
- the free radical initiator included in the core composition is any known polymerization initiator (a co-crossiinking agent) which decomposes during the cure cycle.
- the term "free radical initiator” as used herein refers to a chemical which,
- Suitable initiators include peroxides, persulfates, azo compounds and hydrazides. Peroxides which are readily commercially available are conveniently used in the present invention, generally in amounts of from about 0.1 to about 10.0 and preferably in amounts of from about 0.3 to about 3.0 parts by weight per each 100 parts of elastomer.
- Suitable peroxides for the purposes of the present invention are dicumyl peroxide, n-butyl 4,4'-bis (butylperoxy) valerate, 1 ,1-bis(t- butylperoxy)-3,3,5-trimethyl cyclohexane, di-t-butyl peroxide and 2,5-di-(t-butylperoxy)- 2,5 dimethyl hexane and the like, as well as mixtures thereof. It will be understood that the total amount of initiators used will vary depending on the specific end product desired and the particular initiators employed.
- Luperco 230 or 231 XL sold by Atochem, Lucidol Division, Buffalo, N.Y., and Trigonox 17/40 or 29/40 sold by Akzo Chemie America, Chicago, Illinois.
- Luperco 230 XL and Trigonox 17/40 are comprised of n-butyl 4,4-bis (butylperoxy) valerate; and, Luperco 231 XL and Trigonox 29/40 are comprised of 1 ,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane.
- the one hour half life of Luperco 231 XL is about 112°C
- the one hour half life of Trigonox 29/40 is about 129 °C.
- the core compositions of the present invention may additionally contain any other suitable and compatible modifying ingredients including, but not limited to,
- Papi 94 a polymeric diisocyanate, commonly available from Dow Chemical
- polypropylene powder resin can be added to core composition without an increase in weight of the molded core upon curing, the
- polypropylene powder allows for the addition of higher specific gravity fillers (if desired), such as mineral fillers. Since the crosslinking agents utilized in the polybutadiene core compositions are expensive and/or the higher specific gravity fillers are relatively inexpensive, the addition of the polypropylene powder resin substantially lowers the cost of the golf ball cores while maintaining, or lowering, weight and compression.
- higher specific gravity fillers such as mineral fillers. Since the crosslinking agents utilized in the polybutadiene core compositions are expensive and/or the higher specific gravity fillers are relatively inexpensive, the addition of the polypropylene powder resin substantially lowers the cost of the golf ball cores while maintaining, or lowering, weight and compression.
- the polypropylene (C 3 H ⁇ powder suitable for use in the present invention has a specific gravity of about 0.90 g/cm 3 , a melt flow rate of about 4 to about 12 and a particle size distribution of greater than 99% through a 20 mesh screen.
- polypropylene powder resins include those sold by the Amoco Chemical Co., Chicago, Illinois, under the designations "6400 P", "7000 P” and "7200 P".
- polypropylene powder per each 100 parts of elastomer are included in the present invention.
- Various activators may also be included in the compositions of the present invention.
- zinc oxide and/or magnesium oxide are activators for the polybutadiene.
- the activator can range from about 2 to about 50 parts by
- the weight per 100 parts by weight of the rubbers (phr) component The amount of activation utilized can be reduced in order to lighten the weight of the core.
- reinforcement agents may be added to the composition of the present invention.
- the specific gravity of polypropylene powder is very low, and when compounded, the polypropylene powder produces a lighter molded core. Further, when a lesser amount of activation is used, the core is also lighter. As a result, if necessary, higher gravity fillers may be added to the core composition so long as the specific core weight limitations are met. The amount of
- additional filler included in the core composition is primarily dictated by weight restrictions and preferably is included in amounts of from about 0 to about 100 parts by weight per 100 parts rubber.
- Exemplary fillers include mineral fillers such as limestone, silica, mica, barytes, calcium carbonate, or clays.
- Limestone is ground calcium/magnesium carbonate and is used because it is an inexpensive, heavy filler.
- ground flash filler may be incorporated and is preferably 20 mesh ground up center stock from the excess flash from compression molding. It lowers the cost and may increase the hardness of the ball.
- Fatty acids or metallic salts of fatty acids may also be included in the compositions, functioning to improve moldabil ' rty and processing.
- free fatty acids having from about 10 to about 40 carbon atoms, and preferably having from
- fatty acids stearic acid and linoleic acids, as well as mixtures thereof.
- suitable fatty acids are stearic acid and linoleic acids, as well as mixtures thereof.
- stearic acid and linoleic acids as well as mixtures thereof.
