Nothing Special   »   [go: up one dir, main page]

US20030004274A1 - Golf ball cover containing a blend of ionomer and plastomer, and method of making same - Google Patents

Golf ball cover containing a blend of ionomer and plastomer, and method of making same Download PDF

Info

Publication number
US20030004274A1
US20030004274A1 US10/178,267 US17826702A US2003004274A1 US 20030004274 A1 US20030004274 A1 US 20030004274A1 US 17826702 A US17826702 A US 17826702A US 2003004274 A1 US2003004274 A1 US 2003004274A1
Authority
US
United States
Prior art keywords
golf ball
cover
core
ionomer
ethylene
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.)
Abandoned
Application number
US10/178,267
Inventor
Michael Sullivan
Edward Kaltenbacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topgolf Callaway Brands Corp
Original Assignee
Top Flite Golf Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Top Flite Golf Co filed Critical Top Flite Golf Co
Priority to US10/178,267 priority Critical patent/US20030004274A1/en
Assigned to BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT reassignment BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT SECURITY AGREEMENT Assignors: SPALDING SPORTS WORLDWIDE, INC.
Publication of US20030004274A1 publication Critical patent/US20030004274A1/en
Assigned to THE TOP-FLITE GOLF COMPANY reassignment THE TOP-FLITE GOLF COMPANY CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SPALDING SPORTS WORLDWIDE, INC.
Assigned to CALLAWAY GOLF COMPANY reassignment CALLAWAY GOLF COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TOP-FLITE GOLF COMPANY, THE
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/12Special coverings, i.e. outer layer material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • A63B37/0023Covers
    • A63B37/0029Physical properties
    • A63B37/0034Deflection or compression
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003Golf balls
    • A63B37/0023Covers
    • A63B37/0029Physical properties
    • A63B37/0036Melt flow rate [MFR]
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
    • C08L23/0876Neutralised polymers, i.e. ionomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates generally to golf balls, and more particularly to golf balls having covers containing blends of ionomer and plastomer.
  • Ionomers are partial metal salts of acid containing polymers, such as ethylene based polymers. These include the partial metal salts of copolymers of ethylene and an ethylene-copolymerizable unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, or maleic acid. Metal ions, such as sodium, zinc, lithium, magnesium, and the like are used to neutralize a portion of the acidic group in the copolymer resulting in a thermoplastically reversible crosslinked polymer exhibiting enhanced properties, i.e. durability, etc., for golf ball cover construction as compared to balata-covered balls.
  • metal ions such as sodium, zinc, lithium, magnesium, and the like are used to neutralize a portion of the acidic group in the copolymer resulting in a thermoplastically reversible crosslinked polymer exhibiting enhanced properties, i.e. durability, etc., for golf ball cover construction as compared to balata-covered balls.
  • U.S. Pat. No. 4,567,219 is directed to a cover composition for golf balls with improved impact resistance.
  • the cover comprises a blend of ionomer resin and 1-15 parts by weight of a linear, low-density polyethylene per 100 parts by weight of the ionomer resin.
  • U.S. Pat. No. 5,019,320 discloses a golf ball composition comprising an ionomer resin and a low molecular weight polyethylene wax. This blend also is alleged to provide improved impact resistance.
  • the polyethylene wax is present in a quantity of 0.1 to 6 parts by weight based upon 100 parts by weight of ionomer resin. It would be useful to develop a golf ball cover containing a blend of an ionomer and a non-ionic or non-ionizable polymer in which substantial quantities of the non-ionic and/or non-ionizable polymers can be used while achieving playability properties comparable to those which are obtained using known ionomeric golf ball cover materials.
  • An object of the invention is to provide a golf ball having the playability properties of an ionomeric covered ball while containing reduced quantities of ionomer
  • Another object of the invention is to provide a golf ball having a durable cover.
  • Yet another object of the invention is to provide a golf ball which can be produced in an efficient and economical manner.
  • a further object of the invention is to provide a method for making a golf ball having the characteristics described above.
  • the invention in a preferred form is a golf ball having a core and one or more cover layers, wherein the cover layer contains a blend of ionomer and plastomer.
  • the plastomer is comprised of catalytically polymerized, random copolymers of ethylene and one or more olefin comonomers characterized by a narrow or controlled composition distribution.
  • the plastomer preferably has a dispersion index (M W /M M ), i.e. the ratio of weight average molecular weight to number average molecular weight, of about 1.5 to 4.
  • the olefin comonomer or comonomers are present in amounts of about 10-35 wt % based upon the overall weight of the plastomer.
  • the cover layer contains 10-90, and preferably 20-60, parts of plastomer based upon 100 parts by weight of ionomer.
  • the golf ball has a cut resistance of at least 3 and a Shore D hardness in the range of 40-80.
  • Another preferred form of the invention is a method of making a golf ball comprising the steps of (1) obtaining a core and (2) forming a cover over the core, the cover comprising a blend of ionomer and plastomer.
  • the invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others and the article possessing the features, properties, and the relation of elements exemplified in the following detailed disclosure.
  • the golf balls of the invention have covers which comprise blends of ionomers and non-ionic and/or non-ionizable olefin copolymers which have a uniform, narrow molecular weight, a high comonomer content, and an even distribution of plastomer.
  • the dispersion index of the plastomers generally is about 1.5-4, preferably 1.5-3.5 and more preferably 1.5-2.4.
  • the density is typically in the range of 0.85-0.93 g/cc if unfoamed and 0.10-0.90 g/cc if foamed.
  • the comonomer content typically is in the range of 10-35%, and preferably 15-30%.
  • the melt index (MI) of the plastomer generally is less than 30 with the lower melt index materials providing blends with better low temperature impact. Accordingly a melt index less than about 20 is typical with a melt index of less than 10 being preferred and one of less than 5 being most preferred.
  • the composition distribution breadth index generally is greater than 30%, preferably is at least 45%, and more preferably is at least 50%.
  • the golf balls also include a curing agent for the plastomer.
  • copolymer includes olefin copolymers made from ethylene and one or other olefin monomers.
  • olefin monomers include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl pentene-1, 1,4-hexadiene, norbornene, norbornadiene, vinyl norbornene, ethylidene norbornene, etc.
  • the compositions of the invention further may include additives and fillers as well as a co-agent that can react with the curing agent to aid in crosslinking the plastomer and/or ionomer or to improve processability.
  • Co-agents which have been used for that purpose include triallyl cyanurates, ethylene glycol di(meth)acrylate, tri(meth)acrylates, divinyl benzene and other multifunctional chemicals.
  • the “composition distribution breadth index” is defined as the weight percent of the plastomer molecules which have a comonomer content between 50 percent and 125 percent of the median comonomer content (on a mole basis) of the sample.
  • CDBI composition distribution breadth index
  • the plastomers employed are polyolefin copolymers developed using metallocene single-site catalyst technology.
  • Polyethylene plastomers generally have better impact resistance than polyethylenes made with Ziegler-Natta catalysts. Plastomers exhibit both thermoplastic and elastomeric characteristics.
  • plastomers contain up to about 35 wt % comonomer. Plastomers include but are not limited to ethylene-butene copolymers, ethylene-octene copolymers, ethylene-hexene copolymers, and ethylene-hexene-butene terpolymers, as well as mixtures thereof.
  • the golf ball covers of the invention contain a blend of plastomer and ionomer in a ratio of 10:90 to 90:10, and more preferably 20:80 to 50:50. It has been found that the golf ball cover properties of high impact resistance, good durability and playability are particularly favorable when the ratio of plastomer:ionomer is in the range of 10:90 to 50:50.
  • Other additives such as coloring agents, optical brighteners, processing aids and fillers typically are added in an amount of up to about 10 parts by weight based upon 100 parts by weight of the plastomer-ionomer blend.
  • the plastomers employed in the invention preferably are formed by a single site metallocene catalyst such as those disclosed in EP 29368, U.S. Pat. No. 4,752,597, U.S. Pat. No. 4,808,561, and U.S. Pat. No. 4,937,299, the teachings of which are incorporated herein by reference. Blends of plastomers can be used.
  • plastomers can be produced by solution, slurry and gas phase accesses but the preferred materials are produced by metallocene catalysis using a high pressure process by polymerizing ethylene in combination with other olefin monomers, such as butene-1, hexene-1, octene-1 and 4-methyl-1-pentene in the presence of catalyst system comprising a cyclopentadienyl-transition metal compound and an alumoxane.
  • Plastomers found especially useful in the invention are those sold by Exxon Chemical under the trademark “EXACT” and include linear ethylene-butene copolymers such as EXACT 3024 having a density of about 0.905 g/cc (ASTM D-1505) and a melt index of about 4.5 g/10 min. (ASTM D-2839); EXACT 3025 having a density of about 0.910 g/cc (ASTM D-1505) and a melt index of about 1.2 g/10 min. (ASTM D-2839); EXACT 3027 having a density of about 0.900 g/cc (ASTM D-1505) and a melt index of about 3.5 g/10 min. (ASTM D-2839).
