US20070219019A1

US20070219019A1 - Odorant Golf Balls

Info

Publication number: US20070219019A1
Application number: US11/426,005
Authority: US
Inventors: Kyle Benjamin Matthews
Original assignee: SOUTH PORTE ENTERPRISES LLC
Current assignee: SOUTH PORTE ENTERPRISES LLC
Priority date: 2006-03-16
Filing date: 2006-06-22
Publication date: 2007-09-20

Abstract

A golf ball comprising a polymer and an effective amount of odorant associated with the polymer wherein the odorant distinguishes the golf ball from an otherwise identical second golf ball substantially free of said odorant.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of, and priority to, U.S. Provisional Application No. 60/783,117 filed Mar. 16, 2006. This prior application is hereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

1. Field Of The Invention
This invention relates to odorant-containing golf balls that are useful as a means to identify and distinguish a golf ball. In one embodiment, the odorant golf balls are comprised of a polymer having an odorant encapsulated within the polymer and wherein the odorant is present at a detection threshold.
2. Background
The rules of golf are internationally standardized and are jointly governed by the Royal and Ancient Golf Club of St Andrews (R&A), and the United States Golf Association (USGA). By agreement with the R&A, USGA jurisdiction on the enforcement and interpretation of the rules is limited to the United States and Mexico.
Both the R&A and the USGA have similar rules regarding when a player uses a wrong ball during the course of play. The USGA defines a wrong ball as any ball other than the player's: ball in play; provisional ball, or second ball played under Rule 3-3 or Rule 20-7c in stroke play; and includes another player's ball; an abandoned ball; and the player's original ball when it is no longer in play. A ball in play includes a ball substituted for the ball in play whether or not the substitution is permitted. In the United States Rule 15-3 of the USGA's The Rules of Golf, incorporated herein by reference, states that:
15-3. Wrong Ball

- a. Match Play
- If a player makes a stroke at a wrong ball that is not in a hazard, he loses the hole.
- There is no penalty if a player makes a stroke at a wrong ball in a hazard. Any strokes made at a wrong ball in a hazard do not count in the player's score.
- If the wrong ball belongs to another player, its owner must place a ball on the spot from which the wrong ball was first played.
- If the player and opponent exchange balls during the play of a hole, the first to make a stroke at a wrong ball that is not in a hazard, loses the hole; when this cannot be determined, the hole must be played out with the balls exchanged.
- b. Stroke Play
- If a competitor makes a stroke or strokes at a wrong ball that is not in a hazard, he incurs a penalty of two strokes.
- There is no penalty if a competitor makes a stroke at a wrong ball in a hazard. Any strokes made at a wrong ball in a hazard do not count in the competitor's score.
- The competitor must correct his mistake by playing the correct ball or by proceeding under the Rules. If he fails to correct his mistake before making a stroke on the next teeing ground, or in the case of the last hole of the round, fails to declare his intention to correct his mistake before leaving the putting green, he is disqualified.
- Strokes made by a competitor with a wrong ball do not count in his score.
- If the wrong ball belongs to another competitor, its owner must place a ball on the spot from which the wrong ball was first played.

Therefore, in match play where two golfers face each other to determine who can win the most holes out of an 18 hole match, the golfer playing the wrong ball would lose a hole if he played a wrong ball outside of a hazard. Even more draconian, is the outright disqualification of a player in stroke play for playing a wrong ball.
It is likely that every avid amateur golfer has at one time or another played a wrong ball during the course of play. This is typically because the amateur golfer fails to place a personal marking or denote his ball before teeing off for a round of golf. Often the golfer will come to a ball in play and remember that he failed to mark his ball and not know for certain whether the ball he has found is his or not. This is despite the fact that the golf ball manufacturer places the tradename of the manufacturer and typically a number on the golf ball.
Professional golfers are typically more diligent about knowing the identity of their golf balls before teeing off for a tournament round of golf. Tournaments are often won or lost by a stroke or less and a great deal of money can be earned or loss based on a one or two stroke difference in a golfer's score. However, it takes very little research to learn that professional golfers are not immune to playing the wrong ball during the course of a round of golf.
In 1986 professional golfer, Wayne Grady, was disqualified twice in the same season for playing the wrong ball in both the 1986 Phoenix Open and the 1986 Los Angeles Open.
More recently, on Nov. 20, 2004, during the 2004 UBS Warburg cup, an international competition involving famous players from around the globe, in a match against Arnold Palmer and Jay Haas, professional golfer Mark McNulty mistakenly played his partner, Gary Player's, ball. McNulty explained that after scuffing his ball on the eighth hole his caddie gave him a Callaway No. 4 ball—the same brand and number as that of Player's—in replacement. McNulty had been using a Callaway No. 1, but ran out and his caddie did not inform anyone of the numerical switch.

- “When we got down to the balls (in the fairway), there was one six yards ahead of the other, and seeing that Gary had been slightly behind me most of the day, I presumed that the (forward) ball was mine,” McNulty said.
- “I looked at the back ball and it was a No. 4 and I just said, ‘he didn't out-drive it,’ and that was that. He went ahead and hit a fantastic shot. And it was my call, and it was only when I got to the green that I realized that it was the wrong ball.”

In 1994, at the Las Vegas Invitational, all professional golfer Curt Byrum had to do was finish the tournament and he would have made enough money to retain his professional playing privileges for 1995. But, on the 16th hole of the final round, Byrum mistakenly played the wrong ball and teed off the next hole with it. When Byrum finished the round he discovered the mistake and paid the price by getting disqualified from the tournament.
Despite having every incentive not to play the wrong ball, golfers of all levels can and sometimes do play the wrong ball during the course of a round of golf. The present invention addresses this problem by associating an odorant with a golf ball so that the player or caddie upon receiving the ball will either: 1) remember to mark the ball; 2) remember to denote the tradename and number of the ball; or 3) remember the odorant smell so that the smell of the ball can be used to distinguish the ball from a second ball even if the second ball is of the same make and number as in the Player/McNulty confusion described above.

SUMMARY OF THE INVENTION

The present invention is directed to golf balls with an improved recognition feature. One aspect of the present invention features a golf ball comprising a polymer; and an odorant associated with the polymer wherein the odorant distinguishes the golf ball from a second golf ball substantially free of the odorant means.
In another embodiment the present invention is directed to a golf ball comprising a polymer; and an odorant present at a detection threshold and associated with the polymer.
Other embodiments of the invention include those golf balls wherein the odorant is present at a super detection threshold.
Other embodiments of the invention include those golf balls wherein the odorant is present at a recognition threshold.
Other embodiments of the invention include those golf balls wherein the polymer is selected from the group consisting of transpolybutadiene, transpolyisoprene, polyurethane, polyurea, polyurethane/polyurea, ionomeric resin such as ionic copolymers of ethylene and an unsaturated monocarboxylic acid, which are available under the trademark SURLYN® of E. I. DuPont de Nemours & Co., of Wilmington, Del., castable thermoplastic polyurethanes, thermoset polyurethanes, cationic urethane ionomers, anionic urethane ionomers, urethane epoxies, polyurethane/polyurea ionomers, epoxy resins, polyethylenes, polyamides, polyesters, polycarbonates, polyacrylin, and mixtures thereof.
Other embodiments of the invention include those golf balls wherein the polymer and associated odorant are painted, coated, or surface treated on to the golf ball.
Other embodiments of the invention include those golf balls wherein said odorant is encapsulated within said polymer.
In another embodiment, the present invention is directed to a golf ball comprising a polymer and an odorant wherein the odorant is associated with the polymer and wherein the odorant is present at a detection threshold and the golf ball is therefore distinguishable from an otherwise identical second golf ball substantially free of the odorant.
Other embodiments of the invention include those golf balls wherein the odorant is present at a super detection threshold.
Other embodiments of the invention include those golf balls wherein the odorant is present at a recognition threshold.
Other embodiments of the invention include those golf balls wherein the polymer is selected from the group consisting of transpolybutadiene, transpolyisoprene, polyurethane, polyurea, polyurethane/polyurea, ionomeric resin such as ionic copolymers of ethylene and an unsaturated monocarboxylic acid, which are available under the trademark SURLYN® of E. I. DuPont de Nemours & Co., of Wilmington, Del., castable thermoplastic polyurethanes, thermoset polyurethanes, cationic urethane ionomers, anionic urethane ionomers, urethane epoxies, polyurethane/polyurea ionomers, epoxy resins, polyethylenes, polyamides, polyesters, polycarbonates, polyacrylin, and mixtures thereof.
Other embodiments of the invention include those golf balls wherein said polymer and associated odorant are painted, coated, or surface treated on to said golf ball.
Other embodiments of the invention include those golf balls wherein said odorant is encapsulated within said polymer.
The present invention also relates to a method for manufacturing a golf ball having an odorant associated with a polymer comprising: (a) homogenizing the polymer or pre-polymer components of said polymer with the odorant to form the odorant encapsulating polymer; and (b) molding the odorant encapsulating polymer into a golf ball or golf ball layer wherein the golf ball or golf ball layer is distinguishable from an otherwise identical second golf ball or second golf ball layer substantially free of said odorant.
Other embodiments of the invention include those methods wherein the odorant is present at a detection threshold.
Other embodiments of the invention include those methods wherein the odorant is present at a recognition threshold.
Other embodiments of the invention include those methods wherein the polymer of the odorant encapsulating polymer is selected from the group consisting of transpolybutadiene, transpolyisoprene, polyurethane, polyurea, polyurethane/polyurea, ionomeric resin such as ionic copolymers of ethylene and an unsaturated monocarboxylic acid, which are available under the trademark SURLYN® of E. I. DuPont de Nemours & Co., of Wilmington, Del., castable thermoplastic polyurethanes, thermoset polyurethanes, cationic urethane ionomers, anionic urethane ionomers, urethane epoxies, polyurethane/polyurea ionomers, epoxy resins, polyethylenes, polyamides, polyesters, polycarbonates, polyacrylin, and mixtures thereof.
Other embodiments of the invention include those methods wherein the molding step, c), comprises painting, coating, or surface treating the odorant encapsulating polymer on to said golf ball.
The present invention also relates to an improved golf ball comprising at least one polymer and at least one odorant wherein the improvement comprises incorporating the at least one odorant into the golf ball in an amount at or above the detection threshold of the at least one odorant.
Other embodiments of the invention include those improved golf balls wherein the at least one odorant is present at a super detection threshold.
Other embodiments of the invention include those improved golf balls wherein the at least one odorant is present at a recognition threshold.
Other embodiments of the invention include those improved golf balls wherein the at least one odorant is incorporated into the golf ball by painting, coating or surface treating.
Other embodiments of the invention include those improved golf balls wherein the odorant is encapsulated within the polymer.
The term “odorant”, as used herein, unless otherwise indicated, is a substance or combination of substances capable of eliciting an olfactory response whereas odor is the sensation resulting from stimulation of the olfactory organs.
The term “polymer”, as used herein, unless otherwise indicated, refers to polymers generally, but preferred polymers are those currently favored in the golf ball manufacturing arts including, but not limited to, transpolybutadiene, transpolyisoprene, polyurethane, polyurea, polyurethane/polyurea, and ionomeric resins, such as e.g., poly(ethylene-co-methacrylic acid) (EMAA) which are available under the trademark SURLYN® of E. I. DuPont de Nemours & Co., of Wilmington, Del., or combinations thereof.
The term “substantially free”, as used herein, unless otherwise indicated, means that the odorant is at least not present at a detection threshold. Because different odorants require different concentrations to meet the detection threshold, the term “substantially free” is relative to each individual odorant.
The term “an effective amount”, as used herein, unless otherwise indicated, represents a concentration of odorant associated with an object where a person with an average sense of smell can detect the odorant and distinguish the object from a second object substantially free of the odorant or containing a second, different odorant.
The term “detection threshold”, as used herein, unless otherwise indicated, identifies the concentration at which forty percent (40%) of a human panel can identify the presence of odorant without characterizing the stimulus. For example, four people out of ten all having a normosia (normal or average) sense of smell are capable of identifying the presence of odorant without characterizing the stimulus. Persons suffering from dysomia (distorted sense of smell), anosmia (no sense of smell), hyperosmia (enhanced sense of smell), or phantosomia/parosmia (smelling without an external stimulus) would be excluded from the panel.
The term “super detection threshold”, as used herein, unless otherwise indicated, identifies the concentration at which fifty percent (50%) of a human panel can identify the presence of odorant without characterizing the stimulus. For example, five people out of ten all having a normosia (normal or average) sense of smell are capable of identifying the presence of odorant without characterizing the stimulus. Persons suffering from dysomia (distorted sense of smell), anosmia (no sense of smell), hyperosmia (enhanced sense of smell), or phantosomia/parosmia (smelling without an external stimulus) would be excluded from the panel.
The term “recognition threshold”, as used herein, unless otherwise indicated, is the concentration at which fifty percent (50%) of a human panel can identify an odor or odorant. For example, five people out of ten all having a normosia (normal or average) sense of smell are capable of identifying an odor or odorant. Persons suffering from dysomia (distorted sense of smell), anosmia (no sense of smell), hyperosmia (enhanced sense of smell), or phantosomia/parosmia (smelling without an external stimulus) would be excluded from the panel.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features and advantages of the invention can be ascertained from the following detailed description that is provided in connection with the drawing(s) described below:

FIG. 1 is a cross-sectional view of a two-piece golf ball, wherein the cover is formed from the odorant polymer compositions of the invention;

FIG. 2 is a cross-sectional view of a multi-component golf ball, wherein at least the cover is formed from odorant Surlyn® compositions of the invention;

FIG. 3 is a cross-sectional view of a multi-component golf ball, wherein the cover is formed from the odorant polyurethane or polyurea compositions of the invention and the intermediate layer is formed from a composition including at least one ionomer resin;

FIG. 4 is a cross-sectional view of a multi-component golf ball including a core and a cover, wherein the core is surrounded by a tensioned elastomeric material and the cover is formed from odorant Surlyn® compositions of the invention;

FIG. 5 is a cross-sectional view of a liquid center golf ball wherein the liquid core is surrounded by a tensioned elastomeric material and the cover is formed from the odorant polyurethane or polyurea compositions of the invention;

FIG. 6 is a cross-sectional view of a multi-component golf ball including a core, a thin inner cover layer, and a thin outer cover layer disposed thereon, wherein the thin outer cover layer is formed from the odorant polyurethane or polyurea compositions of the invention;

FIG. 7 is a cross-sectional view of a multi-component golf ball including a core, an outer core layer, a thin inner cover layer, and a thin outer cover layer disposed thereon, wherein the thin outer cover layer cover is formed from odorant Surlyn compositions of the invention; and

