KR102523415B1 - Graphene core for golf ball with soft cover - Google Patents

Abstract

A golf ball 16 comprising a core 12 comprising polybutadiene and graphene, and a soft cover 16 is disclosed herein. The golf ball 10 has a double core 12 with an outer core 12b comprising polybutadiene and graphene. The soft cover 16 is preferably composed of a highly neutralized polymer, a first ionomer, a second ionomer, and an impact modifier.

Description

Graphene core for golf ball with soft cover

The present invention relates generally to the use of graphene in the layers of golf balls, and more particularly to golf balls having a graphene core and soft cover.

A common process for synthesizing exfoliated graphite (individual sheets of exfoliated graphite are also known as graphene or graphene nanoplatelets) involves reacting graphite with an acid such as nitric acid and/or sulfuric acid followed by heat treatment and chemical reduction . Exfoliated graphite is a two-dimensional flat sheet of SP ² -hybrid carbon. Sheets of graphene (individual sheets of reduced exfoliated graphite) are typically a few nanometers thick and a few microns wide (aspect ratio >1000). The high aspect ratio of graphene coupled with high tensile strength (tensile strength in GPa compared to MPa of the polymer) makes it possible to make polymer composites with very high tensile and flexural properties. Graphene's unusually high thermal conductivity (about 3000 W/mk compared to <1 W/mk for typical thermoplastic polymers); It can be used to make thermally conductive composite materials. For thermoset elastomer products, this higher thermal conductivity can mean higher throughput due to shorter, more uniform cure cycles.

Various examples of exfoliated graphite (also called graphene) based composites can be found in the literature. Wang et al. disclose an expanded graphite polyethylene composite for electromagnetic radiation interference (EMI) shielding applications.

US Patent No. 4946892 discloses synthesizing an exfoliated graphene-based composite by compression molding graphite using a polyimide resin under high temperature (200° C.) and high pressure (80 kPa).

Shioyama discloses the synthesis of polyisoprene and polystyrene-based composite materials by in-situ polymerization of styrene and isoprene monomers in the presence of exfoliated graphite.

US Patent No. 5776372 discloses electrically conductive nanocomposites made of expanded graphite and various polymers such as polypropylene, polytetrafluoroethylene and phenolic resins. Pan et al. disclose the synthesis of nylon-6 expanded graphite nanocomposites by polymerization of ε-caprolactam in the presence of expanded graphite.

Chen et al. disclose in-situ polymerization of methyl methacrylate in the presence of expanded graphite to obtain electrically conductive nanocomposites.

Xiao et al. disclose the preparation of exfoliated graphite composites with improved thermal stability by in-situ polymerization of styrene in the presence of exfoliated graphene.

The prior art is not even aware of this problem.

The main object of the present invention is to improve the durability of the golf ball core by incorporating graphene into the core to improve the impact strength of the ball, and to have a soft cover. These benefits can be seen in balls with a single core or a double core with an outer core that is harder than the inner core. Improving the durability of the core by using graphene can increase the mean time to fail (MTTF) when subjected to repeated impacts in a high-speed test rig or when using a golf club in normal play.

Another objective is to improve aging properties by incorporating graphene into the core to better maintain compression and COR over time.

One aspect of the present invention is a golf ball comprising an inner core, an outer core and a cover layer. A cover layer is disposed over the outer core, the cover layer comprising 5 to 45% by weight of highly neutralized polymer, 5 to 45% by weight of the first ionomer, 5 to 45% by weight of the second ionomer, 5 to 45% by weight of the third ionomer, 15 It consists of 5 to 30% by weight of the master batch containing 40% to 40% by weight of the impact modifier, and 1 to 10% by weight of the color master batch. The core, including the inner core and the outer core, has a compression value in the range of 40 to 55. A golf ball has a diameter of 1.68 inches or greater, a mass of less than 45.93 grams, and a COR of greater than 0.790.

In a more preferred embodiment, the outer core comprises graphene material in the range of 0.4 to 2.5 weight percent of the outer core. In an even more preferred embodiment, the graphene material ranges from 0.6 to 1.5 weight percent of the outer core.

Another aspect of the invention is a golf ball comprising an inner core, an outer core and a cover layer. The inner core includes a polybutadiene material. The outer core includes a graphene material and a polybutadiene material in an amount ranging from 0.1 to 5.0 weight percent of the outer core, wherein the outer core has a flexural modulus ranging from 80 MPa to 95 MPa. A cover layer is disposed over the outer core. The cover layer comprises 5 to 45 weight percent highly neutralized polymer, 5 to 45 weight percent first ionomer, 5 to 45 weight percent second ionomer, 5 to 45 weight percent third ionomer, and 15 to 40 weight percent impact modifier. 5 to 30% by weight of the masterbatch and 1 to 10% by weight of the color masterbatch. The double core includes an inner core and an outer core with a compression value ranging from 40 to 55. The diameter of the golf ball is greater than 1.68 inches, the mass is less than 45.93 grams, and the COR is greater than 0.790.

Another aspect of the present invention is a golf ball comprising a double core composed of an inner core and an outer core and a cover layer. The inner core includes a graphene material and polybutadiene in an amount ranging from 0.1 to 5.0% by weight of the inner core. The outer core includes a graphene material and polybutadiene in an amount ranging from 0.1 to 5.0% by weight of the outer core. The outer core has a flexural modulus ranging from 80 MPa to 95 MPa. A cover layer is disposed over the outer core. The cover layer comprises 5 to 45 weight percent highly neutralized polymer, 5 to 45 weight percent first ionomer, 5 to 45 weight percent second ionomer, 5 to 45 weight percent third ionomer, and 15 to 40 weight percent impact modifier. 5 to 30% by weight of the masterbatch, and 1 to 10% by weight of the color masterbatch. The thickness of the cover layer is between 0.025 inches and 0.055 inches. The compression value of the double core is 40 to 55.

Another aspect of the present invention is a golf ball comprising a double core composed of an inner core and an outer core, and a mantle layer and a cover layer. The inner core includes a graphene material and polybutadiene in an amount ranging from 0.1 to 5.0% by weight of the inner core. The outer core includes a graphene material and polybutadiene in an amount ranging from 0.1 to 5.0% by weight of the outer core. The outer core has a flexural modulus ranging from 80 MPa to 95 MPa. A cover layer is disposed over the mantle layer. The cover layer comprises 5 to 45 weight percent highly neutralized polymer, 5 to 45 weight percent first ionomer, 5 to 45 weight percent second ionomer, 5 to 45 weight percent third ionomer, and 15 to 40 weight percent impact modifier. 5 to 30% by weight of the master batch and 1 to 10% by weight of the color master batch. The thickness of the cover layer is between 0.025 inches and 0.055 inches. The cover layer has a Shore D hardness in the range of 35 to 60. Dual cores have compression values ranging from 40 to 55.
Another aspect of the present invention is that the outer core has a tensile modulus of 8 MPa to 10 MPa.

