WO2000038790A1 - Low spin golf ball - Google Patents
Low spin golf ball Download PDFInfo
- Publication number
- WO2000038790A1 WO2000038790A1 PCT/US1999/017861 US9917861W WO0038790A1 WO 2000038790 A1 WO2000038790 A1 WO 2000038790A1 US 9917861 W US9917861 W US 9917861W WO 0038790 A1 WO0038790 A1 WO 0038790A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cover
- golf ball
- ball
- core
- weight
- Prior art date
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- 239000005063 High cis polybutadiene Substances 0.000 description 1
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000001932 carya illinoensis shell powder Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
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- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
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- 229920000588 gutta-percha Polymers 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N linoleic acid group Chemical group C(CCCCCCC\C=C/C\C=C/CCCCC)(=O)O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
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- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
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- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—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
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0029—Physical properties
- A63B37/0033—Thickness
-
- 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
- A63B37/0034—Deflection or compression
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/0051—Materials other than polybutadienes; Constructional details
- A63B37/0052—Liquid cores
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/0051—Materials other than polybutadienes; Constructional details
- A63B37/0053—Thread wound
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/006—Physical properties
- A63B37/0065—Deflection or compression
-
- 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
Definitions
- the present invention relates to golf balls and, more particularly, to improved golf balls (two-piece, wound three-piece, etc.) balls having low spin rates.
- the improvement in the golf balls results from a combination of a softened core and a hard cover made from blends of one or more specific hard, high stiffness ionomers.
- the combination of a soft core and a hard cover leads to an improved golf ball having a lower than anticipated spin rate while maintaining the resilience and durability characteristics necessary for repetitive play.
- the spin rate is further reduced by decreasing the weight of the softened core and/or by increasing the thickness of the cover.
- Spin rate is an important golf ball characteristic for both the skilled and unskilled golfer.
- High spin rates allow for the more skilled golfer, such as PGA professionals and low handicap players, to maximize control of the golf ball. This is particularly beneficial to the more skilled golfer when hitting an approach shot to a green.
- the more skilled golfer generally prefers a golf ball exhibiting high spin rate properties.
- a high spin golf ball is not desirous by all golfers, particularly high handicap players who cannot intentionally control the spin of the ball.
- less skilled golfers have, among others, two substantial obstacles to improving their game: slicing and hooking.
- slicing and hooking When a club head meets a ball, an unintentional side spin is often imparted which sends the ball off its intended course. The side spin reduces one's control over the ball as well as the distance the ball will travel. As a result, unwanted strokes are added to the game.
- a more efficient ball for the less skilled player is a golf ball that exhibits low spin properties.
- the low spin ball reduces slicing and hooking and enhances roll distance for the amateur golfer.
- the present inventors have addressed the need for developing a golf ball having a reduced spin rate after club impact, while at the same time maintaining durability, playability and resiliency characteristics needed for repeated use.
- the reduced spin rate golf ball of the present invention meets the rules and regulations established by the United States Golf Association (U.S.G.A.).
- the U.S.G.A. has set forth five (5) specific regulations that a golf ball must conform to.
- the U.S.G.A. rules require that a ball be no smaller than 1.680 inches in diameter.
- a golf ball can be as large as desired so long as it is larger than 1.680 inches in diameter and so long as the other four (4) specific regulations are met.
- the U.S.G.A. rules also require that balls weigh no more than 1.620 ounces, and that their initial velocity may not exceed 250 s feet per second with a maximum tolerance of 2%, or up to 255 ft./sec. Further, the U.S.G.A. rules state that a ball may not travel a distance greater than 280 yards with a test tolerance of 6% when hit by the U.S.G.A. outdoor driving machine under specific conditions.
- Top-grade golf balls sold in the United States may be generally classified as one of two types: two-piece or three-piece balls.
- the two-piece ball exemplified by the balls sold by Spalding & Evenflo Companies, Inc. (the assignee of the present invention through its 0 wholly owned subsidiary, Lisco, Inc.) under the trademark TOP-FLITE, consists of a solid polymeric core and a separately formed outer cover.
- the so-called three-piece balls exemplified by the balls sold under the trademark TITLEIST by the Acushnet Company, consist of a liquid (e.g., TITLEIST TOUR 384) or solid (e.g., TITLEIST DT) center, elastomeric 5 thread windings about the center, and a cover.
- a liquid e.g., TITLEIST TOUR 384
- solid e.g., TITLEIST DT
- Spalding's two-piece golf balls are produced by molding a natural (balata) or synthetic (i.e. thermoplastic resin such as an ionomer resin) polymeric cover composition around a preformed polybutadiene (rubber) core. During the molding process, the desired dimple pattern is molded into the cover material. In order to reduce the number of coating steps involved in the finishing of the golf balls, a color pigment or dye and, in many instances, an optical brightener, are added directly to the generally "off white” colored polymeric cover composition prior to molding.
- Spalding is the leading manufacturer of two-piece golf balls in the world. Spalding manufactures over sixty (60) different types of two-piece balls which vary distinctly in such properties as playability (i.e. spin rate, compression, feel, etc.), travel distance (initial velocity, C.O.R., etc.), durability (impact, cut and weather resistance) and appearance (i.e.
- the initial velocity of two-piece and three- piece balls is determined mainly by the coefficient of restitution of the core.
- the coefficient of restitution of the core of wound (i.e. three- piece) balls can be controlled within limits by regulating the winding tension and the thread and center composition.
- the coefficient of restitution of the core is a function of the properties of the elastomer composition from which it is made.
- the cover component of a golf ball is particularly influential in effecting the compression (feel), spin rates (control), distance (C.O.R.), and durability (i.e. impact resistance, etc.) of the resulting ball.
- Various cover compositions have been developed by Spalding and others in order to optimize the desired properties of the resulting golf balls.
- top-grade golf balls must meet several other important design criteria.
- a golf ball should be resistant to cutting and must be finished well; it should hold a line in putting and should have good click and feel.
- the ball should exhibit spin and control properties dictated by the skill and experience of the end user.
- the present invention is directed to improved top- grade golf balls (two-piece and three-piece) having reduced spin rates. The improved golf balls offer the less skilled golfer better control over his or her shots and allow for greater distance.
- the spin rate of the ball is further reduced by increasing the thickness of the cover and/or decreasing the weight and softness of the core.
- increasing the cover thickness and/or the overall diameter of the resulting molded golf ball enhanced reduction in spin rate is observed.
- This patent teaches an oversize golf ball having a diameter between 1.700 and 1.730 inches and an oversized core of resilient material (i.e. about 1.585 to 1.595 inches in diameter) so as to o increase the coefficient of restitution.
- the patent discloses that the ball should include a cover having a thickness less than the cover thickness of conventional balls (i.e. a cover thickness of about 0.050 inches as opposed to 0.090 inches for conventional two-piece balls).
- cover thickness i.e. a cover thickness of about 0.050 inches as opposed to 0.090 inches for conventional two-piece balls.
- Spalding in 1915 were of a diameter ranging from 1.630 inches to 1.710 inches. As the diameter of the ball increased, the weight of the ball also increased. These balls were comprised of covers made up of balata/gutta percha and cores made from solid rubber or liquid sacs and 0 wound with elastic thread.
- the LYNX JUMBO balls were also commercially available by Lynx in October, 1979. These balls had a diameter of 1.76 to 1.80 inches. It met with little or no commercial success.
