KR20210023866A - Graphene core for golf balls with soft cover - Google Patents

Abstract

Disclosed herein is a core 12 comprising polybutadiene and graphene, and a golf ball 16 comprising a soft cover 16. The golf ball 10 has a double core 12 having 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 balls with soft cover

The present invention relates generally to the use of graphene in the layers of a golf ball, and more particularly to a golf ball having a graphene core and a 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 acids such as nitric and/or sulfuric acid, followed by heat treatment and chemical reduction. . Exfoliated graphite is a two-dimensional flat sheet made ^{of SP 2 -hybrid carbon.} Graphene (individual sheets of reduced exfoliated graphite) sheets generally have a thickness of several nanometers and a width of several microns (aspect ratio >1000). Due to the high aspect ratio of graphene bonded with high tensile strength (tensile strength of GPa compared to MPa of the polymer), it can be a polymer composite material with very high tensile and flexural properties. The unusually high thermal conductivity of graphene (about 3000 W / mk compared to <1 W / mk for a typical thermoplastic polymer) is; It can be used in the manufacture of thermally conductive composite materials. In the case of thermoset elastomer products, this high thermal conductivity can mean that shorter and more uniform cure cycles can lead to higher yields.

Various examples of exfoliated graphite (also referred to as graphene) based composites can be found in the literature. Wang et al. discloses expanded graphite polyethylene composites for electromagnetic radiation interference (EMI) shielding applications.

U.S. Patent No. 4946892 discloses synthesizing exfoliated graphene-based composites 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.

U.S. Patent No. 5776372 discloses electrically conductive nanocomposites made of expanded graphite and various polymers such as polypropylene, polytetrafluoroethylene and phenolic resins. Pan et al. discloses 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 methylmethacrylate in the presence of expanded graphite to obtain electrically conductive nanocomposites.

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

The prior art does not even recognize this problem.

The main object of the present invention is to improve the durability of the golf ball core by mixing graphene in the core to improve the impact strength of the ball, and to have a soft cover. This advantage can be seen in a ball with a single core or a double core with an outer core that is harder than the inner core. Using graphene to improve the durability of the core can increase the mean time to fail (MTTF) when repeatedly hitting a high-speed test device or 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. The cover layer is disposed over the outer core, and the cover layer is 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 a master batch comprising from to 40% by weight of an impact modifier, and from 1 to 10% by weight of a color master batch. The core comprising the inner core and the outer core has a compression value in the range of 40 to 55. Golf balls are at least 1.68 inches in diameter, weigh less than 45.93 grams, and have a COR of at least 0.790.

In a more preferred embodiment, the outer core comprises a graphene material in the range of 0.4 to 2.5% by weight of the outer core. In an even more preferred embodiment, the graphene material ranges from 0.6 to 1.5% by weight 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 comprises a polybutadiene material. The outer core comprises a graphene material and a polybutadiene material in an amount ranging from 0.1 to 5.0% by weight of the outer core, wherein the outer core has a flexural modulus in the range of 80 MPa to 95 MPa. The cover layer is disposed over the outer core. The cover layer 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 of the third ionomer, and 15 to 40% by weight of an impact modifier. 5 to 30% by weight of the master batch and 1 to 10% by weight of the color master batch. The double core comprises an inner core and the outer core has a compression value in the range of 40 to 55. The golf ball has a diameter of at least 1.68 inches, a mass of less than 45.93 grams and a COR of at least 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 comprises a graphene material and polybutadiene in an amount ranging from 0.1 to 5.0% by weight of the inner core. The outer core comprises 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 in the range of 80 MPa to 95 MPa. The cover layer is disposed over the outer core. The cover layer 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 of the third ionomer, and 15 to 40% by weight of an 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 compression value of the double core is 40 to 55.

Another aspect of the invention is a golf ball comprising a dual core composed of an inner core and an outer core, and a mantle layer and a cover layer. The inner core comprises a graphene material and polybutadiene in an amount ranging from 0.1 to 5.0% by weight of the inner core. The outer core comprises 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 in the range of 80 MPa to 95 MPa. The cover layer is disposed over the mantle layer. The cover layer 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 of the third ionomer, and 15 to 40% by weight of an 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. The double core has a compression value in the range of 40 to 55.

