AU761196B2

AU761196B2 - Improved multi-layer golf ball

Info

Publication number: AU761196B2
Application number: AU32122/99A
Authority: AU
Inventors: Viktor Keller; Thomas Kennedy; John Neill; William Risen; Michael J. Sullivan
Original assignee: Top Flite Golf Co
Current assignee: Topgolf Callaway Brands Corp
Priority date: 1999-03-29
Filing date: 1999-03-29
Publication date: 2003-05-29
Anticipated expiration: 2019-03-29
Also published as: GB2363727A; GB2363727B; CA2366400A1; GB0122981D0; AU3212299A; CA2366400C; WO2000057963A1; JP2002539906A

Description

WO 00/57963 PCT/US99/06748 Improved Multi-Layer Golf Ball Field of the Invention This application is a continuation-in-part of U.S. Application Serial No.

08/631,613 filed April 10, 1996, which is a continuation-in-part of U.S. Application Serial No. 08/591,046 filed on January 25, 1996; and U.S. Application Serial No. 08/542,793 filed on October 13, 1995, which is a continuation-in-part of U.S. Application 08/070,510 filed June 1, 1993, now abandoned.

The present invention relates to golf balls and, more particularly, to improved golf balls comprising multi-layer covers which have a hard inner layer and a relatively soft outer layer.

Background of the Invention Traditional golf ball covers have been comprised of balata or blends of balata with elastomeric or plastic materials. The traditional balata covers are relatively soft and flexible. Upon impact, the soft balata covers compress against the surface of the club producing high spin. Consequently, the soft and flexible balata covers provide an experienced golfer with the ability to apply a spin to control the ball in flight in order to produce a draw or a fade, or a backspin which causes the ball to "bite" or stop abruptly on contact with the green. Moreover, the soft balata covers produce a soft "feel" 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 relatively skilled players.

Despite all the benefits of balata, balata covered golf balls are easily cut and/or damaged if mis-hit. Golf balls produced with balata or balata-containing cover compositions therefore have a relatively short lifespan.

SUBSTITUTE SHEET (RULE 26) 2 As a result of this negative property, balata and its synthetic substitutes, trans-polybutadiene and transpolyisoprene, have been essentially replaced as the cover materials of choice by new cover materials comprising ionomeric resins.

lonomeric resins are polyers containing interchain ionic bonding. As a result of their toughness, durability and flight characteristics, various ionomeric resins sold by E. I. DuPont de Nemours Company under the trademark "Surlyn®" and more recently, by the Exxon Corporation under the trademarks "ESCIR®" and the trade name "lotek", have become the materials of choice for the construction of golf ball covers over the traditional "balata" (transpolyisoprene, natural or synthetic) rubbers. As stated, the softer balata covers, although exhibiting enhanced playability properties, lack the durability (cut and abrasion resistance, fatigue endurance, etc.) properties required for repetitive play.

15 lonomeric resins are generally ionic copolymers of an olefin, such as S: ethylene, and a metal salt of an unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, or maleic acid. Metal ions, such as sodium or zinc, are *I 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 20 golf ball cover construction over balata. However, some of the advantages :gained in increased durability have been offset to some degree by the decreases produced in playability. This is because although the ionomeric resins are very durable, they tend to be very hard when utilized for golf ball cover construction, and thus lack the degree of softness required to impart the spin necessary to control the ball in flight. Since the ionomeric resins are harder than balata, the ionomeric resin covers to not compress as much against the face of the club upon impact, thereby producing less spin. In addition, the harder and more durable ionomeric resins lack the "feel" characteristic associated with the softer balata related covers.

As a result, while there are currently more than fifty (50) commercial grades of ionomers available from both 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 relative content of ethylene and methacrylic and/or acrylic acid groups) and additive ingredients W:\MaryOlDavinSpecd32122-99.doc such as reinforcement agents, etc., a great deal of research continues in order to develop a golf ball cover composition exhibiting not only the improved impact resistance and carrying distance properties produced by the "hard" ionomeric resins, but also the playability "spin", "feel", 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 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 resins have also been formulated in an attempt to produce a golf ball having the overall distance, playability and durability characteristics desired.

15 Such a multi-layered golf ball is produced by, initially, molding a first cover layer on a spherical core and then adding a second layer. The first layer is comprised of a hard, high flexural modulus resinous material such as type 1605 Surlyn® (now designated Surlyn® 8940). Type 1605 Surlyn® (Surlyn® 8940) is a sodium ion based low acid (less than or equal to 15 weight percent 20 methacrylic acid) ionomer resin having a flexural modulus of about 51,000 psi.

An outer layer of a comparatively soft, low flexural modulus resinous material 0 such as type 1855 Surlyn® (now designated Surlyn® 9020) Is molded over the inner cover layer. Type 1855 Surlyn® (Surlyn® 9020) is a zinc ion based low acid (10 weight percent methacrylic acid) ionomer resin having a flexural modulus of about 14,000 psi.

From this it has been established 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 limit of 255 feet per second as provided by the United States Golf Association rules. The relatively soft, low flexural modulus outer layer provides for the advantageous "feel" and playing characteristics of a balata covered golf ball.

W:MaryO\Davn\Specd32122-99.doc In various attempts to produce a durable, high spin ionomer golf ball, the golfing industry has blended the hard ionomer resins with a number of softer ionomic resins. The hard copolymers typically are made from an olefin and an unsaturated carboxylic acid. The soft copolymers are generally made from an olefin, an unsaturated carboxylic acid, and an acrylate ester. It has been found that golf ball covers formed from hard-soft ionomer blends tend to become scuffed more readily than covers made of hard ionomer alone. It would be useful to develop a golf ball having a combination of softness and durability which is better than the softness-durability combination of a golf ball cover made from a hard-soft ionomer blend.

Most professional golfers and good amateur golfers desire a golf ball that provides distance when hit off a driver, control and stopping ability on full iron shots, and high spin on short "touch and feel" shots. Many conventional two- 15 piece and thread wound performance golf balls have undesirable high spin o: 15 rates on full shots. The excessive spin on full shots is a sacrifice made in order to achieve more spin which is desired on the shorter touch shots. It would be beneficial to provide a golf ball which has high spin for touch shots without :generating excessive spin on full shots.

The above discussion of documents, acts, materials, devices, articles 20 and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed in Australia before the priority date of each claim of this application.

Summary of the Invention It would be desirable to provide a golf ball with a soft cover which has good scuff resistance.

Yet another desirable aspect is to provide a golf ball having a favorable combination of spin rate and durability.

A further desirable aspect is to provide a golf ball having a soft cover made from a cover material which is blended with minimal mixing difficulties.

Another desirable aspect is to provide a method of making a golf ball which has a soft cover with good scuff resistance and cut resistance.

W: laryOMDavin\Spedrc32122-99.doc Another desirable aspect is to provide a golf ball which has a high spin on shots of 250 feet or less and an average spin on full shots using a 9 iron.

Yet another desirable aspect is to provide a method of making a durable golf ball with a relatively high spin rate.

A further desirable aspect is to provide a multi-layer golf ball having exceptionally soft feel and high spin rates on short shots while maintaining good distance on full shots.

Yet another desirable aspect is to provide a multi-layer golf ball having a high spin rate on short shots and not having an excessive spin rate on long shots.

Other aspects will be in part obvious and in part pointed out more in detail hereafter.

0 The invention in a preferred form is a golf ball, including: a core, an inner cover layer formed over the core, the inner cover layer having a Shore D 15 hardness of at least 60 as measured on the curved surface thereof, and an outer cover layer formed over the inner cover layer, the outer cover layer having a Shore D hardness of no more than 53 as measured on the curved surface thereof, at least one of the inner and outer cover layers including at least one member selected from the group consisting of polycarbonates, reaction- 20 injection-molded polyurethanes, and styrene-butadiene elastomers, the golf ball having a PGA compression of 100 or less and a coefficient of restitution of at least 0.750.

The outer cover layer preferably has a Shore D hardness of no more than 50. The ball preferably has a PGA compression of 90 or less. In a particularly preferred form of the invention, the outer cover layer comprises a thermoplastic material.

In a preferred form of the invention, the inner cover layer comprises reaction-injection molded polyurethane. In another preferred form, the inner cover layer comprises polycarbonate. The inner cover layer preferably has a Shore D hardness of 60-85, and more preferably 65- The outer cover layer preferably has a Shore D hardness of 30-50.

W:MaryOav Specd32122-99.dc WO 00/57963 PCT/US99/06748 Another preferred form of the invention incorporates polycarbonates in the outer cover layer.

The golf ball of the invention preferably has a core which is a solid or is filled with liquid. The core can be wound or non-wound. A wound core may comprise a liquid, solid, gel or multi-piece center. In one preferred form of the invention, at least one of the inner and outer cover layers has a thickness of 0.01 0.150 inches, more preferably 0.02 0.10 inches, and even more preferably 0.03 0.07 inches.

The outer cover layer preferably has a Shore D hardness of 45 53 as measured on the curved surface thereof. The inner cover layer preferably has a Shore D hardness of 60 -85 as measured on the curved surface thereof.

Yet another preferred form of the invention is a golf ball comprising: a core, an inner cover layer formed from a composition which includes at least 50 weight of at least one material selected from the group consisting of polycarbonates, reaction-injectionmolded polyurethanes, and styrene-butadiene elastomers, and an outer cover layer formed over the inner cover layer, the outer cover layer having a Shore D hardness of no more than 53 as measured on the curved surface thereof, the golf ball having a PGA compression of 100 or less and a coefficient of restitution of at least 0.750.

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others and the article possessing the features, properties, and the relation of elements exemplified in the following detailed disclosure.

Brief Description of the Drawings FIG. 1 is a cross-sectional view of a golf ball embodying the invention illustrating a core 10 and a cover 12 consisting of an inner layer 14 and an outer layer 16 having dimples 18; and FIG. 2 is a diametrical cross-sectional view of a golf ball of the invention having a core 10 and a cover 12 made of an inner layer 14 and an outer layer 16 having dimples 18.

6 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Detailed Description of the Invention The present invention relates to improved multi-layer golf balls, particularly a golf ball comprising a multi-layered cover 12 over a core 10, and method for making same.

The golf balls of the invention, which can be of a standard or enlarged size, have a unique combination of high coefficient of restitution and a high spin rate on short shots.

The core 10 of the golf ball can be formed of a solid, a liquid, or any other substance which will result in an inner ball, i.e. core and inner cover layer, having the desired COR, compression and hardness. The multi-layered cover 12 comprises two layers: a first or inner layer or ply 14 and a second or outer layer or ply 16. The inner layer 14 can be ionomer, ionomer blends, non-ionomer, non-ionomer blends, or blends of ionomer and non-ionomer. The outer layer 16 is softer than the inner layer and can be ionomer, ionomer blends, non-ionomer, non-ionomer blends or blends of ionomer and nonionomer.

In a first preferred embodiment, the inner layer 14 is comprised of a high acid (i.e.

greater than 16 weight percent acid) ionomer resin or high acid ionomer blend. Preferably, the inner layer is comprised of a blend of two or more high acid at least 16 weight percent acid) ionomer resins neutralized to various extents by different metal cations. The inner cover layer may or may not include a metal stearate zinc stearate) or other metal fatty acid salt The purpose of the metal stearate or other metal fatty acid salt is to lower the cost of production without affecting the overall performance of the finished golf ball. In a second embodiment, the inner layer 14 is comprised of a low acid 16 weight percent acid or less) ionomer blend. Preferably, the inner layer is comprised of a blend of two or more low acid 16 weight percent acid or less) ionomer resins neutralized to various extents by different metal cations. The inner cover layer may or may not include a metal stearate zinc stearate) or other metal fatty acid salt. The purpose of the metal stearate or other metal fatty acid salt is to lower the cost of production without affecting the overall performance of the finished golf ball.

It has been found that a hard inner layer provides for a substantial increase in resilience enhanced distance) over known multi-layer covered balls. The softer outer 7 SUBSTITUTE SHEET (RULE 26) N O 00/57963 PCT/US99/06748 layer provides for desirable "feel" and high spin rate while maintaining respectable resiliency. The soft outer layer allows the cover to deform more during impact and increases the area of contact between the club face and the cover, thereby imparting more spin on the ball. As a result, the soft cover provides the ball with a balata-like feel and playability characteristics with improved distance and durability. Consequently, the overall combination of the inner and outer cover layers results in a golf ball having enhanced resilience (improved travel distance) and durability cut resistance, etc.) characteristics while maintaining and in many instances, improving the playability properties of the ball.

The combination of a hard inner cover layer with a soft, relatively low modulus ionomer, ionomer blend or other non-ionomeric thermoplastic elastomer outer cover layer provides for excellent overall coefficient of restitution excellent resilience) because of the improved resiliency produced by the inner cover layer. While some improvement in resiliency is also produced by the outer cover layer, the outer cover layer generally provides for a more desirable feel and high spin, particularly at lower swing speeds with highly lofted clubs such as half wedge shots.

Inner Cover Layer The inner cover layer is harder than the outer cover layer and generally has a thickness in the range of 0.01 to 0.150 inches, preferably 0.02 0.10 inches, and more preferably 0.03 to 0.06 inches for a 1.68 inch ball and 0.03 to 0.07 inches for a 1.72 inch (or more) ball. The core and inner cover layer together form an inrer ball preferably having a coefficient of restitution of 0.770 or more and more preferably 0.780 or more, and a diameter in the range of 1.48 1.66 inches for a 1.68 inch ball and 1.50 1.70 inches for a 1.72 inch (or more) ball. The inner cover layer has a Shore D hardness of 60 or more.

It is particularly advantageous if the golf balls of the invention have an inner layer with a Shore D hardness of 65 or more. The above-described characteristics of the inner cover layer preferably provide an inner ball having a PGA compression of 100 or less. It is found that when the inner ball has a PGA compression of 90 or less, excellent playability results.

8 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 The inner layer compositions of the first and third embodiments include the high acid ionomers such as those developed by E.I. DuPont de Nemours Company under the trademark "Surlyn@" and by Exxon Corporation under the trademark "Escor®" or tradename "lotek", or blends thereof. Examples of compositions which may be used as the inner layer herein are set forth in detail in a continuation of U.S. Serial No. 08/174,765, which is a continuation of U.S. Serial No. 071776,803 filed October 15, 1991, and Serial No. 08/493,089, which is a continuation of 07/981,751, which in turn is a continuation of Serial No. 07/901,660 filed June 19, 1992, 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.

The high acid ionomers which may be suitable for use in formulating the inner layer compositions of the subject first and third embodiments of the invention are ionic copolymers which are the metal, 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 iso- or nbutylacrylate, etc.) can also be included to produce a softer terpolymer. The carboxylic acid groups of the copolymer are partially neutralized approximately 10 100%, preferably 30 70%) by the metal ions. Each of the high acid ionomer resins which may be included in the inner layer cover compositions of the invention contains greater than about 16% by weight of a carboxylic acid, preferably from about 17% to about 25% by weight of a carboxylic acid, more preferably from about 18.5% to about 21.5% by weight of a carboxylic acid.

