Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
  • C08L23/0876—Salts thereof, i.e. ionomers
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0023—Covers
  • A63B37/0024—Materials other than ionomers or polyurethane
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0023—Covers
  • A63B37/0029—Physical properties
  • A63B37/0031—Hardness
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0023—Covers
  • A63B37/0029—Physical properties
  • A63B37/0037—Flexural modulus; Bending stiffness
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle
  • A63B37/004—Physical properties
  • A63B37/0045—Thickness
• • 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
• • 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
  • A63B37/0078—Coefficient of restitution
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0077—Physical properties
  • A63B37/008—Diameter
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0077—Physical properties
  • A63B37/0084—Initial velocity
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0077—Physical properties
  • A63B37/0087—Deflection or compression
• • 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
  • A63B37/0095—Scuff resistance
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines

Definitions

• the invention relates to compositions comprising ionomers and polyamines or tertiary polyamides and articles such as golf balls and films containing the compositions.
• Golf balls and golf ball components may be formed from a variety of compositions, which provides a golf ball manufacturer the ability to alter the feel and aerodynamic characteristics of a particular ball.
• ionomers are copolymers of alpha olefins, particularly ethylene, and
• ionomer covered golf balls possess virtually cut-proof covers, their spin and feel may be inferior compared to balata covered balls.
• Polyurethanes and polyureas have also been recognized as useful materials for golf ball covers. Golf ball covers made of these materials have durability comparable to that of covers made from ionomer resins, but have the softer feel of a balata cover. Golf balls with a polyurethane or polyurea cover do not fully match ionomer resin golf balls with respect to the resilience or rebound of the golf ball cover, however. This property is in part a function of the initial velocity of a golf ball after impact with a golf club. Polyurethane and polyurea covers also have inferior moisture barrier properties compared to ionomer covers. Ethylene acid copolymers neutralized by reaction with diamines are described in
• U.S. Patent No. 3,471 ,460 An ionomer neutralized by reaction with a polyamine, preferably a diamine, that contains at least one R-CH 2 -NH 2 group, and optionally partially neutralized with a base comprising a metal cation, is described in U.S. Patent No. 4,732,944.
• An ionomer composition comprising an ethylene acid copolymer neutralized by reaction with a "basic metal ion salt" and a compound comprising both an amine and a carboxylic acid in the same molecule is described in U.S. Patent Application Publication No. 2006/0014898.
• An ionomer composition having greater than about 70 percent of the acid groups neutralized by reaction with a neutralizing component including ammonium salts and/or monoamine salts is described in U.S. Patent No. 7,160,954.
• HMT hexamethylene tetramine
• Daltons a tertiary polyamine with molecular weight of 140 Da
• Japanese Patent No. 3540453 discloses an ionomer composition modified by the addition of H 2 N-[CH 2 RCH 2 NHCH 2 CH(OH) CH 2 NH] n -CH 2 RCH 2 NH 2 , wherein, R is a divalent alicycle or an aromatic hydrocarbon group, and 1 ⁇ n ⁇ 20.
• Application JP1997-296082 discloses a similar composition wherein a condensed cyclic compound having two or more aminoalkyl groups is also present.
• Japanese Patent Application JP2005-263868 discloses an ionomer composition modified by a diamine compound wherein weight change begins at >150°C, as determined by a gravimetric method according to JIS K7120.
• An example of the amine is reported as "4 and A- diamino-hexylmethane", believed to be 4,4'-diaminodicyclohexylmethane.
• a high performance material to be used in a structural layer of a golf ball, such as a cover, intermediate layer, core or center.
• resins that have a balance of high coefficient of restitution (COR), high flex modulus, low moisture transmission, and good durability.
• the compositions have melt properties suitable for injection molding, and in particular for injection molding in thin layers.
• thermoplastic composition comprising: (a) an E/X/Y ethylene acid copolymer wherein E represents copolymerized units of ethylene, X represents copolymerized units of C 3 to C 8 ⁇ , ⁇ ethylenically unsaturated carboxylic acid, and Y represents copolymerized units of softening comonomer preferably selected from the group consisting of vinyl acetate, alkyl acrylate and alkyl methacrylate, wherein the alkyl groups have from 1 to 8 carbon atoms, wherein the amount of X is about 2 to about 30 weight % of the E/X/Y copolymer, and the amount of Y is 0 to about
• One golf ball comprises a core and a cover and optionally at least one intermediate layer positioned between the core and the cover, wherein the core, the cover or the intermediate layer(s) when present comprises or is prepared from the thermoplastic composition described above.
• thermoplastic composition prepared from the thermoplastic composition described above.
• the terms “comprises,” “comprising,” “includes,” “including,” “containing,” “characterized by,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
• a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
• transitional phrase “consisting of” excludes any element, step, or ingredient not specified in the claim, closing the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith.
• the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
• the transitional phrase “consisting essentially of” limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristic(s) of the claimed invention.
• a 'consisting essentially of claim occupies a middle ground between closed claims that are written in a 'consisting of format and fully open claims that are drafted in a 'comprising' format.
• Optional additives as defined herein, at a level that is appropriate for such additives, and minor impurities are not excluded from a composition by the term "consisting essentially of.
• compositions, processes, a structure, or a portion of a composition, a process, or a structure are described herein using an open-ended term such as
• copolymer refers to polymers comprising copolymerized units resulting from copolymerization of two or more comonomers.
• a copolymer may be described herein with reference to its constituent comonomers or to the amounts of its constituent comonomers, for example "a copolymer comprising ethylene and 15 weight % of acrylic acid", or a similar description.
• Such a description may be considered informal in that it does not refer to the comonomers as copolymerized units; in that it does not include a conventional nomenclature for the copolymer, for example International Union of Pure and Applied Chemistry (IUPAC) nomenclature; in that it does not use product-by-process terminology; or for another reason.