FIG. 8 is a cross-sectional view of a multi-component golf ball including a large core and a thin outer cover layer disposed thereon, wherein the thin outer cover layer is formed from the odorant polyurethane or polyurea compositions of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention contemplates an improved golf ball comprising a polymer and an odorant associated with the polymer. Typically, the odorant is encapsulated in the polymer. The polymer component is preferably an ionomeric resin, such as e.g., poly(ethylene-co-methacrylic acid) (EMAA) which are available under the trademark SURLYN® of E. I. DuPont de Nemours & Co., of Wilmington, Del., but may be any number of common polymers used in golf ball components such as, for example, transpolybutadiene, transpolyisoprene, polyurethane, polyurea and polyurethane/polyurea resins. The compositions of the invention may be included in a variety of golf ball constructions, i.e., one-piece, two-piece, or multilayer balls.
The inclusion of odorants in polymer compositions, which are incorporated, at or above the detection threshold, into various golf components, e.g., covers, results in golf balls that can be distinguished from a second golf ball substantially free of odorants.
Odorant Components
Some materials used in polyurethane or polyurea compositions, typically used to manufacture golf balls, are odorous in nature or may produce odors during reaction with other materials or with oxygen. For example, the odor of curative Ethacure 300 is attributed to dimethyl disulfide (DMDS) once the product reacts with oxygen. In order to combat this problem a golf ball manufacturer may add a masking component to eliminate such odors.
In the present invention odors are not masked but made detectable to the extent that a golfer or his caddie can identify the golf ball by the odor of the golf ball alone. Manufacturers of odorant containing polymers normally suggest that if an odorant is to be perceivable in a product, odorant concentrates should be added at rates of about 0.5% to about 5% by weight. For example, the AromaPoly Fragrance Encapsulated Polymer Concentrates manufactured by Aroma Tech, Somerville, N.J., are customized odorants dispersed in a multi-component polymer. The concentrate can be incorporated into golf ball resins to manufacture golf balls with a fragrance as a unique product feature. The AromaPoly concentrates are suitable for many golf ball manufacturing applications including but not limited to injection molding, extrusion or blow molding. The polymer fragrance concentrates can be made in any number of odorant types and can be customized for specific applications. The polymer fragrance concentrates can be formulated to maintain an odor in the polymer product a few days or up to several months.
Suitable odorant components include, but are not limited to, for example the catalog of fragrances available through Royal Aromatics, Inc., Neptune, N.J.
A nonlimiting list of odorants includes Almond Oil, Aloe Oil, Aloe Vera All Natural 100% EO Blend, Aromatherapy Citrus Blend, Aromatherapy Citrus Blend 100% Organic, Aromatherapy Minty, Aromatherapy Minty 100% Organic, Aromatherapy Wellness, Balance 100% Natural, Balance, Aromatherapy Blend, Balancing Blends, Basil Eucalyptus Rosemary, Calming Blends, Calming Oil, Cedarwood Oil , Chammomile & Clove 100% Natural, Chamomile & Basil EO, Chamomile Oil, Chamomile Tea, Citrus Blends, Communication Blends, Communition Blend, Cool Cucumber Type, Cool Fresh Scent, Cucumber & Lime, Cucumber & Mint, Day Spa, Dorigilan Tea, Energizing Blends, Energy, Eucalyptus & Spearmint (stress relief), BBW Type, Eucalyptus Oil , Fatigue Relief Blends, Fig, Finess Type, Fir Balsam Needle, Floral Blends,,Foot Bath Blends,Gardenia Musk, KITCHEN HERBS, LAVENDER & BASIL 100% EO., LAVENDER & BERGAMOT EO 100%, Lavender & Eucalyptus 100% EO Blend, LAVENDER & GINGER, LAVENDER & NEROLI EO. 100%, LAVENDER & PATCHOULI EO. 100%, LAVENDER & PEPPERMINT 100% EO., Lavender & Rosemary 100% Eo., Lavender & Tangerine 100% Eo., Lavender & Ylang Ylang 100% Eo., Lavender Blends, Lavender, Cinnamon & Rosemary 100% Eo.,Lavender Cinnamon & Rosemary 100% Eo., Lavender Sage & Rosemary, Lavender Ylang & Patchouli, Lemon & Cucumber, Lemon & Cucumber, Lemon & Lavender, Lemon & Lime , Lemon & Mandarin, Mint Blends, Oatmeal Milk And Honey, Ocean Fresh, Orange Citrus Blend, Orange Clove, Passion Fruit , Patchouli Oil , Peaceful Blends, Peaceful Home Blends, Peppermint Oil , Petigrain Oil , Pleasant, Memories, Point Pleasant, Refreshing Blends, Rejuvenating Blends, Relaxing Blends, Retention Blends, Romantic Blends, Sage Clary Oil, Sandalwood Oil , Sensual Blends, Sleep Peacefully Blends, Snoring Remedy Blends, Soothing Relaxing Type, Spa, Fragrance, Spearlyptus, Spearmint Oil , Stress Relief Blends, Study Blends, Summer Rain, Travel Blends, Wheat Germ & Honey, Wisteria, Bath & Body Works Type Black Raspberry Vanilla, Bbw Type, Blue Lavender Palma Rose, Bbw Type, Candy Corn, Bbw Type, Citrus Cream, Bbw Type, Coconut Lime Verbena, Bbw Type, Cool Citrus Basil, Bbw Type, Cotton Blossom Bbw Type, Country Apple Bbw Type, Creamy, Coconut, Bbw Type, Cucumber Melon Bbw Type, Eucalyptus & Spearmint (Stress Relief), Bbw Type , Freesia, Bbw Type , Frosted Snow Drops Bbw Type, Gardenia Lily, Bbw Type, Gingerbread Spice, Bbw Type, Green Clover And Aloe Bbw Type, Green Tea & Cucumber, Bbw Type, Jasmine Vanilla, Bbw Type , Juniper Breeze Bbw Type, Lavender Vanilla, Bbw Type, Lemon Grass & Sage, Bbw Type , Mandarin Peel Type, Bbw Type, Mango Mandarin Bbw Type, Moonlight Path Bbw Type, Night Blooming Jasmine Bbw Type, Orange Ginger ( Awake), Bbw Type , Pear Berries Bbw Type, Pear Sorbet Bbw Type, Pears & Apples, Bbw Type, Peony, Bbw Type, Plumeria, Bbw Type, Red Currant & Thyme, Bbw Type, Rice Flower & Shea Bbw Type, Serenity, Bbw Type , Sunrippen Raspberry Bbw Type, Sweet Cinnamon Pumpkin, Bbw Type, Sweet Pea Bbw Type, Warm Vanilla Sugar Bbw Type, Water Blossom Ivy Bbw Type,Waterfall Mist Bbw Type, White Ginger & Amber Bbw Type, White Tea And Ginger Bbw Type, Ylang Ylang Myrrh, Bbw Type , Christmas Almond & Oatmeal, Alpine Fresh, Alpine Powdery Fragrance, Amaretto, Amaretto Coffee, Apple Cider , Apple Cinnamon, Sweet, Apple Cobbler Delight, Apple Jack , Apple Jack And Peel Claire Burke Type, Apple Martini, Apple Strudel, Autumn Wreath By Yankee Type, Bailey's Irish Cream, Baked Apple Pie , Baked Bread, Balsam Eve, Banana Caramel, Banana Nut Bread Muffin, Banana Nut Cake, Banana Nut Honey, Banana Pudding, Bayberry , Blue Spruce Blueberry, Blueberry Cheesecake, Blueberry Cobbler, Blueberry Cream, Blueberry Muffin, Bramble Berry, Yankee Type, Butter Cookie, Butter Pecan, Butter Pecan Pie, Butter Rum, Butter Scotch Buttercream, Buttercream Vanilla, Buttery Gingerbread, Cabernet Wine, Campfire, Campfire & Marshmellow, Canadian Wilderness, Candied Cherry, Candy Cane , Cappuccino Coffee, Caramel, Carrot Cake, Chai Spice Black Tea, Cheesecake Plain, Cherries & Chestnuts, Cherries In The Snow, Chocolate Mint, Christmas Cheer, Christmas Day, Christmas Eve Pine, Christmas Greetings Christmas Holiday, Christmas Memories Type, Christmas Pine, Christmas Spice, Christmas Splendor, Christmas Tree, Cinnabon Cinnamon Rolls Type, Cinnamon, Cinnamon Apple, Cinnamon Apple Berry Yankee Type, Cinnamon Berry, Cinnamon Bun, Cinnamon Christmas, Cinnamon Sticks, Cinnamon Super Throw For Soy, Claire Burke Original Potpourri, Cocoa Cherry, Country Berry Hotcakes, Country Christmas, Country Kitchen, Country Spice, Country Spice, Cranapple, Cranberry Cranberry Apple, Cranberry Chutney Yankee Candle Type, Cranberry Spice, Creme Brule, Curry, Egg Nog, English Toffee, Evergreen, Fir Balsam Needle, French Vanilla, Frosted Snow Drops Bbw Type, Ginger Snap Cookies, Gingerbread, Gingerbread Spice, Bbw Type, Grandma's Kitchen Type, Green Apple, Green Apple Cinnamon, Holiday Blends, Holiday Pine, Hollyberry, Yankee Type, Home For The Holidays Yankee Candle Type, Home Sweet Home Yankee Type Honey Almond, Honey Apple, Honey Cinnamon, Honey Comb, Hot Buttered Rum, Yankee Type, Hot Cocoa, Mandarin Cranberry Yankee Type, Midori Sour, Mistletoe, Mulled Cider, Oatmeal Milk And Honey, Pine Balsam, Pine Fresh, Pine Mint, Pine Needle Canadian, Pine Oil, Pine Spice, Pineapple, Pinion Pine, Plum, Plum Spice, Pointsettia, Pumpkin Pie, Red Clover & Tea, Yankee Type, Sleigh Ride, Snickerdoodle, Sugar Cookie, Sugar Plum, Sweet Cinnamon Pumpkin, Bbw Type, Tiramisu, Truffle, Vanilla Caramel, Yankee Type, Vanilla Hazelnut, Victorian Christmas, Winter Wonderland, Winterberry, Winterberry, Ye Olde Country Store, Citrus & Fresh Amber White, Aromatherapy Citrus Blend, Aromatherapy Citrus Blend 100% Organic, Baby Magic, Baby Powder, Baby Soft, Bergamot Italy & Mandarin Brazil, Bergamot Oil, Black Current With Green Tea & Citrus, Camay Soap Type, Citrus Blends, Citrus Cream, Bbw Type, Citrus Grove, Citrus Oil Dist., Citrus Spice, Clean & Fresh, Clean Clothes, Clear Musk, Clothesline Fresh, Coast Soap Type, Coconut Lime Verbena, Bbw Type, Cool Citrus Basil, Bbw Type, Cool Cucumber Type, Cool Fresh Scent, Country Clothesline, Cucumber, Cucumber & Lime, Cucumber Melon, Cucumber Melon Bbw Type, Cucumber Salad, Day Spa, Dial Soap Type, Dove Soap Type, Energizing Blends, Florida Water, Fruit Of Life, Fruity Coco Mango, Ginger & Lime, Yankee Type, Hawaiian Tropics Glade Type, Honeysuckle Grapefruit, Island Essence, Island Mango Yankee Type, Laundry Fresh, Lavender & Tangerine 100% Eo., Lemon & Lavender, Lemon & Lime, Lemon & Lime Oil Blended Nat., Lemon & Mandarin, Lemon & Tea, Lemon Bouquet, Lemon Chiffon, Lemon Clean, Lemon Drops, Lemon Fresh, Lemon Graham Cracker, Lemon Grass & Sage, Bbw Type, Lemon Oil, Lemon Peel, Lemon Pound Cake, Lemon Verbena, Lemon Zest, Yankee Type, Lemongrass Oil, Lime Cilantro, Lime Oil, Mandarin Cranberry Yankee Type, Mandarin Peel Type, Bbw Type, Mimosa, Mint Blends, Orange Blossom, Orange Citrus Blend, Orange Clove, Orange Cream Sickle, Orange Flower, Orange Ginger ( Awake), Bbw Type, Orange Oil, Orange Peel, Orange Pekoe Tea, Orange Spice, Orange Vanilla, Orangenia, Papaya, Patchouli & Orange, Pineapple Citrus By Yankee Type, Pineapple Paradise Yankee Type, Pink Grapefruit, Refreshing Blends, Rejuvenating Blends, Snuggles Type, Summer Rain, Sun Washed Linen, Yankee Type, Tangerine Oil, Verbena Oil.
Additional odorants may include musks such as, for example, African Musk, African Musk (Green), Amber, Amber & Oakmoss, Amber African Green, Amber Green, Amber Musk, Amber Nuban, Amber Oakmoss Pine & Lavender, Amber Rose, Amber White, Ambergris, Apple Musk, Believe 100% Natural, Bergamot & Mandarin, Bergamot & Mandarin Yankee Type, Bergamot Blossom, Bergamot Italy & Mandarin Brazil, Best Friends, Blackberry Musk, Ceirra Musk, Cherry Musk, China Musk, China Rain, Citrus Musks, Clean Fresh Musks, Clear Musk, Egyptian Musk, Floral Musks, Freesia & Musk, Yankee Type Fruity Musks, Green Egyptian Musk, Herbal Musks, Honey Rain, Jasmin Musk, Jovan Musk For Women Type, Jungle Kenzo Women Type, Jungle Men Kenzo Type, Kannon For Men Type, Lavender Orage & Mint, Lever 2000 Soap Type, Mens Musks, Midsummer Night, Yankee Type Revised, Pine Musks, Red Egyptian Musk, Strawberry & Musk, Sweet Musks, Vanilla Musk S, White Musk,White Musk Type By The Body Shop, Womens Musks, Woody Musks.
Additional odorants may include fruity odorants such as, for example, Apple, Apple & Honey, Apple Berry, Apple Blossom, Apple Cider, Apple Cinnamon, Sweet, Apple Jack, Apple Macintosh, Apple Mango, Apple Melon, Apple Musk, Apple Orchard, Apple Red Orchad, Apple Red Orchard Yankee Type, Apple Spice, Apricot, Apricot & Honey, Yankee Type, Apricot & Vanilla, Apricot Freesia, Apricot Peach & Pear, Avocado, Awapuhi Sea Berry, Baked Pear, Banana, Banana Berry, Banana Raspberry, Bay Rum, Bayberry, Bergamont & Mandarin, Yankee Type, Bergamot Oil, Berry Blast, Berry Good, Best Friends, Black Berry, Black Cherry, Black Coconut, Black Current, Black Current With Green Tea & Citrus, Black Forest, Black Raspberry Vanilla, Bbw Type, Blackberry & Raspberry, Blackberry Musk, Blackberry Sage, Blissful Blackberry, Bbw Type, Blueberry, Blueberry Cobbler, Blueberry Melon, Blueberry Muffin Yankee Candle Type, Blueberry Pie, Boisenberry, Boysenberry, Bramble Berry, Yankee Type, Bubble Gum, Bump & Grind, Butt Naked, Candied Cherry, Cantaloupe, Cantaloupe Melon, Champagne & Strawberries, Cherries & Chestnuts, Cherries In The Snow, Cherry, Cherry Apple, Cherry Berry, Cherry Blossom, Yankee Type, Cherry Cobbler, Cherry Cola, Cherry Kiss, Cherry Mist, Cherry Musk, Cherry Pineapple, Cherry Vanilla, Chocolate Covered Cherries, Chocolate Covered Raspberry, Chocolatey Orange, Cinnamon Apple Berry Yankee Type, Cinnamon Berry, Cinnamon Clove Apple, Citrus Pine, Coco Mango, Coco Mango For Soy, Cocoa Cherry, Coconut, Coconut & Gardenia, Coconut & Rose, Coconut Bay Yankee Candle Type, Coconut Berries, Coconut Fruity Blend, Coconut Lime Verbena, Bbw Type, Coconut Milk, Coconut Vanilla, Coconut, Mango & Vanilla, Concord Grape, Cool Citrus Basil, Bbw Type, Cool Cucumber Type, Country Berry, Country Berry Hotcakes, Country Cider, Cranapple, Cranberry, Cranberry Apple, Cranberry Chutney Yankee Candle Type, Cranberry Grape, Cranberry Orange, Cranberry Plum, Cranberry Sauce, Cranberry Spice, Cranberry Tart, Creamsicle, Creamy Coconut, Bbw Type, Cucumber & Cantalope, Yankee Type, Cucumber & Lime, Cucumber & Mint, Cucumber & Vanilla, Cucumber Melon, Cucumber Melon Bbw Type, Dark Chocolate & Orange, Dewberry, Dreamsicle, Eat It Raw, Enchanted Apple Type, French Apricot, Fresh Peach, Yankee Type Fresh Pear, Fruit Blend, Fruit Of Life, Fruit Punch For Soy, Fruit Slices, Fruity Coco Mango, Ginger & Lime, Yankee Type, Grand Marnier, Grape, Grape (Mucadine), Grape Fruit Cocktail, Grapefruit Honeysuckle Type, Grapefruit Oil, Grapefruit Passion, Green Apple Cinnamon, Guava, Hawaiian Calalily, Hawaiian Tropics Glade Type, Hollyberry, Yankee Type, Honey Apple, Honey Dew Melon, Honeysuckle Grapefruit, Indonesian Coffee, Island Essence, Island Mango Yankee Type, Island Mango, Yankee Type Revised, Jamaican Fruit, John The Conquerer, Jolly Rancher, Jolly Rancher For Soy, Key Lime, Key Lime Pie, Kiwi, Kiwi Mango, Kiwi Strawberry, Lauren Type, Lemon, Lemon & Cucumber, Lemon & Cucumber, Lemon & Lime, Lemon & Mandarin, Lemon & Tea, Lemon Chiffon, Lemon Clean, Lemon Drops, Lemon Fresh, Lemon Graham Cracker, Lemon Meringue, Lemon Peel, Lemon Pound Cake, Lemon Tea, Lemon Verbena, Lemon Zest, Yankee Type, Lemongrass Oil, Lick Me All Over, Lime Cilantro, Lime Oil, Loganberry, Macintosh & Peach Yankee Type, Macintosh Apple, Mandarin Cranberry Yankee Type, Mandarin Oil, Mandarin Peel Type, Bbw Type, Mango, Mango Macadamia Nut, Mango Papaya For Soy, Melon, Melon & Peaches Berries, Mimosa, Mucadine Grape, Mulberry, Mulled Cider, Orange Blossom, Orange Blossom For Soy, Orange Citrus Blend, Orange Clove, Orange Cream Sickle, Orange Oil, Orange Peel, Orange Pekoe Tea, Orange Spice, Orange Vanilla, Orangenia, Papaya, Patchouli & Orange, Peach, Peaches & Berries, Peaches & Cream, Peaches & Melons, Pear, Pear Berries, Pears & Apples, Pears & Apples, Bbw Type, Pina Colada, Pineapple, Pineapple Berries, Pineapple Citrus By Yankee Type, Pink Grapefruit, Pleasant Memories, Plum, Plum Spice, Pomegranate, Raspberry, Raspberry Vanilla Swirl, Red Apple, Spiced Pear, Yankee Type, Strawberries & Champagne, Vs Type Strawberry, Strawberry & Melons, Strawberry & Peaches, Strawberry Apple, Strawberry Banana Daiquiri, Strawberry Chiffon, Strawberry Melon, Strawberry Peaches, Sugar Plum, Summer Fruit & Jasmine Bbw Type, Sun Ripened Raspberry, Sweet Strawberry, Yankee Type Tangerine Oil, Tropical Fruit, Vanilla, Coconut And Ginger Yankee Type, Watermelon, Watermelon & Berries, Watermelon & Peaches,Wild Cherry, Wild Cherry Bark, Yucca