1 is an exploded partial cut-away view of a golf ball.
2 is a partial exploded view of a golf ball.
3 is an exploded partial cut-away view of a golf ball.
4 is a top perspective view of a golf ball.
5 is a cross-sectional view of key components 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 an inner core layer, an outer core layer, an inner mantle layer, an outer mantle layer and a cover layer of a bone ball.
7A is a cross-sectional view of an inner core layer, an intermediate core layer, an outer core layer, a mantle layer and a cover layer of a golf ball.
8 is a cross-sectional view of the inner core layer under 100 kg load.
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 the core component, mantle component and cover layer of a golf ball.
12 is an exploded partial cut-away view of a four-piece golf ball.
13 is an exploded partial cut-away view of a three-piece golf ball.
14 is an exploded partial cut-away 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 cut-away view of a three-piece golf ball.
18 is a cross-sectional view of a three-piece golf ball having a double core and a cover.
19 is a cross-sectional view of a three-piece golf ball with double, mantle and cover.
20 is a cross-sectional view of a four-piece golf ball with a double core, mantle layer and cover.
21 is a cross-sectional view of a four-piece golf ball having a core, a double mantle layer and a cover.
22 is a graph showing durability test of an outer core using PTM at 175 fps.
23 is a graph of durability test of a dual core using PTM at l75fps.
24 is a graph of durability test of a dual core using PTM at l75fps.
25 is a graph showing durability test of a dual core using PTM at l75fps.
26 is an example of graphene.
27 is a graph of durability test of a dual core using PTM at 175fps.
28 is a durability plot (MTTF) versus the average surface area of graphene.
29 is a graph of the temperature of the outer core of the double core as a function of curing time.

One object of the present invention is to improve the durability of a golf ball core by incorporating graphene into any core in order 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 a dual core with the outer core harder than the inner core. Using graphene to improve the durability of the core or mantle configuration can lead to longer mean time to failure (MTTF) when repeatedly impacted on high-speed test equipment or when golf clubs are used in normal play.

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

In a preferred embodiment, the golf ball is a highly neutralized polymer 5 to 45% by weight, first ionomer 5 to 45% by weight, second ionomer 5 to 45% by weight, third ionomer 5 to 45% by weight, 15 to 40% by weight 5 to 30% by weight of a master batch comprising an impact modifier of, and a core having a cover layer consisting of 1 to 10% by weight of a color master batch. In an alternative embodiment, the cover layer 16 comprises 30-40% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; The second ionomer comprises 10 to 20% by weight, 15 to 25% by weight of a master batch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of 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 and is 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 in which acid groups are 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 include acrylonitrile-butadiene-styrene polymer (ABS), methyl methacrylate-butadiene-styrene polymer (MBS) for poly(vinyl chloride) impact-property modifier and acrylic/methacrylic core for polycarbonate -It is at least one of the shell modifiers.

The polybutadiene-based core was made using the following materials. Corresponding levels (based on weight percent) are noted next to each material: polybutadiene-(40-90%) with at least 60% l,4-cis structure; Polyisoprene-(1-30%); Zinc diacrylate-(10-50%); Zinc oxide-(1-30%); Zinc stearate-(1-20%); Peroxide initiator-(0.1-10%); Zinc penta chlorothiophenol-(0-10%); Pigment-(0-10%); Barium sulfate-(0-20%); Graphene A (0.0l-6%)-(available from various suppliers such as Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., Angstron Materials Inc.) Can have an average surface area of 50 m ^{2 /g);} Graphene B (0.0l-6%) (available from various suppliers such as Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., Angstron Materials Inc.) (Graphene B is 300 to 400) may have an average surface area of m ^{2 /g);} Graphene C (0.0l-6%) (available from various suppliers such as Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., Angstron Materials Inc.) (graphene C is graphene A) Or graphene B has a larger average surface area, and graphene C may have an average surface area of ^{400 to 800 m 2 /g);} Graphene masterbatch (90-99% polybutadiene or polyisoprene and 1-10% graphene masterbatch)-(0.1-50%)-Custom compounding is available 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 shown in the composition in Table 1. There was no graphene in the control group (Composition 1).