  • EXACT 3024 having a density of about 0.905 g/cc (ASTM D-1505) and a melt index of about 4.5 g/10 min.
  • EXACT 3025 having a density of about 0.910 g/cc (ASTM D-1505)
  • EXACT 3031 having a density of about 0.900 g/cc (ASTM D-1505) and a melt index of about 3.5 g/10 min. (ASTM D-2839), as well as EXACT 4049, which is an ethylene-butene copolymer having a density of about 0.873 g/cc (ASTM D-1505) and a melt index of about 4.5 g/10 min. (ASTM D-2839).
  • All of the above EXACT series plastomers are available from EXXON Chemical Co.
  • EXACT plastomers typically have a dispersion index (M w /M n where M w is weight average molecular weight and M n is number average molecular weight) of about 1.5 to 4.0, preferably 1.5-2.4, a density of about 0.86 to about 0.93 g/cc, preferably about 0.87 g/cc to about 0.91 g/cc, a melting point of about 140-220° F., and a melt index (MI) above about 0.5 g/10 mins, preferably about 1-10 g/10 mins as determined by ASTM D-1238, condition E.
  • MI melt index
  • Plastomers which may be employed in the invention include copolymers of ethylene and at least one C 3 -C 20 ⁇ -olefin, preferably a C 4 -C 8 ⁇ -olefin present in an amount of about 5 to about 32 wt %, preferably about 7 to about 22 wt %, more preferably about 9-18 wt %. These plastomers are believed to have a composition distribution breadth index of about 45% or more.
  • Plastomers such as those sold by Dow Chemical Co. under the trade name ENGAGE also may be employed in the invention. These plastomers are believed to be produced in accordance with U.S. Pat. No. 5,272,236, the teachings of which are incorporated herein by reference.
  • These plastomers are substantially linear polymers having a density of about 0.85 g/cc to about 0.93 g/cc measured in accordance with ASTM D-792, a melt index (MI) of less than 30 g/10 minutes, a melt flow ratio (I 10 /I 2 ) of about 7 to about 20, where I 10 is measured in accordance with ASTM D-1238 (190/10) and I 2 is measured in accordance with ASTM D-1238 (190/2.16), and a dispersion index M w /M n which preferably is less than 5, and more preferably is less than about 3.5 and most preferably is from about 1.5 to about 2.5.
  • MI melt index
  • I 10 /I 2 melt flow ratio
  • M w /M n which preferably is less than 5, and more preferably is less than about 3.5 and most preferably is from about 1.5 to about 2.5.
  • These plastomers include homopolymers of C 2 -C 20 olefins such as ethylene, propylene, 4-methyl-1-pentene, and the like, or they can be interpolymers of ethylene with at least one C 3 -C 20 ⁇ -olefin and/or C 2 -C 20 acetylenically unsaturated monomer and/or C 4 -C 18 diolefins.
  • These plastomers have a polymer backbone that is either unsubstituted or substituted with up to 3 long chain branches/1000 carbons.
  • long chain branching means a chain length of at least about 6 carbons, above which the length cannot be distinguished using 13 C nuclear magnetic resonance spectroscopy.
  • the preferred ENGAGE plastomers are characterized by a saturated ethylene-octene backbone and a narrow dispersion index M w /M n of about 2.
  • the fillers include, but are not limited to, clay, talc, asbestos, graphite, glass, mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicates, diatomaceous earth, carbonates such as calcium carbonate, magnesium carbonate and the like, metals such as titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt and beryllium, and alloys of the above metals, metal oxides such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide and the like, particulate synthetic plastic such as high molecular weight polyethylene, polystyrene, polyethylene ionomer resins and the like, particulate carbonaceous materials such as carbon black, natural bitumen and the like, as well as cotton flock, cellulose flock, and leather fiber.
  • the fillers include, but are not limited to, clay, talc, asbestos, graphite
  • the dispersion index M w /M n of plastomers made in accordance with U.S. Pat. No. 5,272,236 most preferably is about 2.0.
  • Non-limiting examples of these plastomers include ENGAGE CL 8001 having a density of about 0.868 g/cc, a melt index of about 0.5 g/10 mins, and a Shore A hardness of about 75; ENGAGE CL 8002 having a density of about 0.87 g/cc, a melt index of about 1 gms/10 min, Shore A hardness of about 75; ENGAGE CL 8003 having a density of about 0.885 g/cc, melt index of about 1.0 gms/10 min, and a Shore A hardness of about 86; ENGAGE EG 8100 having a density of about 0.87 g/cc, a melt index of about 1 gms/10 min., and a Shore A hardness of about 87; ENGAGE 8150 having a density of about 0.868 g
  • the ionomers which are blended with plastomer preferably are various commercially available ionomers sold under the trade name lotek, such as lotek 8000, lotek 8020, lotek 8030 or lotek 7000, lotek 7010, lotek 7020 or lotek 7030. Blends of ionomers can be used, however hard ionomers are preferred.
  • Coloring pigments and optical brighteners also may be included in the compositions of the invention.
  • Useful coloring pigments include, for example, titanium dioxide, the presence of which simplifies the surface painting operation of the finished ball. In some cases, coloring pigments eliminate the need for painting, such as, for example, where the ball is intended for use on driving ranges.
  • the golf balls of the invention have a coefficient of restitution of at least 0.650, and more preferably at least 0.700, a PGA compression of about 60-110 and preferably 80-90, a ball size of 1.68′′-1.75′′, and a ball weight of 45.93 grams or less.
  • a solid, liquid or wound golf ball center is obtained.
  • the center optionally may be covered with one or more non-plastomer inner cover layers prior to application of the plastomer cover layer or layers.
  • the center can be surface treated to facilitate adhesion thereof to a cover composition.
  • Surface treatment can be performed by techniques known in the art, such as corona discharge, ozone treatment, sand blasting, grinding and the like.
  • Non-limiting examples of useful non-plastomer cover compositions include blends of ethylene-acrylic acid or ethylene-methacrylic acid, as well as copolymers neutralized with mono-or divalent metals such as sodium, potassium, lithium, calcium, zinc or magnesium. Such compositions are shown in U.S.
  • the plastomer cover layer or layers are then formed over the core using a conventional molding technique, such as compression molding or injection molding.
  • the golf ball is finished by applying an indicia and a thin top coat with or without the use of a primer coat.
  • the plastomer and ionomer typically are subject to intensive mixing such as in a Banbury mixer, two roll mill, or the like.
  • intensive mixing such as in a Banbury mixer, two roll mill, or the like.
  • the plastomer cover is made by compression molding, the golf ball center is placed between two half-shells and the ball is molded for about 1-3 minutes at 200-300° F. and 100 p.s.i. Subsequently, the molded ball is cooled for about 10 minutes.
  • the cover material is heated to 300-400° F. and injection molded into a cold mold where it is maintained for about 20-60 seconds.
  • Coefficient of restitution is measured by firing a golf ball from an air cannon at about 125 feet per second against a steel plate positioned 12 feet from the muzzle of the cannon. The rebound velocity then is measured. The rebound velocity is divided by the initial velocity of 125 feet per second to give the COR
  • Riehle compression is a measurement of the deformation of a golf ball in inches under a load. Riehle compression can be converted to PGA compression by subtracting Riehle compression values from 160.
  • the “Guillotine Cut Test” employed to measure cut resistance is performed by holding an unfinished ball firmly in a cavity to expose the top half of the ball.
  • a guillotine blade weighing 5 pounds and having inner and outer blade edge angles of 90° and 60° relative to the horizontal, respectively, and a blunt cutting edge of three sixty-fourths inch radius which is designed to simulate the leading edge of an iron is dropped from a height of three feet to strike the ball at a point one-half inch off the top center point.
  • the guillotine blade is guided during the drop by means of a substantially friction-free vertical track.
  • the test can be repeated on the same or on different sections of the ball.
  • Ball failure is defined as permanent damage evidenced by a crack or by removal of a segment from the ball surface.
  • a rating of 1 is excellent and a rating of 4 is poor.
  • the cut-off for a commercially acceptable ball is a rating of 3.
  • a number of golf ball cores were formed primarily from polybutadiene, zinc diacrylate, and free radical initiator having a weight of 36.8 grams, a Riehle compression of 81 (PGA compression of 79), and a coefficient of restitution (COR) of 0.786.
  • the cores had a diameter of 1.55 inches.
  • About 12 of the cores were covered with each of the cover formulation shown below on Table 1.
  • One set of controls was covered with the 1995 Top Flite Z balata cover formulation.
  • the remaining cores were covered with one of four different cover formulations comprising an ionomer-plastomer blend.
  • the covers had a thickness of 0.067 inches. Properties of the molded balls were measured, and are also shown on Table 1 below. All of the cover formulations were mixed in an internal Banbury®-type mixer at an elevated temperature.
  • Example 3 had a coefficient of restitution 10 points higher than control Example C-1 with a Shore D hardness comparable to that of control Example C-1.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed herein is a golf ball having a core and a cover comprising a blend of ionomer and plastomers. The golf ball has an impact resistance and cut resistance comparable to a ball having a non-plastomer cover and containing higher quantities of ionomer.