- metallic salts of fatty acids include zinc stearate.
- the fatty acid component is present in amounts of from about 1 to about 25, preferably in amounts from about 2 to about 15 parts by weight based on 100 parts rubber (elastomer).
- Diisocyanates may also be optionally included in the core compositions when utilized, the diisocyanates are included in amounts of from about 0.2 to about
- diisocyanates 4,4'-diphenylmethane diisocyanate and other polyfunctional isocyanates know to the art.
- dialkyl tin difatty acids set forth in U.S. Patent No. 4,844,471 may also be incorporated into the polybutadiene compositions of the present invention.
- the specific types and amounts of such additives are set forth in the above identified patents, which are incorporated herein by reference.
- the core compositions of the invention are generally comprised of 100 parts by weight of a base elastomer (or rubber) selected from polybutadiene and mixtures of polybutadiene with other elastomers, 10 to 40 parts by weight of at least one metallic salt of an unsaturated carboxylic acid, and 1 to 10 parts by weight of a free radical initiator.
- a base elastomer or rubber selected from polybutadiene and mixtures of polybutadiene with other elastomers
- 10 to 40 parts by weight of at least one metallic salt of an unsaturated carboxylic acid 10 to 40 parts by weight of at least one metallic salt of an unsaturated carboxylic acid
- 1 to 10 parts by weight of a free radical initiator 1 to 10 parts by weight of a free radical initiator.
- additional suitable and compatible modifying agents such as particulate polypropylene resin, fatty acids, and secondary additives such as Pecan shell flour, ground flash (i.e. grindings from previously manufactured cores of substantially identical construction), barium sulfate, zinc oxide, etc. may be added to
- the core compositions to adjust the weight of the ball as necessary in order to have the finished molded ball (core, cover and coatings) to closely approach the U.S.G.A. weight limit of 1.620 ounces.
- the ingredients may be intimately mixed using, for example, two roll mills or a Banbury®
- the elastomer, polypropylene powder resin (if desired), fillers, zinc salt, metal oxide, fatty acid, and the metallic dithiocarbamate (if desired), surfactant (if desired), and tin difatty acid (if desired), are blended for about 7 minutes in an internal mixer such as a Banbury® mixer. As a result of shear during mixing, the temperature rises to about 200°F. The initiator and diisocyanate are then added and the mixing continued until the temperature reaches about 220° F whereupon the batch is discharged onto a two roll mill, mixed for about one minute and sheeted out.
- the sheet is rolled into a "pig” and then placed in a Barwell preformer and slugs are produced.
- the slugs are then subjected to compression molding at about 320°F for about 14 minutes.
- the molded cores are cooled, the cooling effected at room temperature for about 4 hours or in cold water for about one hour.
- the molded cores are subjected to a centerless grinding operation whereby a thin layer of the molded core is removed to produce a round core having a diameter of 1.28 to 1.570 inches (preferably about 1.37 to about 1.54 inches and most preferably, 1.42 inches).
- the cores are used in the as-molded state with
- the mixing is desirably conducted in such a manner that the composition does not reach incipient polymerization temperatures during the blending of the various components.
- the curable component of the composition will be cured by heating the composition at elevated temperatures on the order of from about 275°F to about 350°F, preferably and usually from about 290°F to about 325°F, with molding of the composition effected simultaneously with the curing thereof.
- composition can be formed into a core structure by any one of a variety of molding techniques, e.g. injection, compression, or transfer molding.
- molding techniques e.g. injection, compression, or transfer molding.
- the time required for heating will normally be short, generally from about 10 to about 20 minutes, depending upon the particular curing agent used.
- Those of ordinary skill in the art relating to free radical curing agents for polymers are conversant with adjustments of cure times and temperatures required to effect optimum results with any specific free radical agent.
- the core is removed from the mold and the surface thereof, preferably treated to facilitate adhesion thereof to the covering materials.
- Surface treatment can be effected by any of the several techniques known in the art, such as corona discharge, ozone treatment, sand blasting, and the like.
- surface treatment is effected by grinding with an abrasive wheel.
- the relatively thick inner cover layer which is molded over the core is about 0.200 inches to about 0.055 inches in thickness, and preferably about 0.075 inches thick.
- the outer cover layer is about 0.010 inches to about 0.110 inches in thickness, and preferably 0.055 inches thick. A preferred range for the overall
- thickness of these layers is from about 0.050 inches to about 0.300 inches, more preferably from about 0.075 inches to about 0.250 inches, and most preferably from
- each layer may be as thin as about 0.010 inches and as thick as about 0.200 inches where one layer is weighted, or contains weighting material.