1 is an exploded partial cutaway view of a golf ball.
2 is a partially exploded view of a golf ball.
3 is an exploded partial cutaway view of a golf ball.
4 is a top perspective view of a golf ball.
5 is a cross-sectional view of a core component of a golf ball.
6 is a cross-sectional view of a core component and a mantle component of a golf ball.
7 is a cross-sectional view of the inner core layer, outer core layer, inner mantle layer, outer mantle layer and cover layer of a bone ball.
7A is a cross-sectional view of an inner core layer, middle core layer, outer core layer, mantle layer and cover layer of a golf ball.
8 is a cross-sectional view of the inner core layer under a load of 100 kg.
9 is a cross-sectional view of a core subjected to a load of 100 kg.
10 is a cross-sectional view of a core component and a mantle component of a golf ball.
11 is a cross-sectional view of a core component, mantle component and cover layer of a golf ball.
12 is an exploded partial cutaway view of a 4-piece golf ball.
13 is an exploded partial cutaway view of a three-piece golf ball.
14 is an exploded partial cutaway view of a two-piece golf ball.
15 is a cross-sectional view of a two-piece golf ball.
16 is a cross-sectional view of a three-piece golf ball.
17 is an exploded partial cutaway view of a three-piece golf ball.
18 is a cross-sectional view of a three-piece golf ball with a double core and cover.
19 is a cross-sectional view of a 3-piece golf ball with double, mantle and cover.
20 is a cross-sectional view of a 4-piece golf ball having a double core, mantle layer and cover.
21 is a cross-sectional view of a 4-piece golf ball with a core, double mantle layer and cover.
22 is a graph of endurance testing of an outer core using PTM at 175 fps.
23 is a graph of a durability test of a dual core using PTM at 175 fps.
24 is a graph of a durability test of a dual core using PTM at 175 fps.
25 is a graph of a durability test of a dual core using PTM at 175 fps.
26 is an example of graphene.
27 is a graph of a durability test of a dual core using PTM at 175 fps.
28 is a graphene durability versus average surface area plot (MTTF).
29 is a graph of the temperature of the outer core of a dual core as a function of cure time.

One object of the present invention is to improve the durability of a golf ball core by incorporating graphene into any core to improve the impact strength of the ball. This advantage can be seen in balls designed to have a single piece core with low compression, or in dual cores where the outer core is stiffer than the inner core. Improving the durability of core or mantle constructions using graphene could result in longer mean time to failure (MTTF) when subjected to repeated impacts on high-speed test rigs or when golf clubs are used in normal play.

Another object of the present invention is to improve aging properties by incorporating graphene into the core or mantle layer to better maintain compression and COR over time.

In a preferred embodiment, the golf ball comprises 5 to 45% by weight of highly neutralized polymer, 5 to 45% by weight of the first ionomer, 5 to 45% by weight of the second ionomer, 5 to 45% by weight, 15 to 40% by weight of the third ionomer. A core having a cover layer composed of 5 to 30% by weight of a master batch comprising an impact modifier of , and 1 to 10% by weight of a color master batch. In an alternative embodiment, the cover layer 16 comprises 30 to 40 weight percent of a highly neutralized polymer ("HNP"), 10 to 20 weight percent of the first ionomer; It is composed of 10 to 20% by weight of the second ionomer, 15 to 25% by weight of the master batch containing 20 to 50% by weight of the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier.

A preferred HNP is HPF 2000 available from DuPont Chemical. Another preferred HNP is HPF 1000, also available from DuPont. Another alternative HNP is AD1035, also available from DuPont. Another alternative HNP is AD1172, also available from DuPont.

A preferred ionomer material is SURLYN® 9150 available from DuPont. SURLYN 9150 is an ethylene/methacrylic acid copolymer with acid groups partially neutralized with zinc ions. Another preferred ionomer material is SURLYN® 8150, also available from DuPont. SURLYN 8150 is an ethylene/methacrylic acid copolymer in which acid groups are partially neutralized with sodium ions. Another preferred ionomer material is SURLYN® AD 1022, also available from DuPont.

An alternative ionomer material is SURLYN® 9945 available from DuPont. An alternative ionomer material is SURLYN® 8945 available from DuPont.

Impact modifiers are acrylonitrile-butadiene-styrene polymers (ABS), methyl methacrylate-butadiene-styrene polymers (MBS) impact-property modifiers for poly(vinyl chloride) and acrylic/methacrylic cores for polycarbonates. - one or more of the shell modifiers.

Polybutadiene-based cores were made using the following materials. Corresponding levels (in weight percent) are mentioned next to each material: polybutadiene-(40-90%) with l,4-cis structure greater than 60%; polyisoprene-(1-30%); zinc diacrylate-(10-50%); zinc oxide-(1-30%); zinc stearate-(1-20%); peroxide initiator-(0.1-10%); zinc pentachlorothiophenol-(0-10%); pigment-(0-10%); barium sulfate-(0-20%); Graphene A (0.0 l-6%) - (available from various suppliers such as Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., Angstron Materials Inc.) may have an average surface area of 50 m ² /g); Graphene B (0.0 l-6%) (available from various suppliers including Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., Angstron Materials Inc.) (Graphene B is 300 to 400 m ² /g average surface area); Graphene C (0.0 l-6%) (available from various suppliers including Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., Angstron Materials Inc.) (Graphene C is Graphene A or a larger average surface area than graphene B, and graphene C may have an average surface area of 400 to 800 m ² /g); Graphene masterbatch (masterbatch of 90-99% polybutadiene or polyisoprene and 1-10% graphene) - (0.1-50%) - custom compounding is from Preferred Compounding Corp, Dyna-Mix, Alttran, Callaway (internal compounding) can be done with the help of various suppliers.

Four different single cores (compositions 1 to 4) were prepared as indicated in the compositions in Table 1. The control (composition 1) had no graphene.

Table 1. Solid core (graphene) composition

Composition 1
(Graphene A 0%) Composition 2
(Graphene A 0.4%) composition 3
(Graphene A 0.8%) composition 4
(Graphene A 1.6%) ingredient weight% weight% weight% weight% polybutadiene 62.5 62.3 62.1 61.5 zinc diacrylate 19.9 19.8 19.7 19.6 zinc oxide 6.3 6.2 6.2 6.2 zinc stearate 3.8 3.7 3.7 3.7 peroxide initiator 0.5 0.5 0.5 0.5 zinc pentachlorothiophenol 0.6 0.6 0.6 0.6 pigment 0.1 0.1 0.1 0.1 limestone
(limestone) 0.0 0.0 0.0 0.0 tungsten 0.0 0.0 0.0 0.0 barium sulfate 6.4 6.4 6.4 6.3 Graphene A 0.0 0.4 0.8 1.6 Graphene A in masterbatch 0.0 0.0 0.0 0.0 core properties compression 69.4 74.3 74.6 76.4 COR (coefficient of restitution at 125 fps) 0.801 0.800 0.795 0.790 Durability score or mean time to failure MTTF (shots before crack/failure) 34 60 47 62

Compression is measured by applying a 200 pound load to the core and measuring its deflection in inches. Compression = 180 - (Bending * 1000).