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 during master batch 0.0 0.0 0.0 0.0 Core characteristics compression 69.4 74.3 74.6 76.4 COR (coefficient of restitution at 125fps) 0.801 0.800 0.795 0.790 Durability score or average failure time MTTF (number of shots before crack/failure) 34 60 47 62

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

Durability test of solid core

The core was photographed 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 cracking in each core was recorded for each core, and the cracked core was removed from the rest of the tests. Data were reported using a Weibull plot, and the mean time to failure was reported as shown in Table 1. As shown in Fig. 20, the graphene-modified core endured more shots before failure than the core 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 durability based on these improvements to the core.

In this study, graphene A was introduced into the outer core in a double core structure. The dual core was made by compression molding two outer core halves around an already molded inner core with a diameter of about 0.940" (inch) and a soft compression of deflection of about 0.200 inches under a 200 lb load. Hardening of the inner and outer cores Was carried out at a temperature ranging from 150 to 400°F for a time ranging from 1 to 30 minutes. After molding, the double core was spheroidized to about 1.554" before testing.

Tables 2 and 3 provide details on the composition of the inner and outer cores. Components of this composition were mixed in an internal mixer. Optionally, further mixing was carried out using a two-roll mill.

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

The compression difference represents the difference between the outer core compression (independently molded) and the inner core compression. The larger the difference in compression, the weaker the crack durability during 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
(1.6% graphene) 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 during master batch 0.0 0.0 0.0 0.0 Core characteristics 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 125fps) 0.796 0.795 0.793 0.790 Durability score or average failure time MTTF (number of shots before crack/failure) 50 60 52 57

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

Durability test of double core

The core was photographed 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 cracking in each core was recorded for each core, and the cracked core was removed from the rest of the tests. Data were reported using a Weibull plot, and the mean time to failure was reported as shown in Table 3. As shown in Fig. 21, the graphene-modified core endured more shots before failure compared to the core 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 the crack durability 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%, Cheap Tubes Inc., Ad-Nano Technologies Private Limited, MKnano, XG Sciences Inc., and Angstron Materials Inc.) are available from various suppliers, with an average surface area of 400 to 800. m ² /g) was introduced into the outer core in a double core structure. The dual core was made by compression molding two outer core halves around an already molded inner core with a diameter of about 0.940" and a soft compression of deflection of about 0.200 inches under 200 lb load. The hardening of the inner and outer cores ranged from 1 to 1 It was carried out at a temperature in the range of 150 to 400 F for a time in the range of 30 minutes. After shaping, the double core was spheroidized to about 1.554" before testing.

Tables 4 and 5 provide details on the composition of the inner and outer cores. Components of this composition were mixed in an internal mixer. Optionally, further mixing was carried out using a two-roll mill.

Compression of the outer core is measured by first making a full-sized core separately, measuring the compression, and then forming two halves around the inner core to complete a double core. The compression difference represents the difference between the outer core compression (independently molded) and the inner core compression. The larger the difference in compression, the more susceptible to crack durability during 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 during master batch 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 during master batch 0.0 0.0 0.0 0.0 Core characteristics 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 strength of the core in MPa 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 125fps) 0.795 0.794 0.793 0.789 Durability score or average failure time MTTF (number of shots before crack/failure) 33 67 78 99

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

Twelve cores were tested for each composition mentioned in Table 5. The number of shots before cracking in each core was recorded for each core, and the cracked core was removed from the rest of the tests. Data were reported using a Weibull plot, and the mean time to failure was reported as shown in Table 5. The test stopped after 100 shots. As shown in Fig. 22, the graphene-modified core endured more shots before failure than the core 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 durability based on this improvement to a double core. It is reasonable to assume that adding graphene to the inner core can improve the durability of the entire golf ball, but this study focused only on the outer core.

