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WO1998036801A1 - Compositions de revetement pour balles de golf - Google Patents

Compositions de revetement pour balles de golf Download PDF

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Publication number
WO1998036801A1
WO1998036801A1 PCT/US1998/003457 US9803457W WO9836801A1 WO 1998036801 A1 WO1998036801 A1 WO 1998036801A1 US 9803457 W US9803457 W US 9803457W WO 9836801 A1 WO9836801 A1 WO 9836801A1
Authority
WO
WIPO (PCT)
Prior art keywords
magnesium
ionomer
golf ball
hard
weight percent
Prior art date
Application number
PCT/US1998/003457
Other languages
English (en)
Inventor
Murali Rajagopalan
Original Assignee
Acushnet Company
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 Acushnet Company filed Critical Acushnet Company
Priority to AU63348/98A priority Critical patent/AU6334898A/en
Publication of WO1998036801A1 publication Critical patent/WO1998036801A1/fr

Links

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
    • 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
    • A63B37/003—Coefficient of restitution
    • 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
    • A63B37/0037—Flexural modulus; Bending stiffness
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/007—Characteristics of the ball as a whole
    • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
    • A63B37/0074—Two piece balls, i.e. cover and core
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/007—Characteristics of the ball as a whole
    • A63B37/0077—Physical properties
    • A63B37/0084—Initial velocity
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B37/00—Solid balls; Rigid hollow balls; Marbles
    • A63B37/0003—Golf balls
    • A63B37/007—Characteristics of the ball as a whole
    • A63B37/0077—Physical properties
    • A63B37/0096—Spin rate
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0876—Salts thereof, i.e. ionomers

