GB2357704A - A multi layer golf ball having an increased moment of inertia - Google Patents

Abstract

A golf ball which comprises a core 10, an inner cover layer 14, an outer cover layer 16 and an amount of weighting material disposed in either the inner cover layer 14 or the outer cover layer 16, or both; the inner layer 14 having a flexural modulus of at least 15,000 psi and a hardness of at least 60 on the Shore D scale and the outer layer 16 having a flexural modulus of from 1000 psi to 10,000 psi and a Shore D hardness of about 65 or less. The effective amount of the weighting material may range from 10 to 25 parts material to 100 parts of the material comprising the ball. The golf ball may further comprise at least one discrete region of weighting material disposed in the outer layer, this weighting material being in the form of a visible perimeter weighting material (see figs 3 to 12). The weighting material may comprise metal powders, glass fibres, carbonaceous materials, clay, or various metals, metal oxides or metal stearates.

Description

2357704 PERIMETER WEIGHTED GOLF BALL WITH VISIBLE WEIGHTING

Cross-References to Related Applications

The present application claims priority from U.S. Provisional Application Serial No. 601042,428 filed March 28, 1997, and is a continuation-in-part from U.S. Application Serial No. 081782,221, filed January 13, 1997- Field of the invention

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 multilayer golf balls having one or more layers containing metal particles or other heavy weight filler materials to enhance the perimeter weight of the balls. Such weighting material may be incorporated in one or more of an inner layer or an outer layer. Preferably, the heavy weight filler particles are present in an outer cover layer. Most preferably, the weighting material is visible along the exterior of the ball. The inclusion of the particles along with the is production of a smaller core produces a greater (or higher) moment of inertia. This results in less spin, reduced slicing and hooking and further distance. Additionally, the golf balls of the invention have essentially the same "feel" characteristic of softer balata covered balls.

INTERNATIONAL SEARCH REPORT V 2 Back-ground of the Invention Golf balls utilized in tournament or competitive play today are reguiatec for consistency purposes by the United States Golf Association (U.S.G.A.). In this regard, there are five (5) U.S.G.A. specifications which golf balls must meet unde controlled conditions. These are size, weight, velocity, driver distance and symmetry.

Under the U.S.G.A. specifications, a golf ball can not weigh more thatt 1. 62 ounces (with no lower limit) and must measure at least 1.68 inches (with no upper limit) in diameter. However, as a result of the openness of the upper or lower parameters in size and weight, a variety of golf balls can be made. For example, 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, distan c! and symmetry specifications set by the U.S.G.A.

Additionally, according to 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 is struck at a set club head speed on a U.S.G.A. machine. Furthermore, the over 1 distance of the ball must not exceed 280 yards with a 6% tolerance (296.8 yardE) when hit with a U.S.G.A. specified driver at 160 ft/sec. (clubhead speed) at a 1 degree launch angle as tested by the U.S. G.A. Lastly, the ball must pass th U.S.G.Aadministered symmetry test, i. e., fly consistency (in distance, trajectory an 20 time of flight) regardless of how the ball is placed on the tee.

While the U.S.G.A. regulates five (5) specifications for the purposes of maintaining golf ball consistency, alternative characteristics (i.e., spin, feel, durabilir, distance, sound, visibility, etc.) of the ball are constantly being improved upon by gcif ball manufacturers. This is accomplished by altering the type of materials utilized andlor improving construction of the balls. For example, the proper choice of cover and core materials are important in achieving certain distance, durability and playability properties. Other important factors controlling golf ball performance include, but are not limited to, cover thickness and hardness, core stiffness (typically measured as compression), ball size and surface configuration.

As a result, a wide variety of golf balls have been designed and are available to suit an individual player's game. Moreover, improved golf balls are continually being produced by golf ball manufacturers with technologized advancements in materials and manufacturing processes.

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 perfectly or completely elastic collision and 0 being equivalent to a perfectly or completely inelastic collision.

Resilience (C.O.R.), along with additional factors such as club head speed, club head mass, angle of trajectory, ball size, density, composition and surface configuration (i.e., dimple pattern and area of coverage) as well as environmental conditions (i.e., temperature, moisture, atmospheric pressure, wind, etc.) generally determine the distance a golf ball will travel when hit. Along this line, 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. Since 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 respecl 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 0 the composition of the molded core and of the cover. The molded core andlor cove is may be comprised of one or more layers such as in multi-layered bails. In balk containing a wound core (i.e., balls comprising a liquid or solid center, elasti( windings, and a cover), 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. As in the solid core balls, 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. In the examples of this writing, the coefficient of restitution of a golf ball was measured by propelling a ball horizontally at a speed of 125 +11 feet per second (fps) against it j generally vertical, hard, flat steel plate and measuring the ball's incoming and outgoing velocity electronically. Speeds were measured with a pair of Oehier Mark 55 ballistic screens (available from Oehier Research Austin TX), which provide a timing pulse when an object passes through them. The screens are separated by 3C, 5 and are located 25.2W and 61.2Y from the rebound wail. 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.

As indicated above, 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 +I- fps range so that the C.O.R. is reported as if the ball had an incoming speed of exactly 125.0 fps.

is 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 "regulatiod' ball cannot have an initial velocity exceeding 255 feet per second in an atmosphere of 75OF 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 produce a ball having sufficiently high coefficient of restitution (C.O.R. ) to closely approach the U.S.G.A. limit on initial velocity, while having an ample amount of softness (i.e., hardness) to produce the desired degree of playability (i. e., spin, etc.).

Furthermore, the maximum distance a golf ball can travel (carry and ro when tested on a U.S.G.A. driving machine set at a club head speed of 16) feet/second is 296.8 yards. While golf ball manufacturers design golf balls which closely approach this driver distance specification, there is no upper limit for how. r an individual player can drive a ball. Thus, while golf ball manufacturers produc J balls having certain resilience characteristics in order to approach the maximum distance parameter set by the U.S.G.A. under controlled conditions, 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 i 1 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 wit i respect to the ball's overall carrying distance. In this regard, the dimples provide th -, lift and decrease the drag for sustaining the ball's initial velocity in flight as long s is possible. This is done by displacing the air (i.e., displacing the air resistanca produced by the ball from the front of the ball to the rear) in a uniform manner. Th a shape, size, depth and pattern of the dimple affect the ability to sustain a ball's initiE [I velocity differently.

As indicated above, compression is another property involved in th overall performance of a golf ball. The compression of a ball will influence the soun 1 or "clicW' produced when the ball is properly hit. Similarly, compression can affect t Yeel" of the ball (i.e., hard or soft responsive feel), particularly in chipping and putting.

Moreover, while compression of itself has little bearing on the distancA, performance of a ball, compression can affect the playability of the ball on striking.

The degree of compression of a ball against the club face and the softness of the cover strongly influences the resultant spin rate. Typically, a softer cover will produce a higher spin rate than a harder cover. Additionally, a harder core will produce a higher spin rate than a softer core. This is because at impact a hard core serves to compress the cover of the ball against the face of the club to a much greater degree than a soft core thereby resulting in more "grab" of the ball on the clubface and subsequent higher spin rates. In effect the cover is squeezed between the relatively incompressible core and clubhead. When a softer core is used, the cover is under much less compressive stress than when a harder core is used and therefore does not contact the clubface as intimately. This results in lower spin rates.

The term "compression" utilized in the golf ball trade generally defines the overall deflection that a golf ball undergoes when subjected to a compressive load. For example, PGA compression indicates the amount of change in golf ball's shape upon striking. The development of solid core technology in two- piece balls has is allowed for much more precise control of compression in comparison to thread wound three-piece bails. This is because in the manufacture of solid core bails, the amount of deflection or deformation is precisely controlled by the chemical formula used in making the cores. This differs from wound three-piece balls wherein compression is controlled in part by the winding process of the elastic thread. Thus, 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.

Additionally, cover hardness and thickness are important in producing the distance, piayability 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.

Furthermore, soft covered balls are preferred by the more skilled golfe because he or she can impact high spin rates that give him or her better control oi workability of the ball. Spin rate is an important golf ball characteristic for both thE skilled and unskilled golfer. As just mentioned, 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 skillec golfer when hitting an approach shot to a green. The ability to intentionally producE "back spin", thereby stopping the ball quickly on the green, andlor "side spin" to drav or fade the ball, substantially improves the golfer's control over the ball. Thus, the more skilled golfer generally prefers a golf ball exhibiting high spin rate properties.

However, a high spin golf ball is not desirous by all golfers, particularly is high handicap players who cannot intentionally control the spin of the ball.

Additionally, since a high spinning ball will roll substantially less than a low spinnin golf ball, a high spinning ball is generally short on distance.

In this regard, less skilled golfers, have, among others, two substantiE obstacles to improving their game: slicing and hooking. When a club head meets ball, an unintentional side spin is often imparted which sends the ball off its intende course. The side spin reduces one's control over the ball as well as the distance th ball will travel. As a result, unwanted strokes are added to the game.

Consequently, while the more skilled golfer frequently desires a hig i spin golf ball, 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. Furthermore, since a high spinning ball is generally short on distance, such a ball is not universally desired by even the more skilled golfer.

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 10 to produce a draw or a fade, or a backspin which causes the ball to "bite" or stop abruptly on contact with the green.

Moreover, the soft balata covers produce a soft IdeP' to the low handicap player. Such playability properties (workability, feel, etc.) are particularly important in short iron play with low swing speeds and are exploited significantly by is relatively skilled players.

However, despite all the benefits of baiata, balata covered golf balls are easily cut andlor damaged if mis-hit. Golf balls produced with balata or balatacontaining cover compositions therefore have a relatively short lifespan.

Additionally, soft balata covered balls are shorter in distance. While the softer materials will produce additional spin, this is frequently produced at the expense of the initial velocity of the ball. Moreover, as mentioned above, higher spinning balls tend to roll less.

As a result of these negative properties, balata and its synthetic substitutes, transpolyisoprene and trans-polybutadiene, have been essentially replaced as the cover matedals of choice by new synthetic materials. Included in this group of materials are ionomer resins.

lonomeric resins are polymers in which the molecular chains are cross linked by ionic bonds. As a result of their toughness, durability and flighl characteristics, various ionomeric resins sold by E. 1. DuPont de Nemours 8 Company under the trademark "SurlynW and more recently, by the Exxor Corporation (see U. S. Patent No. 4,911,451) under the trademarks TscoW and thf trade name "lotek', have become the materials of choice for the construction of gol.

ball covers over the traditional "balata" (transpolyisoprene, natural or synthetic' rubbers. As stated, the softer balata covers, although exhibiting enhanced playabilib properties, lack the durability (cut and abrasion resistance, fatigue endurance, etc.' properties required for repetitive play and are limited in distance.

lonomeric resins are generally ionic copolymers of an olefin, such as ethylene, and a metal salt of an unsaturated carboxylic acid, such as acrylic acid, is 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.

Historically, some of the advantages produced by ionomer resins gainel in increased durability were offset to some degree by decreases produced ill playability. This was because although the ionomeric resins were very durable, the V 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 jonomerir.

resin covers did not compress as much hgainst the face of the club upon impact, thereby producing less spin.

In addition, 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.

As a result of these difficuffies and others, a great deal of research has been and is currently being conducted by golf ball manufacturers in the field of ionomer resin technology. There are currently more than fifty (50) commercial grades of ionomers available both from DuPont and Exxon, with a wide range of properties which vary according to the type and amount of metal cations, molecular weight, composition of the base resin (i.e., relative content of ethylene and methacrylic andlor acrylic acid groups) and additive ingredients such as reinforcement agents, etc.

