JP2002536143A - Low spin golf ball with metal, ceramic or composite mantle or inner layer - Google Patents

Abstract

SUMMARY OF THE INVENTION The present invention is a golf ball (100) that includes a soft core (40) and a hard cover (10), wherein the golf ball (100) has reduced spin, for example, when struck during play. Fig. 3 shows a golf ball indicating speed. Golf ball (100) comprises one or more mantle layers (20, 50) comprising one or more metals, ceramics or composites. Golf ball (100) may also optionally include a polymeric spherical substrate (30) disposed within ball (100). The golf ball (100) of the present invention exhibits improved spin, feel and sound absorption. The golf ball (100) of the present invention may also have an increased diameter which helps to further reduce the spin rate. The resulting ball (100) exhibits reduced spin properties without sacrificing durability, playability and elasticity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] Field of the Invention The present invention relates to a golf ball, and more particularly to an improved golf ball having a low spin rate. Improvements in golf balls result from the combination of a hard cover and a relatively soft core made from a blend of one or more specific hard high stiffness ionomers. The combination of a soft core and a hard cover leads to an improved golf ball having a spin rate lower than expected, while maintaining properties such as resilience and durability required for repetitive play.

[0002] In a particularly preferred embodiment, the present invention relates to a golf ball that includes one or more mantle layers formed from a metal, ceramic, or composite material. The golf ball may optionally include a polymeric outer cover and / or an internal polymeric hollow spherical substrate.

[0003] In an additional embodiment of the present invention, the spin rate is further reduced by reducing the weight of the soft core and increasing the thickness of the cover while maintaining the core size. Larger, less dense finished balls exhibit lower spin rates after club impact than conventional balls.

[0004] background spin speed of the invention is an important golf ball characteristic for both experienced golfers and immature golfer. High spin rates allow more skilled golfers, such as PGA professional golfers and low handicap players, to maximize control of the golf ball. This is particularly beneficial for more skilled golfers when hitting an approach shot to the green. The ability to intentionally apply a "backspin", thereby stopping the ball quickly on the green and / or to apply a "sidespin" to draw or fade the ball, is substantially the golfer's control over the ball. To improve. Accordingly, more skilled golfers generally prefer golf balls that exhibit high spin rate characteristics.

[0005] However, high spin golf balls are not desirable for all golfers, especially for players with high handicap, who cannot intentionally control the spin of the ball. In this regard, less skilled golfers have two substantial obstacles that improve their game: slices and hooks. When the club head meets the ball, unintentional side spins are often imparted, thus causing the ball to be driven off its intended course. Side spin reduces control over the ball as well as the distance the ball will fly. As a result, undesirable strokes are added to the game.

As a result, while more skilled golfers want high spin golf balls, those that are more efficient for less skilled players are those that exhibit low spin characteristics. Low spin balls reduce slicing and hooks and increase roll distance for amateur golfers.

[0007] The inventor has a need to develop golf balls having reduced spin rates after club impact, while simultaneously maintaining the durability, playability and resilience properties required for repeated use. Worked on. The reduced spin rate golf ball of the present invention meets the rules and regulations set by the United States Golf Association (USGA).

Along this line, U.S.A. S. G. FIG. A defines five specific rules that golf balls must conform to. U. S. G. FIG. Rule A is that the ball diameter is 1.6
Stipulates that it must not be less than 80 inches. However, despite these limitations, there are no specific restrictions on the maximum allowable diameter of a golf ball. As a result, the golf ball can be as large as desired, as long as it is larger than 1.680 inches in diameter and meets four other specific requirements.

U. S. G. FIG. A. The rule is that the ball weighs no more than 1.620 ounces,
It also specifies that the initial velocity should not exceed 250 feet per second with a maximum tolerance of 2% or be up to 255 feet per second. Further, U. S. G. FIG. A. The rule is that the ball is U.S. S. G. FIG. A. It states that when hit by an outdoor driving machine under certain conditions, it must not fly over 280 yards with a 6% test allowance.

The inventor has determined that the combination of a relatively soft core (ie, a Riehl compressive force of about 75-115) and a hard cover (ie, a Shore D hardness of 65 or more) may result in an overall resulting two-piece golf ball. It has been determined that the spin speed is significantly reduced. The inventor has also learned that increasing the cover thickness, and thus the overall diameter of the resulting molded golf ball, further reduces spin speed.

The finest golf balls sold in the United States can generally be categorized into one of two types: two-piece balls or three-piece balls.
Spalding & Evenflo Companies, Inc. (The assignee of the present invention through its wholly owned subsidiary, Lisco Inc.)
A two-piece ball, exemplified by the ball sold under the FLITE trademark, is comprised of a solid polymer core and a separately formed outer cover. Ac
So-called three-piece balls, exemplified by balls sold under the trademark TITLEIST by the U.S. Company, are liquid (eg, TITLEIST TOUR384) or solid (eg, TITLEIST DT).
) Center, an elastic thread winding around the center and a cover.

[0012] Spalding's two-piece golf balls are made by molding a natural (balata) or synthetic (ie, a thermoplastic resin such as an ionomer resin) polymer cover composition around a preformed polybutadiene (rubber) core. . During the molding process, the desired dimple pattern is molded into the cover material. Prior to molding, to reduce the number of coating processes involved in golf ball finishing,
Color pigments or dyes and, in many cases, optical brighteners are added directly to the polymer cover composition, which is generally "off white" in color. By incorporating pigments and / or optical brighteners into the cover composition molded onto the golf ball core, this process is used to produce white or colored (especially orange, pink and yellow) golf balls. Eliminates the need for a supplemental colored painting process.

With respect to multilayer golf balls, Spalding is the world's most advanced two-piece golf ball maker. Spalding has different playing suitability (ie, spin speed, compression force, feeling, etc.), flight distance (initial speed, COR, etc.), durability (impact resistance) depending on the ball core, cover and coating material. More than 60 different types of two-piece balls that vary significantly in properties such as wear, cut and weather resistance) and appearance (ie whiteness, reflectance, yellowness, etc.) and ball surface morphology (ie dimple pattern) Has been manufactured. As a result, Spalding's two-piece golf balls provide both amateur and professional golfers with a variety of performance characteristics suitable for personal gaming.

For certain components of a golf ball, the nature of the cover may, in certain cases, determine the overall feel, spin (control), coefficient of restitution (C.C.) of the ball.
O. R. ) And can make a great contribution to the initial speed (for example, Mo
(See U.S. Pat. No. 3,819,768 to litor), the initial velocity of two-piece and three-piece balls is determined primarily by the coefficient of restitution of the core. The coefficient of restitution of the core of a wound (ie, three-piece) ball can be controlled within limits by adjusting the winding tension and the composition of the thread and center. For a two-piece ball, the coefficient of restitution of the core is a function of the properties of the elastomer composition from which it is made. The golf ball cover component provides the resulting ball with a compressive force (feel), spin rate (control), distance (COR) and durability (i.e., impact resistance, etc.). Especially affect. Various cover compositions have been developed by Spalding et al. To optimize the desired properties of the resulting golf ball.

Over the past two decades, improvements in cover and core material formulations and changes in dimple patterns have continued to improve the golf ball's flight distance with some variation. However, the finest golf balls must meet some other important design criteria. In order to compete successfully in today's golf ball market, golf balls must be resistant to cutting and must be well-finished. It must keep the line in putting and have good click and feel. In addition, the ball must exhibit spin and control characteristics that are necessarily affected by the end user's skill and experience. The skilled artisan has attempted to incorporate metal layers or metal filler particles into golf balls to alter the physical properties and performance of the golf ball. For example, U.S. Pat. No. 3,031,194 to Strayer relates to the use of a spherical inner metal layer that binds or adheres to a resilient inner component in a golf ball. This golf ball utilizes a liquid-filled core. U.S. Pat. No. 4,863,167 to Matsuki et al.
No. 1 describes a golf ball containing a gravity filler that can be formed from one or more metals disposed within a solid rubber-based core. U.S. Patent Nos. 4,886,275 and 4,995,613 to Walker,
A golf ball having a high density metal-containing core is disclosed. U.S. Pat. No. 4,943,055 to Corley is directed to a weighted warm-up ball having a metal center.

[0016] Prior artisans have also described golf balls having one or more inner layers formed of metal and featuring a hollow center. Davis describes in US Pat. No. 6,978,81.
No. 6 disclosed a golf ball including a ball steel shell having a hollow air-filled center. Kempshall is described in Nos. 704,748; 704,838;
A number of patents have been granted for golf balls having a metal inner layer and a hollow interior, such as U.S. Pat. In U.S. Pat. Nos. 1,182,604 and 1,182,605, Wadsworth describes a golf ball utilizing a concentric spherical shell formed from tempered steel. U.S. Pat. No. 1,568,514 to Lewis describes several embodiments of golf balls utilizing multiple steel shells, one disposed within the ball, with the ball having a hollow center. ing.

The incorporation of glass materials or vitreous materials into golf balls discloses the use of glass shells in US Patent No. 985,741 to Harvey. Sc
Another person skilled in the art, such as US Pat. No. 4,085,937 to Henk, describes incorporating glass microspheres into golf balls.

[0018] In contrast, the use of a polymeric material in an intermediate layer in a golf ball is more common than the use of, for example, glass or other vitreous materials. Kemps
Hall disclosed in U.S. Pat. Nos. 6,696,887 and 7,701,741 the use of a plastic inner coating. Kempshall further described in US Pat. Nos. 6,696,891 and 700,656 the incorporation of a fiber layer with a plastic layer. A number of subsequent approaches have been granted as patents, including the incorporation of a plastic inner layer into golf balls. U.S. Pat. No. 3,534,965 to Harrison disclosed a thermoplastic outer core layer. No. 4,431,193 to Nesbitt describes an internally synthesized polymer layer. U.S. Pat. No. 4,919, to Saito,
No. 434 describes an inner layer of thermoplastic material surrounding the core. Vie
U.S. Pat. No. 5,253,871 to Ilaz et al. discloses an interlayer of an amide block polyether thermoplastic. U.S. Pat. No. 5,480,155 to Molitor et al. Describes a golf ball having a thermoplastic inner shell layer. While satisfactory in many aspects, these patents
In particular, it does not show the use of reinforcing fibers or particles dispersed within the polymer inner layer.

[0019] Prior artisans have attempted to incorporate various particles and filler materials into golf ball cores and interlayers. US Patent No. 3,218,07 to Shakespeare
No. 5 discloses a core having glass fiber particles dispersed within an epoxy matrix. Similarly, US Pat. No. 3,671,477 to Nesbitt discloses an epoxy-based composition containing a wide range of fillers. Rubber interlayers containing various metal fillers are described by Matsuki et al. In U.S. Pat. No. 4,863,167. Similarly, U.S. Pat.
No. 048,838 describes a rubber inner layer having a filler material. More recently, U.S. Patent No. 5,273,286 to Sun discloses a golf ball with an inner layer of reinforced carbon graphite.

[0020] In view of the increasing demands of the current golf industry, there is a need for golf balls with further improved design and construction. Specifically, there is a need for a low spin golf ball that exhibits a high initial velocity or coefficient of restitution (COR), can travel a relatively long distance in regular play, and can be easily and inexpensively manufactured. .

