Classifications

• • 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
• • 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
  • A63B37/005—Cores
  • A63B37/0051—Materials other than polybutadienes; Constructional details
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/005—Cores
  • A63B37/0051—Materials other than polybutadienes; Constructional details
  • A63B37/0059—Ionomer
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/005—Cores
  • A63B37/006—Physical properties
  • A63B37/0061—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
  • A63B37/005—Cores
  • A63B37/006—Physical properties
  • A63B37/0062—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
  • A63B37/005—Cores
  • A63B37/006—Physical properties
  • A63B37/0064—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
  • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
  • A63B37/0074—Two piece balls, i.e. cover and core
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B37/00—Solid balls; Rigid hollow balls; Marbles
  • A63B37/0003—Golf balls
  • A63B37/007—Characteristics of the ball as a whole
  • A63B37/0072—Characteristics of the ball as a whole with a specified number of layers
  • A63B37/0076—Multi-piece balls, i.e. having two or more intermediate layers
• • 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
  • A63B37/0092—Hardness distribution amongst different ball layers
• • A—HUMAN NECESSITIES
  • A63—SPORTS; GAMES; AMUSEMENTS
  • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
  • A63B45/00—Apparatus or methods for manufacturing balls
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

• the present invention relates generally to golf balls. Specifically, this disclosure relates to golf balls including a highly neutralized polymer and a modifier, where the modifier changes the hardness of the highly neutralized polymer.
• golf is an increasingly popular sport at both the professional and amateur levels.
• mass produced golf balls should be able to meet the requirements of golfers of a wide variety of ability levels.
• the materials used in the golf ball's construction may be chosen so as to make the golf ball more suitable for particular types of golfers.
• ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
• Suitable known materials for use in a golf ball include thermoset materials, such as rubber, styrene-butadiene copolymer, polybutadiene, cis- polyisoprene, and trans-polyisoprene.
• thermoset materials such as rubber, styrene-butadiene copolymer, polybutadiene, cis- polyisoprene, and trans-polyisoprene.
• Known materials also include
• thermoplastics such as ionomer resins, polyamides or polyesters, and
• thermoplastic polyurethane elastomers Suitable materials also include polyurea compositions, as well as other materials.
• ionomers are often used to form the various structural components of known golf balls.
• ionomers such as SurlynTM available from E.I. DuPont de Nemours & Company are known to be used for cover layers of golf balls.
• Other types of ionomers generally referred to as highly neutralized polymers, may also be used in golf balls.
• Certain formulations of the highly neutralized polymer may affect various physical properties of the polymer material, and so may affect the play characteristics of a golf ball made from that material.
• various highly neutralized polymers may achieve increased hardness, modulus, and resilience characteristics. These properties of highly neutralized polymers may be advantageous to golf ball covers, cores, or other structural components, in order to achieve desired play characteristics.
• a highly neutralized polymer may have a hardness that is higher than may be preferable.
• a core made from a highly neutralized polymer may be harder than preferable to highly skilled golfers.
• a golf ball's "feel" may be related to the hardness of the material making up the golf ball's core.
• Highly skilled golfers may prefer golf balls that have a soft feel when hit by a golf club.
• a golf ball with a core made from a highly neutralized polymer may therefore fail to achieve a highly skilled golfer's preferred "soft feel.”
• an overly hard core may cause the golf ball to make a higher(or "harder") than desirable sound when stuck by a golf club.
• this disclosure provides a golf ball comprising a core and a cover layer.
• the cover layer substantially surrounds the core.
• At least one of the core and the cover layer is made of a polymer mixture.
• the polymer mixture comprises a polymer and a modifier.
• the polymer comprises a highly neutralized polymer.
• the modifier is selected from the group consisting of process oils, plasticizers, and blends thereof.
• the modifier is present in the polymer mixture in a sufficient amount such that the modifier reduces a hardness of the polymer mixture from a first value, that is approximately the same as a hardness of the highly neutralized polymer, to a second value that is less than the hardness of the highly neutralized polymer.
• this disclosure provides a golf ball comprising an inner core, an outer core layer substantially surrounding the inner core, and at least one cover layer substantially surrounding the interior layer(s).
• At least one of the inner core and the outer core layer is comprised of a polymer mixture.
• the polymer mixture comprises a polymer and a modifier.
• the polymer comprises at least one highly neutralized polymer.