- the LYNX JUMBO balls consisted of a core comprised of 5 wo ⁇ nd core and a cover comprised of natural or synthetic balata.
- An object of the present invention is to produce a U.S.G.A. regulation golf ball having improved low spin properties while maintaining the resilience and durability characteristics necessary for repetitive play.
- the present invention is directed to improved golf balls having a low rate of spin upon club impact.
- the golf balls comprise a soft core and a hard cover.
- the hard cover can be sized to be larger than conventional diameters.
- the low spin rate enables the ball to travel a greater distance.
- the low spin rate provides the less skilled golfer with more control. This is because the low spin rate decreases undesirable side spin which leads to slicing and hooking.
- the combination of a hard cover and a soft core provides for a ball having a lower than anticipated spin rate while maintaining high resilience and good durability.
- the golf ball comprises a core and a cover.
- the core (which may be molded or wound) has a Riehle compression of at least 0.075, preferably 0.075 to about .115, and a PGA compression of about 45 to 85.
- the cover has a Shore. D hardness of at least 65.
- the resulting ball is larger than the standard 1.680 inch golf ball. Its diameter is in the range of about 1.680 to 1.800 inches, more likely in the range of about 1.700 to 1.800 inches, preferably in the range of 1.710 - 1.730 inches, and most preferably in the range of about 1.717 - 1.720 inches. ln a further embodiment, the cover thickness of the ball can vary. The cover thickness ranges from more than the standard 0.0675 inches up to about 0.130, preferably from about 0.0675 to about 0.1275 inches, more preferably in the range of about 0.0825 to 0.0925, s and most preferably in the range of about 0.0860 to 0.0890 inches.
- the core is preferably of a standard size, roughly about 1.540 to 1.545 inches.
- the core used in the present invention is a specially produced softened polybutadiene elastomeric solid core having a conventional diameter of about 1.540 to 1.545 o inches.
- the core is produced from a composition comprising a base elastomer selected from polybutadiene and mixtures of polybutadiene with other elastomers, at least one metallic salt of an unsaturated carboxylic acid (a co-crosslinking agent), and free radical initiator (a co- crosslinking agent).
- a suitable and compatible modifying s ingredient including, but not limited to metal activators, fatty acids, fillers, polypropylene powder and other additives may be included.
- the metallic salt of an unsaturated carboxylic acid is included in the core compositions in order to produce the degree of core softness and 0 weight desired.
- the composition of the core is adjusted so that the molded finished ball falls within the weight parameters set forth by the U.S.G.A. Since the finished golf balls must still meet the U.S.G.A. weight limitation of 1.620 ounces, the core component of the larger and 5 thiqker covered balls are designed to be not only softer, but also lighter in weight.
- the specific gravity of the core is less than that of a standard core since the larger ball must weigh the same as a standard ball.
- the core generally weighs about 36 to 37 grams for an standard sized finished ball and about 33 to 34 grams for an oversized finished ball.
- the core composition produces a softer molded core which still maintains the resilience (C.O.R.), compression (hardness) and durability characteristics required.
- a wound core can also be utilized.
- the overall core has a PGA compression of about 45 to 85, preferably in the range of about 70 - 80. Its Riehle compression is about 0.075 or more, preferably in the range of .075 to .115, and the resilience of the core is about .760 to .780.
- the cover is preferably comprised of a hard, high-stiffness ionomer resin, most preferably a metal cation neutralized high acid ionomer resin containing more than 16% carboxylic acid by weight, or blend thereof.
- the cover has a Shore D hardness of about 65 or greater.
- ionomeric resins are polymers containing interchain ionic bonding.
- various ionomeric resins sold by E.I. DuPont de Nemours & Company under the trademark “Surlyn®” and more recently, by the Exxon Corporation (see U.S. Patent No. 4,911 ,451) under the trademark “Escor®” and the tradename “lotek” have become the materials of choice for the construction of golf ball covers over the traditional "balata” (trans-polyisoprene, natural or synthetic) rubbers.
- Ionomeric resins are generally ionic copolymers of an olefin, such as ethylene, and a metal salt of an unsaturated carboxylic acid, such as acrylic acid, methacrylic acid or maleic acid. In some instances, an additional softening comonomer such as an acrylate can also be included to form a terpolymer.
- the pendent ionic groups in the ionomeric resins interact to form ion-rich aggregates contained in a non- polar polymer matrix.
- the metal ions such as sodium, zinc, magnesium, lithium, potassium, calcium, etc. are used to neutralize some portion of the acid groups in the copolymer resulting in a thermoplastic elastomer exhibiting enhanced properties, i.e., improved durability, etc. for golf ball construction over balata.
- the ionomeric resins utilized to produce cover compositions can be formulated according to known procedures such as those set forth in U. S. Patent No. 3,421 ,766 or British Patent No. 963,380, with neutralization effected according to procedures disclosed in Canadian Patent Nos. 674,595 and 713,631 , wherein the ionomer is produced by copolymerizing the olefin and carboxylic acid to produce a copolymer having the acid units randomly distributed along the polymer chain.
- the ionic copolymer generally comprises one or more ⁇ -olefins and from about 9 to about 20 weight percent of ⁇ , ⁇ - ethylenically unsaturated mono- or dicarboxylic acid, the basic copolymer neutralized with metal ions to the extent desired.
- At least about 20% of the carboxylic acid groups of the copolymer are neutralized by the metal ions (such as sodium, potassium, zinc, calcium, magnesium, and the like) and exist in the ionic state.
- Suitable olefins for use in preparing the ionomeric resins include ethylene, propylene, butene-1 , hexene-1 and the like.
- Unsaturated carboxylic acids include acrylic, methacrylic, ethacrylic, ⁇ - chloroacrylic, crotonic, maleic, fumaric, itaconic acids, and the like.
- the ionomeric resins utilized in the golf ball industry are generally copolymers of ethylene with acrylic (i.e., Escor®) and/or methacrylic (i.e., Surlyn®) acid.
- acrylic i.e., Escor®
- methacrylic i.e., Surlyn®
- two or more types of ionomeric resins may be blended in to the cover compositions in order to produce the desired properties of the resulting golf balls.
- the cover compositions which may be used in making the golf balls of the present invention are set forth in detail but not limited to those in copending U.S. Serial No. 07/776,803 filed October 15, 1991 , and Serial No. 07/901 ,660 filed June 19, 1992, both incorporated herein by reference.
- the cover material is comprised of hard, high stiffness ionomer resins, preferably containing relatively high amounts of acid (i.e., greater than 16 weight percent acid, preferably from about 17 to about 25 weight percent acid, and more preferably from about 18.5 to about 21.5 weight percent) and at least partially neutralized with metal ions (such as sodium, zinc, potassium, calcium, magnesium and the like).
- acid i.e., greater than 16 weight percent acid, preferably from about 17 to about 25 weight percent acid, and more preferably from about 18.5 to about 21.5 weight percent
- metal ions such as sodium, zinc, potassium, calcium, magnesium and the like.
- the preferred cover compositions are made from specific blends of two or more high acid ionomers with other cover additives which do not exhibit the processing, playability, distance and/or durability limitations demonstrated by the prior art.
- the cover composition can also be comprised of one or more low acid ionomers so long as the molded covers exhibit a hardness of 65 or more on the Shore D scale.
- overall finished balls of the invention exhibit significantly lower spin rates than conventional balls of equal size and weight. Further, reduction in spin are also produced by increasing the thickness of the cover and/or by decreasing the weight of the softened core.
