CA2042508C - Golf ball cover composition - Google Patents
Golf ball cover compositionInfo
- Publication number
- CA2042508C CA2042508C CA002042508A CA2042508A CA2042508C CA 2042508 C CA2042508 C CA 2042508C CA 002042508 A CA002042508 A CA 002042508A CA 2042508 A CA2042508 A CA 2042508A CA 2042508 C CA2042508 C CA 2042508C
- Authority
- CA
- Canada
- Prior art keywords
- acrylic acid
- golf ball
- hard
- weight
- ionomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0024—Materials other than ionomers or polyurethane
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0029—Physical properties
- A63B37/0031—Hardness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0029—Physical properties
- A63B37/0037—Flexural modulus; Bending stiffness
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
- A63B37/0074—Two piece balls, i.e. cover and core
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0876—Neutralised polymers, i.e. ionomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/908—Composition having specified shape, e.g. rod, stick, or ball, and other than sheet, film, or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/919—Ionomer resins, carboxylate salt-containing copolymers
Abstract
The present invention is directed to improved cover compositions for golf ball construction and the resulting golf balls produced utilizing the improved cover compositions. The novel golf ball cover compositions of the invention comprise a blend of hard ionomeric resins, preferably acrylic acid based ionomers, and recently developed acrylic acid based soft ionomers.
When the cover compositions of the invention are utilized to manufacture golf balls, the golf balls produced thereby, exhibit properties of improved distance without sacrificing playability and/or durability when compared to known hard-soft ionomer blends.
When the cover compositions of the invention are utilized to manufacture golf balls, the golf balls produced thereby, exhibit properties of improved distance without sacrificing playability and/or durability when compared to known hard-soft ionomer blends.
Description
2~2~
lMPRO~ED GOLF BAL~ COVE~ CONPOSITlONS
Backqround of the Invention The present invention concerns improved hard-soft ionomeric resin mixtures (or blends) which are particularly well suited for the formulation of the cover composition of a golf ball.
More specifically, the present invention relates to novel golf ball cover compositions comprising blends o~ hard ionomer resins with recently developed soft ionomer resins made from acrylic acid based polymers. The new c , sitions o~ t~e present invention, when utilized ~or golf ball co~struction, particularly the construction of two piece gol~ balls, produce gol~ balls exhibiting enhanced travel distance without sacrificing the properti~s of playability and/or durability.
Ionomeric resins are polymers containing interchain ionic bonding. As a result of their toughness, durability, and ~light characteristics, various ionomeric resins sold by E.I. DuPont deNemours ~ Company under the trademark "Surlyn~" and more recently, by the Exxon Corporation (see U.S. Patent No. 4,911,451) under the trademarks "Escor~ and the tradename ~Iotekn, have become the materials ~f choice ~or the con~tru~tion of golf ball covers over the traditional "balata" (trans polyisoprene, natural or synthetic) rubbers. The softer balata covers, although exhi~itinq enhanced playability properties, lack the durability nP~Pcs~ry for repetitive play.
Ionomeric resins are generally ionic copolymers of an olefin such as ethylene and a metal salt of an unsaturated carboxylic acid, such as acrylic acid, m~thacrylic acid, or maleic acid.
Metal ions, such as sodium or zinc, are used to neutralize some portion of the acidic groups in the copolymer resulting in a thermoplastic elastomer exhibiting Pnh~nced properties, i.e.
improved durability, etc., for golf ball cover construction over balata. However, the ad~antages 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 d~ra~le, 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.
As a result, while there are currently more than ~ifty commercial grades of ionomers available from DuPont and Exxon with a wide range of properties which vary according to the type and amount of metal cations, molecular weight, composition of the base resin (i.e. relative content of ethylene and methacrylic and/or acrylic acid groups) and additive ingredients such as reinforcements, etc., a ~reat deal of research continues in order to develop golf ball co~er compositions exhibiting not only the improved impact resistance and carrying distance properties produced by the "hard" ionomeric resins, but also th~ playability (i.e. ~spin~) characteristics previously ~cso~iated with the "soft"
balata covers, properties which are still desired by the more skilled golfer.
In various attempts to produce such an ideal golf ball, the golfing industry has blended the hard ionomeric resins with a number of softer polymeric materials, such as softer polyurethanes.
However, the blends of the hard ionomer resins with the softer polymeric materials have generally been dissatisfactory in that these balls exhibit numerous processing problems. In a~dition, the balls produced by such a combination are usually short on distance.
In addition, various "hard-soft ionomeric blends", i.e.
mixtures of ionomer resins which are significantly different in hardness and/or fl~xural modulus, have been attempted. However, until the development of the specific blend combination set forth in U.S. Patent No. 4,884,814, these balls were not particularly commercially viable~ In this regard, although the balls pro~uc~
using the hard-soft ionomer blends exhibited P~hAnce~ playability characteristics, they lacked the durability needed for continuous play .
U.S. Patent No. 4,884,814, the present inventors previous patent, is directed to the finding that if various ~hard" Surlyn~
methacrylic acid based ionomer resins (i.e. those Surlyn~ resins having a hardness of about 60 to 66 on the Shore D scale as measured in accordance with ASTM method D-2240) were blended with a number of specific "soft" Surlyn~ methacrylic acid based ionomer resins (i.e. those Surlyn~ resins having a hardness from about 25 to 40 as measured on the Shore D scale) that a golf ball cover composition could be produced that is not only softer than the prior art hard ionomer covers but also exhibits a suf~icent degree of durability for repetitive play.
As a result, a golf ball covered in accordance with the ~hard-soft" methylacrylic acid based ionomer blends of the '814 patent, exhibits properties of enhanced playability (i.e. softness and spin) and durability. However, notwiths~ ;n~ the above, some sacrifice in carrying distance is also exhibited in comparison with the balls produced utilizing the hard Surlyn- resins.
The present invention is directed to new golf ball cover compositions which exhibit properties of ~nh~nceA carrying distance (i.e. possess higher coefficient of restitution values) than the hard-so~t ionomer blends set forth in U.S. Patent No. 4,884,814, without sacrificing characteristics such as playability (i.e.
softness and spin) and/or durability. It has been found that these properties can ~e produced using i~pro~ed hard-soft ionomer blends containing recently developed acrylic acid based soft ionomer resins.
2 ~
Su~mary of the Invention The present invention is directed to improved cover compositions for golf ball construction and the resulting golf balls produced utilizing the improved cover compositions. The novel golf ball cover compositions of the invention comprise a blend of hard ionomeric resins, preferably acrylic acid based ionomers, and recently developed acrylic acid based soft ionomers.
When the cover compositions of the invention are utilized to manufacture golf balls, the golf balls pxoduced thereby, exhibit properties of improved distance without sacrificing playability and/or durability when compared to known hard-soft ionomer blends.
Two of the principal properties involved in the performance of ~olf balls are resilience and hardness. Resilience is determined by the coefficient of restitution (C.O.R.), the constant "e", WhiCh is the ratio of the relative velocity of two elastic spheres after direct impact to that be~ore impact. As a result, the coefficient of restitution (i.e. "e") can vary from zero to one, with one ~eing equivalent to an elastic collision and zero being eguivalent to an inelastic collision.
Resilience (C.O.R.), along with additional factors such as clu~head speed, angle of trajectory, and ball configuration ~i.e.
dimple pattern), generally determines the distance a ball will travel when hit. Since cl~lhhe~ speed and the angle of trajectory are not factors easily controllable, particularly by golf ball manu~acturers, the factors of concern among manufacturers are the coefficient o~ restitution ~C.O.R.) and the surface configuration of the ball.
The coefficient of restitution (C.O.R.) in solid core balls is a function of the composition of the molded core and of the cover.
In balls containing a wound core (i.e. 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. Although both the core and the cover contribute to the coefficient of restitution, the present invention is directed solely to the coefficient of restitution which is affected by the cover composition.
In this regard, the coefficient of restitution of a golf ball is generally measured by propelling a ball at a given speed against a hard surface and measuring the ball's incoming and outgoing velocity electronically. As mentioned above, the coefficient of restitution is the ratio of the outgoing velocity to incoming velocity. The coefficient of restitution must be carefully controlled in all commercial golf balls in order for the ball to be within the specifications regulated by the United States Golf Association (U.S.G.A.). Along this line, the U.S.G.A. standards indicate that a "regulation" ball cannot have an initial velocity (i.e. the speed off the club) exceeding 255 feet per second. 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 a sufficiently high coefficient of restitution to closely approach the U.S.G.A. limit on initial velocity, while having an ample degree of softness (i.e. hardness) to produce enhanced playability (i~e. spin, etc.).
The hardness of the ball is the second principal property involved in the performance of a gol~ ball. The hardness of the ball can affect the playability of the ball on striXing and the sound or "click" produced. ~ardness is determined as the deformation (i.e. compression) of the ball under various load conditions applied across the ball's diameter (i.e. the lower the compression value, the harder the material). As indicated in U.S.
Patent No. 4,674,751, "softer" covers permit the accomplished golfer to impart proper spin. This is because the softer covers deform on impact significantly more than balls having "harder"
ionomeric resin covers. As a result, this allows the better player to impart fade, draw, or backspin to the ball thereby ~nh~ncing playability. Such properties can be determined by various "spin 5 ~ ~3 rate tests~, such as the "nine-iron~ spin rate test set forth bel ow .
Accordingly, the present invention is directed to new hard-soft ionomer blends which produce, upon molding around solid or wound cores to formulate a cover composition, golf balls exhibiting enhanced distance (i.e. resilience) without adversely affecti~g, and in many instances, improving the ball's playability (i.e.
hardness/softness) and/or durability (i.e. impact resistance, etc.) characteristics.
These and other objects and features of the invention will be apparent from the following description and from the claims.
Detailed Descri~tion of the Invention The present invention relates to improved cover compositions for golf ball construction. More particularly, the present invention is directed to improved blends of hard and so~t ionomers, which, when utilized to formulate the cover stoc~ cf golf balls, produce gol~ ~alls having ~nh~n~e~ properties, including longer distance with similar or improved playability properties (i.e.
higher Riehle compression, lower Shore hardness values, etc.), when ~- ~red to golf balls produced by the hard-soft ionomer blends o~
the prior art. The improved properties produced by the hard-soft ionomer blends of the present invention are due to the use of recently developed acrylic acid based soft ionomers, which produce cover compositions having lower flexural modulus and hardness (i.e.
enhanced softness) and improved coefficients of restitution when incorporated with the hard ionomer resins indicated below.
The hard (high modulus) ionomers suita~le for use in the present invention include those ionomers having a hardn~ss greater than 50 on the Shore D scale as measured in accordance with ASTM
method D-2240, and a flexural modulus from about 15,000 to about 70,000 psi as measured in accordance with ASTM method D-790.
~2~
The hard ionomer resins utilized to produce the cover compositions are ionic copolymers which are the sodium, zinc, magnesium or lithium salts of the reaction product o~ an olefin having from 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from 3 to ~ carbon atoms. ~he carboxylic acid groups of the copolymer may be totally or partially (i.e. approximately 15-75 percent) neutralized.
Preferably, the hard ionomeric resins are copolymers of ethylene and either acrylic and/or methacrylic acid, with copolymers of ethylene and acrylic acid the most preferred. In addition, two or more types of hard ionomeric resins may be blended into the cover compositions in order to produce the desired properties of the resulting ~olf balls.
Although the scope of the patent embraces all known ~ard ionomeric resins falling within the parameters set forth above, only a relatively limited number of these hard ionomeric resins are c_ ~rcially available. In this regard, the hard ionomeric resins sold by E.I. DuPont de Nemours Company under the trademark "Surlyn~", and the hard ionomer resins sold by Exxon Corporation under either the trademark "Escor~" or the tradename ~Iotek" are examples of commercially available hard ionomeric resins which may be utilized in the present invention in the particular combinations described in detail below.