As noted above, in an alternative embodiment, the spin rate of the ball is further reduced by increasing the cover thickness and / or reducing the weight and softness of the core. It is observed that increasing the thickness of the cover and / or the overall diameter of the resulting molded golf ball results in a greater decrease in spin rate.

With respect to the increased size of the ball, golf ball manufacturers over the years have generally adopted U.S. Pat. S. G. FIG. Golf balls have been manufactured at or near specifications for minimum size and maximum weight as defined by A. However, there have been exceptions, particularly in relation to the production of golf balls as teaching materials. For example, oversized, overweight (and thus unlicensed) golf balls have been sold for use as golf teaching materials. (See U.S. Patent No. 3,201,384 to Barber).

An oversized golf ball is also disclosed in New Zealand Patent No. 192,618 issued Jan. 1, 1980 to the assignee's predecessor. This patent discloses an oversized golf ball having a diameter between 1.700 and 1.730 inches and an oversized core made of an elastic material (i.e., about 1.58 diameter) to increase the coefficient of restitution.
5 to 1.595 inches). Further, the patent discloses that the ball includes a cover having a thickness less than the cover thickness of a conventional ball (ie, a cover thickness of about 0.050 inches versus 0.090 inches for a conventional two-piece ball). It discloses that it should be.

Further, a golf ball made by Spalding in 1915 is 1.
Note also that it had a diameter ranging from 630 inches to 1.710 inches. As the ball diameter increased, so did the weight of the ball.
These balls consisted of a cover made of balata / gap and a core made of solid rubber or liquid bag and wrapped with elastic yarn.

A golf ball known as LYNX JUMBO was also marketed by Lynx in October 1979. These balls are 1.76-1
. It had a diameter of 80 inches. LYNX JUMBO balls have met with little or no commercial success. The LYNX JUMBO ball was composed of a core made of a wound core and a cover made of natural or synthetic balata rubber.

However, none of these golf balls, despite their increased diameter, produce the enhanced spin reduction and overall sporting suitability, distance and durability properties of the present invention, and // U. S. G. FIG. A did not fall within the specified range. It is an object of the present invention to provide a U.S.A. device having improved low spin characteristics while maintaining the resilience and durability characteristics required for repetitive play. S
. G. FIG. The object of the present invention is to manufacture a golf ball conforming to the rule A.

[0027] These and other objects and features of the invention will be apparent from the following summary and description of the invention, and from the claims.

SUMMARY OF THE INVENTION The present invention is directed to an improved golf ball having a low spin rate upon impact of a club. Golf balls include a soft core and a hard cover. The hard cover may be of a size larger than a conventional diameter. A low spin rate allows the ball to fly a longer distance. In addition, low spin rates improve the control of immature golfers. This is because low spin rates reduce unwanted side spins that cause slices and hooks. The combination of a hard cover and a soft core provides a ball with an unexpectedly low spin rate while maintaining high elasticity and good durability.

In a first aspect, the present invention provides a low spin golf ball comprising a core comprising a core component and a spherical mantle containing the core component. The mantle includes a polymeric material and a reinforcing material dispersed in the polymeric material. The core has at least about 7
5 shows a Riehl compression force of 5. The golf ball further includes a polymeric outer cover disposed about the core. The cover may be formed from a range of different materials, but exhibit a Shore D hardness of at least about 65.

In another aspect, the present invention provides a low spin golf ball comprising a core comprising a core component and a vitreous mantle surrounding the core component. The core has a Riehl compression force of about 75 to about 115. The low spin golf ball further includes a polymer outer cover disposed about the mantle. The cover should be at least about 65
Shows the Shore D hardness.

In another aspect, the invention provides a low spin golf ball including a substantially spherical core having an inner core component and a mantle layer disposed about the core component. The mantle layer is formed of metal and the resulting core has a Riehl of about 75 to about 115.
e Indicates compression force. The golf ball further forms a polymeric outer cover around the core. The outer layer has a Shore D hardness of at least about 65.

By using a softer core and a hard cover, the entire finished ball of the present invention exhibits a much lower spin rate than a conventional ball of comparable size and weight. In addition, reduced spin is also produced by increasing the thickness of the cover and reducing the weight of the softened core.

Further applicability of the present invention will become apparent from the detailed description provided hereinafter. However, while the detailed description and specific examples illustrate preferred embodiments of the present invention, they are provided by way of illustration only, and those skilled in the art may make various changes and modifications within the spirit and scope of the invention. It should be understood that it will be clear.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to the development of golf balls having a low spin rate obtained by the combination of a relatively soft core and a hard cover. The low spin golf ball of the present invention is characterized by a relatively soft inner core or core component. That is, the core and any inner mantle layers together are at least about 75, preferably about 75
A Riehle compression force of ~ 160 is shown. Most preferably, the Riehl compression force of the core is from about 80 to about 90. The low spin golf ball of the present invention also features a relatively hard cover. That is, the cover has at least about 65 Shore D
Indicates hardness. After the impact by the club, the low spin rate contributes to a more straight shot if the ball is missed, better flight efficiency and reduced energy loss when impacting the ground, And increase the distance.

In addition, the overall ball diameter of the present invention is 1.680 inches. S. G
. By increasing the value of A above the minimum value, the spin speed is further reduced.
In this embodiment of the invention, the ball, even of a larger diameter, uses a core of substantially the same size as a standard golf ball, where the size difference is due to the additional cover of the ball. Provided by thickness. This larger low spin ball produces greater control and flight efficiency than the standard sized ball embodiment of the present invention.

In all of the preferred embodiments described herein, golf balls preferably use a solid core or core component. It is understood that low spin golf balls may alternatively feature a hollow interior or hollow core. In addition, all preferred embodiment golf balls comprise one or more mantle layers comprising one or more metals, ceramics or composites. Details of the material, form and structure of each component of the golf ball according to the preferred embodiment of the present invention are shown below.

FIG. 1 shows a first preferred embodiment of a low spin golf ball 100 according to the present invention.
Is shown. It will be appreciated that the reference figures are not necessarily to scale. The golf ball 100 of the first preferred embodiment includes an outermost polymer outer cover 10.
, One or more mantle layers 20, an innermost polymer hollow spherical substrate 30, and a core material 40. The golf ball 100 has a plurality of dimples 104 defined along the outer surface 102 of the golf ball 100.

FIG. 2 shows a second preferred embodiment low spin golf ball 200 according to the present invention.
Is shown. The golf ball 200 includes an outermost polymer outer cover 10,
It comprises one or more mantle layers 20 and a core material 40. The golf ball 200 of the second preferred embodiment has a plurality of dimples 204 defined along the outer surface 202 of the ball 200.

FIG. 3 shows a third preferred embodiment low spin golf ball 300 according to the present invention.
Is shown. The golf ball 300 includes one or more mantle layers 20 and a core material 40. This golf ball 300 has an outer surface 3
A plurality of dimples 304 defined along the line 02 are provided.

FIG. 4 shows a fourth preferred embodiment low spin golf ball 400 according to the present invention.
Is shown. The golf ball 400 comprises one or more mantle layers 20, an optional polymeric hollow spherical substrate 30, and a core material 40. The golf ball 400 has a plurality of dimples 404 defined along the outer surface 402 of the ball 400.

FIG. 5 shows a fifth preferred embodiment low spin golf ball 500 according to the present invention.
Is shown. The golf ball 500 of the fifth preferred embodiment includes one or more mantle layers 20, one or more mantle layers 50 made of a material different from the material of the mantle layer 20, the cover 10, and the core material 40. I have. This golf ball 50
At 0 there is a corresponding dimple shown in FIGS.

FIG. 6 shows a sixth preferred embodiment low spin golf ball 600 according to the present invention.
Is shown. The golf ball 600 is similar to the golf ball 500 but the mantle layers 20 and 50 are reversed.

All the preferred embodiments described above, ie, golf balls 100, 200, 300
, 400, 500 and 600, the golf ball uses a core or core component, such as core material 40. Golf balls of all preferred embodiments may instead feature a hollow interior or hollow core. In addition, all preferred embodiment golf balls comprise one or more mantle layers, such as 20 and 50, comprising one or more metals, ceramics or composites. And it is understood that all covers, for example cover 10, may be of single or multi-layer construction. Details of the material, form and structure of each component of the golf ball according to the preferred embodiment of the present invention are shown below.

Riehl compression measures a thousandth of an inch of deformation under a 200 lb. fixed static load (Riehl compression 47 corresponds to a deflection of 0.047 inches under load).

[0045] The PGA compression force is determined by the Ati Engineering, Union City
, New Jersey springs are measured by applying a force (ie, PGA80 =
Riehl80; PGA90 = Riehl70; PGA100 = Riehl
e60).

The coefficient of restitution (COR) is such that the resulting golf ball is transferred from an air cannon to a steel plate located 12 feet from the muzzle of the air cannon at a rate of 125 feet / second. Fire and measure. Next, the rebound speed is measured. Divide the bounce speed by the forward speed to get the coefficient of restitution.

The Shore D hardness is measured according to ASTM test D-2240.

Core In one aspect, the core used in the golf ball of the present invention has a core of about 1.54.
A specially prepared softened polybutadiene elastomer solid core having a conventional diameter of 0 to 1.545 inches. The core comprises at least one base elastomer selected from polybutadiene and a mixture of polybutadiene and another elastomer.
It is prepared from a composition comprising a metal salt of an unsaturated carboxylic acid (heterocrosslinking agent) and a radical initiator (heterocrosslinking agent). In addition, suitable and compatible modifying components include:
Examples include, but are not limited to, metal activators, fatty acids, fillers, polypropylene powder, and other additives.

Among the particular problems, only limited amounts of metal salts of unsaturated carboxylic acids are included in the core composition to create the desired degree of softness and weight of the core. In this regard, if a larger ball is desired as a whole, the composition of the core is such that
. S. G. FIG. A. Is adjusted so as to fall within the weight parameter indicated. The finished golf ball is U.S.A. S. G. FIG. A. Because the weight limit must also be met at 1.620 ounces, the core component of the large, thick covered ball is designed to be not only soft but also lightweight.

In such a situation, the specific gravity of the core is less than the specific gravity of the standard core because the larger ball must have the same weight as the standard ball. The core typically weighs about 36-37 g for standard size finished balls and about 33-34 g for large sized finished balls.

The core component is a softer molded core that still maintains the required properties of elasticity (COR), compressive force (hardness) and durability. The core has an overall PGA compression force in the range of about 0 to 85, preferably about 10 to about 70. Its Riehle compression force is about 75 or more, preferably in the range of about 75 to about 160, and the elasticity of the core is about 0.760 to 0.780.