Definitions

  • This invention relates generally to golf balls and, in particular, to golf ball cover compositions comprising blends of hard magnesium ionomers and very low flexural modulus magnesium ionomers.
  • the golf ball cover compositions of the invention provide golf balls having unexpectedly improved durability when compared to prior art hard-soft ionomer blends.
  • a majority of golf balls sold today have covers formed either of balata or a blend comprising one or more ionomers. Balata covered, wound balls are typically preferred by skilled golfers because such balls have a high spin rate, allowing skilled players to draw or fade the ball, and to stop the ball quickly on the green with approach shots.
  • balls with balata covers are expensive, and are easily cut or otherwise damaged when miss-hit, e.g., by a less than skilled player.
  • Two-piece golf balls having covers which comprise an ionomer or ionomer blend are less expensive than wound, balata covered balls, and are highly resistant to cutting or other damage.
  • these balls have a hard feel and a low spin rate when compared to balata covered balls, so that they are more difficult to control.
  • golf ball manufacturers have attempted to produce golf ball covers that provide the spin rate of balata with the cut resistance of an ionomer, i.e., a copolymer of an ⁇ -olefin and an , ⁇ -unsaturated carboxylic acid, by forming blends of ionomers that differ in hardness, acid content, and in the metal atom used to neutralize the carboxylic acid groups on the polymer chain, none of these . attempts have been fully successful.
  • an ionomer i.e., a copolymer of an ⁇ -olefin and an , ⁇ -unsaturated carboxylic acid
  • U.S. Patent No. 4,526,375 to Nakade discloses covers comprising a single ionomer in which part of the carboxylic acid groups has been neutralized with sodium and another part has been neutralized with magnesium or zinc to
  • U.S. Patent No. 5,000,459 to Issac discloses golf ball covers made from a lithium ionomer resin, wherein up to
  • the resulting golf balls are found to be comparable in durability and initial velocity to golf balls having a cover with lithium ionomer only.
  • a golf ball cover including about 10 to 90 percent by weight of an ethylene-acrylic acid copolymer, containing about 11 percent by weight acrylic acid with about 40 percent of the carboxylic acid groups neutralized with sodium, and about 90 to 10 percent by weight of at least one
  • the exemplified golf balls are said to have the durability of balls having ethylene-methacrylic acid ionomer covers, but with an improved coefficient of restitution.
  • U.S. Patent No. 5,492,972 to Stefani discloses a golf ball cover composition of a blend comprising 95 to 50
  • U.S. Patent No. 4,884,814 to Sullivan discloses golf ball covers comprising blends of a high flexural modulus (“hard”) ionomer and a low flexural modulus (“soft”) ionomer.
  • the hard ionomers are copolymers of an olefin and an unsaturated monocarboxylic acid, neutralized with sodium or zinc, and have a flexural modulus of about 30,000 to 55,000 p.s.i. and a Shore D hardness of about 60 to 66.
  • the soft ionomers are terpolymers of an olefin, an unsaturated monocarboxylic acid, and an acrylate ester.
  • terpolymers are neutralized with zinc or sodium, and have a flexural modulus of about 3,000 to 7,000 p.s.i. and a Shore D hardness of about 25 to 40.
  • the resulting cover is disclosed as being intermediate between balata and hard Surlyn in softness to such a degree that adequate spin can be imparted to the ball by a skilled golfer.
  • U.S. Patent No. 5,120,791 to Sullivan discloses golf ball cover compositions that provide enhanced carrying distance when compared to the golf balls of U.S. 4,884,814 without sacrificing playability or durability.
  • the disclosed compositions are blends of at least one hard ionomeric resin, preferably an acrylic acid ionomer, and at least one acrylic acid based soft ionomer.
  • Hard ionomers neutralized with sodium, zinc, magnesium, or lithium, having a flexural modulus of 15,000 to 70,000 p.s.i. and a Shore D hardness of greater than 50 are disclosed. However, only zinc and sodium ionomers are exemplified.
  • the disclosed soft ionomers are sodium or zinc neutralized terpolymers of an olefin, acrylic acid, and an unsaturated acrylate ester monomer, and have a flexural modulus of about 2,000 to 10,000 p.s.i. and a Shore D hardness of about 20 to 40. Golf balls having such cover blends reportedly have an improved coefficient of restitution and spin rate when compared to prior art golf balls having covers with hard-soft ionomer blends.
  • U.S. Patent No. 5,415,937 to Cadorniga et al. discloses a golf ball cover material of a blend of 80-50% of a high stiffness ionomer and 20 to 50% of a very low modulus ionomer ("VLMI") to improve the feel and playability of the ball when compared to a standard ionomer cover, while retaining the distance and resilience of the prior art balls.
  • High stiffness ionomers are defined as a copolymer of 75 to 80% of an olefin and 20 to 25% of an alpha, beta ethylenically unsaturated carboxylic acid, having 10 to 90% of the acid groups neutralized with sodium, lithium, zinc, or magnesium.
  • the high stiffness ionomers preferably have a melt index of 0.5 to 5.0 g/10 min., a Shore D hardness of at least 70, and a flexural modulus of 60,000 to 120,000 psi.
  • the VLMI are defined as terpolymers, consisting of 67 to 70 % by weight of ethylene, 20 to 23% by weight of n- or iso-butyl-acrylate, and 10% by weight of methacrylic acid, where 10 to 90% of the acid groups are neutralized by sodium, zinc, or lithium.
  • the VLMI preferably have a melt index of 0.5 to 10 g/10 min, a Shore D hardness of 20 to 50, and a flexural modulus of 2,000 to 8,000.
  • Golf balls having covers incorporating the disclosed blends have a slightly improved coefficient of restitution and initial velocity with spin rates that range from slightly better than prior art blends to significantly lower, depending upon the particular blend and the club used in the test, i.e., driver, 5-iron, or pitching wedge.
  • U.S. Patent No. 5,324,783 to Sullivan discloses golf ball covers having an intermediate modulus with improved distance.
  • the covers include a blend of a "relatively low amount", i.e., about 10 to 30 weight percent, of soft ionomer resins and about 90 to 70 weight percent of hard ionomer resins.
  • the soft ionomers are terpolymers of an olefin, acrylic or methacrylic acid, and an unsaturated acrylate ester.
  • U.S. 5,324,783 discloses hard and soft ionomers neutralized with sodium, zinc, magnesium, and lithium, only blends of sodium and zinc ionomers are exemplified and discussed. Golf balls incorporating the disclosed cover composition have an improved spin rate compared to balls incorporating only hard ionomers.