• the modifier is selected from the group consisting of naphthenic process oils, paraffinic process oils, phthalate esters, trimellitates, adipates, sebacate-based plasticizer, maleate-based plasticizer, and blends thereof.
• the modifier is present in the polymer mixture in an amount of from about 1 to about 25 parts by weight per 100 parts by weight of polymer.
• the modifier is also present in the polymer mixture in a sufficient amount such that the modifier reduces a hardness of the polymer mixture from a first value that is approximately the same as a hardness of the highly neutralized polymer to a second value that is less than the hardness of the highly neutralized polymer.
• the second value is at least about 2 Shore D less than the first value.
• This disclosure also provides a method of manufacturing a golf ball comprising, first, receiving a highly neutralized polymer.
• the method includes changing the hardness of the highly neutralized polymer by mixing a modifier therewith to form a polymer mixture.
• the modifier is selected from the group consisting of process oils, plasticizers, and blends thereof.
• the method also includes forming the polymer mixture into a core, and forming a cover layer around the core such that the cover layer substantially surrounds the core.
• the modifier is present in the polymer mixture in a sufficient amount such that the modifier reduces a hardness of the polymer mixture from a first value that is approximately the same as a hardness of the highly neutralized polymer to a second value that is less than the hardness of the highly neutralized polymer.
• the presence of the modifier also reduces a hardness value of the polymer mixture by a first proportion, and reduces the COR value of the core by a second proportion. The first proportion is greater than the second proportion.
• FIG. 1 shows a representative golf ball in accordance with this disclosure, the golf ball being of a two-piece construction
• FIG. 2 shows a second representative golf ball, having a core, an inner cover layer, and an outer cover layer;
• FIG. 3 shows a third representative golf ball, having an inner core, an outer core layer, and a cover layer;
• FIG. 4 shows a fourth representative golf ball, having an inner core, an outer core layer, an inner cover layer, and an outer cover layer.
• this disclosure provides a golf ball including a highly neutralized polymer that has been modified to have a lower hardness through the addition of a modifier.
• the modifier may be a process oil, a plasticizer, or a blend thereof.
• the modifier reduces the hardness by a desired amount while only affecting the COR related properties to a slight degree. Accordingly, a golf ball may have the modified highly neutralized polymer in the core while also achieving a soft "feel" and a high COR.
• compression deformation indicates the deformation amount of the ball, or any portion thereof, under a force; specifically, when the force is increased to become 130 kg from 10 kg, the deformation amount of the ball or portion thereof under the force of 130 kg reduced by the deformation amount of the ball or portion thereof under the force of 10 kg is the compression deformation value of the ball or portion thereof.
• the term "hardness" as used herein is measured generally in accordance with ASTM D-2240.
• the hardness of a golf ball is measured on the land area of a curved surface of a molded ball.
• the hardness of a golf ball subcomponent is measured on the curved surface of the molded sub-component.
• the hardness of a material is measured in accordance with ASTM D-2240 (on a plaque).
• COR coefficient of restitution
• FIGS. 1 -4 show certain embodiments of golf balls in accordance with this disclosure.
• any golf ball discussed herein may generally be any type of golf ball known in the art.
• a golf ball may generally be of any construction conventionally used for golf balls, and may be made of any of the various materials known to be used in golf ball manufacturing.
• any feature disclosed herein including but not limited to various embodiments shown in the FIGS, and various chemical formulas or mixtures may be combined with any other features disclosed here in any combination or subcombination, as may be desired.
• FIG. 1 illustrates two layer or "two-piece" golf ball 100 having core 120 substantially surrounded by cover layer 1 10.
• cover layer 1 10 and core 120 may comprise a modified highly neutralized polymer.
• core 120 may comprise the modified highly neutralized polymer, while cover layer 1 10 may comprise any other suitable material such as polyurethane or an ionomer such as Surlyn®.
• cover layer 1 10 may comprise the modified highly neutralized polymer, while core 120 may be comprised of any other suitable material such as polybutadiene rubber.
• FIG. 2 illustrates three-piece golf ball 200 having a relatively large core 230 substantially surrounded by inner cover layer 220, which itself is encompassed within or substantially surrounded by outer cover layer 210.
• any one or more of the structural components may be comprised of a modified highly neutralized polymer.
• core 230 may comprise the modified highly neutralized polymer, while inner cover layer 220 and outer cover layer 210 may be comprised of conventionally known materials.