- the resilience or coefficient of restitution (COR) of a golf ball is the constant "e,” which is the ratio of the relative velocity of an elastic sphere after direct impact to that before impact.
- e the resilience or coefficient of restitution
- the COR can vary from 0 to 1 , with 1 being equivalent to a perfectly or completely elastic collision and 0 being equivalent to a perfectly or completely inelastic collision.
- COR COR
- club head speed club head mass
- ball weight ball size and density
- spin rate angle of trajectory and surface configuration
- environmental conditions e.g. temperature, moisture, atmospheric pressure, wind, etc.
- COR density and resilience
- the factors or determinants of interest with respect to improved distance are generally the coefficient of restitution (COR) and the surface configuration (dimple pattern, ratio of land area to dimple area, etc.) of the ball.
- COR coefficient of restitution
- the COR of solid core balls is a function of the composition of the core and of the cover.
- the core and/or cover may be comprised of one or more layers such as in multi-layer balls.
- the coefficient of restitution is a function of not only the composition of the center and cover, but also the composition and tension of the elastomeric windings.
- the center and cover of a wound core ball may also consist of one or more layers.
- the COR of the golf balls of the present s invention is a function of the composition and physical properties of the core and cover layer materials such as flex modulus, hardness and particularly, their resilience, i.e. ability to quickly recover from a high impact deformation.
- the coefficient of restitution is the ratio of the outgoing o velocity to the incoming velocity.
- the coefficient of restitution of a golf ball was measured by propelling a ball horizontally at a speed of 125 ⁇ 5 feet per second (fps) and corrected to 125 fps against a generally vertical, hard, flat steel plate and measuring the ball's incoming and outgoing velocity electronically.
- fps 125 ⁇ 5 feet per second
- s Speeds were measured with a pair of Oehler Mark 55 ballistic screens available from Oehler Research, Inc., P.O. Box 9135, Austin, Texas 78766, which provide a timing pulse when an object passes through them. The screens were separated by 36" and are located 25.25" and 61.25" from the rebound wall.
- the ball speed was measured by timing 0 the pulses from screen 1 to screen 2 on the way into the rebound wall (as the average speed of the ball over 36"), and then the exit speed was timed from screen 2 to screen 1 over the same distance.
- the rebound wall was tilted 2 degrees from a vertical plane to allow the ball to rebound slightly downward in order to miss the edge of the cannon 5 that fired it.
- the rebound wall is solid steel 2.0 inches thick.
- the incoming speed should be 125 ⁇ 5 fps but corrected to 125 fps.
- the correlation between COR and forward or incoming speed has been studied and a correction has been made over the ⁇ 5 fps range so that the COR is reported as if the ball had an incoming speed of exactly 125.0 fps.
- the coefficient of restitution must be carefully controlled in all commercial golf balls if the ball is to be within the specifications regulated by the United States Golf Association (U.S.G.A.).
- U.S.G.A. United States Golf Association
- the U.S.G.A. standards indicate that a "regulation" ball cannot have an initial velocity exceeding 255 feet per second in an atmosphere of 75°F. when tested on a U.S.G.A. machine.
- the coefficient of restitution of a ball is related to the ball's initial velocity, it is highly desirable to produce a ball having sufficiently high coefficient of restitution to closely approach the U.S.G.A. limit on initial velocity, while having an ample degree of softness (i.e., hardness) to produce enhanced playability (i.e., spin, etc.).
- PGA compression is another important property involved in the performance of a golf ball.
- the compression of the ball can affect the playability of the ball on striking and the sound or "click” produced.
- compression can affect the "feel” of the ball (i.e., hard or soft responsive feel), particularly in chipping and putting.
- compression utilized in the golf ball trade generally defines the overall deflection that a golf ball undergoes when subjected to a compressive load. For example, PGA compression indicates the amount of change in golf ball's shape upon striking.
- PGA compression related to a scale of 0 to 200 given to a golf ball.
- tournament quality balls have compression ratings around 70 -110, preferably around 80 to 100.
- PGA compression In determining PGA compression using the 0 - 200 scale, a standard force is applied to the external surface of the ball. A ball which exhibits no deflection (0.0 inches in deflection) is rated 200 and a ball which deflects 2/10th of an inch (0.2 inches) is rated 0. Every change of .001 of an inch in deflection represents a 1 point drop in compression. Consequently, a ball which deflects 0.1 inches (100 x .001 inches) has a PGA compression value of 100 (i.e., 200 - 100) and a ball which deflects 0.110 inches (110 x .001 inches) has a PGA compression of 90 (i.e., 200 -110).
- PGA compression in determined by an apparatus fashioned in the form of a small press with an upper and lower anvil.
- the upper anvil is at r st against a 200-pound die spring, and the lower anvil is movable through 0.300 inches by means of a crank mechanism. In its open position the gap between the anvils is 1.780 inches allowing a clearance of 0.100 inches for insertion of the ball.
- the lower anvil As the lower anvil is raised by the crank, it compresses the ball against the upper anvil, such compression occurring during the last 0.200 inches of stroke of the lower anvil, the ball then loading the upper anvil which in turn loads the spring.
- the equilibrium point of the upper anvil is measured by a dial micrometer if the anvil is deflected by the ball more than 0.100 inches (less deflection is simply regarded as zero compression) and the reading on the micrometer dial is referred to as the compression of the ball.
- tournament quality balls have compression ratings around 80 to 100 which means that the upper anvil was deflected a total of 0.120 to 0.100 inches.
- An example to determine PGA compression can be shown by utilizing a golf ball compression tester produced by Atti Engineering Corporation of Newark, N.J. The value obtained by this tester relates to an arbitrary value expressed by a number which may range from 0 to 100, although a value of 200 can be measured as indicated by two revolutions of the dial indicator on the apparatus.
- the value obtained defines the deflection that a golf ball undergoes when subjected to compressive loading.
- the Atti test apparatus consists of a lower movable platform and an upper movable spring-loaded anvil.
- the dial indicator is mounted such that it measures the upward movement of the springloaded anvil.
- the golf ball to be tested is placed in the lower platform, which is then raised a fixed distance.
- the upper portion of the golf ball comes in contact with and exerts a pressure on the springloaded anvil.
- the upper anvil is forced upward against the spring.
- Alternative devices have also been employed to determine compression. For example, Applicant also utilizes a modified Riehle Compression Machine originally produced by Riehle Bros.
- the Riehle compression device determines deformation in thousandths of an inch under a fixed initialized load of 200 pounds. Using such a device, a Riehle compression of 61 corresponds to a deflection under load of 0.061 inches.
- Applicant's compression values are usually measured as Riehle compression and converted to PGA compression.
- additional compression devices may also be utilized to monitor golf ball compression so long as the correlation to PGA compression is known. These devices have been designed, such as a Whitney Tester, to correlate or correspond to PGA compression through a set relationship or formula.
- “Shore D hardness” of a cover is measured generally in accordance with ASTM D-2240, except the measurements are made on the curved surface of a molded cover, rather than on a plaque. Furthermore, the Shore D hardness of the cover is measured while the cover remains over the core. When a hardness measurement is made on a dimpled cover, Shore D hardness is measured at a land area of the dimpled cover.