[0052] The specially prepared core compositions of the present invention and the resulting shaped cores are manufactured using relatively conventional techniques. In this regard, the core composition of the present invention may be based on polybutadiene, a mixture of other elastomers and polybutadiene. Preferably, the base elastomer has a relatively high molecular weight. A wide range for the molecular weight of suitable base elastomers is about 50,0.
From 00 to about 500,000. A more preferred range for the molecular weight of the base elastomer is from about 100,000 to about 500,000. As base elastomer for the core composition, cis-polybutadiene is preferably used; otherwise, blends of other elastomers with cis-polybutadiene are also available. Most preferably, cis-polybutadiene having a weight average molecular weight from about 100,000 to about 500,000 is used. Along this line,
Flex BR-1220 under the trade name Shell Chemical Co.
. High cis-polybutadiene manufactured and sold by Houston, Texas, and under the designation "SKI35" by Muhlstein, H & Co. , Green
Polyisoprene, available from Nwich, Connecticut, is particularly suitable.

The unsaturated carboxylic acid component (heterocrosslinking agent) of the core composition typically comprises one or more selected carboxylic acids and zinc, magnesium, barium, calcium, lithium, sodium, potassium, cadmium, lead, tin. And reaction products of metal oxides or carbonates. Preferably, oxides of polyvalent metals such as zinc, magnesium and cadmium are used, and most preferably, the oxide is zinc oxide.

Examples of unsaturated carboxylic acids useful in the core compositions of the present invention include acrylic acid,
Methacrylic acid, itaconic acid, crotonic acid, sorbic acid and the like and mixtures thereof. Preferably, the acid component is either acrylic acid or methacrylic acid. Usually about 15 to 25 parts by weight, and preferably about 17 to about 21 parts by weight of the carboxylate,
For example, zinc diacrylate is included in the core composition. The unsaturated carboxylic acids and their metal salts are generally soluble or readily dispersible in the elastomer base.

The free radical initiator included in the core composition is any known polymerization initiator (heterocrosslinker) that decomposes during the cure cycle. As used herein, the term "free radical initiator" refers to a chemical that, when added to a mixture of an elastomer formulation and a metal salt of an unsaturated carboxylic acid, promotes crosslinking of the elastomer by the metal salt of the unsaturated carboxylic acid. It means a substance. The amount of the selected initiator present is determined only by the catalyst activity requirements as a polymerization initiator. Suitable initiators include peroxides, persulfates, azo compounds and hydrazides. Peroxides readily available on the market generally contain from about 0.1 to about 10 per 100 parts of elastomer.
It is suitably used in the present invention in an amount of 0, preferably about 0.3 to about 3.0 parts by weight.

Examples of peroxides suitable for the purposes of the present invention include dicumyl peroxide,
n-butyl 4,4′-bis (butylperoxy) valerate, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide and 2,5-di- (t-butylperoxy) -2,5 dimethylhexane, and the like, and mixtures thereof. The total amount of initiator used will vary depending on the particular end product desired and the particular initiator used.

Examples of such commercially available peroxides include Atochem, Lucidol
See Division, Buffalo, N.M. Y. Luperco 230 sold by
Or 231XL, and Akzo Chemie, America, Chicago
There is Trigonox 17/40 or 29/40 sold by o, III.
In this regard, Luperco 230XL and Trigonox 17/40 are composed of n-butyl 4,4-bis (butylperoxy) valerate,
erco 231 XL and Trigonox 29/40 are 1,1-bis (t
-Butylperoxy-3,3,5-trimethylcyclohexane. Luperco 231XL has a one-hour half-life of about 112 ° C.
The one-hour half-life of onox 29/40 is about 129 ° C.

The core composition of the present invention further includes, but is not limited to, metal oxides, fatty acids and diisocyanates and polypropylene powder resins, and any other suitable and compatible modifying agents. Components can be included. For example,
Dow Chemical Co. , Midland, Mich. Papi 94, a polymeric diisocyanate commonly available from E., Ltd., is an optional component in rubber compositions. It is in the range of about 0-5 parts by weight per 100 parts by weight of the rubber (phr) component and acts as a water scavenger. In addition, the addition of the polypropylene powder resin results in a core that is very hard (ie, exhibits low PGA compression), and thus softens the core to normal or sub-normal compression. It has been found that it is possible to reduce the amount of co-crosslinking agent used.

Further, since the polypropylene powder resin can be added to the core composition without increasing the weight at the time of curing the molded core, the addition of the polypropylene powder
Allows for the addition of higher specific gravity fillers, such as inorganic fillers. Since the crosslinker utilized in the polybutadiene core composition is expensive and / or higher specific gravity fillers are relatively inexpensive, the addition of the polypropylene powder resin maintains the weight and compressive force or While substantially reducing the cost of the golf ball core.

[0060] Polypropylene (C ₃ H ₅ ) powders suitable for use in the present invention have a concentration of about 0,1
Specific gravity of 90 g / cm ^3, having a 99% larger particle size distribution through about 4 to about 12 screens melt flow rate and 20 mesh. Examples of such a polypropylene powder resin include “A” with “6400p”, “7000p” and “7200p”.
moco Chemical Co. Inc., sold by Chicago III. Generally, in the present invention, the elastomer 10
Every 0 part contains from 0 to about 25 parts by weight of polypropylene powder.

Various active agents can be included in the compositions of the present invention. For example, zinc oxide and / or magnesium oxide are activators for polybutadiene. The activator may range from about 2 to about 30 parts by weight per 100 parts by weight of the rubber (phr) component.

Further, a filler reinforcing agent can be added to the core composition of the present invention. Specific core weight constraints are met when polypropylene is incorporated into the core composition because the specific gravity of the polypropylene powder is very low, and when compounded, the polypropylene powder creates a lighter molded core. Provided that, higher specific gravity fillers can be added in relatively large amounts. The incorporation of relatively large amounts of cheaper inorganic fillers of higher specific gravity, such as calcium carbonate, may provide additional benefits. Such fillers incorporated into the core composition may be, for example, generally less than about 30 mesh, and preferably less than about 10 mesh.
It must be smaller than 0 mesh US standard size and finely divided. The amount of additional filler included in the core composition is determined primarily by weight constraints, and is preferably included in an amount of about 10 to about 100 parts by weight per 100 parts of rubber. You.

[0063] Preferred fillers are relatively inexpensive and heavy, reduce the cost of the ball and reduce the ball weight to 1.620 oz. S. G. FIG. A. It helps to increase the weight limit closer. However, it is usually larger (i.e. diameter 1.
If a thicker cover composition is to be applied to the core to produce a ball (greater than 680 inches), the use of such fillers and modifiers is 1.6.
U.S. of 20 ounces S. G. FIG. A. Will be restricted to satisfy the maximum weight restriction condition. Examples of fillers are limestone, silica, mica barite, calcium carbonate or clay. Limestone is ground calcium carbonate / magnesium carbonate and is used because it is an inexpensive and heavy filler.

It is also possible to incorporate milled flash filler, which is preferably a center stock milled to 20 mesh from excess flash from compression molding. This can reduce costs and increase the hardness of the ball.

The composition may contain a fatty acid or a metal salt thereof that functions to improve moldability and processing. Generally, free fatty acids having about 10 to about 40 carbon atoms, preferably about 15 to about 20 carbon atoms, are used. Examples of suitable fatty acids include stearic and linoleic acids and mixtures thereof. An example of a suitable metal salt of a fatty acid is zinc stearate. When included in the core composition, the fatty acid component comprises about 1 to about 100 parts rubber (elastomer).
It is present in an amount of about 25, preferably about 2 to about 15 parts by weight.

It is preferred that the core composition include stearic acid as a fatty acid additive in an amount of about 2 to about 5 parts by weight per 100 parts of rubber.

A diisocyanate may optionally be included in the core composition.
If a diisocyanate is utilized, this is about 0% based on 100 parts rubber.
. 2 to about 5.0 parts by weight. Examples of suitable diisocyanates include 4,4'-diphenylmethane diisocyanate and other polyfunctional isocyanates known in the art.

In addition, dialkyltin difatty acids described in US Pat. No. 4,844,471, dispersants disclosed in US Pat. No. 4,838,556, and US Pat. The dithiocarbamates described in No. 582,884 can also be incorporated into the polybutadiene compositions of the present invention. The specific types and amounts of such additives are described in the aforementioned patents incorporated herein by reference.

The core composition of the present invention generally comprises 100 parts by weight of a base elastomer (or rubber) selected from polybutadiene and mixtures thereof with other elastomers, at least one metal salt of unsaturated carboxylic acid 15 to 25 parts by weight, and 1 to 10 parts by weight of a free radical initiator.

As mentioned above, particulate polypropylene resin, fatty acids and secondary additives such as pecan shell powder, ground burs (eg previously ground cores of substantially identical construction), barium sulfate, Additional suitable and compatible modifiers, such as zinc oxide, are added to the core composition to provide a finished molded ball (core, cover and coating) of 1.620 oz. S. G. FIG. It is also possible to adjust the weight of the ball as needed to bring it closer to the A weight limit.

In producing a solid golf ball core using the composition, for example, using a two-roll machine or a Banbury mixer, until the composition becomes homogeneous, usually for about 5 to about 20 minutes. The components can be intimately mixed over a period of time. The order of addition of the components is not critical. The preferred order of compounding is as follows.

Elastomers, polypropylene powder resin (if desired), fillers, zinc salts, metal oxides, in an internal mixer such as a Banbury mixer for about 7 minutes.
Fatty acids and metal dithiocarbamates (if desired), surfactants (if desired)
Then, tin difatty acid (if desired) is blended. As a result of shear during mixing, the temperature rises to about 200 ° F. Next, an initiator and a diisocyanate are added,
Mixing is continued until the temperature reaches about 220 ° F, at which point the batch is discharged onto a two-roll mill and mixed for about 1 minute to form a sheet.

The sheet is rolled into “pigs” and then placed in a Barwell preformer to produce slag. The slag is then subjected to compression molding at about 320 ° F. for about 14 minutes. After molding, the molded core is cooled and cooled for about 4 hours at room temperature or in cold water for about 1 hour. The formed core is subjected to a centerless grinding operation, whereby a thin layer of the formed core can be removed to produce a round core having a diameter of 1.540 to 1.545 inches. Alternatively, the core is used as molded without the grinding work required to achieve roundness.

The mixing is desirably performed in such a way that the composition does not reach the initial polymerization temperature during the compounding of the various components.

Typically, the curable components of the composition will be present at a temperature of from about 275 ° F. to about 350 ° F., preferably, and usually from about 290 ° F.
Heating the composition at an elevated temperature of about 325 ° F. will result in curing. The composition can be formed into a core structure by any one of a variety of molding techniques, for example, injection, compression or transfer molding. When the composition is cured by heating, the time required for heating is usually short, generally about 10 to about 20 minutes, depending on the particular curing agent used. Those skilled in the art of free radical curing agents for polymers will be familiar with adjusting the cure time and temperature required to achieve optimal results with any particular free radical agent. are doing.

After molding, the core is removed from the mold and its surface is optionally treated to facilitate its adhesion to the coating material. The surface treatment can be performed by any of several techniques known in the art, such as corona discharge, ozone treatment, sandblasting, and the like. Preferably, the surface treatment is performed by grinding finish with a grinding wheel.

The core has a thickness of about 0.070 to about 0.130 inches, and preferably about 0.
By being provided with at least one layer of cover material ranging from 0675 to about 0.1275 inches, it is converted to a golf ball.