• IUPAC International Union of Pure and Applied Chemistry
• a description of a copolymer with reference to its constituent comonomers or to the amounts of its constituent comonomers means that the copolymer contains copolymerized units (in the specified amounts when specified) of the specified comonomers. It follows as a corollary that a copolymer is not the product of a reaction mixture containing given comonomers in given amounts, unless expressly stated in limited circumstances to be such.
• polymer refers to polymers consisting essentially of two monomers
• terpolymer refers to polymers consisting essentially of three monomers.
• an article such as a golf ball
• that particular composition may be the same or different in each of the layers or components.
• Resins having a high flex modulus have previously been prepared using ionomers with relatively high levels of acid comonomer. Using this approach, however, an upper limit of about 90 kpsi in flex modulus has been reached. It is desired, nevertheless, to use resins having a flex modulus greater than 90 kpsi, provided other properties such as COR, moisture transmission, durability and moldability remain acceptable.
• resins having a high coefficient of restitution (COR), high flex modulus, low moisture transmission, and good durability are obtained by blending ionomers with a polyamine containing at least three amine groups. More specifically, these polyamines are tertiary amines or hindered secondary amines or polyamides comprising tertiary amides.
• the acid copolymers used to make the compositions described herein are preferably "direct” acid copolymers.
• "Direct" copolymers are polymers in which the copolymerized monomers are part of the polymer backbone or chain. They may be polymerized by adding all monomers simultaneously. In contrast, in graft copolymers, another comonomer is attached to non-terminal repeat units in an existing polymer chain, often by a subsequent free radical reaction.
• the acid copolymers are preferably alpha olefin, particularly ethylene, C 3 to C 8 , ⁇ , ⁇ -ethylenically unsaturated carboxylic acid, particularly acrylic and methacrylic acid, copolymers. They may optionally contain a third softening monomer.
• softening it is meant that the polymer is made less crystalline and has a lower flex modulus than related polymers not having the "softening" monomer.
• Suitable "softening" comonomers are monomers selected from alkyl acrylate and alkyl methacrylate, wherein the alkyl groups have from 1 to 8 carbon atoms, and vinyl acetate.
• the ethylene acid copolymers can be described as E/X/Y copolymers where E represents copolymerized units of ethylene, X represents copolymerized units of the ⁇ , ⁇ ethylenically unsaturated carboxylic acid, and Y represents copolymerized units of a softening comonomer.
• X is present in 2 to 30 weight % of the polymer, and Y is present in from 0 to 45 weight % of the polymer. That is, the amount of X is 2 to 30 weight %, and the amount of Y is 0 to 45 weight %, based on the total weight of the E/X/Y copolymer.
• E/X/Y copolymer wherein Y is 0 weight % of the copolymer may be considered an E/X dipolymer.
• Y When Y is present in the E/X/Y copolymer (i.e., an E/X/Y terpolymer), it may be present in an amount from about 0.1 weight % to 45 weight % of the copolymer, preferably from 5 to 35, or from 5 to 25 weight % of the copolymer.
• copolymers wherein Y is 0% of the copolymer that is, an E/X dipolymer.
• dipolymers wherein the C 3 to C 8 ⁇ , ⁇ -ethylenically unsaturated carboxylic acid are acrylic acid or methacrylic acid.
• acid copolymers include ethylene/acrylic acid and ethylene/methacrylic acid dipolymers.
• an ethylene dipolymer consisting essentially of copolymerized comonomers of ethylene and from about 10 to about 24 weight % of copolymerized comonomers of C 3 to C 8 ⁇ , ⁇ ethylenically unsaturated carboxylic acid is particularly useful for preparing compositions which have a balance of high coefficient of restitution (COR), high flex modulus, low moisture transmission, moldability and good durability.
• the E/X dipolymer may include about 14 to about 22 weight %, more preferably 18 to about 22 weight %, of the copolymerized carboxylic acid.
• a dipolymer comprising ethylene and about 15 weight % of acrylic acid
• a dipolymer comprising ethylene and 15.4 weight % of acrylic acid
• a dipolymer comprising ethylene and about 18 weight % of acrylic acid
• a dipolymer comprising ethylene and about 21 weight % of acrylic acid.
• Ethylene/acrylic acid dipolymers are of note because a given weight of acrylic acid will provide more acid moieties than an equal weight of methacrylic acid.
• dipolymer comprising ethylene and about 19 weight % of methacrylic acid. Also of note is a dipolymer comprising ethylene and about 15 weight % of methacrylic acid.
• the dipolymer may include 18 to 20 weight % of copolymerized methacrylic acid, or about 21 weight % of copolymerized acrylic acid.
• Ethylene acid dipolymers with high levels of acid can be prepared through the use of "co-solvent technology" as described in U.S. Patent No. 5,028,674 or by employing somewhat higher pressures than those at which copolymers with lower acid levels can be prepared.
• the EIXIY copolymers may have melt index flow rates in the range of about 10 g/10 min to about 400 g/10 min, or greater, measured at 190 0 C using a 2160 g weight.
• the copolymers Preferably, have melt index flow rates of about 50 to about 300 g/10 min.
• a dipolymer comprising ethylene and 19 weight % of methacrylic acid having a melt index of 250 g/10 min.
• Unmodified, melt processible ionomers can be prepared from acid copolymers described above by methods known in the art of preparing ionomers.
• unmodified it is meant that the ionomers are not blended with any material that has been added for the purpose of modifying the properties of the unblended ionomer.
• the polyamines and polyamides described herein are considered modifiers.
• Unmodified ionomers include partially neutralized acid copolymers, particularly copolymers prepared from copolymerization of ethylene and acrylic acid or methacrylic acid.
• the unmodified ionomers may be neutralized to any level that does not result in an intractable (i.e., not melt processible) polymer, or one that does not have useful physical properties.
• about 15 to about 90%, more preferably about 30 to about 75% of the acid moieties of the acid copolymer are neutralized to form carboxylate groups.
• the ionomers further comprise, as counterions, one or more cations. Although any positively charged moiety may be suitable, the ionomers used herein preferably comprise cations of one or more alkali metals, alkaline earth metals, and/or transition metals.