The hard ionomeric resins introduced under the designation "EscoP " and now sold under the new designation "Iotek", are somewhat similar to the hard ionomeric resins sold under the "Surlyn~" trademark. However, since the "Iotek" 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 Iotek resins (i.e. the acrylic acid based hard ionomer resins) are the more preferred hard resins for use in the present invention. In addition, various blends of "Iotek" and "Surlyn"
2 ~ 8 hard ionomeric resins, as well as o~er available ionomeric resins, may.be utilized in the present invention.
Examples of commer~ially available hard ionomeric resins which may be utilized in the present invention include the hard sodium ionic copolymer sold under the trade~arX "Surlyn 8940" and the hard zinc ionic copolymer sold under the trademark "Surlyn 9910".
Surlyn 8940 is a copolymer of ethylene with methacrylic acid with about 15 weight percent acid which is about 29% neutralized wit~h 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% neutralized wit~ zinc ions. The average melt flow index of Surlyn 9910 is about 0.7. The typical properties of Surlyn 9~10 and 8940 are set forth below in Table 1.
T~EiLB ~
TY~ical ProPertles of CommerciallY Available Hard SurlYn~ Resins Suitable for Use in the Present Invention ASTM D 8040 9010 11~0 8528 9070 97~0 C~tion t~ Sociiu~ 2ir~C Sodi~_ Sodiu~ Zir,e Zir,e M~le ~o~ index 9n#/1o nlin. D-lZi8 2.8 0.7 0.9 1.3 14.0 l.o Sp C3tiC Gr~vity, g~cm D-792 0.95 0.97 O.ff 0.94 O.ff 0 ff ll-rdn-~, Shore 0 D-2240 ~6 64 ~ ~0 ~2 63 Ter.~il- Str ngth, tkpsi)~ Ypll D-o38 ~4.8) ~3.6) ~5.~) ~4~2~ t3.2) t4.1) 33.1 Z4.8 37.2 Z9.0 Z2.0 Z8.0 rlon~ation, X D~o38 ~71D ~90 350 450 ~0 460 Fl~ural ~odulus, ~krei) ~P~ D-790 (Sl) ~A8) ~ss) ~32) C28; ~80 T~i Ic In40ct tZ3'c) IC~JIR2 ~ft.-lbs,J;"2) D-182Z5 1020 1020 86S 1160 760 1240 tUS) tUS) ~10) ~550) (3~0) tS40) Vicat Temp rature, ~C D-1525 63 o2 58 73 61 n . In addition, examples of the more pertinent acrylic acid based hard ionomer resins suitable for use in the present invention sold under the "Iotek" tradename by the Exxon Corporation include "Iotek 4000" (formerly "~scor 4000"), "Iotelc4010n, "Iotek 8000" (formerly Escor 900), "Iotek 8020", and "Iotek 8030n. The typical properties of the Iote~c hard ionomers are set forth below in Table 2.
2~8 TAEiLB 2 Typical Pro~erties of Iotek Ionomers Re~in Asm Properties ethod Unies 4000 UOtO 8000 8020 8030 C~tion type ~ir,c 2inc ~diur sodiu- ~rAiur l~lt index O-lZ38 9/10 min. 2.5 1.5 O.S 1.6 2.8 Density D~1505 Itg/~3 r~63 963 rJS4 9~ 960 Helting Point 0-3417 'C ~,0 90 ~0 87.5 87.5 Crystallization Poin~ 0-3417 ~C o2 o~4 56 53 55 Vicne Softening Point O-t525 ~r. 62 o3 6t 6~ 67 X ~leight Acrylic Aeid t6 tt X of Acid Grou~os caeion neutrali2ed 30 40 Pl K~e AST~
Pror~erries lle~hod un;~s 4000 OtO 8000 8020 8030 ~3 mm ehick, com,oression mold~d) Tensi~e ~ bre~k D-o38 hP~ 24 26 36 31.5 20 Yi-ld point D-~38 IIP- r~ r~ 21 21 23 Elongatir,n at break D-638 X 395 UO 350 ~tO 3~.5 1X Secant modulus 0~63~i liPa 160 160 300 350 3~,0 Shore Hardness D 0~2240 -~ 55 55 61 58 59 f I l~ Propo~ i e~
t50 micron film Z.2:1 3lo~-u~ r~tio) ~000 4010 ~000 oO20 8030 Taraile at Brrak HD D-8B2 ~IPe 41 39 ~2 52 47.4 TD D-8a2 tlPr 37 38 38 3B 40.5 Yleld ,ooint ~tD D-ô82 hPa tS t7 t7 23 21.6 TD D-88Z liP~ 14 lS 15 21 20.7 Elongation at Break ~D D-3B2 X 3tO Z70 20~0 2,~S 305 TD 0-88Z X 360 340 ZôO 340 345 lX Secdne modulus HD D~ô8Z IlPa Z10 215 3~D 3~0 380 TD D-882 ~Pa 2D0 225 380 35û 345 Dart Drop ~n~ac~ D-170,~ g~micron t2.4 t2.5 20.3 - h ~ O ~
The critical soft (low modulus) ionomers utilized to formulate th~ blends of the present invention are acrylic acid based so~t ionomers. These soft ionomers may be generally characterized as comprised of sodi~m ~r zinc salts of a terpolymer of an ole~in having from about 2 to 8 carbon ato~s, acrylic acid, a~d an unsaturated monomer of the acrylate ester class having from 2 to 22 carbon atoms. Preferably, the soft ionomer is a zinc based ionomer made from an acrylic acid base polymer and an unsaturated monomer o~ the acrylate ester class. The soft (low modulus) ionomers have a hardness from about 20 to about 40 as measured on the Shore D
scale and a flexural modulus from about 2,000 to about 10,000 psi as measured in accordance with ASTM method D-790.
More particularly, the present inventors have discovered that if the new acrylic acid based experimental soft ionomers recently developed by the Exxon Corporation ~or the Spalding sports Worldwide, a division of Spalding & Evenflo Companies, Inc., Tampa, Florida, are utilized with the speci~ic hard ionomers described above, in the combinations more clearly de~ined below and demons~rated in the Examples, not only are improvements in processability and clarity seen, but also th~ overall combinatians, when utilized for golf ball construction, produce golf ball9 having higher coefficient of restitution values (i.e. longer distance) at equal or softer hardness than gol~ ~alls produced by known hard-soft ionomer blends, including the hard-soft ionomer blends utilized to produce Spalding's current Tour Edition~ ball.
In this regard, the inventors have found that when the new ethylene-acrylic acid based soft ionomer resins recently developed by the Exxon Corporation under the designation "Iotek 75Zo"
(referred experimentally by differences in neutralization and melt indexes as LDX 195, LDX 196, LDX 218 and LDX 219) are combined with the known hard ionomers indicated above, 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 balls produced 2 ~
by known hard-soft ionomer blends due to lower overall raw ~aterials cost and improved yields.
While the exact chemical composition of the resins to be sold by Exxon under the designation Iotek 7520 is considered by Exxon to be confidential and proprietary in~or~ation, Exxon's Experimental Product Data sheet lists the following physical properties of the ethylene acrylic acid zinc ionomer developed by Exxon:
~AsL~ 3 Phvsical Pro~erties of Iotek 7520 Pro~ertY ASTM Method ~ T~ical Value Melt Index D-1238 g/lO min. 2 Density D-1505 kg/~ 0.962 Cation Zinc Melting Point D-3417 ~C 66 Crystallization Point D-3417 ~C 49 Vicat Softening Point D-1525 ~C 42 Plaque Pro~erties t2 mm thick Co~ression Molded Plaoues~
Tensile at ~reak D-638 MPa 10 Yield Point D-638 MPa None Elongation at ~reak D-638 % 760 1% Secant Modulus D-638 MPa 22 Shore D Hardness D-2240 32 Flexural Modulus D-790 MPa 26 Zwic~ Rebond ISO 4862 % 52 De Mattia Flex Resistance D-430 Cycles >5000 ~ ~ ~ 2 ~ O ~
In addition, test data collected by the inventors indicates that Iotek ~520 resins have Shore D hardnesses of about ~2-36 (per ASTM ~-2240), melt flow indexes of 3 * .5 g/10 min (at l90 C per ASTM D-1288), a flexural moduluses of about 2500-3S00 psi (per ASTM
D-790). Furth~rmore, testing by an independent testing laboratory by pyrolysis mass spe~Lr,- ~Lly indicates that the Iotek 7520 resins are generally zinc salts o~ a terpolymer of ethylene, acrylic acid, and methyl acrylate.
As mentioned above and more clearly indicated below in the Examples, the recently developed ethylene-acrylic acid based soft ionomers (i.e. the Iotek 7520 resins) produce, when combined with various hard ionomers, particularly the Escor~ hard ionomers, golf balls exhibiting ~nh~nced properties, including longer distance at similar or softer hardness, over known hard-soft i~ r blends including those set forth in the U.s. Patent No. 4,884,814 concerning related subject matter. Alon~ this line, while the '814 patent is directed to various hard-so~t Surlyn~ ior -r blends which are similar to those blends utilized to formulate Spaldin~'s current Tour Edition~ golf ball, the soft Surlyn ior- ?rs (i.e.
Surlyn 8265 and 8269) disclosed therein are of the poly(ethylene-methacrylic acid-butyl acrylate) type. The inventors have now discovered that the use of soft ionomers containing acrylic acid (i.e. Iotek 7520), as opposed to methacrylic acid (i.e. Surlyn a26s and 8269), produce a more desirable golf ball in terms of distance and hardness (softness) while maintaining durability when used in co~bination with various known hard resins.
The superior golf balls of the present invention cont~inin~
the improved hard-soft ionomer blends can be generally produced from a central core and an outer cover wherein the outer cover is made from a co~position comprised of a blend of about 90 to about 10 percent of a hard ionomer of the type indicated above, and about 10 to about 90 percent of an acrylic acid based soft ionn~r.
More preferably, it has been found that a golf ball exhibiting properties of enhanced travel distance (i.e. higher C.O.R. values) with similar or improved playability (i.e. softness characteristics) without a sacrifice in durability, can be produced from a core and a cover, wherein the cover is made from a composition comprised of about 70 to 30 percent of a hard ionomer resin, and about 30 to about 70 percent of an acrylic acid based soft ionomer, depending on the degree of softness desired.
Superior results may be achieved when the hard ionomers utilized are sodium or zinc salts of poly(ethylene acrylic acid) such as those sold by Exxon under the Iotek designation, particularly Iotek 4000 and Iotek 8000, and the soft ionomers utilized are the new acrylic acid based soft ionomers recently developed by Exxon under the designation Iotek 7520. The optimal ranges of hard to soft ionomers are from about 60 to about 40 percent hard ionomer and from about 40 to about 60 percent soft ionomer.
Additional materials may also be added to the compositions of the present invention, including dyes (for example, Ultramarine Blue sold by Whitaker, Clark, and Daniels of South Plainsfield, NJ) (see U.S. Patent No. 4,679,795), pigments such as titanium dioxide, zinc oxide, barium sulfate and zinc sul~ate; W absorbers;
antioxidants; antistatic agents; and stabilizers. ~oreover, the cover compositions of the present invention may also contain so~tening agents, such as plasticizers, processing aids, 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 cover compositions of the present invention may be produced according to conventional melt blending procedures.