Additional odorants may include designer fragrances such as, for example, “Pi” For Men Type “Ralph” Ralph Lauren Type, “She” Type Emporio Armani, “Sugar” For Soy By Fresh Type, 24 Faubourg By Hermes For Women Type, Acqua Di Gio For Men Type, Acqua Di Gio For Women Type, Addict Women Dior Type, Adrienne Vitadini, Av Type, Agree Soap Type, Alfred Sung Type, All About Eve Joop Type, Allure For Men Type, Allure For Women Type, Alyssa Ashley Musk For Women Type, Amarige By Givency For Women Type, Amber Romance For Women By Vs Type, Anais Anais Type, Angel For Men Type, Angel For Women Type, Angel Wings Type, Anite Goutal Type, Anna Sui, Sui Dreams, Annuci Femme Type, Antonia's Flowers Type, Anucci For Men Type, Aquolina Pink Sugar For Women Type, Aramis Type, Armani (Unisex), Type, Armani For Men Type, Armani For Women Type, Armani, Armanimania (Unisex), Type, Aromatics Elixir Type, Aromatonic For Women Type, Attraction Lancome Type, Azzaro For Men Type, Bal A Versailles For Women Type, Banana Republic For Men, Banana Republic For Women, Banana Republic Unisex, Bazar For Women By Christian Lacroix Type, Bcbg Girls Nature Type, Bcbg Girls Star Type, Be Delicious For Men Type, Be Delicious For Women By Dkny Type, Beautiful Type, Beverly Hills 273 Type, Beyond Paradise For Men Type, Beyond Paradise For Women Type, Bijan For Men Type, Bijan For Women Type, Bill Blass For Women Type, Black By Kenneth Cole Type For Men, Black By Kenneth Cole Type For Women, Black Cashmere D. K. Type, Black Code By Armani, Men Type, Black Jeans Versace Type, Blonde For Women By Versace Type, Blue By Ralph Lauren Women Type, Blue Sonata Type, Blue Spruce, Bob Macki Type, Bobbi Brown Beach Type, Body By Victoria Secret Type, Bora Bora For Men, Bora Bora For Women Type, Boss Elements For Men Type, Boss Hugo Type, Boucheron Men Type, Boucheron Women Type, Breathless Victoria Secret Type, Bulgari Black Unisex Type, Bulgari Blv Pour Homme Type, Bulgari Eau Parfum Unisex Type, Bulgari For Men Type, Bulgari For Women Type,Bulgari Pour Homme Type, Bulgari Unisex Type, Burberry Brit For Men Type, Burberry Brit For Women Type, Burberry Touch For Men Type, Burberry Touch For Women Type, By For Men By Dolce & Gabana Type, By For Women By Dolce & Gabana Type, Cabotine For Women Type, Calandre Type, Calvin Klein Eternity Moment Type For Women, Calyx For Women Type, Canoe Type, Carolina Herrera 212 For Men Type, Carolina Herrera 212 For Women Type, Carolina Herrera For Men Type, Carolina Rain For Men Type, Cashmere Mist Type, Casmir Type, Casual Women Type, Ceirra For Wome Type, Celine Dion Type, Champagne Type, Champs Elysees Type, Chance Chanel Type, Chanel #19 Type, Chanel #5 Type, Chanel For Men Type, Chaos By Donna Karen Type, Chaps For Men Type, Charlie Type, Cheap & Chic By Moschino Type, Chic Carolina Herrera Type, Chloe For Women Type, Chloe Narcissus For Women Type, Chrome Type, Ciara Type, Cinema, Ysl Type, Cinnabar Type, Ck1 Summer Type—Unisex, Ck-1 Type, Ck-Be Type, Clinique Simply Type, Coco Chanel Type, Coco Mademoiselle Type, Contradiction For Men Type, Contradiction For Women Type, Cool Water For Men Type, Cool Water For Women Type, Coolwater For Men Type—Limited Edition, Coolwater For Women Type—Limited Edition, Crave Calvin Klein Type, Creed For Women Type, Creed Royal Water Type Men, Creed Silver Mountain Water Type Men, Creed Spring Flowers Type Women, Cristalle For Women Type, Curious, Brittany Spears Type, Curve Crush By Liz Claiborne Type, Curves For Men Type, Curves For Women Type, Czar For Men Type, Dazzling Gold Type, Dazzling Silver Type, Declaration For Men Type, Deep Red Hugo Boss Type For Women, Design Type, Desire Women Type, Diesel For Men Type, Diesel For Women Type, Diesel Plus For Women Type, Diorissimo Type, Diva Type, Dkny Men 2000 Type, Dkny Men Type, Dkny Women Type, Dolce & Gabana Feminine, For Women Type, Dolce & Gabana For Woman Type, Dolce & Gabbana Light Blue Type, Dolce & Gabbana Men Type, Dolce Vita, Donald Trump For Men Type, Drakkar Type, Dream Angels Divine Type, Dream Angels Halo Type Vs., Dream Angels Heavenly Type, Dreamer Men Versace Type, Dune Men Type, Dune Women Type, Dunhill Men Type, Eau De Calone “4711” Type, Eau De Kenzo Type, Eau Sauvage Type, Echo For Men By Davidoff Type, Echo For Women Type, Eddie Bauer Type, Eden Type, Egoiste Platinum For Men Type, Egoiste Type, Egyptian Musk, Ellen Tracy Type, Emerald Jewels For Women, Emeralds And Diamonds For Women type, Emporio Armani “He” Type, English Leather Type, Envy For Women Type, Envy Me By Gucci Women Tpe, Escada Sport Women Type, Escape For Men Type, Escape For Women Type, Estee Type, Eternity Blush Type, Eternity For Men Type, Eternity For Women Type, Euphoria For Women By Calvin Klein Type, Exclamation Type, Fahrenheit Type, Fantasy By Britney Spears Type, Fendi For Men Type, Fendi For Women Type, Fidji Type, Fifth Avenue Type, First Type, Florida Water Type,Flower By Kenzo Type, Freedom For Women Type, Gap Day Type, Gap Dream Type, Gap Earth Type, Gap Heaven Type, Gap So Pink Type, Gendarme Type, Giorgio Aire Type, Giorgio For Men Type, Giorgio For Women Type, Giorgio Ocean Dreams Type, Givenchy Men Type, Givenchy Pi For Men Type, Givenchy Pour Homme Type, Glamorous Type, Gloria Vanderbilt Type Glow Jlo Type, Good Life Men Type, Good Life Women Type, Gravity For Men Type, Green Tea Type Elizabeth Arden, Gucci For Men Type, Gucci For Women Type, Gucci Rush “2”Women Type, Gucci Rush For Women Type, Guess For Men Type, Guess For Women Type, Halo Type Victoria Secret, Halston Women Type, Halston Z-14 Type, Happy For Men Type, Happy For Women Type, Happy Heart Type, Higher By Christian Dior Type, Hot Couture For Women Type, Hugo For Men Type, Hugo For Women Type, Hummer For Men Type, Hypnotic Poison Type, I Love Love Women Type, Ibiza Hippie By Escada Type, Iceberg Men Type, Image By Nino Cerruti Type, In Love Again Type, Intuition For Men Type, Intuition For Women Type, Island Kiss, Escada Type, Issey Miyake For Men, Issey Miyake For Women, J'ador Type For Women, Jazz For Men Type, Jean Paul Gualtier Men Type, Jean Paul Gualtier Women Type, Jessica Mcclintock Type, Jessica Mcclintock Type, Jo Malone Orange Blossom Type, Joop For Men Type, Joop For Women Type, Jovan Musk For Men Type, Jovan Musk For Women Type, Jovan Musk Type, Joy Type, Jungle Kenzo Women Type, Jungle Men Kenzo Type, Kannon For Men Type, Kate Spade Type, Kenneth Cole Reaction For Men Type, Kenneth Cole Reaction For Women Type, Kenzo For Women Type, Kenzo Pour Homme Type, KI For Women Type, Knowing Type Kors Michael Kors Type, Kouros Type, Kush, L'Air Du Temps Type, L'Eau D'Issey For Men Type, L'Eau D'Issey Type, L'Eau Par For Women Kenzo Type, Lagerfield Type, L'air De Temps Type, Latitude Longitude For Men Type, Laura By Laura Biagiotti Type, Lauren Style, Type By Ralph Lauren, Lauren Type, Life By Aramis Type, Liz Candies For Men Type, Liz Claiborne Men Type, Liz Claiborne Women Type, Liz Sport Type, Lovely By Sarah Jessica Parker Type, Luck You Men Type, Luck You Women Type, M7 For Men Type, Magie Noire Type, Magnetism For Women, Escada Type, Mambo For Men Type, Mambo Men Type, Mambo Women Type, Mania For Men Type, Mania For Women Type, Manifesto Type, Mark Jacobs For Women Type, Miami Glow By J. Lo Type, Michael Jordan Jump Type, Michael Kors For Men Type, Michael Kors Type, Miracle For Men Type, Miracle For Women Lancome Type, Must De Cartier Type, Nautica Competition For Men Type, Nautica For Men Type, Nautica For Women Type, Navy For Women Type, New West For Women Type, Nicole Miller For Women Type, Nino Cerrutti Women, Norell Type, Nu By Ysl Type, O Oui De Lancome For Women Type, O Oui De Lancome Type, Obsession For Men Type, Obsession For Women Type, Obsession Night For Men Type, Obsession Night For Women Type, Ocean Dream Type, Old Spice For Men Type, Op Juice For Men Type, Opium For Men Type, Opium For Women Type, Organza Type, Origins Frolic Type, Oscar De Larenta Type, Oxygen For Men Type By Lanvin, Oxygen For Women Lavin Type, Paco “Xs” Men Type, Paco Energy Unisex Type, Paco Type, Paloma Picasso Type, Paradise For Men By Alfred Sung Type, Parfum D'Ete By Kenzo Type, Paris Hilton Women Type, Paris Type, Passion For Men Type, Passion For Women Type Passionate Kisses By Victoria Secret Type, Pattie La Belle Type, Paul Sebastian Type, Perry Ellis 360 Red For Men Type, Perry Ellis 360 Type, Perry ElIlis Red For Women Type, Pheromone Type Unisex, Photo Type, Pi For Men Type, Pierre Cardan Type, Pino Silverstre Type, Pleasures For Men Type, Pleasures For Women Type, Poeme Type, Poison Type, Polo Black For Men Type, Polo Blue Type, Polo Crest Type, Polo For Men Type, Polo Sport Men Type, Polo Sport Women Type, Prada For Women Type, Premium Phat Farm Type For Men, Private Collection Type, Pure Seduction Victoria Secret Type, Quorum Type, Rapture By Victoria Secret Type, Realities Type, Realm For Men Type, Realm For Women Type, Red # 2 For Women Type, Red Door Type, Red For Men Type, Red For Women Type, Red Jeans Versace Type, Rivera Sun Victoria Secret Type, Robert Cavalli Type, Rochas For Men Type,Roma For Women Type, Romance For Men Type, Romance For Women Type, Romance Silver For Men Type, Roxy Love For Women Type,Royal Copenhagen Type, Royal Secret Type, Rush For Women Type Gucci, Safari For Men Type, Safari For Women Type, Sam Sara Type, Sapphires And Jewels, Sculpture For Men Type, Sean Jean, Aka Puffy Combs Cologne Type, Secret Crush V.S. Type, Sensi For Women Type, Sensual Sunset, Victoria Secret Type, Sexy Graffitty, Escada Women Type, Shalimar Type, Shania By Stetson For Women Type, Simply By Clinique Type, Spark For Men By Liz Claiborne Type, Spark For Women By Liz Claiborne Type, Stella By Stella Mccartney Type, Still By Jennifer Lopez Type, Still By Jennifer Lopez Type, Strawberries & Champagne, Vs Type, Sugar For Soy By Fresh Type, Sugar For Women By Fresh, Sun, Moon & Stars Type, Sunflowers Type, Swiss Army Type, Tabutype, Tatiana Type, Tiffany For Men Type, Tommy “T” Type, Tommy Bahama For Men Type, Tommy Bahama For Women Type, Tommy Girl Type, Tommy Hilfiger Type, Touch Of Pink By Lacoste For Women Type, Tresor Type, Tropical Punch Escada Type, True Love Type, True Star For Women Tommy Hilfiger Type, Truth For Women Type, Tuscany For Men Type, Tuscany Per Donna Type, Vanilla Fields Type, Vanilla Lace By Victoria Secret Type, Vanilla Musk Type, Venezia Type Laura Biogotti, Vera Wang Type, Versace “Blue Jeans” Type, Versace “Red Jeans” Type, Versace Blond Type, Versace Vs For Men Type, Versus For Women Type, Very Irresistible By Givenchy Type, Very Sexy For Men Victoria Secret Type, Victoria Secret “Halo” Type, Victoria Secret “Heavenly” Type, Victoria Secret” Divine” Type, Victoria's Secret Pear Glace Type, Victoria's Secret Sweet Temptations Type, Vivid Type, Volupte Type, Weekend For Women By Burberry Type, White Diamond Type, White Linen Type, White Musk Jovan Type, White Musk Type By The Body Shop, White Shoulders Type, Wind Song Prince Matchabelli Type, Wings For Men Type, Wings For Women Type, Youth Dew Type, Ysatis Type, Zino For Men Type.
Additional odorants may include Essential Oils such as for example, Anethol/Anise Star Oil, Armoise Oil, Balsam Copaiba Oil, Balsam Peru Oil, Basil Oil, Bay Oil, Beeswax Abs., Benzoin Resin Siam, Bergamot Oil Italian, Calamus Oil, Camphor Oil White Chinese, Cananga Oil, Caraway Seed Oil,Cardamon Oil, Carrot Seed Oil, Cedarleaf Oil, Cedarwood Oil Vigrina, Celery Seed Oil, Chamomile Oil Blue Cinnamon Leaf Oil Ceylon, Ciste Oil Maroc, Citronella Java, Citronella Oil, Clove Bud Oil, Clove Leaf Oil, Coriander Oil, Corn Mint Oil, Cumin Seed Oil, Cypress Oil, Davana Oil, Elemi Resin, Estragon, Eucalyptus Oil 80/85, Fir Balsam Abs., Fir Balsam Canadian Oil, Galbanum Oil, Geraniol Ex Palma Rosa Oil, Geranium African/Egyptian Oil, Geranium Bourbon Oil, Ginger Oil, Grapefruit Oil White, Guiacwood Oil, Gurjon Balsam Oil, Juniper Berry Oil, Labdanum Resin, Lavandin Grosso, Lavender Absolute Green, Lavender Oil 40/42, Lavender Oil Abrialis, Lavender Oil Spike, Lemon Oil Argentina, Lemon Oil Washed, Lemongrass Oil Guatemalan, Lime Oil Distilled W.I., Litsea Cubeba Oil, Lovage Oil, Mandarin Oil, Mate Abs., Myrrh Resin, Myrtle Oil, Nutmeg Oil, Oakmoss Abs.Solute Brown, Oakmoss Absolute Green, Octea Cymbarum, Olibanum Oil Olibanum Resin, Opoponax Resin, Orange Oil Bitter, Orange Oil Florida M.S, Orange Oil Terpenes, Patchouli Oil Indonesian, Pepper Black Oil, Peppermint Oil, Petigrain Oil, Pimento Leaf Oil, Pine Needle Oil Siberian, Rosemary Oil Spanish, Sage Clary European Oil, Sage Clary Spanish/Dalmation, Sandalwood Oil Indonesian, Spearmint Oil, Spuce Oil Canadian, Styrax Resin, Tagette Oil, Tangerine Oil, Tea Tree Oil, Thyme Oil White,Tolu Resin, Tonka Bean Abs., Vetivert Oil Bourbon, Wormwood Oil American, Ylang Ylang Oil #1, Organic Essential Oils Dill Seed Oil Eec (Anethum Graveolens L.), Pink Grapefruit Oil Nop (Citrus Paradisii), Apricot Kernel Oil Nop (Prunus Armeniaca), Basil Oil Nop (Ocimum Basilicum L.), Bergamot Oil Nop (Citrus Bergamia L. Ssp Bergamia), Blue Chamomile Oil Nop (Matricaria Chamomilla L.), Bulgarian Lavender Oil Nop (Lavandula Angustifolia), Cardamom Oil Nop (Eletteria Cardamomum M.), Cedarwood Oil Nop (Juniperus Virginiana L.), Cinnamon Bark 30% Oil Nop (Cinnamon Zeylenicum B.), Cinnamon Leaf Oil Nop (Cinnamon Zeylenicum B.), Citronella Oil Nop (Cymbopogon Nardus L.), Clary Sage Oil Nop (Salvia Sclarea L.), Clove Bud Oil Nop (Eugenia Caryophilata), Coconut Oil Nop (Coco)(Cocos Nucifera), Eucalyptus Citradora Oil Nop (Eucalyptus Citradora), Eucalyptus Globulus Oil Nop (Eucalyptus Globulus), Eucalyptus Radiata Oil Nop (Eucalyptus Radiata Ssp. Radiata), Eucalyptus Smithii Oil Nop, Evening Prime Rose Oil Nop (Oenothera Biennis), French Cedarwood Oil Nop (Cedus Atlantica M.), Geranium Oil Nop (Pelargonium×Asperum), Ginger Oil Nop (Zingber Officinalis L.), Green Mandarin Oil Nop (Citrus Reticulata), Jojoba Oil Nop (Simmondsia Chinensis), Lavandin Grosso Oil Nop (Lavandula Burnati), Lavandin Super Oil Nop (Lavandula Burnati), Lavender Officinalis Oil Nop (Lavandula Angustifolia), Lavendin Abrialis Oil Nop (Lavandula Burnati), Lemon Oil Nop (Citrus Limonum L.), Lemongrass Oil Nop (Cymbopogon Citratus/Flexuosus), Listea Cubeba Oil Nop (Litsea Citrata Persoon), Marjoram Oil Nop (Thymus Mastechina), Niaouli Nop (Melaleuca Viridiflora G.), Nutmeg Oil Nop (Myristica Fragrans Houttuyn), Olive Oil Nop (Olea Europaea), Orange Oil Nop (Citrus Aurantium Var. Amara), Origan Oil Nop (Thymus Capitatus), Palm Oil Nop (Elaeis Guineensis), Palmarosa Oil Nop (Cymbopogon Martinii), Patchouli Oil Nop (Pogostemon Cablin), Pepper Oil Nop (Piper Nigrum L.), Peppermint Oil Nop (Mentha Piperita L.), Petit Grain Nop (Citrus Aurantium Var Amara), Red Mandarin Oil Nop (Citrus Reticulata), Rose Hip Oil Nop (Rosa Canina), Rosemary Cineol Oil Nop (Rosemarinus Off. Cineoliferum), Rosemary Oil Nop (Rosemarinus Off. Camphor), Safflower Oil Nop (Carthamus Tinctorius), Scotch Pine Oil Nop (Pinus Sylvestris),Sheabutter Oil Nop (Butyrospermum Parkii),Soybean Oil Nop (Glycine Sojo), Spearmint Oil Nop (Mentha Viridis L.), Spike Lavender Oil Nop (Lavandula Latifolia L.F.),Sweet Orange Oil Nop (Citrus Cinensis),Tea Tree Oil Nop (Melaleuca Alternifolia), Thyme Borneol Oil Nop (Thymus Borneoliferum),Vetyver Oil Nop (Vetiveria Zizanoides), Wild Chamomile Oil Nop (Ormenis Mixta),Ylang Complete Oil Nop (Cananga Odorata Geniune),Ylang Ylang I Oil Nop (Cananga Odorata Geniune), Ylang Ylang Ii Oil Nop (Cananga Odorata Geniune).
Additional odorants may include Floral scents such as for example, Amarige By Givency For Women Type, Amber Rose, Apple Blossom, Apricot & Rose, Apricot Freesia, Balancing Blends, Bergamot Blossom, Black Current With Green Tea & Citrus, Black Forest, Blooming Honeysuckle, Blue Bonnett, Blue Gardenia, Blue Grass, Blue Lavender Palma Rose, Bbw Type, Blue Nile, Body By Victoria Secret Type, Cactus Flower Type, Carnation, Casablanca Lily, Citronella, Claire Burke Original Potpourri, Coconut & Gardenia, Coconut & Rose, Cool Cucumber Type, Cotton Blossom Type, Dandelion, Dianthus, Dogwood Blossom, Downy April Fresh Type, English Garden, English Ivy, Envy Me By Gucci Women Tpe, Floral Blends, Floral Fresh, Freesia, Freesia & Musk, Yankee Type, Freesia, Bbw Type, Fresh Cut Roses, Yankee Type, Fresh Linen, Gardenia, Gardenia Lily, Bbw Type, Gardenia Musk, Gardenia Musk, Geranium, Geranium Rose, Ginger Lily, Hawaiian Calalily, Hawthorne, Heather, Hibiscus, Honey Rain, Honey Suckle, Honeysuckle For Soy, Honeysuckle Grapefruit, Hyacinth, Hybiscus, Hydrangea Yankee Type, Irish Moss, Jasmin Musk, Jasmin Tea, Jasmine, Jasmine Bouquet, Jasmine For Soy, Jasmine Musk, Jasmine Vanilla, Bbw Type, Joyful, Jungle Gardenia, Jungle Kenzo Women Type, Jungle Men Kenzo Type, Kenneth Cole Reaction For Women Type, Kitchen Herbs, L'air De Temps Type, Laundry Fresh, Laura By Laura Biagiotti Type, Lavender & Jasmine, Lavender & Neroli Eo. 100%, Lavender & Rose Petals, Lavender & Ylang Ylang 100% Eo., Lavender Bouquet, Lavender Citrus, Lavender Oil, Lavender Sage & Rosemary, Lavender Ylang & Patchouli, Lever 2000 Soap Type, Lilac, Lily Of The Valley, Linden Blossom, Lotus, Magnolia Blossom For Soy, Moonlight Path Bbw Type, Morning Mist, Muguet, Muquet, Narcissus, Nature Fresh, Neroli Blossom, Neroli Oil, New Mown Hay, Ombre Rose, Orange Blossom For Soy, Orange Flower, Orchid, Orris, Osmanthus, Palma Rosa Oil, Passion Flower, Patchouli & Lavender, Peony, Bbw Type, Pleasant Memories, Plumeria, Plumeria, Bbw Type, Pointsettia, Potpourri Blends, Primrose, Rainbows End Type, Rose, Rose Geranium, Rose Petals, Somali Rose, Spring Blends, Spring Fresh, Spring Garden, Summer Fruit & Jasmine Bbw Type, Sweet Pea, Sweet Pea Bbw Type, Sweet Pea, Yankee Type, Tansey Oil, Tea Rose, Tiger Lily, Tuberose Fantasy, Tuberose Oil, Tulip, Vintage Rose, Yankee Type, Violet Blossom, Violet Leaf, Wardia, Water Blossom Ivy Bbw Type, Wedding Day, Yankee Type, White Gardenia, White Rose, Wild Flower, Wine And Roses Type, Wisteria, Ylang Ylang Oil
Additional odorants may include Food Scents such as for example, Almond & Oatmeal, Almond Oil, Almond Raspberry, Amaretto, Amaretto Coffee, Ambrosia, Amish Bread, Amish Friendship Bread, Angel Food Cake, Anise Oil, Apple & Honey, Apple Cider, Apple Cobbler Delight, Apple Jack, Apple Jack And Peel Claire Burke Type, Apple Mango, Apple Martini, Apple Orchard, Apple Red Orchad, Apple Red Orchard Yankee Type, Apple Strudel, Apples And Oak Vc Type, Apricot & Honey, Yankee Type, Apricot & Rose, Apricot & Vanilla, Autumn Wreath By Yankee Type, Aztec Gold Coffee, Bailey's Irish Cream, Baked Apple Pie, Baked Bread, Baked Pear, Bakers Vanilla Filling, Bakers Vanilla For Soy, Banana Caramel, Banana Coconut Cream Pie, Banana Nut Bread, Banana Nut Bread Muffin, Banana Nut Cake, Banana Nut Honey, Banana Pudding, Banana Raspberry, Bay Rum, Birthday Cake, Black Coffee, Black Pepper, Black Raspberry Vanilla, Bbw Type, Blueberry Cheesecake, Blueberry Cobbler, Blueberry Cream, Blueberry Melon, Blueberry Muffin, Blueberry Pancakes & Syrup, Blueberry Pie, Bramble Berry, Yankee Type, Brazilian Nutty Coffee, Bubble Gum, Butter Cookie, Butter Cream Crunch, Butter Cream Yankee Candle Type, Butter Pecan, Butter Pecan Pie, Buffer Rum, Butter Rum, Butter Scotch, Buttercream, Buttercream Vanilla, Buttermilk Pancakes, Buttery Gingerbread, Buttery Popcorn, Candied Cherry, Candy Apple, Candy Cane, Candy Corn, Candy Corn, Bbw Type, Cantaloupe, Cappuccino Coffee, Caramel, Caramel Apple, Caramel Pecan, Caramel Pecan Pie, Carrot Cake, Carved Pumpkin, Chai Latte Soul & Body, Chai Spice Black Tea, Champagne & Strawberries, Chardonnay, Chardonnay & Vanilla, Chardonnay Wine, Cheesecake Plain, Cherries & Chestnuts, Cherry Apple, Cherry Berry, Cherry Cobbler, Cherry Cola, Cherry Pineapple, Cherry Vanilla, Chocolate, Chocolate & Cinnamon, Chocolate Chip Cookie, Yankee Type, Chocolate Covered Cherries, Chocolate Covered Raspberry, Chocolate Mint, Chocolatey Orange, Cinnabon Cinnamon Rolls Type, Cinnamon, Cinnamon & Organic, Cinnamon Apple, Cinnamon Apple Berry Yankee Type, Cinnamon Bun, Cinnamon Buns For Soy Candles, Cinnamon Cider, Cinnamon Clove, Cinnamon Donuts, Cinnamon Honey, Cinnamon Super Throw For Soy, Cinnamon Toast, Cinnamon Vanilla, Citrus Cream, Bbw Type, Cocoa Cherry, Coconut, Coconut Berries, Coconut Fruity Blend, Coconut Milk, Coconut, Mango & Vanilla, Coffee, Coffee Italy, Cognac Oil, Coke & Whiskey, Cola, Concord Grape, Cookie Dough, Cool Citrus Basil, Bbw Type, Cosmopolitian, Cotton Candy, Country Berry Hotcakes, Country Cider, Cranapple, Cranberry, Cranberry Apple, Cranberry Chutney Yankee Candle Type, Cranberry Grape, Cranberry Plum, Cranberry Sauce, Cranberry Tart, Creamsicle, Creamy Coconut, Bbw Type, Creamy Vanilla, Creme Brule, Cucumber, Cucumber & Cantalope, Yankee Type, Cucumber & Lime, Cucumber & Vanilla, Cucumber Melon, Cucumber Melon Bbw Type, Curry, Dark Chocolate & Orange, Dreamsicle, Dusty Mexican Morning, Egg Nog, English Toffee, Ethiopian Magic, Fig, French Vanilla, Fresh Cappuccino Milk, Fruit Punch For Soy, Ginger Snap Cookies, Gingerbread, Gingerbread Spice, Bbw Type, Graham Cracker, Grand Marnier, Grandmas Christmas Rolls, Grapefruit & Jamaican Ginger, Great Pumpkin Patch, Green Apple, Green Apple Cinnamon, Green Tea & Cucumber, Bbw Type, Hazelnut Coffee, Honey Almond, Honey Apple, Honey Cinnamon, Honey Comb, Honey Rain, Honey Vanilla, Hot Buttered Rum, Yankee Type, Hot Coco, Indonesian Coffee, Island Kola Nut, Island Mango, Yankee Type Revised, Jolly Rancher, Jolly Rancher For Soy, Key Lime, Key Lime Pie, Lavender Orage & Mint, Lemon & Cucumber, Lemon & Cucumber, Lemon & Mandarin, Lemon Chiffon Cake, Lemon Graham Cracker, Lemon Meringue, Lemon Pound Cake, Lemon Verbena, Lemon Zest, Yankee Type, Lick Me All Over, Licorice, Liquish, Macaroon Cookie, Macintosh & Peach Yankee Type, Mandarin Cranberry Yankee Type, Mandarin Peel Type, Bbw Type, Mango Macadamia Nut, Maple Syrup, Margarita, Marshmallow, Midori Sour, Mint Blends, Mocha Cappuccino Coffee, Money, Mulled Cider, Nutmeg Oil, Oatmeal Milk And Honey, Orange Chiffon Cake Type For Soy Candles, Orange Ginger (Awake), Bbw Type, Orange Pound Cake, Orangenia, Peaches & Cream, Peanut Butter Brownies, Pears & Apples, Bbw Type, Peppermint Sticks, Pie Filling, Pina Colada, Pineapple Citrus By Yankee Type, Pineapple Upside Down Cake, Popcorn, Pumpkin Pie, Raspberry Cheese Cake, Raspberry Vanilla Swirl, Red Clover & Tea, Yankee Type, Red Currant & Thyme, Bbw Type, Root Beer, Snickerdoodle, Spiced Pear, Yankee Type, Strawberries & Champagne, Vs Type, Strawberry Banana Daiquiri, Strawberry Cheese Cake, Strawberry Chiffon, Sugar Cookie, Sugar Plum, Sugar Plum Spice, Sweet Cinnamon Pumpkin, Bbw Type, Truffle, Turkish Delight, Vanilla, Vanilla Caramel, Yankee Type, Vanilla Fields Type, Vanilla Filling, Vanilla Hazelnut, Vanilla Hazienut, Yankee Type, Vanilla Sandalwood, Yankee Type, Vanilla, Coconut And Ginger Yankee Type, Vermont Maple Syrup, Warm Banana Nut Muffins, Wedding Cake, Wheat Germ & Honey, Ye Olde Country Store. Yellow Cake