• Preferred cations for use in the unmodified ionomers include cations of lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc or aluminum, or combinations of two or more of these cations. Of note are sodium, calcium, potassium and lithium cations. Magnesium and zinc are preferred, and zinc is more preferred.
• At least 20 equivalent %, at least 35 equivalent %, at least 50 equivalent %, or at least 75 equivalent % of the cations in the composition are magnesium cations. More preferably at least 20 equivalent %, at least 35 equivalent %, at least 50 equivalent %, or at least 75 equivalent % of the cations in the composition are zinc cations.
• an ionomer made from a dipolymer comprising ethylene and 19 weight % of methacrylic acid neutralized with sufficient ZnO to produce an ionomer having an Ml of 4.0.
• an ionomer made from a dipolymer comprising ethylene and 15 weight % of methacrylic acid neutralized with ZnO.
• the thermoplastic composition also includes a polyamine compound or a polyamide compound having a molecular weight of greater than 500 Da, not containing an ester moiety or a primary amine moiety, wherein the polyamine comprises comprises at least three moieties that are tertiary amines or hindered secondary amines and wherein the polyamide comprises tertiary amide moieties and no secondary or primary amide moieties.
• Hindered means that sterically bulky groups are adjacent to the secondary amine, such as tertiary or quaternary carbon atoms.
• the polyamines may be monomeric, oligomeric or polymeric.
• Preferred polyamines have molecular weight greater than 1000 Da, or greater than 1500 Da.
• hindered secondary amine moieties examples include 2,2,6,6- tetramethylpiperidine and related materials such as 4-amino-2,2,6,6- tetramethylpiperidine.
• Polyamine derivatives of these monoamines having molecular weights above 500 Da may be prepared by combining by covalent bonding at least three of these secondary amine moieties.
• HALS Hindered Amine Light Stabilizers
• HALS that may be used is CHIMASSORB 119, having the chemical structure R-NH-(CH 2 ) 3 -NR-(CH 2 ) 2 -NR-(CH 2 ) 3 -NH-R, where R is
• CHIMASSORB 944 po!y[f ⁇ -f(1 , 1 ,3,3- tetramethy!buty!amino]-s-triazin8-2.4-diyi]-[(2.2 ! 6,6-tetramethyi-4-piperidy!)imino3- hexamethylene ⁇ [(2 s 2,6,64etramethyl-4 ⁇ piperidyi)imir ⁇ o]]
• CHIMASSORB 944 po!y[f ⁇ -f(1 , 1 ,3,3- tetramethy!buty!amino]-s-triazin8-2.4-diyi]-[(2.2 ! 6,6-tetramethyi-4-piperidy!imino3- hexamethylene ⁇ [(2 s 2,6,64etramethyl-4 ⁇ piperidyi)imir ⁇ o]]
• CHIMASSORB 2020 has the following chemical structure:
• Polyamides comprising tertiary amides include polyvinylpyrrolidone (PVP) and poly(2-ethyl oxazoline). Tertiary amide moieties are those that do not include an N-H bond. Secondary amides have one N-H bond and primary amides have an NH 2 moiety. Notably, these polyamides can function as Lewis bases.
• Polyvinylpyrrolidone, or Povidone, CA number [9003-39-8], Merck Index, 13, 7783, is available commercially from International Specialty Products of Wayne, NJ, as a series of products having average molecular weights of about 10,000 to about 1 ,300,000 Da or more (e.g about 10,000 Da, about 29,000 Da, about 55,000 Da, about 700,000 Da or about 1 ,300,000 Da).
• Copolymers of vinyl pyrrolidone such as poly(1- vinylpyrrolidone-co-styrene), CA number [25086-29-7], may also be used.
• Poly(2-ethyl oxazoline), or N-propionyl substituted linear polyethylenimine, CA number [25805-17-8] is available commercially from International Specialty Products as a series of products having average molecular weights of about 50,000 to about 500,00 Da or more (e.g. about 50, 000 Da, about 200,000 Da or about 500,00 Da). Of note is the material having average molecular weight of about 50,000 Da, which is commercially available under the tradename AQUAZOL 50.
• a number of provisos apply to the present description.
• polyamides containing secondary amide moieties, such as nylons are not contemplated for use in the thermoplastic composition described herein.
• ester moieties and primary amine moieties are not desirable in the polyamine or polyamide. Without being bound by theory, esters or primary amines in the polyamine or polyamide may negatively interact with the ionomer, reducing melt flow.
• thermoplastic compositions Combinations of two or more of the suitable polyamine or polyamide additives may be used in the thermoplastic compositions, however.
• Polyamides may be preferred for use in some of the thermoplastic compositions described herein.
• the amount of polyamine or polyamide may be from about 1 to about 40 weight %, preferably about 3 to about 40 weight %, about 5 to about 35 weight %, about 10 to about 30 weight % or about 15 to about 25 weight %, based on the total weight of the thermoplastic composition.
• thermoplastic compositions comprise an E/X dipolymer comprising 14 to 20 wt% of (meth)acrylic acid, neutralized to form an ionomer comprising zinc cations.
• the preferred thermoplastic compositions further comprise 15 to
• thermoplastic composition 25 wt%, based on the total weight of the thermoplastic composition, of a suitable polyamine or polyamide, and more preferably comprise a polyamine modifier.
• thermoplastic compositions may optionally comprise small amounts of other materials commonly used and well known in the polymer art.
• materials include conventional additives used in polymeric materials including plasticizers; stabilizers, including viscosity stabilizers and hydrolytic stabilizers; primary and secondary antioxidants, such as for example IRGANOX 1010 (commercially available from CIBA); ultraviolet ray absorbers and stabilizers; anti-static agents; dyes; pigments or other coloring agents; fire-retardants; lubricants; processing aids; slip additives; antiblock agents such as silica or talc; release agents; other components known in the art of golf ball manufacture to be useful but not critical to golf ball performance and/or acceptance, such as inorganic fillers as described below, acid copolymer waxes, such as for example Honeywell wax AC540, TiO 2 , which is used as a whitening agent, optical brighteners, and surfactants; and mixtures or combinations of two or more conventional additives.