Generally, the hard ionomer resins are blended with the soft ionomeric resins in a Banbury type mixer, two-roll mill, or extruder prior to molding. The blended composition is then formed into slabs and maintained in such a state until molding is desired.
If nec~ss~ry, further additives such as inorganic fillers, 5~ ~ 4 ~
antioxidants, stabilizers, and/or zinc oxide may be added and uniformly mixed before initiation of the molding process.
The gol~ balls of the present inventi~n can be produced by molding processes currently well known in the gol~ ball art.
Specifically, the golf balls can be produced by injection molding or compression molding the novel cover composi~ions about wound or solid molded cores to produce a golf ball having a diameter o~
about 1.680 inches and weighing about 1.620 ounces. The standards for both the diameter and weight of the balls are established by the United states Golf Association (U.S.G.A.). Although both solid core and wound cores can be utilized in the present invention, as a result their lower cost and superior performance, solid molded cores are preferred over wound cores.
Conventional solid cores are typically compression molded from a slug of uncured or lightly cured elastomer composition comprising a high cis content polybutadiene and a metal salt of an 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 a small amount of a metal oxide such as zinc oxide. In addition, large~
amounts of metal oxide than are needed to achieve the desired coefficient may be included in order to increase the core weiqht 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 iono~ers, 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 p~es-~u~e, a complex curing or cross-linking reaction takes place.
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 cover and above the core as in U.S. Patent No .
4,431,193, and other multilayer and/or non-wound cores.
2~F2~i~)8 Wound cores are generally produced by winding a very large elastic thread around a solid or liquid filled balloon center. The elastic thread is wound around t~e center to produce a finished core of about 1.4 to 1.6 inches in diameter, generally. Since the core material is not an integral part of the present invention, a detailed discussion concerning the specific types of core ~aterials which may be utilized with the cover compositions of the invention are not specifically set forth herein. In this regard, the cover compositions o~ the invention may be used in conjunction with any standard golf ball core.
As indicated, the golf balls of the present invention may be produced by forming covers consisting of the compositions o~ the invention around cores by conventional molding proc~cses~ For example, in compression molding, the cover composition is formed via injection at about 380-F to about 450-F into smooth sur~aced hemispherical shells which are then positioned around the core in a dimpled golf ball mold and subjected to compression molding at 200-300-F for 2-10 minutes, followed by cooling at 50-70-F for 2-10 minutes, to fuse the shells together to form an unitary ball. In addition, the ~olf balls may be produced by injection molding, wherein the cover composition is injected directly around the core placed in the center of a golf ball mold for a period of time at a mold temperature o~ from 50'F to about lOO-F. After molding the golf balls produced may undergo various further processing steps such as buffing, painting, and marking.
The resulting golf balls produced from the novel hard-soft ionomeric resin combinations of the present invention exhibit enhanced distance and playability properties over the art without sacrificing durability. This is due to the use of acrylic acid based ionomers as the soft ionomer in the overall cover stock composition.
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 cleparting from the spirit and scope thereof.
EXAMPT .FS
~ y ~lending the ingredients set forth in the Tables below, a series of cover formulations were produced. In the examples, cover formulations conta;ning the acrylic acid based soft ionomers-hard ionomer blends of the present invention were compared with the hard-soft ionomer blends o~ the prior art including the hard-soft ionomer blend utilized to produce the current Tour Edition~ ball (ses Examples 3 and 11) which is the subject of U.S. Patent No.
4,884,814.
In addition, the properties produced by the cover compositions ~ormulated with the acrylic acid based so~t ionomer-hard ionomer blends of the present invention vere compared to the properties produced by the cover materials representative of the Tour Edition~, Tour Edition~ 100 and the Top Flite~ II balls currently bein~ sold by Spalding & Evenflo Companies, Inc., Tampa, Florida, as well as a wide variety of competitive golf balls available in the market place. Although the specific formulations utilized to produce the Tour Edition~ 100 and Top Flite~ balls are proprietary, these ~ormulations were utilized under the same processing conditions as those set forth below in order to produce covered golf balls for comparison purposes.
Along this line, the current Tour Edition~ ball is unique in that it is a two piece solid core, molded cover ball that meets the needs of golfers who demand superior control, historically obt~ine~
only with balata covered wound balls. It offers superior playability at the sacrifice of coefficient of restitution, which relates directly to distance.
The Tour Edition~ 100 ball has a slightly softer cover than the Tour Edition~ ball and utilizes a unique twin-dimple design.
The Tour Edition~ 100 ball more closely meets the d~ -n~ of the pro tour golfer than any other Spalding ball previously produced.
~2~8 The Top Flite~ ball is considered to be a "hard" Surlyn or Iotek ionomeric resin ball. As a result of the ball's hardness, the Top Flite~ ball is a difficult ball for golfers to control.
Generally, the harder the golf ball, the more difficult it is for a golfer to impart spin to the ball, and hence, control the ball during flight. However, as a result of its outstanding durability and -~; ~ distance, the ball is widely accepted by a large percentage o* golfers.
The present invention is directed to various blends of hard ionomers and acrylic acid based soft ionomers, which, when utilized for golf ball cover construction, produce golf balls closely approaching the superior distance properties exhibited by the c~rrent ~op Flite~ ball wit~out sacrificing the playability characteristics of the current Tour Edition~ ball.
The cover ~o~mulations set forth b~low Ln Tables 4 and 5 were injection molded at 400-F around identical soli~ type cores having a finished diameter o~ 1.545 inches to produce gol~ balls approximately 1.680 inches in diameter having nominal cover thickness of 0.0675 inches. The properties of Riehle compression, coefficient of restitution (C.O.R.), Shore ~ardness, impact resistance, and spin rate for the cover formulation were determined. In ~able5 4 and 5, Examples 3 and 11 are identical, and Examples 19 and 22 are similar in composition (i~e. different neutralization and melt index grades of Iotek 7520 where utilized).
~hese Examples have been set forth for comparison purposes. The data for each example represents the average data for one dozen balls produced according to the desired ~anner. The properties were measured according to the following parameters:
Riehle compression is a measurement of the deformation of a golf ball in inches under a fixed static load of 225 pounds.
Coe~ficient of restitution (C.O.R. ) was measu~e~ by firing the ~esulting golf ~all is an air cannon at a velocity o~ 125 feet per second against a steel plate which is positioned 12 ~eat 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 measured in accordance with ASTM Test 2240.
Cut resistance was measured in accordance with the rollowing procedure: A golf ball is fired at 13S feet per seco~ 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 1-5. 5 represents a cut that extends completely through the cover to the core; a 4 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 2 leaves only a slight crease which is pPrr~nPnt but not as severe as 3; and a 1 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 wed~e or 9-iron wherein the club-head speed is about 80 feet per se~on~ and the ball is launched at an angle of 26 to 34 degrees with an initial velocity of about 110-115 feet per seco~. 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 golf ball when struck at a hammer speed of 143.8 feet per second in accordance wit~ a test as prescribed by the U.S.G.A.
2~2~8 TABL~ ~
Formulations ING~EDIENTS ~ j } 4 5 6 7 8 _ 10 Surlyn 9910 438 -- U6 486 U6 ~~ -- -~ ~~ ~~
Surlyn a94~ t370 -- t08 108 tO~ -- -- -- -- --Surl~n 826~ -- -- l~2 -~ ~~ -~ -~
Sur(yn 8265 -- -- ~62 ~62 -- -- -- -- -- --Surlyn ~Ihi~e ~B1 193 -- 193 193 193 -- -- -- -- --~scor 4000 ~lo~ek 4000) -- 9U4 -- -- -- 300 ~00 SOO -- --Escor 900 ~lot~k Booo) -- 904 -- -- -- 300 400 50û 800 1000 Escor ~i~ 8 -- 193 -- -- -- 193 193 193 -- --LDX~ ot~lt 7520) -~ -- -- -- -- -- ~- ~ 9U, 788 LDX-t96 ~lo~ek 7520) -- -- -- 83Z 119~ 1108 9E18 788 --PQOPERTIES
Shore C H~roness ~,3 95 85 82 79 78 81 85 ô~ 87 lleiqh~, gr~ms 45.6 45.7 45.7 45.7 45.8 45.5 45.ô ~5.7 45.7 ~5.7 C.O.R . .821 .826 .U~ô .804 .JI)3 .803 .805 .809 .807 .812 Riehle Con~ression 49 4~5 55 S~ 57 57 56 54 55 52 3arrel CD~d Cr~ck 110 br-~lu - ~y s_~e~
Cu~ R~is~
~ t,5~rse~ 12 12 24 12 1-2 12 1-2 12 1~Z 1~2 sPrN pRop~RTr~s Spin R-~- trp~ 8707 8147 lW37 1020 10451 10349 10057 9U~3 9903 ff68 L~unch ~ngle 32.10 32.96 30.51 3n.19 29.93 30.07 30.38 30.77 30.77 31.16 1 Surlyn White MB (master batch) is comprised of 74.9% Surlyn~
8528, 23.7% Unitane 0-llO, .24% Ultra Blue, l.05~ Unitex O.B. and .03% Santonox R.
2 Escor (Iotek) White MB (Master Batch) is comprised o~ 74.9% Iotek 4000, 23.7% Unitane 0-llO, .24% Ultra Blue, l.05S Unitex O.B., and .03~ Santonox R.
tor~tetlons INGREDlENtS 11 12 13 14 15 16 L 18 ~9 20 21 22 23 Surlyn 9910 U6 486 486 486 486 - -- -- .. .. .. ..
Surlyn 8960 108 10t3 10a 10B 10~t - ~- -- ~- ~- ~-Surlyn 8269 832 -- 83Z -- 416 -- -- ~- ~- ~- ~- ~-Surlrn 8265 362 362 lBI ~- ~- -- .. .. ..
Suriyn U703 -- U2 36Z 1194 597 -- -- -- ~- -- .. .. ..
tG ilhlte I~IB1 193 193 193 193 1N - - -- -- -- - - --Escor 4000 ~lotek 40t0) -- -- -- -- -- - 857 554 454 354 554 ~54 354 E~cor 900 (lotex 8000) -- -- -- -- -- 857 -- 554 454 354 554 454 354 Escor ~hlte HB2 -- -- ~ 193 t93 193 193 193 193 193 193 c- LDX-218 tlot k 7520) ~- ~- ~_ ~ 950 950 700 900 1100 tlotek ?520) -- ~- ~- _ ~- ~- ~- 700 900 1100 PROPERilES
Ucight gruns 45.5 45.5 45.5 45.5 45.4 45.6 45.6 45.6 45.6 45.6 45.6 45.6 45.6 Riehle Con~?ressJon 53 57 SS 59 57 56 57 52 56 56 52 54 57 C.D.R. .807 .B04 .808 .802 .806 .B07 .800 .8tl .807 .B03 .B10 .805 .802 Shor C
Hsrdness 88 8B 87 86 B7 88 B6 90 87 84 B8 B6 85 Cut Resist~nce Z-4 Z-3 2-4 2-4 2-3 2-' 3-4 2-3 2-4 2-4 2-4 2-4 2-4 t Surlyn Unlte H8 (mDster o tch) Is cosprisec of 74.9X Surlyr~ 8528 23.7X Unltsr~e 0-110 .Z6X Ultre 8tue 1.05X Unitex O.B. IJnd 0.03X Ssntonox R.
2 Escor tlotek) Uhlte HB (Hsst r Betch) i~ conprisec of r4.9x lotek 4000 23.7X Unltene 0-110 .24X Ultra Blue 1.05X Unitex O.B. end .03X Sl~ntor~ox R. ;p~
lMPRO~ED GOLF BAL~ COVE~ CONPOSITlONS
Backqround of the Invention The present invention concerns improved hard-soft ionomeric resin mixtures (or blends) which are particularly well suited for the formulation of the cover composition of a golf ball.