The odorant may be incorporated with a premade colorant or tint, such as those commercially available from Polyone Corporation of Avon Lake, Ohio. These premade colorants or tints generally contain a pigment(s) dispersed in a grind vehicle, e.g., high molecular weight polyols.
Ionomer Composition
As mentioned, the odorant golf ball compositions of the invention may contain ionomer resins, such as, e.g., Surlyn®. Surlyn® is the random copolymer poly(ethylene-co-methacrylic acid) (EMAA). The incorporation of methacrylic acid is typically low (<15 mol. %). Some or all of the methacrylic acid units can be neutralized with a suitable cation, commonly Na⁺ or Zn²⁺. Surlyn® is produced through the copolymerization of ethylene and methacrylic acid via a high pressure free radical reaction, similar to that for the production of low density polyethylene. The methacrylic acid monomer is more reactive with itself than with ethylene. This leads to a higher reactivity ratio, around four, for methacrylic acid, and could give a blocky incorporation of methacrylic acid along the polymer chain. However, by polymerizing under elevated heat and pressure the reactivity ratios are driven toward one, thus promoting a random incorporation of the co-monomers. The neutralization of the methacrylic acid units can be done through the addition of an appropriate base in solution, or in the melt mixing of base and copolymer.
The DuPont manufacturing process for Surlyn® enables tailored combinations of properties including enhanced resilience, broad hardness and stiffness ranges, and resistance to cuts and abrasions which are properties that are all highly desirable for golf ball applications.
Surlyn® ionomers can be melt-processed using conventional injection molding and compression molding methods and equipment, to create parts of various designs and gauges. Because of their performance properties and processing versatility, Surlyn® resins have been widely adopted, in neat or blended form, as premium materials for golf ball covers, mantles, intermediate layers, and other components.
Polyurethane Composition
Also as mentioned, the odorant golf ball compostions of the invention may be polyurethane-based, i.e., a product of a reaction between at least one polyurethane prepolymer and a curing agent, such as hydroxyl-terminated or amine-terminated curing agents, of which the polyurethane prepolymer is a product formed by a reaction between at least one polyol and at least one diisocyanate. The polyurethane-based compositions of the invention are preferably-saturated and, thus, in one embodiment, the composition of the invention is the product of a reaction between at least one saturated polyurethane prepolymer, formed of at least one saturated diisocyanate and at least one saturated polyol, and at least one saturated curing agent.
Isocyanate Component
Saturated isocyanates for use with the polyurethane prepolymer include aliphatic, cycloaliphatic, araliphatic, derivatives thereof, and combinations of these compounds having two or more isocyanate (NCO) groups per molecule. The isocyanates may be organic, modified organic, organic polyisocyanate-terminated prepolymers, and mixtures thereof. The isocyanate-containing reactable component may also include any isocyanate-functional monomer, dimer, trimer, or multimeric adduct thereof, prepolymer, quasi-prepolymer, or mixtures thereof. Isocyanate-functional compounds may include monoisocyanates or polyisocyanates that include any isocyanate functionality of two or more. Suitable isocyanate-containing components include diisocyanates having the generic structure: O═C═N—R—N═C═O, where R is preferably a cyclic or linear or branched hydrocarbon moiety containing from about 1 to 20 carbon atoms. The diisocyanate may also contain one or more cyclic groups. When multiple cyclic groups are present, linear and/or branched hydrocarbons containing from about 1 to 10 carbon atoms can be present as spacers between the cyclic groups. In some cases, the cyclic group(s) may be substituted at the 2-, 3-, and/or 4-positions, respectively. Substituted groups may include, but are not limited to, halogens, primary, secondary, or tertiary hydrocarbon groups, or a mixture thereof.
The number of unreacted NCO groups in the polyurethane prepolymer may be varied to control such factors as the speed of the reaction, the resultant hardness of the composition, and the like. For instance, the number of unreacted NCO groups in the polyurethane prepolymer of isocyanate and polyol may be less than about 14 percent. In one embodiment, the polyurethane prepolymer has from about 5 percent to about 11 percent unreacted NCO groups, and even more preferably has from about 6 to about 9.5 percent unreacted NCO groups. In one embodiment, the percentage of unreacted NCO groups is about 3 percent to about 9 percent. Alternatively, the percentage of unreacted NCO groups in the polyurethane polymer may be about 7.5 percent or less, and more preferably, about 7 percent or less. In another embodiment, the unreacted NCO content is from about 2.5 percent to about 7.5 percent, and more preferably from about 4 percent to about 6.5 percent.
Unsaturated diisocyanates, i.e., aromatic compounds, may also be used with the present invention, although the use of unsaturated compounds in the prepolymer is preferably coupled with the use of a light stabilizer or pigment as discussed below. Examples of unsaturated diisocyanates include, but are not limited to, substituted and isomeric mixtures including 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI), 3,3′-dimethyl-4,4′-biphenyl diisocyanate (TODI), toluene diisocyanate (TDI), polymeric MDI, carbodimide-modified liquid 4,4′-diphenyimethane diisocyanate, para-phenylene diisocyanate (PPDI), meta-phenylene diisocyanate (MPDI), triphenylmethane-4,4′-, and triphenylmethane-4,4″-triisocyanate, napthylene-1,5,-diisocyanate, 2,4′-, 4,4′-, and 2,2-biphenyl diisocyanate, polyphenyl polymethylene polyisocyanate (PMDI), and mixtures thereof.
Polyol Component
Any saturated polyol available to one of ordinary skill in the art is suitable for use in the polyurethane prepolymer. Exemplary polyols include, but are not limited to, polyether polyols, polycaprolactone polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, and mixtures thereof.
When formed, polyurethane prepolymers may contain about 10 percent to about 20 percent by weight of the prepolymer of free isocyanate monomer. Thus, in one embodiment, the polyurethane prepolymer may be stripped of the free isocyanate monomer. For example, after stripping, the prepolymer may contain about 1 percent or less free isocyanate monomer. In another embodiment, the prepolymer contains about 0.5 percent by weight or less of free isocyanate monomer.
The polyurethane prepolymer may be formed with a single curing agent or a blend or mixture of curing agents.
Curative
Saturated curatives that may be used in the present invention include, but are not limited to, hydroxy terminated curing agents, amine-terminated curing agents, and mixtures thereof. Depending on the type of curing agent used, the polyurethane composition may be thermoplastic or thermoset in nature. For example, polyurethanes prepolymers cured with a diol or secondary diamine with 1:1 stoichiometry are thermoplastic in nature. Thermoset polyurethanes, on the other hand, are generally produced from a prepolymer cured with a primary diamine or polyfunctional glycol.
In addition, the type of curing agent used determines whether the polyurethane composition is polyurethane-urethane or polyurethane-urea. For example, a polyurethane prepolymer cured with a hydroxy-terminated curing agent is polyurethane-urethane because any excess isocyanate groups will react with the hydroxyl groups of the curing agent to create more urethane linkages. In contrast, if an amine-terminated curing agent is used with the polyurethane prepolymer, the excess isocyanate groups will react with the amine groups of the amine-terminated curing agent to create urea linkages.
Suitable saturated hydroxy-terminated curing agents include, but are not limited to, ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; dipropylene glycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane; and triisopropanolamine.
Suitable saturated amine-terminated curing agents include, but are not limited to, ethylene diamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyl diamine; and tetrahydroxypropylene ethylene diamine.
Polyurea Composition
The odorant golf ball compositions of the invention may also be polyurea-based, which are distinctly different from polyurethane compositions, but also result in desirable aerodynamic and aesthetic characteristics when used in odorant golf ball components. The polyurea-based compositions are preferably saturated in nature.
Without being bound to any particular theory, it is now believed that substitution of the long chain polyol segment in the polyurethane prepolymer with a long chain polyamine oligomer soft segment to form a polyurea prepolymer, improves shear, cut, and resiliency, as well as adhesion to other components. Thus, the polyurea compositions of this invention may be formed from the reaction product of an isocyanate and polyamine prepolymer crosslinked with a curing agent. For example, polyurea-based compositions of the invention may be prepared from at least one isocyanate, at least one polyether amine, and at least one diol curing agent or at least one diamine curing agent.
Polyamine Component
Any polyamine available to one of ordinary skill in the art is suitable for use in the polyurea prepolymer. Polyether amines are particularly suitable for use in the prepolymer. As used herein, “polyether amines” refer to at least polyoxyalkyleneamines containing primary amino groups attached to the terminus of a polyether backbone. Due to the rapid reaction of isocyanate and amine, and the insolubility of many urea products, however, the selection of diamines and polyether amines is limited to those allowing the successful formation of the polyurea prepolymers. In one embodiment, the polyether backbone is based on tetramethylene, propylene, ethylene, trimethylolpropane, glycerin, and mixtures thereof.
Suitable polyether amines include, but are not limited to, methyidiethanolamine; polyoxyalkylenediamines such as, polytetramethylene ether diamines, polyoxypropylenetriamine, and polyoxypropylene diamines; poly(ethylene oxide capped oxypropylene)ether diamines; propylene oxide-based triamines; triethyleneglycoldiamines; trimethylolpropane-based triamines; glycerin-based triamines; and mixtures thereof. In one embodiment, the polyether amine used to form the prepolymer is Jeffamine D2000 (manufactured by Huntsman Corporation of Austin, Tex.).
Isocyanate Component
Any isocyanate available to one of ordinary skill in the art is suitable for use in the polyurea prepolymer. Isocyanates for use with the present invention include aliphatic, cycloaliphatic, araliphatic, aromatic, any derivatives thereof, and combinations of these compounds having two or more isocyanate (NCO) groups per molecule. The isocyanates may be organic polyisocyanate-terminated prepolymers. The isocyanate-containing reactable component may also include any isocyanate-functional monomer, dimer, trimer, or multimeric adduct thereof, prepolymer, quasi-prepolymer, or mixtures thereof. Isocyanate-functional compounds may include monoisocyanates or polyisocyanates that include any isocyanate functionality of two or more.
Examples of diisocyanates that can be used with the present invention include, but are not limited to, substituted and isomeric mixtures including 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI); 3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI); toluene diisocyanate (TDI); polymeric MDI; and carbodiimide-modified liquid 4,4′-diphenylmethane diisocyanate.
Examples of saturated diisocyanates that can be used with the present invention include, but are not limited to, ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene-diisocyanate (HDI); and octamethylene diisocyanate.
The number of unreacted NCO groups in the polyurea prepolymer of isocyanate and polyether amine may be varied to control such factors as the speed of the reaction, the resultant hardness of the composition, and the like. For instance, the number of unreacted NCO groups in the polyurea prepolymer of isocyanate and polyether amine may be less than about 14 percent. In one embodiment, the polyurea prepolymer has from about 5 percent to about 11 percent unreacted NCO groups, and even more preferably has from about 6 to about 9.5 percent unreacted NCO groups.
When formed, polyurea prepolymers may contain about 10 percent to about 20 percent by weight of the prepolymer of free isocyanate monomer. Thus, in one embodiment, the polyurea prepolymer may be stripped of the free isocyanate monomer. For example, after stripping, the prepolymer may contain about 1 percent or less free isocyanate monomer. In another embodiment, the prepolymer contains about 0.5 percent by weight or less of free isocyanate monomer.
The polyether amine may be blended with additional polyols to formulate copolymers that are reacted with excess isocyanate to form the polyurea prepolymer. In one embodiment, less than about 30 percent polyol by weight of the copolymer is blended with the saturated polyether amine. In another embodiment, less than about 20 percent polyol by weight of the copolymer, preferably less than about 15 percent by weight of the copolymer, is blended with the polyether amine.
Curative
The polyurea composition can be formed by crosslinking the polyurea prepolymer with a single curing agent or a blend of curing agents. The curing agent of the invention is preferably an amine-terminated curing agent, more preferably a secondary diamine curing agent so that the composition contains only urea linkages.
Skilled artisians are aware that the various properties of an odorant golf ball and odorant golf ball components, e.g., hardness, may be controlled by adjusting the ratio of prepolymer to curing agent, which is a function of the NCO content of the prepolymer and molecular weight of the curing agent. For example, the ratio of a polyurea prepolymer with 6 percent unreacted NCO groups cured with 1,4-butanediol is 15.6:1, whereas the ratio of the same prepolymer cured with 4,4′-bis-(sec-butylamino)-dicyclo-hexylmethane (Clearlink 1000) is 4.36:1. The ratio of prepolymer to curing agent for the purposes of this invention is preferably from about 0.5:1 to about 16:1.
Composition Additives
Additional materials conventionally included in polymer compositions may be added to the ionomer, polyurethane and polyurea prepolymers of the invention. These additional materials include, but are not limited to, catalysts, wetting agents, coloring agents, optical brighteners, crosslinking agents, whitening agents such as TiO₂and ZnO, UV absorbers, hindered amine light stabilizers, defoaming agents, processing aids, surfactants, and other conventional additives. For example, wetting additives may be added to the curative blends of the invention to more effectively disperse the odorant(s).
Antioxidants, stabilizers, softening agents, plasticizers, including internal and external plasticizers, impact modifiers, foaming agents, density-adjusting fillers, reinforcing materials, and compatibilizers may also be added to any odorant golf ball composition of the invention. Those of ordinary skill in the art are aware of the purpose of these additives and the amounts that should be employed to fulfill those purposes.
Catalysts
A catalyst may also be employed to promote the reaction between the prepolymer and the curing agent. Suitable catalysts include, but are not limited to bismuth catalyst; zinc octoate; stannous octoate; and tin catalysts such as di-butyltin dilaurate.
The catalyst is preferably added in an amount sufficient to catalyze the reaction of the components in the reactive mixture. In one embodiment, the catalyst is present in an amount from about 0.001 percent to about 5 percent by weight of the composition.
Use of low levels of tin catalysts, typically from about 0 to about 0.04 weight percent of the total composition, requires high temperatures to achieve a suitable reaction rate, which may result in degradation of the prepolymer. Increasing the amount of catalysts to unconventional high levels enables the reduction in process temperatures while retaining comparable cure stages. Use of the higher catalyst level also allows the mixing speeds to be reduced. Thus, in one embodiment, the tin catalyst is present in an amount from about 0.01 percent to about 0.55 percent by weight of the composition. In another embodiment, about 0.05 percent to about 0.4 percent of tin catalyst is present in the composition. In yet another embodiment, the tin catalyst is present in an amount from about 0.1 percent to about 0.25 percent.
