JP2016526936A - Thermoplastic multilayer golf ball - Google Patents

Abstract

A thermoplastic multilayer golf ball having a thermoplastic core center having a first flexural modulus and a diameter of about 21-29 mm; and a radially outer thermoplastic core layer having a second flexural modulus; Having a radially outer thermoplastic cover with a third flexural modulus of up to 000-6,000. The second flexural modulus is greater than the third flexural modulus. The specific gravity of the core layer and the core center differs by at least about 0.1 g / cm 3. The first flexural modulus is up to 15,000 psi and greater than the second flexural modulus that is about 9700, or the second flexural modulus is up to about 15,000 psi and is about 9700. Greater than the first flexural modulus, the first thermoplastic material comprises an ionomer resin and a polyolefin elastomer and has a 10-130 kg compression deformation of at least about 4 mm.

Description

  The present invention relates to a multi-layer golf ball in which the layers have different flexural moduli.

  This section provides information to help understand the present invention, but is not necessarily prior art.

  Golf ball cores and cover layers are typically constructed with a polymer composition comprising, for example, polybutadiene rubber, polyurethane, polyamide, ionomer, and blends of such polymers. Ionomers, particularly ethylene-based ionomers, are a preferred group of polymers for golf ball layers because of their toughness, durability, and a wide range of hardness values.

  Golf ball compositions containing highly neutralized acidic polymers are known. For example, U.S. Patent No. 6,057,028, the entire disclosure of which is incorporated herein by reference, includes: (a) a melt processable, ethylene acid copolymer; (b) an aliphatic, monofunctional organic acid or salt thereof; (c) Disclosed is a highly elastic thermoplastic ionomer resin composition comprising a thermoplastic resin; (d) a cation source; and (e) an optional filler. The ionomer resin can be neutralized to more than 90% of the total acidic groups present and can remain melt processable. This patent discloses the use of highly resilient thermoplastic compositions in one-piece, two-piece, three-piece and multi-layer golf balls.

  The difference in the flexural modulus between layers in a ball having a hardened rubber core is described in, for example, Patent Document 2 by Loper et al. Construction of thermoplastic balls in which all layers are thermoplastic must provide excellent performance characteristics in order to compete with golf balls containing rubber. While various uses for highly neutralized acidic polymers in golf balls have been disclosed, in using a combination of thermoplastic polymers to provide a golf ball structure with the desired spin, feel and COR properties There is a need to improve the golf ball characteristics of

US Pat. No. 7,375,151 US Patent Application Publication No. 2012/0129630

  This section provides a general summary of the disclosure, but is not exhaustive of all or all of the disclosed features.

In one aspect of the disclosed technology, a thermoplastic multilayer golf ball includes a first thermoplastic material having a diameter of about 21 mm to about 29 mm and having a first flexural modulus of up to about 15,000 psi. A second thermoplastic layer disposed radially outward from the core center and surrounding the core center, the core layer having a thickness of at least about 4 mm and a second flexural modulus of up to about 9700 psi A core layer comprising a material and a cover disposed radially outward from the core layer to form an outer structural layer of the ball, the third thermoplastic having a third flexural modulus up to about 6,000 psi A cover including the material. The first flexural modulus is greater than the second flexural modulus, the second flexural modulus is greater than the third flexural modulus, and the specific gravity of the core layer and the core center differs by at least about 0.1 g / cm ³ .

  In the first disclosed embodiment, the ball is preferably completely thermoplastic and does not have a rubber thermoset layer. The ball may have one or more additional core layers. The cover can be a single layer or a multilayer cover. In certain embodiments, the second flexural modulus may be at least about 5,000 psi greater than the third flexural modulus.

In another aspect of the technology, the golf ball has a first flexural modulus of up to about 9700 psi and a 10-130 kg compression deformation of at least 4 mm, and includes a first thermoplastic material comprising an ionomer resin and a polyolefin elastomer. A core center having a diameter of from about 21 mm to about 29 mm; a second core having a thickness of at least about 5 mm and radially outward from the core center and having a second flexural modulus of up to about 15,000 psi A core layer comprising two thermoplastic materials; and a cover disposed radially outward from the core layer comprising 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 are at least About 0.1 g / cm ^{3 is} different.

  Again, the balls are preferably completely thermoplastic and do not have a rubber thermoset layer. The ball may have one or more additional core layers. The cover can be a single layer or a multilayer cover.

  The golf ball has a core center as an innermost core portion and a multilayer core that surrounds the center and includes one or more “core layers” outward from the center. A “core layer” in the context of the present invention is any golf ball layer that exists between the center of the golf ball and the cover. In the description of the present invention, a “cover” is the outermost structure golf ball layer of the ball, or, for two cover layers, each “cover layer” is one of the two outermost structure golf ball layers. It is. A coating layer (whether a paint layer or a clear coating layer) is not considered a structural layer.

  The flexural modulus is measured according to ASTM D790. Specific gravity is measured according to ASTM D792. “Compression deformation” is obtained by subtracting the deformation amount in millimeters under a compression load of 130 kg by the deformation amount in millimeters under a compression load of 10 kg. The amount of deformation of the ball is measured under a force of 10 kg, after which the force is increased to 130 kg and the amount of deformation is measured under a new force of 130 kg. The deformation at 10 kg is subtracted from the deformation at 130 kg to give a 10-130 kg compression deformation and is reported in millimeters.