Dual 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 composition of these dual cores. Components of this composition were mixed in an internal mixer. Optionally, further mixing was carried out using a two-roll mill. The dual core was made by compression molding two outer core halves around an already molded inner core with a diameter of approximately 0.940" and a soft compression of deflection of approximately 0.200 inches under 200 lb load. The hardening of the inner and outer cores ranged from 1 to 1 It was performed at a temperature in the range of 150 to 400 F for a time in the range of 30 minutes. After shaping, the double core was spheroidized to about 1.554 inches before testing.

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

Table 6. Dual core composition with graphene A on 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 characteristics 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 125fps) 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 125fps) 0.795 0.793 0.793 0.792 Durability score or average failure time MTTF (number of shots before crack/failure) 29 24 33 40

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

Twelve cores were tested for each composition mentioned in Table 6. The number of shots before cracking in each core was recorded for each core, and the cracked core was removed from the rest of the tests. Data were reported using the Weibull plot, and the mean time to failure was reported as shown in Table 6. As shown in Fig. 23, the graphene-modified core endured more shots before failure compared to the core without graphene. The best durability was observed in 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 durability based on this improvement to a double core. It is reasonable to assume that adding graphene to the inner core can improve the durability of the entire golf ball, but this study focused only on the outer core.

Dual core with graphene B only on the outer core

In this study, graphene B was introduced into the outer core of the double core structure. The dual core was made by compression molding two outer core halves around a preformed inner core with a diameter of about 0.940” and a smooth compression of about 0.200 inches of deflection under a 200 lb load. Curing of the inner and outer cores was carried out at a temperature in the range of 150 to 400 F for a time in the range of 1 to 30 minutes. After shaping, the double core was spheroidized to about 1.554 inches before testing.

Tables 7 and 8 provide details on the composition of the inner and outer cores. Components of this composition were mixed in an internal mixer. Optionally, further mixing was carried out using a two-roll mill.

Compression of the outer core is measured by first making a full-sized core separately, measuring the compression, and then forming two halves around the inner core to complete a double core. The compression difference represents the difference between the outer core compression (independently molded) and the inner core compression. The larger the difference in compression, the more susceptible to crack durability during 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 200lb 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 master batch 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 composed of an inner core and an outer core was 42.1 for composition 17, 45.8 for composition 18, and 48.7 for composition 19. Compression is measured by applying a load of 200 pounds to the core and measuring its deflection in inches. Compression = 180-(deflection * 1000).

The core was photographed 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 cracking in each core was recorded for each core, and the cracked core was removed from the rest of the tests. Data were reported using a Weibull plot, and the mean time to failure was reported as shown in Table 8. The test was stopped after 100 shots. As shown in Fig. 25, the graphene-modified core endured more shots before failure than the core 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 durability based on the improvement to a double core. It is reasonable to assume that adding graphene to the inner core can 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 nanoplate increases, the average failure time (MTTF) or durability increases. For the same concentration of graphene, nanoplatelets with a higher average surface area last longer in typical durability tests.

Temperature/time experiments were conducted to test whether graphene helps reduce the time required to cure a given rubber core. The control core did not contain graphene, while the modified core contained 1.6% graphene in the outer core. There is no graphene in the inner core. The thermocouple was attached to the outer core of the double core. The temperature of the outer core was recorded while curing the double 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, a core containing graphene reaches a maximum temperature faster than a core not containing graphene. This may be due to the high thermal conductivity of graphene, which allows the outer core to reach higher temperatures faster 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 difference in compression was greatly improved. Graphene reinforcement on the inner and outer cores helps to resist the high stress experienced by the core when struck at high club speeds. Adding graphene to the core composition is very simple and can be dispersed in the polybutadiene mixture during the 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 into polybutadiene or polyisoprene as a masterbatch, making it much easier to disperse and dust free in polybutadiene rubber.

As can be seen from our experiments, the incorporation of graphene into the inner and outer core composition enhances the strength of the outer core and improves the crack endurance protection function in the design of the dual core golf ball, which makes the outer core much more than the soft inner core. If it is harder, it is more susceptible to crack endurance failure.