However, a great deal of research continues in order to develop golf ball cover is compositions exhibiting not only the improved impact resistance and carrying distance properties produced by the "hard" ionomeric resins, but also the playability (i.e., tespin", 'Yeet", etc.) characteristics previously associated with the "soft' balata covers, properties which are still desired by the more skilled golfer.

Consequently, a number of two-piece (a solid resilient center or core with a molded cover) and three-piece (a liquid or solid center, elastomeric winding about the center, and a molded cover) golf balls have been produced by the Applicant and others to address these needs. The different types of materials utilized to formulate the cores, covers, etc. of these balls dramatically alters the balls' overall characteristics.

in addition, multi-layered covers containing one or more ionomer resin have also been formulated in an attempt to produce a golf ball having the overall distance, playability and durability characteristics desired. For example, this was addressed by Spaiding & Eventlo Companies, Inc., the assignee of the presen invention, in U.S. Patent No. 4,431,193 where the construction of a multi- layered go ball having two ionomer resin cover layers is disclosed.

In the examples of the '1193 patent, a mufti-layer golf ball is produced b initially molding a first cover layer on a solid spherical core and then adding a secon layer. The first layer is comprised of a hard, high flexural modulus resinous materia such as type 1605 SurlynO (now designated SurlynC 8940). Type 1605 Surlyn10 (SurlynO 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 51,00) psi. An outer layer of a comparatively soft, low flexural modulus resinous material such as type 1855 SurlynO (now designated Surlyn@ 9020) is molded over the innE r is cover layer. Type 1855 SurlynO (SurlynC 9020) is a zinc ion based low acid (13 weight percent methacrylic acid) ionomer resin having a flexural modulus of abo 11 t 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 provides a ball which serves to attain or approach the maximum initial velocity lirr i of 255 feet per second as provided by the United States Golf Association (U.S.G.A rules. The relatively soft, low flexural modulus outer layer provides essentially gain in the coefficient of restitution but provides for the advantageous "feel" and playing characteristics of a balata covered golf ball.

Unfortunately, however, while the ball of the examples of the '193 patent do exhibit enhanced playability characteristics with improved distance (i. e. enhanced C.O.R. values) over a number of other then known multi-layered balls, the balls suffer from relatively short distance (i.e. lower C.O.R. values) when compared to two-piece, single cover layer balls commercially available today. These undesirable properties make the balls produced in accordance with the limited examples of the '193 patent generally unacceptable by today's standards.

The present invention is directed to new multi-layer golf ball compositions which provide for enhanced coefficient of restitution (Le, improved travel distance) andlor 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 is overall spin rate.

Moreover, 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.

As previously noted, a low spin ball is generally preferred, particularly for the less skilled player. And, as noted, increasing the moment of inertia of the ball tends to reduce the spin rate of the ball. 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 implementec in large scale commercial golf ball manufacturing processes.

These and other objects and features of the invention will be appareni from the following summary of the invention, description of. the preferrec embodiments, the drawings and from the claims.

Summary of the Invention

The present invention provides, in a first aspect, a golf ball comprisinc a core and an outer layer, the outer layer including at least one discrete region of E weighting material that serves to increase the moment of inertia of the golf ball. Ir a preferred embodiment, the weighting material or some indication thereof, is visibif at the ball's exterior surface.

In yet another aspect, the present invention further provides a multi]aye 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 materia having a flexural modulus of at least about 15,000 psi and a Shore D hardness of a least about 60. The outer layer comprises a relatively soft material having a ffilexur modulus of from about 1,000 psi to about 10,000 psi and a Shore D hardness 0 about 65 or less. The golf ball further comprises an effective amount of a weightinl( material disposed in either or both the inner layer or outer layer. The golf ba 1 preferably further comprises at least one discrete region of a weighting materiz 1 disposed in the outer layer. In a most preferred embodiment, the weighting material or some indication thereof, is visible along the ball's exterior.

is These and other objects and features of the invention will be apparent from the following detailed description.

Brief Descfiption of the Drawings 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 filter 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; Is 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 elevatonal 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 elevatonal 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 elevation& view of a preferred embodiment golf ball ill 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 wdh the present invention utilizing a visible multi stripe- shaped perimete - weighting system, FIG. 10 is an elevational view of a preferred embodiment golf ball ill 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 ill accordance with the present invention utilizing a visible ring-shaped perimeter is weighting system; and FIG. 12 is an eievational view of a preferred embodiment golf ball ill accordance with the present invenflon utilizing a visible spiral-shaped perimeter weighting system.

Description of the Preferred Embodiments

The present invention is directed to improved multi-layer golf bail composifions and the resulting regulation balls produced using those compositions.

In this regard, a smaller and lighter core is produced and metal particles, or other heavy weight filler materials, are included in the cover compositions. This results ill a molded golf ball exhibiting enhanced perimeter weighting. Preferably, the particles are included in a relatively thick inner cover layer (or mantle) of a solid, three-piece multi-layered golf ball. In another preferred embodiment, the parficies or other weighting material is disposed in an outer layer. Most preferably, the weighting material is viewable or otherwise visible along the ball'sexterior. 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.

It has been found that the combination of the selection of materials and unique approach of the present invention produces a golf ball with an increased moment of inertia andior a greater radius of gyration and thus generates lower initial spin. This results in a golf ball exhibiting enhanced distance.without substantially effecting the feel and durability characteristics of the ball.

Preferably, the multi-layer golf ball covers of the present invenflon is 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. Additionally, included in the multi-layer golf balls is a second or outer layer or ply comprised of a comparatively softer, low modulus material (i.e., flexural modulus of about 1,000 to about 10,000 psi (ASTM D-790) and Shore D hardness of about 65 or less, more desirably 60 or less). Examples of such materials include a blend of one or more soft ionomer resins or other non-lonomeric thermoplastic or thermosetting elastomer such as polyurethane or polyester elastomer. Metal particles and other heavy weight filler materials (from about 1 to about 100 parts per hundred parts resin (phr), preferabl from about 4 to about 51 phr, and most preferably from about 10 to about 25 ph r) ar included in the first or inner cover layer in order to enhance the moment of inertia c f the golf ball. Such heavy weight filter materials may also be provided in the outer cover layer in these proportions. The multi-layer golf balls of the invention can be c f standard or enlarged size, More preferably, the inner layer or ply of the golf ball of the inventio includes a blend of high acid ionomer resins (greater than 16 weight percent acid) a blend of high modulus low acid ionomers, and has a Shore D hardness of 65 greater. Various amounts of metallic particles or other heavy weight filler material are included in the inner cover layer and the size and weight of the core is reduce in order to produce selective variations in the moment of inertia of the ball. The oute cover layer preferably comprises a blend of low modulus ionomer resins or comprised of polyurethane and has a Shore D hardness of about 45 to 55 (i. e., Shor, is C hardness of about 65 to 75).

In this regard, it has been found that multi-iayer golf balls can b produced having inner and outer cover layers which exhibit improved C.O.R. value and have greater travel distance in comparison with balls made from a single cove layer. In addition, it has been found that use of a softer outer layer adds to th desirable 'Tee]" and a higher spin rate while maintaining respectable resiliency. Th, soft outer layer allows the cover to deform more during impact and increases the are of contact between the club face and the cover, thereby imparting additional spin the ball. As a result, the soft cover provides a multi-layer ball with a balata-like fe( 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. This combination of weight displacement increases the moment of inertia andlor moves the radius of gyration of the ball closer to the outer surface of the ball.

Consequently, selective adjustments in weight arrangement will produce different moments of inertia andior radii of gyration. The overall result is the production of a lower initial spinning multi-layer golf ball which travels farther while maintaining the feel and durability characteristics desired by a golf ball utilized in regulation play.

is 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. By varying the weight, size and density of the components of the golf ball, the moment of inertia of a golf ball can be increased. Such a change can occur in a multi-layered golf ball, including a bal containing one or more cover layers, to enhance distance due to the production a less side spin and improved roll.

Accordingly, the present invention is directed to an improved multi-layei cover which produces, upon molding each layer around a core (preferably a smalle, and lighter solid core) to formulate a mufti-layer cover, a golf ball exhibiting enhancec distance (i.e., improved resilience, less side spin, improved roll) without adversel) affecting, and in many instances, improving the ball's feel (hardness/softness) and/o durability (i.e., cut resistance, fatigue resistance, etc.) characteristics.

Referring to FIGS. 1 and 2, a preferred embodiment golf ball in accordance with the present invention is illustrated. This preferred embodiment golf ball comprises a multi-layered cover 12 disposed over a core 10, and method fo.

is making same. Preferably the core 10 is a solid core, although a wound core having the desired characteristics can also be used.

The mulfi-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 & 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. Preferably, the inner layer is comprised of a blend of two or more high acid (i.e. at least 16 weigt t 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 fatt 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. 1. DuPont de Nemours & Company under the trademark "Surlyng' and by Exxon Corporation under the trademark "Escoroo" or trade name "loteW', 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. 071901,660 filed June 19, 1992, both incorporated herein by reference. Of course, the inner layer high acid ionomer compositions are not limited in any way to those compositions set forth in said copending applications. For example, 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. 071901,680, filed June 19, 1992, incorporated herein by reference, may also be utilized to produce the inner layer of is the mufti-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. Preferably, the ionomeric resins are copolymers of ethylene and either acrylic or methacrylic acid. In some circumstances, 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 resinE which may be included in the inner layer cover compositions of the invention containc greater than about 16% by weight of a carboxylic acid, preferably from about 17% tc about 25% by weight of a carboxyiic acid, more preferably from about 18% to abou 21.5 % by weight of a carboxylic acid.

Although the inner layer cover composition preferably includes a higt acid ionomeric resin and the scope of the patent embraces all known high acic ionomeric resins failing 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 "EscorC and or IoteC, are somewhat similar to the high acid ionomeria, resins available under the "Suriyn&' trademark. However, since the EscorOllotek ionomeric resins are sodium or zinc salts of poly(ethylene-acrylic acid) and the is "Sur"' resins are zinc, sodium, magnesium, etc. salts of poly(ethylene- methacryli(,, 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 SurlynO AD- 8422 (sodiunt cation), Surlyn@ 8162 (zinc cation), SurlynC SEP-503-1 (zinc cation), and SurlynG SEP-503-2 (magnesium cation). According to DuPont, all of these ionomers contaill from about 18.5 to about 21.5% by weight methacrylic acid.

More particularly, SurlynO AD-8422 is currently commercially availabi.

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, Sudyn@ AD-842,' offers the following general properties when compared to Surlyn08920, the stiffest, hardest of all on the low acid grades (referred to as "hard" ionomers in U.S. Patent No. 4,884,814):

LOW ACID HIGH ACID (15 wt% Acid) (>20 wt% Acid) SURLYN@ SURLYNO SURILYNO) 8920 8422-2 8422-3 IONOMER Cation Na Na Na Melt Index 1.2 2.8 1.0 Sodium, Wt% 2.3 1.9 2.4 Base Resin MI 60 60 60 is Mpl, % 88 86 85 FP', OC 47 48.5 45 COMPRESSION MOLDING 2 Tensile Break, psi 4350 4190 5330 Yield, psi 2880 3670 3590 Elongation, % 315 263 289 Flex Mod, K psi 53.2 76.4 88.3 Shore D hardness 66 67 68 DSC second heat, 100C/min heating rate.

2 Samples compression molded at 1150C annealed 24 hours at 600C. 8422-2, -3 were homogenized at 190% before molding.

In comparing SurlynC 8920 to SurlynO 8422-2 and SurlynO 8422-3, it is noted that the high acid SurlyrAD 8422-2 and 8422-3 ionomers have a higher tensile yield, lower elongation, slightly higher Shore D hardness and much higher flexural modulus. SurlynOD 8920 contains 15 weight percent methacrylic acid and is 59% neutralized with sodium.