Although the inner layer cover composition of the first and third embodiments of the invention preferably includes a high acid ionomeric resin and the scope of the patent embraces all known high acid ionomeric resins falling within the parameters set forth above, only a relatively limited number of these high acid ionomeric resins have recently become commercially available.

9 SUBSTITUTE SHEET (RULE 26) S Wo 00/57963 PCT/US99/06748 The high acid ionomeric resins available from Exxon under the designation "Escor' and or "lotek", are somewhat similar to the high acid ionomeric resins available under the "Surlyn®" trademark. However, since the Escor®/lotek ionomeric resins are sodium or zinc salts of poly(ethylene-acrylic acid) and the "Surlyn®" resins are zinc, sodium, magnesium, etc. salts of poly(ethylene-methacrylic acid), distinct differences in properties exist.

Examples of the high acid methacrylic acid based ionomers found suitable for use in accordance with this invention include Surlyn® 8220 and 8240 (both formerly known as forms of Surlyn AD-8422), Surlyn® 9220 (zinc cation), Surlyn® SEP-503-1 (zinc cation), and Surlyn® SEP-503-2 (magnesium cation). According to DuPont, all of these ionomers contain from about 18.5 to about 21.5% by weight methacrylic acid.

More particularly, Surlyrn AD-8422 is currently commercially available from DuPont in a number of different grades AD-8422-2, AD-8422-3, AD-8422-5, etc.) based upon differences in melt index. According to DuPont, Surlyn 8422, which is believed recently to have been redesignated as 8220 and 8240, offers the following general properties when compared to Surlyn® 8920, the stiffest, hardest of all on the low acid grades (referred to as "hard" ionomers in U.S. Patent No. 4,884,814): SUBSTITUTE SHEET (RULE 26) WO 00/57963 WO 0057963PCT/US99/06748 TABLE I HIGH! ACID wt% Acid) SURLYlISQ 8920 (>20 Wt% Acid) SURLflIOD SURLYNOD 8 42 2-2 84 22-3

IONOMER

cation Melt Index Sodium, Wtt Base Resin MI H2P 1

*C

FPI, eC tHa 2.9 1.9 60 96 49.5 Il a 2.4 COMPRESSION MOLDING' Tensile Break, psi 4350 Yield, psi 2990 Elongation, 315 Flex Mod, K psi 53.2 Shore D hardness 66 4190 3670 263 76.4 67 5330 3590 29 89.3 68 IDSC second heat, ionC/min heating rate.

2 samples compression molded at 1501C annealed 24 hours at 600C. 8422-2, -3 were homogenized at 1900C before molding.

SUBSTITUTE SHEET (RULE 26) N O 00/57963 PCT/US99/06748 In comparing Surlyrn 8920 to Surlyn® 8422-2 and Surlyn® 8422-3, it is noted that the high acid Surlyn® 8422-2 and 8422-3 ionomers have a higher tensile yield, lower elongation, slightly higher Shore D hardness and much higher flexural modulus. Surlyn® 8920 contains 15 weight percent methacrylic acid and is 59% neutralized with sodium.

In addition, Surlyn SEP-503-1 (zinc cation) and Surlyn® SEP-503-2 (magnesium cation) are high acid zinc and magnesium versions of the Surlyn® AD 8422 high acid ionomers. When compared to the Surlyn® AD 8422 high acid ionomers, the Surlyn SEP- 503-1 and SEP-503-2 ionomers can be defined as follows: Surlvn® lonomer Ion Melt Index Neutralization AD 8422-3 Na 1.0 SEP 503-1 Zn 0.8 38 SEP 503-2 Mg 1.8 43 Furthermore, Suryn® 8162 is a zinc cation ionomer resin containing approximately by weight 18.5 -21.5% weight) methacrylic acid copolymer that has been 30 neutralized. Surlyn® 8162 is currently commercially available from DuPont.

Examples of the high acid acrylic acid based ionomers suitable for use in the present invention also include the Escor® or lotek high acid ethylene acrylic acid ionomers produced by Exxon such as Ex 1001, 1002, 959, 960, 989, 990, 1003, 1004, 993, 994. In this regard, Escor® or lotek 959 is a sodium ion neutralized ethylene-acrylic neutralized ethylene-acrylic acid copolymer. 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 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: 12 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PTU9/64 PCT/US99/06748 TABLE 2 Exxon High Acid lonomers ESCORID ESCOR® (IOTEK)

(IOTEK)

Property Exl1001 Exl1002 959 Exl1003 Exl1004 960 Melt index, g/10 min. 1.0 1.6 2.1 1.1 2.0 1.8 Cation Na Na Na Zn Zn Zn* Melting Point, OC 83.7 83.7 82 82.5 79 Vicat Softening Point, OC 51.5 51.5 58 56 55 Tensile Break 34.4 MPa 31.7 MPa 34 MPa 24.8 MPa 20.6 MPa 24 MPa Elongation Q Break, 341 348 280 387 437 430 Hardness, Shore D 63 62 65 54 53 57 Flexural Modulus 365 MPa 380 MPa 480 MPa 147 MPa 130 MPa 170 MPa SUBSTITUTE SHEET (RULE 26) N O 00/57963 PCT/US99/06748 TABLE 3 Additional Exxon High Acid lonomers Property Unit EX 989 EX 993 EX 994 EX 990 Melt Index g/10 min. 1.30 1.25 1.32 1.24 Moisture ppm 482 214 997 654 Cation Type Na Li K Zn M+ content by AAS wt 2.74 0.87 4.54 0 Zn content by AAS wt 0 0 0 3.16 Density kg/m 3 959 945 976 977 Vicat softening point 0 C 52.5 51 50 55.0 Crystallization point "C 40.1 39.8 44.9 54.4 Melting point 6C 82.6 81.0 80.4 81.0 Tensile at yield MPa 23.8 24.6 22 16.5 Tensile at break MPa 32.3 31.1 29.7 23.8 Elongation at break 330 260 340 357 1% secant modulus MPa 389 379 312 205 Flexural modulus MPa 340 368 303 183 Abrasion resistance mg 20.0 9.2 15.2 20.5 Hardness Shore D 62 62.5 61 56 Zwick Rebound 61 63 59 48 Furthermore, as a result of the development by the assignee of this application of a number of new high acid ionomers neutralized to various extents by several different types of metal cations, such as by manganese, lithium, potassium, calcium and nickel 14 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 cations, several new high acid ionomers and/or high acid ionomer blends besides sodium, zinc and magnesium high acid ionomers or ionomer blends are now available 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 processing. Consequently, the metal cation neutralized high acid ionomer resins recently produced can be blended to produce substantially 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 extents, high acid copolymers of an alpha-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. 08/493,089, 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 a copolymer containing greater than 16% by weight acid, preferably from about 17 to about 25 weight percent acid, and more preferably about weight percent acid), with a metal cation salt capable of ionizing or neutralizing the copolymer to the extent desired from about 10% to The base copolymer is made up of greater than 16% by weight of an alpha, betaunsaturated carboxylic acid and an alpha-olefin. Optionally, a softening comonomer can be included in the copolymer. Generally, the alpha-olefin 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, maleic acid, fumaric acid, and itaconic acid, with acrylic acid being preferred.

The softening comonomer that can be optionally included in the inner cover layer for the golf ball of the invention may be selected from the group consisting of vinyl esters of aliphatic carboxylic acids wherein the acids have 2 to 10 carbon atoms, vinyl ethers wherein the alkyl groups contains 1 to 10 carbon atoms, and alkyl acrylates or SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 methacrylates wherein the alkyl group contains 1 to 10 carbon atoms. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or the like.

Consequently, examples of a number of copolymers suitable for use to produce the high acid ionomers included in the present invention include, but are not limited to, high acid embodiments of an ethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer, an ethylene/itaconic acid copolymer, an ethylene/maleic acid copolymer, an ethylene/methacrylic acid/vinyl acetate copolymer, an ethylene/acrylic acid/vinyl alcohol copolymer, etc. The base copolymer broadly contains greater than 16% by weight unsaturated carboxylic acid, from about 39 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 copolymer contains about 20% acrylic acid with the remainder being ethylene.

Along these lines, examples of the preferred high acid base copolymers which fulfill the criteria set forth above, are a series of ethylene-acrylic copolymers which are commercially available from The Dow Chemical Company, Midland, Michigan, under the "Primacor" designation. These high acid base copolymers exhibit the typical properties set forth below in Table 4.

16 SUBSTITUTE SHEET (RULE 26) N O 00/57963 WO 0057963PCT/US99/06748 TABLE 4 Typical Properties of Primacor Ethyl ene-Acrylic Acid Copolymiers GRADE PERCENT DENSITY MELT TENSILE FLEXURAL VICAT SHORE D ACID GICC INDEX YD ST MODULUS SOFT PT HARDlNESS G11IOMEN (PSI) (*PSI) (OC) ASTM D-792 D-1238* D-630 D-790 D-1525 D-2240 5980 20.0 0.958 300.0 4800 43 5990 20.0 0.955 1300.0 650 40 42 5981 20.0. 0.960 300.0 900 3200 46 48 5983 20.0 0.958 500.0 850 3100 44 5991 20.0 0.953 2600.0 635 2600 38 *1900C Due to the high molecular weight of the Primacor 5981 grade of the ethyleneacrylic 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 carboxylic acid groups of the high acid copolymer. These include acetate, oxide or hydroxide salts of lithium, calcium, zinc, sodium, potassium, nickel, magnesium, and manganese.

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 17 SUBSTITUTE SHEET (RULE 26) Wvo 00/57963 PCT/US99/06748 acetate, nickel oxide and nickel hydroxide. Sources of magnesium include magnesium oxide, magnesium hydroxide, magnesium acetate. Sources of manganese include manganese acetate and manganese oxide.

The new metal cation neutralized high acid ionomer resins are produced by reacting the high acid base copolymer with various amounts of the metal cation salts above the crystalline melting point of the copolymer, such as at a temperature from about 200°F to about 500°F, preferably from about 250°F to about 350°F under high shear conditions at a pressure of from about 10 psi to 10,000 psi. Other well known blending techniques may also be used. The 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 As indicated below in Table 5 and more specifically in Example I in U.S.

Application Serial No. 08/493,089, 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 acid ethylene/acrylic 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.

18 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE ut-X Ut-I Cation Salt letralIitiOn fori,.Idlof No.

I (14.01) 2(94010 R14010 4(116010) tiel t Infdeg 0.9 $here 0 QMnAc) 7(Imme) a(ltAc) 9( Oll) 14 (Kali) 16(ZPAC) 17(ZnAC) 19(HOAC) ZOC(lgAe) 21(C&ACJ Z2(CmAcl 19.6 23.1 '3.3 26.5 4.3,.

3.38 2.34 5.30 8.26 10.7 '7.9 13.9 9.91 £8.3 33.0 106 71.3 5 .2.3 33.9 36.0 37.9 77.0 T1.5 53.0 36.1 0.6 a81a 4.2 .815 18.6 .815 7' 73 69 (brittte) 73

TT

72 (hr ittts) 74 72 72 T0 67 7' 69 67 74 76 74 A4 Broke .804 .801 .1106 .797 .793 2.8 a%1 controls: 50/50 Blend of loteks 8000/7030 c.o.lt.-.81/63 Sitars 0 flerdness Ou~d'nt Hi1gh Acid Suriyn* 8422 (141 C.0-.A81/O Shore 0 llerdfless Otutont Hi1gh Acid Surtyne 8162 (Zn) C.0.R...8OI£S Share 0 hamrdness Exxon 111gh Acid lbeak EX-960 (IM) 9 6 6 5 Share 0 hasrdness 19 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE 5 (cont.) Ut-I f c msat ong Ulip.- jI ia.Ia 23CHUG0 .2.91 2490) 3.85 4.76 26(1490) 1.96 Contra( for Fannalstions Z3-26 I Ut EoriJliof Na. Cation Salt Ut-I mtgual ItitO Kett 53.5 71.5 89.3 35.T a $0150 lutek a00o17030, it. was norw.atite ta that Ut-I Me.

Share 0 C.0.R. Hardiesy .813 .808 .809 .815 contral accardInety t C

C£O.LL

Z7(IlAC) 13.04 28MUAc) 10.71 Z9(UIAC) 8.26 5.66 Contro( (or Farmitatlan Was. ZT.30 41.1 48.9 36. T 24.4 Is so/so 0.2 0.5 t.a 7.5 latek 800017030.

:aoz .799 .796 786 c.0.n...807 When compared to low acid versions of similar cation neutralized ionomer resins, the new metal cation neutralized high acid lonomer resins exhibit enhanced hardness, modulus and resilience characteristics. These are properties that are particularly desirable in a number of thermoplastic fields, including the field of golf ball manufacturing.

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 the range of hardness beyond that previously obtainable while- maintaining the beneficial properties (i.e.

durability, click, feel, etc.) of the softer low acid ionomer covered balls, such as balls produced utilizing the low acid ionomers; disclosed in U.S. Patent Nos. 4,884,814 and 4,911,451.

Moreover, as a result of the development of a number of new acrylic acid based high acid ionomer resins neutralized to various extents by several different types of metal cations, such as manganese, lithium, potassium, calcium and nickel cations, several new SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 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, the inner cover layer herein) the resulting golf balls will travel further than previously known multi-layered golf balls produced with low acid ionomer resin covers due to the balls' enhanced coefficient of restitution values.

The low acid ionomers which may be suitable for use in formulating the inner layer compositions of the second and third embodiments of the subject invention are ionic copolymers which are the metal, 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 iso- or nbutylacrylate, etc.) can also be included to produce a softer terpolymer. The carboxylic acid groups of the copolymer are partially neutralized approximately 10 100%, 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.

The inner layer compositions include the low acid ionomers such as those developed and sold by E.I. DuPont de Nemours Company under the trademark "Surlyn and by Exxon Corporation under the trademark "Escor®" or tradename "lotek", or blends thereof.

The low acid ionomer resins available from Exxon under the designation "Escor®" and/or "lotek", are somewhat similar to the low acid ionomeric resins available under the "Surlyn®" trademark. However, since the Escor/llotek ionomeric resins are sodium or zinc salts of poly(ethylene-acrylic acid) and the "Surlyn®" resins are zinc, sodium, 21 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 magnesium, etc. salts of poly(ethylene-methacrylic acid), distinct differences in properties exist.

When utilized in the construction of the inner layer of a multi-layered golf ball, 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 ionomers, are processed to produce the covers of multi-layered golf balls, the inner cover layer herein) the resulting golf balls will travel further 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.

As shown in the Examples, use of an inner layer formulated from blends of lower acid ionomers produces multi-layer golf balls having enhanced compression and spin rates. These are the properties desired by the more skilled golfer.

In a third embodiment of the inner cover layer, a blend of high and low acid ionomer resins is used. These can be the ionomer resins described above, combined in a weight ratio which preferably is within the range of 10 90 to 90 10 high and low acid ionomer resins.