In general, this is applicable when the inner core is softer than the outer core. More specifically, if the inner core has a deformation of 0.200" or more under 200 lb load, the double core is 40 compression or more.

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

3 to 7 show an inner core (12a), an outer core (12b), an inner mantle (l4a), an outer mantle (l4b), and 5 to 45% by weight of a highly neutralized polymer, 5 to 45% by weight of a first ionomer, Cover layer consisting of 5 to 45% by weight of a second ionomer, 5 to 45% by weight of a third ionomer, 5 to 30% by weight of a master batch comprising an impact modifier of 15 to 40% by weight, and 1 to 10% by weight of a color master batch A five-piece golf ball 10 comprising 16 is shown. In an alternative embodiment, the cover layer 16 comprises 30-40% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer, 10-20% by weight of the second ionomer, and 20-50% by weight. It consists of 15 to 25% by weight of the master batch containing the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of impact modifier. The inner core 12a contains 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 (l4), and a highly neutralized polymer 5 to 45% by weight, a first ionomer 5 to 45% by weight, a second ionomer 5 To 45% by weight, 5 to 45% by weight of a third ionomer, 5 to 30% by weight of a master batch comprising an impact modifier of 15 to 40% by weight, and a cover layer 16 consisting of 1 to 10% by weight of a color master batch. It shows a five-piece golf ball 10 comprising. In an alternative embodiment, the cover layer 16 comprises 30-40% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer, 10-20% by weight of the second ionomer, and 20-50% by weight. It consists of 15 to 25% by weight of the master batch containing the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of impact modifier. The intermediate core 12b contains 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 (l4a), an outer mantle (14b), and 5 to 45% by weight of a highly neutralized polymer, a first ionomer. 5 to 45% by weight, 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 master batch comprising an impact modifier of 15 to 40% by weight, and 1 to 10 of the color master batches It shows a 6-piece golf ball 10 comprising a cover layer 16 consisting of weight percent. In an alternative embodiment, the cover layer 16 comprises 30-40% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer, 10-20% by weight of the second ionomer, and 20-50% by weight. It consists of 15 to 25% by weight of the master batch containing the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of impact modifier. The inner core 12a contains a polybutadiene mixture containing 0.4 to 2.5% by weight of graphene.

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

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

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

16 and 17 show the core 10, the mantle layer 14 and the highly neutralized polymer 5 to 45 wt%, the first ionomer 5 to 45 wt%, the second ionomer 5 to 45 wt%, with dimples 18 %, 5 to 30% by weight of a master batch comprising 5 to 45% by weight of a third ionomer, 15 to 40% by weight of an impact modifier, and 3 comprising a cover layer 16 consisting of 1 to 10% by weight of a color master batch. -A 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% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer, 10-20% by weight of the second ionomer, and 20-50% by weight. It consists of 15 to 25% by weight of the master batch containing the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of impact modifier.

18 is an inner core 30, and an outer core 32, and 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 a third ionomer. 3-piece golf ball 35 comprising a cover layer 34 consisting of 45% by weight, 5-30% by weight of a master batch comprising 15-40% by weight of an impact modifier, and 1-10% by weight of a color master batch Is shown, wherein the core contains 0.4 to 2.5% by weight of graphene. In an alternative embodiment, the cover layer 34 comprises 30-40% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer, 10-20% by weight of the second ionomer, and 20-50% by weight. It consists of 15 to 25% by weight of the master batch containing the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of impact modifier.