- the core, the inner cover layer and the outer cover layer combine to form a ball having a diameter of 1.680 inches or more, the minimum diameter permitted by the rules of the United States Golf Association and weighing no more than 1.620 ounces.
- the various cover composition layers of the present invention may be produced according to conventional melt blending procedures.
- the outer cover layer when a blend of hard and soft, low acid ionomer resins are utilized, the hard ionomer resins are blended with the soft ionomeric resins and with a masterbatch containing the desired additives in a Banbury® mixer, two-roll mill, or extruder prior to molding. The blended composition is then formed into slabs and maintained in such a state until molding is desired.
- a simple dry blend of the pelletized or granulated resins and color masterbatch may be prepared and fed directly into the injection molding machine where homogenization occurs in the mixing section of the barrel prior to injection into the mold. If necessary, further additives, may be added and uniformly mixed before initiation of the molding process.
- a similar process is utilized to formulate the ionomer resin compositions used to produce the inner cover layer. The metal particles are added and mixed prior to initiation of molding.
- the desired pattern of weighting material is molded along the outer periphery of the golf ball as a radially extending portion of the inner cover or mantle layer. That is, the pattern is molded with the mantle layer such that the pattern extends radially outward to the final radius of the ball, or substantially so, and
- the non-weighted white cover is subsequently molded about the pattern of weighting material.
- plug manufacturing technique could be utilized.
- plugs of the desired pattern of weighting material are incorporated into the outer periphery of the ball to form the visible weighting system.
- Yet another preferred technique for forming a perimeter weighting pattern along the outer periphery of a golf ball is to incorporate the weighting material into the inner layer or mantle of the ball and deposit or otherwise dispose one or more layers of a transparent or semi-transparent material over the pattern of weighting material disposed in the ball.
- a perimeter weighting system in a golf ball by utilizing a single layer, such as a cover layer, that comprises discontinuous areas of distinct materials, i.e., materials having different densities.
- the golf balls of the present invention can be produced by molding processes currently well known in the golf ball art. Specifically, the golf balls can be produced by injection molding or compression molding the relatively thick inner cover layer about smaller and lighter wound or solid molded cores to produce an intermediate golf ball having a diameter of about 1.38 to 1.68 inches, more preferably about 1.50 to 1.67 inches, and most preferably about 1.57 inches.
- the outer layer (preferably .010 inches to .110 inches in thickness) is subsequently molded over the inner layer to produce a golf ball having a diameter of 1.680 inches or more.
- solid cores or wound cores can be used in the present invention so long as the size weight and other physical perimeters are met, as a result of their lower cost and superior performance, solid molded cores are preferred over wound cores.
- the inner cover composition is formed via injection at about 380°F to about 450°F into smooth surfaced hemispherical shells which are then positioned around the core in a mold having the desired inner cover thickness and subjected to compression molding at 200°F to 300°F for about 2 to 10 minutes, followed by cooling at 50°F to 70°F for about 2 to 7 minutes to fuse the shells together to form a unitary intermediate ball.
- the intermediate balls may be produced by injection molding wherein the inner cover layer is injected directly around the core placed at the center of an intermediate ball mold for a period
- the finished golf ball of the present invention possesses the following general features:
- Core preferably a solid core
- Thickness of inner cover layer from about .010 to about .200 inches, preferably .055 to .150, most preferably 0.075 inches.
- Coefficient of Restitution from about .701 to about .820, preferably .750 to .810, most preferably .790 to .800.
- Shore C/D Hardness from about 87/60 to about >100/100, preferably 92/65 to > 100/85, most preferably 97/70.
- Weight from about 45.0 to 45.93 grams, preferably, 45.3 to 45.7 grams, most preferably 45.5 grams.
- Size (diameter), from about 1.680 to 1.720 inches, preferably,
- Cover Thickness (outer cover layer), from about .010 to about .175 inches, preferably .010 to .110, most preferably 0.055 inches.
- Compression from about 59 to about 160, preferably 80 to 96, most preferably 76-85.
- Coefficient of Restitution from about .701 to about .825, preferably .750 to .810, most preferably .785 to .790.
- Shore C/D Hardness from about 35/20 to about 92/65, preferably 40/25 to 90/60, most preferably 87/56.
- Moment of Inertia from about .390 to about .480, preferably .430 to .460, most preferably 0.445.