• inner cover layer 220 may comprise the modified highly neutralized polymer, while core 230 and outer cover layer 210 may be comprised of known materials.
• outer cover layer 210 may comprise the modified highly neutralized polymer, while core 230 and inner cover layer 220 may be comprised of known materials.
• FIG. 3 illustrates three-piece golf ball 300 having a relatively smaller inner core 330, outer core layer 320, and cover layer 310.
• any one or more of the structural components of the golf ball may be comprised of a modified highly neutralized polymer.
• core 330 may comprise the modified highly neutralized polymer, while outer core 320 and cover layer 310 may each be comprised of conventional materials.
• outer core 320 may comprise the modified highly neutralized polymer, while core 330 and cover layer 310 may be comprised of conventional materials.
• cover layer 310 may comprise the modified highly neutralized polymer, while core 330 and outer core 320 may be made from known materials.
• FIG. 4 illustrates four-piece golf ball 400 having inner core 440, outer core layer 430, inner cover layer 420, and outer cover layer 410.
• any one or more of the structural components of the golf ball may be comprised of a modified highly neutralized polymer.
• inner core 440 may be comprised of the modified highly neutralized polymer, while outer core layer 430, inner cover layer 420, and outer cover layer 410 are all each made of conventional materials.
• outer core layer 430 may be comprised of the highly neutralized polymer, while each of inner core 440, inner cover layer 420, and outer cover layer 410 are made of conventional material.
• inner cover layer 420 may comprise the modified highly neutralized polymer, while each of inner core 440, outer core layer 430, and outer cover layer 410 are made of conventional materials.
• outer cover layer 410 may be comprised of the highly neutralized polymer, while each of inner core 440, outer core layer 430, and inner cover layer 420 may be made of known materials.
• the structural components making up the golf ball may have certain sizes.
• Inner core 440 may have a diameter of from about 20 mm to about 30 mm, or from about 21 mm to about 30 mm, or from about 22 mm to about 29 mm, or from about mm 23 to about 27 mm, or about 25 mm.
• Inner cover layer 420 may have a thickness of from about 0.5 mm to about 1 .2 mm.
• Outer cover layer 410 may have a thickness of from about 0.6 mm to about 2 mm.
• outer core layer 430 may have a thickness that is not particularly limited.
• golf ball 400 may be a regulation golf ball that meets USGA requirements. In such embodiments, the USGA requires that the total diameter of the golf ball be at least 1 .680 inches. Therefore, the sum of: the diameter of inner core 440, the thickness of other layers (discussed below), and the thickness of outer core layer 430 may be at least 1 .680 inches (42.67 mm). In some embodiments, the total diameter is equal to about 1 .680 inches.
• outer core 430 may have a thickness of from about 3 mm to about 10 mm, or from about 5 mm to about 8 mm, or about 7 mm.
• the disclosure relates to golf balls having at least 2 layers, or pieces.
• discussion herein below may be directed to a 4-piece ball for convenience, the disclosure is directed to golf balls having at least 2-layers, and as many as 5, 6, or 7 layers, or more.
• the number of layers in the golf ball is limited only by any rules extant at the time of manufacture if the golf ball is to be considered a 'regulation' or 'conforming' golf ball.
• any layer may be made of any material suitable for the purpose.
• an outer cover layer should be tough and resistant to scuffing while being soft enough for a golf club to impart spin easily to the ball.
• thermoplastic polyurethane (TPU) and thermoset polyurethane are suitable for use in outer cover layers, as are known highly neutralized polymers and other ionomers.
• Thermoplastic polyurethane that is not otherwise scuff resistant can be treated to harden the surface, such as by a surface treatment.
• Suitable ionomers include members of the Surlyn® family of ionomeric polymers produced by E. I. DuPont de Nemours and Company and members of the lotek® family of products produced by ExxonMobil Chemical Corporation.
• a highly neutralized polymer may be mixed with a modifier to form a polymer composition having physical properties that are different from the physical properties of the highly neutralized polymer by itself.
• the polymer in the polymer mixture may be a single type of highly neutralized polymer, a mixture of one or more types of highly neutralized polymers, or a mixture of a highly neutralized polymer and another type of polymer.
• a highly neutralized polymer is a type of ionomer.
• An ionomer is generally understood as any polymer material that includes ionized functional groups therein.