In another aspect, the golf balls of the present invention may use wound cores known in the art. A description of the rolled core and its manufacture can be found in the following U.S. Patents:
No. 5,792,008, No. 5,755,628, No. 5,685,785,
No. 5,630,562, No. 5,609,532, No. 5,007,594,
Nos. 4,846,910 and 4,272,079, all of which are incorporated herein by reference.

Mantle The low-spin golf ball of the preferred embodiment of the present invention has a 1 positioned within, preferably adjacent to, the interior of the outer cover layer described in more detail herein.
Contains more than one mantle layer. The mantle layer is formed from a metal, ceramic or composite material. With respect to metals, a wide range of metals can be used for the mantle layer or shell, as described herein. Table 1 below shows suitable metals for use in the preferred embodiment golf balls.

[0080]

[Table 1]

[0081] Preferably, the metals used in the one or more mantle layers are steel, titanium, nickel, or alloys thereof. Usually, metals used for mantles are rigid, hard,
It is preferred to choose one having a relatively high density and a relatively high modulus.

The thickness of the metal mantle monolayer depends on the density of the metal used for that layer, or
If more than one metal mantle layer is used, it depends on the density of the metal in the other layers in the mantle. The thickness of the mantle typically ranges from about 0.001 inches to about 0.050 inches. The preferred thickness of the mantle is from about 0.005 inches to about 0.050 inches. The most preferred range is from about 0.005 inches to about 0.010 inches. Preferably, the thickness of the mantle is uniform and constant at all parts of the mantle.

As mentioned above, the thickness of the metal mantle depends on the density of the metal used for one or more mantle layers. Table 2 below lists typical densities of preferred metals for the mantle.

[0084]

[Table 2]

There are at least two ways to form the metal mantle utilized in the preferred embodiment golf balls. In a first embodiment, two metal part (half) shells are stamped from a sheet metal blank. The two metal half-shells are then welded or otherwise combined and heat treated to relieve stress. It is preferred to heat treat the resulting assembly since the resulting hollow spheres are usually annealed and softened, resulting in "oiling", i.e., deformation of the metal spheres after impact, as occurs during play.

In a second embodiment, the metal mantle is formed by electroplating over a thin, hollow polymer (polymer) sphere, which is described in further detail below. This polymer sphere corresponds to the optional hollow sphere substrate 30 previously described. There are several preferred techniques by which a metal mantle layer can be deposited on a metal substrate. In the first technology category, a conductive layer is formed or deposited on a polymer or metal sphere. Electroplating can be used to sufficiently deposit a metal layer after a conductive salt solution has been applied to the surface of a non-metallic substrate. Alternatively or additionally, a conductive metal surface can be formed on the substrate in question by flash vacuum metallization of a metal material such as aluminum. Such a surface is typically about 3 × 10 ⁻⁶ inches thick. Once deposited, electroplating can be utilized to form the metal layer in question. It is believed that vacuum metallization can be used to sufficiently deposit the desired metal layer. Yet another technique for forming a conductive metal base layer is chemical deposition. For example, copper, nickel, or silver can be easily deposited on non-metallic surfaces. Yet another technique for imparting conductivity to the surface of a non-metallic substrate is to mix an effective amount of conductive particles, such as carbon black, with the substrate prior to molding. Once the conductive surface has been formed, an electroplating process can be used to form the desired metal mantle layer.

Alternatively or additionally, one or more metal mantle layers can be formed on the spherical substrate using various thermal spray coating techniques. Thermal spray is a general term commonly used to refer to processes also known as deposition, including plasma arc spray, electric arc spray, and thermal spray processes for depositing metal and non-metal coatings. The coating can be sprayed from a rod or wire material or from a powder material.

A typical plasma arc spray device utilizes a plasma arc spray gun that excites one or more gases into a highly excited state, ie, a plasma, and then discharges the corresponding substrate, typically under high pressure. The power level, pressure and flow of the arc gas and the flow rates of the powder gas and the carrier gas are usually controllable.

The electric arc spray process utilizes metal, preferably in the form of a wire. This process differs from other thermal spray processes in that there is no external heat source, such as from a gas flame or electrically induced plasma. Heating and melting occur when electrically oppositely charged wires, including the spray material, are fed together such that a control arc occurs at the intersection.
The molten metal is injected and sent to the production substrate by the flow of compressed air or gas.

The flame spray process utilizes flammable gas as a heat source to melt the coating material. Flame spray guns are available for the spray material in rod, wire or powder form. Most flame spray guns are applicable for use with some gas combinations. Acetylene, propane, map gas, and flame spray gas
And oxygen-hydrogen are commonly used.

Another process or technique for depositing a metal mantle on the golf ball spherical substrate of the preferred embodiment is a chemical vapor deposition (CVD) process. In a CVD process, a reactant atmosphere is sent to a processing chamber, where the atmosphere decomposes at the surface of the substrate in question, releasing one material for absorption or accumulation by the workpiece or substrate. The second material is liberated in gaseous form and is removed from the processing chamber together with the excess atmosphere as a mixture called exhaust gas.

Reactant atmospheres typically used in CVD include chlorides, fluorides, bromides and iodides, as well as carbonyls, organometallics, hydrides and hydrocarbons. Hydrogen is often included as a reducing agent. The reactant atmosphere must be reasonably stable until it reaches the substrate where a reaction occurs with reasonably efficient conversion of the reactants. It may be necessary to heat the reactants to create a gaseous atmosphere. Several reactions for deposition occur at substrate temperatures below 200 ° C. Some organometallic compounds are 600
Deposit at a temperature of ° C. Most reactions and reaction products require temperatures above 800 ° C.

Common CVD coatings include nickel, tungsten, chromium, and titanium carbide. CVD nickel is generally separated from nickel carbonyl, Ni (CO) ₄ atmospheres. The properties of the deposited nickel are comparable to those of nickel sulfonate deposited by electrolysis. Tungsten can be deposited by thermal decomposition of tungsten carbonyl at 300-600 ° C or by hydrogen reduction of tungsten hexachloride at 700-900 ° C. The most convenient and most widely used reaction is the hydrogen reduction of tungsten hexafluoride. When depositing chromium on an existing metal layer, this deposition is carried out by a process similar to pack carburization, pack carbonization or by a dynamic flow CVD process. Titanium carbide coatings can be formed by hydrogen reduction of titanium fluoride in the presence of methane or some other hydrocarbon. The substrate temperature is usually 900 to 10 depending on the substrate.
It is in the range of 10 ° C.

[0094] Surface preparation of CVD coatings generally includes degreasing or grit spraying. Further, a CVD pre-coating may be performed. The deposition rate by a CVD reaction generally increases with temperature in a manner specific to each reaction. Deposition at the highest rates is preferred, but has limitations requiring compromised processing.

[0095] Vacuum coating is another class of processes for depositing metals and metal compounds from sources on substrates, such as the sphere substrates used in some preferred embodiment golf balls in a high vacuum environment. It is. Three main techniques are used to achieve such deposition: evaporation, ion plating and sputtering. In each technique, the transfer of steam is performed in an evacuated and controlled environment chamber, and typically at a residual air pressure of 1-10 ^-5 Pascal.

In the evaporation process, the vapor is generated by heating the source material to a temperature such that the vapor pressure significantly exceeds the ambient chamber pressure and produces sufficient vapor for the actual deposition. To coat the entire surface of a substrate, such as the internal spherical substrate utilized in some preferred embodiment golf balls, the surface must be rotated and moved over a vapor source. Deposits produced on a substrate placed at a low angle to the vapor source result in a fibrous, less bonded structure. The deposits resulting from excessive gas scattering are poorly adherent, and the highest quality deposits (deposited layers) that are amorphous and generally dark in color are formed on surfaces substantially perpendicular to the vapor flux. Such precipitates faithfully regenerate the substrate surface texture. Highly polished substrates produce glossy deposits, and the internal properties of the deposits are improved for given deposition conditions.

For most deposition rates, the source material needs to be heated to a certain temperature so that its vapor pressure is at least 1 Pascal or higher. The deposition rate for evaporating high volume vacuum plating is very high. Commercial coating equipment uses a large ingot material source and high power electron beam heating technology to produce 500,000 per minute.
Angstrom material thickness can be deposited.

As noted, the directivity of the deposited atoms from the vapor source generally requires that the substrate be organized in a vapor cloud. To obtain a particular film distribution on the substrate, the shape of the object, the location of the vapor source relative to the component surface, and the characteristics of the evaporation source can be controlled.

Regarding the evaporation source, most elemental metals, semiconductors, compounds and many alloys can be evaporated directly in vacuum. The simplest sources are resistance wires and metal foil. They are generally composed of refractory metals such as tungsten, molybdenum and titanium. The filaments perform a dual function of heating and holding the material for evaporation. Some elements can evaporate directly from the solid phase, so chromium, palladium, molybdenum,
It functions as a sublimation source for vanadium iron and silicon. Crucible sources constitute the largest application in mass production for evaporated refractory metals and compounds. Crucible materials are typically refractory metals, oxides and nitrides, and carbon. The heating can be performed by radiation from the second heat-resistant heating element, by radiation and conduction, and by radial frequency induction heating.

Several techniques are known for achieving evaporation of the evaporation source. Electron beam heating
Provide a flexible heating method that can concentrate heat on the evaporator. The portion of the evaporator closest to the container can be kept at a low temperature, so that interaction can be suppressed. Used 2
The two main electron guns are the linear focusing gun, which uses magnetic and electrostatic focusing, and the bending beam magnetic focusing gun. Another technique for achieving evaporation is the continuous feed fast evaporation method. 1
Fast evaporation of alloys forming a film thickness of 00-150 μm requires a large amount of evaporator electron beam heating source. An electron beam of 45 kW or more has a cross section of 150 × 4
Used to melt evaporants in water cooled copper hearths up to 00 mm.

With respect to the spherical shell substrate material on which one or more metal layers are formed in the golf balls of some preferred embodiments, the first requirement for the material to be coated is that the material be stable in vacuum It is. The material must not generate gas or vapor when exposed to metal vapor. The generation of gas is due to the release of gas absorbed on the surface, the release of gas trapped in the pores of the porous substrate, or the actual evaporation of components of the generating substrate material such as plasticizers used in plastics. Is done.

In addition to the methods described above, sputtering may be used to deposit one or more groups onto an internal hollow sphere substrate, such as substrate 30 used in golf balls of some preferred embodiments. it can. Sputtering is a method in which material is emitted from a solid or liquid surface for the exchange of moments associated with collisions between active particles.
The bombardment species is generally heavy inert gas ions. Argon is most commonly used. The ion source can be an ion beam or a plasma discharge that can strike the material.

In a plasma discharge sputter coating process, a source of coating material called a target is placed in a vacuum chamber that is evacuated and then back-loaded with a processing gas such as argon to a pressure sufficient to maintain a plasma discharge. A negative bias is then applied to the target to provide bombardment by positive ions from the plasma.