• additives are described in the Kirk Othmer Encyclopedia of Chemical Technology, 5 th Edition, John Wiley & Sons (New Jersey, 2004), for example. These conventional ingredients may be present in the compositions in quantities that are generally from 0.01 to 15 weight %, preferably from 0.01 to 10 weight %, so long as they do not detract from the basic and novel characteristics of the composition and do not significantly adversely affect the performance of the composition or of the golf balls prepared from the composition.
• the weight percentages of such additives are not included in the total weight percentages of the thermoplastic compositions defined herein. Typically, many such additives may be present in from 0.01 to 5 weight %, based on the total weight of the thermoplastic composition.
• compositions can be carried out by any known process.
• This incorporation can be carried out, for example, by dry blending, by extruding a mixture of the various constituents, by the conventional masterbatch technique, or the like. See, again, the Kirk-Othmer Encyclopedia.
• compositions may be added to compositions to reduce cost, to affect rheological and mixing properties such as density, flex modulus, mold release, and/or melt flow index and the like, to adjust physical properties such as the modulus, tear strength and the like, to increase or decrease weight, and/or to reinforce the material.
• the amount of filler employed is primarily a function of weight requirements and distribution of the golf ball.
• the fillers may be used to adjust the properties of a golf ball layer, to reinforce the layer, or for any other purpose.
• compositions of the invention can be reinforced by blending with a wide range of density-adjusting fillers, e.g., ceramics, glass spheres (solid or hollow, and filled or unfilled), and fibers, inorganic particles, and metal particles, such as metal flakes, metallic powders, oxides, and derivatives thereof, as is known to those of skill in the art.
• density-adjusting fillers e.g., ceramics, glass spheres (solid or hollow, and filled or unfilled), and fibers, inorganic particles, and metal particles, such as metal flakes, metallic powders, oxides, and derivatives thereof, as is known to those of skill in the art.
• the filler may be chosen to impart additional density to compositions of the previously described components, the selection being dependent upon the type of golf ball desired (i.e., one-piece, two-piece, wound or multilayer), as will be more fully detailed below.
• the filler may be included in one or more layers of the golf ball.
• the filler will be inorganic, having a density from about 4 grams/cubic centimeter (g/cc), or from about 5 g/cc to about 10 g/cc or higher and may be present in amounts between 0 and about 60 weight % based on the total weight of the thermoplastic composition.
• useful fillers include metals such as titanium, tungsten, aluminum, bismuth, nickel, molybdenum, iron, steel, lead, copper, brass, boron, boron carbide whiskers, bronze, cobalt, beryllium, zinc, tin; metal oxides including zinc oxide, iron oxide, aluminum oxide, tin oxide, titanium oxide, magnesium oxide, zinc oxide and zirconium oxide; as well as other well known corresponding salts and oxides thereof.
• fillers include barium sulfate, lead silicate, tungsten carbide, limestone (ground calcium/magnesium carbonate), zinc sulfate, calcium carbonate, zinc carbonate, barium carbonate, clay, tungsten, tungsten carbide, an array of silicas, regrind (recycled core material typically ground to about 30 mesh particle), high-Mooney-viscosity rubber regrind and ground flash filler, and mixtures of two or more of any suitable fillers. It is preferred that the filler materials be non-reactive or almost non-reactive.
• Fillers may be employed in a finely divided form, for example, in a size generally less than about 20 mesh U.S. standard size, preferably from about 100 mesh to about 1000 mesh, except for fibers and flock, which are generally elongated. Flock and fiber sizes are desirably small enough to facilitate processing. Filler particle size will depend upon desired effect, cost, ease of addition, and dusting considerations.
• Fillers may also be used to modify the weight of the core or at least one additional layer for specialty balls, e.g., a lower weight ball is preferred for a player having a low swing speed.
• compositions may be foamed by the addition of at least one physical or chemical blowing or foaming agent.
• foamed polymer allows the golf ball designer to adjust the density or mass distribution of the ball to adjust the angular moment of inertia, and, thus, the spin rate and performance of the ball.
• Foamed materials also offer a potential cost savings due to the reduced use of polymeric material.
• suitable blowing or foaming agents and methods for their use is included in U.S. Patent Appln. No. 12/215,674, filed on June 30, 2008, to which the present application claims priority.
• Other lonomer Compositions are included in U.S. Patent Appln. No. 12/215,674, filed on June 30, 2008, to which the present application claims priority.
• any golf ball or golf ball component described herein may comprise or be prepared from an ionomer composition.
• the term "ionomer composition" refers to a composition that comprises an ionomer and that is different from the thermoplastic composition described herein.
• the ionomer composition may be modified or unmodified, but if modified with a polyamine or polyamide, the polyamine or polyamide has a molecular weight of less than 500 Da; or contains an ester moiety or a primary amine moiety; or does not comprise at least three moieties that are tertiary amines or hindered secondary amines; or comprises secondary or primary amide moieties and no tertiary amide moieties.
• the golf balls or golf ball components described herein may comprise or be prepared from a blend of the thermoplastic compositions described herein with one or more ionomer compositions.
• Suitable E/X/Y copolymers for use in the ionomer compositions are as described above with respect to the thermoplastic compositions.
• Suitable neutralization levels are from 0 to 100%, preferably 50% to 100%, 50% to 100%, 60% to 100%, 70% to 100%,
• the unmodified ionomers may be neutralized to any level that does not result in an intractable (not melt processible) polymer, or a material that does not have useful physical properties.
• Suitable counterions for the ionomers are as described above with respect to the thermoplastic composition described herein.
• Some preferred ionomer compositions are modified with one or more organic acids or with one or more salts of organic acids.