• Ionomeric resins are often ionic copolymers of an olefin and a salt of an unsaturated carboxylic acid.
• the olefin may have from about 2 to about 8 carbon atoms, and may be an alpha-olefin.
• the acid may be an unsaturated monocarboxylic acid having from about 3 to about 8 carbon atoms, and may be an alpha, beta-unsaturated carboxylic acid.
• ionomers are copolymers of ethylene and either acrylic acid or methacrylic acid. Copolymers may be referred to as EAA or EMAA type ionomers. In some instances, an additional co-monomer (such as an acrylate ester, i.e., iso- or n-butylacrylate, etc.) can also be included to produce a terpolymer.
• Terpolymer ionomers may be referred to as E/X/Y type ionomers where E is ethylenic (or olefinic) in nature, X is an alpha, beta-unsaturated carboxylic acid and Y is an acrylate ester.
• E ethylenic (or olefinic) in nature
• X is an alpha, beta-unsaturated carboxylic acid
• Y is an acrylate ester.
• a wide range of ionomers are known to the person of ordinary skill in the art of golf
• the ionomer material may be considered to be a highly neutralized acid polymer.
• a polymer is considered highly neutralized when at least 70% of the acid groups are neutralized by a cation.
• the highly neutralized acid polymer may be neutralized to at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98%, at least 99%, or substantially 100%.
• the acid polymer may be neutralized with a suitable cation source, such as magnesium, sodium, zinc, or lithium.
• Exemplary highly neutralized acid polymer (“HNP”) compositions include HPF resins such as HPF1000, HPF2000, HPF AD1024, HPF AD1027, HPF AD1030, HPF AD1035, HPF AD1040, and combinations thereof, all produced by E. I. DuPont de Nemours and Company.
• the polymer used in the polymer mixture may consist essentially of a mixture of two types of highly neutralized polymers, such as a mixture of HPF1000 and HPF2000.
• the polymer in the polymer mixture may be a blend of a highly neutralized polymer and at least one additional polymer, the at least one additional polymer being a type of polymer other than a highly neutralized polymer.
• the additional polymer may be a rubber or a polyurethane polymer.
• the highly neutralized polymer may comprise at least about 10%, or at least about 25%, or at least about 50%, or at least about 75%, or at least about 90% of the total weight of polymer in the polymer mixture.
• the additional polymer may therefore comprise at most about 90%, or at most about 75%, or at most about 50%, or at most about 25%, or at most about 10% of the total of polymer in the polymer mixture.
• the polymer as discussed variously above may be mixed with a modifier to create a polymer mixture. This polymer mixture may then be used to form any structural component of the golf ball.
• the modifier may be a process oil, a plasticizer, or any mixture thereof.
• the modifier may cause the polymer mixture to have a value of a physical property that differs from the value of that physical property of the highly neutralized polymer.
• the modifier may cause the polymer mixture to have a hardness that is different from the hardness of the highly neutralized polymer by itself. Therefore, the modifier modifies the highly neutralized polymer so as to result in desirable physical properties.
• process oils are generally understood by a person having ordinary skill in the art to be any of a class of non-reactive oils which are incorporated into a material in order to affect the properties of that material.
• Process oils are divided into three general categories: aromatic oils, naphthenic oils, and paraffinic oils.
• ASTM D2226 provides a standard for categorizing a process oil into one of these three types.
• process oils typically are a blend of aromatic, naphthenic, and paraffinic oils, and are classified by the predominant types of properties and characteristics of the oil.
• aromatic oils may have the highest solvency, the darkest colors, but poor color stability.
• Naphthenic oils may have intermediate solvency, and fair color stability.
• paraffinic oils may have the lowest solvency of the three types of process oils, but may have the highest color stability and the lowest volatility.
• the process oil used as a modifier herein may be selected from the group consisting of aromatic process oils, naphthenic process oils, paraffinic process oils, and blends thereof.
• Aromatic oils include the Sundex® family of aromatic oils available from many sources, including American Lubricants & Chemicals, LLC, in Ohio, USA. Aromatic oils may lower viscosity more than the same quantity of naphthenic oil or paraffinic oil. However, aromatic oils may cause concern over potential health issues. Namely, aromatic process oils may be subject to environmental and health related regulations in various jurisdictions.
• the process oil may be selected from the group consisting of paraffinic process oils, naphthenic process oils, and blends thereof.