More specifically, the present invention relates to novel golf ball cover compositions comprising blends o~ hard ionomer resins with recently developed soft ionomer resins made from acrylic acid based polymers. The new c , sitions o~ t~e present invention, when utilized ~or golf ball co~struction, particularly the construction of two piece gol~ balls, produce gol~ balls exhibiting enhanced travel distance without sacrificing the properti~s of playability and/or durability.
Ionomeric resins are polymers containing interchain ionic bonding. As a result of their toughness, durability, and ~light characteristics, various ionomeric resins sold by E.I. DuPont deNemours ~ Company under the trademark "Surlyn~" and more recently, by the Exxon Corporation (see U.S. Patent No. 4,911,451) under the trademarks "Escor~ and the tradename ~Iotekn, have become the materials ~f choice ~or the con~tru~tion of golf ball covers over the traditional "balata" (trans polyisoprene, natural or synthetic) rubbers. The softer balata covers, although exhi~itinq enhanced playability properties, lack the durability nP~Pcs~ry for repetitive play.
Ionomeric resins are generally ionic copolymers of an olefin such as ethylene and a metal salt of an unsaturated carboxylic acid, such as acrylic acid, m~thacrylic acid, or maleic acid.
Metal ions, such as sodium or zinc, are used to neutralize some portion of the acidic groups in the copolymer resulting in a thermoplastic elastomer exhibiting Pnh~nced properties, i.e.
improved durability, etc., for golf ball cover construction over balata. However, the ad~antages 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 d~ra~le, 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.
As a result, while there are currently more than ~ifty commercial grades of ionomers available from DuPont and Exxon with a wide range of properties which vary according to the type and amount of metal cations, molecular weight, composition of the base resin (i.e. relative content of ethylene and methacrylic and/or acrylic acid groups) and additive ingredients such as reinforcements, etc., a ~reat deal of research continues in order to develop golf ball co~er compositions exhibiting not only the improved impact resistance and carrying distance properties produced by the "hard" ionomeric resins, but also th~ playability (i.e. ~spin~) characteristics previously ~cso~iated with the "soft"
balata covers, properties which are still desired by the more skilled golfer.
In various attempts to produce such an ideal golf ball, the golfing industry has blended the hard ionomeric resins with a number of softer polymeric materials, such as softer polyurethanes.
However, the blends of the hard ionomer resins with the softer polymeric materials have generally been dissatisfactory in that these balls exhibit numerous processing problems. In a~dition, the balls produced by such a combination are usually short on distance.
In addition, various "hard-soft ionomeric blends", i.e.
mixtures of ionomer resins which are significantly different in hardness and/or fl~xural modulus, have been attempted. However, until the development of the specific blend combination set forth in U.S. Patent No. 4,884,814, these balls were not particularly commercially viable~ In this regard, although the balls pro~uc~
using the hard-soft ionomer blends exhibited P~hAnce~ playability characteristics, they lacked the durability needed for continuous play .
U.S. Patent No. 4,884,814, the present inventors previous patent, is directed to the finding that if various ~hard" Surlyn~
methacrylic acid based ionomer resins (i.e. those Surlyn~ resins having a hardness of about 60 to 66 on the Shore D scale as measured in accordance with ASTM method D-2240) were blended with a number of specific "soft" Surlyn~ methacrylic acid based ionomer resins (i.e. those Surlyn~ resins having a hardness from about 25 to 40 as measured on the Shore D scale) that a golf ball cover composition could be produced that is not only softer than the prior art hard ionomer covers but also exhibits a suf~icent degree of durability for repetitive play.
As a result, a golf ball covered in accordance with the ~hard-soft" methylacrylic acid based ionomer blends of the '814 patent, exhibits properties of enhanced playability (i.e. softness and spin) and durability. However, notwiths~ ;n~ the above, some sacrifice in carrying distance is also exhibited in comparison with the balls produced utilizing the hard Surlyn- resins.
The present invention is directed to new golf ball cover compositions which exhibit properties of ~nh~nceA carrying distance (i.e. possess higher coefficient of restitution values) than the hard-so~t ionomer blends set forth in U.S. Patent No. 4,884,814, without sacrificing characteristics such as playability (i.e.
softness and spin) and/or durability. It has been found that these properties can ~e produced using i~pro~ed hard-soft ionomer blends containing recently developed acrylic acid based soft ionomer resins.
2 ~
Su~mary of the Invention The present invention is directed to improved cover compositions for golf ball construction and the resulting golf balls produced utilizing the improved cover compositions. The novel golf ball cover compositions of the invention comprise a blend of hard ionomeric resins, preferably acrylic acid based ionomers, and recently developed acrylic acid based soft ionomers.
When the cover compositions of the invention are utilized to manufacture golf balls, the golf balls pxoduced thereby, exhibit properties of improved distance without sacrificing playability and/or durability when compared to known hard-soft ionomer blends.
Two of the principal properties involved in the performance of ~olf balls are resilience and hardness. Resilience is determined by the coefficient of restitution (C.O.R.), the constant "e", WhiCh is the ratio of the relative velocity of two elastic spheres after direct impact to that be~ore impact. As a result, the coefficient of restitution (i.e. "e") can vary from zero to one, with one ~eing equivalent to an elastic collision and zero being eguivalent to an inelastic collision.
Resilience (C.O.R.), along with additional factors such as clu~head speed, angle of trajectory, and ball configuration ~i.e.
dimple pattern), generally determines the distance a ball will travel when hit. Since cl~lhhe~ speed and the angle of trajectory are not factors easily controllable, particularly by golf ball manu~acturers, the factors of concern among manufacturers are the coefficient o~ restitution ~C.O.R.) and the surface configuration of the ball.
The coefficient of restitution (C.O.R.) in solid core balls is a function of the composition of the molded core and of the cover.
In balls containing a wound core (i.e. 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. Although both the core and the cover contribute to the coefficient of restitution, the present invention is directed solely to the coefficient of restitution which is affected by the cover composition.
In this regard, the coefficient of restitution of a golf ball is generally measured by propelling a ball at a given speed against a hard surface and measuring the ball's incoming and outgoing velocity electronically. As mentioned above, the coefficient of restitution is the ratio of the outgoing velocity to incoming velocity. The coefficient of restitution must be carefully controlled in all commercial golf balls in order for the ball to be within the specifications regulated by the United States Golf Association (U.S.G.A.). Along this line, the U.S.G.A. standards indicate that a "regulation" ball cannot have an initial velocity (i.e. the speed off the club) exceeding 255 feet per second. 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 a sufficiently high coefficient of restitution to closely approach the U.S.G.A. limit on initial velocity, while having an ample degree of softness (i.e. hardness) to produce enhanced playability (i~e. spin, etc.).
The hardness of the ball is the second principal property involved in the performance of a gol~ ball. The hardness of the ball can affect the playability of the ball on striXing and the sound or "click" produced. ~ardness is determined as the deformation (i.e. compression) of the ball under various load conditions applied across the ball's diameter (i.e. the lower the compression value, the harder the material). As indicated in U.S.
Patent No. 4,674,751, "softer" covers permit the accomplished golfer to impart proper spin. This is because the softer covers deform on impact significantly more than balls having "harder"
ionomeric resin covers. As a result, this allows the better player to impart fade, draw, or backspin to the ball thereby ~nh~ncing playability. Such properties can be determined by various "spin 5 ~ ~3 rate tests~, such as the "nine-iron~ spin rate test set forth bel ow .
Accordingly, the present invention is directed to new hard-soft ionomer blends which produce, upon molding around solid or wound cores to formulate a cover composition, golf balls exhibiting enhanced distance (i.e. resilience) without adversely affecti~g, and in many instances, improving the ball's playability (i.e.
hardness/softness) and/or durability (i.e. impact resistance, etc.) characteristics.
These and other objects and features of the invention will be apparent from the following description and from the claims.
Detailed Descri~tion of the Invention The present invention relates to improved cover compositions for golf ball construction. More particularly, the present invention is directed to improved blends of hard and so~t ionomers, which, when utilized to formulate the cover stoc~ cf golf balls, produce gol~ ~alls having ~nh~n~e~ properties, including longer distance with similar or improved playability properties (i.e.
higher Riehle compression, lower Shore hardness values, etc.), when ~- ~red to golf balls produced by the hard-soft ionomer blends o~
the prior art. The improved properties produced by the hard-soft ionomer blends of the present invention are due to the use of recently developed acrylic acid based soft ionomers, which produce cover compositions having lower flexural modulus and hardness (i.e.
enhanced softness) and improved coefficients of restitution when incorporated with the hard ionomer resins indicated below.
The hard (high modulus) ionomers suita~le for use in the present invention include those ionomers having a hardn~ss greater than 50 on the Shore D scale as measured in accordance with ASTM
method D-2240, and a flexural modulus from about 15,000 to about 70,000 psi as measured in accordance with ASTM method D-790.
~2~
The hard ionomer resins utilized to produce the cover compositions are ionic copolymers which are the sodium, zinc, magnesium or lithium salts of the reaction product o~ an olefin having from 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from 3 to ~ carbon atoms. ~he carboxylic acid groups of the copolymer may be totally or partially (i.e. approximately 15-75 percent) neutralized.
Preferably, the hard ionomeric resins are copolymers of ethylene and either acrylic and/or methacrylic acid, with copolymers of ethylene and acrylic acid the most preferred. In addition, two or more types of hard ionomeric resins may be blended into the cover compositions in order to produce the desired properties of the resulting ~olf balls.
Although the scope of the patent embraces all known ~ard ionomeric resins falling within the parameters set forth above, only a relatively limited number of these hard ionomeric resins are c_ ~rcially available. In this regard, the hard ionomeric resins sold by E.I. DuPont de Nemours Company under the trademark "Surlyn~", and the hard ionomer resins sold by Exxon Corporation under either the trademark "Escor~" or the tradename ~Iotek" are examples of commercially available hard ionomeric resins which may be utilized in the present invention in the particular combinations described in detail below.
The hard ionomeric resins introduced under the designation "EscoP " and now sold under the new designation "Iotek", are somewhat similar to the hard ionomeric resins sold under the "Surlyn~" trademark. However, since the "Iotek" 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 Iotek resins (i.e. the acrylic acid based hard ionomer resins) are the more preferred hard resins for use in the present invention. In addition, various blends of "Iotek" and "Surlyn"
2 ~ 8 hard ionomeric resins, as well as o~er available ionomeric resins, may.be utilized in the present invention.
Examples of commer~ially available hard ionomeric resins which may be utilized in the present invention include the hard sodium ionic copolymer sold under the trade~arX "Surlyn 8940" and the hard zinc ionic copolymer sold under the trademark "Surlyn 9910".
Surlyn 8940 is a copolymer of ethylene with methacrylic acid with about 15 weight percent acid which is about 29% neutralized wit~h 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% neutralized wit~ zinc ions. The average melt flow index of Surlyn 9910 is about 0.7. The typical properties of Surlyn 9~10 and 8940 are set forth below in Table 1.