Durability test of solid core

The cores were filmed at 150 fps on a pneumatic testing machine (PTM).

Twelve cores were tested for each composition mentioned in Table 1. The number of shots before each core cracked was recorded for each core, and the cracked core was removed from the rest of the test. Data were reported using Weibull plots, and mean times to failure were reported as shown in Table 1. As shown in FIG. 20, the graphene-modified cores withstood more shots before failure compared to cores without graphene. It is reasonable to assume that the durability of a golf ball with a single-piece core of this design will also experience a dramatic increase in crack resistance based on these improvements to the core.

In this study, graphene A was introduced into the outer core in a double-core structure. The duplex core was made by compression molding the two outer core halves around an already molded inner core with a diameter of about 0.940" (inch) and a soft compression of about 0.200 inch of warp under a 200 lb load. Hardening of the inner and outer cores. were performed at temperatures ranging from 150 to 400 °F for times ranging from 1 to 30 minutes. After molding, the duplex cores were spherically ground to approximately 1.554" before testing.

Tables 2 and 3 provide details on the composition of the inner and outer cores. The components of this composition were mixed in an internal mixer. Optionally further mixing was performed using a 2-roll mill.

Compression of the outer core is measured by first making a full-size core separately, measuring the compression, and then molding the two halves around the inner core to complete the double core.

The compression differential represents the difference between outer core compression (independently molded) and inner core compression. The greater the compression difference, the weaker the crack resistance upon impact.

Table 2. Inner core composition

ingredient weight% polybutadiene rubber 69.2 polyisoprene rubber 0.0 zinc diacrylate 14.8 zinc oxide 12.2 zinc stearate 2.1 peroxide initiator 1.0 zinc pentachlorothiophenol 0.6 pigment 0.1 barium sulfate 0.0 Graphene A 0.0 Graphene A Masterbatch 0.0 characteristic compression 0.220

Table 3. Composition of the outer core of the double core

Composition 5
(graphene 0%) Composition 6
(graphene 0.4%) Composition 7
(graphene 0.8%) Composition 8
(graphene 1.6%) ingredient weight% weight% weight% weight% polybutadiene 62.5 62.3 62.1 61.5 zinc diacrylate 19.9 19.8 19.7 19.6 zinc oxide 6.3 6.2 6.2 6.2 zinc stearate 3.8 3.7 3.7 3.7 peroxide initiator 0.5 0.5 0.5 0.5 zinc pentachlorothiophenol 0.6 0.6 0.6 0.6 pigment 0.1 0.1 0.1 0.1 limestone 0.0 0.0 0.0 0.0 tungsten 0.0 0.0 0.0 0.0 barium sulfate 6.4 6.4 6.4 6.3 Graphene A 0.0 0.4 0.8 1.6 Graphene A in masterbatch 0.0 0.0 0.0 0.0 core properties compression 69.4 74.3 74.6 76.4 COR (coefficient of restitution) 0.801 0.800 0.795 0.790 Characteristics of a double core composed of inner and outer cores compression 48.9 50.9 52.1 54.1 COR (coefficient of restitution at 125 fps) 0.796 0.795 0.793 0.790 Durability score or mean time to failure MTTF (shots before crack/failure) 50 60 52 57

Compression is measured by applying a 200 pound load to the core and measuring its deflection in inches. Compression = 180 - (Bending * 1000).

Durability test of double core

The core was filmed at 175 fps on a pneumatic testing machine (PTM).

Twelve cores were tested for each composition mentioned in Table 3. The number of shots before each core cracked was recorded for each core, and the cracked core was removed from the rest of the test. Data were reported using Weibull plots, and mean time to failure was reported as shown in Table 3. As shown in Figure 21, the graphene-modified cores withstood more shots before failure compared to cores without graphene. It is reasonable to assume that the durability of a golf ball with a double core of this design will also greatly increase in crack resistance based on the improvement to the double core.

Dual core with graphene-C only on the outer core

In this study, graphene-C (0.01–6%, available from various suppliers such as Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., Angstron Materials Inc.) and with an average surface area of 400 to 800 m ² /g) was introduced into the outer core in the double core structure. The duplex core was made by compression molding the two outer core halves around an already molded inner core with a diameter of about 0.940" and a soft compression of about 0.200 inch of flex under a 200 lb load. This was done for a time in the range of 30 minutes and at a temperature ranging from 150 to 400 F. After molding, the duplex core was spherically ground to about 1.554" before testing.

Tables 4 and 5 provide details on the composition of the inner and outer cores. The components of this composition were mixed in an internal mixer. Optionally further mixing was performed using a 2-roll mill.

The compression of the outer core is measured by first making a full-size core separately and measuring the compression, then molding the two halves around the inner core to complete the double core. The compression differential represents the difference between outer core compression (independently molded) and inner core compression. The greater the compression difference, the more susceptible to cracking resistance on impact.

Table 4. Inner core composition

ingredient weight% polybutadiene rubber 69.2 polyisoprene rubber 0.0 zinc diacrylate 14.8 zinc oxide 12.2 zinc stearate 2.1 peroxide initiator 1.0 zinc pentachlorothiophenol 0.6 pigment 0.1 barium sulfate 0.0 Graphene C 0.0 Graphene C in masterbatch 0.0 characteristic compression 0.220 inch under 200 lb load

Table 5. External composition of the double core

Composition 9
(Graphene C 0%) Composition 10
(Graphene C 0.4%) composition 11
(Graphene C 0.8%) composition 12
(Graphene C 1.6%) ingredient weight% weight% weight% weight% polybutadiene 62.5 62.3 62.0 61.6 zinc diacrylate 19.9 19.8 19.7 19.6 zinc oxide 6.3 6.2 6.2 6.2 zinc stearate 3.8 3.7 3.7 3.7 peroxide initiator 0.5 0.5 0.5 0.5 zinc pentachlorothiophenol 0.6 0.6 0.6 0.6 pigment 0.1 0.1 0.1 0.1 limestone 0.0 0.0 0.0 0.0 tungsten 0.0 0.0 0.0 0.0 barium sulfate 6.4 6.4 6.4 6.3 graphene-2 0.0 0.4 0.8 1.6 Graphene-2 in masterbatch 0.0 0.0 0.0 0.0 core properties compression 67.0 69.1 68.8 70.8 COR (coefficient of restitution) 0.801 0.798 0.795 0.791 Core stiffness/flexural modulus in MPa (measured on a dog bone shaped hardened core) 97.1 91.3 94.6 81.9 Tensile modulus of core (MbPa) 8.5 9.7 9.6 8.3 Characteristics of a double core composed of inner and outer cores compression 45.0 48.9 48.6 50.4 COR (coefficient of restitution at 125 fps) 0.795 0.794 0.793 0.789 Durability score or mean time to failure MTTF (shots before crack/failure) 33 67 78 99

Compression is measured by applying a 200 pound load to the core and measuring its deflection in inches. Compression = 180 - (Bending * 1000).