In addition, SurlynC SEP-503-1 (zinc cation) and Sudynt SEP-503-2 (magnesium cation) are high acid zinc and magnesium versions of the Surlyn@ AD 8422 high acid ionomers. When compared to the SurlynO AD 8422 high acd ionomers, the Surlyn SEP-503-1 and SEP-503-2 ionomers can be defined as follow;:

Surlyn@ lonomer Ion Melt Index Neutralization % AD 8422-3 Na 1.0 45 SEP 503-1 Zn 0.8 38 SEP 503-2 Mg 1.8 43 Furthermore, SurlynC 8162 is a zinc cation ionomer resin containirg approximately 20% by weight (i.e. 18.5-21.5% weight) methacrylic acid copolymer th at has been 30-70% neutralized. Surlyn@ 8162 is currently commercially available fro -n is DuPont.

Examples of the high acid acrylic acid based ionomers suitable for u e in the present invention also include the EscorO or lotek high acid ethylene acrylic acid ionomers produced by Exxon. In this regard, Escor@ or lotek 959 is a sodiurn ion neutralized ethylene-acrylic neutralized ethyleneacrylic acid copolymel.

According to Exxon, 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 high acid acrylic acid based ionomers are as follows:

PROPER ESCORO GOTEK) 95 ESCMO (10TEK) Mett Index, 9110 min 2.0 1.8 Cation Sodium Zinc MeLting Point, IF 172 174 vicat softening Point, IF 130 131 PROPER ESCORO (IOTEK) 959 ESCORO(I0TEK) 960 TensiLe @ Break, psi 4600 3500 Etongation @ Break, % 325 430 Hardness, Shore D 66 57 FtexuraL Modutus, psi 66,000 27,000 Additional high acid hard ionomer resins are also available from Exxon such as lotek 1002 and lotek 1003. 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:

IOTEK 1002 Property Unit Value Method General properties Melt index g/10 min 1.6 ASTM-D 1238 Density kg/m3 ASTM-D 1505 Cation type Na Meffing point c 83.7 ASTM-D 3417 Crystallization point c 43.2 ASTM-D 3417 Plaque prope Tensile at break Mpa 31.7 ASTM-D 638 Tensile at yield MPa 22.5 ASTM-D 638 Elongaton at break % 348 ASTM-D 638 1% Secant modulus Mpa 418 ASTM-D 638 1% Flexural modulus Mpa 3130 ASTM-D 790 Hardness Shore D 62 ASTM-D 2240 Vicet softening point 0C 51.5 ASTM-D 1525 - IOTEK 1003 Property Unit Value Method General properties Melt index g/10 min 1.1 ASTM-D 1238 Density kglm' ASTM-D 1505 Cation type Zn EXXON c Melting point 82 ASTM-D 3417 Crystallization point 'C 51.5 ASTM-D 3417 Plaque properties Tensile at break MPa 24.8 ASTM-D 638 18 Tensile at yield MPa 14.8 ASTM-D 838 38 Elongation at break % 387 ASTM-D 6 A is 1% Secant modulus MPa 145 ASTM-D 638 1% Flexural modulus MPa 147 ASTM-D 790 Hardness Shore D 54 ASTM-D 2240 Vicat softening point c 56 ASTM-D 15 Furthermore, as a result of the development by the inventors of a number of new high acid ionomers neutralized to various extents by several differet it types of metal cations, such as by manganese, lithium, potassium, calcium and nickel cations, several new high acid ionomers andior high acid ionomer blends besid s sodium, zinc and magnesium high acid ionomers or ionomer blends are now availabIL.

for golf ball cover production. It has been found that these new cation neutralized high acid ionomer blends produce inner cover layer compositions exhibiting enhanced hardness and resilience due to synergies which occur during processinc.

Consequently, the metal cation neutralized high acid ionomer resins recently produced can be blended to produce substantially harder inner cover layers for muld- layered golf balls having higher C.O.R.'s than those produced by the low acid ionomer inner cover compositions presently commercially available.

More particularly, several new metal cation neutralized high acid ionomer resins have been produced by the inventor by neutralizing, to various 5 extents, high acid copolymers of an aipha-olefin and an alpha, beta-unsaturated carboxylic acid with a wide variety of different metal cation salts. This discovery is the subject matter of U.S. Application Serial No. 071901,680, incorporated herein by reference. It has been found that numerous new metal cation neutralized high acid ionomer resins can be obtained by reacting a high acid copolymer (i.e. a copolymer 10 containing greater than 16% by weight acid, preferably from about 17 to about 25 weight percent acid, and more preferably about 20 weight percent acid), with a metal cation salt capable of ionizing or neutralizing the copolymer to the extent desired (i.e. from about 10% to 90%).

The base copolymer is made up of greater than 16% by weight of an is alpha, beta-unsaturated carboxylic acid and an alpha-olefin. Optionally, a softening comonomer can be included in the copolymer. Generally, the alpha-oiefin has from 2 to 10 carbon atoms and is preferably ethylene, and 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, 20 maleic acid, fumaric acid, and itaconic acid, with acrylic acid being preferred.

The softening comonorner that can be optionally included in the invention may be selected f rom 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, and alkyl acrylates or methacrylates - wherein the alkyl group contains 1 to 10 carbon atoms. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacryiate, ettlyl acrylate, ethyl methacrytate, butyl acryiate, butyt methacrylate, or the like.

Consequently, examples of a number of copolymers suitable for use to produce the high acid ionomers included in the present invention include, but are rot limited to, high acid embodiments of an ethylenelacrylic acid copolymer, an ethylenelmethacrylic acid copolymer, an ethyienelitaconic acid copolymer, an ethylenelmaleic acid copolymer, an ethylenelmethacryfic acidlvinyl acetate copolym r, an ethylenelacrylic acidivinyl 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. Preferably, the copolymer contains about 20% by weight unsaturated carboxylic acid and about 80% by weight ethylene. Most preferably, the copolyrT er contains about 20% acrylic acid with the remainder being ethylene.

Along these lines, examples of the preferred high acid base copolymers which fulfil] the criteria set forth above, are a series of ethyleneacrylic copolymers which are commercially available from The Dow Chemical Company, Midlarld, Michigan, under the Trimaco?' designation. These high acid base copolymers exhibit the typical properties set forth below in Table 1.

TABLE 1

Irypical Properties of Primacor Ethylene-AgMiic Acid Copolymers MELT TENSILE FLEKLORAL VICAT PERCENT DENSITY, 211DEX YD. ST FUS SOFT PT SOME D GRADE ACID gLcc 9110min (psi) (psi) CO NSS ASTM D-792 0-1235 D-635 D-790 D-1525 D-2240 5980 20.0 0.958 300.0 4800 43 so MELT TENSILE FLOWRAL VICAT PERCENT DENSITY. INDEX, YO- ST MMLUS SOFT PT SHDRE D GRADE ACID gtcc glln (psi) (psi) CC) MESS 5990 20.0 0.955 1300.0 650 2600 40 42 5990 20.0 0.955 1300.0 650 3200 40 42 5981 20.0 0.960 300.0 900 3200 46 48 5981 20.0 0.960 300.0 900 3200 46 48 5983 20.0 0.958 500.0 850 3100 44 45 5991 20.0 0.953 2600.0 635 2600 38 40 The Mett Index vatues are obtained according to ASTM D-1238, at 1901C, Due to the high molecular weight of the Primacor 5981 grade of the ethyiene-acrylic acid copolymer, 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 carboxyNc is acid groups of the high acid copolymer. These include acetate, oxide or hydroxide salts of lithium, calcium, zinc, sodium, potassium, nickel, magnesium, and manganese.

Examples of such 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 2000 F to about 5000 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 amount of metal cation salt 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%.

As indicated below in Table 2, a number of new types of metal cation neutralized high acid ionomers can be obtained from the above indicated process.

These include new high acid ionomer resins neutralized to various extents with manganese, lithium, potassium, calcium and nickel cations. In addition, when a high is acid ethylenelacrylic acid copolymer is utilized as the base copolymer component of the invention and this component is subsequently neutralized to various extents with the metal cation salts producing acrylic acid based high acid ionomer resins neutralized with cations such as sodium, potassium, lithium, zinc, magnesium, manganese, calcium and nickel, several new cation neutralized acrylic acid based high acid ionomer resins are produced.

- TABLE 2

Metal Cation Neutralized Higgh Acid lonomers wt-% Wt-% Mett Shore D Formutation, No. Cation Satt Neutratization Index C.O.R_ Hardness 1(MaDH) 6.98 67.s 0.9.804 71 2(maCH) 5-66 54.0 2.4.808 73 3(HaOH) 3.84 35.9 12.2.812 69 4(NaOH) 2.91 27.0 17.5.812 (brittLe) 5(MnAc) 19-6 71.7 7.5.809 73 6(NnAC) 23.1 88.3 3.5.814 77 7(MnAc) 15.3 53.0 7.5.810 72 B(MnAc) 26.5 106 0.7.813 (brittte) 9WON) 4.54 71.3 0.6.810 74 10COGN) 3.38 52.5 4.2.818 72 ll(LiON) 2.34 35.9 18.6.815 72 12MON) 5.30 36.0 19.3 Broke 70 13MOH) 8.26 57.9 7.18.804 70 14MON) 10.7 77.0 4.3.801 67 15UnAc) 17.9 71.5 0.2.806 71 16UnAc) 13.9 53.0 0.9.797 69 17UnAc) 9.91 36.1 3.4 -793 67 18(N9AC) 17.4 70,7 2.8.814 74 W(M9Ac) 20.6 87.1 1.5.815 76 20(N9Ac) 13.8 53.8 4.1.814 74 21(caAc) 13.2 69.2 1.1.813 74 22(CaAc) 7.12 34.9 10.1 Boa 70 Controts. 50150 Btend of Ioteks BWO/7030 C.O.R.=.810165 Shore D Hardness OUPont High Acid Surtyno 8422 (Ma) C.O.R.=.811170 Shore D Hardness DuPont High Acid SurtyrO 8162 (Zn) C.O.R.=.807165 Shore D Hardness Emon High Acid lotek EX-960 Qn) C.O.R.=.796165 Shore D Hardness TABLE 2 (continued) Wt-% Wt-% Net t Fonmitation No- Cation SaLt Neutratization Index C.O.R_ 23(M90) 2.91 53.5 2.5.813 24(M90) 3.85 71.5 2.8.808 25(M90) 4.76 89.3 1.1.809 26(Mgo) 1.96 35.7 7.5.815 control for Formulations 23-26 is 50150 lotek 800017030, C.O.R.=.814, Formulation 26 C.O.R. was normalized to that control accordingly TABLE 2 (continued) is vt-Z Vt-X Nett Shore D Fornutation No. Cation Satt Neutratizati Index C.O.R. Hardness 27MAC 13.04 61.1 0.2.802 71 28MA0 10.71 48.9 0.5.799 72 29(NiAc) 8.26 36.7 1.8.796 69 30MA0 5.66 24.4 7.5.786 64 ControL for Formutation Has. 27-30 is 50150 lotek 800017030, C.O.R.=.807 When compared to low acid versions of similar cation neutralize 1 ionomer resins, the new metal cation neutralized high acid ionomer resins exhib t enhanced hardness, modulus and resilience characteristics. These are properties that are particularly desirable in a number of thermoplastic fields, including the fief, J of golf ball manufacturing.

When utilized in the construction of the inner layer of a multi-layered golf ball, it has been found that the new acrylic acid based high acid ionomers extend th a range of hardness beyond that previously obtainable while maintaining the benefici 1 properties (i.e. durability, click, feet, 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.

Moreover, as a result of the development of a number of new acryl c acid based high acid ionomer resins neutralized to various extents by several differeffi - types of metal cations, such as manganese, lithium, potassium, calcium and nickel cations, several new ionomers or ionomer blends are now available for production of 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 distance, can be obtained.