Description

    FIELD OF THE INVENTION
  • The present invention relates generally to golf balls, and more particularly to golf balls having covers containing blends of ionomer and plastomer. [0001]
  • BACKGROUND OF THE INVENTION
  • Traditional golf ball covers were comprised of balata or blends of balata with elastomeric or plastic materials. Balata covered balls provide an experienced golfer with the ability to apply a spin to control the ball in flight. Moreover, the soft balata covers produce a soft “feel” to the low handicap player. However, despite the benefits of balata, balata-covered golf balls are easily cut and/or damaged if mis-hit; thus, balata and its synthetic substitutes, trans-polybutadiene and trans-polyisoprene have been essentially replaced by covers made of ionomers. [0002]
  • Ionomers are partial metal salts of acid containing polymers, such as ethylene based polymers. These include the partial metal salts of copolymers of ethylene and an ethylene-copolymerizable unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, or maleic acid. Metal ions, such as sodium, zinc, lithium, magnesium, and the like are used to neutralize a portion of the acidic group in the copolymer resulting in a thermoplastically reversible crosslinked polymer exhibiting enhanced properties, i.e. durability, etc., for golf ball cover construction as compared to balata-covered balls. [0003]
  • Several attempts have been made to match or improve the performance of an ionomer golf ball by adding non-ionic and non-ionizable polymers thereto. For example, U.S. Pat. No. 4,567,219 is directed to a cover composition for golf balls with improved impact resistance. The cover comprises a blend of ionomer resin and 1-15 parts by weight of a linear, low-density polyethylene per 100 parts by weight of the ionomer resin. U.S. Pat. No. 5,019,320 discloses a golf ball composition comprising an ionomer resin and a low molecular weight polyethylene wax. This blend also is alleged to provide improved impact resistance. The polyethylene wax is present in a quantity of 0.1 to 6 parts by weight based upon 100 parts by weight of ionomer resin. It would be useful to develop a golf ball cover containing a blend of an ionomer and a non-ionic or non-ionizable polymer in which substantial quantities of the non-ionic and/or non-ionizable polymers can be used while achieving playability properties comparable to those which are obtained using known ionomeric golf ball cover materials. [0004]
  • SUMMARY OF THE INVENTION
  • An object of the invention is to provide a golf ball having the playability properties of an ionomeric covered ball while containing reduced quantities of ionomer, [0005]
  • Another object of the invention is to provide a golf ball having a durable cover. [0006]
  • Yet another object of the invention is to provide a golf ball which can be produced in an efficient and economical manner. [0007]
  • A further object of the invention is to provide a method for making a golf ball having the characteristics described above. [0008]
  • Other objects will be in part obvious and in part pointed out more in detail hereafter. [0009]
  • The invention in a preferred form is a golf ball having a core and one or more cover layers, wherein the cover layer contains a blend of ionomer and plastomer. The plastomer is comprised of catalytically polymerized, random copolymers of ethylene and one or more olefin comonomers characterized by a narrow or controlled composition distribution. The plastomer preferably has a dispersion index (M[0010] W/MM), i.e. the ratio of weight average molecular weight to number average molecular weight, of about 1.5 to 4. The olefin comonomer or comonomers are present in amounts of about 10-35 wt % based upon the overall weight of the plastomer.
  • In a particularly preferred form of the invention, the cover layer contains 10-90, and preferably 20-60, parts of plastomer based upon 100 parts by weight of ionomer. The golf ball has a cut resistance of at least 3 and a Shore D hardness in the range of 40-80. [0011]
  • Another preferred form of the invention is a method of making a golf ball comprising the steps of (1) obtaining a core and (2) forming a cover over the core, the cover comprising a blend of ionomer and plastomer. [0012]
  • The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others and the article possessing the features, properties, and the relation of elements exemplified in the following detailed disclosure. [0013]
  • DETAILED DESCRIPTION OF THE INVENTION
  • The golf balls of the invention have covers which comprise blends of ionomers and non-ionic and/or non-ionizable olefin copolymers which have a uniform, narrow molecular weight, a high comonomer content, and an even distribution of plastomer. The dispersion index of the plastomers generally is about 1.5-4, preferably 1.5-3.5 and more preferably 1.5-2.4. The density is typically in the range of 0.85-0.93 g/cc if unfoamed and 0.10-0.90 g/cc if foamed. The comonomer content typically is in the range of 10-35%, and preferably 15-30%. The melt index (MI) of the plastomer generally is less than 30 with the lower melt index materials providing blends with better low temperature impact. Accordingly a melt index less than about 20 is typical with a melt index of less than 10 being preferred and one of less than 5 being most preferred. The composition distribution breadth index generally is greater than 30%, preferably is at least 45%, and more preferably is at least 50%. Preferably the golf balls also include a curing agent for the plastomer. [0014]
  • The term “copolymer” includes olefin copolymers made from ethylene and one or other olefin monomers. Examples of olefin monomers include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl pentene-1, 1,4-hexadiene, norbornene, norbornadiene, vinyl norbornene, ethylidene norbornene, etc. The compositions of the invention further may include additives and fillers as well as a co-agent that can react with the curing agent to aid in crosslinking the plastomer and/or ionomer or to improve processability. Co-agents which have been used for that purpose include triallyl cyanurates, ethylene glycol di(meth)acrylate, tri(meth)acrylates, divinyl benzene and other multifunctional chemicals. [0015]
  • The “composition distribution breadth index” (CDBI) is defined as the weight percent of the plastomer molecules which have a comonomer content between 50 percent and 125 percent of the median comonomer content (on a mole basis) of the sample. For example the CDBI of a sample which had a butene content of 8 mole percent would be the weight percent of the molecules which had butene contents between 6 and 10 mole percent. [0016]