• paraffinic and naphthenic oils include, for example, Sunpar® paraffinic oil, a family of oils commercially available from Sunoco, Inc. of Pennsylvania, USA and HollyFrontier Refining and Marketing; Paralux® paraffinic oil, a family of oils commercially available from Chevron Corporation of California, USA; Unithene® naphthenic oil, a family of oils commercially available from Ergon, Inc. of Mississippi, USA; the family of oils commercially available from Idemitsu USA under the name Diana Process Oil PS, and the family of oils commercially available from ConocoPhilips under the
• suitable process oils may also include low PCA/PHA (polycyclic aromatic/polyaromatic hydrocarbon) oils, including mild extraction solvates (MES), treated distillate aromatic extracts (TDAE), and heavy naphthenic oils.
• low PCA oils are further disclosed in U.S. Pat. No.
• process oils may generally be mixed with the highly neutralized polymer in any amount.
• the process oil may be present in at least a quantity sufficient to affect a property of the highly neutralized polymer.
• the process oil modifier may be present in the polymer mixture in a sufficient amount such that the process oil modifier reduces a hardness of the polymer mixture from a first value, the first value being approximately the same as a hardness of the highly neutralized polymer itself, to a second value that is less than the hardness of the highly neutralized polymer.
• extremely large amounts of process oil modifier may be less than desirable due to "bleeding" of the modifier out of the polymer mixture (i.e., because the modifier is less than entirely miscible with the polymer mixture).
• small quantities may reduce the hardness, but may still leave the polymer mixture with a less than desirable hardness value.
• process oil modifiers used in the present disclosure may be present in the polymer mixture in amounts of less than about 30 parts by weight per 100 parts by weight of polymer. In some embodiments, the process oil modifier may be used in amounts of from about 1 to about 25 parts by weight per 100 parts weight of polymer. In other embodiments, the process oil modifier may be used in amounts of from about 10 to about 25 parts by weight per 100 parts weight of polymer, or from about 1 1 to about 25 parts by weight per 100 parts weight of polymer.
• Process oils may be selected as the modifier for use in golf balls according to this disclosure as a result of a variety of factors. For example, process oils may be more economical than other types of modifiers herein.
• Process oils may also provide better adhesion behavior, i.e., less waxy behavior, between adjacent structural components of the golf ball than other modifiers. This behavior may ensure that no adhesive layer is required to bond adjacent layers within the golf ball, or at least that no additional adhesive layer would be required. Furthermore, process oils may be more compatible with the highly neutralized polymer than other modifiers. This behavior would help avoid "bleeding" of the modifier out of the polymer mixture, both during processing of the polymer mixture and after the golf ball has been manufactured.
• Plasticizers may also be used as the modifier. As is generally known to a person having ordinary skill in the art, plasticizers are a class of dispersants that increase the plasticity of a polymer material. Although the inventors do not wish to be bound by theory, it is believed that plasticizers generally work by embedding themselves between the chains of a polymer, spacing the chains apart (increasing the "free volume"), and thus lowering the glass transition temperature of the plastic and making the polymer softer.
• phthalate based plasticizers may be used as the modifier. Phthalate based plasticizers may be used when good resistance to water and oils is desirable. Some suitable phthalate based plasticizers may include bis(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), bis(n- butyl)phthalate (DnBP, DBP), butyl benzyl phthalate (BBzP), diisodecyl phthalate (DIDP), di-n-octyl phthalate (DOP or DnOP), diisooctyl phthalate (DIOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), and di-n-hexyl phthalate.
• DEHP bis(2-ethylhexyl) phthalate
• DINP diisononyl phthalate
• DnBP bis(n- butyl)phthalate
• trimellitate based plasticizers may be used in particular embodiments when resistance to high temperatures may be desirable.
• Trimellitates may include trimethyl trimellitate (TMTM), tri-(2-ethylhexyl) trimellitate (TEHTM-MG), tri-(n-octyl,n-decyl) trimellitate (ATM), tri-(heptyl,nonyl) trimellitate (LTM), and n-octyl trimellitate (OTM).
• TMTM trimethyl trimellitate
• THTM-MG tri-(2-ethylhexyl) trimellitate
• ATM tri-(n-octyl,n-decyl) trimellitate
• LTM tri-(heptyl,nonyl) trimellitate
• OFTM n-octyl trimellitate
• Adipate based plasticizers may also be used as the modifier. Adipate based plasticizers may be used in some embodiments when resistance to ultraviolet light is a consideration. Adipate based plasticizers may include bis(2- ethylhexyl)adipate (DEHA), dimethyl adipate (DMAD), monomethyl adipate (MMAD), and dioctyl adipate (DOA).