• Suitable organic acids include, without limitation, monofunctional organic acids having fewer than 36 carbon atoms, optionally substituted with from one to three substituents independently selected from C-
• the organic acids may be saturated or unsaturated, and, if unsaturated, may include more than one carbon-carbon double bond.
• the term "mono-functional" refers to acids with one carboxylic acid moiety.
• the suitable organic acids include C4 to
• C36 (for example C-i ⁇ ). more particularly Cg to C2Q, an d even more particularly Cg or C-
• g to C ⁇ g acids are preferred.
• suitable organic acids include, but are not limited to, caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, isostearic acid, behenic acid, erucic acid, oleic acid, iso-oleic acid, and linoleic acid.
• Naturally derived organic fatty acids such as palmitic, stearic, oleic, erucic, behenic acids, and mixtures thereof may also be employed.
• compositions that comprises a named acid may also include other acids that are present in commercial grades of the named acid, at levels that are proportional to their levels in the commercial grade.
• transitional term "consisting essentially of” is applied to compositions that comprise a named acid, other acids that are present in commercial grades of the named acid, at levels that are proportional to their levels in the commercial grade, are not excluded from the composition.
• Suitable E/X/Y copolymers for use in ionomer compositions that are modified with organic acids are as described immediately above.
• Suitable neutralization levels for these modified ionomer compositions are from 0 to 100%, preferably 50% to 100%, 50% to 100%, 60% to 100%, 70% to 100%, 80% to 100%, 90% to 100%, 95% to 100% or about 100%.
• the modified ionomers may be neutralized to any level that does not result in an intractable (not melt processible) polymer, or a material that does not have useful physical properties.
• Suitable counterions for these modified ionomers are as described above with respect to the thermoplastic composition described herein.
• Preferred modified ionomer compositions include the ionomer compositions described in U.S.
• Other preferred modified ionomer compositions are described in U.S. Provisional Appln. No. 61/001 ,454, filed on November 1 , 2007; in U.S. Patent Nos. 6,100,321 ; 6,815;480; and 7,375,151 ; and in U.S. Patent Appln. Publn. Nos. 2003/0050373 and 2003/0114565.
• the ionomer compositions may further comprise one or more fillers, blowing agents, or other additives as described above with respect to the thermoplastic compositions.
• Golf Ball Construction The thermoplastic compositions described herein may be used in golf balls that have any type of construction. General descriptions of golf balls, golf ball structures, golf ball components, the desirable physical properties of golf balls, the selection of materials for performance criteria, and the principles by which golf balls are typically designed are included in U.S. Patent Appln. No. 12/215,674.
• the term "layer” includes any substantially spherical or spherically symmetrical portion of a golf ball, i.e., a golf ball core or center, an intermediate layer, and/or a golf ball cover.
• the term “inner layer” refers to any golf ball layer beneath the outermost structural layer of the golf ball.
• the terms “layer” and “structural layer” include a cover, but do not include a coating layer, top coat, paint layer, or the like.
• the term “multilayer”, when used without specifying a number of layers, refers to a golf ball with at least three structural layers comprising a cover, an intermediate layer and core.
• the term “component” refers to any constituent part of a golf ball. A component may have any shape. Preferred one-piece golf balls
• Preferred one-piece golf balls are made by injection or compression molding a sphere of desired size from the thermoplastic composition described above or its blends with other ionomer compositions or with non-ionomeric thermoplastic resins.
• the ionomer compositions and other resins may be modified or unmodified, and may include conventional additives as described above with respect to the thermoplastic compositions.
• the one-piece ball may include sufficient filler to provide a golf ball having a desired weight or density. Preferably, enough filler is used so that the ball has a density 1.14 gm/cc or a weight of 45 grams.
• One-piece golf balls may be coated, lacquered, or otherwise finished as described below with respect to covers.
• Two-piece balls include a core or center and a cover. They may be manufactured by well-known techniques wherein covers are injection or compression molded over cores.
• the core of a two-piece ball may be made by injection or compression molding a solid of desired size and shape. Preferred core shapes are substantially spherical or spherically symmetrical.
• the core and the cover are prepared from a thermoplastic composition, for example the thermoplastic composition described herein, or from a thermoset composition.
• the compositions of the core and the cover may be the same or different.
• the core and cover compositions are optionally filled with sufficient filler to provide a desired density. Suitable core densities can be, for example, from about 1.14 g/cc to about 1.2 g/cc, depending on the diameter of the core and the thickness and composition of the cover. It may be desirable, for example, to produce a golf ball meeting the weight limit (45 grams or less) and size limit set by the USGA.
• the amount of filler in the cover may be the same as or different from the amount of filler in the core.
• the density of the cover may be the same as or different from the density of the core.
• the innermost layer of the golf ball is known as the center or core.
• a solid core is prepared from a composition that is typically injection-molded or compression-molded to form a substantially spherical or spherically symmetrical solid. Any core material known to one of ordinary skill in the art is suitable for use in the golf balls described herein. Suitable core materials include thermoset materials, such as rubber, styrene butadiene, polybutadiene, isoprene, polyisoprene, trans-isoprene, as well as thermoplastic materials such as ionomer resins, ionomer compositions, polyamides or polyesters, and thermoplastic and thermoset polyurethane or polyurea elastomers. Alternatively, the core can be prepared from the thermoplastic compositions described herein.
• thermoplastic cores comprise or are prepared from one or more ionomer compositions.
• these ionomer core compositions are modified E/X/Y copolymers in which the amount of X is 2 to 25 wt%, preferably 5 to 15 wt%, and the amount of Y is 2 to 50 wt%, preferably 5 to 40 wt%.
• the softening monomer, Y is an alkyl ester of (meth) acrylic acid, and more preferably an alkyl ester of acrylic acid.
• the melt index of the parent acid copolymer is preferably in the range of 20 to 500 g/10 min, measured at 190 0 C using a 2160 g weight.
• Preferred counterions include sodium, zinc, magnesium, and calcium.
• the melt index of the ionomer is preferably about 0.1 to 5 g/10 min, measured at 190 0 C using a 2160 g weight.