  • The plastomers employed are polyolefin copolymers developed using metallocene single-site catalyst technology. Polyethylene plastomers generally have better impact resistance than polyethylenes made with Ziegler-Natta catalysts. Plastomers exhibit both thermoplastic and elastomeric characteristics. In addition to being comprised of a polyolefin such as ethylene, plastomers contain up to about 35 wt % comonomer. Plastomers include but are not limited to ethylene-butene copolymers, ethylene-octene copolymers, ethylene-hexene copolymers, and ethylene-hexene-butene terpolymers, as well as mixtures thereof. [0017]
  • The golf ball covers of the invention contain a blend of plastomer and ionomer in a ratio of 10:90 to 90:10, and more preferably 20:80 to 50:50. It has been found that the golf ball cover properties of high impact resistance, good durability and playability are particularly favorable when the ratio of plastomer:ionomer is in the range of 10:90 to 50:50. Other additives such as coloring agents, optical brighteners, processing aids and fillers typically are added in an amount of up to about 10 parts by weight based upon 100 parts by weight of the plastomer-ionomer blend. [0018]
  • The plastomers employed in the invention preferably are formed by a single site metallocene catalyst such as those disclosed in EP 29368, U.S. Pat. No. 4,752,597, U.S. Pat. No. 4,808,561, and U.S. Pat. No. 4,937,299, the teachings of which are incorporated herein by reference. Blends of plastomers can be used. As is known in the art, plastomers can be produced by solution, slurry and gas phase accesses but the preferred materials are produced by metallocene catalysis using a high pressure process by polymerizing ethylene in combination with other olefin monomers, such as butene-1, hexene-1, octene-1 and 4-methyl-1-pentene in the presence of catalyst system comprising a cyclopentadienyl-transition metal compound and an alumoxane. [0019]
  • Plastomers found especially useful in the invention are those sold by Exxon Chemical under the trademark “EXACT” and include linear ethylene-butene copolymers such as EXACT 3024 having a density of about 0.905 g/cc (ASTM D-1505) and a melt index of about 4.5 g/10 min. (ASTM D-2839); EXACT 3025 having a density of about 0.910 g/cc (ASTM D-1505) and a melt index of about 1.2 g/10 min. (ASTM D-2839); EXACT 3027 having a density of about 0.900 g/cc (ASTM D-1505) and a melt index of about 3.5 g/10 min. (ASTM D-2839). Other useful plastomers include but are not limited to ethylene-hexene copolymers such as EXACT 3031 having a density of about 0.900 g/cc (ASTM D-1505) and a melt index of about 3.5 g/10 min. (ASTM D-2839), as well as EXACT 4049, which is an ethylene-butene copolymer having a density of about 0.873 g/cc (ASTM D-1505) and a melt index of about 4.5 g/10 min. (ASTM D-2839). All of the above EXACT series plastomers are available from EXXON Chemical Co. [0020]
  • EXACT plastomers typically have a dispersion index (M[0021] w/Mn where Mw is weight average molecular weight and Mn is number average molecular weight) of about 1.5 to 4.0, preferably 1.5-2.4, a density of about 0.86 to about 0.93 g/cc, preferably about 0.87 g/cc to about 0.91 g/cc, a melting point of about 140-220° F., and a melt index (MI) above about 0.5 g/10 mins, preferably about 1-10 g/10 mins as determined by ASTM D-1238, condition E. Plastomers which may be employed in the invention include copolymers of ethylene and at least one C3-C20 α-olefin, preferably a C4-C8 α-olefin present in an amount of about 5 to about 32 wt %, preferably about 7 to about 22 wt %, more preferably about 9-18 wt %. These plastomers are believed to have a composition distribution breadth index of about 45% or more.
  • Plastomers such as those sold by Dow Chemical Co. under the trade name ENGAGE also may be employed in the invention. These plastomers are believed to be produced in accordance with U.S. Pat. No. 5,272,236, the teachings of which are incorporated herein by reference. These plastomers are substantially linear polymers having a density of about 0.85 g/cc to about 0.93 g/cc measured in accordance with ASTM D-792, a melt index (MI) of less than 30 g/10 minutes, a melt flow ratio (I[0022] 10/I2) of about 7 to about 20, where I10 is measured in accordance with ASTM D-1238 (190/10) and I2 is measured in accordance with ASTM D-1238 (190/2.16), and a dispersion index Mw/Mn which preferably is less than 5, and more preferably is less than about 3.5 and most preferably is from about 1.5 to about 2.5. These plastomers include homopolymers of C2-C20 olefins such as ethylene, propylene, 4-methyl-1-pentene, and the like, or they can be interpolymers of ethylene with at least one C3-C20 α-olefin and/or C2-C20 acetylenically unsaturated monomer and/or C4-C18 diolefins. These plastomers have a polymer backbone that is either unsubstituted or substituted with up to 3 long chain branches/1000 carbons. As used herein, long chain branching means a chain length of at least about 6 carbons, above which the length cannot be distinguished using 13C nuclear magnetic resonance spectroscopy. The preferred ENGAGE plastomers are characterized by a saturated ethylene-octene backbone and a narrow dispersion index Mw/Mn of about 2.
  • These plastomers also are compatible with many conventional plasticizers and fillers. The fillers include, but are not limited to, clay, talc, asbestos, graphite, glass, mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicates, diatomaceous earth, carbonates such as calcium carbonate, magnesium carbonate and the like, metals such as titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt and beryllium, and alloys of the above metals, metal oxides such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide and the like, particulate synthetic plastic such as high molecular weight polyethylene, polystyrene, polyethylene ionomer resins and the like, particulate carbonaceous materials such as carbon black, natural bitumen and the like, as well as cotton flock, cellulose flock, and leather fiber. Dark colored fillers generally are not preferred for use at the outer surface of the ball if a white ball is desired. Thus, a two-layer cover in which a non-white filler is only present in the inner cover layer can be employed. The amount of filler employed is primarily a function of weight restrictions. For example, weight may be removed from the core and placed in the inner and/or outer cover. This added weight will change the moment of inertia of the ball thereby potentially altering performance. Various commercially available plastomers may be useful in the invention, including those manufactured by Mitsui. [0023]
  • The dispersion index M[0024] w/Mn of plastomers made in accordance with U.S. Pat. No. 5,272,236 most preferably is about 2.0. Non-limiting examples of these plastomers include ENGAGE CL 8001 having a density of about 0.868 g/cc, a melt index of about 0.5 g/10 mins, and a Shore A hardness of about 75; ENGAGE CL 8002 having a density of about 0.87 g/cc, a melt index of about 1 gms/10 min, Shore A hardness of about 75; ENGAGE CL 8003 having a density of about 0.885 g/cc, melt index of about 1.0 gms/10 min, and a Shore A hardness of about 86; ENGAGE EG 8100 having a density of about 0.87 g/cc, a melt index of about 1 gms/10 min., and a Shore A hardness of about 87; ENGAGE 8150 having a density of about 0.868 g/cc, a melt index of about 0.5 gms/10 min, and a Shore A hardness of about 75; ENGAGE 8200 having a density of about 0.87 g/cc, a melt index of about 5 g/10 min., and a Shore A hardness of about 75; and ENGAGE EP 8500 having a density of about 0.87 gms/cc, a melt index of about 5 g/10 min., and a Shore A hardness of about 75.