  “A”, “an”, “the”, “at least one” and “one or more” are used interchangeably to indicate that there is at least one item; an indefinite article is clearly in context Unless indicated otherwise, indicates that there may be multiple such items. All numerical values for parameters herein (eg, quantities or conditions), including the appended claims, shall be expressed as “about”, regardless of whether “about” actually appears before the number. It should be understood that the terminology is changed in all instances. “About” indicates that the stated numerical value allows some inaccuracies (by some approach to accuracy in value; approximately or fairly close to value; almost). If the inaccuracy provided by "about" is not otherwise understood in the prior art by this ordinary meaning, then "about" as used herein is at least a measurement of the usual method, And the variations that may result from the use of such parameters. In addition, disclosure of ranges includes disclosure of all values and further subdivided ranges within the entire range. Each value in a range and the endpoints of the range are all disclosed herein as separate embodiments. In this description of the invention, for convenience, “polymer” and “resin” are used interchangeably to include resins, oligomers and polymers. The terms “including”, “comprising”, “including” and “having” are inclusive and thus identify the presence of the item being described, but other It does not exclude the presence of items. As used herein, the term “or” includes any and all combinations of one or more of the listed items. When the terms first, second, third, etc. are used to distinguish various items from each other, these designations are for convenience only and do not limit the items.

  It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the claims.

1 is a partial cross-sectional view of an embodiment of a multi-layer golf ball showing some aspects of the disclosed technology. Some of the figures are not necessarily to scale.

  A detailed description of exemplary non-limiting embodiments follows.

  As shown in the drawings, the multilayer 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 at least a core center including a first thermoplastic material and a multi-layer core including a core layer radially outward from the core center including a second thermoplastic material. The ball has a cover that includes 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 conventional additives.

The flexural modulus of the second thermoplastic material is preferably at least about 2000 psi, more preferably at least about 3000 psi, even more preferably at least about 4000 psi, or at least about 5000 psi than the flexural modulus of the third thermoplastic material. large. The flexural modulus of the second thermoplastic material is from about 2000 psi, or from about 3000 psi, to about 4000 psi, to about 5000 psi, or to about 6000 psi, or about than the flexural modulus of the third thermoplastic material. May be large up to 7000 psi, or up to about 8000 psi, or up to about 9000 psi. In other embodiments, the flexural modulus of the second thermoplastic material is from about 4000 psi, or from about 5000 psi, to about 6000 psi, or to about 7000 psi, than the flexural modulus of the third thermoplastic material, 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 flexural modulus of the third material 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, up to about 1500 psi, or up to about 1000 psi. In various embodiments, the flexural modulus of the third material is from about 500 psi, or from about 700 psi, or from about 1000 psi, to about 6000 psi, preferably up to about 5000 psi, more preferably up to about 4000 psi, or about 3000 psi. Up to, or up to about 2000 psi, or up to about 1500 psi, or 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 gravity of the core center and core layer differs by at least about 0.1 g / cm ³ .

  In a first disclosed aspect, the flexural modulus of the first thermoplastic material is up to about 15,000 psi, preferably up to about 12,000 psi, up to about 9700 psi, preferably up to about 8000 psi. Greater than the flexural modulus of the thermoplastic material. In a first disclosed aspect, the flexural modulus of the first thermoplastic material is from about 8000 psi, or from about 9000 psi, or from about 10,000 psi, to about 11,000 psi, or 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 flexural modulus of the second thermoplastic material is from about 4000 psi, or from about 4500 psi, or about It can be from 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. In the second disclosed embodiment, this relationship is reversed and the flexural modulus of the second thermoplastic material is up to about 15,000 psi, preferably up to about 12,000 psi, preferably up to about 9700 psi, preferably Greater than the flexural modulus of the first thermoplastic material up to about 8000 psi. In a second disclosed aspect, the flexural modulus of the second thermoplastic material is from about 8000 psi, or from about 9000 psi, or from about 10,000 psi, to about 11,000 psi, or 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 flexural modulus of the first thermoplastic material is from about 4000 psi, or from about 4500 psi, or about It can be from 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. Also, in the second disclosed embodiment, the flexural modulus of the second thermoplastic material can be at least about 10,000 psi greater than the flexural modulus of the third thermoplastic material, for example, 3 can be greater than the flexural modulus of the thermoplastic material from about 10,000 psi to about 12,000 psi, or up to about 13,000 psi.

  The flexural modulus of the first, second and third thermoplastic materials is determined by the nature and amount of the thermoplastic elastomer in the thermoplastic material, the presence, nature and amount of other polymer materials, and the presence and nature of the filler. And depends on a combination of factors, including quantity. In general, the filler increases the flexural modulus of the thermoplastic material. The type and amount of optional filler in each of the polymer and the first, second and third thermoplastic materials are selected and distributed so that the flexural modulus has the desired relationship. In a preferred embodiment, the golf ball does not include any thermoset rubber layer or other thermoset layer.

  The core may have one or more additional core layers. In certain embodiments, the golf ball includes a second core layer between the core layer and the cover. The second core layer includes a fourth thermoplastic material having a flexural modulus greater than that of the second thermoplastic material of the core layer.