- the term “spherical” is used in conjunction with the shell (center). It is understood by those skilled in the art that when referring to golf balls and their components, the term “spherical” includes surfaces and shapes which may have minor insubstantial deviations from the perfect ideal geometric spherical shape. In addition the inclusion of dimples on the exterior surface of the shell, to effect its aerodynamic properties, does not detract from its "spherical” shape for the purposes therein or in the art. Further the internal surface of the shell as well as the core may likewise incorporate intentionally designed patterns and still be considered “spherical” within the scope of this invention.
- the rotational moment of inertia of a golf ball is the resistance to change in spin of the ball and is conventionally measured using an "Inertia Dynamics Moment of Inertia Measuring Instrument".
- Fig. 1 illustrates a partially broken-away view of the improved golf ball of the present invention wherein D is the diameter of the ball; C is the diameter of the core and T is the thickness of the cover.
- the present invention relates to the development of a golf ball having a low spin rate as a result of combining a relatively soft core and a hard cover.
- a lower spin rate after club impact contributes to straighter shots when the ball is mis-hit, greater efficiency in flight, and a lesser degree of energy loss on impact with the ground, adding increased roll or distance.
- the spin rate is still further decreased by up to around 500 r.p.m. or more upon being hit with a No. 9 iron traveling at a speed of 105 feet per second (fps).
- the ball even though of larger diameter, uses substantially the same size core as a standard golf ball, the difference in size is provided by the additional thickness in the cover of the ball. This larger, low spin ball produces even greater control and flight efficiency than the standard size ball embodiment of the present invention.
- the core of the present invention is relatively soft and of similar size. It has a Riehle compression of about 0.075 or more, preferably about 0.075 to about 0.115, and a relatively low PGA compression of about 40 to 85, preferably about 70- 80.
- the specially produced core compositions and resulting molded cores of the present invention are manufactured using relatively conventional techniques.
- the core compositions of the invention may be based on polybutadiene, and mixtures of polybutadiene with other elastomers.
- the base elastomer have a relatively high molecular weight.
- the broad range for the molecular weight of suitable base elastomers is from about 50,000 to about 500,000.
- a more preferred range for the molecular weight of the base elastomer is from about 100,000 to about 500,000.
- cis-polybutadiene is preferably employed, or a blend of cis-polybutadiene with other elastomers may also be utilized. Most preferably, cis-polybutadiene having a weight- average molecular weight of from about 100,000 to about 500,000 is employed.
- the high cis- polybutadiene manufactured and sold by Shell Chemical Co., Houston, Texas, under the tradename Cariflex BR-1220, and the polyisoprene available from Muehlstein, H & Co., Greenwich, Connecticut under the designation "SKI 35" are particularly well suited.
- the unsaturated carboxylic acid component of the core composition is the reaction product of the selected carboxylic acid or acids and an oxide or carbonate of a metal such as zinc, magnesium, barium, calcium, lithium, sodium, potassium, cadmium, lead, tin, and the like.
- a metal such as zinc, magnesium, barium, calcium, lithium, sodium, potassium, cadmium, lead, tin, and the like.
- the oxides of polyvalent metals such as zinc, magnesium and cadmium are used, and most preferably, the oxide is zinc oxide.
- the unsaturated carboxylic acids which find utility in the present core compositions are acrylic acid, methacrylic acid, itaconic acid, crotonic acid, sorbic acid, and the like, and mixtures thereof.
- the acid component is either acrylic or methacrylic acid.
- the carboxylic acid salt such as zinc diacrylate, is included in the core composition.
- the unsaturated carboxylic acids and metal salts thereof are generally soluble in the elastomeric base, or are readily dispersible.
- the free radical initiator included in the core composition is any known polymerization initiator (a co-crosslinking agent) which decomposes during the cure cycle.
- the term "free radical initiator” as used herein refers to a chemical which, when added to a mixture of the elastomeric blend and a metal salt of an unsaturated, carboxylic acid, promotes crosslinking of the elastomers by the metal salt of the unsaturated carboxylic acid.
- the amount of the selected initiator present is dictated only by the requirements of catalytic activity as a polymerization initiator. Suitable initiators include peroxides, persulfates, azo compounds and hydrazides. Peroxides which are readily commercially available are conveniently used in the present invention, generally in amounts of from about 0.1 to about 10.0 and preferably in amounts of from about 0.3 to about 3.0 parts by weight per each 100 parts of elastomer.
- Suitable peroxides for the purposes of the present invention are dicumyl peroxide, n-butyl 4,4'-bis (butylperoxy) valerate, 1 ,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane, di-t-butyl peroxide and 2,5-di-(t-butylperoxy)-2,5 dimethyl hexane and the like, as well as mixtures thereof. It will be understood that the total amount of initiators used will vary depending on the specific end product desired and the particular initiators employed.
- Luperco 230 or 231 XL sold by Atochem, Lucidol Division, Buffalo, N.Y., and Trigonox 17/40 or 29/40 sold by Akzo Chemie America, Chicago, Illinois.
- Luperco 230 XL and Trigonox 17/40 are comprised of n-butyl 4,4-bis (butylperoxy) valerate; and, Luperco 231 XL and Trigonox 29/40 are comprised of 1 ,1-bis(t-butylperoxy)-3,3,5- trimethyl cyclohexane.
- the one hour half life of Luperco 231 XL is about 112°C, and the one hour half life of Trigonox 29/40 is about 129 °C.
- the core compositions of the present invention may additionally contain any other suitable and compatible modifying ingredients including, but not limited to, metal oxides, fatty acids, and diisocyanates and polypropylene powder resin.
- Papi 94 a polymeric diisocyanate, commonly available from Dow Chemical Co., Midland, ML, is an optional component in the rubber compositions. It can range from about 0 to 5 parts by weight per 100 parts by weight rubber (phr) component, and acts as a moisture scavenger.
- polypropylene powder resin can be added to core composition without an increase in weight of the molded core upon curing, the addition of the polypropylene powder allows for the addition of higher specific gravity fillers, such as mineral fillers. Since the crossiinking agents utilized in the polybutadiene core compositions are expensive and/or the higher specific gravity fillers are relatively inexpensive, the addition of the polypropylene powder resin substantially lowers the cost of the golf ball cores while maintaining, or lowering, weight and compression.
- the polypropylene (C 3 H 5 ) powder suitable for use in the present invention has a specific gravity of about 0.90 g/cm 3 , a melt flow rate of about 4 to about 12 and a particle size distribution of greater than 99% through a 20 mesh screen.
- polypropylene powder resins include those sold by the Amoco Chemical Co., Chicago, Illinois, under the designations "6400 P", "7000 P” and "7200 P".
- polypropylene powder per each 100 parts of elastomer are included in the present invention.
- Various activators may also be included in the compositions of the present invention.
- zinc oxide and/or magnesium oxide are activators for the polybutadiene.
- the activator can range from about 2 to about 30 parts by weight per 100 parts by weight of the rubbers (phr) component.
- filler-reinforcement agents may be added to the composition of the present invention. Since the specific gravity of polypropylene powder is very low, and when compounded, the polypropylene powder produces a lighter molded core, when polypropylene is incorporated in the core compositions, relatively large amounts of higher gravity fillers may be added so long as the specific core weight limitations are met. Additional benefits may be obtained by the incorporation of relatively large amounts of higher specific gravity, inexpensive mineral fillers such as calcium carbonate. Such fillers as are incorporated into the core compositions should be in finely divided form, as for example, in a size generally less than about 30 mesh and preferably less than about 100 mesh U.S. standard size. The amount of additional filler included in the core composition is primarily dictated by weight restrictions and preferably is included in amounts of from about 10 to about 100 parts by weight per 100 parts rubber.