  • golf ball cover compositions having improved durability, as well as the initial velocity and carry of two-piece balls having a hard ionomer cover and improved spin characteristics, can be obtained by blending a hard ionomer and a VLMI, where both ionomers are neutralized with the same type of metal atom.
  • the present invention relates to a golf ball comprising a cover and a core, wherein the cover comprises a blend of from about 95 to about 30 weight percent, preferably from about 80 to about 40 weight percent, most preferably from about 60 to about 40 weight percent, of at least one hard magnesium ionomer and from about 5 to about 70 weight percent, preferably from about 20 to about 60 weight percent, most preferably from about 40 to about 60 weight percent, of at least one magnesium VLMI.
  • the hard magnesium ionomer is a copolymer of ethylene and acrylic or methacrylic acid, having an acid content of from about 10 to about 30% by weight, wherein from about 30 to about 70% of the acid groups are neutralized with magnesium atoms.
  • the hard magnesium ionomer has an acid content of from about 15 to about 25% by weight, a flexural modulus of at least about 50,000 psi, and a Shore D hardness of at least about 60.
  • the magnesium VLMI is typically a terpolymer of ethylene acrylic acid or methacrylic acid, and n-butylacrylate or iso-butylacrylate, having an acid content of from about 8 to about 15% by weight, a Shore D hardness of from about 20 to about 40, and a flexural modulus of from about 2,000 to about 20,000 psi.
  • the invention also relates to a method of making a golf ball, comprising forming a cover composition of a blend of a hard magnesium ionomer and a magnesium VLMI, as described above, and molding the cover composition around a golf ball core to form a golf ball.
  • VLMI Very Low Modulus Ionomer
  • ⁇ -olefin such as ethylene
  • softening agent such as n- or iso-butyl-acrylate
  • carboxylic acid such as acrylic or methacrylic acid
  • the present invention relates to golf ball cover compositions having unexpectedly improved durability.
  • the golf ball cover compositions of the invention comprise blends of at least one hard magnesium ionomer and at least one magnesium Very Low Modulus Ionomer ("VLMI") .
  • VLMI Very Low Modulus Ionomer
  • Golf balls having covers incorporating the magnesium ionomer blends of the invention have unexpectedly improved durability and initial velocity, as well as similar or improved playability, when compared to hard-soft ionomer blends of the prior art. It is believed that the unexpectedly improved durability and golf ball properties of the present invention result from improved compatibility of the magnesium ionomers when compared to blends of ionomers neutralized with two or more different metal ions.
  • the golf ball cover compositions of the invention comprise a blend of from about 95 to about 30 weight percent of at least one hard magnesium ionomer, preferably from about 90 to about 40 weight percent, more preferably from about 80 to about 40 weight percent, most preferably from about 60 to about 40 weight percent, and from about 5 to about 70 weight percent of at least one magnesium VLMI, preferably from about 10 to about 60 weight percent, more preferably from about 20 to about 60 weight percent, most preferably from about 40 to about 60 weight percent.
  • the hard, i.e., high flexural modulus, magnesium neutralized ionomers useful in the golf ball cover compositions of the invention have a Shore D hardness of at least about 60, as measured with ASTM method D-2240, a flexural modulus, as measured with ASTM method D-790, of at least 50,000 psi, preferably from about 50,000 to about 80,000 psi, and a melt index from about 0.5 to about 5.0 g/10 min.
  • the hard magnesium ionomers are copolymers of an olefin and an unsaturated carboxylic acid, wherein about 30 to about 70% of the acid groups are neutralized with magnesium.
  • the hard magnesium ionomers are copolymers of ethylene and either acrylic or methacrylic acid, most preferably methacrylic acid.
  • the acid content of the hard magnesium ionomers useful in the invention is from about 10 to about 30% by weight, preferably from about 15 to about 25%.
  • SURLYN® AD8172 is a copolymer of ethylene and methacrylic acid, wherein the acid content is about 15% by weight, and about 40 to 60% of the acid groups are neutralized with magnesium atoms.
  • the magnesium VLMI useful in the cover compositions of the invention are terpolymers of an olefin, such as ethylene, acrylic or methacrylic acid, and n- or iso-butyl acrylate, wherein the acid content ranges from about 8 to about 15% by weight, and from about 30 to about 60% of the acid groups are neutralized with magnesium.
  • Commercially available magnesium VLMI include SURLYN® SEP688A, which has a Shore D hardness of about 45, a flexural modulus of about 4,600 psi. Additional materials conventionally included in golf ball cover compositions may be added to the golf ball cover compositions of the invention.
  • additional materials include, but are not limited to, dyes, whitening agents, UV absorbers, optical brighteners, processing aids, and other conventional additives.
  • Antioxidants, stabilizers, softening agents, plasticizers, processing aids, and reinforcing materials can also be added.
  • Golf balls and golf ball covers comprising the cover compositions of the invention can be made in any conventional manner, including injection molding cover stock formed from the magnesium ionomer blends of the invention around a core or by compression molding pre-formed half-shells of the cover stock into a half-shell mold in a conventional manner.
  • golf balls comprising the magnesium ionomer cover compositions of the invention can be finished by buffing, painting, and stamping, good results have been obtained by placing a mixture of the ionomer resins in a solid, pelletized form in a hopper used to feed the heated barrel of a conventional injection molding machine, which is used to make preformed half-shells for compression molding or directly forming the cover around a core in an injection mold.
  • the golf balls of examples 1 to 4 incorporated 87 compression cores having a diameter of 1.58 inch (4.01 cm).
  • magnesium ionomer blends of the invention provide a combination of improved durability, initial velocity, and spin over a wide range of hard magnesium ionomer and magnesium VLMI concentrations that is not available with prior art golf ball cover compositions.
  • golf balls having covers according to the present invention spin at a rate that is comparable to that of wound, balata covered balls, and have the durability and initial velocity of prior art two piece balls, having hard ionomer covers.
  • Golf balls 5 to 14 incorporate covers injection molded around 87 compression cores having a diameter of 1.58 in. (4.01 cm).
  • Golf ball 15 is a commercially available two-piece ball having a compression molded, Surlyn 8320 and Li ionomer cover.