  • The ionomers which are blended with plastomer preferably are various commercially available ionomers sold under the trade name lotek, such as lotek 8000, lotek 8020, lotek 8030 or lotek 7000, lotek 7010, lotek 7020 or lotek 7030. Blends of ionomers can be used, however hard ionomers are preferred. [0025]
  • Coloring pigments and optical brighteners also may be included in the compositions of the invention. Useful coloring pigments include, for example, titanium dioxide, the presence of which simplifies the surface painting operation of the finished ball. In some cases, coloring pigments eliminate the need for painting, such as, for example, where the ball is intended for use on driving ranges. [0026]
  • The golf balls of the invention have a coefficient of restitution of at least 0.650, and more preferably at least 0.700, a PGA compression of about 60-110 and preferably 80-90, a ball size of 1.68″-1.75″, and a ball weight of 45.93 grams or less. [0027]
  • To form a golf ball according to the invention, a solid, liquid or wound golf ball center is obtained. The center optionally may be covered with one or more non-plastomer inner cover layers prior to application of the plastomer cover layer or layers. If necessary, the center can be surface treated to facilitate adhesion thereof to a cover composition. Surface treatment can be performed by techniques known in the art, such as corona discharge, ozone treatment, sand blasting, grinding and the like. Non-limiting examples of useful non-plastomer cover compositions include blends of ethylene-acrylic acid or ethylene-methacrylic acid, as well as copolymers neutralized with mono-or divalent metals such as sodium, potassium, lithium, calcium, zinc or magnesium. Such compositions are shown in U.S. Pat. No. 5,368,304, the disclosure of which is incorporated herein in its entirety by reference. The plastomer cover layer or layers are then formed over the core using a conventional molding technique, such as compression molding or injection molding. The golf ball is finished by applying an indicia and a thin top coat with or without the use of a primer coat. [0028]
  • The plastomer and ionomer typically are subject to intensive mixing such as in a Banbury mixer, two roll mill, or the like. When the plastomer cover is made by compression molding, the golf ball center is placed between two half-shells and the ball is molded for about 1-3 minutes at 200-300° F. and 100 p.s.i. Subsequently, the molded ball is cooled for about 10 minutes. When the plastomer cover is made by injection molding, the cover material is heated to 300-400° F. and injection molded into a cold mold where it is maintained for about 20-60 seconds. [0029]
  • Coefficient of restitution (COR) is measured by firing a golf ball from an air cannon at about 125 feet per second against a steel plate positioned 12 feet from the muzzle of the cannon. The rebound velocity then is measured. The rebound velocity is divided by the initial velocity of 125 feet per second to give the COR [0030]
  • Riehle compression is a measurement of the deformation of a golf ball in inches under a load. Riehle compression can be converted to PGA compression by subtracting Riehle compression values from 160. [0031]
  • The “Guillotine Cut Test” employed to measure cut resistance is performed by holding an unfinished ball firmly in a cavity to expose the top half of the ball. A guillotine blade weighing 5 pounds and having inner and outer blade edge angles of 90° and 60° relative to the horizontal, respectively, and a blunt cutting edge of three sixty-fourths inch radius which is designed to simulate the leading edge of an iron is dropped from a height of three feet to strike the ball at a point one-half inch off the top center point. The guillotine blade is guided during the drop by means of a substantially friction-free vertical track. Optionally, but not necessarily, the test can be repeated on the same or on different sections of the ball. Ball failure is defined as permanent damage evidenced by a crack or by removal of a segment from the ball surface. A rating of 1 is excellent and a rating of 4 is poor. The cut-off for a commercially acceptable ball is a rating of 3. [0032]
  • Having generally described the invention, the following examples are included for purposes of illustration so that the invention may be more readily understood and are in no way intended to limit the scope of the invention unless otherwise specifically indicated. In the examples, Shore C and Shore D hardness values generally were measured in accordance with ASTM D-2240, except that measurements were made on the curved surface of a golf ball.[0033]
  • EXAMPLES
  • A number of golf ball cores were formed primarily from polybutadiene, zinc diacrylate, and free radical initiator having a weight of 36.8 grams, a Riehle compression of 81 (PGA compression of 79), and a coefficient of restitution (COR) of 0.786. The cores had a diameter of 1.55 inches. About 12 of the cores were covered with each of the cover formulation shown below on Table 1. One set of controls was covered with the 1995 Top Flite Z balata cover formulation. The remaining cores were covered with one of four different cover formulations comprising an ionomer-plastomer blend. The covers had a thickness of 0.067 inches. Properties of the molded balls were measured, and are also shown on Table 1 below. All of the cover formulations were mixed in an internal Banbury®-type mixer at an elevated temperature. [0034]
  • As shown on Table 1, Example 3 had a coefficient of restitution 10 points higher than control Example C-1 with a Shore D hardness comparable to that of control Example C-1. [0035]
  • As will be apparent to persons skilled in the art, various modifications and adaptations of the composition and structure above described will become readily apparent without departure from the spirit and scope of the invention. [0036]
    TABLE 2
    Golf Balls With Covers Formed From Blends
    of lonomer and Plastomer
    Material (pbw) C1 C2 1 2 3 4
    1995 Z-Balata X
    lotek 8000 600 560 560 560
    lotek 7030 448 408 408 408
    lotek 3110 1120
    GLS 6703 400 240
    EXACT 4049 240 240 480 160
    Kraton FG 1901 X 240 160
    Masterbatch 152 152 152 152 152
    Weight (g) 45.2 45.1 44.9 45.1 44.9 45.0
    Comp (Riehle) 84 81 80 78 78 79
    Comp (PGA) 76 79 80 82 82 81
    COR .791 .795 .796 .800 .801 .793
    Shore D (ASTM D-2240) 55 53 53 58 55-56 57
    Shore C (ASTM D-2240) 86 85 89 87
    Guillotine Cut Test 1.5 15 15 15 1.5

