Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
1999-12-13
2002-04-30
Buttner, David J. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S287000, C528S293000, C528S294000, C528S391000, C528S398000, C526S278000, C526S287000, C525S340000, C525S344000, C525S353000, C525S420000, C525S535000, C525S538000, C473S349000, C036S127000, C206S315300
Reexamination Certificate
active
06380349
ABSTRACT:
FIELD OF THE INVENTION
The present invention is directed to compositions and methods for forming certain golf equipment, such as golf shoes, golf clubs, golf gloves, or portions thereof having improved properties with the subject compositions. The compositions of the invention comprise at least one ionomer formed from a sulfonated polymer, a phosphonated polymer, or a carboxylated polymer, their precursors, or a combination thereof.
BACKGROUND OF THE INVENTION
It is well known to even the average golfer that the equipment used in playing the game is subject to a great deal of friction, impact, and other stresses during a typical round of golf. Both the performance and the useful life of such equipment would benefit from the use of materials having improved resilience, dimensional stability, and increased durability. For instance, many types of golf clubs, such as putters, drivers, and wedges, contain polymer inserts in the face of the club. Obviously, since the club face directly strikes a golf ball thousands of times over the life of the club, improved resilience and durability are of great importance. Additionally, club components, such as shafts, grips, and hosels, undergo significant stress during a golf swing and contact with a golf ball and, therefore, could stand to benefit from more durable materials.
Another example is golf gloves, which undergo a lot of friction and wear and tear during a round of golf, not only from contact with, and friction from, golf club grips, but also from weather-related causes, such as excess moisture, heat, and ultraviolet radiation. Liners and, more specifically, polymer-reinforced liners (inner or outer liners), that are constructed of a more durable material, might provide a significant improvement in glove durability. Shoes are another type of golf equipment that receive a lot of stress and friction during a round (or multiple rounds) of golf. Shoe soles are flexed thousands of times per round and hundreds of thousands of times over the life of the shoe, as are the foot-beds and liners inside the shoes. Polymer or plastic spikes are, obviously, repetitively driven into, and scraped against cart paths, pavement, hard ground, and many other types of hard surfaces routinely encountered on golf courses.
Other types of golf equipment that require increased durability include various types of golf carts and course maintenance vehicles, golf bags and their associated framework, support legs and stands, golf tees, and fabrics designed for the potentially harsh (sun, rain, wind, hail, etc.) environments encountered by many golfers throughout the many seasons during which golf is played.
Golf equipment is typically formulated from a variety of different materials. One type of commonly employed polymer are ionomers of an ethylene-methacrylic acid neutralized by a metal ion. However, these conventional ionomeric materials do not entirely solve the problems associated with stress, durability, and repeated impact, as described above. Therefore, it is clear that improved materials, having material properties that address these preferred physical requirements, are necessary.
A handful of references are directed to golf equipment, such as golf clubs, having ionomer resins as part of their construction. U.S. Pat. No. 4,809,978 discloses a golf club head of a wood-type or an iron-type having a face plate formed of an ionomer resin having a Young's modulus in the range of 20 to 50 kg/mm
2
. The thermoplastic ionomer resin is based on ethylene-methacrylic acid neutralized by a metal ion.
U.S. Pat. No. 4,204,684 discloses a golf club head and method of producing the same, wherein the head is fashioned of laminations or layers of resinous or plastic materials bonded together to form an integrated or composite head or body. The laminates are constructed of ethylene-methacrylic acid ionomers neutralized with a metal ion or polyamide resin.
U.S. Pat. Nos. 5,465,969 and 5,507,985 each disclose a golf club having a hollow metal head defining a cavity filled with a thermoplastic material produced from a thermoplastic polymer, a filler, and a chemical blowing agent. Suitable thermoplastic polymer materials include ethylene-methacrylic acid ionomers that have been neutralized by a metal ion and co-polymers of ethylene neutralized with a metal ion, non-neutralized copolymers of ethylene and methacrylic or acrylic acid, polyethylene, and polypropylene.
DE 4015164 discloses embossable foam latex, in pieces or as cut goods, for use in articles, such as sporting goods, golf shoes, golf gloves, and upholstery. A base latex is mixed with a thermoplastic and/or a thermoset polymer, such as a styrene-acrylate copolymer or terpolymer, carboxylated styrene-butadiene copolymer, vinyl acetate homopolymer, copolymer, or terpolymer, and thermoplastic polyurethane.
Several references disclose blends of sulfonated polystyrene ionomers and polyamide-6. For example, R. A. Weiss and X. Lu [
Macromol.,
25:6185-6189 (1992)] disclose that, in compatible sulfonated ionomer/polyamide blends, a complex forms between the metal sulfonate of a sulfonated polystyrene ionomer and the amide moiety of polyamide-6.
U.S. Pat. No. 4,840,982 discloses a blend containing a matrix of an aromatic polymer (which may be polyamide, polyester, polycarbonate, or polyimide) in which is dispersed an impact modifier consisting of a minor portion of a carboxylated or sulfonated elastomer which is formed into an ionomer. A minor portion of a dispersion stabilizer must also be present. None of the above references, however, mention the utility of such materials in golf equipment.
There is still a need, however, for golf equipment having improved durability due to forming such equipment from polymer compositions comprising ionomeric material containing sulfonated, carboxylated, and/or phosphonated ionomers. Forming golf equipment from at least one sulfonated, carboxylated, and/or phosphonated ionomer can dramatically improve the ability to control the mechanical properties of the composition, including tensile and flexural modulus and impact strength.
SUMMARY OF THE INVENTION
The present invention is directed to golf equipment formed at least in part of a composition which comprises at least one ionomer formed from a polymer having at least one moiety selected from the group consisting of sulfonated, carboxylated, or phosphonated acid moieties, and mixtures thereof.
In one embodiment, the ionomer is a reaction product of a metal base and at least one of the sulfonated, carboxylated, phosphonated, or acid moieties. In another embodiment, the metal base comprises at least one metallic cation selected from the group consisting of Li, Na, Zn, Ca, Mg, K, Ti, Zr, W, Mn, Ni, Cu, and Sn. In a further embodiment, from about 1 mol % to about 99 mol % of the moieties of the ionomer are present in an ionic form. In a preferred embodiment, at least about 10 mol % of the moieties of the ionomer are present in an ionic form.
In another embodiment, the polymer is a sulfonated polymer selected from the group consisting of sulfonated thermoplastic elastomers, sulfonated thermoplastic polymers, sulfonated thermoset polymers, and mixtures thereof. Preferably, the sulfonated polymer contains from about 0.1 mol % to about 30 mol % sulfonated moieties. In still another embodiment, the polymer is a sulfonated thermoplastic elastomer having a flexural modulus from about 1,000 psi to about 150,000 psi.
In a further embodiment, the sulfonated thermoplastic elastomer is selected from the group consisting of block copoly(ester-esters); block copoly(ester-ethers); block copoly(amide-esters); block copoly(amide-ethers); block copoly(urethane-esters); block copoly(urethane-ethers); block polystyrene thermoplastic elastomers, ethylene propylene ruber; ethylene-propylene diene terpolymer rubber; a thermoplastic elastomer blend comprising polypropylene and ethylene-propylene-diene terpolymer or ethylene-propylene copolymer rubber wherein the rubber is dynamically vulcanized; and mixtures thereof.
Preferably, the polymer is a sulfonated
Acushnet Company
Buttner David J.
Swidler Berlin Shereff & Friedman, LLP
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