Twelve cores were tested for each composition mentioned in Table 5. The number of shots before each core cracked was recorded for each core, and the cracked core was removed from the rest of the test. Data were reported using Weibull plots, and mean times to failure were reported as shown in Table 5. The test stopped after 100 shots. As shown in FIG. 22, the graphene-modified cores withstood more shots before failure compared to cores without graphene. It is reasonable to assume that the durability of a golf ball with a double core of this design will also experience a dramatic increase in crack resistance based on this improvement to the double core. While it's reasonable to assume that adding graphene to the inner core could improve the durability of the entire golf ball, this study focused only on the outer core.

Double core with graphene A on the inner and outer cores.

In this study, graphene A was introduced into the inner and outer cores in a double-core structure. Table 6 provides details on the inner and outer core compositions of these dual cores. The components of this composition were mixed in an internal mixer. Optionally further mixing was performed using a 2-roll mill. The duplex core was made by compression molding the two outer core halves around an already molded inner core with a diameter of about 0.940" and a soft compression of about 0.200" of flex under a 200 lb load. It was performed for a time in the range of 30 minutes and at a temperature ranging from 150 to 400 F. After molding, the duplex core was spherically ground to about 1.554 inches before testing.

Compression of the outer core was measured by first making a full size core separately and measuring compression, then molding the two halves around the inner core to complete the double core.

Table 6. Double-core composition with graphene A in the inner and outer cores.

composition 13
- inner core composition 14
- inner core composition 15
- inner core composition 16
- inner core ingredient weight% weight% weight% weight% polybutadiene 69.2 69.2 69.1 68.9 zinc diacrylate 14.8 14.8 14.7 14.7 zinc oxide 12.3 12.3 12.2 12.2 zinc stearate 2.1 2.1 2.1 2.1 peroxide initiator 1.0 1.0 1.0 1.0 zinc pentachlorothiophenol 0.6 0.6 0.6 0.6 pigment 0.0 0.0 0.0 0.0 limestone 0.0 0.0 0.0 0.0 tungsten 0.0 0.0 0.0 0.0 barium sulfate 0.0 0.0 0.0 0.0 Graphene A 0.0 0.0 0.2 0.4 inner core properties compression 0.221 0.221 0.219 0.217 composition 13
- outer core composition 14
- outer core composition 15
- outer core composition 16
- outer core ingredient weight% weight% weight% weight% polybutadiene 62.5 62.3 62.3 62.3 zinc diacrylate 19.9 19.8 19.8 19.8 zinc oxide 6.2 6.2 6.2 6.2 zinc stearate 3.7 3.7 3.7 3.7 peroxide initiator 0.5 0.5 0.5 0.5 zinc pentachlorothiophenol 0.6 0.6 0.6 0.6 pigment 0.1 0.0 0.0 0.0 limestone 0.0 0.0 0.0 0.0 tungsten 0.0 0.0 0.0 0.0 barium sulfate 6.5 6.5 6.5 6.5 Graphene A 0.0 0.4 0.4 0.4 Outer Core Characteristics compression 67.8 67.6 67.6 67.6 COR (coefficient of restitution at 125 fps) 0.800 0.796 0.796 0.796 Characteristics of a double core composed of inner and outer cores compression 47.3 48.1 49.0 48.3 COR (coefficient of restitution at 125 fps) 0.795 0.793 0.793 0.792 Durability score or mean time to failure MTTF (shots before crack/failure) 29 24 33 40

Compression is measured by applying a 200 pound load to the core and measuring its deflection in inches. Compression = 180 - (Warpage * 1000).

Twelve cores were tested for each composition mentioned in Table 6. The number of shots before each core cracked was recorded for each core, and the cracked core was removed from the rest of the test. Data were reported using Weibull plots, and mean time to failure was reported as shown in Table 6. As shown in FIG. 23, the graphene-modified cores withstood more shots before failure compared to cores without graphene. The best durability was observed for balls with graphene in the inner and outer cores. It is reasonable to assume that the durability of a golf ball with a double core of this design will also experience a dramatic increase in crack resistance based on this improvement to the double core. While it's reasonable to assume that adding graphene to the inner core could improve the durability of the entire golf ball, this study focused only on the outer core.

Double core with graphene B only on the outer core

In this study, graphene B was introduced into the outer core of a double-core structure. The duplex core was made by compression molding the two outer core halves around an already molded inner core with a diameter of about 0.940” and a soft compression of about 0.200 inches of flex under a 200 lb load. Curing of the inner and outer cores was performed at temperatures ranging from 150 to 400 F for times ranging from 1 to 30 minutes. After molding, the duplex core was spherically ground to about 1.554 inches before testing.

Tables 7 and 8 provide details on the composition of the inner and outer cores. The components of this composition were mixed in an internal mixer. Optionally further mixing was performed using a 2-roll mill.

The compression of the outer core is measured by first making a full size core separately and measuring the compression, then molding the two halves around the inner core to complete the double core. The compression differential represents the difference between outer core compression (independently molded) and inner core compression. The greater the compression difference, the more susceptible to cracking resistance on impact.

Table 7. Inner core composition

ingredient weight% polybutadiene rubber 69.2 polyisoprene rubber 0.0 zinc diacrylate 14.8 zinc oxide 12.2 zinc stearate 2.1 peroxide initiator 1.0 zinc pentachlorothiophenol 0.6 pigment 0.1 barium sulfate 0.0 Graphene-B 0.0 Graphene-B Masterbatch 0.0 characteristic compression 0.220 inches under 200 lb load

Table 8. Composition of the outer core of the double core.

composition 17 composition 18 composition 19 ingredient weight% weight% weight% polybutadiene 62.5 62.0 61.6 zinc diacrylate 19.9 19.7 19.6 zinc oxide 6.3 6.2 6.2 zinc stearate 3.8 3.7 3.7 peroxide initiator 0.5 0.5 0.5 zinc pentachlorothiophenol 0.6 0.6 0.6 pigment 0.1 0.1 0.1 limestone 0 0 0 tungsten 0 0 0 barium sulfate 6.4 6.4 6.3 Graphene B 0 0.8 1.6 Graphene B masterbatch 0 0 0

The compression of composition 17 is 64.3, the compression of composition 18 is 68.0, and the compression of composition 19 is 67.1. The compression of the double core consisting of an inner core and an outer core is 42.1 for composition 17, 45.8 for composition 18 and 48.7 for composition 19. Compression is measured by applying a 200 pound load to the core and measuring its deflection in inches. Compression = 180 - (Warpage * 1000).