The sputter coating chamber is typically evacuated to a pressure in the range of 0.001 to 0.00001 Pascal before backfilling with argon to a pressure of 0.1 to 10 Pascal. The strength of the plasma discharge, and thus the achievable ion flux and sputtering rate, depends on the cathode electrode configuration and the effective use of the magnetic field to confine the plasma electrons. The deposition rate in sputtering depends on the target sputtering rate and the size of the apparatus. Also, the deposition rate depends on the processing gas pressure because high pressure limits the path of the sputter bundle to the substrate.

Ion plating can be used to form one or more metal mantle layers in the golf ball of the present invention. Ion plating is a general term applied to atomic film deposition processes in which the surface of the substrate and / or the deposited film are energetic particle bundles (usually high enough to change the interface region or film properties). , Gas ions). Such changes occur in film adhesion to the substrate, film morphology, film density, film stress, or surface coverage due to deposited film material.

The ion plating is usually performed in an inert gas discharge system similar to the discharge system used in sputtering deposition, except that the base is a sputtering cathode and the collision surface has a complicated shape. Basically, the ion plating apparatus consists of a vacuum chamber and a pumping device, typically a conventional vacuum deposition unit. It also has a membrane atomic vapor source and an inert gas inlet. In the case of a conductive sample, the workpiece is a high voltage electrode insulated from the surrounding equipment. In a more generalized situation, the work piece holder is a high voltage electrode, with a conductive or non-conductive material for plating attached to the holder. When the plating sample is attached to the high voltage electrode or holder, and the coating material is attached to the filament evaporation source, the apparatus is closed, and the pump is suctioned for 0.001 to 0.00.
The pressure is in the range of 01 Pascal. When the desired vacuum is achieved, the chamber is back-loaded with argon to a pressure of about 1-0.1 Pascal. Thereafter, a potential of -3 to -5 kilovolts is introduced to the high voltage electrode, i.e. the sample or sample holder, and to the ground of the device. A glow discharge occurs between the electrodes, which causes the sample to be bombarded by high energy argon ions generated by the discharge. This is similar to DC sputtering. Thereafter, the coating source is excited and the coating material is evaporated to a glow discharge.

Another class of materials that may be used to form one or more metal mantle layers is a nickel titanium alloy. These alloys are known for being superelastic and are about 50% (atomic) nickel and 50% titanium. Even under stress, superelastic nickel-titanium alloy can withstand strain deformation of up to 8%. When the stress is slowly released, the superelastic component returns to its original shape. Other shape memory alloys, including copper zinc aluminum alloy and copper aluminum nickel alloy, can also be used. Table 3 below shows various physical, mechanical, and transformation properties of these preferred shape memory alloys.

[0108]

[Table 3]

As noted, the aforementioned mantle may also include one or more metallic or vitreous materials. Preferred ceramics include silica, soda lime, lead silicate,
Examples include, but are not limited to, borosilicates, aluminoborosilicates, aluminosilicates, and various glass ceramics. In particular, a wide range of ceramic materials can be used for the ceramic mantle layer. Table 4 below shows suitable ceramic materials.

[0110]

[Table 4]

It is also preferred to use ceramic matrix composites, for example various ceramics reinforced with silicon carbide fibers or whiskers. Table 5 below shows
1 shows the characteristics of a typical silicon carbide reinforced ceramic.

[0112]

[Table 5]

It is also preferred to provide a ceramic matrix of aluminum oxide, Al ₂ O ₃ reinforced with silicon carbide fibers or whiskers. Typical properties of such a reinforced matrix are shown in Table 6 below.

[0114]

[Table 6]

A further preferred embodiment of the ceramic composite mantle is the use of multi-directional continuous ceramic fibers dispersed in a ceramic composite. Typical properties of such a support are shown in Table 7 below.

[0116]

[Table 7]

When forming a ceramic mantle, two approaches are mainly used. In a first preferred method, two half ceramic shells are formed. The half ceramic shells each use a stitch area along the bond interface area to improve the bond strength. The shells are then adhesively bonded together using one or more suitable adhesives known in the art.

In a second preferred method, the ceramic mantle layer is deposited over the core or hollow spherical substrate (both described in more detail below) by one of several deposition techniques. I have. When a composite matrix using fibers is formed, the fibers (if continuous) can be applied by wrapping single or multi-strands onto a core or hollow spherical substrate, either in a wet or dry state. When using the wetting method, one or several strands are passed through an epoxy resin bath before being wound to a particular diameter around the core of a golf ball. Either during or after winding, the wound core is compression molded using heat and medium pressure in a smooth spherical cavity. After removal of the molded article, a dimpled cover is molded around the wound center using compression, injection or transfer molding techniques. The ball is then trimmed, surface treated, stamped and clearcoated.

If the ceramic mantle layer is formed by a drying technique, the fibers can be impregnated with the same epoxy resin as in an immersion bath, for example when the wetting method described above is used, and shaped as described above.

If the fibers are discontinuous, the chopped fibers and liquid epoxy resin can be applied to the core by spraying the spinning core or spherical substrate simultaneously. Next, the wet wound center is cured by molding as described above.

When considering the use of discontinuous fibers, important factors are the ratio of length to diameter of the fiber, the shear strength between the fiber and the matrix, and the amount of fiber. All of these variables affect the overall strength of the compound mantle.

The thickness of the ceramic mantle typically ranges from about 0.001 inches to about 0.070 inches. Preferred thicknesses range from about 0.005 inches to about 0.040 inches. The most preferred range is from about 0.010 inches to about 0.020 inches.

As the thickness of the ceramic layer increases, weight and stiffness generally increase, and thus
The PGA compression force also increases. This is typically the limiting factor, the PGA compression force. Ball compression forces in excess of PGA 110 are generally undesirable. PGA4
PGA compression forces less than 0 are typically too soft. The overall ball compression can be adjusted by changing or adapting the core compression, i.e., a soft core requires a relatively thick mantle and a hard core requires a thin mantle within said thickness.

[0124] As noted, the mantle may include a ceramic composite. In addition to dispersing the glass and / or carbon fibers in various matrix materials, such as ceramic, epoxy, thermoset and thermoplastic materials, other preferred fibers include boron carbide. The use of aramid (Kevlar), cotton, flax, jute, hemp and silk fibers is also contemplated. Most preferred non-ceramic fibers are carbon, glass and aramid fibers.

Typical properties of fibers suitable for forming the reinforcement material are shown in Tables 8 and 9 below.

[0126]

[Table 8]

[0127]

[Table 9]

One or more of these fibers can be used in ceramic, epoxy, thermoset and / or thermoplastic matrix materials when forming the mantle layer. Suitable epoxy, thermoset and / or thermoplastic materials are shown below.

The composite material may also be formed from various epoxy molding materials including, for example, carbon or glass fibers dispersed in an epoxy matrix. Table 10 below shows:
It shows the typical properties of such epoxy molding compositions.

[0130]

[Table 10]

The composite mantle layer may also be formed from a composite of glass fibers dispersed within a thermoset matrix, such as a polyimide material, silicone, vinyl ester, polyester or melamine. is there. Table 11 below shows typical properties of such composite thermosetting molding materials.

[0132]

[Table 11]

[0133] The composite mantle layer of the preferred embodiment may also be formed from various nylon molding materials including glass or carbon fibers dispersed within a nylon matrix. Table 12 below shows typical properties of such a composite nylon mantle.

[0134]

[Table 12]

[0135] The composite mantle layer may also include, for example, acrylonitrile-butadiene-styrene (
ABS), polystyrene (PS), styrene-acrylonitrile (SAN) or a styrenic molding material comprising glass or carbon fibers dispersed in a styrene material including styrene-maleic anhydride (SMA). . Table 13 below shows typical properties of such materials.

[0136]

[Table 13]

Preferred composite mantles also include reinforced thermoplastic materials such as those comprising glass or carbon fibers dispersed within, for example, acetal copolymer (AC), polycarbonate (PC) and / or liquid crystal polymer (LCP). May be formed from Table 14 below
Shows typical properties of such materials.

[0138]

[Table 14]

The composite material of the preferred embodiment is also formed from one or more thermoplastic molding materials, such as high density polyethylene (HDPE), polypropylene (PP), polybutylene terephthalate (PBT) or polyethylene terephthalate (PET). And may include mica or glass fibers. Table 15 below shows typical properties of such materials.

[0140]

[Table 15]

[0141] The composite mantle layer of the preferred embodiment may also include various polyphenylenes, such as polyphenylene ether (PP) in which fibers of glass or graphite are dispersed.
E), polyphenylene oxide (PPO) or polyphenylene sulfide (PP
It may be formed from a thermoplastic material containing S). Typical properties of such materials are shown in Table 16 below.

[0142]

[Table 16]

Further preferred composite materials are various polyaryl thermoplastic materials reinforced with glass fibers or carbon fibers. Table 17 below shows typical properties of such composites. It should be noted that PAS is a polyarylsulfone, PSF is a polysulfone, and PES is a polyethersulfone.

[0144]

[Table 17]

Other thermoplastic materials may be used for composite mantles that include reinforced polyetherimide (PEI) or polyetheretherketone (PEEK) reinforced by glass or carbon fiber.

[0146]

[Table 18]

The thickness of the composite polymeric material base mantle is generally from about 0.001 inches to about 0 inches.
. It is in the range of 100 inches. The most preferred range is from about 0.010 inches to about 0
. 030 inches.

When forming a mantle from a polymeric material, two approaches are primarily used. First
In the preferred method, two half rigid polymer shells are formed. The half shells each use a stitching region along the bond interface region to improve the bond strength. The shells are then adhesively bonded together using one or more suitable adhesives known in the art.

In a second preferred method, the polymer mantle layer is coated over a core or hollow spherical substrate (both are described in more detail herein) by one of several deposition techniques. Is attached. When a composite matrix using fibers is formed, the fibers (if continuous) can be applied by wrapping single or multi-strands onto a core or hollow spherical substrate, either in a wet or dry state. When using the wetting method, one or several strands are passed through an epoxy or suitable resin bath before being wound to a specific diameter around the core of the golf ball. Either during or after winding, the wound core is compression molded using heat and medium pressure in a smooth spherical cavity. After removal of the molded article, a dimpled cover is molded around the wound center using compression, injection or transfer molding techniques. The ball is then trimmed, surface treated, stamped and clearcoated.

If the polymer mantle layer is formed by a drying technique, the fibers can be impregnated with the same epoxy resin as in an immersion bath, for example when the above-mentioned wetting method is used, and shaped as described above.

If the fibers are discontinuous, the chopped fibers and liquid resin can be applied to the rotating core or the spherical substrate by spraying them simultaneously on the core. Next, the wet wound center is cured by molding as described above.

When considering the use of discontinuous fibers, important factors are the ratio of length to diameter of the fiber, the shear strength between the fiber and the matrix, and the amount of fiber. All of these variables affect the overall strength of the compound mantle.

In preparing the golf balls of the preferred embodiment, the polymeric outer cover layer (if used) may be molded (eg, by injection molding or compression molding) around the mantle.

Polymer Hollow Spheres As described in other aspects, the present invention also provides golf balls that optionally include polymer hollow spheres adjacent to a mantle. The sphere may be located inside the mantle, or outside the mantle, relative to the center of the ball. The sphere may also be located adjacent to the mantle, or may have one or more layers of other materials that separate the sphere from the mantle. Polymer hollow spheres can be formed from almost any relatively strong plastic material. The thickness of the hollow sphere ranges from about 0.005 inches to about 0.010 inches. The inner hollow sphere is joined by techniques known to spin bonding, solvent welding or other plastic processing techniques.
It can be formed using half shells. Alternatively, the hollow spheres may be formed by blow molding.