- the preferred fillers are relatively inexpensive and heavy and serve to lower the cost of the ball and to increase the weight of the ball to closely approach the U.S.G.A. weight limit of 1.620 ounces.
- Exemplary fillers include mineral fillers such as limestone, silica, mica, barytes, calcium carbonate, or clays. Limestone is ground calcium/magnesium carbonate and is used because it is an inexpensive, heavy filler.
- ground flash filler may be incorporated and is preferably 20 mesh ground up center stock from the excess flash from compression molding. It lowers the cost and may increase the hardness of the ball.
- Fatty acids or metallic salts of fatty acids may also be included in the compositions, functioning to improve moldability and processing.
- free fatty acids having from about 10 to about 40 carbon atoms, and preferably having from about 15 to about 20 carbon atoms, are used.
- suitable fatty acids are stearic acid and linoleic acids, as well as mixtures thereof.
- suitable metallic salts of fatty acids include zinc stearate.
- the fatty acid component is present in amounts of from about 1 to about 25, preferably in amounts from about 2 to about 15 parts by weight based on 100 parts rubber (elastomer).
- the core compositions include stearic acid as the fatty acid adjunct in an amount of from about 2 to about 5 parts by weight per 100 parts of rubber.
- Diisocyanates may also be optionally included in the core compositions when utilized, the diioscyanates are included in amounts of from about 0.2 to about 5.0 parts by weight based on 100 parts rubber.
- exemplary of suitable diisocyanates is 4,4'-diphenylmethane diisocyanate and other polyfunctional isocyanates know to the art.
- dialkyl tin difatty acids set forth in U.S. Patent No. 4,844,471 may also be incorporated into the polybutadiene compositions of the present invention.
- the specific types and amounts of such additives are set forth in the above identified patents, which are incorporated herein by reference.
- the core compositions of the invention are generally comprised of 100 parts by weight of a base elastomer (or rubber) selected from polybutadiene and mixtures of polybutadiene with other elastomers, 15 to 25 parts by weight of at least one metallic salt of an unsaturated carboxylic acid, and 0.1 to 10 parts by weight of a free radical initiator.
- a base elastomer or rubber
- additional suitable and compatible modifying agents such as particulate polypropylene resin, fatty acids, and secondary additives such as Pecan shell flour, ground flash (i.e. grindings from previously manufactured cores of substantially identical construction), barium sulfate, zinc oxide, etc. may be added to the core compositions to adjust the weight of the ball as necessary in order to have the finished molded ball (core, cover and coatings) to closely approach the U.S.G.A. weight limit of 1.620 ounces.
- the ingredients may be intimately mixed using, for example, two roll mills or a Banbury mixer until the composition is uniform, usually over a period of from about 5 to about 20 minutes.
- the sequence of addition of components is not critical. A preferred blending sequence is as follows.
- the elastomer, polypropylene powder resin (if desired), fillers, zinc salt, metal oxide, fatty acid, and the metallic dithiocarbamate (if desired), surfactant (if desired), and tin difatty acid (if desired), are blended for about 7 minutes in an internal mixer such as a Banbury mixer.
- an internal mixer such as a Banbury mixer.
- the initiator and diisocyanate are then added and the mixing continued until the temperature reaches about 220°F whereupon the batch is discharged onto a two roll mill, mixed for about one minute and sheeted out.
- the sheet is rolled into a "pig” and then placed in a Barwell preformer and slugs are produced.
- the slugs are then subjected to compression molding at about 320°F for about 14 minutes.
- the molded cores are cooled, the cooling effected at room temperature for about 4 hours or in cold water for about one hour.
- the molded cores are subjected to a centerless grinding operation whereby a thin layer of the molded core is removed to produce a round core having a diameter of 1.540 to 1.545 inches.
- the cores are used in the as-molded state with no grinding needed to achieve roundness.
- the mixing is desirably conducted in such a manner that the composition does not reach incipient polymerization temperatures during the blending of the various components.
- the curable component of the composition will be cured by heating the composition at elevated temperatures on the order of from about 275°F to about 350°F, preferably and usually from about 290°F to about 325°F, with molding of the composition effected simultaneously with the curing thereof.
- the composition can be formed into a core structure by any one of a variety of molding techniques, e.g. injection, compression, or transfer molding.
- the time required for heating will normally be short, generally from about 10 to about 20 minutes, depending upon the particular curing agent used.
- free radical curing agents for polymers are conversant with adjustments of cure times and temperatures required to effect optimum results with any specific free radical agent.
- the core is removed from the mold and the surface thereof, preferably treated to facilitate adhesion thereof to the covering materials.
- Surface treatment can be effected by any of the several techniques known in the art, such as corona discharge, ozone treatment, sand blasting, and the like.
- surface treatment is effected by grinding with an abrasive wheel.
- wound cores may also be incorporated in the golf balls of the present invention.
- Such wound cores would include a generally spherical center and a rubber thread layer, or windings, enclosing the outer surface of the center.
- the generally spherical center of the wound cores may be a solid center or a liquid center.
- the solid center can consist of one or more layers.
- the solid center can comprise a molded polybutadiene rubber sphere which, although smaller in size, is of similar construction to the molded cores in the two- piece molded golf balls described above.
- Suitable solid centers used in the invention are not particularly limited to, but include those made of vulcanized rubber. Such solid centers may be prepared by adding to butadiene rubber, additives such as vulcanizing agents, accelerators, activating agents, fillers, modifiers and aids and then subjecting the mixture to vulcanization and molding.
- the solid center (whether of single unitary construction or of multi-layers) generally is from 1 to 1.5 inches in diameter, preferably 1.0625 to 1.42 inches, with a weight of 15 grams to 36 grams, preferably 16.5 to 30 grams.
- a liquid center can be incorporated into the wound core of the present invention.
- the liquid center consists of a hollow spherical bag or sack of conventional vulcanized rubber filled with a liquid, paste or gel.
- a liquid include water, glycerin, sugar-water solutions, corn-syrup, saline solutions, oils, etc. and/or combinations thereof.
- pastes can be produced by adding clay, sodium sulfate, barytes, barium sulfate to a minor amount
- the specific gravity of the liquid is, in general, .6 to 3 and the specific gravity of the paste is from .6 to 3 and the gels from .6 to 3.
- the bag or sack is, in general, from .05" to .150" in thickness, preferably 0.08 to .105 inches in thickness.
- the liquid center generally is from 1 to 1.25 inches in diameter, preferably 1.0625 to 1.14 inches, with a weight of 5.5 to 25.5 grams, preferably 15 to 21 grams.
- the wound core is formed by winding conventional thread rubber around the outer periphery of the solid or liquid center.
- the s thread rubber may include, for example, those prepared by subjecting natural rubber, or a blend of natural rubber and polyisoprene rubber to vulcanization and molding. The winding process is under high tension to produce a threaded layer over the solid or liquid center. Conventional techniques may be employed in winding the thread o rubber and known compositions may be used.
- the thread rubber is not limited with respect to specific gravity, dimension and gage, it usually has a specific gravity of .9 to 1.1 , a width of .047 to .094 and a gage of .012 to .026 inches.
- the rubber thread layer has a radial thickness of .010 to 5 .315 inches and comprises a wound core having an outer diameter of 1.52 to 1.63 inches.
- the overall weight of the wound core is 33 to 44 grams, preferably 35 to 39 grams.