The cores were filmed at 175 fps on a pneumatic testing machine (PTM). Twelve cores were tested for each composition mentioned in Table 8. The number of shots before each core cracked was recorded for each core, and the cracked core was removed from the rest of the test. Data were reported using Weibull plots, and mean times to failure were reported as shown in Table 8. The test was stopped after 100 shots. As shown in FIG. 25, the graphene-modified cores withstood more shots before failure compared to cores without graphene. It is reasonable to assume that the durability of a golf ball with a double core of this design will also experience a dramatic increase in crack resistance based on the improvement to the double core. It's reasonable to assume that adding graphene to the inner core could improve the durability of the entire golf ball, but this study focused only on the outer core.

As shown in FIG. 26, as the average surface area of the graphene nanoplatelets increases, the mean time to failure (MTTF) or durability increases. For the same concentration of graphene, nanoplatelets with higher average surface area last longer in general durability tests.

A temperature/time experiment was conducted to test whether graphene helps reduce the time required to cure a given rubber core. The modified core contained 1.6% graphene in the outer core while the control core had no graphene. There is no graphene in the inner core. A thermocouple was attached to the outer core of the double core. The temperature of the outer core was recorded while curing the duplex core. The temperature inside the outer core of the double core was recorded as a function of time as shown in FIG. 27 . As shown in FIG. 27, cores containing graphene reach the maximum temperature faster than cores without graphene. This may be due to graphene's high thermal conductivity, which allows the outer core to reach higher temperatures more quickly than the core without graphene.

Novelty of this process: By incorporating graphene into the inner and outer cores, the durability of the double core with a large compression difference is greatly improved. The graphene reinforcement on the inner and outer core helps resist the high stress the core experiences when hit with high club speeds. Adding graphene to the core composition is very simple and can be dispersed into the polybutadiene mixture during a two-roll milling process. Due to the high thermal conductivity of graphene, the incorporation of graphene can increase the overall thermal conductivity of the core. If the thermal conductivity of the graphene-reinforced core is high, the curing cycle can be shortened. The shorter the curing cycle, the higher the yield. Optionally, graphene is introduced as a masterbatch in polybutadiene or polyisoprene to make the polybutadiene rubber much more easily dispersed and dust free.

As our experiments show, the incorporation of graphene into the inner and outer core compositions enhances the strength of the outer core and improves the crack-resistant protection in the design of a dual-core golf ball, indicating that the outer core is significantly better than the softer inner core. Harder cases are more susceptible to crack endurance failure.

Generally, this is applicable where the inner core is softer than the outer core. More specifically, if the inner core has a strain of 0.200" or greater under a 200 lb load, the double core is greater than 40 compression.

This is particularly important if the ball is a four-piece structure with a single mantle layer less than 0.050" thick, or more specifically less than 0.040", the goal of this study being 0.036" thick.

3 to 7 show an inner core (12a), an outer core (12b), an inner mantle (14a), an outer mantle (14b), and 5 to 45% by weight of a highly neutralized polymer, 5 to 45% by weight of a first ionomer, A cover layer composed of 5 to 45% by weight of the second ionomer, 5 to 45% by weight of the third ionomer, 5 to 30% by weight of a masterbatch comprising 15 to 40% by weight of an impact modifier, and 1 to 10% by weight of a color masterbatch. A five-piece golf ball 10 including (16) is shown. In an alternative embodiment, the cover layer 16 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier. The inner core 12a includes a polybutadiene mixture containing 0.4 to 2.5% by weight of graphene.

7A shows an inner core (12a), an intermediate core (12b), an outer core (12c), a mantle (14), and 5 to 45% by weight of a highly neutralized polymer, 5 to 45% by weight of a first ionomer, and 5 to 45% by weight of a second ionomer. A cover layer 16 composed of 5 to 30% by weight of a masterbatch, and 1 to 10% by weight of a color masterbatch comprising 5 to 45% by weight of a third ionomer, 5 to 45% by weight of a third ionomer, 15 to 40% by weight of an impact modifier, It shows a 5-piece golf ball 10 comprising: In an alternative embodiment, the cover layer 16 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier. The intermediate core 12b includes a polybutadiene mixture containing 0.4 to 2.5% by weight of graphene.

10 and 11 show an inner core (12a), an intermediate core (12b), an outer core (12c), an inner mantle (14a), an outer mantle (14b), and 5 to 45% by weight of a highly neutralized polymer, a first ionomer. 5 to 30 wt% masterbatch comprising 5 to 45 wt%, 5 to 45 wt% second ionomer, 5 to 45 wt% third ionomer, 15 to 40 wt% impact modifier, and 1 to 10 color masterbatches A six-piece golf ball 10 is shown including a cover layer 16 composed of weight percent. In an alternative embodiment, the cover layer 16 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier. The inner core 12a includes a polybutadiene mixture containing 0.4 to 2.5% by weight of graphene.

12 shows a dual core, boundary layer and 5 to 45 wt% highly neutralized polymer, 5 to 45 wt% first ionomer, 5 to 45 wt% second ionomer, 5 to 45 wt% third ionomer, 15 to 40 wt% A four-piece golf ball comprising a cover layer composed of 5 to 30% by weight of a masterbatch containing 5% to 30% by weight of an impact modifier, and 1 to 10% by weight of a color masterbatch. In an alternative embodiment, the cover layer comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt% second ionomer, 20-50 wt% impact modifier. It is composed of 15 to 25% by weight of the master batch containing, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier. The outer core includes a polybutadiene mixture containing 0.4 to 2.5 weight percent graphene.

13 shows core, boundary layer and 5-45 wt% highly neutralized polymer, 5-45 wt% first ionomer, 5-45 wt% second ionomer, 5-45 wt% third ionomer, 15-40 wt% A three-piece golf ball comprising a cover layer composed of 5 to 30% by weight of a masterbatch containing an impact modifier of , and 1 to 10% by weight of a color masterbatch. In an alternative embodiment, the cover layer comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt% second ionomer, 20-50 wt% impact modifier. It is composed of 15 to 25% by weight of the master batch containing, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier. The core includes a polybutadiene mixture containing 0.4 to 2.5% by weight of graphene.

14 and 15 show core 25 and highly neutralized polymer 5 to 45 wt%, first ionomer 5 to 45 wt%, second ionomer 5 to 45 wt%, third ionomer 5 to 45 wt%, 15 to 45 wt% A two-piece golf ball is shown comprising a cover layer 30 composed of 5 to 30% by weight of a masterbatch containing 40% by weight of an impact modifier, and 1 to 10% by weight of a color masterbatch. In an alternative embodiment, the cover layer 30 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier. The core includes a polybutadiene mixture containing 0.4 to 2.5% by weight of graphene.