T~EiLB ~
TY~ical ProPertles of CommerciallY Available Hard SurlYn~ Resins Suitable for Use in the Present Invention ASTM D 8040 9010 11~0 8528 9070 97~0 C~tion t~ Sociiu~ 2ir~C Sodi~_ Sodiu~ Zir,e Zir,e M~le ~o~ index 9n#/1o nlin. D-lZi8 2.8 0.7 0.9 1.3 14.0 l.o Sp C3tiC Gr~vity, g~cm D-792 0.95 0.97 O.ff 0.94 O.ff 0 ff ll-rdn-~, Shore 0 D-2240 ~6 64 ~ ~0 ~2 63 Ter.~il- Str ngth, tkpsi)~ Ypll D-o38 ~4.8) ~3.6) ~5.~) ~4~2~ t3.2) t4.1) 33.1 Z4.8 37.2 Z9.0 Z2.0 Z8.0 rlon~ation, X D~o38 ~71D ~90 350 450 ~0 460 Fl~ural ~odulus, ~krei) ~P~ D-790 (Sl) ~A8) ~ss) ~32) C28; ~80 T~i Ic In40ct tZ3'c) IC~JIR2 ~ft.-lbs,J;"2) D-182Z5 1020 1020 86S 1160 760 1240 tUS) tUS) ~10) ~550) (3~0) tS40) Vicat Temp rature, ~C D-1525 63 o2 58 73 61 n . In addition, examples of the more pertinent acrylic acid based hard ionomer resins suitable for use in the present invention sold under the "Iotek" tradename by the Exxon Corporation include "Iotek 4000" (formerly "~scor 4000"), "Iotelc4010n, "Iotek 8000" (formerly Escor 900), "Iotek 8020", and "Iotek 8030n. The typical properties of the Iote~c hard ionomers are set forth below in Table 2.
2~8 TAEiLB 2 Typical Pro~erties of Iotek Ionomers Re~in Asm Properties ethod Unies 4000 UOtO 8000 8020 8030 C~tion type ~ir,c 2inc ~diur sodiu- ~rAiur l~lt index O-lZ38 9/10 min. 2.5 1.5 O.S 1.6 2.8 Density D~1505 Itg/~3 r~63 963 rJS4 9~ 960 Helting Point 0-3417 'C ~,0 90 ~0 87.5 87.5 Crystallization Poin~ 0-3417 ~C o2 o~4 56 53 55 Vicne Softening Point O-t525 ~r. 62 o3 6t 6~ 67 X ~leight Acrylic Aeid t6 tt X of Acid Grou~os caeion neutrali2ed 30 40 Pl K~e AST~
Pror~erries lle~hod un;~s 4000 OtO 8000 8020 8030 ~3 mm ehick, com,oression mold~d) Tensi~e ~ bre~k D-o38 hP~ 24 26 36 31.5 20 Yi-ld point D-~38 IIP- r~ r~ 21 21 23 Elongatir,n at break D-638 X 395 UO 350 ~tO 3~.5 1X Secant modulus 0~63~i liPa 160 160 300 350 3~,0 Shore Hardness D 0~2240 -~ 55 55 61 58 59 f I l~ Propo~ i e~
t50 micron film Z.2:1 3lo~-u~ r~tio) ~000 4010 ~000 oO20 8030 Taraile at Brrak HD D-8B2 ~IPe 41 39 ~2 52 47.4 TD D-8a2 tlPr 37 38 38 3B 40.5 Yleld ,ooint ~tD D-ô82 hPa tS t7 t7 23 21.6 TD D-88Z liP~ 14 lS 15 21 20.7 Elongation at Break ~D D-3B2 X 3tO Z70 20~0 2,~S 305 TD 0-88Z X 360 340 ZôO 340 345 lX Secdne modulus HD D~ô8Z IlPa Z10 215 3~D 3~0 380 TD D-882 ~Pa 2D0 225 380 35û 345 Dart Drop ~n~ac~ D-170,~ g~micron t2.4 t2.5 20.3 - h ~ O ~
The critical soft (low modulus) ionomers utilized to formulate th~ blends of the present invention are acrylic acid based so~t ionomers. These soft ionomers may be generally characterized as comprised of sodi~m ~r zinc salts of a terpolymer of an ole~in having from about 2 to 8 carbon ato~s, acrylic acid, a~d an unsaturated monomer of the acrylate ester class having from 2 to 22 carbon atoms. Preferably, the soft ionomer is a zinc based ionomer made from an acrylic acid base polymer and an unsaturated monomer o~ the acrylate ester class. The soft (low modulus) ionomers have a hardness from about 20 to about 40 as measured on the Shore D
scale and a flexural modulus from about 2,000 to about 10,000 psi as measured in accordance with ASTM method D-790.
More particularly, the present inventors have discovered that if the new acrylic acid based experimental soft ionomers recently developed by the Exxon Corporation ~or the Spalding sports Worldwide, a division of Spalding & Evenflo Companies, Inc., Tampa, Florida, are utilized with the speci~ic hard ionomers described above, in the combinations more clearly de~ined below and demons~rated in the Examples, not only are improvements in processability and clarity seen, but also th~ overall combinatians, when utilized for golf ball construction, produce golf ball9 having higher coefficient of restitution values (i.e. longer distance) at equal or softer hardness than gol~ ~alls produced by known hard-soft ionomer blends, including the hard-soft ionomer blends utilized to produce Spalding's current Tour Edition~ ball.
In this regard, the inventors have found that when the new ethylene-acrylic acid based soft ionomer resins recently developed by the Exxon Corporation under the designation "Iotek 75Zo"
(referred experimentally by differences in neutralization and melt indexes as LDX 195, LDX 196, LDX 218 and LDX 219) are combined with the known hard ionomers indicated above, 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 balls produced 2 ~
by known hard-soft ionomer blends due to lower overall raw ~aterials cost and improved yields.
While the exact chemical composition of the resins to be sold by Exxon under the designation Iotek 7520 is considered by Exxon to be confidential and proprietary in~or~ation, Exxon's Experimental Product Data sheet lists the following physical properties of the ethylene acrylic acid zinc ionomer developed by Exxon:
~AsL~ 3 Phvsical Pro~erties of Iotek 7520 Pro~ertY ASTM Method ~ T~ical Value Melt Index D-1238 g/lO min. 2 Density D-1505 kg/~ 0.962 Cation Zinc Melting Point D-3417 ~C 66 Crystallization Point D-3417 ~C 49 Vicat Softening Point D-1525 ~C 42 Plaque Pro~erties t2 mm thick Co~ression Molded Plaoues~
Tensile at ~reak D-638 MPa 10 Yield Point D-638 MPa None Elongation at ~reak D-638 % 760 1% Secant Modulus D-638 MPa 22 Shore D Hardness D-2240 32 Flexural Modulus D-790 MPa 26 Zwic~ Rebond ISO 4862 % 52 De Mattia Flex Resistance D-430 Cycles >5000 ~ ~ ~ 2 ~ O ~
In addition, test data collected by the inventors indicates that Iotek ~520 resins have Shore D hardnesses of about ~2-36 (per ASTM ~-2240), melt flow indexes of 3 * .5 g/10 min (at l90 C per ASTM D-1288), a flexural moduluses of about 2500-3S00 psi (per ASTM
D-790). Furth~rmore, testing by an independent testing laboratory by pyrolysis mass spe~Lr,- ~Lly indicates that the Iotek 7520 resins are generally zinc salts o~ a terpolymer of ethylene, acrylic acid, and methyl acrylate.
As mentioned above and more clearly indicated below in the Examples, the recently developed ethylene-acrylic acid based soft ionomers (i.e. the Iotek 7520 resins) produce, when combined with various hard ionomers, particularly the Escor~ hard ionomers, golf balls exhibiting ~nh~nced properties, including longer distance at similar or softer hardness, over known hard-soft i~ r blends including those set forth in the U.s. Patent No. 4,884,814 concerning related subject matter. Alon~ this line, while the '814 patent is directed to various hard-so~t Surlyn~ ior -r blends which are similar to those blends utilized to formulate Spaldin~'s current Tour Edition~ golf ball, the soft Surlyn ior- ?rs (i.e.
Surlyn 8265 and 8269) disclosed therein are of the poly(ethylene-methacrylic acid-butyl acrylate) type. The inventors have now discovered that the use of soft ionomers containing acrylic acid (i.e. Iotek 7520), as opposed to methacrylic acid (i.e. Surlyn a26s and 8269), produce a more desirable golf ball in terms of distance and hardness (softness) while maintaining durability when used in co~bination with various known hard resins.
The superior golf balls of the present invention cont~inin~
the improved hard-soft ionomer blends can be generally produced from a central core and an outer cover wherein the outer cover is made from a co~position comprised of a blend of about 90 to about 10 percent of a hard ionomer of the type indicated above, and about 10 to about 90 percent of an acrylic acid based soft ionn~r.
More preferably, it has been found that a golf ball exhibiting properties of enhanced travel distance (i.e. higher C.O.R. values) with similar or improved playability (i.e. softness characteristics) without a sacrifice in durability, can be produced from a core and a cover, wherein the cover is made from a composition comprised of about 70 to 30 percent of a hard ionomer resin, and about 30 to about 70 percent of an acrylic acid based soft ionomer, depending on the degree of softness desired.
Superior results may be achieved when the hard ionomers utilized are sodium or zinc salts of poly(ethylene acrylic acid) such as those sold by Exxon under the Iotek designation, particularly Iotek 4000 and Iotek 8000, and the soft ionomers utilized are the new acrylic acid based soft ionomers recently developed by Exxon under the designation Iotek 7520. The optimal ranges of hard to soft ionomers are from about 60 to about 40 percent hard ionomer and from about 40 to about 60 percent soft ionomer.
Additional materials may also be added to the compositions of the present invention, including dyes (for example, Ultramarine Blue sold by Whitaker, Clark, and Daniels of South Plainsfield, NJ) (see U.S. Patent No. 4,679,795), pigments such as titanium dioxide, zinc oxide, barium sulfate and zinc sul~ate; W absorbers;
antioxidants; antistatic agents; and stabilizers. ~oreover, the cover compositions of the present invention may also contain so~tening agents, such as plasticizers, processing aids, 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 cover compositions of the present invention may be produced according to conventional melt blending procedures.
Generally, the hard ionomer resins are blended with the soft ionomeric resins in a Banbury type mixer, two-roll mill, or extruder prior to molding. The blended composition is then formed into slabs and maintained in such a state until molding is desired.
If nec~ss~ry, further additives such as inorganic fillers, 5~ ~ 4 ~
antioxidants, stabilizers, and/or zinc oxide may be added and uniformly mixed before initiation of the molding process.
The gol~ balls of the present inventi~n can be produced by molding processes currently well known in the gol~ ball art.
Specifically, the golf balls can be produced by injection molding or compression molding the novel cover composi~ions about wound or solid molded cores to produce a golf ball having a diameter o~
about 1.680 inches and weighing about 1.620 ounces. The standards for both the diameter and weight of the balls are established by the United states Golf Association (U.S.G.A.). Although both solid core and wound cores can be utilized in the present invention, as a result their lower cost and superior performance, solid molded cores are preferred over wound cores.
Conventional solid cores are typically compression molded from a slug of uncured or lightly cured elastomer composition comprising a high cis content polybutadiene and a metal salt of an 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 a small amount of a metal oxide such as zinc oxide. In addition, large~
amounts of metal oxide than are needed to achieve the desired coefficient may be included in order to increase the core weiqht 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 iono~ers, 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 p~es-~u~e, a complex curing or cross-linking reaction takes place.
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 cover and above the core as in U.S. Patent No .
4,431,193, and other multilayer and/or non-wound cores.
2~F2~i~)8 Wound cores are generally produced by winding a very large elastic thread around a solid or liquid filled balloon center. The elastic thread is wound around t~e center to produce a finished core of about 1.4 to 1.6 inches in diameter, generally. Since the core material is not an integral part of the present invention, a detailed discussion concerning the specific types of core ~aterials which may be utilized with the cover compositions of the invention are not specifically set forth herein. In this regard, the cover compositions o~ the invention may be used in conjunction with any standard golf ball core.