  The first, second and third thermoplastic materials generally comprise at least one thermoplastic elastomer. Non-limiting examples of suitable thermoplastic elastomers that can be used to make golf ball cores and covers include addition copolymer metal cation ionomers ("ionomer resins") containing from 4 to about 8 carbon atoms. Block copolymer of α-olefin and ethylene by metallocene catalyst, thermoplastic polyamide elastomer (for example, polyether block polyamide), thermoplastic polyester elastomer, poly (styrene-butadiene-styrene), poly (styrene-ethylene-co-butylene) -Styrene), and thermoplastic styrene block copolymer elastomers such as poly (styrene-isoprene-styrene), thermoplastic polyurethane elastomers, thermoplastic polyurea elastomers, and in these thermoplastic elastomers Including dynamic vulcanized rubber in the thermoplastic matrix polymer.

The ionomer resin, which is a metal cation ionomer of an addition copolymer of ethylenically unsaturated acids, is preferably an alpha-olefin of C ₃ to C ₈ α, β-ethylenically unsaturated carboxylic acid, especially acrylic or methacrylic acid, In particular, a copolymer of ethylene. The copolymer may also contain a softening monomer such as an alkyl acrylate or methacrylate, for example a C ₁ to C ₈ alkyl acrylate or methacrylate ester. The α, β-ethylenically unsaturated carboxylic acid monomer can be 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; The softening polymer, when present, is preferably 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 about 50 weight percent of the copolymer. Present up to weight percent.

  Non-limiting specific examples of acid-containing ethylene copolymers include ethylene / acrylic acid / n-butyl acrylate, ethylene / methacrylic acid / n-butyl acrylate, ethylene / methacrylic acid / isobutyl acrylate, ethylene / acrylic acid / isobutyl acrylate, Ethylene / methacrylic acid / n-butyl methacrylate, ethylene / acrylic acid / methyl methacrylate, ethylene / acrylic acid / methyl acrylate, ethylene / methacrylic acid / methyl acrylate, ethylene / methacrylic acid / methyl methacrylate, and ethylene / acrylic acid / n- Butyl methacrylate copolymer. Preferred acid-containing ethylene copolymers are ethylene / methacrylic acid / n-butyl acrylate, ethylene / acrylic acid / n-butyl acrylate, ethylene / methacrylic acid / methyl acrylate, ethylene / acrylic acid / ethyl acrylate, ethylene / methacrylic acid / ethyl acrylate. And copolymers of ethylene / acrylic acid / methyl acrylate. In various embodiments, the most preferred acid-containing ethylene copolymers are ethylene / (meth) acrylic acid / n-butyl acrylate, ethylene / (meth) acrylic acid / ethyl acrylate, and ethylene / (meth) acrylic acid / methyl acrylate copolymers. including.

  The ionomer resin can be a high acid ionomer resin. Generally, an ionomer prepared by neutralizing an acid copolymer containing at least about 16% by weight copolymerized acid residues based on the total weight of the unneutralized ethylene acid copolymer is a "high acid" ionomer. Conceivable. In these highly elastic ionomers, the acid monomer, particularly acrylic acid or methacrylic acid, is present from about 16% to about 35% by weight. In various embodiments, the copolymerized carboxylic acid is about 16%, or about 17%, or about 18.5%, or about 20% to about 21.5% by weight of the unneutralized copolymer. Or up to about 25%, or up to about 30%, or up to about 35% by weight. High acid ionomers can be combined with "low acid" ionomers where the copolymerized carboxylic acid is less than 16% by 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 combinations of these cations; in various embodiments, alkali metals, alkaline earth metals, or Zinc cation is particularly preferred. In various embodiments, the ionomer's acidic groups are from about 10%, or from about 20%, or from about 30%, or from about 40%, to about 60%, or to about 70%, or about 75%. Or up to about 80%, or up to about 90%.

  A sufficiently high molecular weight monomeric organic acid, or a salt of such an organic acid, can be used to increase the acid copolymer or ionomer to a level above that which would render the ionomer alone unmeltable. Can be added to the acid copolymer or ionomer so that can be neutralized. High molecular weight, monomeric organic acids, salts thereof, can be about 1% before they are neutralized, or at a level of neutralization, provided that the resulting ionomer remains melt processable. And can be added to the ethylene-unsaturated acid copolymer after optionally neutralizing to a level between about 100%. Generally, when high molecular weight, monomeric organic acids are included, the acidic groups of the copolymer are at least about 40% to about 100%, preferably at least about 90% to about 100%, most preferably 100%. It can be neutralized without losing processability. Such high neutralization without loss of processability, in particular to a level of greater than 70%, greater than 80%, greater than 90%, greater than 95%, or most preferably 100% is (a ) Melt blending an ethylene-α, β-ethylenically unsaturated carboxylic acid copolymer, or a melt processable salt of the copolymer with an organic acid or salt of an organic acid; and (b) preferably greater than 90%, preferably To increase the level of neutralization of all acid moieties in the mixture to greater than 95%, or preferably to 100%, to the desired level to reduce the total acid in the organic acid or salt, and copolymer or ionomer. This can be done by adding a sufficient amount of cation source to 110% of the amount required to sum. In order to obtain 100% neutralization, it is preferred to add a slight excess of up to 110% cation source in excess of the stoichiometrically required to obtain 100% neutralization.

  High molecular weight, monomeric saturated or unsaturated acids may have from 8 or 12 or 18 carbon atoms up to 36 carbon atoms or up to 36 carbon atoms. Non-limiting suitable examples of high molecular weight, monomeric saturated or unsaturated organic acids are stearic acid, behenic acid, erucic acid, oleic acid and linoleic acid, and their salts, especially barium, lithium of these fatty acids Sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium or calcium salts. These can be used in combination.