More preferably, it has been found that when two or more of the above indicated high acid ionomers, particularly blends of sodium and zinc high acid ionomers, are processed to produce the covers of multi-layered golf balls, (i.e., the inner cover layer herein) the resulting golf balls will travel farther than previously known multi-layered golf balls produced with low acid ionomer resin covers due to the balls' enhanced coefficient of restdution values.

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 Clefin is having from about 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from about 3 to 8 carbon atoms. Preferably, the ionomeric resins are copolymers of ethylene and either acrylic or methacrylic acid. In some circumstances, an additional comonomer such as an acrylate ester (i.e., iso- or n butylacryllate, 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 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.

When utilized in the construction of the inner layer of an additional embodiment of a multi-layered golf ball of the present invention, it has been found that the low acid ionomer blends extend the range of compression and spin rates beyond that previously obtainable. More preferably, it has been found that when two or more low acid ionomers, particularly blends of sodium and zinc high acid ionomers, are processed to produce the covers of multi-layered golf balls, (i.e., the inner cover layer herein) the resulting golf balls will travel farther and at an enhanced spin rate than previously known multi-layered golf balls. Such an improvement is particularly noticeable in enlarged or oversized golf balls.

With respect to the outer layer 16 of the preferred embodiment multi layered cover of the present invention, the outer cover layer is comparatively softer than the inner layer. The softness provides for the enhanced feel and playabifity characteristics typically associated with batata 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 is 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 Hytrele, a polyurethane sold by BASF under the designation Baytece or a polyester amide such as that marketed by Elf Atochern S.A. under the trademark Pebaxe. The outer layey is fairly thin (i.e. from about 0.010 to about 0.110 in thickness, more desirably 0.03 to 0.06 inches in thicknessfor a 1.680 inch ball and 0.04 to 0.07 inches in thickness for a 1,72 inch ball), but thick enough to achieve desired playability characteristics while minimizing expense.

Preferably, 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. Specifically, 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. 10 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 composifton hardlsoft blends include ionic copolymers which are the sodium, zinc, is 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 20 acrylic andlor methacrylic acid, with copolymers of ethylene and acrylic acid being the most preferred. Two or more types of hard ionorneric resins may be blended into the outer cover layer compositions in order to produce the desired properties of the resulting golf balls. As discussed earlier herein, the hard ionomeric resins introduced under 25 the designation EscorC and sold under the designation IoteC are somewhat similar - to the hard ionomeric resins sold under the Surlyn@ trademark. However, since the 1oteC 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. As more specifically indicated in the data set forth below, the hard 9oteC resins (i.e., the acrylic acid based hard ionomer resins) are the more preferred hard resins for use in formulating the outer layer blends for use in the present invention. In addition, various blends of 9oteC and SurlynO 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 include the hard sodium ionic copolymer sold under the trademark Surlyn08940 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 is which is about 29 percent neutralized with sodium ions. This resin has an average melt flow index of about 2.8. Surlyn09910 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 Surlyn09910 is about 0.7.

The typical properties of Surlyn09910 and 8940 are set forth below in Table 3:

TABLE 3

Typical Properties of Commercially Available Hard Surlyn@ Resins Suitable for Use in the Inner and Outer Layer Blends of the Present Invention ASTN D 8940 9910 8920 8528 9970 9730 Cation Type Sodium Zinc Sodium Sodium Zinc Zinc Melt flow index, gms/10 min. D-1238 2.8 0.7 0.9 1.3 14.0 1.6 specific Gravity, gIcTI? D-792 0.95 0.97 0.95 0-94 0.95 0.95 - 37 ASTH D 8940 9910 8920 8528 9970 973D Hardness, Shore D D-2240 66 64 j6- 90- j2- j3 TensiLe Strength, (kpsi), M1)a D-638 (4.8) (3.6) (5.4) (4.2) (3.2) (4.1) 33.1 24.8 37.2 29.0 22.0 28.0 0 ELongation, % D-638 470 290 350 450 460 460 Ftexurat Modutus, (kpsi) MPa D-790 (51) (48) (55) (32) (28) (30) 350 330 380 220 190 210 TensiLe Impact (23IC) Kilm2 (ft.-Lbs.lin2 D-1822S 1020 1020 865 1160 760 1240 (485) (485) (410) (550) (360) (590) Vicat Temperature, -C D-1525 63 62 58 73 61 73 Examples of the more pertinent acrylic acid based hard ionomer resin suitable for use in the present inner and outer cover composition sold under the IoteW' tradename by the Exxon Corporation include lotek 4000, lotek 4010, lotek 8000, lotek 8020 and lotek 8030. The typical properties of these and other lotek hard ionomers suited for use in formulating the inner and outer layer cover compositions are set forth below in Table 4:

TABLE 4

Typical Properties of lotek lonomers Resin ASTM Properties Method Units 4000 4010 8000 8020 8030 Cation type zinc zinc sodium sodium sodium Melt index D-1238 g/10 min. 2.5 1.5 0.8 1.6 2.8 Density D-1505 k91m3 963 963 954 960 960 Melting Point D-3417 C 90 90 90 87.5 87.5 Crystallization Point D-3417 C 62 64 56 53 55 Vicat Softening Point D-1525 C 62 63 61 64 67 Weight ic Acid 16 11 of Acid Groups cation neutralized 30 40 (3 mm thicK so compression molded) Tensile at break D-638 Mpa 24 26 36 31.5 28 Yield point D-638 M12a none none 21 21 23 Elongation at break D-638 % 395 420 350 410 395 1% Secant modulus D-638 Mpa 160 160 300 350 390 - Plaque ASTM Properties Method Units 4000 4010 8000 8020 8030 Shore Hardness D D-2240 -- 55 55 61 so 59 Film Properties (50 micron film 2.21 Blow-up ratio) 4000 4010 8000 8020 8030 Tensile at Break MD D-882 Mpa 41 39 42 52 47.4 TO 0-882 Mpa 37 38 38 38 40.5 is Yield paint MD D-882 Mpa is 17 17 23 21.6 TO D-882 Mpa 14 Is 15 21 20.7 Elongation at Break MD D-882 % 310 270 260 295 305 M D-882 % 360 340 280 340 345 1% Secant modulus MD D-882 Mpa 210 215 390 380 380 TO D-882 Mpa 200 225 380 350 345 Dart Drop Impact D-1709 91mi=n 12.4 12,5 20.3 Resin ASTM Properties Method Units 7010 7020 7030 Cation type zinc zinc zinc Melt Index D-1238 9110 min. 0.8 1.5 2.5 Density D-1505 kghn' 960 960 960 Melting Point 0-3417 C 90 90 90 Crystallization Point D-3417 C - - - Vicat Softening Point D-1525 -C 60 63 62.5 %Weight Acrylic Acid - - - % of Acid Groups Cation Neutralized - - Plaque ASTM Properties Method Units 7010 7020 7030 (3 mm thick, compression molded) Tensile at break D-638 Mpa 38 38 38 Yield Point D-638 Mpa none none none fflongation at break D.638 % 500 420 395 1 % Secant modulus D-638 Mpa, - - - Shore Hardness D D-2240 - 57 55 55 Comparatively, soft ionomers are used in formulating the hardlsoft 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 add 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.

Certain ethylene-acrylic acid based soft ionomer resins developed by the Exxon Corporation under the designation Iotek 7520" (referred to experimentally by differences in neutralization and melt indexes as I-DX 195, I-DX 196, I-DX 218 and I-DX 219) may be combined with known hard ionomers such as those indicated above is 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 muld-layer balls produced by other known hard-soft ionorner blends as a result of the lower overall raw materials costs and improved yields.

While the exact chemical composition of the resins to be sold by Exxon under the designation iotek 7520 is considered by Exxon to be confidential and proprietary information, Exxon's experimental product data sheet lists the following physical properties of the ethylene acrylic acid zinc ionomer developed by Exxon:

- 40 TABLE5

Ph"ical Properties of lotek 7520 Proper ASTN Meth Units Typical Vat Melt Index D-1238 9110 min. 2 Density D-1505 0.962 Cation Zinc Melting Point D-3417 c 66 Crystallization Point D-3417 c 49 Vicat softening Point D-1525 c 42 PLa Propwties (2 m thick csion Molded Plaques) Tensile at Break D-638 Mpa 10 Yield Point D-638 MPa None Elongation at Break D-638 % 760 1% Secant Modulus D-638 MPa 22 Shore D Hardness D-2240 32 Ftexurat Modulus D-790 Mpa 26 Zwick Rebo und ISO 4862 % 52 De Mattia Flex Resistance D-430 Cycles >5000 In addition, 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 19O.C. per ASTM D-1288), and a flexural modulus o 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 generally zinc salts of a terpolymer of ethylene, acrylic acid, and methyl acrylate.

Furthermore, the inventors have found that a newly developed grade o so an acrylic acid based soft ionomer available from the Exxon Corporation under the designation lotek 7510, is also effective, when combined with the hard ionomers indicated above in producing golf ball covers exhibiting higher C.O.R. values at equal or softer hardness than those produced by known hard-soft ionomer blends. In this regard, 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 Sudyn 8625 and the Surlyn 8629 combinations disclosed in U.S. Patent No.

4,884,814).

In addition, 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.

is 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 those of lotek 7520 are set forth below:

TABLE6

Physical ProRerties of lotek 7610 in Comparison to lotok 7520 IOTEK 7520 IOTEK 7510 W, 9110 min 2.0 0.8 10TEK 7520 IOTEK 7510 Density, glcc 0.96 0.97 Melting Point, 'F 151 149 Vicat Softening Point, 'F 108 109 Flex Modulus, psi 3800 5300 Tensile Strength, psi 1450 1750 Elongation, % 760 690 Hardness, Shore D 32 35 It has been determined that when hardlsoft ionomer blends are used for the outer cover layer, good results are achieved when the relative combination is in a range of about 90 to about 10 percent hard ionomer and about 10 to about 91) percent soft ionomer. The results are improved by adjusting the range to about 715 to 25 percent hard ionomer and 25 to 75 percent soft ionomer. Even better resuU are noted at relative ranges of about 60 to 90 percent hard ionomer resin and about is 40 to 60 percent soft ionomer resin.

Specific formulations which may be used in the cover composition am, included in the examples set forth in U. S. Patent No. 5,120,791 and 4, 884,814. The present invention is in no way limited to those examples.

Moreover, in alternative embodiments, the outer cover layer formulatioi I may also comprise a soft, low modulus non-ionomeric thermoplastic elastomer including a polyester polyurethane such as B.F. Goodrich Company's EstanelP polyester polyurethane X-4517. According to B.F. GOODRICH, EstaneO X-4517 has the following properties:

Properties of EstaneS X-4517 Tensile 1430 100% 815 Properties of EstaneO X-4517 (continued) 200% 1024 300% 1193 Elongation 641 Youngs Modulus 1826 Hardness AID 88139 Bayshore Rebound 59 Solubility in Water Insoluble Melt processing temperature >350.F (>177.C) Specific Gravity (H20=1) 1.1-1.3 Other soft, relatively low modulus non-ionomeric thermoplastic elastomers may also be utilized to produce the outer cover layer as long as the nonis ionomeric thermoplastic elastomers produce the ptayability and durability characteristics desired without adversely effecting the enhanced spin characteristics produced by the low acid ionomer resin compositions. These include, but are not limited to 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 Atochern S.A.