As indicated, the golf balls of the present invention may be produced by forming covers consisting of the compositions o~ the invention around cores by conventional molding proc~cses~ For example, in compression molding, the cover composition is formed via injection at about 380-F to about 450-F into smooth sur~aced hemispherical shells which are then positioned around the core in a dimpled golf ball mold and subjected to compression molding at 200-300-F for 2-10 minutes, followed by cooling at 50-70-F for 2-10 minutes, to fuse the shells together to form an unitary ball. In addition, the ~olf balls may be produced by injection molding, wherein the cover composition is injected directly around the core placed in the center of a golf ball mold for a period of time at a mold temperature o~ from 50'F to about lOO-F. After molding the golf balls produced may undergo various further processing steps such as buffing, painting, and marking.
The resulting golf balls produced from the novel hard-soft ionomeric resin combinations of the present invention exhibit enhanced distance and playability properties over the art without sacrificing durability. This is due to the use of acrylic acid based ionomers as the soft ionomer in the overall cover stock composition.
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 cleparting from the spirit and scope thereof.
EXAMPT .FS
~ y ~lending the ingredients set forth in the Tables below, a series of cover formulations were produced. In the examples, cover formulations conta;ning the acrylic acid based soft ionomers-hard ionomer blends of the present invention were compared with the hard-soft ionomer blends o~ the prior art including the hard-soft ionomer blend utilized to produce the current Tour Edition~ ball (ses Examples 3 and 11) which is the subject of U.S. Patent No.
4,884,814.
In addition, the properties produced by the cover compositions ~ormulated with the acrylic acid based so~t ionomer-hard ionomer blends of the present invention vere compared to the properties produced by the cover materials representative of the Tour Edition~, Tour Edition~ 100 and the Top Flite~ II balls currently bein~ sold by Spalding & Evenflo Companies, Inc., Tampa, Florida, as well as a wide variety of competitive golf balls available in the market place. Although the specific formulations utilized to produce the Tour Edition~ 100 and Top Flite~ balls are proprietary, these ~ormulations were utilized under the same processing conditions as those set forth below in order to produce covered golf balls for comparison purposes.
Along this line, the current Tour Edition~ ball is unique in that it is a two piece solid core, molded cover ball that meets the needs of golfers who demand superior control, historically obt~ine~
only with balata covered wound balls. It offers superior playability at the sacrifice of coefficient of restitution, which relates directly to distance.
The Tour Edition~ 100 ball has a slightly softer cover than the Tour Edition~ ball and utilizes a unique twin-dimple design.
The Tour Edition~ 100 ball more closely meets the d~ -n~ of the pro tour golfer than any other Spalding ball previously produced.
~2~8 The Top Flite~ ball is considered to be a "hard" Surlyn or Iotek ionomeric resin ball. As a result of the ball's hardness, the Top Flite~ ball is a difficult ball for golfers to control.
Generally, the harder the golf ball, the more difficult it is for a golfer to impart spin to the ball, and hence, control the ball during flight. However, as a result of its outstanding durability and -~; ~ distance, the ball is widely accepted by a large percentage o* golfers.
The present invention is directed to various blends of hard ionomers and acrylic acid based soft ionomers, which, when utilized for golf ball cover construction, produce golf balls closely approaching the superior distance properties exhibited by the c~rrent ~op Flite~ ball wit~out sacrificing the playability characteristics of the current Tour Edition~ ball.
The cover ~o~mulations set forth b~low Ln Tables 4 and 5 were injection molded at 400-F around identical soli~ type cores having a finished diameter o~ 1.545 inches to produce gol~ balls approximately 1.680 inches in diameter having nominal cover thickness of 0.0675 inches. The properties of Riehle compression, coefficient of restitution (C.O.R.), Shore ~ardness, impact resistance, and spin rate for the cover formulation were determined. In ~able5 4 and 5, Examples 3 and 11 are identical, and Examples 19 and 22 are similar in composition (i~e. different neutralization and melt index grades of Iotek 7520 where utilized).
~hese Examples have been set forth for comparison purposes. The data for each example represents the average data for one dozen balls produced according to the desired ~anner. The properties were measured according to the following parameters:
Riehle compression is a measurement of the deformation of a golf ball in inches under a fixed static load of 225 pounds.
Coe~ficient of restitution (C.O.R. ) was measu~e~ by firing the ~esulting golf ~all is an air cannon at a velocity o~ 125 feet per second against a steel plate which is positioned 12 ~eat 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 measured in accordance with ASTM Test 2240.
Cut resistance was measured in accordance with the rollowing procedure: A golf ball is fired at 13S feet per seco~ 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 1-5. 5 represents a cut that extends completely through the cover to the core; a 4 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 2 leaves only a slight crease which is pPrr~nPnt but not as severe as 3; and a 1 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 wed~e or 9-iron wherein the club-head speed is about 80 feet per se~on~ and the ball is launched at an angle of 26 to 34 degrees with an initial velocity of about 110-115 feet per seco~. 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 golf ball when struck at a hammer speed of 143.8 feet per second in accordance wit~ a test as prescribed by the U.S.G.A.
2~2~8 TABL~ ~
Formulations ING~EDIENTS ~ j } 4 5 6 7 8 _ 10 Surlyn 9910 438 -- U6 486 U6 ~~ -- -~ ~~ ~~
Surlyn a94~ t370 -- t08 108 tO~ -- -- -- -- --Surl~n 826~ -- -- l~2 -~ ~~ -~ -~
Sur(yn 8265 -- -- ~62 ~62 -- -- -- -- -- --Surlyn ~Ihi~e ~B1 193 -- 193 193 193 -- -- -- -- --~scor 4000 ~lo~ek 4000) -- 9U4 -- -- -- 300 ~00 SOO -- --Escor 900 ~lot~k Booo) -- 904 -- -- -- 300 400 50û 800 1000 Escor ~i~ 8 -- 193 -- -- -- 193 193 193 -- --LDX~ ot~lt 7520) -~ -- -- -- -- -- ~- ~ 9U, 788 LDX-t96 ~lo~ek 7520) -- -- -- 83Z 119~ 1108 9E18 788 --PQOPERTIES
Shore C H~roness ~,3 95 85 82 79 78 81 85 ô~ 87 lleiqh~, gr~ms 45.6 45.7 45.7 45.7 45.8 45.5 45.ô ~5.7 45.7 ~5.7 C.O.R . .821 .826 .U~ô .804 .JI)3 .803 .805 .809 .807 .812 Riehle Con~ression 49 4~5 55 S~ 57 57 56 54 55 52 3arrel CD~d Cr~ck 110 br-~lu - ~y s_~e~
Cu~ R~is~
~ t,5~rse~ 12 12 24 12 1-2 12 1-2 12 1~Z 1~2 sPrN pRop~RTr~s Spin R-~- trp~ 8707 8147 lW37 1020 10451 10349 10057 9U~3 9903 ff68 L~unch ~ngle 32.10 32.96 30.51 3n.19 29.93 30.07 30.38 30.77 30.77 31.16 1 Surlyn White MB (master batch) is comprised of 74.9% Surlyn~
8528, 23.7% Unitane 0-llO, .24% Ultra Blue, l.05~ Unitex O.B. and .03% Santonox R.
2 Escor (Iotek) White MB (Master Batch) is comprised o~ 74.9% Iotek 4000, 23.7% Unitane 0-llO, .24% Ultra Blue, l.05S Unitex O.B., and .03~ Santonox R.
tor~tetlons INGREDlENtS 11 12 13 14 15 16 L 18 ~9 20 21 22 23 Surlyn 9910 U6 486 486 486 486 - -- -- .. .. .. ..
Surlyn 8960 108 10t3 10a 10B 10~t - ~- -- ~- ~- ~-Surlyn 8269 832 -- 83Z -- 416 -- -- ~- ~- ~- ~- ~-Surlrn 8265 362 362 lBI ~- ~- -- .. .. ..
Suriyn U703 -- U2 36Z 1194 597 -- -- -- ~- -- .. .. ..
tG ilhlte I~IB1 193 193 193 193 1N - - -- -- -- - - --Escor 4000 ~lotek 40t0) -- -- -- -- -- - 857 554 454 354 554 ~54 354 E~cor 900 (lotex 8000) -- -- -- -- -- 857 -- 554 454 354 554 454 354 Escor ~hlte HB2 -- -- ~ 193 t93 193 193 193 193 193 193 c- LDX-218 tlot k 7520) ~- ~- ~_ ~ 950 950 700 900 1100 tlotek ?520) -- ~- ~- _ ~- ~- ~- 700 900 1100 PROPERilES
Ucight gruns 45.5 45.5 45.5 45.5 45.4 45.6 45.6 45.6 45.6 45.6 45.6 45.6 45.6 Riehle Con~?ressJon 53 57 SS 59 57 56 57 52 56 56 52 54 57 C.D.R. .807 .B04 .808 .802 .806 .B07 .800 .8tl .807 .B03 .B10 .805 .802 Shor C
Hsrdness 88 8B 87 86 B7 88 B6 90 87 84 B8 B6 85 Cut Resist~nce Z-4 Z-3 2-4 2-4 2-3 2-' 3-4 2-3 2-4 2-4 2-4 2-4 2-4 t Surlyn Unlte H8 (mDster o tch) Is cosprisec of 74.9X Surlyr~ 8528 23.7X Unltsr~e 0-110 .Z6X Ultre 8tue 1.05X Unitex O.B. IJnd 0.03X Ssntonox R.
2 Escor tlotek) Uhlte HB (Hsst r Betch) i~ conprisec of r4.9x lotek 4000 23.7X Unltene 0-110 .24X Ultra Blue 1.05X Unitex O.B. end .03X Sl~ntor~ox R. ;p~
3 Sur(yr~ 8Z70 Is e lou ~lus 2fnc neuttell2ed poly~ethyl. . l jllc ~ 1~ i~ljl ecrrlAte) loriomer slmll r In con~osltlon and properties to the ~
sodl~ neutrall2ed Surlyr~ U65 anci ii269 ~oft lonomers. ~' Discussion of the ExamDles The above examples indicate that the use o~ the new acrylic acid based soft ionomers (i.e. the Iotek 7520 resins) in combination with relatively hard ionomers (i.e. SurlynD 9910 and 8940, more preferably, Iotek 4000 or 8000) produce golf balls exhibiting higher C.O.R. values (i.e. thus better distance) while maintaining, and in many instances improving, the so~tness and playability characteristics of the balls when compared to golf balls produced with the methyacrylic acid based soft ionomers ~i.e.
Surlyn~ 8265 and 8269) currently used in the Tour Edition~ ball.
In addition, the examples indicate that the improvements in softness and/or distance properties are produced without the expense of the cover composition~s overall durability. As a r~sult, the new ionomer cover formulations o~ the present invention produce golf ~alls which are longer in distance and softer than any other prior Spalding golf ball.
Môre particularly, Examples 1-2 represent gol~ ball cover compositions produced utilizing only hard ionomer5. Whil~ thQse cover compositions produce golf balls exhibiting high C.O.R. (i.e.
greater than .820) values, these balls are too hard to offer sufficient playability (Shore C Hardness greater than 90, and Riehle Compression less than 50) .
Example 3 and Examples 11-15 represent the hard-soft ionomer cover blends which are the subject of U.S. Patent No. 4~8a4~8l4~
and are essentially equivalent to the current Tour Edition~ ball.
Examples 12-lS vary dep~nd;n~ on the type of methacrylic acid based 50~t Surlyn~ ionomer utilized.