Claims (39)

We claim:
1. A golf ball having a core and a cover wherein said cover comprises an at least partially miscible blend of at least one ionomer resin and at least one metallocene catalyzed polyolefin resin.
2. The golf ball according to claim 1, wherein the ionomer resin comprises ethylene and methacrylic or acrylic acid.
3. The golf ball according to claim 2, wherein the ionomer resin is a terpolymer.
4. The golf ball according to claim 1, wherein the metallocene catalyzed polyolefin resin comprises a copolymer of ethylene and at least one olefin comonomer selected from the group consisting of propylene, butene, hexene, octene, pentene and norbornene.
5. The golf ball according to claim 1, wherein the cover comprises from about 90-10 percent ionomer resin and from about 10-90 percent metallocene catalyzed polyolefin resin.
6. The golf ball according to claim 1, wherein the cover comprises from about 80-50 percent ionomer resin and from about 20-50 percent metallocene catalyzed polyolefin resin.
7. A golf ball comprising a cover and a core according to claim 1, wherein the golf ball has a diameter of from about 1.68 to about 1.75 inches.
8. A golf ball having a core and a cover wherein said cover comprises from about 90 to 10 percent of at least one ionomer resin selected from the group consisting of ethylene-methacrylic acid and ethylene-acrylic acid copolymers neutralized by mono, di or tri-valent metallic derivatives; and from about 10 to 90 percent of at least one non-ionic metallocene catalyzed copolymer of an olefin with a lower alkyl substituent having from about 1 to about 18 carbon atoms.
9. A golf ball according to claim 8 wherein the cover comprises from about 80-50 percent ionomer resin and from about 20-50 percent non-ionic metallocene catalyzed copolymer.
10. A golf ball comprising a cover and a core according to claim 8, wherein the golf ball has a diameter of from about 1.68 to about 1.75 inches.
11. A golf ball comprising a cover and a core wherein the cover comprises an at least partially miscible blend of at least one ionomer and at least one metallocene catalyzed polymer having the formula:
Figure US20030004274A1-20030102-C00001
wherein
R1 is hydrogen;
R2 is hydrogen or lower alkyl selected from the group consisting of CH3, C2H5, C3H7, C4H9, and C5H11;
R3 is hydrogen or lower alkyl selected from the group consisting of CH3, C2H5, C3H7, C4H9, and C5H11;
R4 is selected from the group consisting of CH3, C2H5, C3H7, C4H9, C5H11, C6H13, C7H15, C8H17, C9H19, C10H21, and phenyl, in which from 0 to 5 H within R4 can be replaced by substituents selected from the group consisting of COOH, SO3H, NH2, F, Cl, Br, I, OH, SH, silicone, lower alkyl esters and lower alkyl ethers, with the proviso that R3 and R4 can be combined to form a bicyclic ring;
R5 is hydrogen, lower alkyl including C1-C5, carbocycilc, aromatic or heterocyclic;
R6 is hydrogen, lower alkyl including C1-C5 carbocyclic, aromatic or heterocyclic; and
wherein x ranges from 99 to 50 weight per cent of the polymer, y ranges from 1 to 50 weight per cent of the polymer and z ranges from 0 to 49 weight per cent of the polymer.
12. A golf ball comprising a core and a cover according to claim 11 wherein R2 is hydrogen.
13. A golf ball composing a cover and a core according to claim 11 wherein the golf ball core has a diameter of about 1.58 inches.
14. A golf ball comprising a cover and a core according to claim 11 wherein the golf ball has a diameter from about 1.68 to about 1.80 inches.
15. A golf ball comprising a cover and a core according to claim 11 wherein the golf ball has a diameter of from about 1.710 to about 1.730 inches.
16. A golf ball comprising a cover and a core according to claim 11 wherein the core is a single piece of material.
17. A golf ball comprising a cover and a core according to claim 11 wherein the core is a solid or liquid center at least partially covered with a wound thread.
18. A golf ball having a core and a cover, said cover comprising a blend of two or more ionomer resins with one or more non-ionic copolymers and an olefin with attached lower alkyl groups having from about 1 to about 18 carbon atoms said olefin comonomer produced using a metallocene catalyst.
19. A golf ball according to claim 18 having multiple cover or core layers.
20. A golf ball having a core and a cover wherein said cover comprises one or more ionomer resins having a flexural modulus of from about 50 psi to about 150,000 psi and a non-ionic metallocene catalyzed copolymer of an olefin having a flexural modulus of from about 500 psi to 200,000 psi.
21. A golf ball having a core and a cover wherein said cover comprises an at least partially miscible blend of at least one ionomer resin and at least one polyolefin resin, wherein the polyolefin resin is formed with a metallocene catalyst.
22. A golf ball having a core and a cover wherein said cover comprises from about 99 to 1 phr of at least one ionomer resin chosen from the group consisting of ethylene-methacrylic acid and ethylene-acrylic acid copolymers neutralized by mono, di or tri-valent metallic derivatives; and from about 1 to 99 phr of at least one non-ionic metallocene catalyzed copolymer of an olefin with a lower alkyl substituent having from about 1 to about 18 carbon atoms.
23. A golf ball having improved spin comprising a core and a cover wherein said cover comprises from about 95 to 5 phr of at least one ionomer resin chosen from the group consisting of ethylene-methacrylic acid and ethylene-acrylic acid copolymers neutralized by mono, di or tri-valent metallic derivatives; and from about 5 to 95 phr of at least one non-ionic metallocene catalyzed copolymer of an olefin with a lower alkyl substituent having from about 1 to about 18 carbon atoms.
24. A golf ball according to claim 22 wherein the cover comprises from about 95-30 percent ionomer and from about 5-70 percent metallocene catalyzed copolymer.
25. A golf ball according to claim 22 wherein the cover comprises from about 95-50 percent ionomer and from about 5-50 percent metallocene catalyzed copolymer.
26. A golf ball according to claim 22 wherein the olefin has a flexural modulus between about 500 psi and about 150,000 psi.
27. A golf ball according to claim 22 wherein the olefinic polymer is a copolymer in which the monomers are selected from the group consisting of butene, hexene, and octene.
28. A golf ball according to claim 22 wherein the olefinic polymer is a copolymer of butene, hexene, or norbornene.
29. A golf ball according to claim 22 wherein the olefinic polymer is a copolymer of ethylene and butene.
30. A golf ball according to claim 22 wherein the olefinic polymer is a copolymer of butene and hexene.
31. A golf ball according to claim 22 wherein the olefinic polymer is a copolymer of ethylene and octene.
32. A golf ball according to claim 23 wherein the olefinic polymer is a copolymer of ethylene and norbornene.
33. A golf ball according to claim 23 wherein the olefinic polymer is a polymer of ethylene and propylene and diene monomer.
34. The golf ball according to claim 11 wherein the ionomer comprises ethylene and methacrylic or acrylic acid.
35. The golf ball according to claim 34 wherein the ionomer is a terpolymer.
36. The golf ball according to claim 18 wherein the ionomers comprise ethylene and methacrylic or acrylic acid.
37. The golf ball according to claim 36 wherein the ionomer is a terpolymer.
38. The golf ball according to claim 21 wherein the ionomer comprises ethylene and methacrylic or acrylic acid.
39. The golf ball according to claim 38 wherein the ionomer is a terpolymer.
US10/178,267 1997-03-03 2002-06-24 Golf ball cover containing a blend of ionomer and plastomer, and method of making same Abandoned US20030004274A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/178,267 US20030004274A1 (en) 1997-03-03 2002-06-24 Golf ball cover containing a blend of ionomer and plastomer, and method of making same