Similarly, a castable, thermosetting polyurethane produced by BASF under the trade designation BaytecO has also shown enhanced cover formulation properties. According to BAS17, BaytecO (such as Baytec@ RE 832), relates to a group of reactive elastomers having outstanding wear resistance, high mechanical strength, high elasticity and good resistance to weathering, moisture and chemicals. The BaytecO RE-832 system gives the following typical physical properties:

p ASIN Test Net unit vat- Tear StreMth D624 PLI 180 Die C - Proper ASTN Test Method unit Vatue Stress at 100% Modutus D412 psi 320 200% Modutus 460 300% Modutus 600 Uttimate Strength D412 psi 900 ELongation at Break D412 % 490 Taber Abrasion D460, H-1B mg/1000 cycies 350 Part A Part B Comt 1 Properties 1 s-te) (Resin) Viscosity @ 25% mPa.s 2500 2100 Density @ 25% g/cm 1.08 1.09 NCO, % 9.80 HydroxyL Number, Mg KON/9 88 Component A is a modified diphenylmethane diisocyanate (niDI) prepoLymer and component 8 is a potyether polyot btend.

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 filter materials.

As used herein, the term "heavy weight filler materialC 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.

As noted above, it has been found that increasing the weight of the ball towards the outer perimeter produces an increase in the ball's moment of inertia.

Preferably, 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 moment of inertia of the ball without affecting the ball's feet and durability characteristics. However, as described below, it may in some instances be preferred to incorporate 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, KeviarO 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. Representatives of such 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 is understood that the foregoing materials may be in other forms besides powders.

Examples of various suitable heavy filler materials which can be included in the present invention are as follows:

Filler Type Spec. Gravity graphite fibers 1.5-1.8 precipitated hydrated silica 2.0 clay 2.62 talc 2.85 asbestos 2.5 glass fibers 2.55 aramid fibers (KeviarC) 1.44 mica 2.8 calcium metasilicate 2.9 PCTIUS98106163 46 Filler Typ Spec. Gravi barium sulfate 4.6 zinc suffide 4.1 silicates 2.1 diatomaceous earth 2.3 calcium carbonate 2.71 magnesium carbonate 2.20 Metals and Alloys (powders) titanium 4.51 tungsten 19.35 aluminum 2.70 bismuth 9.78 nickel 8.90 molybdenum 10.2 is iron 7.86 copper 8.94 brass 8.2-8.4 boron 2.364 bronze 8.70-8.74 cobalt 8.92 beryllium 1.84 zinc 7.14 fin 7.31 Metal Oxides zinc oxide 5.57 iron oxide 5.1 aluminum oxide 4.0 titanium dioxide 3.94.1 magnesium oxide 3.3-3.5 zirconium oxide 5.73 Metal Stearates zinc stearate 1.09 calcium stearate 1.03 - 47 Filler Type Spec. Gravity barium stearate 1.23 lithium stearate 1.01 magnesium stearate 1.03 Particulate carbonaceous materials graphite 13-1.8 carbon black 1.8 natural bitumen 1.2-1.4 cotton flock 1.3-1.4 cellulose flock 1.15-1.5 leather fiber 1.2-1.4 The amount and type of heavy weight filler material utilized is dependent is upon the overall characteristics of the low spinning multi-layered golf bail 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.

Additional materials may be added to the cover compositions (both inner and outer cover layer) of the present invention including dyes (for example, Ultramarine Blue sold by Whitaker, Clark and Daniels of South Plainsfield, N.J.) (see

U.S. Patent No. 4,679,795); pigments such as titanium dioxide, zinc oxide, barium sulfate and zinc sulfate, and optical brighteners, LIV absorbers; antioxidants; antistatic agents; and stabilizers. Further, the 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 bail's moment of inertia and reduce the overall spin rate. In a most preferred embodiment, golf balls with weighted perimeters utilize a visible pattern of weighting material disposed along a portion of the outer periphery of the ball. Although not wishing to be bound to ary particular theory, it is believed that 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 alorg the ball's outer periphery. Moreover, for the most preferred embodiment balls utilizir g a visible pattern of weighting material, the shape of such pattern can also serve c s.

is a unique identifier of the ball. Furthermore, by providing a weighting system that s visible or otherwise viewable along a golf ball's exterior, a consumer may readi y determine whether a particular golf ball comprises a weighting system.

The present invention provides an array of particularly preferred pattenis of weighting material. FIG. 3 illustrates a preferred embodiment golf ball 30 n accordance with the present invention utilizing a visible star-shaped perimet r weighting system 32. This system comprises a first pattern preferably centered about a dimple, and having a plurality, namely five (5), radially extending arms extendi ig outward from the center of the pattern or dimple. The sides of each radia ly 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 on the opposite side of the ball 30. This second pattern is most preferably directly opposite from the first pattern and is of equal size and mass as the first pattern.

These considerations are described in greater detail below.

FIG. 4 is an elevationai 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.

is 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 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 and mass as the first pattern.

so FIG. 6 illustrates a preferred embodiment golf ball 60 in accordance with the present invention utilizing a visible radiused pentagon-shaped perimeter weighting system 62. 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 patten) of the system 62 also extends over an additional five (5) dimples. The golf ball 6Q further comprises a second visible radiused pentagon-shaped perimeter weighting system pattern located on the opposite side of the ball 60. The second pattern is most preferably directly opposite from the first pattern and is of equal size and mas as the first pattern. 10 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 slighti larger in width than the diameter of a typical dimple on the golf ball 70. The striple preferably extends around the circumference of the ball 70. is FIG. 8 illustrates a preferred embodiment golf ball 80 in accordance wit l the present invention utilizing a double striped perimeter weighting system 82. It ca l be seen that the stripes preferably intersect one another at right angles, and that th, a 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 th a 20 circumference of the ball 80. It is also preferred that the stripes are equal in widtI, or approximately so. FIG. 9 is an elevational view of a preferred embodiment golf ball 90 i i accordance with the present invention utilizing a multi-stripe perimeter weightin3 system 92. As shown in FIG. 9, the mufti 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 greater than the diameter of a typical dimple on the ball 90. And, the stripes are of equal width. Each stripe preferably extends around the circumference of the ball 90.

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.

Most preferably, 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 is shown in FIG. 11. The system comprises a plurality of rings 114 and 116 and a center weighted dimple or spot 118. Preferably, 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.

It will be understood that in all of the foregoing preferred embodiments, it is particularly preferred that the center of mass of the weighted ball coincides with the geometrical center of the ball, i.e., its centerpoint. This is the primary reason for providing a second identical pattern of weighting material on an opposite side from a first pattern. If a single pattern of weighting material is provided on only one side of a ball, the resulting center of mass of the ball will be offset from the ball's centerpoint.

In preparing golf balls in accordance with the present invention, 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 is 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 composMon comprising a high cis content polybutadiene and a metal salt of an a, P, ethylenically unsaturated carboxylic acid such as zinc mono or diacrylate or methacrylate. To achieve higher coefficients of restitution in the core, the manufacturer may include fillers such as small amounts of a metal oxide such as zinc oxide. In addition, lesser amounts of metal oxide can be included in orderto lighten the core weight so that the finished ball more closely approaches the U.S.G.A. upper weight limit of 1.620 ounces. Other materials may be used in the 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.

It will be understood that a wide array of other core configurations and materials could be utilized in conjunction with the present invention. For example, 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 specially produced core compositions and resuffing molded cares of the present invention are manufactured using relatively conventional techniques.

In this regard, 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. As a base elastomer for the core composition, cis- polybutadiene is preferably employed, or a blend of cis-polybutadiene with other elastomers may also be utilized. Most preferably, cis-polybutadiene having a weight- average molecular weight of from abo ut 100,000 to about 500,000 is employed. Along this line, R has been found that the high cis-polybutadiene manufactured and sold by Shell Chemical Co., Houston, Texas, under the tradename Carblex BR-1220, the high cis- polybutadiene sold by Bayer Corp. under the designation Taktene 220, and the polyisoprene available from Muehistein, H & Co., Greenwich, Connecticut under the designation "SKI 3W are particularly well suited.

The unsaturated carboxyfic acid component of the core composition (a co-crosslinking agent) 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. Preferably, 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. Preferably, the acid component is either acrylic or methacrylic acid. Usually, from about 15 to about 25, and preferably from about 17 to about 21 parts by weight of the carboxylic acid salt, such is as zinc diacrylate, is included in the core composition. 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-crosslinking agent) which decomposes during the cure cycle. The term 1ree radical initiatoC' as used herein refers to a chemical which, when added to a mixture of the elastorneric blend and a metal salt of an unsaturated, carboxylic acid, promotes crosslinking of the elastomers, by the metal salt of the unsaturated carboxylic, acid. The amount of the selected initiator present is dictated only by the requirements of catalytic activity as a polymerization initiator. 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.

Exemplary of suitable peroxides for the purposes of the present invention are dicumyi 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.

Examples of such commercially available peroxides are Luperco 230 or 231 XL sold by Atochem, Lucidol Division, Buffalo, N.Y., and Trigonox 17140 or 29140 sold by Akzo Chemie America, Chicago, Illinois. In this regard Luperco 230 XL and is Trigonox 17140 are comprised of n-butyl 4,4-bis (butylperoxy) valerate; and, Luperco 231 XL and Trigonox 29140 are comprised of 1,1-bis(t- butylperoxy)-3,3,5-trimethyI cyclohexane. The one hour half life of Luperco 231 XL is about 112%, and the one hour half life of Trigonox 29140 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, metal oxides, fatty acids, and diisocyanates and poiypropylene powder resin. For example, Papi 94, a polymeric dfisocyanate, commonly available from Dow Chemical Co., Midland, M1, is an optional component in the rubber compositions. It can range from about 0 to 5 parts by weight per 100 parts by weight rubber (phr) component, and acts as a moisture scavenger. In addition, it has been found that the addition o a polypropylene powder resin results in a core which is too hard (i.e. exhibits toy compression) and thus allows for a reduction in the amount of crosslinking agen utilized to soften the core to a normal or below normal compression.

Furthermore, because polypropylene powder resin can be added to core composition without an increase in weight of the molded core upon curing, the addition of the polypropylene powder allows for the addition of higher specific gravit fillers (if desired), such as mineral fillers. Since the crosslinking agents utilized in the polybutadiene core compositions are expensive andlor the higher specific gravitr fillers are relatively inexpensive, the addition of the polypropylene powder resin substantially lowers the cost of the golf ball cores while maintaining, or towering, weight and compression.

The polypropylene (C3H powder suitable for use in the preser t invention has a specific gravity of about 0.90 g/cm3, a melt flow rate of about 4 t) is about 12 and a particle size distribution of greater than 99% through a 20 mesh screen. Examples of such polypropyiene powder resins include those sold by th Amoco Chemical Co., Chicago, Illinois, under the designations "6400 P', '7000 P' and '7200 P'. Generally, from 0 to about 25 parts by weight polypropylene powder per each 100 parts of elastomer are included in the present invention.

Various activators may also be included in the compositions of th present invention. For example, zinc oxide andlor magnesium oxide are activatols for the polybutadiene. The activator can range from about 2 to about 50 parts ty weight per 100 parts by weight of the rubbers (phr) component. The amount of activation utilized can be reduced in order to tighten the weight of the core.

Moreover, reinforcement agents may be added to the composition of the present invention. As noted above, 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.

As indicated, ground flash filler may be incorporated and is preferably mesh ground up center stock from the excess flash from compression molding.

is 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 moldability and processing. Generally, free fatty acids having from about 10 to about 40 carbon atoms, and preferably having from about 15 to about 20 carbon atoms, are used. Exemplary of suitable fatty acids are stearic acid and linoleic acids, as well as mixtures thereof. Exemplary of suitable metallic salts of fatty acids include zinc stearate. When included in the core compositions, 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 parts rubber (elastomer).