Examples 6-10 and 16-23 represent the hard-soft ionomer blends o~ the present invention. When compared to the prior art gol~
balls (i.e. Examples 3 and Examples 11-15), these ~olf balls have higher C.O.R. values, while exhibiting improved playability characteristics. This is particularly demonstrated in Examples 19 .25~
and 22, the preferred embodiments of the present invention, ~hich are representative of the chemical composition of the new Tour Edition~ ball (i.e. the Tour Edition~ 90 ball) soon to be introduced into the marketplace.
In addition, the data set forth in the Examples also indicate that the hard acrylic acid based ionomeric resins (i.e. Iotek 4000 and 8000), which are sodium or zinc salts of poly(ethylene acrylic acid), produce, when utilized with the new acrylic acid based soft ionomers of the present invention, cover compositions exhibiting enhanced C.O.R. values (thus, Lmproved travel distance) at the same or similar hardness when compared with hard methyacrylic acid based ionomeric resins (i.e. Surlyn~ 9910 and 8940) which are sodium or zinc salts of poly(ethylene methacrylic acid~. ~his can be seen in comparing Examples 6-~0 with Examples 4 and 5. Thus, the more preferred compositions of the present invention comprise hard-soft ionomer blends co~prised of acrylic acid based hard ionomeric resins with the acrylic acid based so~t ionomeric resins.
Furthermore, because the new acrylic acid based soft ionomeric resins available from Exxon under the Iotek designation (i.e. Iotek 7520) contain no wax or other processing additives (i.e. it is believed that Surlyn~ 8265 and 8269 use 0.5-1 wt.S o~ a bis-stearamide wax to prev~nt clumping and mixin~ during processing), fairly substantial cost savings can be produced due to the potential elimination of epoxy primer, thereby red~lcin~ ~olatile emissions and improving w~iteness. Moreover, use of the acrylic acid based soft Iotek ionomer resin orfers a signiricant cost savings over t~e soft methacrylic acid based Surlyn~ ionomers not only in the overall cost per pound, but also because the new acrylic acid based sof~ionomers are substantially softer than the methacrylic acid based Surlyn~ blends, lower levels can be utilized.
In addition to the above indicated test results, the distance and playability properties of the more preferred formulations of the present invention (i.e. Examples 19 and 22, which are ';~ % ~ ~ ~
representative of the chemical composition of Spalding's new, longer distance and slightly softer, Tour Edition~ 90 golf ball) were cf ,-red with various combinations of Spalding's current Tour Edition~ (TE), Tour Edition~ 100 (TE 100), and Top Flight~ II (TF
II) golf balls, as well as a number of competitive golf balls, and the following performance results were produced.
DIST~NC~ T~ST
Club: 90 Deg. Metal Wood Driver Club Head Speed (fps) 160 ~nunch Condit~ons 8eforc Test After Test L-unch Angt- 8 3 N/A
Ball Spced tfps~ 239 N/~
Spin RAte trpm) 3232 N/A
Turt Conditior~ Firm firm and Dry ~ind t mph 3 nph T-mp-raeure ~/A 90 Rel~tive Numid~ty N/A N~A
TEST RES~LTS
8ALL TYPE TRAJ, FT CARRY 01FF, D LL TOTAL DtFF
TFII ' 1 6 4~54 O0 00 6 18 5 ~3 30 0 TE 100 '4 4 6 8~S1 ~-3 '' 2 0 15 5'67 ' -6 2 TE ~O '' 8 6 5S1 ~3 ' 1 0 19 6'7' -Z 1 TlTLEtST 8ALATA ' 7 6 645 2-9 h 4 5 21 0'6~ ~ -6 9 TITLEIST DT '' 9 6 6S0 D~4 B 2 4 18 5'k~ 4 8 ~AXFLI ST ~- 1 6 8"47 D-7 B-0 3 12 9 '50 0 -13 4 MAXFLt 3ALATA '_ 1 6 6 46 -8 ' 1 7 19 9'6O Z -7 2 PRECEPT BALAT~ 1~ 4 6 8'47 _-7 ' 2 0 16 4''~ 7 -9 6 $
TABr~B 7 DISTI~NC~ T~ST
Club: 5 iron Club ~ead Speed (fps) 125 ~ch Conditions 8efore Test ~fter Test l.aunch Angle (deg. ) N/A II~A
B~ I l Sp~ed ( f ps ) 11/A I~A
Spin R~te trPn) ~I~A II~A
Turf Cond . F i r~ F i n~
U~ ~ 7 ~ph Talper3ture N/~
R~l-tive Hunidity R/A Il/A
TEST RESULTS
aA~L Tl'P~ tRAJ. FT.CARR~ Q~~, OE1r. ROL~. ~, DIFF, TFtl 24.1 6.0177.~ 0.0 2.117.3 195.1 -0.1 TE 100 23.1 5.9173.9 3.9 1.8lt.8 192.t 2.4 TE 90 22.5 5.9176.4 -1.4 2.8lt.8 1ff.3 O.û
TltLElST 3AUT,~ 22.6 s.a 173.7 4.14.4 21.0 194.6 -0.6 TITLEIST DT 22.5 5.9176.6 -1.2 2.31~.9 193.S ~1.7 IWtFLI ST Z3.8 5.91n.0 ~s.8 Z.5 19.4 191.4 -3.t MU~FLI 8AUTA 23.9 5.8173.5 -4.3 4.321.5 195.0 -0.2 PRECEPT 8ALATA Z3.8 5.B 170.3 ~7.5 3.~ 20.8 191.1 4.1 Comments: Statistical analysis of the results shows that ~or TE 90 vs. ~4) of the competitive brands (Titleist 3alataj Maxfli St., Maxfli Balata, Balata Precept) the differences in total distance are very significant. This means the longer total distance is likely due to differences in ball performance and is not due to random choice.
2~
TABL~3 8 SPIN 'r~3ST
Full Standard Ball Tvl~e Sauare Hit1 Deviation Tour Edition 9701 550 Tour Edition 10010181 290 Tour Edition so9581 630 Top Flite XL 7635 772 Titleist ~84 Tour 100 9775 99 Titleist Tour 100 9830 232 Titleist DT 90 7700 882 ~axfli ST 8228 735 Maxfli DDH 9~76 231 Bridgestone Precept 9050 253 Wilson Staff 6989 719 1 The full (square hit) was performed utilizing a Johnny Miller Finesse wedge with its face oriented for a square hit.
In view of the above test results, as well as additional ~ata produced by internal testing, the following perfor~ance profile of the more preferred formulation of the present invention (i.e.
Examples 19 and 22 concerning the new softer Tour Edition~ 90 golf ball) has been developed:
1. In machine tests, the Tour Edition~ 90 distance off the #5 iron and driver is longer than the current Tour Edition0 100 with slightly lower trajectory.
5~2~0~
2. The Tour Edition~ 90 is equal to the Top ~lite~
I~ in distance off the ~5 iron and although two yards shorter than the Top Flitea II off the driver, it is significantly longer off the driver than the top competitive brands.
3. Spin off a full #~ iron is equal to the Tour Edition~ and slightly less than the Tour Edition~ ~00.
sodl~ neutrall2ed Surlyr~ U65 anci ii269 ~oft lonomers. ~' Discussion of the ExamDles The above examples indicate that the use o~ the new acrylic acid based soft ionomers (i.e. the Iotek 7520 resins) in combination with relatively hard ionomers (i.e. SurlynD 9910 and 8940, more preferably, Iotek 4000 or 8000) produce golf balls exhibiting higher C.O.R. values (i.e. thus better distance) while maintaining, and in many instances improving, the so~tness and playability characteristics of the balls when compared to golf balls produced with the methyacrylic acid based soft ionomers ~i.e.
Surlyn~ 8265 and 8269) currently used in the Tour Edition~ ball.
In addition, the examples indicate that the improvements in softness and/or distance properties are produced without the expense of the cover composition~s overall durability. As a r~sult, the new ionomer cover formulations o~ the present invention produce golf ~alls which are longer in distance and softer than any other prior Spalding golf ball.
Môre particularly, Examples 1-2 represent gol~ ball cover compositions produced utilizing only hard ionomer5. Whil~ thQse cover compositions produce golf balls exhibiting high C.O.R. (i.e.
greater than .820) values, these balls are too hard to offer sufficient playability (Shore C Hardness greater than 90, and Riehle Compression less than 50) .
Example 3 and Examples 11-15 represent the hard-soft ionomer cover blends which are the subject of U.S. Patent No. 4~8a4~8l4~
and are essentially equivalent to the current Tour Edition~ ball.
Examples 12-lS vary dep~nd;n~ on the type of methacrylic acid based 50~t Surlyn~ ionomer utilized.
Examples 6-10 and 16-23 represent the hard-soft ionomer blends o~ the present invention. When compared to the prior art gol~
balls (i.e. Examples 3 and Examples 11-15), these ~olf balls have higher C.O.R. values, while exhibiting improved playability characteristics. This is particularly demonstrated in Examples 19 .25~
and 22, the preferred embodiments of the present invention, ~hich are representative of the chemical composition of the new Tour Edition~ ball (i.e. the Tour Edition~ 90 ball) soon to be introduced into the marketplace.
In addition, the data set forth in the Examples also indicate that the hard acrylic acid based ionomeric resins (i.e. Iotek 4000 and 8000), which are sodium or zinc salts of poly(ethylene acrylic acid), produce, when utilized with the new acrylic acid based soft ionomers of the present invention, cover compositions exhibiting enhanced C.O.R. values (thus, Lmproved travel distance) at the same or similar hardness when compared with hard methyacrylic acid based ionomeric resins (i.e. Surlyn~ 9910 and 8940) which are sodium or zinc salts of poly(ethylene methacrylic acid~. ~his can be seen in comparing Examples 6-~0 with Examples 4 and 5. Thus, the more preferred compositions of the present invention comprise hard-soft ionomer blends co~prised of acrylic acid based hard ionomeric resins with the acrylic acid based so~t ionomeric resins.
Furthermore, because the new acrylic acid based soft ionomeric resins available from Exxon under the Iotek designation (i.e. Iotek 7520) contain no wax or other processing additives (i.e. it is believed that Surlyn~ 8265 and 8269 use 0.5-1 wt.S o~ a bis-stearamide wax to prev~nt clumping and mixin~ during processing), fairly substantial cost savings can be produced due to the potential elimination of epoxy primer, thereby red~lcin~ ~olatile emissions and improving w~iteness. Moreover, use of the acrylic acid based soft Iotek ionomer resin orfers a signiricant cost savings over t~e soft methacrylic acid based Surlyn~ ionomers not only in the overall cost per pound, but also because the new acrylic acid based sof~ionomers are substantially softer than the methacrylic acid based Surlyn~ blends, lower levels can be utilized.
In addition to the above indicated test results, the distance and playability properties of the more preferred formulations of the present invention (i.e. Examples 19 and 22, which are ';~ % ~ ~ ~
representative of the chemical composition of Spalding's new, longer distance and slightly softer, Tour Edition~ 90 golf ball) were cf ,-red with various combinations of Spalding's current Tour Edition~ (TE), Tour Edition~ 100 (TE 100), and Top Flight~ II (TF
II) golf balls, as well as a number of competitive golf balls, and the following performance results were produced.