16 and 17 show a core 10 with dimples 18, mantle layer 14 and 5-45 wt% highly neutralized polymer, 5-45 wt% first ionomer, 5-45 wt% second ionomer. %, 3 to 45% third ionomer, 5 to 30% by weight masterbatch comprising 15 to 40% by weight impact modifier, and 3 to 3 comprising a cover layer 16 composed of 1 to 10% by weight color masterbatch -Piece golf ball 5 is shown, wherein the core contains 0.4 to 2.5% by weight of graphene. In an alternative embodiment, the cover layer 16 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier.

18 shows an inner core 30, and an outer core 32, and 5 to 45 wt% of a highly neutralized polymer, 5 to 45 wt% of a first ionomer, 5 to 45 wt% of a second ionomer, and 5 to 45 wt% of a third ionomer. A three-piece golf ball (35) comprising a cover layer (34) composed of 45% by weight, 5 to 30% by weight of a masterbatch containing 15 to 40% by weight of an impact modifier, and 1 to 10% by weight of a color masterbatch. , wherein the core contains 0.4 to 2.5% by weight of graphene. In an alternative embodiment, the cover layer 34 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier.

19 shows core 40, mantle layer 42 and highly neutralized polymer 5-45 wt%, first ionomer 5-45 wt%, second ionomer 5-45 wt%, third ionomer 5-45 wt% , showing a three-piece golf ball 45 comprising a cover layer 44 composed of 5 to 30% by weight of a masterbatch containing 15 to 40% by weight of an impact modifier, and 1 to 10% by weight of a color masterbatch; , wherein the core contains 0.4 to 2.5% by weight of graphene. In an alternative embodiment, the cover layer 44 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-30 wt% first ionomer, 10-30 wt% second ionomer, 10-30 wt% third ionomer, 15-30 wt% It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier.

20 shows an inner core 50, an outer core 52, a mantle layer 54 and 5 to 45 wt% of a highly neutralized polymer, 5 to 45 wt% of a first ionomer, 5 to 45 wt% of a second ionomer, 3-ionomer 5-45 wt%, 15-40 wt% impact modifier masterbatch 5-30 wt%, and color masterbatch 1-10 wt% 4-piece golf comprising a cover layer (34) A ball 55 is shown, wherein the core contains between 0.4 and 2.5 weight percent graphene. In an alternative embodiment, the cover layer 56 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt% second ionomer, 20-50 wt% It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier.

21 shows a core 60, an inner mantle 62, an outer mantle 64 and 5 to 45 wt% highly neutralized polymer, 5 to 45 wt% first ionomer, 5 to 45 wt% second ionomer, and a third 4-piece golf ball comprising a cover layer 66 composed of 5 to 45% by weight of ionomer, 5 to 30% by weight of a masterbatch containing 15 to 40% by weight of an impact modifier, and 1 to 10% by weight of a color masterbatch (65), wherein the core comprises 0.4 to 2.5 weight percent graphene. In an alternative embodiment, the cover layer 66 comprises 30-40 wt% highly neutralized polymer ("HNP"), 10-20 wt% first ionomer, 10-20 wt%, 20-50 wt% second ionomer. It is composed of 15 to 25% by weight of the masterbatch containing an impact modifier, and 5 to 15% by weight of the color masterbatch. In another alternative embodiment, the cover layer comprises 35-45 weight percent highly neutralized polymer (“HNP”), 10-20 weight percent first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch. In yet another alternative embodiment, the cover layer comprises 10 to 30 weight percent highly neutralized polymer, 10 to 30 weight percent first ionomer, 10 to 30 weight percent second ionomer, 10 to 30 weight percent third ionomer, 15 to 30 weight percent. It consists of 15 to 25% by weight of the master batch containing 30% by weight of the impact modifier and 1 to 10% by weight of the color master batch. In yet another alternative embodiment, the cover layer comprises 10-30 wt% highly neutralized polymer, 10-90 wt% first ionomer, 0-30 wt% second ionomer, 0-30 wt% third ionomer, 15-90 wt% It is composed of 15 to 25% by weight of a masterbatch and 1 to 10% by weight of a color masterbatch containing 30% by weight of an impact modifier.

Optional mantle components preferably consist of an inner mantle layer and an outer mantle layer. The mantle component preferably has a thickness ranging from 0.05 inches to 0.15 inches, more preferably from 0.06 inches to 0.08 inches. The outer mantle layer preferably consists of a blend of ionomer materials. One preferred embodiment includes SURLYN 9150 material, SURLYN 8940 material, SURLYN AD 1022 material and a master batch. The SURLYN 9150 material is preferably present in an amount ranging from 20 to 45% by weight of the cover, more preferably from 30 to 40% by weight. SURLYN 8945 is preferably present in an amount ranging from 15 to 35% by weight of the cover, more preferably from 20 to 30% by weight and most preferably 26% by weight. SURLYN 9945 is preferably present in an amount ranging from 30 to 50% by weight of the cover, more preferably from 35 to 45% by weight and most preferably 41% by weight. SURLYN 8940 is preferably present in an amount ranging from 5 to 15% by weight of the cover, more preferably from 7 to 12% by weight and most preferably 10% by weight.

DuPont's SURLYN 8320 is an ultra-low modulus ethylene/methacrylic acid copolymer in which acid groups are partially neutralized using sodium ions. Also, DuPont's SURLYN 8945 is a highly acidic ethylene/methacrylic acid copolymer in which acid groups are partially neutralized with sodium ions. Also, DuPont's SURLYN 9945 is a highly acidic ethylene/methacrylic acid copolymer in which acid groups are partially neutralized with zinc ions. Also, DuPont's SURLYN 8940 is an ethylene/methacrylic acid copolymer in which acid groups are partially neutralized with sodium ions.

Embodiments having an inner mantle preferably have an inner mantle composed of a blend of ionomers, preferably comprising a terpolymer and two or more highly acidic (greater than 18% by weight) ionomers neutralized with sodium, zinc, magnesium or other metal ions. It has a mantle layer. The material for the inner mantle layer preferably has a Shore D plaque hardness in the range of 35 to 77, more preferably in the range of 36 to 44, and most preferably about 40. The thickness of the outer mantle layer preferably ranges from 0.025 inches to 0.050 inches, more preferably about 0.037 inches. The mass of the insert comprising the double core and inner mantle layer is preferably between 32 grams and 40 grams, more preferably between 34 and 38 grams, and most preferably about 36 grams. The inner mantle layer is composed of HPF material alternatively available from DuPont.