A fourth embodiment of the inner cover layer is primarily or fully non-ionomeric thermoplastic material. Suitable non-ionomeric materials include metallocene catalyzed polyolefins or polyamides, polyamidelionomer blends, polycarbonates, polyphenylene etherlionomer blends, etc., which have a Shore D hardness of a 60 and preferably have a flex modulus of greater than about 30,000 psi, or other hardness and flex modulus values which are comparable to the properties of the ionomers described above. Other suitable materials include but are not limited to thermoplastic or thermosetting polyurethanes/polyureas, including castable polyurethanes/polyureas, reaction injection moldable polyurethanes/polyureas and injection moldable polyurethanes/polyureas, thermoplastic block polyesters, such as a polyester elastomer marketed by DuPont under the trademark Hytrel®, thermoplastic block poolyamides, such as a polyester amide marketed by Elf Atochem S.A. under the trademark Pebax®, a blend of two or more non- 22 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 ionomeric thermoplastic elastomers, or a blend of one or more ionomers and one or more non-ionomeric thermoplastic elastomers. These materials can be blended with the ionomers described above in order to reduce cost relative to the use of higher quantities of ionomer.

Outer Cover Layer While the core with the hard inner cover layer formed thereon provides the multilayer golf ball with power and distance, the outer cover layer 16 is comparatively softer than the inner cover layer. The softness provides for the feel and playability characteristics typically associated with balata or balata-blend balls. The outer cover layer or ply is comprised of a relatively soft, low modulus (about 1,000 psi to about 10,000 psi) and, in one embodiment, low acid (less than 16 weight percent acid) ionomer, an ionomer blend, a non-ionomeric thermoplastic or thermosetting material such as, but not limited to, a metallocene catalyzed polyolefin such as EXACT material available from EXXON, a thermoplastic or thermoset polyurethane/polyurea, including castable polyurethanes/polyureas, reaction injection moldable polyurethanes/polyureas, and injection moldable polyurethanes/polyureas, polycarbonates, thermoplastic block polyesters, such as a polyester elastomer marketed by DuPont under the trademark Hytrel®, thermoplastic block polyamides, such as a polyester amide marketed by Elf Atochem S.A. under the trademark Pebax®, a blend of two or more non-ionomeric thermoplastic or thermosetting materials, or a blend of one or more ionomers and one or more non-onomeric thermoplastic materials. The outer layer is from about 0.010 to about 0.150 inches in thickness, preferably 0.02 0.10 inches, more desirably 0.03 to 0.06 inches in thickness for a 1.680 inch ball and 0.03 to 0.07 inches in thickness for a 1.72 inch or more ball), but thick enough to achieve desired playability characteristics while minimizing expense. Thickness is defined as the average thickness of the non-dimpled areas of the outer cover layer. The outer cover layer 16 has a Shore D hardness of 55 or less, more preferably 53 or less, and even more preferably 50 or less.

23 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 In one embodiment, the outer cover layer preferably is formed from an ionomer which constitutes at least 75 weight of an acrylate ester-containing ionic copolymer or blend of acrylate ester-containing ionic copolymers. This type of outer cover layer in combination with the core and inner cover layer described above results in golf ball covers having a favorable combination of durability and spin rate. The one or more acrylate estercontaining ionic copolymers each contain an olefin, an acrylate ester, and an acid. In a blend of two or more acrylate ester-containing ionic copolymers, each copolymer may contain the same or a different olefin, acrylate ester and acid than are contained in the other copolymers. Preferably, the acrylate ester-containing ionic copolymer or copolymers are terpolymers, but additional monomers can be combined into the copolymers if the monomers do not substantially reduce the scuff resistance or other good playability properties of the cover.

For a given copolymer, the olefin is selected from the group consisting of olefins having 2 to 8 carbon atoms, including, as non-limiting examples, ethylene, propylene, butene-1, hexene-1 and the like. Preferably the olefin is ethylene.

The acrylate ester is an unsaturated monomer having from 1 to 21 carbon atoms which serves as a softening comonomer. The acrylate ester preferably is methyl, ethyl, n-propyl, n-butyl, n-octyl, 2-ethylhexyl, or 2-methoxyethyl 1-acrylate, and most preferably is methyl acrylate or n-butyl acrylate. Another suitable type of softening comonomer is an alkyl vinyl ether selected from the group consisting of n-butyl, n-hexyl, 2-ethylhexyl, and 2-methoxyethyl vinyl ethers.

The acid is a mono- or dicarboxylic acid and preferably is selected from the group consisting of methacrylic, acrylic, ethacrylic, a-chloroacrylic, crotonic, maleic, fumaric, and itaconic acid, or the like, and half esters of maleic, fumaric and itaconic acid, or the like.

The acid group of the copolymer is 10 100% neutralized with any suitable cation, for example, zinc, sodium, magnesium, lithium, potassium, calcium, manganese, nickel, chromium, tin, aluminum, or the like. It has been found that particularly good results are obtained when the neutralization level is about 50 100%.

24 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 The one or more acrylate ester-containing ionic copolymers each has an individual Shore D hardness of about 5 64. The overall Shore D hardness of the outer cover is or less, and generally is 40 55. It is preferred that the overall Shore D hardness of the outer cover is in the range of 40 50 in order to impart particularly good playability characteristics to the ball.

The outer cover layer of the-invention is formed over a core to result in a golf ball having a coefficient of restitution of at least 0.770, more preferably at least 0.780, and most preferably at least 0.790. The coefficient of restitution of the ball will depend upon the properties of both the core and the cover. The PGA compression of the golf ball is 100 or less, and preferably is 90 or less.

The acrylate ester-containing ionic copolymer or copolymers used in the outer cover layer can be obtained by neutralizing commercially available acrylate estercontaining acid copolymers such as polyethylene-methyl acrylate-acrylic acid terpolymers, including ESCOR ATX (Exxon Chemical Company) or poly (ethylene-butyl acrylatemethacrylic acid) terpolymers, including NUCREL (DuPont Chemical Company).

Particularly preferred commercially available materials include ATX 320, ATX 325, ATX 310, ATX 350, and blends of these materials with NUCREL 010 and NUCREL 035. The acid groups of these materials and blends are neutralized with one or more of various cation salts including zinc, sodium, magnesium, lithium, potassium, calcium, manganese, nickel, etc. The degree of neutralization ranges from 10 100%. Generally, a higher degree of neutralization results in a harder and tougher cover material. The properties of non-limiting examples of commercially available un-neutralized acid terpolymers which can be used to form the golf ball outer cover layers of the invention are provided below in Table 6.

SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Table 6 Trade Name Melt Index Acid No. Flex modulus Hardness dglmin KOH/g MPa (Shore D) ASTM 01238 (ASTM 0790) ATX 310 6 45 80 44 ATX 320 5 45 50 34 ATX325 20 45 9 ATX 350 6 15 20 28 Nucrel 010 11 60 40 Nucrel 035 35 60 59 The ionomer resins used to form the outer cover layers can be produced by reacting the acrylate ester-containing acid copolymer with various amounts of the metal cation salts at a temperature above the crystalline melting point of the copolymer, such as a temperature from about 200°F to about 5000F, preferably from about 2500F to about 3500F, under high shear conditions at a pressure of from about 100 psi to 10,000 psi.

Other well known blending techniques may also be used. The amount of metal cation salt utilized to produce the neutralized ionic copolymers 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. When two or more different copolymers are to be used, the copolymers can be blended before or after neutralization. Generally, it is preferable to blend the copolymers before they are neutralized to provide for optimal mixing.

The compatibility of the acrylate ester-containing copolymers with each other in a copolymer blend produces a golf ball outer cover layer having a surprisingly good scuff resistance for a given hardness of the outer cover layer. The.golf ball according to the invention has a scuff resistance of no higher than 3.0. It is preferred that the golf ball has a scuff resistance of no higher than about 2.5 to ensure that the golf ball is scuff resistant when used in conjunction with a variety of types of clubs, including sharp-grooved irons, 26 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 which are particularly inclined to result in scuffing of golf ball covers. The best results according to the invention are obtained when the outer cover layer has a scuff resistance of no more than about 2.0. The scuff resistance test is described in detail below.

Additional materials may also be added to the inner and outer cover layer of the present invention as long as they do not substantially reduce the playability properties of the ball. Such materials include dyes (for example, Ultramarine Blue sold by Whitaker, Clark, and Daniels of South Plainsfield, (see U.S. Pat. No. 4,679,795), pigments such as titanium dioxide, zinc oxide, barium sulfate and zinc sulfate; UV absorbers; antioxidants; antistatic agents; and stabilizers. Moreover, the cover compositions of the present invention may also contain softening agents such as those disclosed in U.S. Patent Nos.

5,312,857 and 5,306,760, including plasticizers, metal stearates, processing acids, etc., and reinforcing materials such as glass fibers and inorganic fillers, as long as the desired properties produced by the golf ball covers of the invention are not impaired.

The outer layer in another embodiment of the invention includes a blend of a soft (low acid) ionomer resin with a small amount of a hard (high acid) ionomer resin. 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 on the Shore D scale. 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.

Soft ionomers primarily are used in formulating the hard/soft blends of the cover compositions. These ionomers include acrylic acid and methacrylic acid based soft ionomers. They are generally characterized as comprising sodium, zinc, or other monoor divalent metal cation salts of a terpolymer of an olefin having from about 2 to 8 carbon atoms, methacrylic acid, acrylic acid, or another a, 11- unsaturated carboxylic acid, and an unsaturated monomer of the acrylate ester class having from 1 to 21 carbon atoms. The soft ionomer is preferably made from an acrylic acid base polymer in an unsaturated monomer of the acrylate ester class.

27 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Certain ethylene-acrylic acid based soft ionomer resins developed by the Exxon Corporation under the designation "lotek 7520" (referred to experimentally by differences in neutralization and melt indexes as LDX 195, LDX 196, LDX 218 and LDX 219) may be combined with known hard ionomers such as those indicated above to produce the inner and outer cover layers. The combination produces higher C.O.R.s at equal or softer hardness, higher melt flow (which corresponds to improved, more efficient molding, i.e., fewer rejects) as well as significant cost savings versus the outer layer of multi-layer balls produced by other known hard-soft ionomer blends as a result of the lower overall raw materials costs and improved yields.

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 190C. per ASTM D-1288), and a flexural modulus of about 2500 3500 psi (per ASTM 0-790). 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 inventor has found that a grade of 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 Surlyn® 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. values 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 28 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 important in production where the soft covered balls tend to have lower yields caused by sticking in the molds and subsequent punched pin marks from the knockouts.

According to Exxon, lotek 7510 is of similar chemical composition as lotek 7520 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 neutralized and lotek 7510 is estimated to be about 40 60 neutralized.

The typical properties of lotek 7510 in comparison of those of lotek 7520 in comparison of those of lotek 7520 are set forth below: TABLE 7 Physical Properties of lotek 7510 in Comparison to lotek 7520 Property Unit IOTEK 7520 IOTEK 7510 Melt Index g/10 min. 2.0 0.8 Density g/cc 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 The hard ionomer resins utilized to produce the outer cover layer composition hard/soft blends include ionic copolymers which are the sodium, zinc, magnesium, lithium, etc. 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 approximately 15 75 percent) neutralized.

29 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 The hard ionomeric resins are likely copolymers of ethylene and acrylic and/or methacrylic acid, with copolymers of ethylene and acrylic acid being the most preferred.

Two or more types of hard ionomeric resins may be blended into the outer cover layer compositions in order to produce the desired properties of the resulting golf balls.

As discussed earlier herein, the hard ionomeric resins introduced under the designation Escor® and sold under the designation "lotek" are somewhat similar to the hard ionomeric resins sold under the Surlyn® trademark. However, since the "lotek" ionomeric resins are sodium or zinc salts of poly(ethylene-acrylic acid) and the Surlyn® resins are zinc or sodium salts of poly(ethylene-methacrylic acid) some distinct differences in properties exist. As more specifically indicated in the data set forth below, the hard "lotek" resins the acrylic acid based hard ionomer resins) are the more preferred hard resins for use in formulating the layer blends for use in the present invention. In addition, various blends of "lotek" and Surlyn® hard ionomeric resins, as well as other available ionomeric resins, may be utilized in the present invention in a similar manner.

Examples of commercially available hard ionomeric resins which may be used in the present invention in formulating the outer cover blends include the hard sodium ionic copolymer sold under the trademark Surlyn® 8940 and the hard zinc ionic copolymer sold under the trademark Surlyn® 9910. Surlyn 8940 is a copolymer of ethylene with methacrylic acid and about 15 weight percent acid which is about 29 percent neutralized with sodium ions. This resin has an average melt flow index of about 2.8. Surlyn® 9910 is a copolymer of ethylene and methacrylic acid with about 15 weight percent acid which is about 58 percent neutralized with zinc ions. The average melt flow index of Surlyn® 9910 is about 0.7. The typical properties of Surlyn® 9910 and 8940, as well as other Surlyn® resins, are set forth below in Tables 8 and 9: SUBSTITUTE SHEET (RULE 26) WO 00/5796 3 PCT/US99/06748 TABLE 8 Typical Properties of Commercially Available Hard Surlyn@ Resins Suitable for Use in the Present Invention ASTM D 8a4 gola 8M2 8526 370 3730 Cation tyeSodium Zinc Sodium Sodium Zinc Zinc MeftlDow idex. gmsMO min. D-1238 2.8 0.7 0.9 1. 14.0 1.6 Specific gravity. lcni' D-792 0.96 0.07 0.96 0.94 0.96 0.9 llardness.Shore 0-2240 66 64 66 60- a. 63 Tensil strength. (lqxsQ 0438 (3A6 (4.1) Wa33.1 24.8 37.2 29.0 22.1 28.3 Elongaion. 0463 470 2r0 360 460 460 460 Flexural Modulus. Ocials) 0-79 (61) (48) (6m (32) (28) FWa 360 330 380 220 190 210 Tensile Impact KJ/ms 0-1822 1020 1020 66 1160 760 1240 (&bs.in 1 (486 (485) (410) (550) (30j60 Vicm Temperature. IC D-1526 83 1 68 73 61 73 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Table 9 Properties of Additional Hard Surlvyn Resins SURLYN® SURLYNO SURLYN@ IONOMER 8920 8140 9120 Cation, Na Na Zn Melt Flow Index gms/10 min. 0.9 2.6 1.3 MP °C 84 88 FP °C 52 49 Tensile Strength kpsi 5.4 5.0 3.8 Yield Strength kpsi 2.2 2.8 2.4 Elongation 350 340 280 Flex Modulus kpsi 55 71 64 Shore D Hardness 66 70 69 Examples of the more pertinent acrylic acid based hard ionomer resin suitable for use in the cover compositions sold under the "lotek" tradename by the Exxon Corporation include lotek, but are not limited to, 8000, 8010, 8020, 8030, 7030, 7010, 7020, EX 1001 1009, lotek 959 and lotek 960, as well as the materials listed above on Tables 2 and 3.