Density-Adiusting Filler(s)
Fillers may be added to the odorant containing polymer compositions of the invention to affect Theological and mixing properties, the specific gravity (i.e., density-modifying fillers), the modulus, the tear strength, reinforcement, and the like. The fillers are generally inorganic, and suitable fillers include numerous metals, metal oxides and salts, such as zinc oxide and tin oxide, as well as barium sulfate, 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 mixtures thereof.
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.
Blowing or Foaming Agent(s)
The compositions of the invention may be foamed by the addition of the at least one physical or chemical blowing or foaming agent. The use of a 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.
Blowing or foaming agents useful include, but are not limited to, organic blowing agents, such as azobisformamide; azobisisobutyronitrile; diazoaminobenzene; N,N-dimethyl-N,N-dinitrosoterephthalamide; N,N-dinitrosopentamethylene-tetramine; benzenesulfonyl-hydrazide; benzene-1,3-disulfonyl hydrazide; diphenylsulfon-3-3, disulfonyl hydrazide; 4,4′-oxybis benzene sulfonyl hydrazide; p-toluene sulfonyl semicarbizide; barium azodicarboxylate; butylamine nitrile; nitroureas; trihydrazino triazine; phenyl-methyl-uranthan; p-sulfonhydrazide; peroxides; and inorganic blowing agents such as ammonium bicarbonate and sodium bicarbonate. A gas, such as air, nitrogen, carbon dioxide, etc., can also be injected into the composition during the injection molding process.
Additionally, a foamed composition of the present invention may be formed by blending microspheres with the composition either during or before the molding process. Polymeric, ceramic, metal, and glass microspheres are useful in the invention, and may be solid or hollow and filled or unfilled. In particular, microspheres up to about 1000 micrometers in diameter are useful.
Either injection molding or compression molding may be used to form a layer or a core including a foamed polymeric material. For example, a composition of the present invention can be thermoformed and, thus, can be compression molded. For compression molded grafted metallocene catalyzed polymer blend layers, half-shells may be made by injection molding a grafted metallocene catalyzed polymer blend in a conventional half-shell mold or by compression molding sheets of foamed grafted metallocene catalyzed polymer. The half-shells are placed about a previously formed center or core, cover, or mantle layer, and the assembly is introduced into a compression molding machine, and compression molded at about 250° F. to 400° F. The molded balls are then cooled while still in the mold, and finally removed when the layer of grafted metallocene catalyzed polymer blend is hard enough to be handled without deforming. Additional core, mantle, and cover layers are then molded onto the previously molded layers, as needed, until a complete ball is formed.
Light Stabilizers
The compositions of the invention may contain at least one light stabilizing component to prevent significant yellowing from unsaturated components contained therein. The use of a light stabilizer is preferred, for instance, for compositions having a difference in yellowness (*Y) of about 15 or greater, but also may be added to compositions having a difference in yellowness of from about 12 to about 15. As used herein, light stabilizer may be understood to include hindered amine light stabilizers, ultraviolet (UV) absorbers, and antioxidants.
As discussed above, dyes, as well as optical brighteners and fluorescent pigments may also be included in the golf ball covers produced with odorant containing polymers formed according to the present invention. Such additional ingredients may be added in any amounts that will achieve their desired purpose while not interfering with the added odorant.
Composition Blends
The compositions of the invention may include from about 1 percent to about 99 percent ionomer resin, polyurethane or polyurea, depending on whether the compositions are ionomer-based, polyurethane-based or polyurea-based, however, the compositions may be blended with other materials. In one embodiment, the composition contains about 10 percent to about 90 percent of ionomer, polyurethane or polyurea, preferably from about 10 percent to about 75 percent ionomer, polyurethane or polyurea, and contains about 90 percent to 10 percent, more preferably from about 90 percent to about 25 percent other polymers and/or other materials as described below.
Other polymeric materials suitable for blending with the compositions of the invention include castable thermoplastic or thermoset polyurethanes, cationic and anionic urethane ionomers and urethane epoxies, polyurethane/polyurea ionomers, epoxy resins, polyethylenes, polyamides and polyesters, polycarbonates, polyacrylin, and mixtures thereof. Examples of suitable urethane ionomers are disclosed in U.S. Pat. No. 5,692,974, the disclosure of which is hereby incorporated by reference in its entirety. Other examples of suitable polyurethanes are described in U.S. Pat. No. 5,334,673, the entire disclosure of which is incorporated by reference herein. Examples of suitable polyureas used to form the polyurea ionomer listed above are discussed in U.S. Pat. No. 5,484,870. In particular, the polyureas of U.S. Pat. No. 5,484,870 are prepared by reacting a polyisocyanate and a polyamine curing agent to yield polyurea, which are distinct from the polyureas of the present invention which are formed from a polyurea prepolymer and curing agent. Examples of suitable polyurethanes cured with epoxy group containing curing agents are disclosed in U.S. Pat. No. 5,908,358. The disclosures of the above patents are incorporated herein by reference in their entirety. These examples are intended to be non-limiting examples of blends to be used with the present invention.
Golf Ball Core Layer(s)
The cores of the golf balls formed according to the invention may be solid, semi-solid, hollow, fluid-filled or powder-filled, one-piece or multi-component cores. The term “semi-solid” as used herein refers to a paste, a gel, or the like. Any core material known to one of ordinary skill in that art is suitable for use in the golf balls of the invention. Suitable core materials include thermoset materials, such as rubber, styrene butadiene, polybutadiene, isoprene, polyisoprene, trans-isoprene, as well as thermoplastics such as ionomer resins, polyamides or polyesters, and thermoplastic and thermoset polyurethane elastomers. As mentioned above, the ionomer, polyurethane or polyurea compositions of the present invention may also be incorporated into any component of a golf ball, including the core.
In one embodiment, the golf ball core is formed from a composition including a base rubber (natural, synthetic, or a combination thereof, a crosslinking agent, and a filler. In another embodiment, the golf ball core is formed from a reaction product that includes a cis-to-trans catalyst, a resilient polymer component having polybutadiene, a free radical source, and optionally, a crosslinking agent, a filler, or both.
Free Radical Source(s)
A free-radical source, often alternatively referred to as a free-radical initiator, is preferred in the composition and method. The free-radical source is typically a peroxide, and preferably an organic peroxide, which decomposes during the cure cycle. Suitable free-radical sources include organic peroxide compounds, such as di-t-amyl peroxide, di(2-t-butyl-peroxyisopropyl)benzene peroxide or .alpha.,.alpha.-bis(t-bu-tylperoxy)diisopropylbenzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane or 1,1-di(t-butylperoxy)3,3,5-trimethyl cyclohexane, dicumyl peroxide, di-t-butyl peroxide, 2,5-di-(t-butylperoxy)-2,5-dimethyl hexane, n-butyl-4,4-bis(t-butylperoxy)valerate, lauryl peroxide, benzoyl peroxide, t-butyl hydroperoxide, and the like, and any mixture thereof.
Crosslinking Agent(s)
Crosslinkers may be included to increase the hardness of the reaction product. Suitable crosslinking agents include one or more metallic salts of unsaturated fatty acids having 3 to 8 carbon atoms, such as acrylic or methacrylic acid, or monocarboxylic acids, such as zinc, calcium, or magnesium acrylate salts, and the like, and mixtures thereof. Examples include, but are not limited to, one or more metal salt diacrylates, dimethacrylates, and monomethacrylates, wherein the metal is magnesium, calcium, zinc, aluminum, sodium, lithium, or nickel. Preferred acrylates include zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof. In one embodiment, zinc methacrylate is used in combination with the zinc salt of pentachlorothiophenol.
Antioxidant
Typically, antioxidants are included in conventional golf ball core compositions because antioxidants are included in the materials supplied by manufacturers of compounds used in golf ball cores. Without being bound to any particular theory, higher amounts of antioxidant in the reaction product may result in less trans-isomer content because the antioxidants consume at least a portion of the free radical source. Thus, even with high amounts of the free radical source in the reaction product described previously, such as for example about 3 phr, an amount of antioxidant greater than about 0.3 phr may significantly reduce the effective amount of free radicals that are actually available to assist in a cis-to-trans conversion.
Other Additives
Additional materials conventionally included in golf ball compositions may be added to the polybutadiene reaction product of the invention. These additional materials include, but are not limited to, density-adjusting fillers, coloring agents, reaction enhancers, crosslinking agents, whitening agents, UV absorbers, hindered amine light stabilizers, defoaming agents, processing aids, and other conventional additives. Stabilizers, softening agents, plasticizers, including internal and external plasticizers, impact modifiers, foaming agents, excipients, reinforcing materials and compatibilizers can also be added to any composition of the invention. All of these materials, which are well known in the art, are added for their usual purpose in typical amounts.
Golf Ball Intermediate Layer(s)
When the golf ball of the present invention includes an intermediate layer, such as an inner cover layer or outer core layer, i.e., any layer(s) disposed between the inner core and the outer cover of a golf ball, this layer can include any materials known to those of ordinary skill in the art including thermoplastic and thermosetting materials. For example, the intermediate layer may be formed from any of the ionomer, polyurethane, polyurea, and polybutadiene materials discussed above.
The intermediate layer may also likewise include one or more homopolymeric or copolymeric materials, such as:
(1) Vinyl resins, such as those formed by the polymerization of vinyl chloride, or by the copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride;
(2) Polyolefins, such as polyethylene, polypropylene, polybutylene and copolymers such as ethylene methylacrylate, ethylene ethylacrylate, ethylene vinyl acetate, ethylene methacrylic or ethylene acrylic acid or propylene acrylic acid and copolymers and homopolymers produced using a single-site catalyst or a metallocene catalyst;
(3) Polyurethanes, such as those prepared from polyols and diisocyanates or polyisocyanates and those disclosed in U.S. Pat. No. 5,334,673;
(4) Polyureas, such as those disclosed in U.S. Pat. No. 5,484,870;
(5) 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), and blends of polyamides with SURLYN, polyethylene, ethylene copolymers, ethyl-propylene-non-conjugated diene terpolymer, and the like;
(6) Acrylic resins and blends of these resins with poly vinyl chloride, elastomers, and the like;
(7) Thermoplastics, such as urethanes; olefinic thermoplastic rubbers, such as blends of polyolefins with ethylene-propylene-non-conjug-ated diene terpolymer; block copolymers of styrene and butadiene, isoprene or ethylene-butylene rubber; or copoly(ether-amide), such as PEBAX, sold by ELF Atochem of Philadelphia, Pa.;
(8) Polyphenylene oxide resins or blends of polyphenylene oxide with high impact polystyrene as sold under the trademark NORYL by General Electric Company of Pittsfield, Mass.;
(9) Thermoplastic polyesters, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/glycol modified and elastomers sold under the trademarks HYTREL by E. I. DuPont de Nemours & Co. of Wilmington, Del., and LOMOD by General Electric Company of Pittsfield, Mass.;
(10) Blends and alloys, including polycarbonate with acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers, and the like, and polyvinyl chloride with acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomers; and
(11) Blends of thermoplastic rubbers with polyethylene, propylene, polyacetal, nylon, polyesters, cellulose esters, and the like.
In one embodiment, the intermediate layer includes polymers, such as ethylene, propylene, butene-1 or hexane-1 based homopolymers or copolymers including functional monomers, such as acrylic and methacrylic acid and fully or partially neutralized ionomer resins and their blends, methyl acrylate, methyl methacrylate homopolymers and copolymers, imidized, amino group containing polymers, polycarbonate, reinforced polyamides, polyphenylene oxide, high impact polystyrene, polyether ketone, polysulfone, poly(phenylene sulfide), acrylonitrile-butadiene, acrylic-styrene-acrylonitrile, poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethelyne vinyl alcohol), poly(tetrafluoroethylene) and their copolymers including functional comonomers, and blends thereof.
Ionomers
The intermediate layer may also include ionomeric materials, such as ionic copolymers of ethylene and an unsaturated monocarboxylic acid, which are available under the trademark SURLYN® of E. I. DuPont de Nemours & Co., of Wilmington, Del., or IOTEK® or ESCOR® of Exxon. These are copolymers or terpolymers of ethylene and methacrylic acid or acrylic acid totally or partially neutralized, i.e., from about 1 to about 100 percent, with salts of zinc, sodium, lithium, magnesium, potassium, calcium, manganese, nickel or the like.
Non-Ionomeric Thermoplastic Materials
In another embodiment, the intermediate layer includes at least one primarily or fully non-ionomeric thermoplastic material. Suitable non-ionomeric materials include polyamides and polyamide blends, grafted and non-grafted metallocene catalyzed polyolefins or polyamides, polyamide/ionomer blends, polyamide/nonionomer blends, polyphenylene ether/ionomer blends, and mixtures thereof. Examples of grafted and non-grafted metallocene catalyzed polyolefins or polyamides, polyamide/ionomer blends, polyamide/nonionomer blends are disclosed in co-pending U.S. patent application Ser. No. 10/138,304, filed May 6, 2002, entitled “Golf Ball Incorporating Grafted Metallocene Catalyzed Polymer Blends,” the entire disclosure of which is incorporated by reference herein.
Resilient Polymer—Reinforcing Polymer Blend
The intermediate layer may include a resilient polymer component, which is preferably used as the majority of polymer in the intermediate layer to impart resilience in the cured state, and a reinforcing polymer component as a blend.
Resilient polymers suitable for use in the intermediate layer include polybutadiene, polyisoprene, styrene-butadiene, styrene-propylene-diene rubber, ethylene-propylene-diene (EPDM) and mixtures thereof.
Other Additives
Additional materials may be included in the intermediate layer compositions outlined above. For example, catalysts, coloring agents, optical brighteners, crosslinking agents, whitening agents such as TiO₂and ZnO, UV absorbers, hindered amine light stabilizers, defoaming agents, processing aids, surfactants, and other conventional additives may be added to the intermediate layer compositions of the invention. In addition, antioxidants, stabilizers, softening agents, plasticizers, including internal and external plasticizers, impact modifiers, foaming agents, density-adjusting fillers, reinforcing materials, and compatibilizers may also be added to any of the intermediate layer compositions. One of ordinary skill in the art should be aware of the requisite amount for each type of additive to realize the benefits of that particular additive.
Odorant-Containing Golf Ball Cover(s)
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.
In one embodiment, at least one cover layer includes about 1 percent to about 99 percent of the odorant containing ionomer composition of the invention. In particular, the cover may include ionomeric materials, such as ionic copolymers of ethylene and an unsaturated monocarboxylic acid, which are available under the trademark SURLYN® of E. I. DuPont de Nemours & Co., of Wilmington, Del., or IOTEK® or ESCOR® of Exxon. These are copolymers or terpolymers of ethylene and methacrylic acid or acrylic acid totally or partially neutralized, i.e., from about 1 to about 100 percent, with salts of zinc, sodium, lithium, magnesium, potassium, calcium, manganese, nickel or the like.
In another embodiment, at least one cover layer includes about 1 percent to about 99 percent of the odorant containing polyurethane composition of the invention. In particular, the cover may be formed from the reaction product of an isocyanate and a polyol, which is cured with a hydroxy-terminated or amine-terminated curing agent. In one embodiment, the cover layer is formed with a composition including a saturated isocyanate, a saturated polyol, and a modified curative blend, which includes a curing agent and a freezing point depressing agent.
In addition, odorant containing polyurea compositions of the invention may be used to form at least one cover layer of a golf ball of the present invention. For example, the cover layer may be formed with the reaction product of an isocyanate and a polyamine, which is cured with a modified curative blend formed from a curing agent and a freezing point depressing agent. In one embodiment, the cover layer(s) may be formed from the reaction product of a saturated isocyanate and a saturated polyether amine, which is cured with a modifed curative blend preferably including an amine-terminated curing agent and an amine-terminated freezing point depressing agent.