• DEHA bis(2- ethylhexyl)adipate
• DMAD dimethyl adipate
• MMAD monomethyl adipate
• DOA dioctyl adipate
• plasticizers may include sebacate-based plasticizer such as dibutyl sebacate (DBS), or maleates based plasticizer such as dibutyl maleate (DBM) or diisobutyl maleate (DIBM).
• DBS dibutyl sebacate
• DBM dibutyl maleate
• DIBM diisobutyl maleate
• the plasticizer may generally be present in the polymer mixture in any amount.
• the plasticizer may be present in a minimum quantity sufficient to affect a physical property of the polymer mixture.
• the plasticizer may be present in the polymer mixture in amounts of less than about 30 parts by weight per 100 parts by weight of polymer.
• the plasticizer modifier may be used in amounts of from about 1 to about 25 parts by weight per 100 parts weight of polymer.
• the plasticizer modifier may be used in amounts of from about 10 to about 25 parts by weight per 100 parts weight of polymer, or from about 1 1 to about 25 parts by weight per 100 parts weight of polymer.
• certain materials may be used to compatibilize the modifier with the polymer in the polymer mixture.
• the modifier may have a less than desirable level of miscibility with the highly neutralized polymer.
• Such compatibilizers may ensure that the modifier does not bleed or leach out of the polymer mixture after manufacturing, as well as aid in the manufacturing process.
• Compatibilizers may be useful when the structural component of the golf ball comprising the polymer mixture is a cover layer or outer cover layer.
• an inner layer such as the core, outer core, or inner cover
• the compatibilizers may be useful to prevent bleeding and leaching.
• Compatibilizers may also be particularly useful in embodiments when the modifier is a process oil.
• Compatibilizers may include maleic anhydride, silanes, and titanates.
• silanes have the general formula Si n H 2n +2- Typically, n is less than about 8, as larger molecules are only difficultly made.
• titanates are compounds known to the skilled practitioner.
• Ken-React® family of titanate coupling agents available from Kenrich Petrochemical, Inc., of New Jersey, USA, are suitable titanates.
• Suitable titanates include monoalkoxy titanates, such as KR ® TTS (Titanium IV 2- propanolato, tris isooctadecanoato-O) and KR 7 (Titanium IV bis 2-methyl-2- propenoato-O, isooctadecanoato-O 2-propanolato); oxyacetate chelate titanates, such as KR® 134S (Titanium IV bis[4-(2-phenyl)2-propyl-2] phenolato,
• oxoethylenediolato and KR 138S Tianium IV bis(dioctyl)pyrophosphato-O, oxoethylenediolato, (adduct), (dioctyl) (hydrogen)phosphite
• A,B ethylene chelate titanates such as KR® 212 (Titanium IV bis(dioctyl)phosphato-O, ethylenediolato) and KR 238S (Titanium IV bis(dioctyl)pyrophosphato-O, ethylenediolato (adduct), bis(dioctyl)hydrogen phosphite);
• quaternary titanates such as KR® 138D
• cycloheteroatom titanates such as KR ® OPPR (Titanium IV bis octanolato, cyclo(dioctyl)pyrophosphato-O, O) and KR OPP2 (Titanium IV bis
• the polymer mixture may also include other ingredients in addition to the polymer, the modifier, and optionally the compatibilizer.
• the polymer mixture may also include one or more fatty acids. Fatty acids are known to be used to control the physical properties of a polymer. The presence of a fatty acid may therefore further affect the physical properties, such as hardness, of the polymer mixture comprising the highly neutralized polymer.
• a fatty acid is a carboxylic acid with a long unbranched aliphatic tail.
• the tail may be saturated or unsaturated.
• the fatty acid may have any chain length of from about five carbons to about 30 carbons.
• Representative saturated fatty acids that may be used in this disclosure include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, and mixtures thereof.
• unsaturated fatty acids that may be used in this disclosure include myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, a-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, and mixtures thereof.
• Unsaturated fatty acids may be used in either or both of the cis or trans species.
• these various additive materials may be a pulverulent material that may tend to become airborne and be difficult to distribute evenly in the HNP.