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US81144797A 1997-03-03 1997-03-03
US22345098A 1998-12-30 1998-12-30
US10/178,267 US20030004274A1 (en) 1997-03-03 2002-06-24 Golf ball cover containing a blend of ionomer and plastomer, and method of making same

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US22345098A Continuation 1997-03-03 1998-12-30

Publications (1)

Publication Number Publication Date
US20030004274A1 true US20030004274A1 (en) 2003-01-02

Family

ID=25206575

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/785,617 Expired - Fee Related US6552126B2 (en) 1997-03-03 2001-02-16 Golf ball cover containing a blend of ionomer and plastomer, and method of making same
US10/178,267 Abandoned US20030004274A1 (en) 1997-03-03 2002-06-24 Golf ball cover containing a blend of ionomer and plastomer, and method of making same

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US09/785,617 Expired - Fee Related US6552126B2 (en) 1997-03-03 2001-02-16 Golf ball cover containing a blend of ionomer and plastomer, and method of making same

Country Status (1)

Country Link
US (2) US6552126B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030130396A1 (en) * 2001-09-13 2003-07-10 Peter Voorheis Golf ball cores comprising a halogenated organosulfur compound

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6552126B2 (en) * 1997-03-03 2003-04-22 Spalding Sports Worldwide, Inc. Golf ball cover containing a blend of ionomer and plastomer, and method of making same
JP3594575B2 (en) * 2000-12-12 2004-12-02 住友ゴム工業株式会社 Multi-piece solid golf ball
CN101005933A (en) * 2004-08-25 2007-07-25 纳幕尔杜邦公司 Process for manufacturing thermoplastic components for golf balls
US9108082B2 (en) * 2011-12-19 2015-08-18 Taylor Made Golf Company, Inc. Golf ball composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4752597A (en) * 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
US4808561A (en) * 1985-06-21 1989-02-28 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4937299A (en) * 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US5703166A (en) * 1995-01-24 1997-12-30 Acushnet Company Golf ball compositions based on blends of olefinic ionomers and metallocene catalyzed polymers
US20010005698A1 (en) * 1997-03-03 2001-06-28 Spalding Sports Worldwide, Inc. Golf ball cover containing a blend of lonomer and plastomer, and method of making same