The cover layer(s) may also be formed from composition blends as discussed above. For example, in one embodiment, at least one cover layer is formed from a blend of about 10 percent to about 90 percent polyurethane, preferably saturated, and about 90 percent to about 10 percent other polymers and/or other materials. In another embodiment, at least one cover layer is formed from a blend of about 10 percent to about 90 percent polyurea, preferably saturated, and about 90 percent to about 10 percent other polymers and/or other materials. In yet another embodiment, the cover compositions include from about 10 percent to about 75 percent polyurethane or polyurea and about 90 percent to about 25 percent other polymers and/or other materials, such as those listed above.
Golf ball covers may also be formed of one or more homopolymeric or copolymeric materials, such as:
(1) Vinyl resins, such as those formed by the polymerization of vinyl chloride, or by the copolymerization of vinyl chloride with vinyl acetate, acrylic esters or vinylidene chloride;
(2) Polyolefins, such as polyethylene, polypropylene, polybutylene and copolymers such as ethylene methylacrylate, ethylene ethylacrylate, ethylene vinyl acetate, ethylene methacrylic or ethylene acrylic acid or propylene acrylic acid, and copolymers and homopolymers produced using a single-site catalyst;
(3) Polyurethanes, thermoplastic or thermoset, saturated or unsaturated, aliphatic or aromatic, acid functionalized, such as those prepared from polyols or amines and diisocyanates or polyisocyanates and those disclosed in U.S. Pat. No. 5,334,673 and U.S. patent application Ser. No. 10/072,395;
(4) Polyureas, thermoplastic or thermoset, saturated or unsaturated, aliphatic or aromatic, acid functionalized, such as those disclosed in U.S. Pat. No. 5,484,870;
(5) 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), reinforced polyamides, and blends of polyamides with ionomers, polyethylene, ethylene copolymers, ethyl-propylene-non-conjugated diene terpolymer, and the like;
(6) Acrylic resins and blends of these resins with poly vinyl chloride, elastomers, and the like;
(7) Thermoplastics, such as urethanes; olefinic thermoplastic rubbers, such as blends of polyolefins with ethylene-propylene-non-conjug- ated diene terpolymer; block copolymers of styrene and butadiene, isoprene or ethylene-butylene rubber; or copoly(ether-amide), such as PEBAX, sold by ELF Atochem of Philadelphia, Pa.;
(8) Polyphenylene oxide resins or blends of polyphenylene oxide with high impact polystyrene as sold under the trademark NORYL by General Electric Company of Pittsfield, Mass.;
(9) Thermoplastic polyesters, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/glycol modified and elastomers sold under the trademarks HYTREL by E. I. DuPont de Nemours & Co. of Wilmington, Del., and LOMOD by General Electric Company of Pittsfield, Mass.;
(10) Ethylene, propylene, 1-butene or 1-hexane based homopolymers or copolymers including functional monomers, such as acrylic and methacrylic acid or fully or partially neutralized ionomer resins, and their blends, methyl acrylate, methyl methacrylate homopolymers and copolymers, low acid ionomers, high acid ionomers, and blends thereof;
(11) Blends and alloys, including polycarbonate with acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers, and the like, and polyvinyl chloride with acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomers; and
(12) Blends of thermoplastic rubbers with polyethylene, propylene, polyacetal, nylon, polyesters, cellulose esters, and the like.
The cover may also be at least partially formed from the polybutadiene reaction product discussed above with respect to the core.
As discussed elsewhere herein, the composition may be molded onto the golf ball in any known manner, such as by casting, compression molding, injection molding, reaction injection molding, or the like. One skilled in the art would appreciate that the molding method used may be determined at least partially by the properties of the composition. For example, casting may be preferred when the material is thermoset, whereas compression molding or injection molding may be preferred for thermoplastic compositions.
Golf Ball Construction
The odorant compositions of the present invention may be used with any type of ball construction. For example, the ball may have a one-piece, two-piece, or three-piece design, a double core, a double cover, an intermediate layer(s), a multi-layer core, and/or a multi-layer cover depending on the type of performance desired of the ball. As used herein, the term “multilayer” means at least two layers. For example, the compositions of the invention may be used in a core, intermediate layer, and/or cover of a golf ball, each of which may have a single layer or multiple layers.
As described above in the core section, a core may be a one-piece core or a multilayer core, both of which may be solid, semi-solid, hollow, fluid-filled, or powder-filled. A multilayer core is one that has an innermost component with an additional core layer or additional core layers disposed thereon. For example, FIG. 1 shows a golf ball 1 having a core 2 and an odorant containing cover 3. In one embodiment, the golf ball of FIG. 1 represents a core 2 of polybutadiene reaction material or other conventional materials and an odorant containing cover 3 including the odorant containing ionomer composition of the invention. In another embodiment, the golf ball of FIG. 1 represents a core 2 formed from polybutadiene reaction material and an odorant-containing cover 3 including the odorant-encapsulated polyurea and/or polyurethane compositions of the invention.
In addition, when the golf ball of the present invention includes an intermediate layer, such as an inner cover layer or outer core layer, i.e., any layer(s) disposed between the inner core and the outer cover of a golf ball, this layer may be incorporated, for example, with a single layer or a multilayer cover, with a one-piece core or a multilayer core, with both a single layer odorant-containing cover and core, or with both a multilayer odorant-containing cover and a multilayer core. As with the core, the intermediate layer may also include a plurality of layers. It will be appreciated that any number or type of intermediate layers may be used, as desired.
FIG. 2 illustrates a multilayer golf ball 11, including an odorant-containing cover 13, at least one intermediate layer 14, and a core 12. In one embodiment, the golf ball 11 of FIG. 2 may include a core 12 of polybutadiene reaction material, an intermediate layer 14, and an odorant-containing cover 13 formed of an odorant-encapsulated ionomeric resin, such as Surlyn®. However, in other embodiments, the odorant-containing cover 13 in the golf ball of FIG. 2 may be formed from an odorant-encapsulated polyurea and/or polyurethane, etc. composition of the invention. In addition, the golf ball 21 of FIG. 3 has a core 22 of polybutadiene reaction material or other conventional core materials, at least one ionomer intermediate layer 24, and odorant-containing cover 23 including the saturated odorant-encapsulated polyurethane or saturated odorant-encapsulated polyurea compositions of the invention.
The intermediate layer may also be a tensioned elastomeric material wound around a solid, semi-solid, hollow, fluid-filled, or powder-filled center. A wound layer may be described as a core layer or an intermediate layer for the purposes of the invention. As an example, the golf ball 31 of FIG. 4 may include a core layer 32, a tensioned elastomeric layer 34 wound thereon, and a cover layer 33. In particular, the golf ball 31 of FIG. 4 may have a core 32 made of a polybutadiene reaction product, an intermediate layer including a tensioned elastomeric material 34 and an odorant-containing cover 33 made from Surlyn®. The tensioned elastomeric material may be formed of any suitable material known to those of ordinary skill in the art. In yet another embodiment, the wound, liquid center golf ball 41 of FIG. 5 has a hollow spherical core shell 42 with its hollow interior filled with a liquid 43, a thread rubber layer including a tensioned elastomeric material 44 and an odorant-containing cover 45 formed from the polyurethane or polyurea compositions of the invention.
In one embodiment, the tensioned elastomeric material incorporates the polybutadiene reaction product discussed above. The tensioned elastomeric material may also be formed of conventional polyisoprene. In another embodiment, the polyurea composition of the invention is used to form the tensioned elastomeric material. In another embodiment, solvent spun polyether urea, as disclosed in U.S. Pat. No. 6,149,535, which is incorporated in its entirety by reference herein, is used to form the tensioned elastomeric material in an effort to achieve a smaller cross-sectional area with multiple strands.
In one embodiment, the tensioned elastomeric layer is a high tensile filament having a tensile modulus of about 10,000 kpsi or greater, as disclosed in co-pending U.S. patent application Ser. No. 09/842,829, filed Apr. 27, 2001, entitled “All Rubber Golf Ball with Hoop-Stress Layer,” the entire disclosure of which is incorporated by reference herein. In another embodiment, the tensioned elastomeric layer is coated with a binding material that will adhere to the core and itself when activated, causing the strands of the tensioned elastomeric layer to swell and increase the cross-sectional area of the layer by at least about 5 percent.
The intermediate layer may also be formed of a binding material and an interstitial material distributed in the binding material, wherein the effective material properties of the intermediate layer are uniquely different for applied forces normal to the surface of the ball from applied forces tangential to the surface of the ball. Examples of this type of intermediate layer are disclosed in U.S. patent application Ser. No. 10/028,826, filed Dec. 28, 2001, entitled, “Golf Ball with a Radially Oriented Transversely Isotropic Layer and Manufacture of Same,” the entire disclosure of which is incorporated by reference herein. In one embodiment of the present invention, the interstitial material may extend from the intermediate layer into the core. In an alternative embodiment, the interstitial material can also be embedded in the cover, or be in contact with the inner surface of the cover, or be embedded only in the cover.
At least one intermediate layer may also be a moisture barrier layer, such as the ones described in U.S. Pat. No. 5,820,488, which is incorporated by reference herein. Any suitable film-forming material having a lower water vapor transmission rate than the other layers between the core and the outer surface of the ball, i.e., cover, primer, and clear coat. Examples include, but are not limited to polyvinylidene chloride, vermiculite, and a polybutadiene reaction product with fluorine gas. In one embodiment, the moisture barrier layer has a water vapor transmission rate that is sufficiently low to reduce the loss of COR of the golf ball by at least 5 percent if the ball is stored at 100° F. and 70 percent relative humidity for six weeks as compared to the loss in COR of a golf ball that does not include the moisture barrier, has the same type of core and cover, and is stored under substantially identical conditions.
Prior to forming the cover layer, the inner ball, i.e., the core and any intermediate layers disposed thereon, may be surface treated to increase the adhesion between the outer surface of the inner ball and the cover. Examples of such surface treatment may include mechanically or chemically abrading the outer surface of the subassembly. Additionally, the inner ball may be subjected to corona discharge or plasma treatment prior to forming the cover around it. Other layers of the ball, e.g., the core, also may be surface treated. Examples of these and other surface treatment techniques can be found in U.S. Pat. No. 6,315,915, which is incorporated by reference in its entirety.
Likewise, the cover may include a plurality of layers, e.g., an inner cover layer disposed about a golf ball center and an outer cover layer formed thereon. For example, FIG. 6 may represent a golf ball 51 having a core 52, a thin inner cover layer 54, and a thin odorant-containing outer cover layer 53 disposed thereon. In particular, the core 51 may be formed of a polybutadiene reaction material, the inner cover layer 54 formed of an ionomer blend, and the outer cover layer 53 formed of the odorant-containing polyurethane and/or polyurea compositions of the invention. In addition, FIG. 7 may represent a golf ball 61 having a core 62, an outer core layer 65, a thin inner cover layer 64, and a thin odorant-containing outer cover layer 63 disposed thereon. In one embodiment, the core 62 and the outer core layer 65 are formed of the polybutadiene reaction material but differ in hardness, the inner cover layer 64 is formed of an ionomer blend, and the odorant-containing outer cover layer 63 is formed of the ionomeric resin, Surlyn®. Furthermore, the compositions of the invention may be used to form a golf ball 71, shown in FIG. 8, having a large core 72 and a thin odorant-containing outer cover layer 73. In one embodiment, the large core 72 is formed of a polybutadiene reaction material and the thin odorant-containing outer cover layer 73 is formed of the polyurethane or polyurea compositions of the invention, preferably acid functionalized, wherein the acid groups are at least partially neutralized.
While hardness gradients are typically used in a golf ball to achieve certain characteristics, the present invention also contemplates the compositions of the invention being used in a golf ball with multiple cover layers having essentially the same hardness, wherein at least one of the layers has been modified in some way to alter a property that affects the performance of the ball.
In one such embodiment, both cover layers can be formed of the same material and have essentially the same hardness, but the layers are designed to have different coefficient of friction values. In another embodiment, the compositions of the invention are used in a golf ball with multiple cover layers having essentially the same hardness, but different rheological properties under high deformation. Another aspect of this embodiment relates to a golf ball with multiple cover layers having essentially the same hardness, but different thicknesses to simulate a soft outer cover over hard inner cover ball.
In another aspect of this concept, the cover layers of a golf ball have essentially the same hardness, but different properties at high or low temperatures as compared to ambient temperatures. In particular, this aspect of the invention is directed to a golf ball having multiple cover layers wherein the odorant-containing outer cover layer composition has a lower flexural modulus at reduced temperatures than the odorant containing inner cover layer, while the layers retain the same hardness at ambient and reduced temperatures, which results in a simulated soft outer cover layer over a hard inner cover layer feel. Certain polyureas may have a much more stable flexural modulus at different temperatures than ionomer resins and thus, could be used to make an effectively “softer” layer at lower temperatures than at ambient or elevated temperatures.
Yet another aspect of this concept relates to an odorant golf ball with multiple cover layers having essentially the same hardness, but different properties under wet conditions as compared to dry conditions. Wettability of a golf ball layer may be affected by surface roughness, chemical heterogeneity, molecular orientation, swelling, and interfacial tensions, among others. Thus, non-destructive surface treatments of a golf ball layer may aid in increasing the hydrophilicity of a layer, while highly polishing or smoothing the surface of a golf ball layer may decrease wettability. U.S. Pat. Nos. 5,403,453 and 5,456,972 disclose methods of surface treating polymer materials to affect the wettability, the entire disclosures of which are incorporated by reference herein. In addition, plasma etching, corona treating, and flame treating may be useful surface treatments to alter the wettability to desired conditions. Wetting agents may also be added to the golf ball layer composition to modify the surface tension of the layer.
Methods of Forming Layers
The golf balls of the invention may be formed using a variety of application techniques such as compression molding, flip molding, injection molding, retractable pin injection molding, reaction injection molding (RIM), liquid injection molding (LIM), casting, vacuum forming, powder coating, flow coating, spin coating, dipping, spraying, and the like. Conventionally, compression molding and injection molding are applied to thermoplastic materials, whereas RIM, liquid injection molding, and casting are employed on thermoset materials. These and other manufacture methods are disclosed in U.S. Pat. Nos. 6,207,784, 5,484,870, and, the disclosures of which are incorporated herein by reference in their entirety.
Forming the Core Layer(s)
The cores of the invention may be formed by any suitable method known to those of ordinary skill in art. When the cores are formed from a thermoset material, compression molded is a particularly suitable method of forming the core. In a thermoplastic core embodiment, on the other hand, the cores may be injection molded.
For example, methods of converting the cis-isomer of the polybutadiene resilient polymer core component to the trans-isomer during a molding cycle are known to those of ordinary skill in the art. Suitable methods include single pass mixing (ingredients are added sequentially), multi-pass mixing, and the like. The crosslinking agent, and any other optional additives used to modify the characteristics of the golf ball center or additional layer(s), may similarly be combined by any type of mixing. Suitable mixing equipment is well known to those of ordinary skill in the art, and such equipment may include a Banbury mixer, a two-roll mill, or a twin screw extruder. Suitable mixing speeds and temperatures are well-known to those of ordinary skill in the art, or may be readily determined without undue experimentation. Furthermore, U.S. Pat. Nos. 6,180,040 and 6,180,722 disclose methods of preparing dual core golf balls. The disclosures of these patents are hereby incorporated by reference in their entirety.