- the core is converted into a golf ball by providing at least one layer of covering material thereon, ranging in thickness from about 0.070 to about 0.130 inches and preferably from about 0.0675 to about 0.1275 inches.
- the cover has a Shore D hardness of 65 or greater. Its composition includes a hard, high stiffness preferably high acid ionomer s such as that sold by E.I. DuPont de Nemours & Company under the trademark "Surlyn®” and by Exxon Corporation under the trademark “Escor®” or tradename “lotek”, or blends thereof.
- the cover may comprise any ionomer which either alone or in combination with other ionomers o produces a molded cover having a Shore D hardness of at least 65.
- cover compositions which may be used are set forth in detail in s copending U.S. Serial No. 07/776,803 filed October 15, 1991 , and Serial No. 07/901 ,660 filed June 19, 1992, both incorporated herein by reference. Of course, the cover compositions are not limited in any way to those compositions set forth in said copending applications.
- the high acid ionomers suitable for use in the present o invention are ionic copolymers which are the metal, i.e., sodium, zinc, magnesium, etc., salts of the reaction product of an olefin having from about 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having from about 3 to 8 carbon atoms.
- the ionomeric resins are copolymers of ethylene and either acrylic or methacrylic acid. 5
- an additional comonomer such as an acrylate ester (i.e., iso- or n-butylacrylate, etc.) can also be included to produce a softer terpolymer.
- the carboxylic acid groups of the copolymer are partially neutralized (i.e., approximately 10-75%, preferably 30-70%) by the metal ions.
- Each of the high acid ionomer resins included in the cover compositions of the invention contains greater than about 16% by weight of a carboxylic acid, preferably from about 17% to about 25% by weight of a carboxylic acid, more preferably from about 18.5% to about 21.5 % by weight of a carboxylic acid.
- the cover composition preferably includes a high acid ionomeric resin and the scope of the patent embraces all known high acid ionomeric resins falling within the parameters set forth above, only a relatively limited number of these high acid ionomeric resins are currently available.
- the high acid ionomeric resins o available from E.I. DuPont de Nemours Company under the trademark “Surlyn®”, and the high acid ionomer resins available from Exxon Corporation under the trademark “Escor®” or tradename “lotek” are examples of available high acid ionomeric resins which may be utilized in the present invention.
- the high acid ionomeric resins available from Exxon under the designation "Escor®” and or “lotek” are somewhat similar to the high acid ionomeric resins available under the "Surlyn®” trademark.
- Escor®/lotek ionomeric resins are sodium or zinc salts of poly(ethylene acrylic acid) and the "Surlyn®” resins are zinc, 0 sodium, magnesium, etc. salts of poly(ethylene methacrylic acid), distinct differences in properties exist.
- Examples of the high acid methacrylic acid based ionomers found suitable for use in accordance with this invention include Surlyn® AD-8422 (sodium cation), Surlyn® 8162 (zinc cation), 5 Surlyn® SEP-503-1 (zinc cation), and Surlyn® SEP-503-2 (magnesium cation). According to DuPont, all of these ionomers contain from about 18.5 to about 21.5% by weight methacrylic acid.
- Surlyn® AD-8422 is currently commercially available from DuPont in a number of different grades (i.e., AD-8422-2, AD-8422-3, AD-8422-5, etc.) based upon differences in melt index. According to DuPont, Surlyn® AD-8422 offers the following general properties when compared to Surlyn® 8920 the stiffest, hardest of all on the low acid grades (referred to as "hard” ionomers in U.S. Patent No. 4,884,814):
- Surlyn® 8920 contains 15 weight percent methacrylic acid and is 59% neutralized with sodium.
- Surlyn® SEP-503-1 (zinc cation) and Surlyn® SEP-503-2 (magnesium cation) are high acid zinc and magnesium versions of the Surlyn® AD 8422 high acid ionomers.
- the Surlyn SEP-503-1 and SEP-503-2 ionomers can be defined as follows:
- Surlyn® 8162 is a zinc cation ionomer resin containing approximately 20% by weight (i.e. 18.5-21.5% weight) methacrylic acid copolymer that has been 30-70% neutralized. Surlyn® 8162 is currently commercially available from DuPont.
- high acid acrylic acid based ionomers suitable for use in the present invention include the Escor® or lotek high acid ethylene acrylic acid ionomers produced by Exxon.
- Escor® or lotek 959 is a sodium ion neutralized ethylene-acrylic acid copolymer.
- loteks 959 and 960 contain from about 19.0 to about 21.0% by weight acrylic acid with approximately 30 to about 70 percent of the acid groups neutralized with sodium and zinc ions, respectively.
- the physical properties of these high acid acrylic acid based ionomers are as follows:
- the base copolymer is made up of greater than 16% by weight of an alpha, beta-unsaturated carboxylic acid and an alpha- olefin.
- a softening comonomer can be included in the copolymer.
- the alpha-olefin has from 2 to 10 carbon atoms and is preferably ethylene
- the unsaturated carboxylic acid is a carboxylic acid having from about 3 to 8 carbons. Examples of such acids include acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, with acrylic acid being preferred.
- the softening comonomer that can be optionally included in the invention may be selected from the group consisting of vinyl esters of aliphatic carboxylic acids wherein the acids have 2 to 10 carbon atoms, vinyl ethers wherein the alkyl groups contains 1 to 10 carbon atoms, and alkyl acrylates or methacrylates wherein the alkyl group contains 1 to 10 carbon atoms.
- Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or the like.
- examples of a number of copolymers suitable for use to produce the high acid ionomers included in the present invention include, but are not limited to, high acid embodiments of an ethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer, an ethylene/itaconic acid copolymer, an ethylene/maleic acid copolymer, an ethylene/methacrylic acid/vinyl acetate copolymer, an ethylene/acrylic acid/vinyl alcohol copolymer, etc.
- the base copolymer broadly contains greater than 16% by weight unsaturated carboxylic acid, from about 30 to about 83% by weight ethylene and from 0 to about 40% by weight of a softening comonomer.
- the copolymer contains about 20% by weight unsaturated carboxylic acid and about 80% by weight ethylene. Most preferably, the copolymer contains about 20% acrylic acid with the remainder being ethylene.
- examples of the preferred high acid base copolymers which fulfill the criteria set forth above, are a series of ethylene-acrylic copolymers which are commercially available from The
- this copolymer is the more preferred grade utilized in the invention.
- the metal cation salts utilized in the invention are those salts which provide the metal cations capable of neutralizing, to various extents, the carboxylic acid groups of the high acid copolymer. These include acetate, oxide or hydroxide salts of lithium, calcium, zinc, sodium, potassium, nickel, magnesium, and manganese.
- lithium ion sources are lithium hydroxide monohydrate, lithium hydroxide, lithium oxide and lithium acetate.
- Sources for the calcium ion include calcium hydroxide, calcium acetate and calcium oxide.
- Suitable zinc ion sources are zinc acetate dihydrate and zinc acetate, a blend of zinc oxide and acetic acid.
- Examples of sodium ion sources are sodium hydroxide and sodium acetate.
- Sources for the potassium ion include potassium hydroxide and potassium acetate.
- Suitable nickel ion sources are nickel acetate, nickel oxide and nickel hydroxide.
- Sources of magnesium include magnesium oxide, magnesium hydroxide, magnesium acetate.
- Sources of manganese include manganese acetate and manganese oxide.