Diisocyanates may also be optionally included in the core composition when utilized, the diisocyanates are included in amounts of from about 0. 2 to abou 5.0 parts by weight based on 100 parts rubber. Exemplary of suitable diisocyanate is 4,4'-diphenyimethane diisocyanate and other polyfunctional isocyanates know tc the art.

Furthermore, the dialkyl tin difatty acids set forth in U.S. Patent No, 4,844,471, the dispersing agents disclosed in U.S. Patent No. 4,838,556, and th dithiocarbamates set forth in U.S. Patent No. 4,852,884 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 is one metallic salt of an unsaturated carboxylic acid, and 1 to 10 parts by weight of a free radical initiator.

As indicated above, additional suitable and compatible modifying agents such as pardcuiate 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.

In producing golf ball cores utilizing the present compositions, the ingredients may be intimately mixed using, for example, two roil mills or a BanburyO mixer until the composition is uniform, usually over a period of from about 5 to about minutes. The sequence of addition of components is not critical. A preferred blending sequence is as follows.

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 BanburyO mixer. As a result of shear during mixing, the temperature rises to about 2000F. The initiator and diisocyanate are then added and the mixing continued until the temperature reaches about 220OF 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 is about 320OF for about 14 minutes. After molding, 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). Alternatively, the cores are used in the as- molded state with no grinding needed to achieve roundness.

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.

Usually the curable component of the composition will be cured b heating the composition at elevated temperatures on the order of from about 2750F to about 3500F, preferably and usually from about 290OF to about 325017, with moidin of the composition effected simultaneously with the curing thereof. The compositior can be formed into a core structure by any one of a variety of molding techniques e.g. injection, compression, or transfer molding. When the composition is cured by heating, the time required for heating will normally be short, generally from about 1 (1 to about 20 minutes, depending upon the particular curing agent used. Those ol ordinary skill in the art relating to free radical curing agents for polymers ard conversant with adjustments of cure times and temperatures required to effect optimum results with any specific free radical agent.

After molding, the core is removed from the mold and the surfarA 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 is such as corona discharge, ozone treatment, sand blasting, and the like. Preferably surface treatment is effected by grinding with an abrasive wheel.

The relatively thick inner cover layer which is molded over the core 1 about 0.200 inches to about 0.055 inches in thickness, and preferably about 0.075 inchesthick. The outer cover layer is about 0.010 inches to about 0.110 inches if) thickness, and preferably 0.055 inches thick. A preferred range for the overa 1 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 fron) about 0.100 inches to about 0.200 inches. Individually, 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. Together, 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. In the case of 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 BanburyO 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. Alternatively, 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, is may be added and uniformly mixed before initiation of the moiding 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.

Golf balls comprising the preferred embodiment visible perimeter weighting system can be formed according to the teachings herein. A wide array of techniques can be utilized to incorporate relatively high density weighting material into or along the outer periphery of a golf ball, and preferably such that the material is deposited or formed into a desired pattern, and most preferably, such that the weighting material is visible from the ball's exterior.

Preferably, 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 of 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 moided about the pattern of weighting material.

Adthough this is a preferred method, it is also contemplated that a plup manufacturing technique could be utilized. In that technique, plugs of the desirec pattern of weighting material are incorporated into the outer periphery of the ball tc 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 otherMse dispose one of more layers of a transparent or semi-transparent material over the pattern ol is weighting material disposed in the ball.

In all of the foregoing techniques, the incorporation of weighting materia in a particular pattern is utilized to increase the moment of inertia of the ball. ThiE results in increasing the travel distance of the ball by decreasing initial spin rates, ye, maintaining playability of the ball by increasing terminal spin rates. That is incorporation of patterns of weighting material in a golf ball decreases the spin decay of the ball from the point of impact to the time at which the ball is at rest.

Moreover, it is also wfthin the scope of the present invention to provide a perimeter weighfing system in a golf ball by utilizing a single layer, such as a covet 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. Although either 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.

is In compression molding, the inner cover composition is formed via injection at about 380F to about 450OF 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 20017 to 3000 F for about 2 to 10 minutes, followed by cooling at 50OF to 70OF for about 2 to 7 minutes to fuse the shells together to fbrm a unitary intermediate ball. In addition, 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 of time in a mold temperature of from 50'F to about 1000F. Subsequently, the outer cover layer is molded about the core and the inner layer by similar compression or injection molding techniques to form a dimpled golf ball of a diameter of 1.680 inches, or more. After molding, the golf balls produced may undergo various furthe processing steps such as buffing, painting and marking as disclosed in U. S, Patent No. 4,911,451.

he finished golf ball of the present invention possesses the following general features:

A) Core (preferably a solid core) 1) Weight, from about 18 to 39 grams, preferably, 25 to 30 gramg most preferably 297-29.8 grams.

2) Size (diameter), from about 1.2B to 1.57 inches, preferably, 1.37 to 1.54 inches, most preferably 1.42 inches.

3) Specific gravity, from about 1.05 to 1.30, preferably 1. 10 to 1.2% most preferably 1.2.

4) Compression (Riehie), from about 60 to about 170, preferably 11 is to 140, most preferably 117 to 124.

5) Coefficient of Restitution (C.O.R.), from about.700 to about.80c, preferably.740 to.780, most preferably.765 to.770.

B) Inner Cover Layer (Mantle) and Core 1 Weight, from about 25.9 to 43.0 grams, preferably, 29 to 40 grams, most preferably 38.4 grams.

2) Size (diameter), from about 1.38 to 1.68 inches, preferably, 1.50 to 1.67 inches, most preferably 1.57 inches.

i 3) Thickness of inner cover layer, from about.010 to about.200 inches, preferably.055 to.150, most preferably 0.075 inches.

4) Specific gravity (inner cover layer only), from about.96 to 1.80, preferably 1.00 to 1.30, most preferably 1.05.

* 5) Compression (Riehie), from about 59 to about 169, preferably 80 to 96, most preferably 84-92.

6) Coefficient of Restitution (C.O.R.), from about.701 to about.820, preferably.750 to.810, most preferably.790 to.800.

7) Shore CID Hardness, from about 87160 to about >1001100, preferably 92165 to >100185, most preferably 97170.

C. Outer Cover Layer. Inner Cover Layer and Core 1) Weight, from about 45.0 to 45.93 grams, preferably, 45.3 to 45.7 grams, most preferably 45.5 grams.

2) Size (diameter), from about 1.680 to 1.720 inches, preferably, 1.680 to 1.700 inches, most preferably 1.68 inches.

3) Cover Thickness (outer cover layer), from about.010 to about inches, preferably.010 to. 110, most preferably 0.055 inches.

4) Compression (Rlehie), from about 59 to about 160, preferably 80 to 96, most preferably 76-85.

5) Coefficient of RestiMion (C.O.R.), from about.701 to about.825, preferably.750 to.810, most preferably.785 to.790.

6) Shore CID Hardness, from about 35120 to about 92165, preferably 40125 to 90160, most preferably 87156.

7) Moment of Inertia, from about.390 to about.480, preferably.430 to.460, most preferably 0.445.

The most preferred characteristic noted above are included in Applicant's soon to be commercialized "Strata Advance" balls. These balls ("Strata Advance 90" and "Strata Advance 100') contain smaller and lighter cores and heavier and thicker thermoplastic inner cover layers. The enhanced weight in the inner cover layer is produced, in part, through the inclusion of 10 phr of powdered brass. The displacement of weight from the core to the inner cover layer produces a golf ball with a greater moment of inertia, reduced spin and longer travel distance without affecting the balis'feel and durability characteristics. The components and physical properties of these balls are shown below.

CME Fotati Advance 90 Ad"me 100 R Carif Lex 1220 n n (High Cis-poLybutadi-) Taktene 220 30 30 (High Cis-poLybutadiene) Zinc Oxide 31 30.5 TG Regrind 20 20 (core regrind) Zinc Diacrytate 17.5 18.5 Zinc Stearate is 15 231 XL Peroxide 0.9 0.9 Cwe Da Size 1.4211 1.4211 0.003 Weight (gram) 29.7 29.7 0.3 C" (RlebLe) 124 117 +1- 5 C.O.R..765.770.015 Spec. Grav. 1.2 1.2 - Foroutatiom Modutus Spec. Grav. Distance 90 Distance 100 Rang lotek 1002 380 MPa 0.95 45 45 lotek 1003 147 MPe 0.95 45 45 Powdered Brass ---- 8.5 10 10 Btend ModuLus (Estimated) 264 MPa 264 MPa Spec. Gray- BLend 1.05 1.05 Nwtte Dat size 1.5711 1.57p 0.003 Thickness 0.07511 0.07511 0.003 Weight (grew) 38.4 38.4 +P 0.3 Comp (Riehie) 92 84 4 is COR.795.800.015 Shore CID 97170 97170 1 t FormuLatiom Modutus Advance 90 Advance 100 R Iotek 7510 35 MPa 58.9 58.9 lotek a000 320 MPa 33.8 33.8 lotek 7030 155 MPa 7.3 7.3 BLend ModuLur.

(Estimated) 140 MPe 140 MPa Spec. Grav. Blend 0.98 0.98 Whitener Pac Unitane 0-1101 2.3 phr 2-3 phr Eastobrite 08-12 0.025 phr 0.025 phr Uttra Marine Blue3 0.042 phr 0.042 phr Santonox R4 0.004 phr 0.004 phr utt oat Size 1.6811 1.68P 0.003 Cover Thickness 0.05511 0.05511 +p 0.003 Kenijm Pigments Inc. Savannah. CA Easmianchemicals. Kingsport, TX Whittaker. Clark. & Daniels Inc., Plainfleld. NJ Monsanto Co., St. Louis. MO Forinutations Modul Advance 90 Advance 10 Rang Weight (grams) 45.5 45.5 0.4 Comp (Riehte) 80 76 +1- 4 C.O.R..785.790 +p.015 Shore CID 87156 87156' +/- 1 Moment of inertia 0.445 0.445 ------ With respect to Applicant's currently available multi-layer golf balls (i. e,, "Strata Tour"), the cores of the new balls are substantially smaller (1.42" versus 1.47") and lighter (29.7 grams versus 32.7 grams) have thicker (i.e., 0. 07T, versus 0.050") and heavier (8.7 grams versus 5.7 grams) inner cover layers. 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:

is tt-rata 100 Strata 90 úore Data size 1.4711 1.4711 Weight 32.79 32.79 Comp (Riehte) 99 106 C.O.R..770-.795.765-395 Specific Gravity 1.209 1.209 Hardness (Shore C) 74-78 78-81 -Mantte or Inner_19"r Data Size 1.57 1.57 Weight 38.49 38.49 Comp (RiehLe) 85 85 C.O.R..795-310.795-.810 Thickness 0.05011 0.05011 Hardness (Shore C/D) 97170 97170 Specific Gravity 0.95 0.95 i Outer Layer Data Cover Hardness (Shore CID) 78147 n/47 Thickness 0.05511 0.05sty Specific Gravity 0.97 0.97 Final Bati. Data Size 1.6811 1.68n Weight 45.49 45.49 Comp (Riehte) 76 81 C.O.R..785-.810.783-310 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 is with soft balata and balata-like covers of the prior art. In addition, the balls spin less and travel farther.

The present invention is further illustrated by the following examples in which the parts of the specific ingredients are by weight. It is to be understood that the present invention is not limited to the examples, and various changes and modifications may be made in the invention without departing from the spirit and scope thereof.

Example 1

A number of mufti-layer golf balls (solid cores plus inner and outer cover layers) containing metallic particles andlor heavy weight filler additives in the inner cover layer were prepared according to the procedures described above. The moment of inertia (91CM2) of these balls were compared with commercially available - two piece, three piece and other multi-layered balls. The results are set forth in tl Tables below.

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 moldilig 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 coms and Sample No. 23 for 1.47 inch cores.