The typical properties of the remainder of these and other lotek ionomers suited for use in formulating the cover compositions are set forth below in Tables 10 and 11: 32 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE Typical Properties of lotek loflomers

ASTM

Resin Properties Metho Units 710 7020 70= 8000 602 8=3 Cationi Mm zinc zinc zinc .oIum sdu sodf.m ment Indlex D-1238 gllmin 0.8 1.5 2.5 OA 1.6 Density 0-1506 WgmI .968 966 964 957 956 96 Melting Point 0-3417 c 83.5 84 85 83 84 87 Crystallzaton Point 0-4i17 C 55 56 58 45 47 4 MWeaSoftening Point 0-1S25 *C 60 60 60 4 54.5 55.5 Tensile strength at break D-638 hV3e 24.5 23.5 22.6 33 32.5 32 YleW strength~ 0438 M30 14 13 12 19 18.A 18 Elongation at break 0.63 44 450 460 370 380 410 11% Secantnmodulus D-638 W. 150 135 125 280 280 280 Shtore Haidness 0-224 54 63 2 60 60 Flex modulus (3mm) 0-790 Mg 10 75 155 ,4 SUBSTITUTE SHEET (RULE 26) WOo 00/57963 PCT/US99/06748 TABLE 11 Examples of Exxon High Molecular Weight lonomers PROPERTY ExiOOS Exl006 Exl007 Ex1008 Ex1009 7310 Melt Index, g/10 min. 0.7 1.3 1.0 1.4 0.8 Cation Na Na Zn Zn Na Zn Melting Point, °C 85.3 86 85.8 86 91.3 91 Vicat Softening Point,"C 54 57 60.5 60 56 69 Tensile Break, MPa 33.9 33.5 24.1 -23.6 32.4 24 Elongation Break, 403 421 472 427 473 520 Hardness, Shore D 58 58 51 50 56 52 Flexural Modulus, MPa 289 290 152 141 282 150 It has been determined that when hard/soft ionomer blends are used for the outer cover layer, good results are achieved when the relative combination is in a range of about 3 25 percent hard ionomer and about 75 97 percent soft ionomer.

Moreover, in alternative embodiments, the inner and/or outer cover layer formulation may also comprise up to 100 wt of a non-ionomeric thermoplastic or thermoset material including a polyester polyurethane such as B.F. Goodrich Company's Estane® polyester polyurethane X-4517 or a reaction-injection molded material such as one or more of the Bayflex RIM polyurethanes from Bayer. The non-ionomeric thermoplastic material may be blended with a soft ionomer. For example, polyamides blend well with soft ionomer. According to B.F. Goodrich, Estane@ X-4517 has the following properties: 34 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Prooerties of Estane® X-4517 Tensile 100% 200% 300% Elongation Youngs Modulus Hardness A/D Dayshore Rebound Solubility in Water Melt processing temperature Specific Gravity (H 2 0=1) 1430 815 1024 1193 641 1826 88/39 59 Insoluble >350°F (>177 0

C)

1.1 -1.3 Other soft, relatively low modulus non-ionomeric thermoplastic or thermoset materials may also be utilized to produce the inner and/or outer cover layers as long as the non-ionomeric materials produce the playability and durability characteristics desired without adversely affecting the enhanced travel distance characteristic produced by the high acid ionomer resin composition. 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.; non-ionomeric thermoset polyurethanes including but not limited to those disclosed in U.S. Patent 5,334,673; cross-linked metallocene catalyzed polyolefins; ionomer/rubber blends such as those in Spalding U.S. Patents 4,986,545; 5,098,105 and 5,187,013; styrene-butadienestyrene block copolymers, including functionalized styrene-butadiene-styrene block copolymers, styrene-ethylene-butadiene-styrene (SEBS) block copolymers such as KRATON materials from Shell Chemical Co., including functionalized SEBS block copolymers; and, Hytrel polyester elastomers from DuPont and Pebax polyesteramides from Elf Atochem S.A.

SUBSTITUTE SHEET (RULE 26) WOw 00/57963 PCT/US99/06748 Core The cores of the inventive golf balls typically have a coefficient of restitution of about 0.750 or more, more preferably 0.770 or more and a PGA compression of about or less, and more preferably 70 or less. The core used in the golf ball of the invention preferably is a solid and can be wound or liquid filled. The term "solid cores" as used herein refers not only to one piece cores but also to those cores having a separate solid layer beneath the covers and over the central core. The cores have a weight of 25 grams and preferably 30 40 grams. When the golf ball of the invention has a solid core, this core can be compression molded from a slug of uncured or lightly cured elastomer composition comprising a high cis content polybutadiene and a metal salt of an a, 13, ethylenically unsaturated carboxylic acid such as zinc mono- or diacrylate or methacrylate.

To achieve higher coefficients of restitution and/or to increase hardness in the core, the manufacturer may include a small amount of a metal oxide such as zinc oxide. In addition, larger amounts of metal oxide than are needed to achieve the desired coefficient may be included in order to increase the core weight so that the finished ball more closely approaches the U.S.G.A. upper weight limit of 1.620 ounces. Non-limiting examples of other materials which may be used in the core composition including compatible rubbers or ionomers, and low molecular weight fatty acids such as stearic acid. Free radical initiator catalysts such as peroxides are admixed with the core composition so that on the application of heat and pressure, a curing or cross-linking reaction takes place.

As indicated above, a thread wound core may comprise a liquid, solid, gel or multipiece center. The thread wound core is typically obtained by winding a thread of natural or synthetic rubber, or thermoplastic or thermosetting elastomer such as polyurethane, polyester, polyamide, etc. on a solid, liquid, gel or gas filled center to form a thread rubber layer that is then covered with one or more mantle or cover layers. Additionally, prior to applying the cover layers, the thread wound core may be further treated or coated with an adhesive layer, protective layer, or any substance that may improve the integrity of the wound core during application of the cover layers and ultimately in usage as a golf ball.

Since the core material is not an integral part of the present invention, further detailed 36 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 discussion concerning the specific types of core materials which may be utilized with the cover compositions of the invention are not specifically set forth herein.

Method of Making Golf Ball In preparing golf balls in accordance with the present invention, a hard inner cover layer is molded (by injection molding or by compression molding) about a core (preferably a solid core). A comparatively softer outer layer is molded over the inner layer.

The solid core for the multi-layer ball is about 1.2 1.6 inches in diameter, although it may be possible to use cores in the range of about 1.0 2.0 inches. Conventional solid cores are typically compression or injection molded from a slug or ribbon of uncured or lightly cured elastomer composition comprising a high cis content polybutadiene and a metal salt of an a, 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, larger amounts of metal oxide than those that are needed to achieve the desired coefficient are often included in conventional cores in order to increase 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.

The inner cover layer which is molded over the core is about 0.01 inches to about 0.10 inches in thickness, preferably about 0.03 0.07 inches thick. The inner ball which includes the core and inner cover layer preferably has a diameter in the range of 1.25 to 1.60 inches. The outer cover layer is about 0.01 inches to about 0.10 inches in thickness.

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 1.62 ounces.

37 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 In a particularly preferred embodiment of the invention, the golf ball has a dimple pattern which provides coverage of 65% or more. The golf ball typically is coated with a durable, abrasion-resistant, relatively non-yellowing finish coat.

The various cover composition layers of the present invention may be produced according to conventional melt blending procedures. Generally, the copolymer resins are blended in a Banbury type mixer, two-roll mill, or extruder prior to neutralization. After blending, neutralization then occurs in the melt or molten state in the Banbury mixer.

Mixing problems are minimal because preferably more than 75 wt and more preferably at least 80 wt of the ionic copolymers in the mixture contain acrylate esters, and in this respect, most of the polymer chains in the mixture are similar to each other. The blended composition is then formed into slabs, pellets, etc,, and maintained in such a state until molding is desired. Alternatively, a simple dry blend of the pelletized or granulated resins which have previously been neutralized to a desired extent and colored 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 such as an inorganic filler, etc., may be added and uniformly mixed before initiation of the molding process. A similar process is utilized to formulate the high acid ionomer resin compositions used to produce the inner cover layer. In one embodiment of the invention, a masterbatch of non-acrylate ester-containing ionomer with pigments and other additives incorporated therein is mixed with the acrylate ester-containing copolymers in a ratio of about 1 7 weight masterbatch and 93 99 weight acrylate estercontaining copolymer.

The golf balls of the present invention can be produced by molding processes which include but are not limited to those which are currently well known in the golf ball art. For example, the golf balls can be produced by injection molding or compression molding the novel cover compositions around a wound or solid molded core to produce an inner ball which typically has a diameter of about 1.50 to 1.67 inches. The outer layer is subsequently molded over the inner layer to produce a golf ball having a diameter of 1.620 inches or more, preferably about 1.680 inches or more. Although either solid cores or 38 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 wound cores can be used in the present invention, as a result of their lower cost and superior performance, solid molded cores are preferred over wound cores. The standards for both the minimum diameter and maximum weight of the balls are established by the United States Golf Association In compression molding, the inner cover composition is formed via injection at about 3800F to about 450°F into smooth surfaced hemispherical shells which are then positioned around the core in a mold having the desired inner cover thickness and subjected to compression molding at 2000 to 3000 F for about 2 to 10 minutes, followed by cooling at 0 to 706F for about 2 to 7 minutes to fuse the shells together to form 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'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 further processing steps such as buffing, painting and marking as disclosed in U.S. Patent No. 4,911,451.

The resulting golf ball produced from the hard inner layer and the relatively softer, low flexural modulus outer layer provide for an improved multi-layer golf ball which provides for desirable coefficient of restitution and durability properties while at the same time offering the feel and spin characteristics associated with soft balata and balata-like covers of the prior art.

Unique Spin Characteristics As indicated above, the golf ball of the invention is unique in that it provides good distance when hit with a driver, good control off of irons, and excellent spin on short chip shots. This golf ball is superior to conventional soft covered two-piece or wound balls in that it has lower spin off of a driver and higher spin on short shots.

39 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 The spin factor of the ball of the invention may be specified in the manner described below.

Step 1. A golf ball testing machine is set up in order that it meets the following conditions for hitting a 1995 Top-Flite Tour Z-balata 90 ball produced by Spalding Evenflo Companies.

Club Launch Angle Ball Speed Spin Rate 9 iron 21 1.5 160.5 9.0 9925 ±600 The machine is set up such that the above conditions are met for each test using 10 Zbalata 90 golf balls which are hit 3 times each at the same machine setting. The thirty measurements of spin rate are averaged to obtain Na.

Step 2. Ten golf balls of the invention (Ball X) are hit 3 times each using the same machine setting as was used for the Z-balata balls and spin data is collected. Any clearly erratic spin test result is eliminated and replaced by a new test with the same ball. The thirty measurements of spin rate are averaged to obtain N.x.

Step 3. The machine is set up in order that it meets the following conditions for hitting a 1995 Z-balata 90 ball, the conditions being intended to replicate a 30-yard chip shot: Club Launch Angle Ball Speed Spin Rate Sand Wedge 28 4.5 58.0 4.0 4930 770 The machine is set up such that the above conditions are met for each test using 10 Zbalata 90 golf balls which are hit 3 times each at the same machine setting. The thirty measurements of spin rate are averaged to obtain Nswm.

Step 4. The 10 golf balls used in Step 2 are hit three times each using the same machine setting as was used in Step 3 and spin data is collected. Any clearly erratic spin test result is eliminated and replaced by a new test with the same ball. The thirty measurements of spin rate are averaged to obtain Nsw.x.

SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCTIUS99/06748 Step 5. The numerical values of N 9 N9.x, Nswzs and Nswx are inserted into the following formula to obtain a spin factor Nsw-x Nsw.ze Spin factor x 100 Ng.x NBizB The golf ball of the invention has a spin factor of 3.0 or more, more preferably or more, and most preferably 8.0 or more.

Definitions Coefficient Of Restitution As is apparent from the above discussions, two principal properties involved in golf ball performance are resilience and PGA compression. The resilience or coefficient of restitution (COR) of a golf ball is the constant which is the ratio of the relative velocity of an elastic sphere after direct impact to that before impact. As a result, the COR can vary from 0 to 1, with 1 being equivalent to a perfectly or completely elastic collision and 0 being equivalent to a perfectly or completely inelastic collision.

COR, along with additional factors such as club head speed, club head mass, ball weight, ball size and density, spin rate, angle of trajectory and surface configuration dimple pattern and area of dimple coverage) as well as environmental conditions (e.g.

temperature, moisture, atmospheric pressure, wind, etc.) generally determine the distance a 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 size, density and resilience (COR) 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 dub 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 these are not factors of concern among golf 41 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 ball manufacturers. The factors or determinants of interest with respect to improved distance are generally the coefficient of restitution (COR) and the surface configuration (dimple pattern, ratio of land area to dimple area, etc.) of the ball.

The COR of solid core balls is a function of the composition of the core and of the cover. The core and/or cover may be comprised of one or more layers such as in multilayered balls. In balls containing a wound core balls comprising a liquid or solid center, elastic 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, the center and cover of a wound core ball may also consist of one or more layers. The COR of the golf balls of the present invention is a function of the composition and physical properties of the core and cover layer materials such as flex modulus, hardness and particularly, their resilience, i.e. ability to quickly recover from a high impact deformation.

The coefficient of restitution is the ratio of the outgoing velocity to the incoming velocity. In the examples of this application, the coefficient of restitution of a golf ball was measured by propelling a ball horizontally at a speed of 125± 5 feet per second (fps) and corrected to 125 fps against a generally vertical, hard, flat steel plate and measuring the ball's incoming and outgoing velocity electronically. Speeds were measured with a pair of Oehler Mark 55 ballistic screens available from Oehler Research, Inc., P.O. Box 9135, Austin, Texas 78766, which provide a timing pulse when an object passes through them.

The screens were separated by 36" and are located 25.25" and 61.25" from the rebound wall. The ball speed was measured by timing the pulses from screen I to screen 2 on the way into the rebound wall (as the average speed of the ball over and then the exit speed was timed from screen 2 to screen 1 over the same distance. The rebound wall was tilted 2 degrees from a vertical plane to allow the ball to rebound slightly downward in order to miss the edge of the cannon that fired it. The rebound wall is solid steel inches thick.

As indicated above, the incoming speed should be 125 L5 fps but corrected to 125 fps. The correlation between COR and forward or incoming speed has been studied and 42 SUBSTITUTE SHEET (RULE 26) WO~ 00/57963 PCT/US99/06748 a correction has been made over the fps range so that the COR is reported as if the ball had an incoming speed of exactly 125.0 fps.

The coefficient of restitution must be carefully controlled in all commercial golf balls if the ball is to be within the specifications regulated by the United States Golf Association As mentioned to some degree above, the U.S.G.A. standards indicate that a "regulation" ball cannot have an initial velocity exceeding 255 feet per second in an atmosphere of 75°F. when tested on a U.S.G.A. machine. Since the coefficient of restitution of a ball is related to the ball's initial velocity, it is highly desirable to produce a ball having sufficiently high coefficient of restitution to closely approach the U.S.G.A. limit on initial velocity, while having an ample degree of softness hardness) to produce enhanced playability spin, etc.).

PGA Compression PGA compression is another important property involved in the performance of a golf ball. The compression of the ball can affect the playability of the ball on striking and the sound or "click" produced. Similarly, compression can affect the "feel" of the ball hard or soft responsive feel), particularly in chipping and putting.

Moreover, while compression itself has little bearing on the distance 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.