- Cariflex 1220 70 70 High Cis-polybutadiene
- Eastobrite OB-1 2 0.025 phr 0.025 phr
- the cores of the new balls are substantially smaller (1.42" versus
- the balls of the present invention produce lower spin and greater distance in comparison with the existing multi-layer golf balls.
- the difference in physical properties is shown in the table which follows:
- the resulting golf balls of the present invention (i.e., the "Strata Advance” balls) provide for desirable coefficient of restitution, compression, and durability properties while at the same time offering the feel characteristics associated with soft balata and balata-like covers of the prior art. In addition, the balls spin less and travel farther.
- a number of multi-layer golf balls (solid cores plus inner and outer cover layers) containing metallic particles and/or heavy weight filler additives in the inner
- the cores of the golf balls used in this Example ranged in diameter from 1.42 to 1.47 inches, weighed 26.1 to 32.5 grams, and had a specific gravity of 1.073 to 1.216. These cores were comprised of high cis-polybutadiene, zinc diacrylate, zinc oxide, zinc stearate, peroxide, etc. and were produced according to molding procedures set forth above. Representative formulations of the molded cores (1.42 inches and 1.47 inches) are set forth below in Sample Nos. 20-23 for 1.42 inch cores and Sample No. 23 for 1.47 inch cores.
- the inner thermoplastic cover layer (or mantle layer) used in this E ⁇ xample comprised of a 50%/50% blend of ethylene acrylic acid ionomer resins, i.e., lotek 1002 and lotek 1003. These ionomers exhibit the characteristics generally defined above.
- Riehle compression is a measurement of the deformation of a golf ball in thousandths of inches under a fixed static load of 200 pounds (a Riehle compression of 47 corresponds to a deflection under load of 0.047 inches).
- PGA compression is determined by a force applied to a spring
- Coefficient of restitution was measured by firing the resulting golf ball in an air cannon at a velocity of 125 feet per second against a steel plate which is positioned 12 feet from the muzzle of the cannon. The rebound velocity was then measured. The rebound velocity was divided by the forward velocity to give the coefficient of restitution. The following properties were noted:
- Sample Nos. 20-23 the level of heavy filler present in the inner cover layer is related to the increase in the moment of inertia of the balls.
- Sample No. 20 has 4 parts of tungsten filler compared to the 26.2 and 51 parts found in Sample Nos. 21 and 22, respectively, and the moment of inertia increased accordingly with the filler level.
- a number of golf balls were produced in order to evaluate the effectiveness of transferring the weight of a golf ball from the central core to the inner cover layer.
- four (4) different core formulations i.e., Core Formulations A-D
- Core Formulations C and D were produced wherein the weight in two of the cores, i.e., Core Formulations C and D, was reduced.
- Core Formulation E the core currently utilized in Spalding's two-piece Top-Flite Z-Balata 100 production
- the weight and/or specific gravity of the core can be decreased (i.e., compare Core Formulations C and D with Core Formulations B and
- Two multi-layer golf balls having relatively thick (about 0.075") inner cover layers (or mantles) containing about ten percent (10%) of powdered brass (Zinc Corp. of America, Monica, PA) were prepared and the moment of inertia property of the balls was evaluated.
- Different solid polybutadiene cores of the same size (i.e., 1.42"), weight (29.7g) and specific gravity (i.e., 1.2) were utilized but the cores different with respect to compression (Riehle) and C.O.R.
- Blend Modulus 264 MPa 264 MPa
- the above multi-layer balls of the present invention having a thick inner cover layer (or mantle) comprising a blend of high acid ionomer resins and about 10% of a heavy weight filler material over a soft cross-linked polybutadiene core with a cover layer of soft thermoplastic material, exhibited an increased moment of inertia.
- the effects produced by increasing the moment of inertia and increasing the inner cover layer thickness of a multi-layer golf ball was observed by comparing a multi-layer golf ball produced by the present invention (i.e., "Strata Distance 90-EX") with a commercially available multi-layer golf ball sold by Spalding under the designation "Strata Tour 90".
- the "Strata Distance 90-EX” ball contains a thick high acid ionomer resin inner cover layer over a soft cross-linked polybutadiene core with an outer cover layer of soft ionomer resin. Further, the mantle or inner cover layer
- a stripe is placed around a great circle of the ball to create a visual equator which is used to measure the spin rate in the photographs.
- the balls are hit a minimum of three times each ball, so that for a given type, there will be nine hits to yield information on the launch angle, ball speed and spin rate. Further, the balls are hit in
- a strobe light is used to produce up to 10 images of the ball's
- the strobe is controlled by a computer based counter timer board running with a clock rate of 100,000 Hertz. This means that the strobed images of the ball are known in time to within 1/100,000 second.