Embodiments with an outer mantle have an outer mantle layer preferably composed of a blend of ionomers comprising two or more highly acidic (greater than 18% by weight) ionomers neutralized with sodium, zinc or other metal ions. The blend of ionomers preferably includes a master batch. Preferably the material of the outer mantle layer preferably has a Shore D plaque hardness in the range of 55 to 75, more preferably in the range of 65 to 71, most preferably about 67. The thickness of the outer mantle layer preferably ranges from 0.025 inches to 0.040 inches, more preferably about 0.030 inches. The mass of the total insert including the core, inner mantle layer and outer mantle layer is preferably between 38 grams and 43 grams, more preferably between 39 and 41 grams, and most preferably about 41 grams.

In an alternative embodiment, the inner mantle layer is preferably composed of a blend of ionomers, preferably comprising two or more highly acidic (greater than 18% by weight) ionomers neutralized with sodium, zinc or other metal ions. . The blend of ionomers preferably includes a master batch. In this embodiment, the material of the inner mantle layer preferably has a Shore D plaque hardness in the range of 55 to 75, more preferably in the range of 65 to 71, and most preferably approximately 67. The thickness of the outer mantle layer is preferably between 0.025 inches and 0.040 inches, more preferably about 0.030 inches. Also in this embodiment, the outer mantle layer 14b preferably comprises a terpolymer and an ionomer comprising at least two highly acidic (greater than 18% by weight) ionomers neutralized with sodium, zinc, magnesium or other metal ions. It consists of a blend of In this embodiment, the material for the outer mantle layer l4b preferably has a Shore D plaque hardness in the range of 35 to 77, more preferably in the range of 36 to 44, and most preferably about 40. The thickness of the outer mantle layer preferably ranges from 0.025 inches to 0.100 inches, more preferably from 0.070 inches to 0.090 inches.

In another embodiment where the inner mantle layer is thicker than the outer mantle layer and the outer mantle layer is harder than the inner mantle layer, the inner mantle layer preferably comprises a terpolymer and at least two neutralized with sodium, zinc, magnesium or other metal ions. It consists of a blend of ionomers, including two highly acidic (greater than 18% by weight) ionomers. In this embodiment, the material for the inner mantle layer preferably has a Shore D plaque hardness in the range of 30 to 77, more preferably in the range of 30 to 50, and most preferably about 40. In this embodiment, the material for the outer mantle layer preferably has a Shore D plaque hardness of 40 to 77, more preferably 50 to 71, most preferably about 67. In this embodiment, the thickness of the inner mantle layer preferably ranges from 0.030 inches to 0.090 inches, and the thickness of the outer mantle layer ranges from 0.025 inches to 0.070 inches.

Preferably the inner core has a diameter ranging from 0.75 inches to 1.20 inches, more preferably from 0.85 inches to 1.05 inches, and most preferably about 0.95 inches. Preferably the inner core (12a) has a Shore D hardness in the range of 20 to 50, more preferably in the range of 25 to 40, most preferably about 35. Preferably the inner core has a mass in the range of 5 g to 15 g, 7 g to 10 g, most preferably about 8 g.

Preferably the outer core has a diameter of from 1.25 inches to 1.55 inches, more preferably from 1.40 inches to 1.5 inches, and most preferably about 1.5 inches. Preferably the outer core has a Shore D surface hardness of 40 to 65, more preferably 50 to 60, most preferably about 56. Preferably the outer core is formed of polybutadiene, zinc diacrylate, zinc oxide, zinc stearate, peptizer and peroxide. Preferably the combined inner core and outer core have a mass in the range of 25 g to 35 g, 30 g to 34 g, most preferably about 32 g.

Preferably the inner core has a deflection of at least 0.230 inches under a load of 220 pounds and the core has a deflection of at least 0.080 inches under a load of 200 pounds. As shown in Figures 8 and 9, a mass 50 is loaded onto the inner core and core. As shown in Figures 8 and 9, the mass is 100 kg, about 220 pounds. Under a load of 100 kg, the inner core preferably has a deflection of 0.230 inches to 0.300 inches. Under a load of 100 kg, the core preferably has a deflection of 0.08 inch to 0.150 inch. Alternatively, the load is 200 pounds (approximately 90 kg) and the deflection of the core 12 is greater than 0.080 inches. In addition, the compression deformation of the inner core from a starting load of 10 kg to an end load of 130 kg is in the range of 4 mm to 7 mm, more preferably 5 mm to 6.5 mm. The dual-core deflection differential allows for low spin off the tee for greater distance and high spin on approach shots.

In an alternative embodiment of the golf ball shown in FIG. 7A , golf ball 10 includes an inner core 12a, an intermediate core 12b, an outer core 12b, a mantle 14 and a cover 16. . The golf ball 10 preferably has a diameter of 1.68 inches or greater, a mass in the range of 45 grams to 47 grams, a COR of 0.79 or greater, and a deflection under 100 kg load of 0.07 mm or greater.

In a preferred embodiment, the golf ball has a dual core and 5 to 45 weight percent of a highly neutralized polymer, 5 to 45 weight percent of a first ionomer, 5 to 45 weight percent of a second ionomer, and 5 to 45 weight percent of a third ionomer. and a cover layer composed of ionomer, 5 to 30 weight percent master batch comprising 15 to 40 weight percent impact modifier, and 1 to 10 weight percent color master batch. The cover preferably has a hardness ranging from 30 to 60 Shore D, more preferably from 45 to 55 Shore D. The inner core preferably has a diameter of 1.1 to 1.5 inches, most preferably 1.25 inches. The double core (consisting of an inner core and an outer core) preferably has a diameter of 1.55 inches to 1.65 inches, most preferably 1.59 inches to 1.6 inches. The golf ball preferably has a diameter of at least 1.68 inches. The golf ball preferably has a mass of less than 45.93 grams, preferably in the range of 45.0 to 45.93 grams. The golf ball preferably has a COR of at least 0.790. The golf ball preferably has an INSTRON compression in the range of 0.10 to 0.13 inches.

As used herein, the "Shore D hardness" of golf ball layers is generally measured according to ASTM D-2240 type D, but the measurement may be made on the curved surface of a golf ball component rather than on a plaque. A measurement on the ball will indicate that the measurement was made on the ball. Regarding the hardness of the material of the golf ball layer, measurements are made on the plaque according to ASTM D-2240. Additionally, the Shore D hardness of the cover is measured while the cover remains over the mantle and core. When measuring the hardness of a golf ball, it is preferable to measure the Shore D hardness in the land area of the cover.

As used herein, the "Shore A hardness" of a cover is generally measured according to ASTM D-2240 type A, but the measurement may be made on the curved surface of the golf ball component rather than on the plaque. A measurement on the ball will indicate that the measurement was made on the ball. Regarding the hardness of the material of the golf ball layer, measurements are made on the plaque according to ASTM D-2240. Additionally, the Shore A hardness of the cover is measured while the cover remains over the mantle and core. When measuring the hardness of a golf ball, it is preferable to measure the Shore A hardness in the land area of the cover.