- the new metal cation neutralized high acid ionomer resins are produced by reacting the high acid base copolymer with various amounts of the metal cation salts above the crystalline melting point of the copolymer, such as at a temperature from about 200° F to about 500° F, preferably from about 250° F to about 350° F under high shear conditions at a pressure of from about 10 psi to 10,000 psi. Other well known blending techniques may also be used.
- the amount of metal cation salt utilized to produce the new metal cation neutralized high acid based ionomer resins is the quantity which provides a sufficient amount of the metal cations to neutralize the desired percentage of the carboxylic acid groups in the high acid copolymer.
- the extent of neutralization is generally from about 10% to about 90%.
- Control for Formulations 23-26 is 50/50 lotek 8000/7030
- the new metal cation neutralized high acid ionomer resins exhibit enhanced hardness, modulus and resilience characteristics. These are properties that are particularly desirable in a number of thermoplastic fields, including the field golf ball manufacturing.
- the new acrylic acid based high acid ionomers extend the range of hardness beyond that previously obtainable while maintaining the beneficial properties (i.e. durability, click, feel, etc.) of the softer low acid ionomer covered balls, such as balls produced utilizing the low acid ionomers disclosed in U.S. Patent Nos. 4,884,814 and 4,911 ,451 , and the recently produced high acid blends disclosed in U.S. Application Serial No. 776,803.
- ionomer resins may be used in the cover compositions, such as low acid ionomer resins, so long as the molded cover produces a Shore D hardness of 65 or more. Properties of some of these low acid ionomer resins are provided in the following table:
- compatible additive mate ⁇ als may also be added to produce the cover compositions of the present invention.
- additive materials include dyes (for example, Ultramarine Blue sold by Whitaker, Clark, and Daniels of South Painsfield, NJ), and pigments, i.e. white pigments such as titanium dioxide (for example Unitane 0-110) zinc oxide, and zinc sulfate, as well as fluorescent pigments.
- dyes for example, Ultramarine Blue sold by Whitaker, Clark, and Daniels of South Painsfield, NJ
- pigments i.e. white pigments such as titanium dioxide (for example Unitane 0-110) zinc oxide, and zinc sulfate, as well as fluorescent pigments.
- white pigments such as titanium dioxide (for example Unitane 0-110) zinc oxide, and zinc sulfate, as well as fluorescent pigments.
- the amount of pigment and/or dye used in conjunction with the polymeric cover composition depends on the particular base ionomer mixture utilized and the particular pigment and/or dye utilized.
- the concentration of the pigment in the polymeric cover composition can be from about 1% to about 10% as based on the weight of the base ionomer mixture. A more preferred range is from about 1% to about 5% as based on the weight of the base ionomer mixture. The most preferred range is from about 1% to about 3% as based on the weight of the base ionomer mixture.
- the most preferred pigment for use in accordance with this invention is titanium dioxide.
- cover compositions of this invention may also contain softening agents, such as plasticizers, 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.
- optical brighteners such as those disclosed in U.S. Patent No. 4,679,795, may also be included in the cover composition of the invention.
- suitable optical brighteners which can be used in accordance with this invention are Uvitex OB as sold by the Ciba-Geigy Chemical Company, Ardsley, N.Y.
- Uvitex OB is thought to be 2,5-Bis(5-tert-butyl-2-benzoxazoly)thiophene.
- Examples of other optical brighteners suitable for use in accordance with this invention are as follows: Leucopure EGM as sold by Sandoz, East Hanover, N.J. 07936.
- Leucopure EGM is thought to be 7-(2n- naphthol(1 ,2-d)-triazol-2yl)-3phenyl-coumarin.
- Phorwhite K-20G2 is sold by Mobay Chemical Corporation, P.O. Box 385, Union Metro Park, Union, N.J. 07083, and is thought to be a pyrazoline derivative, Eastobrite OB-1 as sold by Eastman Chemical Products, Inc. Kingsport, Tenn., is thought to be 4,4-Bis(-benzoxaczoly) stilbene.
- the above- mentioned Uvitex and Eastobrite OB-1 are preferred optical brighteners for use in accordance with this invention.
- the percentage of optical brighteners utilized must not be excessive in order to prevent the optical brightener from functioning as a pigment or dye in its own right.
- the percentage of optical brighteners which can be used in accordance with this invention is from about 0.01 % to about 0.5% as based on the weight of the polymer used as a cover stock. A more preferred range is from about 0.05% to about 0.25% with the most preferred range from about 0.10% to about .020% depending on the optical properties of the particular optical brightener used and the polymeric environment in which it is a part.
- the additives are admixed with a ionomer to be used in the cover composition to provide a masterbatch (M.B.) of desired concentration and an amount of the masterbatch sufficient to provide the desired amounts of additive is then admixed with the copolymer blends.
- M.B. masterbatch
- cover compositions when processed according to the parameters set forth below and combined with soft cores at thicknesses defined herein to produce covers having a Shore D hardness of 65, provide golf balls with reduced spin ratio. It is noted, however, that the high acid ionomer resins provide for more significant reduction in spin rate than that observed for the low acid ionomer resins.
- the cover compositions and balls of the present invention may be produced according to conventional melt blending procedures.
- the ionomeric resins are blended along with the masterbatch containing the desired additives in a Banbury type mixer, two-roll mill, or extruded prior to molding.
- the blended composition is then formed into slabs or pellets, etc. and maintained in such a state until molding is desired.
- a simple dry blend of the pelletized or granulated resins and color masterbatch may be prepared and fed directly into the injection molding machine where homogenization occurs in the mixing section of the barrel prior to injection into the mold.
- further additives such as an inorganic filler, etc., may be added and uniformly mixed before initiation of the molding process.
- golf balls of the present invention can be produced by molding processes currently well known in the golf ball art. Specifically, the golf balls can be produced by injection molding or compression molding the novel cover compositions about the soft cores to produce a golf ball having a diameter of about 1.680 inches or greater and weighing about 1.620 ounces. In an additional embodiment of the invention, larger molds are utilized to produce the thicker covered oversized golf balls. As indicated, the golf balls of the present invention can be produced by forming covers consisting of the compositions of the invention around the softer cores by conventional molding processes.
- the cover composition in compression molding, is formed via injection at about 380°F to about 450°F into smooth surfaced hemispherical shells which are then positioned around the core in a 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.
- the golf 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 of from 50°F to about 100°F. After molding the golf balls produced may undergo various further finishing steps such as buffing, painting, and marking as disclosed in U.S. Patent No.
- Example 1 Using the ingredients tabled below, golf ball cores having a finished diameter of about 1.540 to about 1.545 inches were produced by compression molding and subsequent removal of a surface layer by grinding. Each core was formulated using 100 parts elastomer (rubber). In the formulations, the amounts of remaining ingredients are expressed in parts by weight, and the weight, degrees of coefficient of restitution and compression (both Riehle and PGA) achieved are set forth below. The data for these examples are the averages for twelve cores which were produced for each example. The properties of the molded cores produced from each formulation were measured according to the parameters set forth above.
- 'BR-l-t-iO is a polybutadiene manufactured and sold by Shell Chemical Co., Houston, Texas.
- 2 6400 P. is a powdered polypropylene available from Amco Chemical Co., Chicago, Illinois.
- ⁇ Trig 17/40 is a peroxide manufactured and sold by Akzo Chemie, Chicago, Illinois (one hour half life is at 129°C).
- Vapi 94 is a polymeric diisocynanate available from Dow Chemical Co., Midland, Michigan.