- each picture in the field of view, is a reference system giving a level line reference and a length reference.
- Each picture is digitized
- a #9 iron with the following specifications is used for the test: 1984 Tour Edition Custom Crafted 9 Iron with V grooves, 140 pitch.
- the shaft is a Dynamic Gold R3.
- the club has a D2.0 swing weight, length of 35 7/8 inches, lie of 62 degrees, with face angle at 0, the loft is 47 1 / degrees.
- the club's overall weight is 453 grams.
- the grip is an Eaton Green Victory M60 core grip. The club is held in the "wrist" mechanism of the Miya Epoch
- the machine is manufactured by Miya Epoch of America, Inc., 2468 W. Torrance Blvd., Torrance, CA 90501. A line is drawn along the base of the machine, extending out along the direction
- the ball impacts a stopping curtain of Kevlar 8-10 feet downrange, and a square shot is one in which the direction of the ball
- test #92461 Average ball speed of all types together should be around 100-125 feet per second, and launch angle should be around 26 to 34 degrees.
- results indicate that the increase produced in the moment of inertia by enlarging the thickness and weight of the inner cover layer while reducing the weight and size of the core resulted in a multi-layer ball (i.e., the Strata Distance 90- EX) having less spin and farther distance than the existing multi-layer golf ball (i.e., Strata Tour 90). Furthermore, the results indicate that the ball of the present invention traveled farther than other commercially available high spinning golf balls.
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9922126A GB2337936B (en) | 1997-03-28 | 1998-03-27 | Perimeter weighted golf ball with visible weighting |
AU67843/98A AU739478B2 (en) | 1997-03-28 | 1998-03-27 | Perimeter weighted golf ball with visible weighting |
JP54187598A JP4073043B2 (en) | 1997-03-28 | 1998-03-27 | Peripheral weighted golf ball with visible weight |
CA002291053A CA2291053A1 (en) | 1997-03-28 | 1998-03-27 | Perimeter weighted golf ball with visible weighting |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US4242897P | 1997-03-28 | 1997-03-28 | |
US60/042,428 | 1997-03-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998043711A1 true WO1998043711A1 (en) | 1998-10-08 |
Family
ID=21921885
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/006163 WO1998043711A1 (en) | 1997-03-28 | 1998-03-27 | Perimeter weighted golf ball with visible weighting |
Country Status (3)
Country | Link |
---|---|
CA (1) | CA2291053A1 (en) |
GB (1) | GB2337936B (en) |
WO (1) | WO1998043711A1 (en) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002536136A (en) * | 1999-02-11 | 2002-10-29 | スポルディング、スポーツ、ワールドワイド、インク | Low-spin golf ball using extra weight |
GB2371758B (en) * | 1999-11-01 | 2003-12-03 | Spalding Sports Worldwide Inc | Perimeter weighted golf ball with visible weighting |
JP2005523134A (en) * | 2002-04-25 | 2005-08-04 | ファイヤーストーン ポリマーズ エルエルシー | Rubber composition for producing golf ball components |
WO2013012796A3 (en) * | 2011-07-15 | 2013-05-10 | Nike International Ltd. | Golf ball having an aerodynamic coating including micro surface roughness |
US8529375B2 (en) | 2010-01-20 | 2013-09-10 | Nike, Inc. | Golf ball having increased moment of inertia |
US8556750B2 (en) | 2010-01-20 | 2013-10-15 | Nike, Inc. | Golf ball with cover having varying hardness |
US8568250B2 (en) | 2010-07-07 | 2013-10-29 | Nike, Inc. | Golf ball with cover having zones of hardness |
US9033825B2 (en) | 2009-09-30 | 2015-05-19 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9033826B2 (en) | 2009-09-30 | 2015-05-19 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9108085B2 (en) | 2009-09-30 | 2015-08-18 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9186557B2 (en) | 2009-09-30 | 2015-11-17 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9186558B2 (en) | 2009-09-30 | 2015-11-17 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9199133B2 (en) | 2009-09-30 | 2015-12-01 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9259623B2 (en) | 2009-09-30 | 2016-02-16 | Nike International, Ltd. | Golf ball having an aerodynamic coating including micro surface roughness |