Forming the Intermediate Layer(s)
The intermediate layer may also be formed from using any suitable method known to those of ordinary skill in the art. For example, an intermediate layer may be formed by blow molding and covered with a dimpled cover layer formed by injection molding, compression molding, casting, vacuum forming, powder coating, and the like.
Forming the Cover Layer(s)
The odorant-containing polymer compositions of the invention may be applied over an inner ball using a variety of application techniques such as spraying, compression molding, dipping, spin coating, or flow coating methods that are well known in the art. In one embodiment, the odorant-containing ionomer, polyurethane or polyurea compositions are used to form a cover over the core using a combination of casting and compression molding. Conventionally, compression molding and injection molding are applied to thermoplastic cover materials, whereas RIM, liquid injection molding, and casting are employed on thermoset cover materials.
U.S. Pat. No. 5,733,428, the entire disclosure of which is hereby incorporated by reference, discloses a useful method for forming a polyurethane cover on a golf ball core. Because this method relates to the use of both casting thermosetting and thermoplastic material as the golf ball cover, wherein the cover is formed around the core by mixing and introducing the material in mold halves, the polyurea compositions of the invention may also be used employing the same casting process.
For example, once either of the odorant-containing polyurethane or polyurea composition is mixed, an exothermic reaction commences and continues until the material is solidified around the core, and thereby physically encapsulating the odorant within the cover layer. It is important that the viscosity be measured over time, so that the subsequent steps of filling each mold half, introducing the core into one half and closing the mold can be properly timed for accomplishing centering of the core cover halves fusion and achieving overall uniformity. A suitable viscosity range of the curing mix for introducing cores into the mold halves is determined to be approximately between about 2,000 cP and about 30,000 cP, with the preferred range of about 8,000 cP to about 15,000 cP.
To start the cover formation, mixing of the prepolymer, curative and odorant is accomplished in a motorized mixer inside a mixing head by feeding through lines metered amounts of curative and prepolymer with odorant. Top preheated mold halves are filled and placed in fixture units using centering pins moving into apertures in each mold. At a later time, the cavity of a bottom mold half, or the cavities of a series of bottom mold halves, is filled with similar mixture amounts as used for the top mold halves. After the reacting materials have resided in top mold halves for about 40 to about 100 seconds, preferably for about 70 to about 80 seconds, a core is lowered at a controlled speed into the gelling reacting mixture.
A ball cup holds the ball core through reduced pressure (or partial vacuum). Upon location of the core in the halves of the mold after gelling for about 4 to about 12 seconds, the vacuum is released allowing the core to be released. In one embodiment, the vacuum is released allowing the core to be released after about 5 seconds to 10 seconds. The mold halves, with core and solidified cover half thereon, are removed from the centering fixture unit, inverted and mated with second mold halves which, at an appropriate time earlier, have had a selected quantity of reacting prepolymer and curing agent introduced therein to commence gelling.
Similarly, U.S. Pat. No. 5,006,297 and U.S. Pat. No. 5,334,673 both also disclose suitable molding techniques that may be utilized to apply the castable reactive liquids employed in the present invention. However, the method of the invention is not limited to the use of these techniques; other methods known to those skilled in the art may also be employed. For instance, other methods for holding the ball core may be utilized instead of using a partial vacuum.
Dimples
The use of various dimple patterns and profiles provides a relatively effective way to modify the aerodynamic characteristics of a golf ball. As such, the manner in which the dimples are arranged on the surface of the odorant-containing ball can be by any available method. For instance, the ball may have an icosahedron-based pattern, such as described in U.S. Pat. No. 4,560,168, or an octahedral-based dimple patterns as described in U.S. Pat. No. 4,960,281.
Golf Ball Post-Processing
The odorant golf balls of the present invention may be painted, coated, or surface treated for further benefits. For example, golf ball covers frequently contain a fluorescent material and/or a dye or pigment to achieve the desired color characteristics. An odorant golf ball of the invention may also be treated with a base resin paint composition, however, as disclosed in U.S. Patent Publication No. 2002/0,082,358, which includes a 7-triazinylamino-3-phenylcoumarin derivative as the fluorescent whitening agent to provide improved weather resistance and brightness. In certain embodiments the odorant can be incorporated into the golf ball in this manner.
In addition, trademarks or other indicia may be stamped, i.e., pad-printed, on the outer surface of the ball cover.
The golf balls of the invention may also be subjected to dye sublimation, wherein at least one golf ball component is subjected to at least one sublimating ink that migrates at a depth into the outer surface and forms an indicia. The at least one sublimating ink preferably includes at least one of an azo dye, a nitroarylamine dye, or an anthraquinone dye. U.S. patent application Ser. No. 10/012,538, filed Dec. 12, 2001, entitled, “Method of Forming Indicia on a Golf Ball,” the entire disclosure of which is incorporated by reference herein.
Protective and decorative coating materials, as well as methods of applying such materials to the surface of a golf ball cover are well known in the golf ball art. Generally, such coating materials comprise urethanes, urethane hybrids, epoxies, polyesters and acrylics. If desired, more than one coating layer can be used. The coating layer(s) may be applied by any suitable method known to those of ordinary skill in the art. In one embodiment, the coating layer(s) is applied to the golf ball cover by an in-mold coating process, such as described in U.S. Pat. No. 5,849,168, which is incorporated in its entirety by reference herein. In one embodiment the odorant of the present invention may be incorporated into the golf ball in this manner.
Golf Ball Properties
The properties such as hardness, modulus, core diameter, intermediate layer thickness and cover layer thickness of the odorant-containing golf balls of the present invention have been found to affect play characteristics such as spin, initial velocity and feel of the present golf balls. For example, the flexural and/or tensile modulus of the intermediate layer are believed to have an effect on the “feel” of the golf balls of the present invention.
Component Dimensions
Dimensions of golf ball components, i.e., thickness and diameter, may vary depending on the desired properties. For the purposes of the invention, any layer thickness may be employed. Non-limiting examples of the various embodiments outlined above are provided here with respect to layer dimensions.
The present invention relates to golf balls of any size. While USGA specifications limit the size of a competition golf ball to more than 1.68 inches in diameter, golf balls of any size can be used for leisure golf play. The preferred diameter of the golf balls is from about 1.68 inches to about 1.8 inches. The more preferred diameter is from about 1.68 inches to about 1.76 inches. A diameter of from about 1.68 inches to about 1.74 inches is most preferred, however diameters anywhere in the range of from 1.7 to about 1.95 inches can be used. Preferably, the overall diameter of the core and all intermediate layers is about 80 percent to about 98 percent of the overall diameter of the finished ball.
The core may have a diameter ranging from about 0.09 inches to about 1.65 inches. In one embodiment, the diameter of the core of the present invention is about 1.2 inches to about 1.630 inches. In another embodiment, the diameter of the core is about 1.3 inches to about 1.6 inches, preferably from about 1.39 inches to about 1.6 inches, and more preferably from about 1.5 inches to about 1.6 inches. In yet another embodiment, the core has a diameter of about 1.55 inches to about 1.65 inches.
The core of the golf ball may also be extremely large in relation to the rest of the ball. For example, in one embodiment, the core makes up about 90 percent to about 98 percent of the ball, preferably about 94 percent to about 96 percent of the ball. In this embodiment, the diameter of the core is preferably about 1.54 inches or greater, preferably about 1.55 inches or greater. In one embodiment, the core diameter is about 1.59 inches or greater. In another embodiment, the diameter of the core is about 1.64 inches or less.
When the core includes an inner core layer and an outer core layer, the inner core layer is preferably about 0.9 inches or greater and the outer core layer preferably has a thickness of about 0.1 inches or greater. In one embodiment, the inner core layer has a diameter from about 0.09 inches to about 1.2 inches and the outer core layer has a thickness from about 0.1 inches to about 0.8 inches. In yet another embodiment, the inner core layer diameter is from about 0.095 inches to about 1.1 inches and the outer core layer has a thickness of about 0.20 inches to about 0.03 inches.
The cover typically has a thickness to provide sufficient strength, good performance characteristics, and durability. In one embodiment, 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 range of thicknesses for an intermediate layer of a golf ball is large because of the vast possibilities when using an intermediate layer, i.e., as an outer core layer, an inner cover layer, a wound layer, a moisture/vapor barrier layer. When used in a golf ball of the invention, the intermediate layer, or inner cover layer, may have a thickness about 0.3 inches or less. In one embodiment, the thickness of the intermediate layer is from about 0.002 inches to about 0.1 inches, preferably about 0.01 inches or greater. In one embodiment, the thickness of the intermediate layer is about 0.09 inches or less, preferably about 0.06 inches or less. In another embodiment, the intermediate layer thickness is about 0.05 inches or less, more preferably about 0.01 inches to about 0.045 inches. In one embodiment, the intermediate layer, thickness is about 0.02 inches to about 0.04 inches. In another embodiment, the intermediate layer thickness is from about 0.025 inches to about 0.035 inches. In yet another embodiment, the thickness of the intermediate layer is about 0.035 inches thick. In still another embodiment, the inner cover layer is from about 0.03 inches to about 0.035 inches thick. Varying combinations of these ranges of thickness for the intermediate and outer cover layers may be used in combination with other embodiments 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 embodiment, the ratio of the thickness of the intermediate layer to the outer cover layer is about 1 or less. The core and intermediate layer(s) together form an inner ball preferably having a diameter of about 1.48 inches or greater for a 1.68-inch ball. In one embodiment, the inner ball of a 1.68-inch ball has a diameter of about 1.52 inches or greater. In another embodiment, the inner ball of a 1.68-inch ball has a diameter of about 1.66 inches or less. In yet another embodiment, a 1.72-inch (or more) ball has an inner ball diameter of about 1.50 inches or greater. In still another embodiment, the diameter of the inner ball for a 1.72-inch ball is about 1.70 inches or less.
Hardness
Most golf balls consist of layers having different hardnesses, e.g., hardness gradients, to achieve desired performance characteristics. The present invention contemplates odorant golf balls having hardness gradients between layers, as well as those odorant golf balls with layers having the same hardness.
It should be understood, especially to one of ordinary skill in the art, that there is a fundamental difference between “material hardness” and “hardness, as measured directly on a golf ball.” Material hardness is defined by the procedure set forth in ASTM-D2240 and generally involves measuring the hardness of a flat “slab” or “button” formed of the material of which the hardness is to be measured. Hardness, when measured directly on a golf ball (or other spherical surface) is a completely different measurement and, therefore, results in a different hardness value. This difference results from a number of factors including, but not limited to, ball construction (i.e., core type, number of core and/or cover layers, etc.), ball (or sphere) diameter, and the material composition of adjacent layers. It should also be understood that the two measurement techniques are not linearly related and, therefore, one hardness value cannot easily be correlated to the other.
Compression
Compression values are dependent on the diameter of the component being measured. The Atti compression of the core, or portion of the core, of golf balls prepared according to the invention is preferably less than about 80, more preferably less than about 75. As used herein, the terms “Atti compression” or “compression” are defined as the deflection of an object or material relative to the deflection of a calibrated spring, as measured with an Atti Compression Gauge, that is commercially available from Atti Engineering Corp. of Union City, N.J. Atti compression is typically used to measure the compression of a golf ball. In another embodiment, the core compression is from about 40 to about 80, preferably from about 50 to about 70. In yet another embodiment, the core compression is preferably below about 50, and more preferably below about 25.
Initial Velocity and COR
There is currently no USGA limit on the COR of a golf ball, but the initial velocity of the golf ball cannot exceed 250.±0.5 feet/second (ft/s). Thus, in one embodiment, the initial velocity is about 245 ft/s or greater and about 255 ft/s or greater. In another embodiment, the initial velocity is about 250 ft/s or greater. In one embodiment, the initial velocity is about 253 ft/s to about 254 ft/s. In yet another embodiment, the initial velocity is about 255 ft/s. While the current rules on initial velocity require that golf ball manufacturers stay within the limit, one of ordinary skill in the art would appreciate that the golf ball of the invention would readily convert into a golf ball with initial velocity outside of this range.
As a result, of the initial velocity limitation set forth by the USGA, the goal is to maximize COR without violating the 255 ft/s limit. In a one-piece solid golf ball, the COR will depend on a variety of characteristics of the ball, including its composition and hardness. For a given composition, COR will generally increase as hardness is increased. In a two-piece solid golf ball, e.g., a core and a cover, one of the purposes of the cover is to produce a gain in COR over that of the core. When the contribution of the core to high COR is substantial, a lesser contribution is required from the cover. Similarly, when the cover contributes substantially to high COR of the ball, a lesser contribution is needed from the core.
The present invention contemplates golf balls having CORs from about 0.7 to about 0.85. In one embodiment, the COR is about 0.75 or greater, preferably about 0.78 or greater. In another embodiment, the ball has a COR of about 0.8 or greater.
In addition, the inner ball preferably has a COR of about 0.780 or more. In one embodiment, the COR is about 0.790 or greater.
Flexural Modulus
Accordingly, it is preferable that the golf balls of the present invention 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 flexural moduli of the cover layer is preferably about 2,000 psi or greater, and more preferably about 5,000 psi or greater.
Specific Gravity
The specific gravity of a cover or intermediate layer including the odorant-containing polymer compositions of the invention is preferably at least about 0.7.
Adhesion Strength
The adhesion, or peel, strength of the polymer compositions of the invention is preferably about 5 lb_f/in or greater. In one embodiment, the adhesion strength is about 25 lb_f/in or less. For example, the adhesion strength is preferably about 10 lb_f/in or more and about 20 lb_f/in or less. In another embodiment, the adhesion strength is about 20 lb_f/in or greater, preferably about 24 lb_f/in or greater. In yet another embodiment, the adhesion strength is about 26 lb_f/in or greater. In still another embodiment, the adhesion strength is about 20 lb_f/in to about 30 lb_f/in.
Shear/Cut Resistance
The cut resistance of a golf ball cover may be determined using a shear test having a scale from 1 to 9 assessing damage and appearance. In one embodiment, the damage rank is preferably about 3 or less, more preferably about 2 or less. In another embodiment, the damage rank is about 1 or less. The appearance rank of a golf ball of the invention is preferably about 3 or less. In one embodiment, the appearance rank is about 2 or less, preferably about 1 or less.
Light Stability
As discussed above, the compositions of the invention may be inherently light stable, i.e., include no aromatic components The light stability of the cover may be quantified by the difference in yellowness index (*Y1), i.e., yellowness measured after a predetermined exposure time—yellowness before exposure. In one embodiment, the *Y1 is about 10 or less after 5 days (120 hours) of exposure, preferably about 6 or less after 5 days of exposure, and more preferably about 4 or less after 5 days of exposure. In one embodiment, the *Y1 is about 2 or less after 5 days of exposure, and more preferably about 1 or less after 5 days of exposure.