• these ionomers are modified with one or more organic acids or with one or more salts of organic acids.
• Preferred organic acids include caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, isostearic acid, behenic acid, erucic acid, oleic acid, iso-oleic acid.
• the modifier(s) are present in an amount of about 5 to 50 wt% or about 10 to 50 wt%, based on the total weight of the ionomer core composition.
• Preferred counterions and preferred neutralization levels are as set forth above with respect to ionomer compositions. Magnesium is more preferred, however, and more preferably at least about 80% to 100% of the acid moieties of the E/X/Y copolymer and of the organic acid are neutralized.
• the core has an average diameter such that the thickness of the cover and any additional layers can be added to the diameter of the core to provide a golf ball of desired size, for example, at least about 1.68 inches in diameter.
• the outermost structural layer of a golf ball is known as the cover.
• the cover provides the interface between the ball and a club. Properties that are desirable for the cover are good moldability, high abrasion resistance, high tear strength, high resilience, and good mold release, among others.
• the covers can be made by any suitable method, including, without limitation, casting, injection molding, reaction injection molding, or compression molding a cover composition.
• Covers can be made from any conventional golf ball cover material such as ionomer resins, ionomer compositions, balata rubber, thermoset/thermoplastic polyurethanes and the like. Covers may also be prepared from the thermoplastic compositions described herein, or from blends of two or more suitable materials.
• the cover typically has a thickness that is adequate to provide sufficient strength, good performance characteristics, and durability.
• cover layers may be from about 0.005 inch to about 0.35 inch in thickness.
• the cover thickness is from about 0.02 inches to about 0.35 inches.
• the cover preferably has a thickness of about 0.02 inches to about 0.12 inches, preferably about 0.1 inches or less.
• the cover may have a thickness of about 0.1 inches or less, preferably about 0.07 inches or less.
• the cover of a golf ball, or the surface of a one-piece ball may be painted, coated, or surface treated for further benefits.
• the golf ball may be coated with a urethane lacquer or otherwise finished for appearance purposes; however, such a coating, painting and/or finishing generally does not have a significant effect on the performance characteristics of the ball.
• a two-piece golf ball comprising a cover that comprises or is prepared from the thermoplastic composition described herein and a thermoset rubber core.
• a two-piece golf ball comprising a cover that comprises or is prepared from the thermoplastic composition described herein and a thermoplastic core.
• the core comprises or is prepared from the thermoplastic composition described herein.
• a wound golf ball comprising a cover that comprises or is prepared from the thermoplastic composition described herein and a thermoset rubber core.
• Multilayer golf balls contain one or more additional layers between the cover and the core or center. These additional layers are also known as mantles or intermediate layers. Suitable covers and centers for multilayer balls are as described above with respect to two-piece golf balls.
• Multilayer balls may be manufactured by well-known technigues wherein an injection or compression molded core is covered by one or more intermediate layers or mantles and a cover.
• the various layers of the golf balls are made by injection or compression molding a sphere or layer of desired size or thickness.
• Any of the cover, the core, or the intermediate layer(s) may comprise or be prepared from a thermoplastic composition, for example the thermoplastic composition described herein.
• any of the structural layers may comprise or be prepared from a thermoset composition.
• any of the golf ball components may optionally include sufficient filler to provide a golf ball having a desired density, for example one that meets the size and weight limits set by the USGA.
• the amount of filler employed in the core and/or mantle(s) can be varied from 0 to about 60 weight % depending on the size (thickness) of the components and the desired distribution of the weight in the ball.
• enough filler is used so that the ball has an overall density of about 1.14 gm/cc.
• the filler can be used in the core and not in the mantle, in the mantle and not in the core, or in both.
• the intermediate layer may comprise or be prepared from ionomer resins, ionomer compositions, the thermoplastic compositions described herein, or non- ionomeric compositions including, but not limited to, polyvinyl chloride, copolymers of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride, polyolefins, such as polyethylene, polypropylene, polybutylene copolymers and homopolymers produced using a single-site catalyst or a metallocene catalyst, polyphenylene ether, copolymers such as ethylene methylacrylate, ethylene ethylacrylate, ethylene vinyl acetate, ethylene methacrylic acid, ethylene acrylic acid, propylene acrylic acid, polyamides such as poly(hexamethylene adipamide) and others prepared from diamines and dibasic acids, as well as those from amino acids such as poly(caprolactam).
• polyvinyl chloride copolymers of vinyl chloride with vinyl acetate, acrylic
• thermoplastic or thermosetting polyurethanes include but are not limited to, thermoplastic or thermosetting polyurethanes, thermoplastic block polyesters, for example, a polyester elastomer such as that marketed by DuPont under the trademark HYTREL®, or thermoplastic block polyamides, for example, a polyether amide such as that marketed by EIf Atochem S. A. under the trade name PEBAX, a blend of two or more non-ionomeric thermoplastic elastomers, or a blend of one or more ionomers and one or more non- ionomeric thermoplastic elastomers.
• mixtures of two or more of any of the suitable materials described above, including polyamide/ ionomer blends, polyphenylene ether/ionomer blends, etc. may also be used in the intermediate layer.
• At least one intermediate layer may also be a moisture barrier layer, such as the ones described in U.S. Patent 5,820,488.
• a moisture barrier layer such as the ones described in U.S. Patent 5,820,488.
• Other suitable materials for use in moisture vapor barrier layers include the ionomer compositions described in U.S. Patent Application Nos. 11/789,831 , filed on April 25, 2007; 11/201 ,893, filed on August 11 ,
• the ionomer may include so-called "low acid” or “high acid” ionomers, as well as blends of low acid and high acid ionomers.
• ionomers prepared by neutralizing acid copolymers including up to about 15 percent acid are considered low acid ionomers, while those including greater than about 15 percent acid are considered high acid ionomers.