US9320942B2 (en) | 2010-01-20 | 2016-04-26 | Nike, Inc. | Golf ball with cover layer having zones of differing materials |
US9381404B2 (en) | 2009-09-30 | 2016-07-05 | Nike, Inc. | Golf ball having an increased moment of inertia |
US9409064B2 (en) | 2009-09-30 | 2016-08-09 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5971871A (en) * | 1991-11-27 | 1999-10-26 | Spalding Sports Worldwide, Inc. | Multi-layer golf ball |
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US1482232A (en) * | 1920-02-06 | 1924-01-29 | Robert H Hazeltine | Game ball |
US1529708A (en) * | 1922-11-01 | 1925-03-17 | Morris William George | Golf and similar ball |
US3331605A (en) * | 1965-06-01 | 1967-07-18 | Robert C Special | Golf ball including diametrical concentrated weight plane |
US5439227A (en) * | 1992-08-31 | 1995-08-08 | Bridgestone Sports Co., Ltd. | Multi-piece solid golf ball |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6015356A (en) * | 1997-01-13 | 2000-01-18 | Lisco, Inc. | Golf ball and method of producing same |
-
1998
- 1998-03-27 WO PCT/US1998/006163 patent/WO1998043711A1/en active IP Right Grant
- 1998-03-27 GB GB9922126A patent/GB2337936B/en not_active Expired - Fee Related
- 1998-03-27 CA CA002291053A patent/CA2291053A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US1482232A (en) * | 1920-02-06 | 1924-01-29 | Robert H Hazeltine | Game ball |
US1529708A (en) * | 1922-11-01 | 1925-03-17 | Morris William George | Golf and similar ball |
US3331605A (en) * | 1965-06-01 | 1967-07-18 | Robert C Special | Golf ball including diametrical concentrated weight plane |
US5439227A (en) * | 1992-08-31 | 1995-08-08 | Bridgestone Sports Co., Ltd. | Multi-piece solid golf ball |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002536136A (en) * | 1999-02-11 | 2002-10-29 | スポルディング、スポーツ、ワールドワイド、インク | Low-spin golf ball using extra weight |
AU758607B2 (en) * | 1999-02-11 | 2003-03-27 | Callaway Golf Company | Low spin golf ball utilizing perimeter weighting |
GB2362580B (en) * | 1999-02-11 | 2003-12-10 | Spalding Sports Worldwide Inc | Low spin golf ball utilizing perimeter weighting |
GB2371758B (en) * | 1999-11-01 | 2003-12-03 | Spalding Sports Worldwide Inc | Perimeter weighted golf ball with visible weighting |
JP2005523134A (en) * | 2002-04-25 | 2005-08-04 | ファイヤーストーン ポリマーズ エルエルシー | Rubber composition for producing golf ball components |
US9186557B2 (en) | 2009-09-30 | 2015-11-17 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9259623B2 (en) | 2009-09-30 | 2016-02-16 | Nike International, Ltd. | Golf ball having an aerodynamic coating including micro surface roughness |
US9409064B2 (en) | 2009-09-30 | 2016-08-09 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9381404B2 (en) | 2009-09-30 | 2016-07-05 | Nike, Inc. | Golf ball having an increased moment of inertia |
US9033825B2 (en) | 2009-09-30 | 2015-05-19 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9033826B2 (en) | 2009-09-30 | 2015-05-19 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9108085B2 (en) | 2009-09-30 | 2015-08-18 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9199133B2 (en) | 2009-09-30 | 2015-12-01 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US9186558B2 (en) | 2009-09-30 | 2015-11-17 | Nike, Inc. | Golf ball having an aerodynamic coating including micro surface roughness |
US8529375B2 (en) | 2010-01-20 | 2013-09-10 | Nike, Inc. | Golf ball having increased moment of inertia |
US9320942B2 (en) | 2010-01-20 | 2016-04-26 | Nike, Inc. | Golf ball with cover layer having zones of differing materials |
US8556750B2 (en) | 2010-01-20 | 2013-10-15 | Nike, Inc. | Golf ball with cover having varying hardness |
US8568250B2 (en) | 2010-07-07 | 2013-10-29 | Nike, Inc. | Golf ball with cover having zones of hardness |
WO2013012796A3 (en) * | 2011-07-15 | 2013-05-10 | Nike International Ltd. | Golf ball having an aerodynamic coating including micro surface roughness |
Also Published As
Publication number | Publication date |
---|---|
GB9922126D0 (en) | 1999-11-17 |
GB2337936B (en) | 2001-06-06 |
GB2337936A (en) | 1999-12-08 |
CA2291053A1 (en) | 1998-10-08 |
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