A wide range of polymeric materials can be used for forming polymeric hollow spheres. It is generally preferred to use a thermoplastic material as the material of the shell. Typically, such materials should exhibit, inter alia, good flow, moderate stiffness, high abrasion resistance, high tear strength, high elasticity and good release.

Synthetic polymer materials that may be used in the present invention include homopolymer and copolymer materials, including: (1) polymerization of vinyl chloride, or vinyl chloride and acetic acid. Vinyl resins formed by copolymerization with vinyl, acrylic acid esters or vinylidene chloride; (2) polyolefins such as polyethylene, polypropylene, polybutylene and copolymers such as polyethylene methyl acrylate;
Polyethylene ethyl acrylate, polyethylene vinyl acetate, polyethylene methacrylate or polyethylene acrylate or polypropylene acrylate or a terpolymer prepared from these and acrylates and their metal ionomers, grafted with acrylic acid or anhydride-modified polyolefin (3) polyurethanes, such as those prepared from polyols and diisocyanates or polyisocyanates; (4) polyamides, such as poly (hexamethylene adipamide) and those prepared from diamines and dibasic acids ,
Also prepared from amino acids, such as poly (caprolactam) and blends of polyamide with Surlyn, polyethylene, ethylene copolymer, EDPA, etc .; (5) acrylic resins and blends of this resin with polyvinyl chloride, elastomers, etc .; (6) thermoplastic rubber, for example, urethane, olefinic thermoplastic rubber,
For example, a blend of polyolefin and EPDM, a block copolymer of styrene and butadiene or isoprene or ethylene-butylene rubber, a polyether block amide; (7) a polyphenylene oxide resin or a blend of polyphenylene oxide and high impact polystyrene; (8) Thermoplastic polyester such as P
ET, PBT, PETG and E.I. I. DuPont De Nemours & C
ompany of Wilmington, Del. Trademark HYTREL by
(9) Polycarbonates and ABS, PBT, P
Blends and alloys containing ET, SMA, PE elastomers and the like and PVC and ABS or EVA or other elastomers; (10) blends of thermoplastic rubbers with polyethylene, polypropylene, polyacetal, nylon, polyester, cellulose ester and the like.

It is also within the scope of the present invention to add materials to the polymeric spherical substrate composition of the present invention that do not affect the fundamental new properties of the composition. Such materials include antioxidants, antistatic agents and stabilizers.

Cover The cover is preferably made of a rigid, high-rigidity ionomer resin, most preferably 1%.
It consists of a highly acidic ionomer resin or a blend thereof neutralized with metal cations containing more than 6% by weight of carboxylic acids. Cover is over 65 Shore D
Has hardness. The cover may be in the form of a single layer, and multiple cover layers are also available.

With respect to the ionomer cover composition of the present invention, an ionomer resin is a polymer containing interchain ionic bonds. As a result of its toughness, durability, and flight characteristics
And more recently, Exxon Corporation (US Pat. No. 4,91,91).
1,451) -Resin is the material of choice for golf ball cover construction compared to traditional "balata" (natural or synthetic trans-polyisoprene) rubber.

The ionomer resin is generally an ionic copolymer of an olefin such as ethylene and a metal salt of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or maleic acid. In some cases, additional softening comonomer copolymers, such as acrylates, may be included to form terpolymers. The pendant ionic groups in the ionomer resin interact to form ion-rich aggregates contained within the non-polar polymer matrix. Metal ions such as sodium, zinc, magnesium, lithium, potassium, calcium, etc. are used to neutralize some of the acidic groups in the copolymer, resulting in an enhancement for the structure of golf balls compared to balata Thermoplastic elastomers exhibiting improved properties, such as improved durability.

[0161] The ionomer resin utilized to produce the cover composition is obtained by copolymerizing an olefin and a carboxylic acid to produce a copolymer having acidic units randomly distributed along the polymer chain. Canadian Patent 672, from which ionomers are formed
Known procedures, such as those described in U.S. Pat. No. 3,421,766 or British Patent No. 963,380, wherein the neutralization is performed according to the procedures disclosed in U.S. Pat. Can be prescribed according to Broadly, the ionic copolymer generally comprises one or more α-olefins and from about 9 to about 20.
Contains a weight percent of an α, β-ethylenically unsaturated mono- or dicarboxylic acid, a basic copolymer neutralized to the desired extent with metal ions.

At least about 20% of the carboxylic acid groups of the copolymer are (sodium, potassium,
Neutralized by metal ions (such as zinc, calcium, magnesium, etc.)
Exists in the ionic state. Suitable olefins for use in preparing ionomer resins include ethylene, propylene, butene-1, hexene-1, and the like. Unsaturated carboxylic acids include acrylic, methacrylic, ethacrylic, α-chloroacrylic, croton, maleic, fumaric, itaconic acid and the like. Golfbo
Furthermore, more than one type of ionomer resin can be included in the cover composition to produce the desired properties of the resulting golf ball.

A cover composition that can be used in making the golf balls of the present invention is disclosed in co-pending US patent application Ser. No. 07 / 07,071, filed Oct. 15, 1991, both of which are incorporated herein by reference. No./776,803 and No. 07 filed on Jun. 19, 1992
/ 901,660, but is not limited thereto. In summary, the cover material preferably comprises a relatively high amount of acid (i.e., greater than 16 weight percent, preferably about 17 to about 25 weight percent, and more preferably about 18.5 to about 21.5 weight percent acid). ) And is at least partially neutralized with metal ions (eg, sodium, zinc, potassium, calcium, magnesium, etc.) and is composed of a tough, tough ionomer resin.
High acid resins are compounded and melt processed to produce compositions that exhibit enhanced hardness and coefficient of restitution values compared to low acid ionomers or blends of low acid ionomer resins containing up to 16 weight percent acid.

A preferred cover composition is a specific formulation of two or more highly acidic ionomers with other cover additives that do not exhibit processing, sporting suitability, distance and / or durability limitations demonstrated by the prior art. Made from things. However, as more specifically indicated below, the cover composition may be comprised of one or more low acid ionomers, as long as the molded cover exhibits a hardness of 65 or more on the Shore D scale.

[0165] The cover has a Shore D hardness of 65 or more. The composition is hard, rigid,
Preferably high acid ionomers, such as E. coli. I. DuPont de Nemour
by s & Company Instead, the cover may include any ionomer, alone or in combination with other ionomers, that produces a molded cover having a Shore D hardness of at least 65.
These include lithium ionomers or blends of ionomers with harder nonionic polymers such as nylon, polyphenylene oxide and other compatible thermoplastics. As briefly described above, examples of cover compositions that may be used are described in detail in US Pat. No. 5,688,869, which is incorporated herein by reference. It should be understood that the cover compositions are not in any way limited to those compositions described in the aforementioned co-pending applications. Highly acidic ionomers suitable for use in the present invention are the metals of the reaction product of an olefin having about 2 to 8 carbon atoms and an unsaturated monocarboxylic acid having about 3 to 8 carbon atoms, i.e., sodium. Ionic copolymers that are salts of zinc, magnesium, and the like. Preferably, the ionomer resin is a copolymer of ethylene and either acrylic acid or methacrylic acid. Under some circumstances, additional comonomers such as acrylates (i.e., iso- or n-butyl acrylate, etc.)
It can be included to produce a softer terpolymer. The carboxylic acid groups of the copolymer are partially neutralized by metal ions (i.e., about 10-75%
, Preferably 30-70%). Each of the highly acidic ionomer resins included in the cover composition of the present invention comprises greater than about 16% by weight, preferably from about 17 to 25% by weight, more preferably from about 18.5 to about 21.5% by weight. Contains carboxylic acids.

The cover composition preferably includes a high acid ionomer resin, and while the scope of the patent covers all known high acid ionomer resins falling within the parameters set forth above,
At present, only a relatively limited number of these highly acidic ionomer resins are available. In this regard, E.I. I. Dupont de Nemours & C
"Surlyn" The high acid ionomer resins available under the trade name are examples of available high acid ionomer resins that can be utilized in the present invention.

[0167] Because of the salt of (ethylene methacrylic acid) such as zinc, sodium and magnesium, there is a clear difference in properties.

Highly acidic and methacrylic acid known to be suitable for use according to the invention
ON). According to DuPont, all of these ionomers are about 18.
Contains 5 to about 21.5% by weight methacrylic acid.

[0169] In a number of different grades (ie, AD-8422-2, AD-84
22-3, AD-8422-5, etc.) are commercially available from DuPont. Du
Pont (Referred to as "hard" ionomer in patent 4,884,814) When provided, they provide the following general properties:

[0170]

[Table 19]

[0171] Tensile yield, lower elongation, slightly higher Shore D hardness and much higher bending trajectory
Contains crylic acid and is 59% neutralized with sodium.

[0172] Surlyn SEP-503-1 and SEP when compared to highly acidic ionomers
The -503-2 ionomer can be defined as follows.

[0173]

[Table 20]

[0174] (18.5 to 21.5% by weight) of a methacrylic acid copolymer I have.

Examples of highly acidic, acrylic acid based ionomers suitable for use in the present invention
This is an ethylene-acrylic acid copolymer neutralized with ethylene. According to Exxon, I
Oteks 959 and 960 contain about 19.0 to about 21.0% by weight acrylic acid, with about 30 to about 70 percent of the acidic groups being neutralized with sodium and zinc ions, respectively. The physical properties of these highly acidic, acrylic acid based ionomers are as shown below.

[0176]

[Table 21]

In addition, the inventors have developed a number of new highly acidic ionomers that have been neutralized to varying degrees by several different types of metal cations, such as with manganese, lithium, potassium, calcium, and nickel cations, resulting in the current golf In addition to the sodium, zinc and magnesium highly acidic ionomers or ionomer blends, several new highly acidic ionomers and / or highly acidic ionomer blends are available for the manufacture of ball covers. It has been discovered that these new cation neutralized high acid ionomer formulations produce cover compositions that exhibit high hardness and resilience due to the synergistic effects that occur during processing. As a result, the compounding of a recently formed high acid ionomer resin neutralized with metal cations results in a higher C.I. than that produced by currently marketed low acid ionomer covers. O. R. A golf ball having a substantially harder cover with

More specifically, by neutralizing the highly acidic copolymers of alpha, beta unsaturated carboxylic acids and alpha olefins to varying degrees with a variety of different metal cation salts, the inventors A highly acidic ionomer resin neutralized with the new metal cation was produced. This discovery is the subject of U.S. Patent Application No. 901 680, which is incorporated herein by reference. To the desired degree (
That is, about 10% to 90%) a metal cation salt capable of ionizing or neutralizing the copolymer and a highly acidic copolymer (i.e., more than 16% by weight, preferably about 17 to
Reacting about 25 weight percent, and more preferably about 20 weight percent acid) to obtain highly acidic ionomer resins neutralized with a number of new metal cations. It's been found.