• the intermediate layer includes a low acid ionomer in which the acid is present in about 10 to
• the softening comonomer may be selected from the group consisting of vinyl esters of aliphatic carboxylic acids wherein the acids have 2 to 10 carbon atoms, vinyl ethers wherein the alkyl groups contains 1 to 10 carbon atoms, and alkyl acrylates or methacrylates wherein the alkyl group contains 1 to 10 carbon atoms.
• Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or the like.
• the intermediate layer includes at least one high acid ionomer, for low spin rate and maximum distance.
• the acrylic or methacrylic acid is present in about 15 to about 35 weight percent, and the ionomer has a high modulus.
• the high modulus ionomer includes about 16 percent by weight of a carboxylic acid, preferably from about 17 percent to about 25 percent by weight of a carboxylic acid, more preferably from about 18.5 percent to about 21.5 percent by weight of a carboxylic acid.
• an additional comonomer such as an acrylate ester (i.e., iso- or n-butylacrylate, etc.) can also be included to produce a softer terpolymer.
• the additional comonomer may be selected from the group consisting of vinyl esters of aliphatic carboxylic acids wherein the acids have 2 to 10 carbon atoms, vinyl alkyl ethers wherein the alkyl groups contains 1 to 10 carbon atoms, and alkyl acrylates or methacrylates wherein the alkyl group contains 1 to 10 carbon atoms.
• Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, or the like.
• examples of a number of copolymers suitable for use to produce the high modulus ionomers include, but are not limited to, high acid ethylene/acrylic acid copolymers, an ethylene/methacrylic acid copolymer, an ethylene/itaconic acid copolymer, an ethylene/maleic acid copolymer, an ethylene/methacrylic acid/vinyl acetate copolymer, an ethylene/acrylic acid/vinyl alcohol copolymer, and the like.
• intermediate layers Preferred for use in intermediate layers are ionomer compositions and their blends with other materials that are suitable for use in intermediate layers. Particularly preferred for use in intermediate layers are the thermoplastic compositions described herein, and their blends with other materials that are suitable for use in intermediate layers.
• the range of thicknesses for the intermediate layer is large because of the vastly different constructions that are possible, i.e., an outer core layer, an inner cover layer, a wound layer, a moisture/vapor barrier layer, and the like.
• suitable intermediate layers, or inner cover layers may have a thickness of about 0.3 inches or less. Varying combinations of ranges of thickness for the intermediate and outer cover layers may be used in combination with other golf balls described herein.
• the ratio of the thickness of the intermediate layer to the outer cover layer is preferably about 10 or less, preferably from about 3 or less. In another golf ball, the ratio of the thickness of the intermediate layer to that of the outer cover layer is about 1 or less.
• the core and intermediate layer(s) together may be considered to form an "inner ball" preferably having a diameter of about 1.48 inches or greater for a golf ball having a diameter of 1.68 inch.
• the core itself may have more than one layer.
• the core includes an inner core layer and an outer core layer
• the inner core layer may be preferably about 0.9 inches or greater in thickness and the outer core layer preferably has a thickness of about 0.1 inches or greater.
• Preferred multilayer golf balls and golf balls of note include, without limitation, those set forth in the following Table. TABLE: Preferred Multilayer Golf Balls
• the multilayer golf ball has more than one mantle, only one of the mantles need include the component listed in the Table.
• the materials for the other intermediate layer(s) are selected independently from the suitable materials described herein.
• the composition of each mantle may be the same as or different from the composition(s) of the other mantle(s).
• thermoplastic composition is an abbreviation for "the thermoplastic composition described herein".
• polyurethane refers to thermoset or thermoplastic polyurethanes.
• thermoplastic compositions described herein can provide tailored resiliency as indicated by the coefficient of restitution (COR).
• Coefficient of restitution is measured by firing a sphere that is 1.50 to 1.68 inches in diameter at an initial velocity of 125 feet/second against a steel plate positioned 3 feet from the point where initial velocity is determined and dividing the velocity of rebound from the plate by the initial velocity.
• COR may be determined on a sphere prepared from a single composition or a sphere having two or more layers (for example, a finished golf ball).
• thermoplastic composition that when formed into a sphere of 1.50 to 1.68 inches in diameter exhibits a rebound velocity of greater than 94 ft/sec, or greater than 99 ft/sec, when the sphere is fired at an initial velocity of 125 ft/sec against a steel plate positioned 3 feet from the point where initial velocity is determined.
• Examples include a golf ball comprising a core, a cover prepared from an ionomer composition or a polyurethane; and an intermediate layer comprising or prepared from the thermoplastic composition described herein wherein the composition of intermediate layer when formed into a sphere of 1.50 to 1.68 inches in diameter exhibits a rebound velocity of greater than 94 ft/sec, or greater than 99 ft/sec, when the sphere is fired at an initial velocity of 125 ft/sec against a steel plate positioned 3 feet from the point where initial velocity is determined.
• thermoplastic compositions described herein when formed into such a sphere, may have a coefficient of restitution of greater than about 0.6, preferably greater than about 0.5, more preferably greater than about 0.68, most preferably greater than about 0.7.
• the golf balls have an intermediate layer with a flexural modulus of about 500 psi to about 500,000 psi. More preferably, the flexural modulus of the intermediate layer is about 1 ,000 psi to about 250,000 psi. Most preferably, the flexural modulus of the intermediate layer is about 2,000 psi to about 200,000 psi.
• the thermoplastic compositions described herein may have flexural modulus greater than 60, 80, 90, 100, 110, or 120 kpsi. Of note is a thermoplastic composition having a flexural modulus of greater than 80 kpsi, or 100 kpsi, measured according to ASTM D-790 B.
• thermoplastic compositions described herein are useful for high modulus intermediate layers or cover layers.
• examples include a golf ball comprising a core, a cover prepared from an ionomer or a polyurethane; and an intermediate layer comprising or prepared from the thermoplastic composition described herein having a flexural modulus of greater than 80 kpsi, or 100 kpsi, measured according to ASTM D-790 B.
• the flexural modulus of the cover layer is preferably about 2,000 psi or greater, and more preferably about 5,000 psi or greater.