The above cores exhibited the following general characteristics:

For SamLes WO.5 1-16 For SawLes No.s 17-19 Size 1.4741 size 1.4711 Weight (grams) 32.7 weight (grams) 32.7 Comp (Richte) 100 Ccap (Richte) 99 is Spec. Grav. 1.209 C.O.R..763 C.O.R..761 The inner thermoplastic cover layer (or mantle layer) used in tl Example comprised of a 500/6150% blend of ethylene acrylic acid ionomer resins, LI lotek 1002 and lotek 1003. These ionomers exhibit the characteristics genera defined above.

A series of golf balls were formulated with inner cover layers containi ig 5 phr of various metal particles or heavy weight fillers and 47.5% lotek 1002 a id 47.5% lotek 1003. Two (2) control balls were also produced(Sample Nos. 14 a 1d 25 15 below) containing no fillers (i.e., 50% lotek 1002 and 50% lotek 1003). T le general properties of the balls were measured according to the following perimetes:

- Riehie compression is a measurement of the deformation of a golf ball in thousandths of inches under a fixed static load of 200 pounds (a Riehie compression of 47 corresponds to a deflection under load of 0.047 inches).

PGA compression is determined by a force applied to a spring (i.e., 80 PGA = 80 Riehie; 90 PGA = 70 Riehie; and 100 PGA = 60 Riehie) and manufactured by OK Automation, Sinking Spring, PA 19608.

Coefficient of restitution (C.O.R.) 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.

is The following properties were noted:

SIZE WEIGHT COMP. (RIEHLE) C.O.R.

Sample Center & Molded Center & Molded Center Molded Center & Molded No. Additive to Mantle Mantle Cover Mantle Cover L Mantle Cover Mantle Cover 1 Bismuth Powder 1.573 1.686 38.8 45.89 84 79 0.7921 0.7765 2 Boron Powder 1.574 1.686 38.8 45.79 83 79 0.7943 0.7754 3 Brass Powder 1.575 1.686 38.9 45.9 84 80 0.7944 0.7757 4 Bronze Powder 1.573 1.686 38.8 45.89 84 80 0.7936 0.7770 Cobalt Powder 1.573 1.686 38.9 45.88 82 79 0.7948 0.7775 W (n 10 6 Copper Powder 1.574 1.686 38.9 45.9 84 80 0.7932 0.7762 4 7 Inconel Metal Powder 1.574 1.687 39.0 45.94 83 80 0.7926 0.7757 m 8 Iron Powder 1.575 1.686 38.9 45.98 83 79 0.7928 0.7759 U) m 9 Molybdenum Powder 1.575 1.686 38.9 45.96 84 80 0.7919 0.7765 m Nickel Powder 1.574 1.686 38.9 45.96 85 79 0.37917 0.7753 11 Stainless Steel Powder 1.574 1.687 38.9 45.92 86 78 0.7924 0.7757 12 Titanium Metal Powder 1.574 1.687 39.0 45.92 84 79 0.7906 0.7746 13 Zirconium Oxide Powder 1.575 1.686 38.9 45.92 85 80 0.7920 0.7761 14 Control 1.574 1.686 38.5 45.63 86 80 0.7925 0.7771 is Aluminum Flakes 1.575 1.687 39.0 45.91 84 77 0.7830 16 Aluminum Tadpoles 1.576 1.687 39-0 45.96 83 78 0.7876 0.7717 17 Aluminum Flakes 1.576 1.686 38.9 45.92 77 0.7829 0.7676 18 Carbon Fibers 1.576 1.687 38.9 45.88 79 74 0.7784 0.7633 L-29- Control 1.576 1.687 38.7 45.74 82 79 0.7880 0.7737 In addition to the samples produced above, a number of further samples were produced wherein the size and weight of the cores were reduced and the thickness and weight of the inner cover layers were increased. This can be seen in Sample Nos. 20-23 (below) when the following formulations were utilized.

SAMPLE NOS.

21 22 23a 23 Core Data Cariflex: 1220 70 70 70 70 70 Taktene 220 30 30 30 30 30 Zinc Oxide 34 20 6 31.5 34 TG Regrind 20 20 20 16 20 Zinc UjaaWe 17.5 1 B 18.5 20 17.5 (ZDA) Zinc Stearate 15 is is 16 is 231 XL Peroxide 0.9 0.9 0.9 0.9 0.9 Color Pink Orange Green Pink Size (in 1.42 1.42 1.42 1.47 1.42 Weight (gram) 29.4 27.9 26.1_ 32.5 29A S.G. 1.216 1.146 1.073 1.209 1.216 Comp. (R) 130 128 130 106 130 C.O.R..757.772.765.757 Mande Data 20 21 22 23a 23 lotek 1002 so 50 so so 50 lotek 1003 50 so 50 so so Tungsten 4 26.2 51 4 Thickness- 0.07T 0.07W 0.07T 0.05T 0.075 S.G. 0.98 1.19 1.405 0.96 0.98 Weight Onams) 38.3 3EL2 38.5 38.5 38-2 Comp. (Richle) 92 93 91 86 C.O.R. 797 801 804 797 797 is Ball Data Cover Material lotek 8000 19% lotek 8OW 19% lotek 8000 19% lotek 8000 19% lotek 7510 42% lotek 7030 19% lotek 7030 19% lotek 7030 19% lotek 7030 19% latek 7520 42% lotek 7520 iotek 7520 lotek 7520 lotek 7520 lotek 8000 8.7% 52.4% 52.4% 52.4% 52.4% lotek 7030 7.3% 2810 MB 9.56% 2810 MB 9,56% 2810 MB 9.56% 2810 M8 9.56% Dimple 422 Tri 422 Tri 422 Tri 422 Tri 422 Tri Size (inches) 1.684 1.684 1.685 1.684 1.686 Weight (grams) 45.4 45.5 45.6 45.8 45.5 Comp (RiLhle) 82 73 83 81 85 C.O.R..789 791.791.788 -781 Shore D 57 57 57 57 48 The moment of inertia characteristic of the balls utilized in this Example (i.e., the balls of the invention and commercially available balls) was measured using Moment of Inertia Measuring Instrument Model 5050 made by Inertia Dynamics of Wallingford, CT. It consists of a horizontal pendulum with a top-mounted cage to hold the ball. The period of oscillation of the pendulum back and forth is a measure of the is moment of inertia of the item in the cage. The machine is calibrated using known objects (sphere, cylinder) whose moments are easily calculated or are known.

Actual use of the instrument is as follows. The pendulum is swung with the cage empty. This determines the moment of the machine, less any objects. The ball to be tested is then placed in the cage and the pendulum is swung again. The pedod of oscillation will be longer, as the moment of inertia is greater with the ball in the device.

The two pedods are used to calculate the moment of inertia of the ball, using the formula: 1=194.0(tA2-TA2) where the 194.0 is the calibration constant for the machine, the T is the period of oscillation of the empty instrument, and t is the period of oscillation of the instrument with the ball loaded.

The following results were obtained:

Core Moment Ball Type Sample Size Mantle Additive phr of Inertia Ball Size Muni-Layer 1 1.47 lotek 1002JIW3 Bismuth 5 0.447 1.68 MulWLayer 2 1.47 lotek 1002J1003 Boron 5 0.443 1.68 Myer 3 1.47 1 100211003 Brass 5 0.449 1.68 Layer 4 1.47 lotek 100211003 Bronze 5 0.446 1.68 Multi-Layer 5 1.47 lot" 1002f1003 Cobalt 5 0.449 1.68 MuRPLayer 6 1.47 1 10OW1003 Copper 5 0.447 1.68 Multi-Layer 7 1.47 1 100211003 Inconel 5 0.450 1.68 is Multi-Layer a 1.47 1 1W2J1003 Iron 5 0.450 1.65 9 1.47 lotek 1OW1003 Molybdenum 5 0.448 1.68 MultPLayer 10 1.47 1 1002J1003 Nickel 5 0.452 1.68 Stainless Multi-Layer 11 1.47 k 1007J1003 Steel 5 0A51 1.6B Layer 12 1.47 lotek 11X12J1003 Titanium 5 0.447 1.68 Zirconium Multi-Layer 13 1.47 1 1 1W2J1003 Oxide 5 0.448 1.68 None Multi-Layer 14 1.47 1002J1003 (control) 0 0.441 1,68 Aluminum Ltyer 15 1.47 lotek 1W2/1003 Flakes 5 0.449 1.68 Aluminum mub. 16 1.47 1 lotek 1007J1003 Tadpoles 5 0.443 1.68 Aluminum Muk 17 1.47 lotek 1002M003 Flakes 5 0.446 1.65 Carbon Multi-Layer 18 1.47 lotek 1007J1003 Fibers 5 0.443 1.68 None L%M-Layer 19 1.47 lotek 1002J1003 (control) 0 0.442 1.68 Muffi-Layer 20 1.42 k 1007J1003 Tungsten 4 0.436 1.68 Mukf 21 1.42 k 1007J1003 Tungsten 26.2 0A50 1.68 Multi-Layer 22 1.42 100211003 Tungsten 51 0.460 1.68 MUM-Layer 23 1.47 lotek 1002J1003 non (control) 0 0.441 1.6a L-I S Tour 1.47 Hard lowme, none 0 0.444 1.68 -16 Core Moment Ball Type Sample size Mantle Additive phr of Inertia Ball Size Precept Dynawing DC 144 Soft lonomer Unknown -- 0.433 1,68 Wilson Ultra T02 multi-layer Tour Balata 1.52 Hard lonorner (as Colorant) Low 0.453 1.68 Mufti-Layer 3 Precept Tour Ti02 Piece DC Wound Hard lonorner (as Colorant) Low 0.405 1.68 Tideist Tour 3-Piece Balata Wound None 0.407 1.68 Tifleist Tour 3-Fiece Balata Wound None - - 0.412 1.68 2-Piece Top Flite XL 1.545 None - - 0.445 1.68 Top Flite Z 2-Piece Baleta 1.545 None - 0.448 1.68 2-Piece Top Flite Oversize Magna 1.545 None - - 0.465 2-Piew Top Ffite Oversize Magna EX 1.57 None - - 0.463 1.72 The above results demonstrate that the inclusion of metal particles or other heavy weight filler materials in the inner cover layer produces a higher moment of inertia than the same ball without the materials. This can be seen in comparing Sample Nos. 14 and 19 containing no metal particles in the inner cover layer with Sample Nos. 1-13 and 15-18 containing such heavy weight fillers.

Moreover, as shown in 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. In this regard, 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.

Example 2

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. In this regard, four (4) different core formulations (i.e.. Core Formulations A-D) were produced wherein the weight in two of the cores, i.e., Core Formulations C and D, was reduced. These formulations were compared to Core Formulation E, the core currently utilized in Spalding's two-piece Top-Flite Z-Balata 100 production ball.

Core Formulations Materials A a C D E Cariflex 1220 70 70 70 70 70 Taktene 220 30 30 30 30 30 Zinc Oxide 26.7 25 5 5 18 Zinc Stearate 0 0 0 0 20 Zinc Diacrylate (MA) 22.5 24 24 22.5 29.7 Stearic Acid 2 2 2 2 0 TG Regrind 16 16 16 16 10.4 is 231 XL Peroxide 0.9 0.9 0.9 0.9 0.9 Properties Size (inches) 1AT' 1AT' 1.47" 1.47" 1.47' Specific Gravity 1.19 1.17 1.07 1.07 1.15 Weight (grams) 34.4 31.8 29.1 29.3 38.1 Compression (Riehie) 106 83 91 114 78 C.O.R..771.789.790.774.799 As shown above, the weight andior specific gravity of the core can be decreased (i.e., compare Core Formulations C and D with Core Formulations B and A) without substantially effecting the C.O.R. values of the core. In turn, the effectiveness of increasing the weight of the inner cover layer (or mantle) was evaluated by adding a heavy filter material such as tungsten powder to the inner cover (mantle) formulations. This is shown in the mantle and cover formulations set forth below.