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

Abstract

Balle de golf dont le revêtement contient entre 95 et 30 % d'un ionomère de Mg dur et entre 5 et 70 % d'un ionomère de Mg de très faible module. L'ionomère de Mg dur est généralement un copolymère neutralisé d'éthylène et d'acide acrylique ou méthacrylique, dont la teneur en acide est située entre 10 et 30 %. L'ionomère de Mg de très faible module est un terpolymère neutralisé d'éthylène, d'acide acrylique ou méthacrylique et d'acrylate de n-butyle ou d'acrylate d'isobutyle, dont la teneur en acide est située entre environ 8 et 15 %.
PCT/US1998/003457 1997-02-25 1998-02-23 Compositions de revetement pour balles de golf WO1998036801A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63348/98A AU6334898A (en) 1997-02-25 1998-02-23 Golf ball cover compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US80657297A 1997-02-25 1997-02-25
US08/806,572 1997-02-25

Publications (1)

Publication Number Publication Date
WO1998036801A1 true WO1998036801A1 (fr) 1998-08-27

Family

ID=25194338

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/003457 WO1998036801A1 (fr) 1997-02-25 1998-02-23 Compositions de revetement pour balles de golf

Country Status (2)

Country Link
AU (1) AU6334898A (fr)
WO (1) WO1998036801A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000025868A1 (fr) * 1998-11-05 2000-05-11 Acushnet Company Compositions pour balle de golf

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994024204A2 (fr) * 1993-04-08 1994-10-27 E.I. Du Pont De Nemours And Company Composition de materiau de revetement pour balle de golf
GB2286594A (en) * 1994-02-09 1995-08-23 Bridgestone Sports Co Ltd Golf balls and their covers
WO1997002318A1 (fr) * 1995-06-30 1997-01-23 E.I. Du Pont De Nemours And Company Compositions douces d'ionomeres, leurs melanges, leur utilisation en tant que materiaux de structure pour balles de golf

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994024204A2 (fr) * 1993-04-08 1994-10-27 E.I. Du Pont De Nemours And Company Composition de materiau de revetement pour balle de golf
GB2286594A (en) * 1994-02-09 1995-08-23 Bridgestone Sports Co Ltd Golf balls and their covers
WO1997002318A1 (fr) * 1995-06-30 1997-01-23 E.I. Du Pont De Nemours And Company Compositions douces d'ionomeres, leurs melanges, leur utilisation en tant que materiaux de structure pour balles de golf

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000025868A1 (fr) * 1998-11-05 2000-05-11 Acushnet Company Compositions pour balle de golf

Also Published As

Publication number Publication date
AU6334898A (en) 1998-09-09

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