EXAMPLES

The following non-limiting prophetic examples are merely illustrative of the preferred embodiments of the present invention, and are not to be construed as limiting the invention, the scope of which is defined by the appended claims. Parts are by weight unless otherwise indicated.
Odorant-Encapsulated Surlyn® Golf Ball Cover
Table 1 illustrates the components used to make an odorant-containing Surlyn® golf ball cover composition.

TABLE 1

Odorant-Encapsulated Surlyn ® Golf Ball Cover

	Example 1	Example 2
Chemicals^†	Weight (g)	Weight (g)

Surlyn 8140*	301.2	300.5
Surlyn 6120**	200.8	200.1
Odorant****	25.1	25.1

*Surlyn 8140 is a copolymer comprising about 81% ethylene and about 19% methacrylic acid, wherein about 50% of the acid groups are neutralized with sodium ions
**Surlyn 6120 is a copolymer comprising about 81% ethylene and about 19% methacrylic acid, wherein about 50% of the acid groups are neutralized with magnesium ions.
****The odorant is Coke & Whiskey essential oil manufactured by Royal Aromatics, Inc.
^†The Surlyn blend material is compounded to a target specific gravity of about 1.125 using barium sulfate and titanium dioxide.

A golf ball if made having the cover formulated from the compositions above would possess the approximate physical properties and the ball performance results listed in Table 2.

TABLE 2

Odorant-Encapsulated Surlyn ® Golf Ball Cover

	Physical Properties	Example 1	Example 2

Cover Hardness (Shore D)	71	72
Weight (g)	45.20	45.58
C.O.R. 150 f/s	0.790	0.796
Shear Resistance	Good	Good
Odorant Detection Threshold	Yes	Yes

All patents and patent applications cited in the foregoing text are expressly incorporated herein by reference in their entirety. The invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed, because these embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

Claims

1. A golf ball comprising:

a) a polymer; and

b) an odorant present at a detection threshold and associated with said polymer.

2. The golf ball of claim 1 wherein the odorant is present at a super detection threshold.

3. The golf ball of claim 1 wherein the odorant is present at a recognition threshold.

4. The golf ball of claim 1 wherein the polymer is selected from the group consisting of transpolybutadiene, transpolyisoprene, polyurethane, polyurea, polyurethane/polyurea, ionomeric resin, castable thermoplastic polyurethanes, thermoset polyurethanes, cationic urethane ionomers, anionic urethane ionomers, urethane epoxies, polyurethane/polyurea ionomers, epoxy resins, polyethylenes, polyamides, polyesters, polycarbonates, polyacrylin, and mixtures thereof.

5. The golf ball of claim 1 wherein said polymer and associated odorant are painted, coated, or surface treated on to said golf ball.

6. The golf ball of claim 1 wherein said odorant is encapsulated within said polymer.

7. A golf ball comprising:

a) a polymer;

b) an odorant;

c) wherein said odorant is associated with said polymer; and

d) wherein said odorant is present at a detection threshold and said golf ball is therefore distinguishable from an otherwise identical second golf ball substantially free of said odorant.

8. The golf ball of claim 7 wherein the odorant is present at a super detection threshold.

9. The golf ball of claim 7 wherein the odorant is present at a recognition threshold.

10. The golf ball of claim 7 wherein the polymer is selected from the group consisting of transpolybutadiene, transpolyisoprene, polyurethane, polyurea, polyurethane/polyurea, ionomeric resin, castable thermoplastic polyurethanes, thermoset polyurethanes, cationic urethane ionomers, anionic urethane ionomers, urethane epoxies, polyurethane/polyurea ionomers, epoxy resins, polyethylenes, polyamides, polyesters, polycarbonates, polyacrylin, and mixtures thereof.

11. The golf ball of claim 10 wherein said polymer and associated odorant are painted, coated, or surface treated on to said golf ball.

12. The golf ball of claim 11 wherein said odorant is encapsulated within said polymer.

13. A method for manufacturing a golf ball having an odorant associated with a polymer comprising:

a) homogenizing the polymer or the pre-polymer components of said polymer with the odorant to form an odorant encapsulating polymer; and

b) molding the odorant encapsulating polymer into a golf ball or golf ball layer wherein the golf ball or golf ball layer is distinguishable from an otherwise identical second golf ball or second golf ball layer substantially free of said odorant.

14. The method of claim 13 wherein the odorant is present at a detection threshold.

15. The method of claim 13 wherein the odorant is present at a recognition threshold.

16. The method of claim 13 wherein the polymer of the odorant encapsulating polymer is selected from the group consisting of transpolybutadiene, transpolyisoprene, polyurethane, polyurea, polyurethane/polyurea, ionomeric resin, castable thermoplastic polyurethanes, thermoset polyurethanes, cationic urethane ionomers, anionic urethane ionomers, urethane epoxies, polyurethane/polyurea ionomers, epoxy resins, polyethylenes, polyamides, polyesters, polycarbonates, polyacrylin, and mixtures thereof.

17. The method of claim 13 wherein the molding step, c), comprises painting, coating, or surface treating the odorant encapsulating polymer on to said golf ball.

18. An improved golf ball comprising at least one polymer and at least one odorant wherein the improvement comprises incorporating said at least one odorant into said golf ball in an amount at or above the detection threshold of said at least one odorant.

19. The golf ball of claim 18 wherein the at least one odorant is present at a super detection threshold.

20. The golf ball of claim 18 wherein the at least one odorant is present at a recognition threshold.

21. The golf ball of claim 18 wherein said at least one odorant is incorporated into said golf ball by painting, coating or surface treating.

22. The golf ball of claim 18 wherein said odorant is encapsulated within said polymer.