FIG. 19 shows the core 40, the mantle layer 42, and 5 to 45% by weight of a highly neutralized polymer, 5 to 45% by weight of the first ionomer, 5 to 45% by weight of the second ionomer, and 5 to 45% by weight of the third ionomer. , A three-piece golf ball 45 comprising a cover layer 44 composed of 5 to 30% by weight of a master batch comprising 15 to 40% by weight of an impact modifier, and 1 to 10% by weight of a color master batch, and , Here, the core contains 0.4 to 2.5% by weight of graphene. In an alternative embodiment, the cover layer 44 comprises 30-40% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer, 10-20% by weight of the second ionomer, and 20-50% by weight. It consists of 15 to 25% by weight of the master batch containing the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of 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, and 3 4-piece golf comprising a cover layer 34 consisting of 5 to 45% by weight of ionomer, 5 to 30% by weight of a master batch comprising 15 to 40% by weight of an impact modifier, and 1 to 10% by weight of a color master batch Ball 55 is shown, wherein the core contains 0.4 to 2.5% by weight of graphene. In an alternative embodiment, the cover layer 56 comprises 30-40% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer, 10-20% by weight of the second ionomer, and 20-50% by weight. It consists of 15 to 25% by weight of the master batch containing the impact modifier, and 5 to 15% by weight of the color master batch. In another alternative embodiment, the cover layer comprises 35-45% by weight of a highly neutralized polymer (“HNP”), 10-20% by weight of the first ionomer; 10 to 20% by weight of the second ionomer, 15 to 25% by weight of a master batch including 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of a highly neutralized polymer, 10 to 30% by weight of the first ionomer, 10 to 30% by weight of the second ionomer, 10 to 30% by weight of the third ionomer, 15 to It consists of 15 to 25% by weight of a master batch and 1 to 10% by weight of a color master batch comprising 30% by weight of impact modifier. In another alternative embodiment, the cover layer comprises 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to It consists of 15 to 25% by weight of the master batch and 1 to 10% by weight of the color master batch containing 30% by weight of impact modifier.

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

The optional mantle component preferably consists of an inner mantle layer and an outer mantle layer. The mantle component preferably has a thickness in the range of 0.05 inches to 0.15 inches, more preferably 0.06 inches to 0.08 inches. The outer mantle layer is preferably composed of a blend of ionomer materials. One preferred embodiment comprises SURLYN 9150 material, SURLYN 8940 material, SURLYN AD 1022 material and master batch. The SURLYN 9150 material is preferably present in an amount ranging from 20 to 45% by weight, more preferably from 30 to 40% by weight of the cover. 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 from 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 from 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 from 10% by weight.

DuPont's SURLYN 8320 is an ultra-low modulus ethylene/methacrylic acid copolymer that uses sodium ions to partially neutralize acid groups. In addition, DuPont's SURLYN 8945 is a highly acidic ethylene/methacrylic acid copolymer that partially neutralizes acid groups with sodium ions. In addition, DuPont's SURLYN 9945 is a highly acidic ethylene/methacrylic acid copolymer that partially neutralizes acid groups with zinc ions. In addition, 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 consist of a blend of terpolymers and preferably ionomers comprising two or more highly acidic (>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 36 to 44, most preferably about 40. The thickness of the outer mantle layer is preferably in the range of 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 32 to 40 grams, more preferably 34 to 38 grams, and most preferably about 36 grams. The inner mantle layer is made of HPF material, available alternatively from DuPont.

Embodiments with an outer mantle have an outer mantle layer, preferably composed of a blend of ionomers, preferably comprising two or more highly acidic (>18% by weight) ionomers neutralized with sodium, zinc or other metal ions. The blend of ionomers preferably comprises a master batch. Preferably the material of the outer mantle layer has a Shore D plaque hardness of preferably in the range of 55 to 75, more preferably 65 to 71, and most preferably about 67. The thickness of the outer mantle layer is preferably in the range of 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 38 to 43 grams, more preferably 39 to 41 grams, and most preferably about 41 grams.

In an alternative embodiment, the inner mantle layer preferably consists of a blend of ionomers, preferably comprising two or more highly acidic (>18% by weight) ionomers neutralized with sodium, zinc or other metal ions. . The blend of ionomers preferably comprises 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 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. Further, in this embodiment, the outer mantle layer 14b is preferably an ionomer comprising a terpolymer and two or more highly acidic (>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 14b preferably has a Shore D plaque hardness in the range of 35 to 77, more preferably 36 to 44, most preferably about 40. The thickness of the outer mantle layer is preferably in the range of 0.025 inches to 0.100 inches, more preferably 0.070 inches to 0.090 inches.