• the flexural modulus of the cover is from about 10,000 psi to about 150,000 psi. More preferably, the flexural modulus of the cover layer is about 15,000 psi to about 120,000 psi. Most preferably, the flexural modulus of the cover layer is about 18,000 psi to about 1 10,000 psi.
• the flexural modulus of the cover layer is about 100,000 psi or less, preferably about 80,000 or less, and more preferably about 70,000 psi or less.
• the cover layer when the cover layer has a hardness of about 50 Shore D to about 60 Shore D, the cover layer preferably has a flexural modulus of about 55,000 psi to about 65,000 psi.
• the ratio of the flexural modulus of the intermediate layer to the cover layer is about 0.003 to about 50. In another golf ball, the ratio of the flexural modulus of the intermediate layer to the cover layer is about 0.006 to about 4.5. In yet another golf ball, the ratio of the flexural modulus of the intermediate layer to the cover layer is about 0.11 to about 4.5.
• the thermoplastic compositions described herein are used in a golf ball with multiple cover layers having essentially the same hardness, but with differences in their flexural moduli.
• the difference between the flexural moduli of the two cover layers is preferably about 5,000 psi or less.
• the difference in flexural moduli is about 500 psi or greater.
• the difference in the flexural moduli between the two cover layers, wherein at least one is reinforced is about 500 psi to about 10,000 psi, preferably from about 500 psi to about 5,000 psi.
• the difference in flexural moduli between the two cover layers formed of unreinforced or unmodified materials is about 1 ,000 psi to about 2,500 psi.
• compositions with specific resilience, compression, hardness and/or flex modulus will largely depend upon the type of golf ball desired (i.e., one-piece, two-piece, wound, or multi-layered), and in the type of performance desired for the resulting golf ball as detailed above.
• Coefficient of Restitution is measured by firing an injection-molded neat sphere of the resin the size of a golf ball from an air cannon at a velocity determined by the air pressure.
• the initial velocity generally employed is 125 feet/second.
• the sphere strikes a steel plate positioned three feet away from the point where initial velocity is determined, and rebounds through a speed-monitoring device located at the same point as the initial velocity measurement.
• the return velocity divided by the initial velocity is the COR.
• melt index refers to melt index as determined according to ASTM D1238 at 190 0 C using a 2160 g weight, with values of Ml reported in g/10 minutes.
• the Shore D hardness of a material is measured generally in accordance with
• Shore D hardness of multilayer spheres is measured with all layers present. When a hardness measurement is made on a dimpled sphere, Shore D hardness is measured at a land area of the dimpled sphere.
• Water vapor transmission rate (WVTR or MVTR) was measured on a PERMATRAN-W Model 700 instrument (available from MOCON, Inc., Minneapolis, MN) operated according to operating instructions at 38.1 0 C and 100% RH.
• Impact Durability is the average number of hits to failure of balls fired by an air cannon of a COR tester at 175 or 135 ft/sec which impact a flat metal plate at a perpendicular angle.
• Scuff resistance was determined in the following manner: a D-2 tool steel plate machined to simulate a sharp grooved pitching wedge with square (box) grooves was mounted on a swing arm that swings in a horizontal plane. The simulated club face was oriented for a hit on a golf ball at a 54° angle. The machine was operated at a simulated club head speed of 140 feet per second. Balls were prepared as described below from each of the test compositions. Comparison balls with polyurethane covers were obtained commercially. At least three balls of each composition were tested and each ball was hit once. After testing, the balls were rated according to the following criteria (see Table A). A stereo optical inspection microscope (2x to 1Ox) or equivalent was used to view the balls.
• Scuff damage was characterized by the presence of indented lines, lifts or groove bands.
• Indented lines are visible lines created by permanent displacement of the resin, but without cutting, breaking or discontinuity of the surface.
• Lifts are scuffs in which the resin is displaced enough that the surface is broken such that a portion of the resin is separated from the bulk of the ball. Severe lifts include flaps, whiskers or strands.
• Groove bands are bands of resin missing from the bulk of the ball corresponding in dimension to a single groove of the club face. The ratings were assigned numerical values based on the criteria in Table A.
• compositions were prepared by melt blending the ionomer resins and the modifier employing a Werner & Pfleiderer twin-screw extruder. After blending, the compositions were extruded into the appropriate shapes for mechanical property testing. The materials were injection molded into flex bars and tensile test pieces and then tested for Shore D hardness, room temperature flex modulus, and room temperature tensile properties after aging for a period of at least two weeks at room temperature. The compositions were molded into spheres of about 1.53 to1.54 inch diameter, and the spheres were tested for golf ball properties, such as Atti compression, coefficient of restitution (COR), Shore D Hardness, and drop rebound.
• Atti compression Atti compression
• COR coefficient of restitution
• Shore D Hardness Shore D Hardness
• compositions were also molded over commercial thermoset rubber cores to afford balls with diameter of about 1.68 inch.
• the balls were tested for golf ball properties, such as Atti compression, coefficient of restitution (COR), durability and scuff resistance.
• Atti compression Atti compression
• COR coefficient of restitution
• durability durability
• scuff resistance scuff resistance
• Films were prepared by melting the composition in a twin screw extruder, exiting through a coat-hanger shaped sheet die to make a film of about 76 to about 104 micron thickness.
• Amine-1 CHIMASSORB 944, available from CIBA.
• PVP-1 A polyvinylpyrrolidone, 30,000 Dalton molecular weight, available from
• PVP-2 A polyvinylpyrrolidone, 15,000 Dalton molecular weight, available from ISP.
• PVP-3 A polyvinylpyrrolidone, 90,000 Dalton molecular weight, available from ISP.
• PEO-1 A poly(2-ethyl oxazoline, 50,000 Dalton molecular weight, available from ISP.
• AO-1 antioxidant IRGANOX 1010 available from CIBA.
• n aq means an aqueous solution with n % by weight. * * "failed” balls broke or were misshapen

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