• a pulverulent material may be available in combination with a carrier such as a dispersant oil, for example.
• a carrier such as a dispersant oil, for example.
• the total amount of oil from all sources in the HNP typically should be less than about 35 parts per hundred parts HNP by weight, or less than about 15 parts per hundred parts HNP by weight, or less than about 10 parts per hundred HNP by weight.
• the layers, or pieces also may include further components such as fillers and/or additives.
• Fillers and additives may be used based on any of a variety of desired characteristics, such as enhancement of physical properties, UV light resistance, and other properties.
• a light stabilizer is added.
• Light stabilizers may include hindered amines, UV stabilizers, or a mixture thereof.
• Inorganic or organic fillers can be also added to any layer.
• Suitable inorganic fillers may include silicate minerals, metal oxides, metal salts, clays, metal silicates, glass fibers, natural fibrous minerals, synthetic fibrous minerals or a mixture thereof.
• Suitable organic fillers may include carbon black, fullerene and/or carbon nanotubes, melamine colophony, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and/aliphatic dicarboxylic acid esters, carbon fibers or a mixture thereof.
• the inorganic and organic fillers may be used individually or as a mixture thereof.
• the total amount of the filler may be from about 0.5 to about 50 percent by weight of the layer.
• the outermost layer of a golf ball also may include at least one white pigment to aid in better visibility.
• the white pigment may be selected from the group consisting of titanium dioxide, zinc oxide, and mixtures thereof.
• the modifier may affect the hardness.
• highly neutralized polymers have high hardness values.
• the hardness of a highly neutralized polymer used in this disclosure may be at least about 40 Shore D, at least about 50 Shore D, or at least about 60 Shore D. As discussed above, this high hardness value may prevent the golf ball from having a soft feel when hit by a golf club, and may also cause the golf ball to have a less than desirable sound when struck.
• the highly neutralized polymer used in the polymer mixture may have a first hardness value.
• the presence of the modifier may then change a hardness value of the polymer mixture from the first value to a second hardness value, where the second hardness value is different from the first hardness value.
• the presence of the modifier reduces a hardness value of the polymer mixture from a first value (that is the same as the hardness of the highly neutralized polymer) to a second value that is less than the hardness of the highly neutralized polymer.
• the difference between the first value and the second value may generally be any measurable difference in hardness.
• the second value may be at least about 2 Shore D less than the first value, or at least about 3 Shore D, or at least about 5 Shore D, or at least about 8 Shore D, or at least about 10 Shore, or at least about 12 Shore D, or at least about 15 Shore D, or at least about 20 Shore D.
• the polymer mixture may have hardness of about 48 Shore D, or about 47 Shore D, or about 45 Shore D, or about 42 Shore D, or about 40 Shore D, or about 38 Shore D, or about 35 Shore D, or about 30 Shore D as a result of the modifier.
• This change in hardness may also be expressed as a proportion.
• the proportion by which the hardness changes as a result of the presence of the modifier may be at least about 1 %, at least about 2%, at least about 3%, at least about 5%, at least about 8%, at least about 10%, at least about 15%, or at least about 20%.
• a golf ball that includes the polymer mixture may both include highly neutralized polymer and achieve lower hardness value. This may be especially conducive to a soft feel and preferable sound in embodiments where the core (or inner core) is comprised of the polymer mixture.
• the inclusion of the modifier may also affect physical properties of the polymer mixture other than the hardness.
• the modifier may affect the resilience of the material, as measured by a COR of the golf ball or golf ball component made from the polymer mixture.
• the modifier may reduce the COR.
• a higher COR is generally preferable, in order to achieve better energy transfer between a golf club head face and the golf club during a drive.
• a golf ball with a highly neutralized polymer core (or inner core) may have a rather high COR, equal to about 0.84 or more. Therefore, even if the modifier reduces this COR value, the COR may still be within an acceptable range. This golf ball including the modifier may accordingly achieve a soft feel while maintaining a high COR.
• a core or inner core comprised of a highly
• the neutralized polymer by itself may have a COR value of from about 0.79 to about 0.89, or from about 0.8 to about 0.89.
• the inclusion of the modifier may reduce the COR by at least any measurable amount.
• the COR of a core or inner core comprised of the polymer mixture may have a value that is at most about 0.01 less than a value of the core or inner core comprised of the highly neutralized polymer by itself.