43 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 For example, PGA compression indicates the amount of change in golf ball's shape upon striking.

In the past, PGA compression related to a scale of from 0 to 200 given to a golf ball.

The lower the PGA compression value, the softer the feel of the ball upon striking. In practice, tournament quality balls have compression ratings around 70 110, preferably around 80 to 100.

In determining PGA compression using the 0 200 scale, a standard force is applied to the external surface of the ball. A ball which exhibits no deflection (0.0 inches in deflection) is rated 200 and a ball which deflects 2/10th of an inch (0.2 inches) is rated 0. Every change of .001 of an inch in deflection represents a 1 point drop in compression.

Consequently, a ball which deflects 0.1 inches (100 x .001 inches) has a PGA compression value of 100 200-100) and a ball which deflects 0.110 inches (110 x .001 inches) has a PGA compression of 90 200 110).

In order to assist in the determination of compression, several devices have been employed by the industry. For example, PGA compression is determined by an apparatus fashioned in the form of a small press with an upper and lower anvil. The upper anvil is at rest against a 200-pound die spring, and the lower anvil is movable through 0.300 inches by means of a crank mechanism. In its open position the gap between the anvils is 1.780 inches allowing a clearance of 0.100 inches for insertion of the ball. As the lower anvil is raised by the crank, it compresses the ball against the upper anvil, such compression occurring during the last 0200 inches of stroke of the lower anvil, the ball then loading the upper anvil which in turn loads the spring. The equilibrium point of the upper anvil is measured by a dial micrometer if the anvil is deflected by the ball more than 0.100 inches (less deflection is simply regarded as zero compression) and the reading on the micrometer dial is referred to as the compression of the ball. In practice, tournament quality balls have compression ratings around 80 to 100 which means that the upper anvil was deflected a total of 0.120 to 0.100 inches.

An example to determine PGA compression can be shown by utilizing a golf ball compression tester produced by Ai Engineering Corporation of Newark, N.J. The value 44 SUBSTITUTE SHEET (RULE 26) Iww pCT/US99/06748 WO 00/57963 ressed by a number which may obtained by thtester relates to an arbitrary value exp d a indicated by range from 0 to 100, although a value of 200 can be measured as indicated by tesw ons of the dial indicator on the apa compressive loading. e Atti test deflection that a golf ball undergoes when subjected to er movable spring-oaded anvil.

apparatUS consists of a lower movable platform and an upper movable springoaded avi Td nsitsthat it measures the upward movement of the The dial indi c a to r l ballto be tested is placed in the lowertat wih a exerts spraised a fixed distance. The upper portion of the golf ball comes in contactf the golf baand to be apressure on the springloaded anvil. Depending upon the distancession. Foe pressed the upper anvil is forced upward against the spring.

compressed, the upper a also been employed to deter n Macne Originally Alternative devices have also een employed to restene compression example, Applicant also utilizes a modified Riehle ompression Machine oto evariginall produced by Riehle Bros. Testing Machine compver bahil, PA to evaluate compression of the various components ores, mantle cover balls, finished balls, etc.) ofhe golf balls. The ehe compression device deterines deormati in thousandths under a fixed initialized load of 200 pound s in such a device, aPGA of 61 corresponds to a deflection under load of 0.061 inches.

AdditionallY an approximate relationship between Riehle compressiOn antd pA ompression ests for balls of the same size. It has been determined oula GA compression corresponds to pGA compression by the general forula

GA

reon P d compression. suentlY. 80 Riehe compression Riehle compression Re c compressi on se rresponds to 90 pGA compression 160 Riehle compressin PGA compression. For oo O compression, t repOrting purposes, Applicant'S compression vle compreson and converted to PGA compression. monitor 9 urer o additional compression devices may also be utilized to i Furthball e long as the orrelation to pGA compression is know. These devices have been designed, such as a Whitney Tester, to orrelate or compression through a set relationship or formula.

SUBSTITUTE SHEET (RULE 26) PCT/US99/067 4 8 WO 00/57963 Shore D Hardnessmeasured generally in accordance As used herein, "Shore D hardness" of a cover s measured generally in accordance with ASTM 0-2240, except the measurements are made on the curved surface of a molded cover, rather than on a plaque. Furthermore, the Shore D hardness of the cover is measured while the cover remains over the core. When a hardness measurement is made on a dimpled cover, Shore D hardness is measured at a land area of the dimpled cover.

Fillers In a particularly preferred form of the invention, at least one layer of the golf ball contains at least 0.01 parts by weight of a filler. Fillers preferably are used to adjust the density, flex modulus, mold release, and/or melt flow index of a layer. More preferably, at least when the filler is for adjustment of density or flex modulus of a layer, it is present in an amount of at least five parts by weight based upon 100 parts by weight of the layer composition. With some fillers, up to about 200 parts by weight probably can be used.

A density adjusting filler according to the invention preferably is a filler which has a specific gravity which is at least 0.05 and more preferably at least 0.1 higher or lower than the specific gravity of the layer composition. particularly preferred density adjusting fillers have specific gravities which are higher than the specific gravity of the resin composition by 0.2 or more, even more preferably by 2.0 or more.

Aflex modulus adjusting filler according to the invention is a filler which, when used in an amount of e.g. I 100 parts by weight based upon 100 parts by weightof resin composition, will raise or lower the flex modulus (ASTM D-790) of the resin composition by at least 1% and preferably at least 5% as compared to the flex modulus of the resin composition without the inclusion of the flex modulus adjusting filler.

A mold release adjusting filler is a filler which allows for the easier removal of a part from a mold, and eliminates or reduces the need for external release agents which otherwise could be applied to the mold. A mold release adjusting filler typically is used in an amount of up to about 2 wt% based upon the total weight of the layer.

A melt flow index adjusting filler is a filler which increases or decreases the melt flow, or ease of processing of the composition.

46 SUBSTITUTE SHEET (RULE 26) pCT/US99/06 74 8 WO 00/57963 hat increase adhesion of materials within The layers may contain coupling agents that increase heson f matrialayes w a particular layer e.g. to couple a filler to a resin composition, or between adjacent layers.

Non-limiting examples of coupling agents include titanates, zirconates and silanes.

Non-limiting examin a of 2 w/o based upon the total weight Coupling agents typically are used in amounts f 0 ed of the composition in which the coupling agent is included.

o he co sit adusting filler is used control the moment of inertia, and thus the initial A density adusting fier is used to codtion in one or more layers, and particularly spin rate of the ball and spin decay. The add aition in one o e laresin cmpstin in the outer cover layer of a filler with a lower specificgrit than would result results in a decrease In moment of inertia and a higher initial spin rate than would result resuts in a decrease In moment of inertiathe cover layers, and particularly in ifno filler were used. The addition in one or more of t cvr aes n pticr in the outer cover layer of a filler with a higher specific gravity than the resin composition, results in an increase in moment of inertia and a lower iitia si rat.

gravity fillers are preferred as less volume is used to achieve the desired inner cover total ting fillers are also preferred as they have minimal effect on COR.

preiht Nonreinforcably, the filler does not chemicalso rea with the resin composition to a substantial Preferably, the filler does not chemically xample, z~inc oxide is used in a shell degree, although some reaction may occur when, for ex layer which contains some ionomer.y have a specific g y in he densitesity-educing fillers for use in the invention gravity in the range of 1.0 20. The dens more preferably 006-0.90 T lex preferably have a specific gravity of 0.06 1.4, and me pefeb t e hol modulus increasing fillers have a reinforcing or stffening effect due to their morphology, their interaction with the resin, or their inherent physical properties. The flex modulus reducing fillers have an opposite efect due t their reltvel flo enhancing effec due to the matrix resin. The melt flow index increasing fillers have a flow enhancing effect due to their relatively high melt flow versus the mat melt flow index ecmatrix have an opposite effect due to their relatively low melt flow index vers e ma Fillers which may be employed in layers other than the outer cover layer may be or are typically in a finely divided form, for example, in a size generally less than about mesh, preferably less than about 100 mesh U.S. standard size, except for fibers and flock, 47 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 which are generally elongated. Flock and fiber sizes should be small enough to facilitate processing. Filler particle size will depend upon desired effect, cost, ease of addition, and dusting considerations. The filler preferably is selected from the group consisting of precipitated hydrated silica, clay, talc, asbestos, glass fibers, aramid fibers, mica, calcium metasilicate, barium sulfate, zinc sulfide, lithopone, silicates, silicon carbide, diatomaceous earth, polyvinyl chloride, carbonates, metals, metal alloys, tungsten carbide, metal oxides, metal stearates, particulate carbonaceous materials, micro balloons, and combinations thereof. Non-limiting examples of suitable fillers, their densities, and their preferred uses are as follows: 48 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Filler Table

L--

Filler Type Precipitated hydrated silica Clay Talc Talc Asbestos Glass fibers Aramid fibers (KEVLAR®) Mica Calcium metasilicate Barium sulfate Zinc sulfide Lithopone Silicates Spec. Grav. Comments 2.0 1,2 2.62 1,2 2.85 1,2 2.5 1,2 2.55 1,2 1.44 1,2 2.8 1,2 2.9 1,2 4.6 1,2 4.1 1,2 4.2-4.3 1,2 2.1 1,2 3.18 1,2 3.2 1,2 15.6 1 2.3 1,2 1.41 1,2 2.71 1,2 2.20 1,2 4.51 1 19.35 1 2.70 1 Silicon carbide platelets Silicon carbide whiskers Tungsten carbide Diatomaceous earth Polyvinyl chloride Carbonates i Calcium carbonate Magnesium carbonate Metals and Alloys (oowders) Titanium Tungsten Aluminum

I

Aluminum 49 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748

I

Bismuth 9.78 1 Nickel 8.90 1 Molybdenum 10.2 1 Iron 7.86 1 Steel 7.8-7.9 1 Lead 11.4 1,2 Copper 8.94 1 Brass 8.2 -8.4 1 Boron 2.34 1 Boron carbide whiskers 2.52 1,2 Bronze 8.70- 8.74 1 Cobalt 8.92 1 Beryllium 1.84 1 Zinc 7.14 1 Tin 7.31 1 Metal Oxides Zinc oxide 5.57 1,2 Iron oxide 5.1 1,2 Aluminum oxide Titanium oxide 3.9 -4.1 1,2 Magnesium oxide 3.3 3.5 1,2 Zirconium oxide 5.73 1,2 Metal Stearates Zinc stearate 1.09 3,4 Calcium stearate 1.03 3,4

II

Barium stearate 1.23 I 3,4 I SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Lithium stearate 1.01 3,4 Magnesium stearate 1.03 3,4 Particulate carbonaceous materials Graphite 1.5-1.8 1,2 Carbon black 1.8 1,2 Natural bitumen 1.2 1.4 1,2 Cotton flock 1.3-1.4 1,2 Cellulose flock 1.15-1.5 1,2 Leather fiber 1.2 1.4 1,2 Micro balloons Glass 0.15-1.1 1,2 Ceramic 0.2-0.7 1,2 Fly ash 0.6 0.8 1,2 Coupling Agents Adhesion Promoters Titanates 0.95-1.17 Zirconates 0.92-1.11 Silane 0.95- 1.2

COMMENTS:

1 Particularly useful for adjusting density of the cover layer.

2 Particularly useful for adjusting flex modulus of the cover layer.

3 Particularly useful for adjusting mold release of the cover layer.

4 Particularly useful for increasing melt flow index of the cover layer.

All fillers except for metal stearates would be expected to reduce the melt flow index of the cover layer.

The amount of filler employed is primarily a function of weight requirements and distribution.

51 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 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: Ionic Terpolymer-Containing Cover A set of two-piece golf balls was made with solid cores and a cover composition of 75 weight NUCREL 035, which is an acrylate ester-containing acid terpolymer, and 25 weight of a masterbatch containing 4.5 weight MgO in Surlyn 1605 ("MgO Masterbatch"). The terpolymer was reacted with the masterbatch at a temperature of about 250 F under high shear conditions at a pressure of about 0 to 100 psi. The magnesium in the masterbatch neutralized acid groups of the terpolymer at a level of about 62% neutralization. The molded balls were finished with polyurethane primer and top coats. The PGA compression, coefficient of restitution, Shore C hardness, scuff resistance, spin rate and cold crack of the golf balls were determined. The results are shown on Table 12 below.

To measure cold crack, the finished golf balls were stored at -10°F for at least 24 hours and were then subjected to 5 blows in a coefficient machine at 165 ft/sec.

The balls were allowed to return to room temperature and were then visually inspected for cover cracking. None of the golf balls experienced cracking.

Coefficient of restitution was measured by firing the resulting golf ball in an air cannon at a velocity of 125 feet per second against a steel plate which was 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. Shore hardness was determined in general accordance with ASTM Test 2240, but was measured on a non-dimpled area of the surface of the golf ball.

52 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Comparative Example 1: Ionic Copolymer Cover (Non-Terpolymer) A set of 12 two-piece golf balls was made according to the same procedure as that of Example 1 with the exception that NUCREL 925, a non-acrylate ester-containing acid copolymer was substituted for NUCREL 035. The resulting golf ball cover was too hard, resulting in four breaks during cold crack testing. The results are shown on Table 12.

Comparative Example 2: lonomer Non-Ionic Terpolymer Blend The procedure of Example 1 was repeated with the exception that the MgO Masterbatch was replaced by pure Surlyn® 1605. All of the golf ball covers broke during cold crack testing. The results are shown on Table 12.

Comparative Example 3: lonomer Non-Ionic Copolymer Blend The procedure of Comparative Example 1 was repeated with the exception that the MgO masterbatch was replaced by pure Surlyn® 1605. The results are shown on Table 12. When subjected to cold crack testing, all of the golf ball covers broke.

As can be seen from the results of Example 1 and Comparative Examples 1 3, inferior golf balls are obtained when a hard, non-acrylate ester-containing copolymer is used instead of a softer, acrylate ester-containing terpolymer, and when either an acrylate ester-containing acid terpolymer or a non-acrylate ester-containing acid copolymer is not neutralized with metal ions.

53 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE 12 Experiment No.

Cover Material Weight PGA COR Comp. (xl0 0 0 45.2 104 .783 Shore C Hardness Cold Crack so No breaks 1-1 75% Nucrel 0351 MgO MB in Surlyn 1605 Comp. 1 75% Nucrel925/ MgO MB in Surlyn 1605 Comp. 2 75% Nucrel 035/ Surlyn 1605 Comp. 3 75% Nucrel925/ Surlyn 1605 111 .798 4 breaks 45.1 99 .774 45.2 106 .790 70 All broke 75 All broke Example 2: Ionic Terpolymers An acrylate ester-containing terpolymer sold as ESCOR ATX 325 (Exxon Chemical Co.) was 57% neutralized with lithium cations. The ionomeric material, which also contained titanium dioxide, brightener, etc. from a white masterbatch, was placed over a solid golf ball core and the golf ball was primed and top coated. The properties of the resulting golf ball are shown on Table 13. This procedure was repeated using different combinations of terpolymers with cations and cation blends at the degrees of neutralization which are shown on Table 11. In the cation blends, mole ratios were about 1:1:1. All of the ATX materials shown on Table 13 are ESCOR

ATX

materials available from Exxon Chemical Co. The Nucrel materials are available from DuPont Chemical Co. Primacor 3440 is available from Dow Chemical Co.