The base copolymer is made up of greater than 16% by weight of alpha, beta unsaturated carboxylic acids and alpha olefins. In some cases, a softening comonomer can be included in the copolymer. Generally, the alpha-olefin will have from 2 to 10 carbon atoms, preferably ethylene, and the unsaturated carboxylic acid will have from about 3 to 8 carbon atoms.
Carboxylic acid with two carbons. Examples of such acids include acrylic acid, methacrylic acid, methacrylic acid, chloroacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, with acrylic acid being preferred.

In the present invention, the softening comonomer which may be optionally contained includes an acid of 2 to 10
Vinyl ester of aliphatic carboxylic acid having 1 to 10 carbon atoms, alkyl group having 1 to 10
Can be selected from the group consisting of vinyl ethers containing 10 carbon atoms and alkyl acrylates or methacrylates in which the alkyl group contains 1 to 10 carbon atoms. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like.

As a result, examples of a number of copolymers suitable for use to produce the highly acidic ionomers included in the present invention include, without limitation, ethylene / acrylic acid copolymers, Ethylene / methacrylic acid copolymer, ethylene / itaconic acid copolymer,
Highly acidic embodiments such as ethylene / maleic acid copolymer, ethylene / methacrylic acid / vinyl acetate copolymer, ethylene / acrylic acid / vinyl alcohol copolymer are included. The base copolymer generally contains more than 16% by weight of unsaturated carboxylic acid, about 30 to about 83% by weight of ethylene and 0 to about 40% by weight of softening comonomer. Preferably, the copolymer comprises about 20% by weight of unsaturated carboxylic acid and about 80% by weight.
Contains by weight ethylene. Most preferably, the copolymer contains about 20% acrylic acid, with the balance being ethylene.

Along this line, examples of preferred highly acidic base copolymers that meet the criteria set forth above include Dow Chemical Company, Midland,
There is a series of ethylene-acrylic copolymers commercially available from Michigan under the designation "Primacor". These highly acidic base copolymers exhibit the typical properties shown in Table 22 below.

[0183]

[Table 22]

Because of the high molecular weight of Primacor 5981 grade ethylene-acrylic acid copolymer, this copolymer is a more preferred grade utilized in the present invention.

The metal cation salts utilized in the present invention are those that provide metal cations with the ability to neutralize the carboxylic acid groups of the highly acidic copolymer to varying degrees. These include salts of acetates, oxides or hydroxides of lithium, calcium, zinc, sodium, potassium, nickel, magnesium and manganese.

Examples of such lithium ion sources include lithium hydroxide monohydrate, lithium hydroxide, lithium oxide and lithium acetate. Sources of calcium ions include calcium hydroxide, calcium acetate and calcium oxide. Suitable sources of zinc ions are zinc acetate dihydrate and zinc acetate, a blend of zinc oxide and acetic acid. Examples of sodium ion sources include sodium hydroxide and sodium acetate. Potassium ion sources include potassium hydroxide and potassium acetate. Suitable sources of nickel ions are nickel acetate, nickel oxide and nickel hydroxide. Magnesium sources include magnesium oxide, magnesium hydroxide, and magnesium acetate. Manganese sources include manganese acetate and manganese oxide.

[0187] The high acid ionomer resin neutralized with the new metal cations provides a high acid base copolymer at a pressure of about 10 psi to 10,000 psi under high shear conditions of about 200 psi.
Produced by reacting with varying amounts of a metal cation salt at a temperature above the crystalline melting point of the copolymer, such as a temperature of from about F to about 500 F, preferably about 250 F to 350 F. . Other well-known compounding techniques can also be used. The amount of the highly acidic base ionomer resin neutralized with the new metal cation is an amount that provides a sufficient amount of the metal cation to neutralize the carboxylic acid groups in the highly acidic copolymer by the desired percentage. . The degree of neutralization is generally from about 10% to about 90%.

More specifically, as shown in Table 23 below, US Patent Application No. 90
As shown in Example 1 in US Pat. No. 1,680, a number of new classes of highly acidic ionomers neutralized with metal cations can be obtained from the process described above. This includes a new highly acidic ionomer R neutralized to varying degrees with manganese, lithium, potassium, calcium and nickel cations. Further, a highly acidic ethylene / acrylic acid copolymer is utilized as the base copolymer component of the present invention, which component is then neutralized to various degrees with metal cation salts to form sodium, potassium, lithium, zinc, magnesium. When producing acrylic acid-based highly acidic ionomer resins that are neutralized with cations such as manganese, calcium and nickel, several new cation neutralized acrylic acid-based highly acidic ionomer resins are produced.

[0189]

[Table 23]

When compared to a lower acid version of a similar cation neutralized ionomer resin,
Highly acidic ionomer resins neutralized with new metal cations exhibit enhanced hardness, modulus and resilience properties. These are properties that are particularly desired in the field of thermoplastics, including golf ball manufacturing.

When utilized in golf ball cover manufacturing, new acrylic acid based highly acidic ionomers are disclosed in US Pat. Nos. 4,884,814 and 4,911,451.
-Acid low-ion ionomer covered balls, such as the ball made utilizing the low-acid ionomer disclosed in U.S. Patent No. 5,075,055 and the recently formed high-acid blend disclosed in U.S. Patent No. 5,688,869. It has been discovered that it extends the hardness range beyond that previously obtained while maintaining the advantageous properties of (i.e., durability, click, feel, etc.). In addition, the development of a number of new acrylic acid-based highly acidic ionomer resins neutralized to varying degrees with several different types of metal cations, such as manganese, lithium, potassium, calcium and nickel cations, resulted in golf Several new ionomers or ionomer blends are available for ball making. By using these highly acidic ionomer resins, higher C.I. O. R. As a result, a harder and more rigid golf ball having a longer flight distance can be obtained.

As further seen in the examples below, other ionomer resins, such as low acid ionomer resins, may be used in the cover composition as long as the molded cover produces a Shore D hardness of 65 or more. it can. Some properties of these low acid ionomer resins are shown in Table 24 below.

[0193]

[Table 24]

In addition to the ionomers described above, it is also possible to add compatible additive materials to produce the cover compositions of the present invention. These additive materials include dyes such as Whitaker, Clark, and Daniels o.
f Ultramarine Blue sold by South Painsfield, NJ) and pigments, i.e. titanium dioxide (e.g. Unitane O-
110), white pigments such as zinc oxide and zinc sulfate, and fluorescent pigments. As shown in U.S. Pat. No. 4,884,814, the amount of pigment and / or dye used in conjunction with the polymer cover composition depends on the particular base ionomer mixture utilized and the particular base ionomer utilized. It depends on the pigment and / or dye.
The concentration of the pigment in the polymer cover composition can be from about 1% to about 10% based on the weight of the base ionomer mixture. A more preferred range is from about 1% to about 5% based on the weight of the base ionomer mixture. The most preferred range is from about 1% to about 3% based on the weight of the base ionomer mixture. The most preferred pigment for use according to the present invention is titanium dioxide.

Furthermore, since there are various white hues, that is, bluish white, yellowish white, and the like, a trace amount of blue pigment can be added to the cover material composition to give it a bluish white appearance. However, if a different hue of white is desired, different pigments can be added to the cover composition in the amounts required to produce the desired color.

Furthermore, the addition of compatible materials to the cover composition of the present invention that does not affect the basic novel properties of the composition of the present invention is within the scope of the present invention. . Among such materials are antioxidants (ie, Santonox®), antistatic agents, stabilizers and processing agents. The cover composition of the present invention contains a softening agent such as a plasticizer and a reinforcing material such as glass fiber or an inorganic filler, as long as the desired properties produced by the golf ball cover of the present invention are not impaired. Can also.

In addition, optical brighteners such as those disclosed in US Pat. No. 4,679,795 can be included in the cover compositions of the present invention. Suitable optical brighteners that can be used according to the present invention are Ciba-Geigy Che
medical Company, Ardsley, N.M. Y. Uvitex OB as marketed by the company. Uvitex OB is 2,5-bis (5
-Tert-butyl-2-benzoxazoly) thiophene.
Examples of other optical brighteners suitable for use in accordance with the present invention are as follows: Sandoz, East Hanover, NJ. J. Leucopure EGM as sold by 07936. Leucopure EG
M is believed to be 7- (2n-naphthol (1,2-d) -triazol-2-yl) -3phenyl-coumarin. Phorwhite K-20G2
Is described in Mobay Chemical Corporation, P.S. O. Box
385, Union Metro Park, Union, N.W. J. 0708
3 and is considered to be a pyrazoline derivative. Eas
tman Chemical Products, Inc. Kingsport
Tenn. Eastobrite OB-1 sold by 4,4,4
-Bis (-benzoxazolyl) stilbene is believed to be. U above
vitex and Eastobrite OB-1 are preferred optical brighteners for use in accordance with the present invention.

In addition, because many optical brighteners are colored, the percentage of optical brightener utilized prevents the optical brightener from functioning itself as a pigment or dye. Therefore, it must not be excessive.

The percentage of optical brightener that can be used in accordance with the present invention is from about 0.01% to about 0.5% based on the weight of the polymer used as the cover stock. A more preferred range is from about 0.05% to about 0.25%, depending on the optical properties of the particular optical brightener used and the polymer environment of which it is a part. The preferred range is from about 0.10% to about 0.020%.

Generally, the additives are mixed with the ionomer to be used in the cover composition to provide the desired concentration of the masterbatch (MB) to provide the desired amount of additive. A sufficient amount of the masterbatch is then mixed with the blend of copolymers.

The cover composition described above is processed according to the parameters set forth below, and when combined with a soft core at a thickness as defined herein to produce a cover having a Shore D hardness of 65, the spin rate To provide a golf ball having a reduced value. However, high acid ionomer resins provide even more significant spin rate reductions than those found with low acid ionomer resins.

The cover compositions and shaped balls of the present invention can be manufactured according to conventional melt compounding procedures. At this point, the ionomer resin is compounded with a masterbatch containing the desired additives in a Banbury-type mixer, two-roll mill, or extruded prior to molding. The compounded composition is then shaped into slabs, pellets, or the like, and maintained in this state until molding is desired. Alternatively, a simple dry blend of pelletized or granulated resin and a color masterbatch can be prepared and fed directly to an injection molding machine, where the homogenization occurs within the mixing section of the barrel prior to injection into the mold. Transformation occurs. If necessary, further additives such as inorganic fillers and the like can be added and homogeneously mixed before starting the molding process.

Further, the golf balls of the present invention can be manufactured by molding processes currently well known in the golf ball art. Specifically, about 1.680
Golf balls can be made by injection molding or compression molding the novel cover composition around a soft polybutadiene core to produce golf balls having a diameter of greater than inches and a weight of about 1.620 ounces. In an additional embodiment of the present invention, a larger mold is utilized to produce an oversized golf ball with a thicker cover. As indicated, the golf balls of the present invention can be made by forming a cover of the composition of the present invention around a softer polybutadiene core by conventional molding processes. For example, in compression molding, the cover composition may be about 380 ° F. to about 450 ° F.
Formed in the form of a hemispherical shell with a smooth surface via injection at F, this shell is then centered about the core in a dimpled golf ball mold,
Undergo compression molding at 200-300 ° F. for 2-10 minutes, then 50-200 minutes for 2-10 minutes
Cooled and fused at 70 ° F to form a unitary ball. In addition, golf balls can be manufactured by injection molding, in which case the cover composition can be made up of 50
It is injected directly around a core located at the center of the golf ball mold over a period of time at a mold temperature of about 100 ° F to about 100 ° F. After molding, the manufactured golf ball is
Various further finishing steps, such as buffing, painting and marking, as disclosed in U.S. Pat. No. 4,911,451 can be performed.