  Thermoplastic polyolefin elastomers are sometimes used in thermoplastic materials for golf balls. These are, for example, α having 4 to about 8 carbon atoms that are regulated by single-site metallocene catalysis in a high-pressure process in the presence of a catalyst system comprising a cyclopentadienyl-transition metal compound and an alumoxane. -Block copolymer of olefin and ethylene by metallocene catalyst. Non-limiting examples of alpha-olefin softening comonomers include hexane-1 or octene-1; octene-1 is the preferred comonomer to use. These materials are commercially available from, for example, ExxonMobil under the trade name Exact® and from the Dow Chemical Company under the trade name Engage®.

  In various embodiments, the thermoplastic material comprises a metal salt of an unsaturated fatty acid, an alpha-olefin and ethylene metallocene-catalyzed copolymer having from 4 to about 8 carbon atoms, acrylic acid and methacrylic acid. And a combination of a metal ionomer of a copolymer of ethylene. This material is filed as described in US Pat. No. 7,375,151 by Statz et al., The entire contents of which are both incorporated herein by reference, or filed March 15, 2013. Kennedy, US patent application Ser. No. 13 / 825,112, “Process for Making Thermoplastic Golf Ball Material and Golf Ball with Thermoplastic Material”. A thermoplastic material having a flexural modulus of up to about 9700 psi (which is the second thermoplastic material in the first disclosed aspect but the first thermoplastic material in the second disclosed aspect) is: It may comprise an ionomer resin and a polyolefin elastomer and may have a 10-130 kg compression deformation of from about 4 mm to about 8 mm, preferably from about 4 mm to about 6 mm.

  Suitable thermoplastic styrene block copolymer elastomers that may be used in golf ball thermoplastic materials are 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 can be prepared, for example, by living anionic polymerization by sequential addition of diene and styrene to form a soft block using butyl lithium as an initiator. Thermoplastic styrene block copolymer elastomers are described in, for example, Kraton Polymers U.S. Pat. S. It is commercially available under the trademark Kraton® sold by LLC, Houston, TX. Other such elastomers use other polymerizable, hard, non-rubber monomers in place of styrene, including meta (acrylate) esters such as methyl methacrylate and cyclohexyl methacrylate, and other vinylarylenes such as alkyl styrene. Can be made as a block copolymer.

  Thermoplastic polyurethane elastomers such as thermoplastic polyester-polyurethanes, polyether-polyurethanes, and polycarbonate-polyurethanes can be used in thermoplastic materials, particularly in the third thermoplastic material for the cover. Thermoplastic polyurethane elastomers include polyesters including polycaprolactone polyesters and polyurethanes polymerized using polyethers as polymeric diol reactants. These polymeric diol-based polyurethanes are polymeric diols (polyester diol, polyether diol, polycaprolactone diol, polytetrahydrofuran diol, or polycarbonate diol), one or more polyisocyanates, and optionally one or more chains. It is adjusted by the reaction of the extension compound. A chain extension compound, when the term is used, is a compound having two or more functional groups that react with isocyanate groups, such as diols, amino alcohols, and diamines. Preferably, the polymeric diol-based polyurethane is substantially linear (ie, substantially all of the reactants are difunctional).

The diisocyanate used in making the polyurethane elastomer can be aromatic or aliphatic. Useful diisocyanate compounds used to prepare thermoplastic polyurethanes include isophorone diisocyanate (IPDI), methylene bis-4-cyclohexyl isocyanate (H ₁₂ MDI), cyclohexyl diisocyanate (CHDI), m-tetramethylxylene diisocyanate (m- TMXDI), p-tetramethylxylene diisocyanate (p-TMXDI), 4,4′-methylenediphenyl diisocyanate (also known as 4,4′-diphenylmethane diisocyanate, MDI), 2,4-, or 2,6- Toluene diisocyanate (TDI), ethylene diisocyanate, 1,2-diisocyanate propane, 1,3-diisocyanate propane, 1,6-diisocyanate hexane (hexamethylene diene) Isocyanate or HDI), 1,4-butylene diisocyanate, lysine diisocyanate, meta-xylene diisocyanate, and para-xylene diisocyanate (XDI), 4-chloro-1,3-phenylene diisocyanate, 1,5-tetrahydro-naphthalene diisocyanate, 4, , 4'-dibenzyl diisocyanate, as well as combinations thereof, but are not limited thereto. Non-limiting examples of higher order functional polyisocyanates that can be used in limited quantities to produce branched thermoplastic polyurethanes (along with monofunctional alcohols or monofunctional isocyanates as required) are: 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.

  Non-limiting examples of suitable diols that can be used as extenders include ethylene glycol and lower oligomers of ethylene glycol, including diethylene glycol, triethylene glycol, and tetraethylene glycol; propylene glycol, and dipropylene glycol Lower propylene glycol oligomers, including tripropylene glycol and tetrapropylene glycol; cyclohexanedimethanol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,4-butanediol, 2, Bis (2-hydroxyethyl) ate of 3-butanediol, 1,5-pentanediol, 1,3-propanediol, butylene glycol, neopentyl glycol, resorcinol and hydroquinone P-xylene-α, α'-diol; bis (2-hydroxyethyl) ether of p-xylene-α, α'-diol; m-xylene-α, α'-diol As well as combinations thereof. Other active hydrogen-containing chain extenders containing at least two active hydrogen groups can be used, such as dithiols, diamines, or hydroxy, thiols, and, among others, alkanolamines, aminoalkyl mercaptans and hydroxyalkyls It may be a compound having a mixture of amine groups such as mercaptan. Suitable diamine extenders include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetraamine, and combinations thereof. Other typical chain extenders are amino alcohols such as ethanolamine, propanolamine, butanolamine and combinations thereof. The molecular weight of the chain extender preferably ranges from about 60 to about 400. Alcohols and amines are preferred.