54 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 The spin rate of the golf ball was measured by striking the resulting golf balls with a pitching wedge or 9-iron wherein the club-head speed is about 80 feet per second and the ball was launched at an angle of 26 to 34 degrees with an initial velocity of 100 115 feet per second. The spin rate was measured by observing the rotation of the ball in flight using stop action Strobe photography or via the use of a high speed video system.

The scuff resistance test was conducted in the following manner: a Top-Flite tour pitching wedge (1994) with box grooves was obtained and was mounted in a Miyamae driving machine. The club face was oriented for a square hit. The forwardlbackward tee position was adjusted so that the tee was four inches behind the point in the downswing where the club was vertical. The height of the tee and the toeheel position of the club relative to the tee were adjusted in order that the center of the impact mark was about 314 of an inch above the sole and was centered toe to heel across the face. The machine was operated at a club head speed of 125 feet per second. A minimum of three samples of each ball were tested. Each ball was hit three times.

After testing, the balls were rated according to the following chart: Rating Type of damage 1 Little or no damage (groove markings or dents) 2 Small cuts and/or ripples in cover 3 Moderate amount of material lifted from ball surface but still attached to ball 4 Material removed or barely attached The balls that were tested were primed and top coated.

As shown on Table 13, many of the cover materials resulted in golf balls having a scuff resistance of 1.5 or less, and others had a scuff resistance rating of 1.5 SUBSTITUTE SHEET (RULE 26) W'O 00/57963 PCT/US99/06748 Comparative Example 4: Hard/Soft lonomer Blend A golf ball with a cover formed from a blend of a commercially available hard sodium ionomer and a commercially available soft acrylate ester-containing zinc ionomer in which the blend contains less than 60 wt soft ionomer was subjected to the same testing as the golf balls of Example 2. The results are shown on Table 13.

56 SUBSTITUTE SHEET (RULE 26) WO 00/57963 W0 0057963PCT/US99/06748 TABLE 13 Experiment Cover Cation No. Material PGA COR Shore D Scuff Neutralization Comp. (XIOOO)Hardnes Resist.

S

Spin Rate Iron at 105 if/sec) Comp. 4 hard-soft Zn/Na ionomer blend I (control) 2-1 ATX 325 U 2-2 ATX 325 Li/ZnK 2-3 ATX 320 U 2-4 ATX 320 LI/ZnK Nucrel 010 U 2-6 Nucrel 010 U/ZnK 2-7 Nucrel 035 U 2-8 Nucrel 035 LI/ZnK 2-9 ATX 310 U 2-10 ATX 310 LI/Zn/K 2-11 ATX 325 LI 2-12 ATX 325 U/ZnK 2-13 60% ATX (U) 325-U

ATX

320-unneut.

2-14 76-/ATX320 (UJzrnJK) -U/Zn/K 25%/ATX320 -unneut.

2-15 60%/ATX325 L/nK -Li/Zn/K 3440-urineut 2-16 ATX 320 Unneut.

2-17 ATX 325 Unneut.

2-18 ATX 325 u 2-19 ATX 325 U 2-20 ATX 325 LI/ZnK 2-21 ATX 325 U/Zn/K 2-22 ATX 325 U/ZnK 60% 90 57%a 86 65% 86 S7% N.T 65% 87 89 89 87 87 53% 88 60% 88 Me% 83 65%/ 82 28.51/6 89 48% 87 39% 8 88 8 50% 95 304% 96 787 68 4.0 787 51 787 50 N.T. 56 790 65 803 65 802 65 801 62 798 62 802 62 801 63 797 796 63 7T7 9,859 10,430 10,464 10,299 10,355 7,644 7,7 8,931 8,915 8,892 8,244 776 64 1.6 779 64 1.6 775 42 795 791 4 791 48 N.T. N.T. 47 60% 30% 50% 91 90 91 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Example 3: Ionic Terpolymers The procedure of Example 2 was repeated with the exception that single cations of lithium, magnesium, sodium and potassium were used in the cover material. The results are shown on Table 14.

As indicated on Table 14, the scuff resistance of the golf balls was 3.0 or better.

The scuff resistance of the balls with covers made of an acrylic acid terpolymer was For a given terpolymer, the scuff resistance did not change when different cations were used for neutralization.

TABLE 14 Experiment Cover Cation PGA COR Shore D Scuff No. Material Neutralization Comp. (x1000) Hardness Resistance 3.1 Nucrel 035 U 100 90 792 62 3-2 Nucrel 035 Mg 100 89 792 62 3-3 ATX 325 U 100 86 790 51 3-4 ATX 325 Mg 100 85 791 51 ATX 325 Na 81 85 790 51 3-6 ATX 325 K 95 85 791 51 Comparative Example Several intermediate balls (cores plus inner cover layers) were prepared in accordance with conventional molding procedures described above. The inner cover compositions were molded around 1.545 inch diameter cores weighing 36.5 grams with a specific gravity of about 1.17 such that the inner cover had a wall thickness of about 58 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 0.0675 inches and a specific gravity of about 0.95, with the overall ball measuring about 1.680 inches in diameter.

The cores utilized in the examples were comprised of the following ingredients: 100 parts by weight high cis-polybutadiene, 31 parts by weight zinc diacrylate, about 6 parts by weight zinc oxide, 20 parts by weight zinc stearate, 17 18 parts by weight calcium carbonate, and small quantities of peroxide, coloring agent and a polymeric isocyanate sold as Papi 94 (Dow Chemical The molded cores exhibited PGA compressions of about 100 and C.O.R. values of about .800.

The inner cover compositions designated herein as compositions A E utilized to formulate the intermediate balls are set forth in Table 15 below. The resulting molded intermediate balls were tested to determine the individual compression (Riehle), Shore C hardness, spin rate and cut resistance properties. These results are also set forth in Table 15 below.

The data of these examples are the average of twelve intermediate balls produced for each example. The properties were measured according to the following parameters: Cut resistance was measured in accordance with the following procedure: A golf ball was fired at 135 feet per second against the leading edge of a pitching wedge wherein the leading edge radius is 1/32 inch, the loft angle is 51 degrees, the sole radius is 2.5 inches and the bounce angle is 7 degrees.

The cut resistance of the balls tested herein was evaluated on a scale of I to The number I represents a cut that extends completely through the cover to the core.

A 2 represents a cut that does not extend completely through the cover but that does break the surface. A 3 does not break the surface of the cover but does leave a permanent dent. A 4 leaves only a slight crease which is permanent but not as severe as 3. A 5 represents virtually no visible indentation or damage of any sort.

The spin rate of the golf ball was measured by striking the resulting golf balls with a pitching wedge or 9 iron wherein the club head speed is about 105 feet per second and the ball is launched at an angle of 26 to 34 degrees with an initial velocity 59 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 of about 110 to 115 feet per second. The spin rate was measured by observing the rotation of the ball in flight using stop action Strobe photography.

Initial velocity is the velocity of a ball when struck at a hammer speed of 143.8 feet per second in accordance with a test as prescribed by the U.S.G.A.

As will be.noted, compositions A, B and C include high acid ionomeric resins, with composition B further including zinc stearate. Composition D represents the inner layer Surlyn® 1605) used in U.S. Patent No. 4,431,193. Composition E provides a hard, low acid ionomeric resin.

The purpose behind producing and testing the balls'of Table 15 was to provide a subsequent comparison in properties with the multi-layer golf balls of the present invention.

Table Molded Intermediate Golf Balls Ingredients of Inner Cover Compositions A B C D E lotek 959 50 50 lotek 960 50 50 Zinc Stearate 50 Surlyn) 8162 75 Surlyn@ 8422 25 Surlyn 1605 100 lotek 7030 lotek 8000- Properties of Molded Intermediate Balls Compression 58 58 60 63 62 C.O.R. .811 .810 .807 .793 .801 Shore C Hardness 98 98 97 96 96 Spin Rate 7,367 6,250 7,903 8,337 7;956 Cut Resistance 4-5 4-5 4-5 4-5 As shown in Table 15 above, the high acid ionomer resin inner cover layer (molded intermediate balls A C) have lower spin rates and exhibit substantially higher SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 resiliency characteristics than the low acid ionomer resin based inner cover layers of balls D and E.

Example 4 Multi-layer balls in accordance with the present invention were then prepared.

Specifically, the inner cover compositions used to produce intermediate golf balls from Table 15 were molded over the solid cores to a thickness of about 0.0375 inches, thus forming the inner layer. The diameter of the solid core with the inner layer measured about 1.620 inches. Alternatively, the intermediate golf balls of Table 15 were ground down using a centerless grinding machine to a size of 1.620 inches in diameter to produce an inner cover layer of 0.0375 inches.

The size of 1.620 inches was determined after attempting to mold the outer cover layer to various sizes (1.600", 1.610", 1.620", 1.630" and 1.640") of intermediate (core plus inner layer) balls. It was determined that 1.620" was about the largest "intermediate" ball core plus inner layer) which could be easily molded over with the soft outer layer materials of choice. The goal herein was to use as thin an outer layer as necessary to achieve the desired playability characteristics while minimizing the cost of the more expensive outer materials. However, with a larger diameter final golf ball and/or if the cover is compression molded, a thinner cover becomes feasible.

With the above in mind, an outer cover layer composition was blended together in accordance with conventional blending techniques. The outer layer composition used for this portion of the example is a relatively soft cover composition such as those listed in U.S. Patent No. 5,120,791. An example of such a soft cover composition is a soft/55% hard low acid ionomer blend designated by the inventor as 'TE-90". The composition of TE-90 is set forth as follows: 61 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Outer Cover Layer Composition lotek 8000 22.7 weight lotek 7030 22.7 weight lotek 7520 45.0 weight White MB 1 9.6 weight 'White MB consists of about 23.77 weight percent T10, 0.22 weight percent Uvitex OB, 0.03 weight percent Santonox R, 0.05 weight percent Ultramarine blue and 75.85 weight percent lotek 7030.

The above outer layer composition was molded around each of the 1.620 diameter intermediate balls comprising a core plus one of compositions A D, respectively. In addition, for comparison purposes, Surlyn® 1855 (new Surlyn® 9020), the cover composition of the '193 patent, was molded about the inner layer of composition D (the intermediate ball representative of the '193 patent). The outer layer was molded to a thickness of approximately 1.680 inches in diameter. The resulting balls (a dozen for each example) were tested and the various properties thereof are set forth in Table 16 as follows: TABLE 16 Finished Balls Inoredlentsi I 1 L Iver Cover Composltion A I C 0 Oucer Cover corposltion TE-90 TE-90 TE-90 TE-90 Surtyn* 9020 Proprtcles of Molded Finished Setll: Compression 63 63 69 70 61 C.o.R. .7T. .778 .780 .7 a .sT Shore C IHrdness 88 88 88 69 Spin 8.825 6885 8,814 8,990 8,846 Cut Resiscance 3-4 3-4 3-4 3-4 1-2 62 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 As it will be noted in finished balls 1 4, by creating a multi-layer cover utilizing the high acid ionomer resins in the inner cover layer and the hard/soft low acid ionomer resin in the outer cover layer, higher compression and increased spin rates are noted over the single layer covers of Table 12. In addition, both the C.O.R. and the Shore C hardness are reduced over the respective single layer covers of Table 12. This was once again particularly true with respect to the multi-layered balls containing the high acid ionomer resin in the inner layer finished balls 1 In addition, with the exception of prior art ball 5 the '193 patent), resistance to cutting remains good but is slightly decreased.

Furthermore, it is also noted that the use of the high acid ionomer resins as the inner cover material produces a substantial increase in the finished balls overall distance properties. In this regard, the high acid ionomer resin inner covers of balls 1 3 produce an increase of approximately 10 points in C.O.R. over the low acid ionomer resin inner covers of balls 4 and about a 25 point increase over the prior art balls Since an increase in 3 to 6 points in C.O.R. results in an average increase of about 1 yard in distance, such an improvement is deemed to be significant.

Several other outer layer formulations were prepared and tested by molding them around the core and inner cover layer combination to form balls each having a diameter of about 1.68 inches. First, B.F. Goodrich Estane® X-4517 polyester polyurethane was molded about the core molded with inner layer cover formulation A.

DuPont Surlyrn 9020 was molded about the core which was already molded with inner layer D. Similar properties tests were conducted on these golf balls and the results are set forth in Table 17 below.

63 SUBSTITUTE SHEET (RULE 26) WOb 00/57963 PCT/US99/06748 TABLE 17 Finished Balls Ingredients: Inner Cover Layer Composition Outer Cover Layer Composition Properties of Molded Finished Balls: Compression

C.O.R.

Shore C Hardness Spin Cut Resistance

A

Estane® 4517

D

Surlyn® 9020 67 .774 74 10,061 3-4 61 .757 89 8,846 1-2 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 The ball comprising inner layer formulation D and Surlyn® 9020 identifies the ball in the Nesbitt 4,431,193 patent. As is noted, the example provides for relatively high softness and spin rate though it suffers from poor cut resistance and low C.O.R.

This ball is unacceptable by today's standards.

As for the Estane® X-4517 polyester polyurethane, a significant increase in spin rate over the TE-90 cover is noted along with an increase in spin rate over the cover is noted along with an increased compression. However, the C.O.R. and Shore C values are reduced, while the cut resistance remains the same. Furthermore, both the Estane@ X-4517 polyester polyurethane and the Surlyn® 9020 were relatively difficult to mold in such thin sections.

Example In order to analyze the change in characteristics produced by multi-layer golf balls (standard size) having inner cover layers comprised of ionomer resin blends of different acid levels, a series of experiments was run. A number of tests were performed, varying the type of core, inner cover layer and outer cover layer. The results are shown below on Table 18: SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE 18 INNER COjPt alTER COMP

SHORE

smmoe S CORE LAYER TNICM2ESS COR CU -TICYURESS (Rhiele) MR_ q SPIN 8 1042 YELLOW NONE SEE BELOW TOP GRAE 0.055" .61 .800 68 7331 9 1042 YELLOW MONE SEE BELOW 959(960 0.055"- 56 .808 73 6516 SPECIAL 1.47 959/960 0.050. 65/.&805 959f960 0.055"1 .8 .830 73 6258 11 1042 YELLOW MORE SEE BELOW SD 90 0.055", 62 .792 63 6421 12 SPECIAL 1.47" TOP GRACE 0.050- 66/. "9 SD 90 0.055", 55 .311. 63 8265 13 SPECIAL 1.47" 959/960 0.050" 65/.805 SO 90 0.055" 53 .813 63 82-54 14 SPECIAL 1.470 TOP GMAE 0.050" 66/.799 TOP GRACE 0.05" 51 .819 68 7390 1042 YELLOW NONE SEE BELOW Z.SALATA 0.055- 67 .782 55 91.79 M6 SPECIAL 1.47H 959/960 0.050ft 651.805 Z-BALATA 0.05511 61 .800 55 94326 17 SPECIAL 1.47'" TOP GRAE 0.050" 661-799 2.BALATA 0.055" 60 .798 55 9262 1042 TELLMO'JG4"2. CDRc.780 SPECIAL 1.47* CORtECP"67, COR.782 In this regard, 'Top Grade" or "TG" is a low acid inner cover lonomer resin blend comprising of.70.6% lotek 8000, 19.9% lotek 7010 and 9.6% white masterbatch.