The invention has been described with reference to the preferred embodiments. Obviously, upon reading and understanding the above detailed description, modifications and alterations to other forms will occur. It is intended that the invention be regarded as including all such alterations and modifications as fall within the scope of the appended claims or their equivalents.

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of a first preferred embodiment of a low spin golf ball of the present invention including a polymer outer cover, one or more mantle layers, and an optional polymer hollow layer.

FIG. 2 is a partial cross-sectional view of a second preferred embodiment of the low spin golf ball of the present invention including a polymeric outer cover, one or more mantle layers and a core material.

FIG. 3 is a partial cross-sectional view of a third preferred embodiment of the low spin golf ball of the present invention, including one or more mantle layers and a core material.

FIG. 4 is a partial cross-sectional view of a fourth preferred embodiment of a low spin golf ball of the present invention including one or more mantle layers, an optional polymeric hollow spherical substrate, and a core material.

FIG. 5 is a partial cross-sectional view of a fifth preferred embodiment of the low spin golf ball of the present invention including a polymeric outer cover, a first mantle layer, a second mantle layer, and a core material.

FIG. 6 shows a low spin of a sixth preferred embodiment of the present invention including a polymer outer cover and first and second mantle layers in an alternating arrangement compared to the arrangement of the embodiment shown in FIG. 5; FIG. 2 is a partial cross-sectional view of a golf ball.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 F term (Reference) 4J002 AB012 AD032 BB021 BB111 BC031 BC041 BC061 BF011 BN151 CC181 CD001 CE001 CF061 CF071 CG001 CH071 CH091 CL011 CL031 CL062 CM041 CN011 CN031 CP031 DA016 DJ006 DK006 DL006 FA042 FA046 FD012 FD016 GC01 GF00 4J100 AA02P AA03P AA04P AA16P AJ01Q AJ02Q AJ03Q AJ08Q AJ09Q AK07R AK08R AK09R AK12R AK13R AK14R AK20R BA17H BB01Q CA04 CA05 CA31 DA47 HA31 HB36 HB39 HC27 JA01 JA57

Claims (50)

[Claims] 1. A core comprising a core component and a spherical mantle containing said core component, said mantle comprising (i) a polymeric material and (ii) a reinforcing material dispersed in said polymeric material. A core having a Riehl compressive force of at least about 75, wherein the core is selected from the group consisting of a high acid ionomer, a low acid ionomer, an ionomer blend, a non-ionomeric elastomer, a thermosetting material, and combinations thereof. Low-spin golf ball, comprising a polymeric outer cover having a Shore D hardness of at least about 65. 2. The mantle polymer material of claim 1, wherein the mantle polymer material is selected from the group consisting of an epoxy-based material, a thermoset material, a nylon-based material, a styrene material, a thermoplastic material, and combinations thereof. Golf ball 3. The thermosetting material is selected from the group consisting of a polyimide thermosetting resin, a silicone thermosetting resin, a vinyl ester thermosetting resin, a polyester thermosetting resin, a melamine thermosetting resin, and a combination thereof. 3. The golf ball according to claim 2, which is selected. 4. The method according to claim 1, wherein the nylon base material is nylon 6, nylon 6/10.
3. The golf ball of claim 2, wherein the golf ball is selected from the group consisting of, nylon 6/6, nylon 11, and combinations thereof. 5. The golf ball of claim 2, wherein the styrene material is selected from the group consisting of acrylonitrile-butadiene styrene, polystyrene, styrene-acrylonitrile, styrene maleic anhydride, and combinations thereof. 6. The thermosetting material is selected from the group consisting of acetal copolymer, polycarbonate, liquid crystal polymer, polyethylene, polypropylene, polybutylene terephthalate, polyethylene terephthalate, polyphenylene, polyaryl, polyether and combinations thereof. 3. The golf ball according to claim 2, wherein 7. The golf of claim 1, wherein said reinforcing material is selected from the group consisting of silicon carbide, glass, carbon, boron carbide, aramid material, cotton, flux, jute, hemp, silk and combinations thereof. ball. 8. The golf ball of claim 1, wherein the golf ball further comprises a second mantle adjacent the mantle containing the core component. 9. The method of claim 8, wherein the second mantle comprises a ceramic selected from the group consisting of silica, soda lime, lead silicate, borosilicate, aluminoborosilicate, aluminosilicate and combinations thereof. Golf ball. 10. The golf ball according to claim 8, wherein said second mantle includes at least one metal selected from the group consisting of steel, titanium, chromium, nickel and alloys thereof. 11. The golf ball according to claim 10, wherein the second mantle includes a nickel titanium alloy. 12. The golf ball of claim 1, wherein the mantle has a thickness in a range from about 0.001 inches to about 0.100 inches. 13. The golf ball of claim 12, wherein the mantle has a thickness in a range from about 0.010 inches to about 0.030 inches. 14. The golf ball of claim 9, wherein the second mantle comprising ceramic has a thickness in a range from about 0.001 inches to about 0.070 inches. 15. The method according to claim 15, wherein the second mantle is about 0.005 inches to about 0.040.
The golf ball of claim 14, having a thickness in the range of inches. 16. The method of claim 16, wherein the second mantle is between about 0.010 inches and about 0.020 inches.
16. The golf ball of claim 15, having a thickness of inches. 17. The method of claim 17, wherein the second mantle is between about 0.001 inches and about 0.050 inches.
The golf ball of claim 10, having a uniform thickness in the range of inches. 18. The golf ball of claim 17, wherein the thickness of the second mantle ranges from about 0.005 inches to about 0.050 inches. 19. The golf ball of claim 18, wherein the thickness of the second mantle ranges from about 0.005 inches to about 0.010 inches. 20. The method of claim 1, wherein the cover comprises more than 16% by weight of a copolymer of an alpha, beta unsaturated carboxylic acid and about 10 to about 90% of the carboxyl groups of the copolymer are neutralized with a metal cation. The golf ball of claim 1, comprising at least one high acid ionomer resin comprising an alpha olefin. 21. The cover of claim 17, wherein the cover comprises about 17 to about 25% by weight of a copolymer of an alpha, beta unsaturated carboxylic acid and about 10 to about 90 of the carboxyl groups of the copolymer.
21. The golf ball of claim 20, wherein the golf ball comprises at least one high acid ionomer resin comprising at least one alpha olefin neutralized with a metal cation. 22. The cover of claim 1, wherein the cover comprises about 18.5 to about 21.5% by weight of a copolymer of an alpha, beta unsaturated carboxylic acid and about 10% of carboxyl groups of the copolymer.
22. The golf ball of claim 21, wherein the golf ball comprises at least one high acid ionomer resin comprising from about 90% to about 90% of an alpha olefin neutralized with a metal cation. 23. The golf ball of claim 1, wherein the cover has a thickness greater than 0.0675 inches. 24. The golf ball of claim 23, wherein the cover has a thickness greater than 0.0675 inches and up to 0.130 inches. 25. The cover having an inner cover layer and an outer cover layer,
The golf ball according to claim 1. 26. The golf ball of claim 1, wherein the golf ball has a diameter of about 1.680 to 1.800 inches. 27. The golf ball of claim 26, wherein said golf ball has a diameter of about 1.700 to 1.800 inches. 28. The golf ball of claim 27, wherein said golf ball has a diameter of about 1.710 to 1.730 inches. 29. The golf ball of claim 28, wherein said golf ball has a diameter of about 1.717 to 1.720 inches. 30. The golf ball of claim 1, further comprising an innermost polymeric hollow spherical substrate disposed adjacent to an inner surface in front of the mantle. 31. The golf ball according to claim 30, wherein the support has a thickness of about 0.005 to about 0.010 inches. 32. A core component and a vitreous mantle surrounding said core component,
A golf ball comprising a core having a Riehl compressive force of about 75 to about 115 and a polymeric outer cover disposed about the mantle and having a Shore D hardness of at least about 65. 33. The vitreous mantle comprising silica, soda lime, lead silicate,
33. The golf ball of claim 32, comprising a ceramic selected from the group consisting of borosilicate, aluminoborosilicate, aluminosilicate, and combinations thereof. 34. The golf ball of claim 32, wherein the vitreous mantle includes a reinforcing material dispersed within the mantle. 35. The reinforcing material comprises silicon carbide, glass, carbon, boron carbide,
35. The golf ball of claim 34, wherein the golf ball is selected from the group consisting of an aramid material, cotton, flux, jute, hemp, silk and combinations thereof. 36. The vitreous mantle comprising a polymer material selected from the group consisting of an epoxy-based material, a thermoset material, a nylon-based material, a styrene material, a thermoplastic material, and combinations thereof. 33. The golf ball according to claim 32, further comprising a near second mantle. 37. The golf ball according to claim 36, wherein the second mantle further comprises a reinforcing material. 38. A second material, comprising a metal, closest to said vitreous mantle.
33. The golf ball according to claim 32, further comprising a mantle. 39. The golf ball of claim 38, wherein said second mantle comprises a metal selected from the group consisting of steel, titanium, chromium, nickel and alloys thereof. 40. The golf ball according to claim 39, wherein the second mantle comprises a nickel titanium alloy. 41. The golf ball of claim 32, wherein the polymeric outer cover comprises greater than about 16% by weight of a high acid ionomer. 42. The core according to claim 41, wherein the core has a Riehl compression force of 80-90.
33. The golf ball of claim 32, having a diameter of 540 to about 1.545 inches. 43. The golf ball of claim 32, wherein the golf ball has a diameter from about 1.70 to about 1.80 inches. 44. The golf ball of claim 43, wherein the golf ball has a diameter of about 1.710 to about 1.730 inches. 45. The golf ball of claim 44, wherein the golf ball has a diameter from about 1.717 to about 1.720 inches. 46. The cover has an inner cover layer and an outer cover layer.
A golf ball according to claim 32. 47. A substantially spherical core having an inner core component and a mantle layer disposed about the core component, wherein the mantle layer comprises at least one metal, and wherein the core comprises about 75 to A low spin golf ball, comprising: a substantially spherical core exhibiting a Riehl compressive force of about 115; and a polymer outer cover disposed about said core and exhibiting a Shore D hardness of at least about 65. 48. The golf ball of claim 47, wherein said metal of said mantle is selected from the group consisting of steel, titanium, chromium, nickel and alloys thereof. 49. The golf ball of claim 47, wherein the golf ball further comprises a second mantle layer adjacent the mantle layer disposed around the core. 50. The golf ball of claim 47, wherein the cover has a thickness between about 0.0675 inches and about 0.130 inches.