  In addition to difunctional extenders, small amounts of trifunctional extenders such as trimethylolpropane, 1,2,6-hexanetriol and glycerol, or monofunctional active hydrogen compounds such as butanol or dimethylamine are also included. Can be. The amount of trifunctional extender or monofunctional compound employed can be, for example, up to 5.0 equivalent percent based on the total weight of active hydrogen and reaction products containing the groups used.

  The polyester diol used in forming the thermoplastic polyurethane elastomer is generally prepared by condensation polymerization of one or more polyacid compounds and one or more polyol compounds. Preferably, the polyacid compound and polyol compound are difunctional, i.e., diacid compounds, and may include small amounts of monofunctional, trifunctional, and higher order functional materials, Although it may provide a slightly branched but uncrosslinked polyester polyol component, the diol is used to prepare a substantially linear polyester diol. Suitable dicarboxylic acids are 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 polymerizable esters (eg, methyl esters), and acid halides (eg, acid chlorides), and mixtures thereof, but are not limited thereto. Suitable polyols include those already mentioned, in particular diols. Typical catalysts for esterification polymerization are protonic acids, Lewis acids, titanium alkoxides, and dialkyltin oxides.

Polymer polyether or polycaprolactone diol reactants for preparing thermoplastic polyurethane elastomers react diol initiators, such as 1,3-propanediol or ethylene or propylene glycol, with lactones or alkylene oxide chain extenders. Can be obtained. Lactones that can be ring-opened by active hydrogen are known in the art. Examples of suitable lactones are ε-caprolactone, γ-caprolactone, β-butyrolactone, β-propriolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone Including, but not limited to, lactone, γ-decanolactone, δ-decanolactone, γ-nonanelactone, γ-octanelactone, and combinations thereof. In one preferred embodiment, the lactone is ε-caprolactone. Useful catalysts include those described above for polyester synthesis. Alternatively, the reaction can be initiated by forming a sodium salt of the hydroxyl group on the molecule that will react with the lactone ring. In other embodiments, the diol initiator can react with an oxirane-containing compound or cyclic ether to produce a polyether diol to be used in polyurethane elastomer polymerization. The alkylene oxide polymer segments are ethylene oxide, propylene oxide, 1,2-cyclohexene oxide, 1-butene oxide, 2-butene oxide, 1-hexene oxide, tert-butyl ethylene oxide, phenyl glycidyl ether, 1-decene oxide, isobutylene oxide, Including, but not limited to, polymerization products of cyclopentene oxide, 1-pentene oxide, and combinations thereof. The oxirane-containing or cyclic ether-containing compound is preferably selected from ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and combinations thereof. Alkylene oxide polymerization is typically base-catalyzed. The polymerization is charged with a catalytic amount of caustic, such as, for example, a hydroxyl functional initiator compound and potassium hydroxide, sodium methoxide or potassium tert-butoxide, and maintains available monomers for the reaction. Can be carried out by adding alkylene oxide at a rate sufficient to. Two or more different alkylene oxide monomers can be copolymerized randomly by simultaneous addition or polymerized in blocks by sequential addition. Homopolymers or copolymers of ethylene oxide or propylene oxide are preferred. Tetrahydrofuran is produced by a cationic ring-opening reaction using counter ions such as SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbCl ₆ ⁻ , BF ₄ ⁻ , CF ₃ SO ₃ ⁻ , FSO ₃ ⁻ , and ClO ₄ ⁻ . It can be polymerized. Initiation is by formation of a third oxonium ion. The polytetrahydrofuran segment can be prepared as a “living polymer” and can be terminated by reaction with hydroxyl groups of diols such as any of those described above. Polytetrahydrofuran is also known as polytetramethylene ether glycol (PTMEG).

  Aliphatic polycarbonate diols that can be used in making thermoplastic polyurethane elastomers are dialkyl carbonates (such as diethyl carbonate), diphenyl carbonates, or (5) in the presence of catalysts such as alkali metals, tin catalysts or titanium compounds. It can be prepared by reaction of diols with dioxolanes (such as cyclic carbonates having 6 and 6 membered rings). Useful diols include, but are not limited to, any of those already mentioned. Aromatic polycarbonates are usually prepared from the reaction of bisphenols, such as bisphenol A, with phosgene or diphenyl carbonate.

  In various embodiments, the polymeric diol preferably has a weight average molecular weight of at least about 500, more preferably at least about 1000, and even more preferably at least about 1800, and a weight average molecular weight of up to about 10,000. High molecular diols having a weight average molecular weight of up to about 5000, in particular up to about 4000, may also be preferred. The polymeric diol advantageously has a weight average molecular weight in the range from about 500 to about 10,000, preferably from about 1000 to about 5000, and more preferably from about 1500 to about 4000. The weight average molecular weight can be determined by ASTM D4274.