"9591960" is a 50/50 wt/wt blend of lotek 959/960. In this regard, Escor® or lotek 959 is a sodium ion neutralized ethylene-acrylic neutralized ethylene-acrylic acid copolymer. 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.

66 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Furthermore, the low acid ionomer formulation for "SD 90" and "Z-Balata" are set forth below: SD Cover ZB Cover 17.2% Surlyn 8320 19% lotek 8000 Surlyn 8120 19% lotek 7030 49% Surlyn 9910 52.5% lotek 7520 16.4% Surlyn 8940 9.5% white MB 9.7% white MB The data clearly indicates that higher C.O.R. and hence increase travel distance can be obtained by using multi-layered covered balls versus balls covered with single layers. However, some sacrifices in compression and spin are also noted. Further, as shown in comparing Example Nos. 12 vs. 13, Example Nos. 17 vs. 16, etc. use of lower acid level inner cover layers and relatively soft outer cover layers 50 wt.% or more soft ionomer) produces softer compression and higher spin rates than the golf balls comprised of high acid inner cover layers. Consequently, use of blends of.low acid ionomer resins to produce the inner layer of a multi-layer covered golf ball, produces not only enhanced travel distance but also enhanced compression and spin properties.

Example 6 Multi-layer oversized golf balls were produced utilizing differentionomer resin blends as the inner cover layer core plus inner cover layer is defined as "mantel").

The "ball data" of the oversized multi-layer golf balls in comparison with production samples of 'Top-Flite® XL" and Top-Flite® Z-Balata" is set forth below.

67 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 top-Fti te* Top-Flite* 18 19 20 XL Z-Galate size 1.43 1..3 1.43 1.545 COR .787 .787 .787 Mantel OData Material TG IG TG Size .161 1.61 1.61 Thickness .090 .090 .090 Mantel Data (cont'd) Shore 0 68 68 68 Conpression 57 57 57 COR .815 .815 .815 Bait Data Cover TG Z8 So TG Z Size 1.725 1.723 1.726 1.681 1.683 Ueight 45.2 45.1 45.2 4.5.3 Shore 0 68 56 63 a S6 Copression 45 55 49 53 77 COR .820 .800 .810 .809 .797 spin 7230 9268 8397 7133 9287 The results indicate that use of multi-layer covers enhances C.O.R. and travel distance. Further, the data shows that use of a blend of low acid ionomer resins 'Top Grade') to form the inner cover layer in combination with a soft outer cover or produces enhanced spin and compression characteristics. The overall combination results in a relatively optimal golf ball with respect to characteristics of travel distance, spin and durability.

Example 7 Golf balls 7 1, 7 2, 7 3 and 7 4 having the formulations shown on Table 19 were formed.

68 SUBSTITUTE SHEET (RULE 26) WO 00/57963 Wo 0057963PCT/US99/06748 Table 19 Chemical Compo nent 7-1 7-2 7-3 7.4 Core Data Size 1.47r- 1.47" 1.47r 1.47" Weight 32.7g 32.7g 32.7g 32.7g PGA Compression 70 60 70 COR 780 770 780 770 Composition High cis poybutadiene 100 100 100 100 Zinc o~dde 30.5 31.6 30.5 31.6 Core regrind 16 16 16 16 Zinc Stearate 16 16 16 16 Zinc Diac3)Iate 22 20 22 initiator 0.9 0.9 0.9 0.9 Inner Cover Layer size 1.57" 1.57" 1.57" 1.57" Weight 38.4g 38.4g 38.4g 38.4g PGA Compression 83 75 83 ICOR 801 795 801 795 Thiknss 0.050r 0.050 0.050" 0.050 Hardness (Shore CID) 97070 97170 97170 97170 Composition lotek 1002 50% 50% 500A iotek 1003 50% 50% 50% SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Chemical Component 7-1 7-2 7.3 7-4 Outer Cover Layer Hardness (Shore CID) 71/46 71/46 71146 71146 Thickness 0.055" 0.055" 0.055" 0.055" Composition lotek 7510 92.8% 92.8% 42% 42% lotek 7520 42% 42% lotek 7030 7.2% 7.2% 7.3% 7.3% lotek 8000 8.7% 8.7% Whitener Package Unitane 0-110 2.3 phr 2.3 phr 2.3 phr 2.3 phr Eastobrite OB1 0.025 phr 0.025 phr 0.025 phr 0.025 phr Ultra Marine Blue 0.042 phr 0.042 phr 0.042 phr 0.042 phr Santanox R 0.004 phr 0.004 phr 0.004 phr 0.004 phr Final Ball Data Size 1.68" 1.68" 1.68" 1.68" Weight 45.4g 45.4g 45.4g 45.4g PGA Compression 85 78 85 78 COR 793 785 793 785 The balls of Example 7 2 were tested by a number of professional quality golfers using a driver, 5-iron, 9-iron, and sand wedge or pitching wedge. Each player used his own clubs and hit both the ball of Example 7 2 and a control ball, which was the 1995 two-piece Top-Flite Tour Z-balata 90. The Z-balata 90 has a 1.545" core of about 36.8g with a PGA compression of about 80 and a COR of about .794. The cover of the Z-balata 90 is about 0.068 in. thick, and is a blend of lotek 8000 and lotek 7510 with or without masterbatch containing lotek 7030. The cover has a Shore D hardness of about 55. The ball has a PGA compression of about 79 and a COR of about 0.788.

Each player hit six of the balls of Example 7 2 and six Z-balata control balls one time SUBSTITUTE SHEET (RULE 26) W6 00/57963 PCT/US99/06748 each. For each shot, measurements were made of the initial launch conditions of the golf ball, including launch angle and ball speed. Furthermore, spin rates at initial launch, carry distance, and total distance were measured. The players hit full shots with the driver 5-iron (51) and 9-iron With the sand wedge or pitching wedge the players hit about 30 yard chip shots. Data points were removed if determined to be "wild points." A point was said to be wild if it fell outside 2 standard deviations of the 6-hit average. Initial launch conditions were determined using a highly accurate high speed stop action video photography system. The results are shown on Table 21.

As shown on Table 21, multi-layer ball 7 2 was longer than the Z-balata control when hit with a 5-iron but only slightly longer than the Z-balata ball using a driver and 9-iron. The multi-layer ball 7 2 and the two-piece control were generally the same in overall distance using a driver. In each case, the multi-layer ball 7 2 had a higher spin rate off the 30-yard chip shot than the Z-balata. The spin rate of the ball of Example 7 2 was an average of 11.6% higher than the spin rate of the Z-balata control in the 30 yard chip shot.

71 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE 2-Piece Control Player Club LA B.S. Spin Cary TCal LA B.S. Spin Cany Total (deg) (fps) (rp) (yds) yds) (deg.) (fps) (rpm) (y (s) 1 1W 10.4 262.2 3537 272.5 288.9 10.0 262.3 3247 271.6 292.2 2 1W 9.5 240.1 3124 238.1 253.6 8.9 238.3 2935 236.3 257.4 3 1W 8.6 258.8 3695 254.1 259.9 63 251.2 3357 247.6 260.8 4 1W 10.9 252.6 2639 271.6 289.8 12.5 251.4 3066 279.0 296.7 1W 9.5 211.7 3627 237.2 255.2 9.4 208.7 3415 235.0 259.8 6 1W 10.2 242.0 3105 263.8 2832 11.0 243.9 2903 267.6 288.4 7 1W 11.5 214.9 3069 265.4 279.0 11.6 212.6 3165 262.9 274.4 8 1W 9.7 239.5 3129 263.6 288.8 9.3 2353 2884 257.2 276.8 9 1W 11.7 211.2 2939 231.4 255.8 11.3 208.5 2032 222.2 244.3 1W 10.2 244.0 2797 243.3 250.2 9.7 239.6 3072 236.8 251.1 11 1W 247.4 263.8 13.8 2158 3916 245.4 268.8 AVE 10.2 237.7 3168 253.5 269.8 10.3 233.4 3090 251.1 270.1 1 51 12.4 207.3 5942 196.3 209.8 11.8 206.3 5507 196.2 207.8 2 51 178.3 184.2 14.9 199.4 5094 182.2 187.8 3 51 10.9 196.8 6462 185.2 188.9 11.5 197.0 6009 187.4 193.4 4 51 14.4 205.5 6683 207.8 213.7 14.7 208.3 6601 207.5 217.8 51 13.6 163.3 6734 182.9 189.4 14.2 180.9 6380 184.2 190.7 6 51 12.4 204.5 5771 201.0 210.5 129 208.4 5414 206.0 218.3 7 51 14.1 184.3 6013 194.8 198.1 13.1 182.7 6000 192.9 200.0 8 51 12.8 187.2 6149 188.0 2003 131 191.6 6183 191.7 202.0 9 51 13.2 176.5 6000 168.2 173.7 13.6 172.5 6166 169.7 174.3 51 13.9 199.9 7214 1752 1782 14.9 199.1 6237 169.0 170.2 11 51 14.2 179.5 6669 181.9 187.8 157 181.2 5338 184.0 190.7 AVE 13.2 192.5 6364 187.4 194.1 13.7 193.4 5903 188.4 19.7 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Player Club LA B.S. Spin Carry TOWa L B.S. Spin Carry Total (deg) (fps) (rpmn) Cys)Cyds) (deg) (fps) (rprn) CYds) (yds) 1 91 20.0 168.1 9865 152.5 1595 20.4 172. 9210 153.4 159.6 2 91 21.8 165.9 9770 132.7 137.0 23.0 164.7 8949 132.7 134.6 3 91 19.9 154.3 10764 128.8 134.3 19.9 156.5 10161 129.8 135.0 4 91 227 166.4 10551 140.0 148.8 23.9 165.7 O99 150.3 154.2 91 22.1 147.4 9682 137.1 138.1 22.2 148.5 9324 139.3 141.7 6 91 19.4 169.7 893 153.3 158.0 19.7 168.2 8588 15112 7 91 20.4 151.1 989 147.5 150.0 21.6 150.3 908.4 148.6 151.3 8 91 18.5 143.0 9408 142.0 147.5 18.3 141.8 9038 141.2 144.8 9 9? 20.0 134.5 9124 124.9 128.8 20.1 132.9 8834 125.0 128.9 91 23.2. 156.1 10803 122.7 124.1 23.2 155.6 11017 116.2 116.3 1 11 91 21.5 149.4 9729 131.0 134.5 23.4 151.7 866 1333 136.8 AVE. 20.9 155.1 98S49 138.0 141.9 21.4 155.3 935 138.7 142.4 I SW 29.2 56.4 5647 24.8 58.9 8679 2 SW 26.6 57.4 5446 25.2 57.8 5647 3 SW 25.8 64.1 4925 24.3 63.5 4 SW 30.9 60.9 5537 31.1 57.9 6158 SW 20.3 58.7 4152 19.0 56.3 4288 6 SW 34.3 57.1 3796 32.4 61.5 4700 7 SW 30.5 51.5 4712 29.3 52.3 5374 AVE 28.2 67.7 4911- 26.6 W.3 6485- SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/067 4 8 Example 8 The ball of Example 7 2 was compared to a number of competitive products in distance testing using a driving machine in which the ball was struck with a club. The results are shown on Table 19 below. The distance test shows that Example 7 2 is about the same distance as the Z-balata 90 control and longer than the Titleist HP-2 Tour (soft covered two-piece) and Titleist Tour Balata 100 ball (Balata covered wound ball). The other balls that were tested include the Maxfli (Dunlop) XS100, Maxfli (Dunlop) XF100, and the GIGA Top-Flite golf ball sold by Spalding in Japan. In Table 19, the ball of Example 7 2 is the longest ball.

TABLE 21 Dpistance Report Test Number: 131951 Club Head Speed: 157.35 Club Name: TFT 10.5 DEG MW (DRIVER) No. Balls/Type: Average Test Conditions: 9 Launch Angles 217.8 Ball Speed (fps): 3390 Spin Rate (rpm):

FIRM

Turf Condition: 2.55 135.20 Wind (mph/dir): 0.61 91.59 Temp./RH 1015 P-Bar (mbar): Ball Te PTime CarDiff CtrDev Rll TDist TDiff HP2TOUR 8.7 6.0 230.4 -4.1 3.0 9.9 240.3 -4.3 9.0 6.1 231.8 -2.7 5.4 9.1 241.0 -3.6 GIGA 8.8 6.0 234.5 0.0 5.7 10.2 244.6 0.0 Example 7-2 8.3 5.9 229.6 -4.9 3.8 11.1 240.7 -3.9 Titleist Tour8 236.9 -7.7 Balata 100 9.2 6.2 229.2 -5.3 7.8 7. 236.9 74 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Distance Report Test Number 0203963 Club Head Speed: 126.18 Club Name: TFT 5 IRON No Balls/Type: 12 Average Test Conditions: Launch Angles 14 Ball Speed (fps): 180.1 Spin Rate (rpm): 5424 Turf Condition:

FIRM

Wind (mph/dir): 6.23 171.38 TempJRH(deg/%/): 62.20 98.16 P-Bar (mbar): 1015 Ball Type Traj PTime Carry Car Diff Ctr Dev Roll T Dist T Diff HP2TOUR 25.3 6.0 156.0 -7.4 -3.0 1.5 157.5 25.2 6.0 157.1 -6.3 -3.3 2.2 159.3 -7.7 GIGA 25.0 6.0 162.2 -1.2 -3.1 2.9 165.1 -1.9 Example 7-2 23.5 6.0 163.4 0.0 -3.3 3.7 167.0 0.0 Titleist Tour Balata 100 23.9 6.0 158.7 -4.7 -2.3 2.5 161.2 -5.8 ZB 100 26.1 6.0 155.6 -7.8 -4.5 2.0 157.6 -9.4 XS 100 23.9 6.0 161.3 -2.3 -5.6 2.6 163.9 -3.1 XF 100 24.5 6.0 152.0 -11.4 -6.2 1.6 153.7 -13.3 Example 9 A number of golf ball cores having the following formulation were made:

PARTS

High-cis polybutadiene 100 Zinc oxide Core regrind 16 Zinc stearate 16 Zinc diacrylate 21 Peroxide (231 xl) 0.9 The cores had a diameter of 1.470", a weight of 32.5 g, a PGA compression of 57 and a COR of 0.768.

SUBSTITUTE SHEET (RULE 26) WO 00157963 PCT/US99/06748 The cores were divided into four sets a'nd each set was covered with one of the mantle formulations shown below on Table 22.