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2741480A (en) 1953-02-04 1956-04-10 Worthington Ball Company Golf ball
US2924593A (en) 1956-08-23 1960-02-09 Hercules Powder Co Ltd Polymerization of ethylene using as a catalyst the product formed by mixing a bis(cyclopentadienyl) zirconium salt with an alkyl metallic compound
US3491073A (en) 1965-08-13 1970-01-20 Dow Chemical Co Process for the polymerization of olefins
US3421766A (en) 1965-12-13 1969-01-14 Uniroyal Inc Composition of matter and golf ball made therefrom
US3384612A (en) 1966-02-01 1968-05-21 Du Pont Golf ball
US3454676A (en) 1966-02-01 1969-07-08 Du Pont Blends of ionomer resins and elastomers
CA849081A (en) 1967-03-02 1970-08-11 Du Pont Of Canada Limited PRODUCTION OF ETHYLENE/.alpha.-OLEFIN COPOLYMERS OF IMPROVED PHYSICAL PROPERTIES
DE2608863A1 (en) 1976-03-04 1977-09-08 Basf Ag Ethylene polymerisation using Ziegler catalyst system - contg. bis-cyclopentadienyl-titanium di-alkyl cpd., aluminium tri-alkyl cpd. and water
JPS5952643B2 (en) 1977-01-27 1984-12-20 三井化学株式会社 ethylene copolymer
IT1110494B (en) 1978-08-02 1985-12-23 Montedison Spa ETHYLENE POLYMERS AND PROCEDURE FOR THEIR PREPARATION
US4274637A (en) 1979-01-31 1981-06-23 Questor Corporation Golf ball having cellular cover
US4409366A (en) 1980-10-14 1983-10-11 Henry Schmelzer Homogeneous blends of a trans-isomer of polyisoprene
JPS57105411A (en) 1980-12-23 1982-06-30 Mitsubishi Petrochem Co Ltd Ethylenic copolymer
JPS58191705A (en) 1982-05-06 1983-11-09 Mitsui Petrochem Ind Ltd Ethylene copolymerized rubber
FR2532649B1 (en) 1982-09-07 1986-08-29 Bp Chimie Sa COPOLYMERIZATION OF ETHYLENE AND HEXENE-1 IN A FLUIDIZED BED
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
US4530914A (en) 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4935474A (en) 1983-06-06 1990-06-19 Exxon Research & Engineering Company Process and catalyst for producing polyethylene having a broad molecular weight distribution
JPS6014879A (en) 1983-07-06 1985-01-25 住友ゴム工業株式会社 Composition for covering golf ball
JPS6088016A (en) 1983-10-21 1985-05-17 Mitsui Petrochem Ind Ltd Ethylene copolymer
JPH0698206B2 (en) 1985-05-01 1994-12-07 ブリヂストンスポーツ株式会社 Solid Golf Ball
CA1276748C (en) 1985-07-29 1990-11-20 Michitake Uoi Styrene polymers
US5055438A (en) 1989-09-13 1991-10-08 Exxon Chemical Patents, Inc. Olefin polymerization catalysts
US4892851A (en) 1988-07-15 1990-01-09 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US4861028A (en) 1988-07-29 1989-08-29 Wilson Sporting Goods Co. Game ball
DE3835044A1 (en) 1988-10-14 1990-04-19 Hoechst Ag Process for the preparation of cycloolefin polymers
JP2712740B2 (en) 1989-04-24 1998-02-16 ブリヂストンスポーツ株式会社 Golf ball
US5026798A (en) 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5338610A (en) 1989-12-13 1994-08-16 Lisco, Inc. Golf ball compositions
US5244969A (en) 1990-01-10 1993-09-14 Sumitomo Rubber Industries, Ltd. Golf ball
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
US5123659A (en) 1991-03-01 1992-06-23 Wilson Sporting Goods Co. Game ball
US5246783A (en) 1991-08-15 1993-09-21 Exxon Chemical Patents Inc. Electrical devices comprising polymeric insulating or semiconducting members
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5272016A (en) 1992-03-23 1993-12-21 Viskase Corporation Multilayer stretch/shrink film
JP3230613B2 (en) 1992-09-01 2001-11-19 住友ゴム工業株式会社 Golf ball
JP2652505B2 (en) * 1993-05-20 1997-09-10 住友ゴム工業株式会社 Golf ball
US5415905A (en) 1993-09-29 1995-05-16 Exxon Chemical Patents Inc. Dispersible film
US6013734A (en) * 1997-04-29 2000-01-11 Montell North America Inc. Thermoplastic olefin composition containing an ethylene polymer for making molded parts having a good paint adhesion/durability balance

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4937299A (en) * 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US4808561A (en) * 1985-06-21 1989-02-28 Exxon Chemical Patents Inc. Supported polymerization catalyst
US4752597A (en) * 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
US5703166A (en) * 1995-01-24 1997-12-30 Acushnet Company Golf ball compositions based on blends of olefinic ionomers and metallocene catalyzed polymers
US20010005698A1 (en) * 1997-03-03 2001-06-28 Spalding Sports Worldwide, Inc. Golf ball cover containing a blend of lonomer and plastomer, and method of making same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030130396A1 (en) * 2001-09-13 2003-07-10 Peter Voorheis Golf ball cores comprising a halogenated organosulfur compound
US6881794B2 (en) * 2001-09-13 2005-04-19 Acushnet Company Golf ball cores comprising a halogenated organosulfur compound

Also Published As

Publication number Publication date
US6552126B2 (en) 2003-04-22
US20010005698A1 (en) 2001-06-28

Similar Documents

Publication Publication Date Title
US5703166A (en) Golf ball compositions based on blends of olefinic ionomers and metallocene catalyzed polymers
US6241626B1 (en) Golf ball containing plastomer and method of making same
US6350815B1 (en) Golf ball cover compositions
US5824746A (en) Golf balls incorporating foamed metallocene catalyzed polymer
AU722705B2 (en) Golf ball with ionomeric cover and method of making same
US4986545A (en) Golf ball compositions
US5324783A (en) Golf ball cover compositions
US5098105A (en) Golf ball compositions
JP2657618B2 (en) Golf ball
JPH0680718A (en) High-acid ionomer and golf ball cover composition containing same
US20120010347A1 (en) Golf ball material, golf ball and method for preparing golf ball material
USRE37597E1 (en) Golf ball covers
US5971869A (en) Golf ball composition
JP3375004B2 (en) Golf ball
US6552126B2 (en) Golf ball cover containing a blend of ionomer and plastomer, and method of making same
US6800695B2 (en) Golf ball cover compositions
AU675854B2 (en) Golf ball
AU761460B2 (en) Golf ball containing plastomer and method of making same
US7871341B2 (en) Golf ball material, golf ball and method for preparing golf ball material
AU733427B2 (en) Golf ball with ionomeric cover and method of making same
WO2000024478A1 (en) Golf ball containing plastomer and method of making same
AU735662B2 (en) Multi-layer golf ball

Legal Events

Date Code Title Description
AS Assignment

Owner name: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT, CA

Free format text: SECURITY AGREEMENT;ASSIGNOR:SPALDING SPORTS WORLDWIDE, INC.;REEL/FRAME:013438/0276

Effective date: 19980331

AS Assignment

Owner name: THE TOP-FLITE GOLF COMPANY, MASSACHUSETTS

Free format text: CHANGE OF NAME;ASSIGNOR:SPALDING SPORTS WORLDWIDE, INC.;REEL/FRAME:013753/0072

Effective date: 20030528

AS Assignment

Owner name: CALLAWAY GOLF COMPANY, CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:TOP-FLITE GOLF COMPANY, THE;REEL/FRAME:014007/0688

Effective date: 20030915

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION