WO2014193810A1 - Thermoplastic multi-layer golf ball - Google Patents
Thermoplastic multi-layer golf ball Download PDFInfo
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- WO2014193810A1 WO2014193810A1 PCT/US2014/039531 US2014039531W WO2014193810A1 WO 2014193810 A1 WO2014193810 A1 WO 2014193810A1 US 2014039531 W US2014039531 W US 2014039531W WO 2014193810 A1 WO2014193810 A1 WO 2014193810A1
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- flexural modulus
- golf ball
- thermoplastic
- core
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Classifications
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0077—Physical properties
- A63B37/0086—Flexural modulus; Bending stiffness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0024—Materials other than ionomers or polyurethane
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0023—Covers
- A63B37/0029—Physical properties
- A63B37/0037—Flexural modulus; Bending stiffness
-
- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
- A63B37/004—Physical properties
- A63B37/0045—Thickness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
- A63B37/004—Physical properties
- A63B37/0049—Flexural modulus; Bending stiffness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/0051—Materials other than polybutadienes; Constructional details
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/006—Physical properties
- A63B37/0064—Diameter
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/006—Physical properties
- A63B37/0066—Density; Specific gravity
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/005—Cores
- A63B37/006—Physical properties
- A63B37/0069—Flexural modulus; Bending stiffness
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
- A63B37/0075—Three piece balls, i.e. cover, intermediate layer and core
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/0003—Golf balls
- A63B37/007—Characteristics of the ball as a whole
- A63B37/0077—Physical properties
- A63B37/0091—Density distribution amongst the different ball layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- Golf ball core and cover layers are typically constructed with polymer compositions including, for example, polybutadiene rubber, polyurethanes, polyamides, ionomers, and blends of such polymers.
- lonomers, particularly ethylene- based ionomers, are a preferred group of polymers for golf ball layers because of their toughness, durability, and wide range of hardness values.
- thermoplastic ball in which all layers are thermoplastic, must provide good performance characteristics to compete with rubber-containing golf balls. While various uses for highly neutralized acid polymers in golf balls have been discovered, there is a need to improve golf ball characteristics when using combinations of thermoplastic polymers to provide golf ball constructions having desirable spin, feel, and COR properties.
- a thermoplastic multi-layer golf ball has a core center with a diameter from about 21 mm to about 29 mm and includes a first thermoplastic material having a first flexural modulus up to about 15,000 psi, a core layer disposed radially outward from and enclosing the core center, the core layer having a thickness of at least about 4 mm and including a second thermoplastic material having a second flexural modulus of up to about 9700 psi, and a cover disposed radially outwardly from the core layer and forming an outer structural layer of the ball, the cover including a third thermoplastic material having a third flexural modulus of up to about 6,000 psi.
- the first flexural modulus is greater than the second flexural modulus
- the second flexural modulus is greater than the third flexural modulus
- the specific gravities of the core layer and the core center differ by at least about 0.1 g/cm 3 .
- the ball preferably is fully thermoplastic and has no rubber thermoset layer.
- the ball may have one or more further core layers.
- the cover may be a single-layer or multi-layer cover.
- the second flexural modulus may be at least about 5,000 psi greater than the third flexural modulus.
- a golf ball has a core center that has a diameter of from about 21 mm to about 29 mm and includes a first thermoplastic material that includes an ionomer resin and a polyolefm elastomer and has a 10-130 kg compression deformation of at least about 4 mm and a first flexural modulus of up to about 9700 psi; a core layer disposed radially outward from the core center with a thickness of at least about 5 mm and including a second thermoplastic material having a second flexural modulus of up to about 15,000 psi; and a cover disposed radially outward from the core layer that includes a third thermoplastic material having a third flexural modulus of up to about 5,000 psi.
- the second flexural modulus is at least about 10,000 psi greater than the third flexural modulus, the second flexural modulus is greater than the first flexural modulus, and the specific gravity of the core layer and the specific gravity of the core center differ by at least about 0.1 g/cm 3 .
- the ball preferably is fully thermoplastic and has no rubber thermoset layer.
- the ball may have one or more further core layers.
- the cover may be a single-layer or multi-layer cover.
- the golf ball has a multi-layer core including a core center as an innermost core part and one or more "core layers" outward from and enclosing the center.
- a “core layer” for this invention is any golf ball layer lying between the center and the cover of the golf ball.
- a “cover” is the outermost structural golf ball layer of the ball or, for two cover layers, each "cover layer” is one of the two outermost structural golf ball layers. Coating layers (whether paint layers or clear coating layers) are not considered to be structural layers.
- Flexural modulus is measured according to ASTM D790.
- the Figure is a partial cross-sectional view of an embodiment of a multi-layer golf ball that illustrates some aspects of the disclosed technology.
- the parts of the Figure are not necessarily to scale.
- a multi-layer golf ball 100 has a core center 110, a core layer 120 that is radially outward from the core center 110, and a cover 130 that forms the outermost layer of the golf ball 100.
- Each of the core center, the core layer, and the cover includes a thermoplastic material.
- the disclosed golf ball has a multi-layer core that includes at least a core center including a first thermoplastic material and a core layer radially outward from the core center including a second thermoplastic material.
- the ball has a cover including a third thermoplastic material.
- Each of the first, second, and third thermoplastic materials may include at least one thermoplastic elastomer.
- Each of the first, second, and third thermoplastic materials may also include one or more non-elastomeric polymers, plasticizers, fillers, and customary additives.
- the second thermoplastic material's flexural modulus is greater than the third thermoplastic material's flexural modulus, preferably by at least about 2000 psi, more preferably at least about 3000 psi, and still more preferably at least about 4000 psi or at least about 5000 psi.
- the second thermoplastic material's flexural modulus may be greater than the third thermoplastic material's flexural modulus by from about 2000 psi or from about 3000 psi up to about 4000 psi or up to about 5000 psi or up to about 6000 psi or up to about 7000 psi or up to about 8000 psi or up to about 9000 psi.
- the second thermoplastic material's flexural modulus may be greater than the third thermoplastic material's flexural modulus by from about 4000 psi or from about 5000 psi up to about . up to about 6000 psi or up to about 7000 psi or up to about 8000 psi or up to about 9000 psi or up to about 10,000 psi or up to about 11,000 psi or up to about 12,000 psi or up to about 13,000 psi or up to about 14,000 psi.
- the third material's flexural modulus is up to about 6000 psi, preferably up to about 5000 psi, more preferably up to about 4000 psi or up to about 3000 psi or up to about 2000 psi or up to about 1500 psi or up to about 1000 psi.
- the third material's flexural modulus may be from about 500 psi or from about 700 psi or from about 1000 psi up to about 6000 psi, preferably up to about 5000 psi, more preferably up to about 4000 psi or up to about 3000 psi or up to about 2000 psi or up to about 1500 psi or may be from about 1500 psi or from about 2000 psi up to about 6000 psi, preferably up to about 5000 psi, more preferably up to about 4000 psi or up to about 3000 psi.
- the specific gravities of the core center and the core layer differ by at least about 0.1 g/cm 3 .
- the first thermoplastic material's flexural modulus is up to about 15,000 psi, preferably up to about 12,000 psi, and is greater than the second thermoplastic material's flexural modulus, which is up to about 9700 psi, preferably up to about 8000 psi.
- the first thermoplastic material's flexural modulus may be from about 8000 psi or from about 9000 psi or from about 10,000 psi up to about 11,000 psi or up to about 12,000 psi or up to about 13,000 psi or up to about 14,000 psi or up to about 15,000 psi, while the second thermoplastic material's flexural modulus may be from about 4000 psi or from about 4500 psi or from about 5000 psi up to about 6000 psi or up to about 7000 psi or up to about 8000 psi or up to about 9000 psi or up to about 9700 psi.
- thermoplastic material's flexural modulus being up to about 15,000 psi, preferably up to about 12,000 psi, and being greater than the first thermoplastic material's flexural modulus, which is up to about 9700 psi, preferably up to about 8000 psi.
- the second thermoplastic material's flexural modulus may be from about 8000 psi or from about 9000 psi or from about 10,000 psi up to about 1 1,000 psi or up to about 12,000 psi or up to about 13,000 psi or up to about 14,000 psi or up to about 15,000 psi, while the first thermoplastic material's fiexural modulus may be from about 4000 psi or from about 4500 psi or from about 5000 psi up to about 6000 psi or up to about 7000 psi or up to about 8000 psi or up to about 9000 psi or up to about 9700 psi.
- the second thermoplastic material's fiexural modulus may be at least about 10,000 psi greater than the third thermoplastic material's fiexural modulus, from example from about 10,000 psi to about 12,000 psi or to about 13,000 psi greater than the third thermoplastic material's fiexural modulus.
- the fiexural moduli of the first, second, and third thermoplastic materials depend on a combination of factors, including the nature and amount of thermoplastic elastomers in the thermoplastic materials, the presence, nature, and amount of other polymeric materials, and the presence, nature, and amount of fillers. In general, fillers increase the flexural modulus of a thermoplastic material. The polymers and the type and amount of any filler of each of the first, second, and third thermoplastic materials are selected and apportioned so that the flexural moduli have the desired relationship. In preferred embodiments, the golf ball is free from any thermoset rubber layer or other thermoset layer.
- the first, second, and third thermoplastic materials generally include at least one thermoplastic elastomer.
- suitable thermoplastic elastomers that can be used in making the golf ball core and cover include metal cation ionomers of addition copolymers ("ionomer resins"),
- thermoplastic polyamide elastomers e.g., polyether block
- thermoplastic polyester elastomers thermoplastic styrene block copolymer elastomers such as poly(styrene-butadiene-styrene), poly(styrene-ethylene- co-butylene-styrene), and poly(styrene-isoprene-styrene), thermoplastic polyurethane elastomers, thermoplastic polyurea elastomers, and dynamic vulcanizates of rubbers in these thermoplastic elastomers and in other thermoplastic matrix polymers.
- Ionomer resins which are metal cation ionomers of addition copolymers of ethylenically unsaturated acids, are preferably alpha-olefm, particularly ethylene, copolymers with C 3 to Cg ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, particularly acrylic or methacrylic acid.
- the copolymers may also contain a softening monomer such as an alkyl acrylate or methacrylate, for example a Ci to Cs alkyl acrylate or methacrylate ester.
- the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer may be from about 4 weight percent or about 6 weight percent or about 8 weight percent up to about 20 weight percent or up to about 35 weight percent of the copolymer, and the softening monomer, when present, is preferably present in a finite amount, preferably at least about 5 weight percent or at least about 11 weight percent, up to about 23 weight percent or up to about 25 weight percent or up to about 50 weight percent of the copolymer.
- the most preferred acid-containing ethylene copolymers include ethylene/(meth)acrylic acid/n-butyl acrylate, ethylene/(meth)acrylic acid/ethyl acrylate, and ethylene/(meth)acrylic acid/methyl acrylate copolymers.
- the ionomer resin may be a high acid ionomer resin.
- ionomers prepared by neutralizing acid copolymers including at least about 16 weight % of copolymerized acid residues based on the total weight of the unneutralized ethylene acid copolymer are considered "high acid” ionomers.
- the acid monomer, particularly acrylic or methacrylic acid is present in about 16 to about 35 weight %.
- copolymerized carboxylic acid may be from about 16 weight %, or about 17 weight % or about 18.5 weight % or about 20 weight % up to about 21.5 weight % or up to about 25 weight % or up to about 30 weight % or up to about 35 weight % of the unneutralized copolymer.
- a high acid ionomer may be combined with a "low acid" ionomer in which the copolymerized carboxylic acid is less than 16 weight % of the unneutralized copolymer.
- the acid moiety in the ethylene-acid copolymer is neutralized by any metal cation. Suitable preferred cations include lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum, or a combination of these cations; in various embodiments alkali metal, alkaline earth metal, or zinc cations are particularly preferred.
- the acid groups of the ionomer may be neutralized from about 10% or from about 20% or from about 30% or from about 40% to about 60% or to about 70% or to about 75% or to about 80% or to about 90%.
- a sufficiently high molecular weight, monomeric organic acid or salt of such an organic acid may be added to the acid copolymer or ionomer so that the acid copolymer or ionomer can be neutralized, without losing processability, to a level above the level that would cause the ionomer alone to become non-melt- processable.
- the high-molecular weight, monomeric organic acid its salt may be added to the ethylene-unsaturated acid copolymers before they are neutralized or after they are optionally partially neutralized to a level between about 1 and about 100%, provided that the level of neutralization is such that the resulting ionomer remains melt-processable.
- the acid groups of the copolymer may be neutralized from at least about 40 to about 100%, preferably from at least about 90% to about 100%, and most preferably 100% without losing processability.
- Such high neutralization, particularly to levels greater than 70%, greater than 80%, greater than 90%, greater than 95%, or most preferably 100%, without loss of processability can be done by (a) melt- blending the ethylene-a, -ethylenically unsaturated carboxylic acid copolymer or a melt-processable salt of the copolymer with an organic acid or a salt of organic acid, and (b) adding a sufficient amount of a cation source up to 110% of the amount needed to neutralize the total acid in the copolymer or ionomer and organic acid or salt to the desired level to increase the level of neutralization of all the acid moieties in the mixture preferably to greater than 90%, preferably greater than 95%, or preferably to 100%.
- the high molecular weight, monomeric saturated or unsaturated acid may have from 8 or 12 or 18 carbon atoms to 36 carbon atoms or to less than 36 carbon atoms.
- Nonlimiting suitable examples of the high-molecular weight, monomeric saturated or unsaturated organic acids include stearic, behenic, erucic, oleic, and linoleic acids and their salts, particularly the barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, or calcium salts of these fatty acids. These may be used in combinations.
- Thermoplastic polyolefm elastomers may also be used in the thermoplastic materials of the golf ball. These are metallocene-catalyzed block copolymers of ethylene and a-olefins having 4 to about 8 carbon atoms that are prepared by single-site metallocene catalysis, for example in a high pressure process in the presence of a catalyst system comprising a cyclopentadienyl-transition metal compound and an alumoxane.
- Nonlimiting examples of the a-olefin softening comonomers include hexane-1 or octene-1; octene-1 is a preferred comonomer to use. These materials are commercially available, for example, from ExxonMobil under the tradename ExactTM and from the Dow Chemical Company under the tradename EngageTM.
- the thermoplastic material includes a combination of a metal ionomer of a copolymer of ethylene and at least one of acrylic acid and methacrylic acid, a metallocene-catalyzed copolymer of ethylene and an a- olefin having 4 to about 8 carbon atoms, and a metal salt of an unsaturated fatty acid.
- This material may be prepared as described in Statz et al, U.S. 7,375,151 or as described in Kennedy, "Process for Making Thermoplastic Golf Ball Material and Golf Ball with Thermoplastic Material, U.S. Patent Appl. No. 13/825112, filed 15 March 2013, the entire contents of both being incorporated herein by reference.
- thermoplastic styrene block copolymer elastomers that may be used in the thermoplastic materials of the golf ball include poly(styrene- butadiene-styrene), poly(styrene-ethylene-co-butylene-styrene), poly(styrene- isoprene-styrene), and poly(styrene-ethylene-co-propylene) copolymers.
- These styrenic block copolymers may be prepared by living anionic polymerization with sequential addition of styrene and the diene forming the soft block, for example using butyl lithium as initiator.
- thermoplastic polyurethane elastomers such as thermoplastic polyester-polyurethanes, polyether-polyurethanes, and polycarbonate-polyurethanes may be used in the thermoplastic materials, particularly in the third thermoplastic material for the cover.
- the thermoplastic polyurethane elastomers include polyurethanes polymerized using as polymeric diol reactants polyethers and polyesters including polycaprolactone polyesters.
- polymeric diol-based polyurethanes are prepared by reaction of the polymeric diol (polyester diol, polyether diol, polycaprolactone diol, polytetrahydrofuran diol, or polycarbonate diol), one or more polyisocyanates, and, optionally, one or more chain extension compounds.
- Chain extension compounds are compounds having two or more functional groups reactive with isocyanate groups, such as the diols, amino alcohols, and diamines.
- the polymeric diol-based polyurethane is substantially linear (i.e., substantially all of the reactants are difunctional).
- HDI hexamethylene diisocyanate
- XDI para-xylylenediisocyanate
- 4-chloro-l,3- phenylene diisocyanate 1,5-tetrahydro-naphthalene diisocyanate, 4,4'-dibenzyl diisocyanate, and combinations of these.
- Nonlimiting examples of higher-functionality polyisocyanates that may be used in limited amounts to produce branched thermoplastic polyurethanes (optionally along with monofunctional alcohols or monofunctional isocyanates) include 1,2,4-benzene triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, triphenylmethane-4,4',4"- triisocyanate, isocyanurates of diisocyanates, biurets of diisocyanates, allophanates of diisocyanates, and the like.
- Nonlimiting examples of suitable diols that may be used as extenders include ethylene glycol and lower oligomers of ethylene glycol including diethylene glycol, triethylene glycol, and tetraethylene glycol; propylene glycol and lower oligomers of propylene glycol including dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; cyclohexanedimethanol, 1 ,6-hexanediol, 2-ethyl-l,6- hexanediol, 1 ,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,3-propanediol, butylene glycol, neopentyl glycol, dihydroxyalkylated aromatic compounds such as the bis (2- hydroxyethyl) ethers of hydroquinone and resorcinol; p-xylene-a,a'-
- a small amount of a trifunctional extender such as trimethylolpropane, 1,2,6-hexanetriol and glycerol, or monofunctional active hydrogen compounds such as butanol or dimethylamine, may also be included.
- the amount of trifunctional extender or monofunctional compound employed may be, for example, 5.0 equivalent percent or less based on the total weight of the reaction product and active hydrogen containing groups used.
- Suitable dicarboxylic acids include, without limitation, glutaric acid, succinic acid, malonic acid, oxalic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, suberic acid, azelaic acid, dodecanedioic acid, their anhydrides and
- Alkylene oxide polymer segments include, without limitation, the polymerization products of ethylene oxide, propylene oxide, 1 ,2-cyclohexene oxide, 1-butene oxide, 2-butene oxide, 1-hexene oxide, tert-butylethylene oxide, phenyl glycidyl ether, 1- decene oxide, isobutylene oxide, cyclopentene oxide, 1-pentene oxide, and
- the oxirane- or cyclic ether-containing compound is preferably selected from ethylene oxide, propylene oxide, butylene oxide,
- the alkylene oxide polymerization is typically base-catalyzed.
- the polymerization may be carried out, for example, by charging the hydroxyl-functional initiator compound and a catalytic amount of caustic, such as potassium hydroxide, sodium methoxide, or potassium tert-butoxide, and adding the alkylene oxide at a sufficient rate to keep the monomer available for reaction.
- caustic such as potassium hydroxide, sodium methoxide, or potassium tert-butoxide
- Two or more different alkylene oxide monomers may be randomly copolymerized by coincidental addition or polymerized in blocks by sequential addition. Homopolymers or copolymers of ethylene oxide or propylene oxide are preferred.
- the reaction of the polyisocyanate, polymeric diol, and diol or other chain extension agent is typically carried out at an elevated temperature in the presence of a catalyst.
- Typical catalysts for this reaction include organotin catalysts such as stannous octoate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, tertiary amines, zinc salts, and manganese salts.
- organotin catalysts such as stannous octoate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, tertiary amines, zinc salts, and manganese salts.
- organotin catalysts such as stannous octoate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin oxide, tertiary amines,
- Suitable thermoplastic polyurea elastomers may be prepared by reaction of one or more polymeric diamines or polyols with one or more of the polyisocyanates already mentioned and one or more diamine extenders.
- suitable diamine extenders include ethylene diamine, 1,3 -propylene diamine, 2-methyl-pentamethylene diamine, hexamethylene diamine, 2,2,4- and 2,4,4- trimethyl-l,6-hexane diamine, imino-bis(propylamine), imido-bis(propylamine), N- (3-aminopropyl)-N-methyl-l ,3-propanediamine), 1 ,4-bis(3-aminopropoxy)butane, diethyleneglycol-di(aminopropyl)ether), 1 -methyl-2,6-diamino-cyclohexane, 1 ,4- diamino-cyclohexane, 1,3- or l,4-
- polyoxyethylene diamines polyoxypropylene diamines, poly(oxyethylene- oxypropylene) diamines, and poly(tetramethylene ether) diamines.
- the amine- and hydroxyl-functional extenders already mentioned may be used as well.
- trifunctional reactants are limited and may be used in conjunction with monofunctional reactants to prevent crosslinking.
- Polymerization may be carried out, for example, at temperatures of from about 180° C. to about 300° C.
- suitable polyamide block copolymers include NYLON 6, NYLON 66, NYLON 610, NYLON 11, NYLON 12,
- thermoplastic materials of the golf ball core and cover may include combinations of thermoplastic elastomers.
- a thermoplastic elastomers in one embodiment, a
- the first thermoplastic material includes an ionomer resin and a polyolefm elastomer.
- First thermoplastic materials with this combination may have a 10-130 kg compression deformation of at least about 4 mm, preferably at least about 6 mm.
- the flexural modulus of a thermoplastic material may be increased by including a filler.
- Various fillers may be included, and the filler may also be selected to modify the specific gravity, hardness, or other properties of the thermoplastic material.
- suitable fillers include 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, beryllium and alloys of these), metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide and the like), particulate synthetic plastics (such as high molecular weight polyethylene, polystyrene, polyethylene ionomeric resins and the like),
- Various heavy-weight or light-weight fillers may be included in the different thermoplastic materials of the golf ball to result in desirable relationships between the specific gravities of the different layers.
- the core layer and the core center have a difference in specific gravity difference of at least about 0.1 g/cm 3 .
- the specific gravity of the core layer is at least about 0.1 g/cm 3 greater than the specific gravity of the core center, while in other embodiments the specific gravity of the core center is at least about 0.1 g/cm 3 greater than the specific gravity of the core layer.
- the cover may also contain additives such as hindered amine light stabilizers such as piperidines and oxanalides, ultraviolet light absorbers such as benzotriazoles, triazines, and hindered phenols, fluorescent materials and fluorescent brighteners, dyes such as blue dye, and antistatic agents.
- additives such as hindered amine light stabilizers such as piperidines and oxanalides, ultraviolet light absorbers such as benzotriazoles, triazines, and hindered phenols, fluorescent materials and fluorescent brighteners, dyes such as blue dye, and antistatic agents.
- one of the first and second thermoplastic materials has a flexural modulus of up to about 15,000 psi, preferably from about 8,000 psi to about 15,000 psi, , while the other of the first and second thermoplastic materials has a flexural modulus from about 4000 psi up to about 9700 psi.
- the flexural modulus of the core center is greater than the flexural modulus of the core layer.
- the core layer may have a thickness of at least about 4 mm or at least about 5 mm.
- the core layer may be up to about 10 mm or up to about 9 mm or up to about 8 mm or up to about 7 mm thick.
- the golf ball has a second core layer between the core layer and the cover.
- the second core layer includes a fourth thermoplastic material with a fourth flexural modulus of from about 30,000 psi to about 120,000 psi and that is greater than the flexural modulus of the core layer.
- the fourth flexural modulus is from about 40,000 psi or from about 50,000 psi or from about 60,000 psi to about 115,000 psi or to about 110,000 psi or to about 100,000 psi to or to about 90,000 psi.
- thermoplastic polymers that may be used are the grades of ionomer resins sold by DuPont Company, Wilmington DE under the name Surlyn® 6910, 9910, 8920, 7930, 7940, 8940, 8941, 9945, 8945, 9950, 9520, 9721, 6120, 8140, 8150, 9120, 9150, 8527, 8528, 9650, and 8660, and DuPont's HPF1000.
- the fourth flexural modulus of the second core layer is at least three times the second flexural modulus of the core layer and at least 30 times the third flexural modulus of the cover.
- the thermoplastic materials may be made by conventional methods, such as melt mixing in a single- or twin-screw extruder, a Banbury mixer, an internal mixer, a two-roll mill, or a ribbon mixer.
- the first thermoplastic material is formed into a core center and the second thermoplastic material is formed into a core layer around the core center by usual methods, for example by injection molding with a mold temperature in the range of 150° C. to 230° C. If there is a second core layer, the fourth thermoplastic material may be formed in a layer over the core layer by the same methods.
- the molded core including core center, core layer, and optionally second core layer or further core layers may be ground to a desired diameter of from 21 mm to 29 mm after cooling. Grinding can also be used to remove flash, pin marks, and gate marks due to the molding process.
- a cover layer is molded over the core.
- the third thermoplastic material used to make the cover may preferably include one or more of thermoplastic polyurethane elastomers, thermoplastic polyurea elastomers, and the metal cation salts of copolymers of ethylene with ethylenically unsaturated carboxylic acids.
- the cover may be formed on the multi-layer core by injection molding, compression molding, casting, and so on.
- a core fabricated beforehand may be set inside a mold, and the cover material may be injected into the mold.
- the cover is typically molded on the core by injection molding or compression molding.
- another method that may be used involves pre-molding a pair of half-covers from the cover material by die casting or another molding method, enclosing the core in the half- covers, and compression molding at, for example, between 120° C. and 170° C. for a period of 1 to 5 minutes to attach the cover halves around the core.
- the core may be surface-treated before the cover is formed over it to increase the adhesion between the core and the cover.
- suitable surface preparations include mechanical or chemical abrasion, corona discharge, plasma treatment, or application of an adhesion promoter such as a silane or of an adhesive.
- the cover typically has a dimple pattern and profile to provide desirable aerodynamic characteristics to the golf ball.
- the cover may have a thickness of from about 0.5 mm to about 4 mm. If there are two cover layers, typically, the cover layers may each independently have a thickness of from about 0.3 mm to about 2.0 mm, preferably from about 0.8 mm to about 1.6 mm.
- the golf balls can be of any size, although the USGA requires that golf balls used in competition have a diameter of at least 1.68 inches (42.672 mm) and a weight of no greater than 1.62 ounces (45.926 g). For play outside of USGA competition, the golf balls can have smaller diameters and be heavier.
- the golf ball After a golf ball has been molded, it may undergo various further processing steps such as buffing, painting and marking.
- the golf ball has a dimple pattern that coverage of 65% or more of the surface.
- the golf ball typically is coated with a durable, abrasion—resistant and relatively non-yellowing finish coat.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/892,970 US20160107040A1 (en) | 2013-05-31 | 2014-05-27 | Thermoplastic Multi-Layer Golf Ball |
KR1020157034446A KR20150139985A (en) | 2013-05-31 | 2014-05-27 | Thermoplastic multi-layer golf ball |
JP2015563086A JP2016526936A (en) | 2013-05-31 | 2014-05-27 | Thermoplastic multilayer golf ball |
CN201480030818.6A CN105246561A (en) | 2013-05-31 | 2014-05-27 | Thermoplastic multi-layer golf ball |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361829280P | 2013-05-31 | 2013-05-31 | |
US61/829,280 | 2013-05-31 | ||
US14/061,189 US20140357412A1 (en) | 2013-05-31 | 2013-10-23 | Thermoplastic multi-layer golf ball |
US14/061,189 | 2013-10-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014193810A1 true WO2014193810A1 (en) | 2014-12-04 |
Family
ID=51985753
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2014/039531 WO2014193810A1 (en) | 2013-05-31 | 2014-05-27 | Thermoplastic multi-layer golf ball |
Country Status (5)
Country | Link |
---|---|
US (2) | US20140357412A1 (en) |
JP (1) | JP2016526936A (en) |
KR (1) | KR20150139985A (en) |
CN (1) | CN105246561A (en) |
WO (1) | WO2014193810A1 (en) |
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Also Published As
Publication number | Publication date |
---|---|
JP2016526936A (en) | 2016-09-08 |
US20140357412A1 (en) | 2014-12-04 |
CN105246561A (en) | 2016-01-13 |
US20160107040A1 (en) | 2016-04-21 |
KR20150139985A (en) | 2015-12-14 |
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