TABLE 22 MANTLE FORMULATIONS Mantle Type A B C D (control) Surlyn 8940 656 880 1610 Surlyn 9910 1964 2180 535 Surlyn 8120 300 160 475 Surlyn 8320 700 400 1000 lotek 7030 380 380 380 lotek 1002 2000 lotek 1003 2000 The mantle covered cores had the following physical properties: TABLE 23 MANTLE-COVERED CORES A B C D Size (Pole) (Inches) 1.577 1.576 1.572 1.573 Weight 38.6 38.5 38.3 38.4 PGA Compression 71 74 70 76 COR .7795 .7831 .7768 .7946 Std. Dev. COR .0051 .0026 .0016 .0012 Shore C 92 94 90 97 Shore D 62 65 61 76 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Each set of mantle-covered cores was divided into three subsets and a cover layer having one of the cover formulations shown below on Table 24 was formed over the mantled cores. The "whitener package" on Table 24 has the same formulation as that shown above on Table 19.

TABLE 24 COVER FORMULATIONS X Y Cover Type lotek 7520 (g) lotek 7510 (g) lotek 8000 (g) lotek 7030 (g) Whitener package (g) 1660 1660 304 282 94 1480 1480 664 282 94 1300 1300 1024 282 94 The balls had the mantle and cover combinations and properties shown below on Table 77 SUBSTITUTE SHEET (RULE 26) TABLE BALL PROPERTIES

ON,

Example No. 9-1 9-2 9-3 9-4 9-5 9-6 9-7 9-8 9-9 9-10 9-11 9-12 Mantle A A A B B B C C C D D D Cover X Y Z X Y Z X Y Z X Y Z Size (inch) 1.6820 1.6810 1.6820 1.6820 1.6820 1.6820 1.6820 1.6820 1.6810 1.6820 1.6820 1.6810 Weight 45.68 45.57 45.58 45.77 45.62 45.58 45.63 145.58 45.48 45.67 45.65 45.57 PGA Comip. 73.5 74.3 74.7 .77.4 76.7 .76.3 70.8 71.9 73.3 79.5 80 82.5 COR .7639 .7665 .7680 1.7701 .7703 .7704 .7607 7630 .7661 .7771 .7798 .7839 Std. Dev. COR .0041 .0027 .0037 .0077 .0034 .0023 .0037 .0030 .0028 .0034 .0028 .0020 Shore C 71 76 81 71 76 81 70 76 80 71 76 8 1 Shore D 46 50 53 46 50 53 46 49 52 47 51 53 WO 00/57963 PCT/US99/06748 Ball 9-10 was the control.

The results from Table 25 demonstrate that a multi-layer ball having a mantle hardness of 60D or greater (Ex. 9-7, 9-8, and preferably 63D (Ex. 9-1, 9-2, 9-3) or greater give a ball having a COR of at least 0.761 (Ex. 9-7) and while a harder mantle (Ex. 9-4, 9-5, 9-6, 9-10, 9-11, 9-12) will generaly give higher COR, the mantle also contributes to a harder PGA compression. Versus the control ball (Ex. 9-10) it is demonstrated that softer compressions can be obtained with slightly softer mantles while maintaining a good COR. Likewise versus the control, higher COR balls may be designed (Ex. 9-11, 9-12) that still have a relatively soft compression for good feel.

Example A number of golf balls were made having the core and cover formulations and the physical properties shown on Tables 26 and 27. The balls of Examples 10-1, 10-2 and 10-5 are part of the invention. The balls of Examples 10-3, 10-4 and 10-6 are controls based upon the cover layer chemistry of comparative Example 2 of U.S. Patent No. 5,586,950. The balls of Example 10-4 are replicas of comparative Example 2 of U.S. Patent No. 5,586,950.

For all of the balls, the cores were molded and centerless ground to the appropriate size. The mantles of Examples 10-1 to 10-4 were injection molded in a 1.63" injection mold. The mantles for the balls of Examples 10-5 and 10-6 also were injection molded. All of the outer cover layers were injection molded.

79 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE 26 Core Data Core Type (see Table 2) Core Size (in.) Mantle Data Ingredients lotek 1002 lotek 1003 Surlyn 9910 Surlyn 8940 Surlyn 8920 TiO, Diameter (in.) Thickness (in.) Shore C/D Hardness (measured on ball) Cover Data Cover Type (see Table 2) Size (in.) Thickness (in.) Shore C/D Hardness (measured on ball) Compression (Riehle)

COR

EX.

10-1

A

1.50 phr 50 50

EX.

10-2

A

1.50

EX.

10-3

A

1.50

EX.

10-4

A

1.50

EX.

10-5

B

1.47

EX.

10-6

B

1.47 phr phr phr 50 50 phr phr 50 50 50 35 15 2 2 1.625 1.625 0.063 0.063 97/70 96/68 1 0 9 2 2 .625 1.625 .063 0.063 7/70 96/68 #1 1.70 0.038 75/49 63 800 #1 1.70 0.038 75/49 66 795 #2 1.70 0.038 84/57 60 805 #2 1.70 0.038 83/57 1.57 0.050 97/70 #1 1.68 0.055 72/48 1.57 0.050 97/70 #2 1.68 0.055 83/56 63 83 798 779 787 SUBSTITUTE SHEET (RULE 26) WO 00/57963 WO 0057963PCT/US99/06748 TABLE 27 Core Formulations Cover Formulations Materials (phr) BR 1220 (High cis polybutadiene) Taktene 220 (High cis polybutadiene) Zinc Oxide TG Regrind Zinc Stearate Zinc Diacrylate Masterbatch A Masterbatch B Luperco 231 XL peroxide 27 30 22.3 10 20 26 A* i 1 31.5 16 16 20 Materials (phr) lotek 8000 lotek 7 510 lotek 7520 Masterbatch C Surlyn 1557 Surlyn 1855 Surlyn 8265 Surlyn 8269 Ti0 2 #1 #2 8.5 41 41 9.5 2 0.15 0.9 0.9 81 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 Example 11 A number of golf balls were made with mantles comprising a blend of polycarbonate and metallocene catalyzed polyolefin.

Cores having the formulation shown below on Table 30 were obtained and covered with a mantle layer formed from 83 parts by weight of Lexan ML 5776-7539 (GE) and 17 parts by weight of a maleic anhydride modified metallocene catalyzed polyolefin obtained from Exxon Chemical Co. and designated by Exxon as MDX-96-2.

According to Exxon, MDX-96-2 contains 1.7 wt% maleic anhydride. This material was added as an impact modifier. The mantles were then covered with the same cover formulation as was used in Examples 7-3 and 7-4. The results are shown below on Table 28.

Example 12 A number of golf balls were made using a nylon-ionomer graft copolymer as the mantle layer. The formulations and physical properties of the balls are shown below on Table Example 13 The procedure of Example 11 was repeated with the exception that Lexan SP131OR-112 was used. This Lexan material was found to have a plaque Shore D hardness of 85 when tested in the lab. The plaque was stored at room temperature for several weeks before the Shore D hardness measurement was made.

Example 14 The procedure of Example 11 was repeated with the exception of Capron 8351, a nylon-ionomer graft copolymer available from Allied-Signal, was used in the mantle layer in place of the polycarbonate and a different maeic anhydride modified metallocene catalyzed polyolefin was used, MDX 95-2. The formulations and physical properties of the balls are shown below on Table The properties of Capron 8351 are shown below on Table 28.

82 SUBSTITUTE SHEET (RULE 26) WOj 00/57963 PCT/US99/06748 TABLE 28 CAPRON 8351 Flexurals at 23 C Modulus, kpsi 235 Strength, kpsi 9.7 Notched Izod at 23 C, ft-lb/in 22.9 Failure Mode

NB

at -40 C, ft-lb/in 4.9 Failure Mode

CB

Drop Weight at 23 C Impact Strength, ft-lbs 148 Failure Mode

D

Impact Strength, -40 C Failure Mode Tensiles at 23 C Strength at Break, kpsi 9.4 -Strength at Yield, kpsi 7.3 Yield Elongation 3% Ultimate Elongation 277% Example The procedure of Example 14 was repeated with the exception that Capron Ultratough, also known as Capron XA-2571, was used in place of Capron 8351. The properties of Capron XA-2571 are shown below on Table 29.

83 SUBSTITUTE SHEET (RULE 26) WO 00/57963 PCT/US99/06748 TABLE 29 CAPRON XA-2571 Flexurals at 23 C Modulus, kpsi Strength, kpsi 240 9.7 Notched Izod at 23 C, ft-lb/in Failure Mode NB at -40 C, ft-lb/in 20.0 Failure Mode CB Drop Weight at 23 C Impact Strength, ft-lbs 114 Failure Mode D Impact Strength, -40 C 160 Failure Mode D Tensiles at 23 C Strength at Break, kpsi 8.4 Strength at Yield, kpsi 6.9 Yield Elongation 7% Ultimate Elongation 200% SUBSTITUTE SHEET (RULE 26) WO 00/57963 WO 0057963PCT/US99/06748 TABLE Chemical Component EXAMPLE,11 EXAMPLE 12 EXAMPLE 13 EXAMPLE 14 Core Data Size 1.4r' 1.4r, 1.47" 1.47" Weight 32.7g 32.7g 32.7g 32.7g PGA Compression 78 78 78 78 COR (x 1000) 764 7641 764 764 Composition (pph) High cis polytnztadiene 100 100 100 100 Zinc o~de 6 6 6 8 Core regrind 10 10 10 Zinc Stearate 20 20 20 Zinc Diacrylate 20.5 20.5 20.5 20.5 initiator 0.9 0.9 0.9 0.9 Inner Cover Layer Size 1.64" 1.64" 1.64"164 Weight 39.2g 39.2g 38.7 39.7 PGA Compression 95 97 9697 COR (x 1000) 638 748 605 771 Thickness .100" .10D" .100" Hardness (Shore C) 95 98 95 9 (Shore 0) 80 78 75 Composition (wtA) MDX 96-2 17% 17%A MDX 95-2 17% 17% LN SP131 OR -112 -83%A IN ML 5776-7539 83% CAPRON 8351 83% CAPRON XA 2571 83% SUBSTITUTE SHEET (RULE 26) PCT/US99/067 48 WO 00/57963 Chemical Component EXAMPLE'li EXA1 outer Cover Layer Hardness (Shore CDO) 71148 Thickness 0.055" Composition (wtA) lotek 7510 42% lotek 7520 42% lotek 70 3 0 73 Ultra Marine Blue0.4 h Santanox R 0.004 phr Final B ali D a ta1 3 Size1.3 Weight 46.7g' pGA compression 93 COR X1000 748 86 SUBSTITUTE SHEET (RULE 26) PCT/US99/06 748 WO 00/57963 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.

87 SUBSTITUTE SHEET (RULE 26)

Claims

1. A golf ball including: a core; an inner cover layer formed over the core, the inner cover layer having a Shore D hardness of at least 60 as measured on the curved surface thereof, and an outer cover layer formed over the inner cover layer, the outer cover layer having a Shore D hardness of no more than 53 as measured on the curved surface thereof, at least one of the inner and outer cover layers including at least one member selected from the group consisting of polycarbonates, reaction- injection-molded polyurethanes, and styrene-butadiene elastomers, i: the golf ball having a PGA compression of 100 or less and a coefficient 15 of restitution of at least 0.750. a l

2. A golf ball according to claim 1, wherein the outer cover layer has a Shore D hardness of no more than S 20 3. A golf ball according to any one of the preceding claims, wherein the ball has a PGA compression of 90 or less.

4. A golf ball according any one of the preceding claims, wherein the outer cover layer includes a thermoplastic material. A golf ball according to any one of claims 1 to 3, wherein the inner cover layer includes a reaction-injection-molded polyurethane.

6. A golf ball according to any one of claims 1 to 3 or 5, wherein the outer cover layer includes a reaction-injection-molded polyurethane.

7. A golf ball according to any one of claims 1 to 4 or 6, wherein the inner cover layer includes a polycarbonate. W:\MaryO\Davin\Spec32122-99.doc 89

8. A golf ball according to any one of the preceding claims, wherein the inner cover layer has a Shore D hardness of at least

9. A golf ball according to any one of claims 1 to 7, wherein the inner cover layer has a Shore D hardness of 60-85. A golf ball according to any one of claims 1 to 3, 5, 7, 8 or 9, wherein the outer cover layer includes a polycarbonate.

11. A golf ball according to any one of claims 1 to 3, 5, 7, 8 or 9, wherein the outer cover layer includes polyurethane. 0*

12. A golf ball according to claim 11, wherein the polyurethane includes a reaction-injection-molded polyurethane. a.

13. A golf ball according to any one of the preceding claims, wherein the outer cover layer has a Shore D hardness of 30-50. a

14. A golf ball according to any one of claims 1 to 12 when neither directly or 20 indirectly dependent on claim 2, wherein the outer cover layer has a Shore D hardness of 30-53.

15. A golf ball according to claim 1, wherein the inner cover layer includes at least one member selected from the group consisting of polycarbonates, reaction-injection-molded polyurethanes, and styrene-butadiene elastomers.

16. A golf ball according to any one of the preceding claims, wherein the outer cover layer includes ionomer.

17. A golf ball according to any one of claims 9 to 16, wherein the inner cover layer has a Shore D hardness of at least

18. A golf ball according to any one of the preceding claims, wherein the inner cover layer has a thickness of about 0.01 0.15 inches. W:\MaryO\Davln\Speci\32122-99.doc

19. A golf ball according to any one of the preceding claims, wherein the outer cover layer has a thickness of about 0.01 0.15 inches.

20. A golf ball according to any one of the preceding claims, wherein the outer cover layer has a thickness of 0.03 inches to 0.07 inches.

21. A golf ball according to any one of the preceding claims, wherein the inner cover layer has a thickness of 0.03 inches to 0.07 inches.

22. A golf ball according to any one of the preceding claims, wherein the outer cover layer has a Shore D hardness of 45-53 as measured on the curved surface thereof. 15 23. A golf ball according to any one of the preceding claims, wherein the 0 :to •inner cover layer has a Shore D hardness of 60-85 as measured on the curved S surface thereof. e*

24. A golf ball according to any one of the preceding claims, wherein the 20 core is solid or liquid filled. o* o

25. A golf ball according to any one of the preceding claims, wherein the core is wound.

26. A golf ball including: a core, an inner cover layer formed from a composition which includes at least weight of at least one material selected from the group consisting of polycarbonates, reaction-injection-molded polyurethanes, and styrene- butadiene elastomers, and an outer cover layer formed over the inner cover layer, the outer cover layer having a Shore D hardness of no more than 53 as measured on the curved surface thereof, the golf ball having a PGA compression of 100 or less and a coefficient of restitution of at least 0.750. W:\MaryO\DavinSpec32122-99.doc 91

27. A golf ball according to claim 26, wherein the material is thermoplastic.

28. A golf ball according to claim 27, wherein the material is a thermoset.

29. A golf ball according to any one of the preceding claims, wherein the inner cover layer includes a styrene-butadiene elastomer. A golf ball according to any one of the embodiments substantially as herein described with reference to the accompanying drawings. DATED: 27 June 2002 PHILLIPS ORMONDE FITZPATRICK 15 Attorneys for: SPALDING SPORTS WORLDWIDE, INC. **00 *0 0 0 0 00 0 00 *i W:WlaryO\DavinSpedh32122-99.doc