In another embodiment wherein 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 is preferably at least two neutralized with a terpolymer and sodium, zinc, magnesium or other metal ions. It consists of a blend of ionomers comprising high acidic (>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 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 and 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 in the range of 0.75 inches to 1.20 inches, more preferably 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 25 to 40, and most preferably about 35. Preferably the inner core has a mass in the range of 5g to 15g, 7g to 10g, most preferably about 8g.

Preferably the outer core has a diameter of 1.25 inches to 1.55 inches, more preferably 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 and 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 and outer cores 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. 8 and 9, the mass 50 is loaded onto the inner core and core. 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. It is preferred that the core has a deflection of 0.08 inches to 0.150 inches under a load of 100 kg. Alternatively, the load is 200 pounds (approximately 90 kg) and the deflection of the core 12 is at least 0.080 inches. In addition, the compressive deformation of the inner core from 10 kg of starting load to 130 kg of ending load is in the range of 4 mm to 7 mm, more preferably 5 mm to 6.5 mm. The dual core deflection difference allows for low spin off the tee, providing greater distance and higher spin on approach shots.

In an alternative embodiment of the golf ball shown in FIG. 7A, the golf ball 10 comprises 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 more, a mass in the range of 45 grams to 47 grams, a COR of 0.79 or more, and a deformation under a 100 kg load of 0.07 mm or more.

In a preferred embodiment, the golf ball has a double core and 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 A cover layer consisting of an ionomer, 5 to 30% by weight of a master batch comprising 15 to 40% by weight of an impact modifier, and 1 to 10% by weight of a color master batch. The cover preferably has a hardness in the range of 30 to 60 Shore D, more preferably 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 dual 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 the golf ball layers is generally measured according to ASTM D-2240 type D, but the measurement can be made on the curved surface of the golf ball component rather than on the plaque. If you measure on the ball, it will indicate that the measurement has been made on the ball. Regarding the hardness of the material of the golf ball layer, measurements are made on plaques according to ASTM D-2240. In addition, the Shore D hardness of the cover is measured while the cover remains on the mantle and core. When measuring hardness for 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 the cover is generally measured according to ASTM D-2240 type A, but the measurement can be made on the curved surface of the golf ball component rather than on the plaque. If you measure on the ball, it will indicate that the measurement has been made on the ball. Regarding the hardness of the material of the golf ball layer, measurements are made on plaques according to ASTM D-2240. In addition, the Shore A hardness of the cover is measured while the cover remains on 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 recovery factor (COR) of a golf ball is a constant "e", which is the ratio of the relative velocity of the elastic sphere after direct impact to the relative velocity of the elastic sphere before impact. As a result, COR("e") can vary from 0 to 1, where 1 corresponds to a perfect or complete elastic collision and 0 corresponds to a perfect or complete 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 generally When this is correct, determine the distance traveled. 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 size, density and elasticity (COR) of the ball, and other factors. The initial speed of the club, the mass of the club, and the angle at which the ball breaks off is basically provided by the golfer on hitting. Club head speed, club head mass, trajectory angle, and environmental conditions are not determinants that can be controlled by golf ball producers, and ball size and weight are set by U.S.G.A, so these are not considerations of golf ball manufacturers. The factor or determinant of interest with regard to the improved distance is generally the surface composition of the COR and balls.

The coefficient of restitution is the ratio of the entry speed and the entry speed. In an example of this application, the coefficient of restitution of a golf ball is measured by propelling the ball horizontally at a rate of 125 +/- 5 fps (feet per second) and calibrated to 125 fps for a generally vertical, hard and flat steel plate, and The speed of entry and exit is measured electronically. Velocity was measured with a pair of ballistic screens providing timing pulses as the object passes through it. The screen is separated by 36 inches and is located 25.25 inches and 61.25 inches from the rebound wall. The ball velocity is measured by timing the pulses from Screen 1 to Screen 2 on the way to the rebound wall (as the average velocity of a ball exceeding 36 inches), then the exit velocity is timed from Screen 2 to Screen 1 for the same distance. I got it. The rebound wall is tilted 2 degrees from the vertical plane, resulting in the ball rebounding slightly downwards to deflect the edge of the cannon that fired the ball. The recoil wall is solid steel.