The elasticity or coefficient of restitution (COR) of a golf ball is a constant "e" that is the ratio of the relative velocity of an elastic sphere after direct impact to the relative velocity of the elastic sphere before impact. Consequently, COR("e") can vary from 0 to 1, where 1 corresponds to a perfect or completely elastic collision and 0 corresponds to a perfect or completely inelastic collision.

COR and environmental conditions (e.g. temperature, moisture, atmospheric pressure, wind, etc.) along with additional factors such as club head speed, club head mass, ball weight, ball size and density, spin speed, trajectory angle and surface composition are usually Determines the distance traveled when hit. Along this line, the distance a golf ball travels under controlled environmental conditions is a function of the speed and mass of the club, the ball's size, density and elasticity (COR), and other factors. The initial velocity of the club, the mass of the club and the angle at which the ball departs are basically provided by the golfer at the time of hitting. Club head speed, club head mass, trajectory angle and environmental conditions are not determinants within the golf ball manufacturer's control, and ball size and weight are set by the U.S.G.A. so these are not golf ball manufacturers' considerations. The factor or determinant of interest with respect to improved distance is usually the COR and the surface configuration of the ball.

The coefficient of restitution is the ratio of the exit velocity to the entry velocity. In this application example, the coefficient of restitution of a golf ball is measured by propelling the ball horizontally at a speed of 125 +/- 5 feet per second (fps) and calibrated to 125 fps against a generally vertical, hard, flat steel plate, It electronically measures entry and exit speeds. Velocity was measured with a pair of ballistic screens that provided timing pulses as objects passed. The screens are separated by 36 inches and are positioned 25.25 inches and 61.25 inches from the rebound wall. Ball velocity is measured by timing the pulse from screen 1 to screen 2 on the way to the rebound wall (as the average velocity of the ball over 36 inches), then exit velocity is timed from screen 2 to screen 1 over the same distance. was The rebound wall was tilted 2 degrees from the vertical plane, resulting in the ball rebounding slightly down to deflect the edge of the cannon that fired it. The rebound wall is solid steel.

As indicated above, the entry speed is 125 ± 5 fps, but it should be corrected to 125 fps. The correlation between COR and exit or entry velocity was studied and corrections were made in the ±5 fps range, so the COR is reported as if the ball had an entry velocity of exactly 125.0 fps.

Measurements for warpage, compression, hardness, etc. are preferably performed on the finished golf ball as opposed to making measurements on each layer during manufacturing.

Preferably, in a 5-layer golf ball including an inner core, an outer core, an inner mantle layer, an outer mantle layer and a cover, the hardness/compression of the layers is higher than that of the inner core and the inner core having the greatest warpage (lowest hardness). An outer core with less warpage (bonded to the inner core), an inner mantle layer having a hardness lower than the hardness of the combined outer core and inner core, an outer mantle layer having a hardness layer of a golf ball, and a hardness lower than that of the outer mantle layer. Includes a cover with hardness. These measurements are preferably performed on a finished golf ball dismantled for measurement.

Claims (12)

As a golf ball,
an inner core comprising a polybutadiene material;
an outer core comprising a polybutadiene material and a graphene material; and
A masterbatch comprising 5 to 45% by weight of a highly neutralized polymer, 5 to 45% by weight of a first ionomer, 5 to 45% by weight of a second ionomer, 5 to 45% by weight of a third ionomer, and 15 to 40% by weight of an impact modifier. 5 to 30% by weight, and a cover layer composed of 1 to 10% by weight of the color master batch;
wherein the golf ball has a diameter of at least 1.68 inches, a mass of less than 45.93 g, and a COR of at least 0.790. As a golf ball,
an inner core comprising a polybutadiene material;
an outer core comprising graphene and polybutadiene material in an amount ranging from 0.1% to 5.0% by weight of the outer core, the outer core having a flexural modulus ranging from 80 MPa to 95 MPa; and
30-40% by weight highly neutralized polymer, 10-20% by weight first ionomer; A cover layer composed of 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch,
A golf ball comprising a dual core comprising an inner core and an outer core having a compression value in the range of 40 to 55. As a golf ball,
an inner core comprising a polybutadiene material;
an outer core comprising graphene and polybutadiene materials; and
30-40% by weight highly neutralized polymer, 10-20% by weight first ionomer; A cover layer composed of 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a masterbatch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color masterbatch,
wherein the golf ball has a diameter of at least 1.68 inches, a mass of less than 45.93 g, and a COR of at least 0.790. As a golf ball,
an inner core comprising a polybutadiene material;
an outer core made of polybutadiene material; and
A master batch comprising 10 to 30% by weight of a highly neutralized polymer, 10 to 74% by weight of a first ionomer, 0 to 30% by weight of a second ionomer, 0 to 30% by weight of a third ionomer, and 15 to 30% by weight of an impact modifier. 15 to 25% by weight and a cover layer consisting of 1 to 10% by weight of the color masterbatch,
wherein the golf ball has a diameter of at least 1.68 inches, a mass of less than 45.93 g, and a COR of at least 0.790. 4. The golf ball according to any one of claims 1 to 3, wherein the graphene material is in an amount ranging from 0.4% to 2.5% by weight of the outer core. 4. The golf ball according to any one of claims 1 to 3, wherein the graphene material is in an amount ranging from 0.6% to 1.5% by weight of the outer core. The impact modifier according to any one of claims 1 to 4, wherein the impact modifier is a methyl methacrylate-butadiene-styrene polymer (MBS) impact property modifier for poly(vinyl chloride) and an acrylic/methacrylic core-shell for polycarbonate. At least one of the modifiers, a golf ball. 4. The golf ball according to any one of claims 1 to 3, wherein the graphene material has a surface area of 400 to 800 m ² /g. 5. A golf ball according to any one of claims 1 to 4, wherein the cover layer has a Shore D hardness in the range of 35 to 60. The golf ball according to any one of claims 1 to 4, wherein the outer core has a tensile modulus of 8 MPa to 10 MPa. As a golf ball,
An inner core comprising a polybutadiene material and a graphene material;
an outer core comprising a polybutadiene material and a graphene material; and
A masterbatch comprising 5 to 45% by weight of a highly neutralized polymer, 5 to 45% by weight of a first ionomer, 5 to 45% by weight of a second ionomer, 5 to 45% by weight of a third ionomer, and 15 to 40% by weight of an impact modifier. 5 to 30% by weight, and a cover layer composed of 1 to 10% by weight of the color master batch;
wherein the golf ball has a diameter of 1.68 or greater, a mass of less than 45.93 g, and a COR of 0.790 or greater. The golf according to claim 11, wherein the impact modifier is at least one of a methyl methacrylate-butadiene-styrene polymer (MBS) impact property modifier for poly(vinyl chloride) and an acrylic/methacrylic core-shell modifier for polycarbonate. ball.

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