  The reaction of polyisocyanates, polymeric diols and diols or other chain extenders is typically carried out at elevated temperatures in the presence of a catalyst. Typical catalysts for this reaction include stannous octanoic acid, dibutyltin dilaurate, ditintin diacetate, organotin catalysts such as dibutyltin oxide, tertiary amines, zinc salts, and manganese salts. In general, for elastomeric polyurethanes, the ratio of polymeric diol, such as polyester diol, to the extender can vary within a relatively wide range, mainly depending on the desired flexural modulus of the final polyurethane elastomer. . For example, the equivalent ratio of polyester diol to extender can be in the range of 1: 0 to 1:12, more preferably 1: 1 to 1: 8. Preferably, the diisocyanate employed is such that the total ratio of equivalents of isocyanate to equivalents of active hydrogen-containing material is in the range of 1: 1 to 1: 1.05, more preferably 1: 1 to 1.02. Is proportional to The polymeric diol segment is typically about 35% to about 65% by weight of the polyurethane polymer, preferably about 35% to about 50% by weight of the polyurethane polymer.

  Suitable thermoplastic polyurea elastomers can be prepared by reaction of one or more polymeric diamines or polyols with one or more polyisocyanates and one or more diamine extenders already mentioned. Non-limiting examples of suitable diamine extenders include ethylenediamine, 1,3-propylenediamine, 2-methyl-pentamethylenediamine, hexamethylenediamine, 2,2,4- and 2,4,4-trimethyl-1 , 6-hexanediamine, imino-bis (propylamine), imido-bis (propylamine), N- (3-aminopropyl) -N-methyl-1,3-propanediamine), 1,4-bis (3 -Aminopropoxy) butane, diethylene glycol-di (aminopropyl) ether), 1-methyl-2,6-diamino-cyclohexane, 1,4-diamino-cyclohexane, 1,3- or 1,4-bis (methylamino) Cyclohexane, isophoronediamine, 1,2- or 1,4-bis (sec-butylamino) -cyclohexane, N N′-diisopropyl-isophoronediamine, 4,4′-diamino-dicyclohexylmethane, 3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane, Ν, Ν′-dialkylamino-dicyclohexylmethane, and 3, 3'-diethyl-5,5'-dimethyl-4,4'-diamino-dicyclohexylmethane. Polymeric diamines include polyoxyethylene diamine, polyoxypropylene diamine, poly (oxyethylene-oxypropylene) diamine, and poly (tetramethylene ether) diamine. The amine and hydroxyl functional extenders already mentioned can be used as well. Generally, as before, trifunctional reactants are limited and can be used in combination with monofunctional reactants to prevent crosslinking.

  Suitable thermoplastic polyamide elastomers are: (1) (a) oxalic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, or any other dicarboxylic acid already mentioned (B) ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, or decamethylenediamine, 1,4-cyclohexanediamine, m-xylylenediamine, or any other diamine already mentioned, etc. (2) Ring-opening polymerization of a cyclic lactam such as ε-caprolactam or ω-laurolactam; (3) 6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, or 12- Polycondensation of aminocarboxylic acids such as aminododecanoic acid; or (4) Copolymerization of cyclic lactams with dicarboxylic acids and diamines to prepare carboxylic acid functional polyamide blocks, followed by reaction with polymer ether diols (polyoxyalkylene glycols) such as any of those already mentioned Can be obtained. The polymerization can be carried out, for example, at a temperature from about 180 ° C to about 300 ° C. Specific examples of suitable polyamide block copolymers include elastomers based on NYLON6, NYLON66, NYLON610, NYLON11, NYLON12, copolymerized NYLON MXD6, and NYLON46. Thermoplastic poly (ether amide) block copolymer elastomer (PEBA) is commercially available from Arkema under the trademark Pebax®.

  Thermoplastic polyester elastomers have blocks of monomer units with low chain lengths that form crystalline regions and blocks of softened segments with monomer units with relatively higher chain lengths. Thermoplastic polyester elastomers are commercially available from DuPont under the trademark Hytrel®.

  The golf ball core and cover thermoplastic material may comprise a combination of thermoplastic elastomers. In one embodiment, the thermoplastic material comprises a copolymer of ethylene and at least one of acrylic acid and methacrylic acid, a metallocene-catalyzed copolymer of ethylene and an α-olefin having 4 to about 8 carbon atoms, and Includes metal ionomer combinations of metal salts of unsaturated fatty acids. This material is described in US Pat. No. 7,375,151 by Statz et al. Or US Patent Application No. 13,825,112 filed on March 15, 2013 by Kennedy. Which may be adjusted as described in “Process for Making Thermoplastic Golf Ball Material and Golf Ball With Thermoplastic Material, the entire contents of both of which are incorporated herein by reference.

  In various embodiments, the first thermoplastic material includes an ionomer resin and a polyolefin elastomer. The first thermoplastic material comprising this combination may have a 10-130 kg compression deformation of at least about 4 mm, preferably at least about 6 mm.

  In various embodiments, at least one of the first thermoplastic material, the second thermoplastic material, and the third thermoplastic material is an ionomer resin, a polyamide elastomer, a polyurethane elastomer, a thermoplastic polyester elastomer, and Including polymers selected from these combinations.

  The first and second thermoplastic materials can include other polymers. In one embodiment, the first and second thermoplastic materials are incorporated into the thermoplastic elastomer matrix via dynamic vulcanization of rubber, in any of these thermoplastic elastomers, or in other thermoplastic polymers. To obtain a dispersion domain of the cured rubber. One such composition is described in US Pat. No. 7,148,279 by Voorheis et al., Which is incorporated herein by reference. In various embodiments, the first thermoplastic material may include a thermoplastic dynamic vulcanizate of rubber in a non-elastomeric matrix resin such as polypropylene. The thermoplastic vulcanizate commercially available from ExxonMobil under the trade name Santoprene® is considered to be the vulcanization domain of EPDM in polypropylene.