DIST~NC~ T~ST
Club: 90 Deg. Metal Wood Driver Club Head Speed (fps) 160 ~nunch Condit~ons 8eforc Test After Test L-unch Angt- 8 3 N/A
Ball Spced tfps~ 239 N/~
Spin RAte trpm) 3232 N/A
Turt Conditior~ Firm firm and Dry ~ind t mph 3 nph T-mp-raeure ~/A 90 Rel~tive Numid~ty N/A N~A
TEST RES~LTS
8ALL TYPE TRAJ, FT CARRY 01FF, D LL TOTAL DtFF
TFII ' 1 6 4~54 O0 00 6 18 5 ~3 30 0 TE 100 '4 4 6 8~S1 ~-3 '' 2 0 15 5'67 ' -6 2 TE ~O '' 8 6 5S1 ~3 ' 1 0 19 6'7' -Z 1 TlTLEtST 8ALATA ' 7 6 645 2-9 h 4 5 21 0'6~ ~ -6 9 TITLEIST DT '' 9 6 6S0 D~4 B 2 4 18 5'k~ 4 8 ~AXFLI ST ~- 1 6 8"47 D-7 B-0 3 12 9 '50 0 -13 4 MAXFLt 3ALATA '_ 1 6 6 46 -8 ' 1 7 19 9'6O Z -7 2 PRECEPT BALAT~ 1~ 4 6 8'47 _-7 ' 2 0 16 4''~ 7 -9 6 $
TABr~B 7 DISTI~NC~ T~ST
Club: 5 iron Club ~ead Speed (fps) 125 ~ch Conditions 8efore Test ~fter Test l.aunch Angle (deg. ) N/A II~A
B~ I l Sp~ed ( f ps ) 11/A I~A
Spin R~te trPn) ~I~A II~A
Turf Cond . F i r~ F i n~
U~ ~ 7 ~ph Talper3ture N/~
R~l-tive Hunidity R/A Il/A
TEST RESULTS
aA~L Tl'P~ tRAJ. FT.CARR~ Q~~, OE1r. ROL~. ~, DIFF, TFtl 24.1 6.0177.~ 0.0 2.117.3 195.1 -0.1 TE 100 23.1 5.9173.9 3.9 1.8lt.8 192.t 2.4 TE 90 22.5 5.9176.4 -1.4 2.8lt.8 1ff.3 O.û
TltLElST 3AUT,~ 22.6 s.a 173.7 4.14.4 21.0 194.6 -0.6 TITLEIST DT 22.5 5.9176.6 -1.2 2.31~.9 193.S ~1.7 IWtFLI ST Z3.8 5.91n.0 ~s.8 Z.5 19.4 191.4 -3.t MU~FLI 8AUTA 23.9 5.8173.5 -4.3 4.321.5 195.0 -0.2 PRECEPT 8ALATA Z3.8 5.B 170.3 ~7.5 3.~ 20.8 191.1 4.1 Comments: Statistical analysis of the results shows that ~or TE 90 vs. ~4) of the competitive brands (Titleist 3alataj Maxfli St., Maxfli Balata, Balata Precept) the differences in total distance are very significant. This means the longer total distance is likely due to differences in ball performance and is not due to random choice.
2~
TABL~3 8 SPIN 'r~3ST
Full Standard Ball Tvl~e Sauare Hit1 Deviation Tour Edition 9701 550 Tour Edition 10010181 290 Tour Edition so9581 630 Top Flite XL 7635 772 Titleist ~84 Tour 100 9775 99 Titleist Tour 100 9830 232 Titleist DT 90 7700 882 ~axfli ST 8228 735 Maxfli DDH 9~76 231 Bridgestone Precept 9050 253 Wilson Staff 6989 719 1 The full (square hit) was performed utilizing a Johnny Miller Finesse wedge with its face oriented for a square hit.
In view of the above test results, as well as additional ~ata produced by internal testing, the following perfor~ance profile of the more preferred formulation of the present invention (i.e.
Examples 19 and 22 concerning the new softer Tour Edition~ 90 golf ball) has been developed:
1. In machine tests, the Tour Edition~ 90 distance off the #5 iron and driver is longer than the current Tour Edition0 100 with slightly lower trajectory.
5~2~0~
2. The Tour Edition~ 90 is equal to the Top ~lite~
I~ in distance off the ~5 iron and although two yards shorter than the Top Flitea II off the driver, it is significantly longer off the driver than the top competitive brands.
3. Spin off a full #~ iron is equal to the Tour Edition~ and slightly less than the Tour Edition~ ~00.
4. Durability in lab testing is equal to the Tour Edition~ or Tour Edition~ loo.
As a result, the new hard-soft ionomer blends of the present invention produce golf balls exhibiting properties of enhanced distance and playability without sacrificing durability.
The invention has been described with reference to the preferred embodiment. ObViously, modifications and alterations will occur to others upon reading and underst~n~i~g the prece~
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 app~n~ed claims or the equivalents thereof.
As a result, the new hard-soft ionomer blends of the present invention produce golf balls exhibiting properties of enhanced distance and playability without sacrificing durability.
The invention has been described with reference to the preferred embodiment. ObViously, modifications and alterations will occur to others upon reading and underst~n~i~g the prece~
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 app~n~ed claims or the equivalents thereof.
Claims (14)
1. A golf ball comprising a core and a cover, wherein said cover comprises:
from about 90 to about 10 percent by weight of a hard ionomer which is a sodium or zinc salt of the copolymer of an olefin having from 2 to 8 carbon atoms and an unsaturated monocarboxylic acid from 3 to 8 carbon atoms, wherein said hard ionomer has a hardness greater than 50 on the Shore D scale and a flexural modulus of from about 15,000 to about 70,000 psi; and, from about 10 to about 90 percent by weight of an acrylic acid based soft ionomer which is a sodium or zinc salt of a terpolymer of an olefin having 2 to 8 carbon atoms, acrylic acid, and an unsaturated monomer of the acrylate ester class having from 2 to 22 carbon atoms, wherein said soft ionomer has a hardness from about 20 to about 40 on the Shore D scale and a flexural modulus of from about 2,000 to 10,000 psi.
from about 90 to about 10 percent by weight of a hard ionomer which is a sodium or zinc salt of the copolymer of an olefin having from 2 to 8 carbon atoms and an unsaturated monocarboxylic acid from 3 to 8 carbon atoms, wherein said hard ionomer has a hardness greater than 50 on the Shore D scale and a flexural modulus of from about 15,000 to about 70,000 psi; and, from about 10 to about 90 percent by weight of an acrylic acid based soft ionomer which is a sodium or zinc salt of a terpolymer of an olefin having 2 to 8 carbon atoms, acrylic acid, and an unsaturated monomer of the acrylate ester class having from 2 to 22 carbon atoms, wherein said soft ionomer has a hardness from about 20 to about 40 on the Shore D scale and a flexural modulus of from about 2,000 to 10,000 psi.
2. The golf ball of claim 1, wherein the hard ionomer is a sodium or zinc salt of the copolymer of ethylene and acrylic acid.
3. The golf ball of claim 1, wherein the soft ionomer is a zinc salt of a terpolymer of ethylene, acrylic acid and methyl acrylate.
4. The golf ball of claim 2, wherein said cover composition comprises from about 70 to about 30 percent by weight of the hard ionomer and from about 30 to about 70 by weight percent of the soft ionomer.
5. The golf ball of claim 3, wherein said cover composition comprises from about 70 to about 30 percent by weight of the hard ionomer and from about 30 to about 70 by weight percent of the soft ionomer.
6. The golf ball of claim 1, wherein said cover composition comprises from about 60 to about 40 percent by weight of the hard ionomer and from about 40 to about 60 percent by weight of the soft ionomer.
7. The golf ball of claim 6, wherein said cover composition comprises from about 60 to about 40 percent by weight of the hard ionomer and from about 40 to about 60 percent by weight of the soft ionomer.
8. A golf ball comprising a core and a cover, wherein said cover comprises a blend of from about 70 to about 30 percent by weight of an acrylic acid based hard ionomer and from about 30 to about 70 percent by weight of an acrylic acid based soft ionomer.
9. A golf ball comprising a core and a cover, wherein said cover comprises a blend of from about 70 to about 30 percent by weight of a hard ionomer which is a sodium or zinc salt of an ethylene-acrylic acid copolymer and from about 30 to about 70 percent by weight of a soft ionomer which is a zinc salt of a terpolymer of ethylene, acrylic acid and methyl acrylate.
10. The golf ball of claim 9, wherein the hard ionomer is a blend of from about 70 to about 30 weight percent of an ethylene-acrylic acid copolymer which is neutralized with a zinc ion and from about 30 to about 70 weight percent of an ethylene-acrylic acid copolymer which is neutralized with a sodium ion.
11. The golf ball of claim 9, wherein the hard ionomer is a blend of from about 70 to about 30 weight percent of an ethylene-acrylic acid copolymer containing about 16% by weight acrylic acid with about 30% of the carboxylic acid groups neutralized by zinc ions and from about 30 to 70 weight percent of an ethylene-acrylic acid copolymers containing about 11% by weight acrylic acid having about 40% of the carboxylic acid groups neutralized with sodium ions
12. The golf ball of claim 1, wherein said cover comprises a mixture of one or more pigments, an optical brighteners and/or dye
13. The golf ball of claim 8, wherein said cover comprises a mixture of one or more pigments, an optical brighteners and/or dye.
14. The golf ball of claim 9, wherein said cover comprises a mixture of one or more pigments, an optical brighteners and/or dye.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/559,177 US5120791A (en) | 1990-07-27 | 1990-07-27 | Golf ball cover compositions |
| US559,177 | 1990-07-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2042508A1 CA2042508A1 (en) | 1992-01-28 |
| CA2042508C true CA2042508C (en) | 1999-01-05 |
Family
ID=24232588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002042508A Expired - Lifetime CA2042508C (en) | 1990-07-27 | 1991-05-14 | Golf ball cover composition |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US5120791A (en) |
| JP (1) | JP2979272B2 (en) |
| AU (1) | AU653929B2 (en) |
| CA (1) | CA2042508C (en) |
| GB (1) | GB2247682B (en) |
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| GB221515A (en) * | 1922-07-29 | 1924-10-06 | Lewis Ferry Moody | Improvements in machining the blades of hydraulic turbine runners |
| NL128027C (en) * | 1961-08-31 | 1900-01-01 | ||
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| US4431193A (en) * | 1981-08-25 | 1984-02-14 | Questor Corporation | Golf ball and method of making same |
| US4690981A (en) * | 1983-03-21 | 1987-09-01 | E. I. Du Pont De Nemours And Company | Ionomers having improved low temperature properties |
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| US4911451A (en) * | 1989-03-29 | 1990-03-27 | Sullivan Michael J | Golf ball cover of neutralized poly(ethylene-acrylic acid) copolymer |
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| US5120791A (en) * | 1990-07-27 | 1992-06-09 | Lisco, Inc. | Golf ball cover compositions |
-
1990
- 1990-07-27 US US07/559,177 patent/US5120791A/en not_active Expired - Lifetime
-
1991
- 1991-03-22 AU AU73769/91A patent/AU653929B2/en not_active Ceased
- 1991-05-02 GB GB9109526A patent/GB2247682B/en not_active Expired - Lifetime
- 1991-05-14 CA CA002042508A patent/CA2042508C/en not_active Expired - Lifetime
- 1991-07-26 JP JP3274469A patent/JP2979272B2/en not_active Expired - Fee Related
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1992
- 1992-04-08 US US07/865,212 patent/US5324783A/en not_active Expired - Lifetime
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|---|---|
| GB9109526D0 (en) | 1991-06-26 |
| GB2247682A (en) | 1992-03-11 |
| GB2247682B (en) | 1995-02-08 |
| US5324783A (en) | 1994-06-28 |
| JP2979272B2 (en) | 1999-11-15 |
| AU653929B2 (en) | 1994-10-20 |
| CA2042508A1 (en) | 1992-01-28 |
| US5120791A (en) | 1992-06-09 |
| AU7376991A (en) | 1992-01-30 |
| JPH053931A (en) | 1993-01-14 |
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