- core formulations A and B produce softer cores.
- Formulation A is appropriate for a molded ball having an overall diameter of about 1.720 inches (i.e., 1.717"). It has less filler, hence a lower specific gravity, than formulation B which is appropriate for a smaller ball, one having a diameter of about 1.680 inches.
- Formulations C and D are for conventional harder cores. Formulation C is slightly heavier and used for a ball having a diameter of about 1.680 inches. Formulation D is used for producing a ball having a diameter of about 1.720 inches (1.717").
- EXAMPLE 2 Cover compositions were produced by blending the following constituents:
- 'lotek 7520 is a relatively soft, low acid, ionomer resin produced by Exxon.
- 2 MB 74.9 wt-% lotek 7030, 23.8 wt-% Ti0 2 , 0.01 wt-% Unitex OB, 0.002 wt-% ultra marine blue and 300 ppm Santonox R.
- formulation 2 is the hardest. It is comprised of two hard, high acid ionomer resins, lotek 959 has an acid content of about 19% to 21% and lotek 960 also has an acid content of about 19 to 21 %.
- Formulation 3 provides the softest of the three cover formulations and is substantially similar to the formulation used in the TOP-FLITE TOUR EDITION 90 golf ball. Formulation 3 is comprised of lotek 8000 and lotek 7030, both hard, low acid ionomers, and lotek 7520, a soft, low-acid ionomer, in the amounts set forth above.
- Formulation 1 provides intermediate hardness, and is essentially the same formulation used in the TOP FLITE XL II ball (see U.S. Patent No. 4,911 ,481). EXAMPLE 3
- Example 2 The cover formulations set forth in Example 2 were injection molded at about 400°F around cores of formulations A-D in
- Example 1 in a manner to permit uniform injection of the selected cover s composition over each core.
- Each of the cores had an identical finished diameter of about 1.541-1.543 inches to produce golf balls of approximately 1.720 (1.717) inches (cores A and D) or about 1.680 inches (cores B and C) in diameter.
- the cover thickness varied between about 0.069 and about 0.088 inches. All materials were o molded under essentially identical conditions. The properties of Riehle compression, PGA compression, coefficient of restitution (C.O.R.), barrel durability (100 blows), cover hardness and spin rate were determined. The results are set forth in Table 3 below.
- the data for each example represents the average data s for one dozen balls produced according to the desired manner.
- the properties were measured according to the following parameters: Coefficient of restitution (C.O.R.) and Shore D hardness was measured as indicated above.
- the barrel test or barrel durability test involves o firing golf balls at 135 ft./sec. (at 72°F), into a 5-sided container, the walls of which are steel plates that have grooves milled into them to simulate a golf club face.
- the balls are subjected to 100 to 300 blows and are inspected at regular intervals for breakage (i.e. any signs of cover 5 cracking or delamination).
- NB no breakage.
- the spin rate of the golf ball was measured by striking the resulting golf balls with a 9-iron wherein the club-head speed is about 105 feet per second and the ball is launched at an angle of 26 to 34 degrees with an initial velocity of about 110-115 feet per second.
- the spin rate was measured by observing the rotation of the ball in flight using stop action Strobe photography.
- Tour Edition 90 1.68 56 104 .802 NB 87/56 9621
- Molded ball spin test results show that notwithstanding differences in ball size, the combination of a soft core (cores A and B) with a hard cover (cover formulations 1 and 2) minimizes spin rate. Even in the instance where harder cores are used (cores C and D) the s golf ball with the hardest cover formulation tested (formulation 2) provides for golf balls having the lowest spin rate.
- the balls having the larger diameter (A, 1-3) are lower in spin than balls B,1-3, respectively.
- the C.O.R. and compression are controlled s mainly by the core formulation, with a hard fast core giving a harder, faster ball.
- the thicker cover As ball diameter increases upon increasing the cover thickness (core diameter remains the same), the thicker cover (0.0888 versus 0.0690 inches) provides for significant C.O.R. pick-up from center to ball. Further, the increased cover thickness plays a role in 0 added spin reduction observed for the larger balls.
- EXAMPLE 4 A series of wound three-piece golf balls (with both solid and liquid centers) were produced having low spin characteristics. Specifically, these balls were produced having the following properties:
- a 1.4 inches in diameter solid center was produced utilizing the following ingredients:
- Center Size 1.4 inches in diameter
- Center Weight 29.40 grams
- the solid centers were covered by windings comprising of .024" thick X 1/16" wide, P/N 1511 , elastomeric thread available from Fulflex Inc., Middletown, Rhode Island.
- the wound core exhibited the following characteristics:
- the wound cores were covered with a cover composition having the following formulation:
- Dimple Pattern modified tetrakaidecahedron (D335C - Hogan Pattern)
- Liquid centers (1 1 / ⁇ " diameter) from Abbott Labs, Chicago, Illinois, P/N 65 W 155L were utilized having the
- Liquid Composition water/glycerin based Abbott o proprietary formulation
- Bag Composition sulphur cured rubber compound (Abbott proprietary formulation
- the wound liquid centers had the following general properties:
- the wound cores were covered with the same
- the covered balls had the following characteristic:
- Dimple Pattern modified tetrakaidecahedron
- the solid center wound three-piece golf balls ie. Top-
- Flite® Dot 4SS97 produced substantially less spin than the Top Flite® XL golf ball, a solid centered two-piece golf ball. Similarly, the liquid
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2000590738A JP2002533178A (en) | 1998-12-23 | 1999-08-04 | Low spin golf ball |
CA002356180A CA2356180A1 (en) | 1998-12-23 | 1999-08-04 | Low spin golf ball |
GB0116680A GB2361435A (en) | 1998-12-23 | 1999-08-04 | Low spin golf ball |
AU55494/99A AU758040B2 (en) | 1998-12-23 | 1999-08-04 | Low spin golf ball |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US22038898A | 1998-12-23 | 1998-12-23 | |
US09/220,388 | 1998-12-23 |
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WO2000038790A1 true WO2000038790A1 (en) | 2000-07-06 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1999/017861 WO2000038790A1 (en) | 1998-12-23 | 1999-08-04 | Low spin golf ball |
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JP (1) | JP2002533178A (en) |
AU (1) | AU758040B2 (en) |
CA (1) | CA2356180A1 (en) |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5368304A (en) * | 1993-04-28 | 1994-11-29 | Lisco, Inc. | Low spin golf ball |
US5846141A (en) * | 1997-04-23 | 1998-12-08 | Acushnet Company | Golf ball |
Family Cites Families (1)
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JP2915108B2 (en) * | 1990-08-10 | 1999-07-05 | 住友ゴム工業株式会社 | Golf ball |
-
1999
- 1999-08-04 WO PCT/US1999/017861 patent/WO2000038790A1/en active IP Right Grant
- 1999-08-04 JP JP2000590738A patent/JP2002533178A/en active Pending
- 1999-08-04 GB GB0116680A patent/GB2361435A/en not_active Withdrawn
- 1999-08-04 CA CA002356180A patent/CA2356180A1/en not_active Abandoned
- 1999-08-04 AU AU55494/99A patent/AU758040B2/en not_active Ceased
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5368304A (en) * | 1993-04-28 | 1994-11-29 | Lisco, Inc. | Low spin golf ball |
US5846141A (en) * | 1997-04-23 | 1998-12-08 | Acushnet Company | Golf ball |
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GB2361435A (en) | 2001-10-24 |
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