Mantle and Cover Formulations Materials 1 2 3 4 lotek 8000 50 50 --- 33 lotek 7030 50 50 -- - lotek 959 -- - 50 lotek 960 50 lotek 7510 57.5 TG White MB 9.5 Tungsten Powder 62.5 80 Zinc Stearate - 50 The finished ball properties of the various combinations of care, mantle is and outer cover formulations are as follows:

sample Sample Sample Sample sample sample Sample sample #24 25 #26 #27 028 #29 #30 #31 COM Dma Type A B c D c D D E Size 1.47 1Ar 1.4r 1.4r 1.47" 1.47' 1.4r 1.57 S.G. 1.19 1.17 1.07 1.07 1.07 1.07 1.07 1.15 ht 32.4 31.8 29.1 29.3 29.1 29.3 29.3 38.1 106 83 91 1114 91 114 114 78 C.O.R..771.789 -790.774.790.7741.774.799 0 FR M Dab M 1 1 2 2 3 FonulatIon sim 1.57 1.57 1.57 1.57 1.57 1.57 1.57 &G. 0.95 0.95 0.95 0.95 1.53 1.53 les WMAN 37.8 37.6 34.8 34.7 37.8 37.7 37.4 ECOM. 93 77 83 100 83 100 99 O.R..7937.804.810.801.806 -795.716-.802 - Sampi Sample Sample sampi Samp sample Sampi Sample 24 #25 #26 27 #28 #29 #30 #31 Finished Ball Data Cover 4 4 4 4 4 4 4 4 Formulation size 1.681 1.681 1.682 1.682 1.681 1.681 1.681 1.682 S.G. 0.97 0.97 0.97 0.97 0.97 0.97 0.97 0.97 WeiOt 45 44.8 41.9 419 45 1 44 R 44.5 45.4 Corno. 80 69 74 86 74 84 83 76 C.O.R..787.801.8w.787.799.790.787.802 EMoment of 0.433834 0A31195 Not Not 0.454017 69 Not 0 %:nt c Tested Tested 0.4491 Tested lnertia The results indicate that the displacement of weight from the core to the is mantle or inner cover layer enhances the moment of inertia of the balls. This is demonstrated particularly in comparing Sample Nos. 24-25 with Sample Nos. 28-30.

Accordingly, the formulation of a lighter core with a heavier inner cover or mantle layer produces a ball having an increased moment of inertia.

Example 3

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 (Riehie) and C.O.R. The two multi- layer golf balls produced had the following cover properties.

CORE Formulations Sample 32 Sample #33 Cariflex 1220 70 70 (High Cia-polybutadiene) 1 Fonnulations Sample #32 Sample #33 Taktene 220 30 30 (High Cis-polybutadiene) Zinc Oxide 31 30.5 TG Regrind 20 20 (Core regrind) Zinc Diacrylate 17.5 18.5 Zinc Stearate 15 15 231 XL Peroxide 0.9 0.9 Core Data Size 1.47' 1.47' Weight (grams) 29.7 29.7 Comp (Riehie) 124 117 C.O.R..765.770 is Spec. Grav. 1.2 1.2 MANTLE Formulations Modulus Spec. Grav. Sample #32 Sample 933 lotek 1002 380 MPa 0.95 45 45 lotek 1003 147 MPa 0.95 45 45 Powdered Brass - 8.5 10 10 Blend Modulus 264 MPa 264 MPa (Estimated) Spec. Gfav. Blend 1.05 1.05 Mantle Data size 1.5T' 1.57" Thb 0.07T 0.075' Weight (grams) 38.4 38A Comp (Riehie) 92 84 C.O.R..795.800 Shore CID 97[70 97170 COVER Formulations Modulus Sample #32 Sample #33 lotek 7510 35 MPa 58.9 58.9 lotek 8000 320 MPa 33.8 33.8 lotek 7030 155 Mpa 7.3 7.3 Formulations Modulus Sample #32 Sample #33 Blend Modulus (Estimated) 140 MPa 140 MPa Spec. Grav. Blend 0.95 0.98 Whitener Packa-ge Unitane 0-110 2.3 phr 2.3 phr Eastobrite OB-1 0.025 phr 0.025 phr Ultra Marine Blue 0.042 phr 0.042 phr Santonox R 0.004 phr 0.004 phr Ball Data Size 1.6Er' 1.W Cover Thickness 0.05T 0.0561 Weight 45.5 45.5 is Comp (Rieble) 80 76 C.O.R..785.790 Shore CID 87156 87156 Mornent of Inertia 0.445 0.445 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.

This can be seen by comparing the moment of inertia of the control balls of Example 1 (i.e., Sample Nos. 14, 19 and 23) which possessed a moment of inertia of approximately.441 and the balls of the invention above (i.e., Sample Nos. 32-33) which exhibited a moment of inertia of.445.

Example 4

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 muiti-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 th designation "Strata Tour 9W. The "Strata Distance 90-EX' ball contains a thick hig acid ionomer resin inner cover layer over a soft cross-linked polybutadiene core wit an outer cover layer of soft ionomer resin. Further, the mantle or inner cover laye is filled with 5 phr of powdered tungsten.

In addition, the spin and distance characteristics of the muffi-layer gol balls were also compared with SpaMing's 7op-Flite Z-Balata 9W golf ball (a 1.68,' two-piece ball having a soft ionomer resin cover) and Acushnet Company's "Titieis Tour Balata 10W golf ball (a 1.68", two-piece ball having a soft synthetic balat cover). The distance and spin characteristics were determined according to th following parameters:

Three balls of each type being tested are checked for static data to insure they are within reasonable limits individually for size, weight, compression and coefficient. They must, at the least, be reasonably is similar to one another for static data.

A stripe is piaced 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 random order to randomize effects due to machine variations.

A strobe light is used to produce up to 10 images of the ball's flight on Polaroid film. 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 11100,000 second.

In each picture, in the field of view, is a reference system giving a level line reference and a length reference. Each picture is digitized on a 1000 lines per inch resolution digitizing tablet, giving positions of the reference and the stripes on the multiple images of the balls. From this information, the ball speed, launch angle and spin rate can be obtained.

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 35 718 inches, lie of 62 degrees, with face angle at, 0, the loft is 47 Y2 degrees. The club's overall weight is 453 grams. The grip is an Eaton Green Victory M60 core grip.

is The club is held in the 'yrisf' mechanism of the Miya Epoch Robo Ill Driving Machine so that the machine will strike the ball squarely, driving the ball straight away from the tee in line with the swing of the club. 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 of the hit ball. The ball impacts a stopping curtain of Keviar 8-10 feet downrange, and a square shot is one in which the direction of the ball from the tee is parallel to the line drawn along the front base of the driving machine.

Average ball speed of all types together should be around 100125 feet per second, and launch angle should be around 26 to 34 degrees.

During testing the following characteristics were noted:

Test Conditions: (test #92461) Club.- 10 Degree Driver Ball Speed: 227.1 fps Club Head Speed: 16 fps Spin Rate: 3033 rpm Launch angle: 9.1 Turf Conditions: Firm DISTANCE RESULTS SPIN RES S(RPM) 9 Iron 9, Iron Ball Type Traj. Carry Roll Total (a-) 125 fps Strata Tour 90 15 250.7 5.2 255.8 9273 5029 Z-Balata 90 15.1 250.6 1.3 255.4 9314 4405 Strata is Distance 90-EX 15.5 2541.4 1.4 258.1 9033 4308 Titleist Tour Balata 100 14.8, 247.6 0.7 250.7 10213 4978 The 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 bail (i.e., the Strata Distance go EX) having less spin and farther distance than the existing muffi-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.

The invention has been described with reference to the preferred embodiment. Obviously, modifications and alterations will occur to others upon reading and understanding the proceeding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (25)

1. A multi-layer golf ball having an increased moment of inertia, said golf ball comprising:

a core; an inner layer disposed about said core, said inner layer comprising a first material having a flexural modulus of at least about 15,000 psi and a hardness of at least about 60 on the Shore D scale; an outer layer disposed about said inner layer, said outer layer comprising a second 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; and an effective amount of a weighting material disposed in at least one of said inner layer and said outer layer.

2. The golf ball of claim 1 wherein said weighting material is disposed in said inner layer and said effective amount of said weighting material ranges from about 1 to about 100 parts of said weighting material per 100 parts of said first material.

3. The golf ball of claim 2 wherein said effective amount of said weighting material ranges from about 4 to about 5 1 parts of said weighting material per 100 parts of said first material.

4. The golf ball of claim 3 wherein said effective amount of said weighting material ranges from about 10 to about 25 parts of said weighting material per 100 parts of said first material.

5. The golf ball of claim 1 further comprising: at least one discrete region of a weighting material disposed in said outer layer.

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6. The golf ball of claim 5 wherein said weighting material disposed in said outer layer comprises at least one of metal powders, carbonaceous materials, glass, high strength polyamide fibers, and combinations thereof.

7. The golf ball of claim 6 wherein said metal powders are selected from the group consisting of 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, aluminurn tadpoles, and combinations thereof.

8. The golf ball of claim 6 wherein said carbonaceous materials are selected from the group consisting of graphite, carbon black, cotton flack, leather fiber, and combinations thereof.

9. The golf ball of claim 5 wherein said weighting material disposed in said outer layer ranges in size from about 10 mesh to about 325 mesh.

10. The golf ball of claim 5 wherein said weighting material disposed in said outer layer comprises an agent selected ftom the group consisting of graphite fibers, precipitated hydrated silica, clay, talc, asbestos, glass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate, zinc sulfide, silicates, diatornaceous earth, calcium carbonate, magnesium carbonate, and combinations thereof.

11. The golf ball of claim 5 wherein said weighting material disposed in said outer layer comprises a metal selected from the group consisting of titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt, beryllium, zinc, tin, and combinations thereof.

12. The golf ball of claim 5 wherein said weighting material disposed in said outer layer comprises a metal oxide selected from the group consisting of zinc 87 oxide, iron oxide, aluminum oxide, titanium dioxide, magnesium oxide, zirconium oxide, and combinations thereof

13. The golf ball of claim 5 wherein said weighting material disposed in said outer layer comprises a metal stearate selected from the group consisting of zinc stearate, calcium stearate, barium stearate, lithium stearate, magnesium stearate, and combinations thereof.

14. The golf ball of claim 5 wherein said weighting material disposed in said outer layer comprises a particulate carbonaceous material selected from the group consisting of graphite, carbon black, natural bitumen, cotton flock, cellulose flock, leather fiber, and combinations thereof.

15. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a visible star-shaped perimeter weighting pattern.

16. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a visible contoured-shaped perimeter weighting pattern.

17. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a visible pentagon-shaped perimeter weighting pattern.

18. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a visible radiused pentagon-shaped perimeter weighting pattern.

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19. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a visible single stripe-shaped perimeter weighting pattern.

20. The golf ball of claim 5 wherein said at least one discrete region of io weighting material is in the form of a double stripe-shaped perimeter weighting pattern.

21. The golf ball of claim,(wherein said at least one discrete region of weighting material is in the form of a multi-stripe-shaped perimeter weighting pattern.

22. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a stripe and dimple-shaped perimeter weighting pattern.

23. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a ring-shaped perimeter weighting pattern.

24. The golf ball of claim 5 wherein said at least one discrete region of weighting material is in the form of a spiral-shaped perimeter weighting pattern.

25. A golf ball according to claim 1 and as substantially hereinbefore described with reference to the accompanying drawings.