  Depending on the elastomer selected for each thermoplastic material, one or more plasticizers may be incorporated. One example of such a plasticizer is a high molecular weight, monomeric organic acid, or a salt thereof that can be incorporated with, for example, an ionomer polymer as described above, such as zinc stearate, calcium stearate, barium stearate, Includes metal stearates such as lithium stearate and magnesium stearate. For most thermoplastic elastomers, the percentage of hard-to-soft segments is adjusted if lower hardness is desired rather than by adding a plasticizer.

  The flexural modulus of the thermoplastic material can be increased by including a filler. Various fillers may be included and the filler may be selected to modify the specific gravity, hardness or other properties of the thermoplastic material. Non-limiting examples of suitable fillers are clay, talc, asbestos, graphite, glass, mica, calcium metasilicate, barium sulfate, zinc sulfide, aluminum hydroxide, silicate, diatomaceous earth, (calcium carbonate, magnesium carbonate Carbonates, such as (titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, copper, brass, boron, bronze, cobalt, beryllium, and alloys thereof), zinc oxide, etc. Metal oxides (e.g., iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide, and the like), high molecular weight polyethylene, polystyrene, polyethylene ionomer resins, and the like Of) fine particle synthetic plastic, (carbon black, natural bitumen) Including emissions, and the like) particulate carbonaceous material ones like, and, cotton flock, cellulose flock, and / or the leather fiber. Non-limiting examples of heavy weight fillers that can be used to increase specific gravity include titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, steel, lead, copper, brass, boron, boron carbide whiskers, bronze Cobalt, beryllium, zinc, tin, and metal oxides (such as zinc oxide, iron oxide, aluminum oxide, titanium oxide, magnesium oxide, zirconium oxide). Non-limiting examples of light weight fillers that can be used to reduce specific gravity include particulate plastic, glass, ceramics, and hollow spheres, regrinds, or foams thereof. Fillers that can be used in the core center and core layer of golf balls are typically in finely divided form.

Various heavy or light weight fillers can be included in the different thermoplastic materials of the golf ball to provide the desired relationship between the specific gravity 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 . In various embodiments, 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 greater than the specific gravity of the core layer. About 0.1 g / cm ³ larger. These relationships can be obtained in thermoplastic materials by including heavy weight fillers or more heavy weight fillers to achieve higher specific gravity. Alternatively or additionally, light weight fillers may be included, or fillers may not be included, achieving a lower specific gravity.

  The cover can be made of a pigment such as a yellow or white pigment, in particular a white pigment such as titanium dioxide or zinc oxide. In general, titanium dioxide is used as a white pigment, for example, in an amount from about 0.5 or 1 part to about 8 or 10 parts by weight, based on 100 parts by weight of polymer. It is done. In various embodiments, the white cover can be dyed with a small amount of blue pigment or brightener.

  Conventional additives may be included in the thermoplastic material, such as dispersants, antioxidants such as phenol, phosphite and hydrazide, processing aids, surfactants, stabilizers and the like. Covers include hindered amine light stabilizers such as piperidine and oxanilides, ultraviolet light absorbers such as benzotriazole, triazine and hindered phenol, fluorescent materials and fluorescent whitening agents, dyes such as blue dyes, and antistatic agents And other additives.

  In various embodiments, 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, On the other hand, the other of the first and second thermoplastic materials has a flexural modulus from about 4000 psi to about 9700 psi. Non-limiting examples of thermoplastic polymers that can be used having a flexural modulus of up to about 15,000 are DuPont Company under the names Surlyn® 6320, 8020, 8120, 8320, 9020, 9320 and 9320W. , And ionomer resins sold by Wilmington DE, and DuPont's HPF2000 and HPF AD1035 ionomer resins; polyolefin elastomers such as Engage ™ 8180; Hwa Pao Resins Chemical Co. Ltd .. Grades of thermoplastic polyester polyurethanes and thermoplastic polyether polyurethanes, including G35D50N and G38D50N. The thermoplastic polymer can be mixed by the amount of filler or other polymer that provides the flexural modulus of the thermoplastic material up to the desired value. In certain preferred embodiments, the flexural modulus at the core center is greater than the flexural modulus of the core layer.

  The core layer can have a thickness of at least about 4 mm or at least about 5 mm. The core layer can 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. In certain embodiments, the golf ball has a second core layer between the core layer and the cover. The second core layer includes a fourth thermoplastic material having a fourth flexural modulus greater than the flexural modulus of the core layer, from about 30,000 psi to about 120,000 psi. Preferably, 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. Or up to about 90,000 psi. Non-limiting examples of thermoplastic polymers that can be used include Surlyn® 6910, 9910, 8920, 7930, 7940, 8940, 8941, 9945, 8945, 9950, 9520, 9721, 6120, 8140, 8150, 9120, The ionomer resin sold by DuPont Company, Wilmington DE under the names 9150, 8527, 8528, 9650 and 8660, and the grade of DuPont's HPF1000. In certain embodiments, the fourth flexural modulus of the second core layer is at least 3 times the second flexural modulus of the core layer and at least 30 times the third flexural modulus of the cover. is there.

