# US 9,433,828 B2 · Dual core golf ball having negative-hardness-gradient thermoplastic inner core and steep positive-hardness-gradient thermoset outer core layer

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- Number: US 9,433,828 B2
- Document ID: US9433828B2
- Status: Granted
- Kind: B2
- Application number: 14/576,349
- Filed: 2014-12-19
- Published: 2015-04-16
- Granted: 2016-09-06
- Earliest claimed: 2007-11-14
- Assignees: Acushnet Company
- Applicants: Acushnet Company
- Inventors: Michael J. Sullivan; Mark L. Binette; Robert Blink; David Bulpett; Brian Comeau
- Web page: https://patentgrep.com/patent/US9433828B2

## CPC

- A63B 37/0092: {Hardness distribution amongst different ball layers}
- A63B 37/0003: {Golf balls}
- A63B 37/0006: {Arrangement or layout of dimples}
- A63B 37/0019: {Specified dimple depth}
- A63B 37/002: {Specified dimple diameter}
- A63B 37/0043: {Hardness}
- A63B 37/0044: {Hardness gradient}
- A63B 37/0045: {Thickness}
- A63B 37/0051: {Materials other than polybutadienes; Constructional details}
- A63B 37/0059: {Ionomer}
- A63B 37/00621: {Centre hardness}
- A63B 37/00622: {Surface hardness}
- A63B 37/0063: {Hardness gradient}
- A63B 37/0064: {Diameter}
- A63B 37/0076: {Multi-piece balls, i.e. having two or more intermediate layers}
- A63B 37/02: Special cores {(balls with finger holes A63B37/0001, golf ball cores A63B37/005)}
- A63B 45/00: Apparatus or methods for manufacturing balls (working of plastics or substances in a plastic state B29)
- C08K 5/09: Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K 5/098: Metal salts of carboxylic acids
- C08L 23/0876: Salts thereof, i.e. ionomers
- C08L 77/00: Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain (of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08); Compositions of derivatives of such polymers
- A63B: APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT (apparatus for passive exercising, massage A61H)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A golf ball includes a thermoplastic HNP inner core layer having a center hardness less than the surface hardness to define a positive hardness gradient. An outer core layer is disposed about the inner core and is formed from a thermoset rubber composition. The core layer has an inner surface hardness less than the outer surface hardness to define a positive hardness gradient. Inner and outer cover layers are disposed about the outer core layer. The HNP composition includes an acid copolymer of ethylene and an α,β-unsaturated carboxylic acid; a non-acid polymer comprising polyolefins, polyamides, polyesters, polyethers, polyurethanes, metallocene-catalyzed polymers, single-site catalyst polymerized polymers, ethylene propylene rubber, ethylene propylene diene rubber, styrenic block copolymer rubbers, alkyl acrylate rubbers, or functionalized derivatives thereof; an organic acid or salt thereof; and a cation source in an amount sufficient to neutralize at least about 80% of the acid groups.

## Claims

### Claim 1

A golf ball comprising:
an inner core layer comprising a thermoplastic highly neutralized polymer composition and having a geometric center hardness less than a surface hardness to define a positive hardness gradient;
an outer core layer disposed about the inner core, the outer core comprising a thermoset rubber composition and having an inner surface hardness less than an outer surface hardness to define a positive hardness gradient; and
a cover layer disposed about the outer core layer, the cover layer comprising an inner cover layer and an outer cover layer;
wherein the highly neutralized polymer composition comprises an acid copolymer of ethylene and an α,β-unsaturated carboxylic acid; a non-acid polymer comprising ethylene-n-butyl acrylate present in an amount of about 20 wt % or greater based on the total weight of the highly neutralized polymer composition, or functionalized derivatives thereof; an organic acid or salt thereof; and a cation source present in an amount sufficient to neutralize at least about 80% of the acid groups present in the composition.

### Claim 2 (depends on 1)

The golf ball of claim 1, wherein the acid copolymer of ethylene and an α,β-unsaturated carboxylic acid optionally includes a softening monomer comprising alkyl acrylates or methacrylates.

### Claim 3 (depends on 1)

The golf ball of claim 1, wherein the α,β-unsaturated carboxylic acid comprises acrylic acid and methacrylic acid and is present in the acid copolymer in an amount of from about 10 wt % to 25 wt % based on a total weight of the acid copolymer.

### Claim 4 (depends on 1)

The golf ball of claim 1, wherein the organic acid salt comprises magnesium oleate present in an amount of about 30 parts or greater per 100 parts of acid copolymer and non-acid copolymer combined.

### Claim 5 (depends on 1)

The golf ball of claim 1, wherein the acid groups of the copolymer are neutralized by 90% or greater.

### Claim 6 (depends on 5)

The golf ball of claim 5, wherein the acid groups of the copolymer are neutralized by about 100%.

### Claim 7 (depends on 1)

The golf ball of claim 1, wherein the organic acid or salt thereof comprises barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium salts, or salts of fatty acids.

### Claim 8 (depends on 7)

The golf ball of claim 7, wherein the fatty acid salt comprises stearic acid, behenic acid, erucic acid, oleic acid, linoelic acid or dimerized derivatives thereof.

### Claim 9 (depends on 1)

The golf ball of claim 1, wherein the thermoplastic inner core further comprises an ethylene/acid copolymer or ionomer.

### Claim 10 (depends on 1)

The golf ball of claim 1, wherein the inner core layer has a diameter of about 1.0 inches to about 1.30 inches.

### Claim 11

A golf ball comprising:
an inner core layer comprising a thermoplastic highly neutralized polymer composition and having a geometric center hardness less than a surface hardness to define a positive hardness gradient, the center hardness being about 30 Shore D to 65 Shore D and the surface hardness being 40 Shore D to about 65 Shore D;
an outer core layer disposed about the inner core, the outer core being formed from a substantially homogenous thermoset composition comprising a diene rubber and having an inner surface hardness less than an outer surface hardness to define a positive hardness gradient of about 11 Shore D to about 25 Shore D; and
a cover layer disposed about the outer core layer, the cover layer comprising an inner cover layer comprising an ionomer and an outer cover layer comprising a polyurethane;
wherein the highly neutralized polymer composition comprises an acid copolymer of ethylene and an α,β-unsaturated carboxylic acid; a non-acid polymer comprising polyolefins, polyamides, polyesters, polyethers, polyurethanes, metallocene-catalyzed polymers, single-site catalyst polymerized polymers, alkyl acrylate rubber, ethylene propylene rubber, ethylene propylene diene rubber, styrenic block copolymer rubbers, alkyl acrylate rubbers, or functionalized derivatives thereof; an organic acid or salt thereof; and a cation source present in an amount sufficient to neutralize at least about 80% of the acid groups present in the composition.

### Claim 12 (depends on 11)

The golf ball of claim 11, wherein the inner cover layer has a Shore D hardness of about 55 or greater and the outer cover layer has a Shore D hardness of about 60 or less.

### Claim 13 (depends on 11)

The golf ball of claim 11, wherein the acid groups of the copolymer are neutralized by 90% or greater.

### Claim 14 (depends on 13)

The golf ball of claim 13, wherein the acid groups of the copolymer are neutralized by about 100%.

### Claim 15 (depends on 11)

The golf ball of claim 11, wherein the inner core layer has a diameter of about 1.0 inches to about 1.30 inches.