• a core or inner core comprised of the highly neutralized polymer by itself without the modifier may have a first COR value
• a substantially identical core or inner core comprised of the polymer mixture may have a second COR value, where the second COR value is less than the first COR value.
• the second COR value may be at most about 0.05 less than the first COR value, or at most about 0.10, or at most about 0.15, or at most about 0.20, or at most about 0.25.
• This change in COR may also be expressed as a proportion.
• the difference between the first COR value and the second COR value may be less than about 1 %, or less than about 2%, or less than about 3%, or less than about 5%, or less than about 7%, or less than about 10%, or less than about 12%, or less than about 15%, or less than about 20%.
• the change in hardness may be desirable while the change in COR may be undesirable. Therefore, the proportion by which the hardness changes may have a relation to the proportion by which the COR changes.
• the proportion by which the hardness is reduced may be greater than the proportion by which the COR is reduced.
• the proportion by which the hardness is reduced may be referred to as the first proportion, while the proportion by which the COR is reduced may be referred to as the second proportion.
• the relationship between the first proportion and the second proportion may be expressed as a ratio.
• the ratio of the first proportion to the second proportion may be greater than about 2:1 , or greater than about 3:1 , or greater than about 4:1 , or greater than about 5:1 .
• any of the above discussed values of the first proportion and the second proportion may be exhibited in combination, depending on the amount of modifier in the polymer mixture. For example, in one
• the first proportion may be at least about 10%, and the second proportion may at most about 5%. In another embodiment, the first proportion may be more than 5% while the second proportion is less than 5%.
• This disclosure also provides a method of manufacturing a golf ball.
• the method uses the addition of the modifier to the highly neutralized polymer to control the hardness of the resulting polymer mixture. This method therefore produces a golf ball having a desirable hardness value, with only minimal undesirable changes in other physical properties such as resilience.
• composition of various components, modifiers, additives, etc. and the amounts and effects thereof are equally applicable to the method disclosed herein.
• the method includes a step of receiving a highly neutralized polymer.
• This step encompasses receiving a highly neutralized polymer precursor, such as an unreacted batch of monomers (and/or oligomers) and neutralization ion source, that can be reacted to form a highly neutralized polymer.
• the method next includes a step of changing the hardness of the highly neutralized polymer by mixing a modifier therewith to form a polymer mixture.
• This mixing may occur through mixing/kneading on a sheeting mill, or through mixing in an extruder.
• the materials may be mixed (melt blended) in any suitable fashion, such as a twin screw extruder, a Banbury type mixer or a two roll mill.
• the highly neutralized polymer may be pre-heated prior to mixing.
• the highly neutralized polymer may be polymerized from a precursor and mixed with the modifier substantially simultaneously.
• the modifier may be selected from the group consisting of process oils, plasticizers, and blends thereof. More specifically, the modifier may be selected from the group consisting of naphthenic process oils, paraffinic process oils, phthalate esters, trimellitates, adipates, sebacate-based plasticizer, maleate-based plasticizer, and blends thereof.
• the modifier may be present in the polymer mixture in an amount of from about 1 1 to about 25 parts by weight per 100 parts by weight of highly neutralized polymer, or other amounts as discussed above.
• the modifier may be present in the polymer mixture of the method in a sufficient amount such that the modifier reduces a hardness of the polymer mixture from a first value that is approximately the same as a hardness of the highly neutralized polymer to a second value that is less than the hardness of the highly neutralized polymer.
• the presence of the modifier may also reduce a hardness value of the polymer mixture by a first proportion, and may reduce the COR value of the core by a second proportion, where the first proportion may be greater than the second proportion.
• the method also includes a step of forming the polymer mixture into a core. This step may be done substantially simultaneously with the step of mixing, and/or with the step of forming the highly neutralized polymer from a precursor. Alternatively, the step of forming the core may be done sequentially after the above discussed steps.
• the core may be formed by any process known to be used in golf ball manufacturing, such as compression molding or injection molding.
• the method also includes a step of forming a cover layer around the core, such that the cover layer substantially surrounds the core.
• the cover layer may be formed in accordance with various golf ball manufacturing
• the method may also include other conventional golf ball manufacturing steps, such as finishing and clear coating steps, as may be desired.
• HNP or a blend of HNPs
• a process oil or a blend of process oils, or a plasticizer, in the ratios set forth in the Tables.
• the resultant products have properties and characteristics consistent with the disclosure herein. Table 1

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