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

Measurements of deflection, compression, hardness, etc. are preferably performed on a finished golf ball as opposed to performing measurements on each layer during manufacture.

Preferably, in a five-layer golf ball comprising an inner core, an outer core, an inner mantle layer, an outer mantle layer and a cover, the hardness/compression of the layers is greater than that of the inner core, inner core with the greatest deflection (lowest hardness). The outer core with less deflection (bonded with the inner core), the inner mantle layer having a hardness lower than the hardness of the outer core and inner core bonded, the outer mantle layer with the hardness layer of the golf ball, and the hardness of the outer mantle layer. Includes a cover having a hardness. These measurements are preferably carried out on a finished golf ball that has been disassembled 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
Master batch comprising 5 to 45% by weight of highly neutralized polymer, 5 to 45% by weight of first ionomer, 5 to 45% by weight of second ionomer, 5 to 45% by weight of third ionomer, 15 to 40% by weight of impact modifier 5 to 30% by weight, and a cover layer consisting of 1 to 10% by weight of the color master batch,
The golf ball has a diameter of 1.68 or more, a mass of less than 45.93 g, and a COR of 0.790 or more. 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 of highly neutralized polymer, 10-20% by weight of first ionomer; A cover layer consisting of 10 to 20% by weight of a second ionomer, 15 to 25% by weight of a master batch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch,
A golf ball, wherein the dual core comprising an inner core and an outer core has a compression value in the range of 40 to 55. As a golf ball,
An inner core comprising a polybutadiene material;
An outer core containing graphene and polybutadiene material; And
30-40% by weight of highly neutralized polymer, 10-20% by weight of first ionomer; A cover layer consisting of 10 to 20% by weight of a second ionomer, 15 to 25% by weight of a master batch containing 20 to 50% by weight of an impact modifier, and 5 to 15% by weight of a color master batch,
The golf ball has a diameter of 1.68 inches or more, a mass of less than 45.93 g, and a COR of 0.790 or more. As a golf ball,
An inner core comprising a polybutadiene material;
An outer core containing a polybutadiene material; And
Master batch comprising 10 to 30% by weight of highly neutralized polymer, 10 to 90% by weight of first ionomer, 0 to 30% by weight of second ionomer, 0 to 30% by weight of third ionomer, 15 to 30% by weight of impact modifier Including a cover layer consisting of 15 to 25% by weight and 1 to 10% by weight of the color master batch,
The golf ball has a diameter of 1.68 inches or more, a mass of less than 45.93 g, and a COR of 0.790 or more. The golf ball according to any one of claims 1 to 4, wherein the graphene material is in an amount ranging from 0.4% to 2.5% by weight of the outer core. The golf ball according to any one of claims 1 to 4, wherein the graphene material is in an amount ranging from 0.6% to 1.5% by weight of the outer core. The method of any one of claims 1 to 4, wherein the impact modifier is a methyl methacrylate-butadiene-styrene polymer (MBS) impact modifier for poly(vinyl chloride) and an acrylic/methacrylic core-shell for polycarbonate. One or more of the modifiers, the golf ball. The golf ball according to any one of claims 1 to 4, wherein the graphene material has a surface area of ^{400 to 800 m 2 /g.} 5. A golf ball according to any of the preceding claims, 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
Master batch comprising 5 to 45% by weight of highly neutralized polymer, 5 to 45% by weight of first ionomer, 5 to 45% by weight of second ionomer, 5 to 45% by weight of third ionomer, 15 to 40% by weight of impact modifier 5 to 30% by weight, and a cover layer consisting of 1 to 10% by weight of the color master batch,
The golf ball has a diameter of 1.68 or more, a mass of less than 45.93 g, and a COR of 0.790 or more. The method of claim 11, wherein the impact modifier is at least one of a methyl methacrylate-butadiene-styrene polymer (MBS) impact modifier for poly(vinyl chloride) and an acrylic/methacrylic core-shell modifier for polycarbonate, golf zero.

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