  The thermoplastic material can be made by conventional methods such as melt mixing in a single or twin screw extruder, Banbury mixer, internal mixer, two roll mill, or ribbon mixer. The first thermoplastic material is formed at the core center and the second thermoplastic material is applied to the core layer around the core center by conventional methods, for example, by injection molding at a molding temperature in the range of 150 ° C. to 230 ° C. It is formed. If there is a second core layer, the fourth thermoplastic material may be formed in layers on the core layer by a similar method. Molded cores that include the core center, core layer, and optionally a second core layer or additional core layers can be ground to a desired diameter of 21 mm to 29 mm after cooling. Grinding may be used to remove flash, pin marks and gate marks resulting from the molding process.

  The cover layer is formed on the core. In various embodiments, the third thermoplastic material used to make the cover is preferably a thermoplastic polyurethane elastomer, a thermoplastic polyurea elastomer, and a metal of an ethylenically unsaturated carboxylic acid and ethylene copolymer. One or more of the cationic salts may be included.

  The cover can be formed on the multilayer core by injection molding, compression molding, casting or the like. For example, when the cover is formed by injection molding, a pre-manufactured core can be set inside the mold and the cover material can be injected into the mold. The cover is typically molded on the core by injection molding or compression molding. Alternatively, another method that may be used is to pre-mold a pair of half covers from the cover material by die casting or another molding method, enclosing the core in the half covers, and, for example, Attach half of the cover around the core, including compression molding between 120 ° C and 170 ° C for a period of 1 to 5 minutes. The core can be surface treated before the cover is formed thereon, increasing the adhesion between the core and the cover. Non-limiting examples of suitable surface treatments include mechanical or chemical polishing, corona discharge, plasma treatment, or application of an adhesion promoter such as silane, or adhesive. The cover typically has a dimple pattern and profile to provide the desired aerodynamic characteristics to the golf ball.

  Typically, the cover can have a thickness of about 0.5 mm to about 4 mm. When two cover layers are present, typically the cover layers independently have a thickness of about 0.3 mm to about 2.0 mm, preferably about 0.8 mm to about 1.6 mm. obtain.

  The USGA requires that golf balls used in competitions have a diameter of at least 1.68 inches (42.672 mm) and a weight not exceeding 1.62 ounces (45.926 g). Can be of any size. For games outside of USGA competition, golf balls can have a smaller diameter and can be heavier.

  After the golf ball is molded, it can undergo various further processing steps such as buffing, painting and marking. In a particularly preferred embodiment of the present invention, the golf ball has a dimple pattern having a coverage of 65% or more of the surface. Golf balls are typically coated with a durable, wear-resistant, and relatively non-yellowing finish coat.

  Since the description is merely exemplary in nature, variations that do not depart from the gist of the disclosure are part of the invention. Variations are not to be regarded as a departure from the spirit and scope of the disclosure.

Claims (15)

A core center comprising a first thermoplastic material having a diameter of about 21 mm to about 29 mm and having a first flexural modulus of up to about 15,000 psi;
A core layer disposed radially outward from the core center and comprising a second thermoplastic material having a thickness of at least about 4 mm and a second flexural modulus of up to about 9700 psi. A core layer;
A cover disposed radially outward from the core layer, the cover comprising 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, and the specific gravity of the core layer and the specific gravity of the core center are at least about 0.1 g / cm. ³ different golf balls.   The golf ball of claim 1, wherein the third flexural modulus is up to about 5,000 psi. The golf ball of claim 1, wherein 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. The golf ball of claim 1, wherein the core center specific gravity is at least about 0.1 g / cm ³ greater than the core layer specific gravity.   5. The golf ball of claim 1, wherein the third flexural modulus is up to about 2,000 psi.   6. The golf ball of claim 1, wherein the core layer has a thickness of at least about 5 mm and the second flexural modulus is up to about 8,000 psi.   7. The golf ball of claim 1, wherein the second flexural modulus is at least about 5,000 psi greater than the third flexural modulus.   The golf ball according to claim 1, wherein the golf ball does not include a thermosetting rubber layer. A first flexural modulus up to about 9700 psi and a 10-130 kg compression deformation of at least about 4 mm, comprising a first thermoplastic material comprising a polyolefin elastomer and an ionomer resin, and having a diameter of from about 21 mm to about 29 mm Having a core center;
A core layer disposed radially outward from a core center, the core layer comprising a second thermoplastic material having a thickness of at least about 5 mm and a second flexural modulus of up to about 15,000 psi; A core layer;
A cover disposed radially outward from the core layer, the cover comprising a third thermoplastic material having a third flexural modulus up to about 5,000 psi;
The second flexural modulus is greater than the first flexural modulus, the second flexural modulus is at least about 10,000 psi greater than the third flexural modulus, and the specific gravity of the core layer and the specific gravity of the core center are at least about Golf balls that differ by 0.1 g / cm ³ . The golf ball of claim 9, wherein 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. The golf ball of claim 9, wherein the core center specific gravity is at least about 0.1 g / cm ³ greater than the core layer specific gravity.   The golf ball of claim 9, wherein the third flexural modulus is up to about 2,000 psi.   13. A golf ball according to any one of claims 9 to 12, wherein the first thermoplastic material has a 10-130 kg compression deformation of at least about 6 mm.   The golf ball according to claim 9, wherein the golf ball does not include a thermosetting rubber layer.   A second core layer is further included between the core layer and the cover, and the second core layer includes a fourth thermoplastic material having a fourth flexural modulus of about 30,000 psi to about 120,000 psi. The golf ball according to any one of claims 9 to 14.

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