KR100786513B1 - Highly neutralized ethylene copolymers and their use as golf ball components - Google Patents

Abstract

The present invention relates to thermoplastics having high elasticity (high resilience) and ductility (low hardness) and their use as golf ball parts. The present invention provides a highly neutralized melt processable ethylene acid copolymer and a highly neutralized melt processable ethylene acid copolymer by incorporating an aliphatic monofunctional organic acid into the acid copolymer and then neutralizing all acids to a level higher than 90%. It is about how to.

Coefficient of Repulsion, Ionomer, Arti Hardness, Neutralization, Thermoplastic

Description

Highly neutralized ethylene copolymers and their use as golf ball components {HIGHLY-NEUTRALIZED ETHYLENE COPOLYMERS AND THEIR USE IN GOLF BALLS}             

This application is partly pending application of US patent application Ser. No. 09 / 588,894, which claims priority to co-pending US patent application Ser. No. 09 / 422,142.

The present invention relates to copolymers of highly neutralized melt processable ethylene with C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acids and methods for their preparation. The invention also relates to copolymers having a degree of neutralization greater than 90%, in particular copolymers having a degree of neutralization of almost 100% or 100%. To prepare such copolymers, a sufficient amount of a particular organic acid (or salt) is incorporated into the copolymer before the copolymer is neutralized to high levels.

The present invention particularly relates to (1) copolymers of ethylene and C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acids whose crystallinity is reduced by addition of softening monomers or other methods; 2) A highly neutralized (more than 90% neutralizing) meltable polymer comprising a sufficient amount of nonvolatile non-moving material such as an organic acid (or salt) that can significantly or completely inhibit ethylene crystallinity. Materials other than organic acids (or salts) can also be used.

The present invention, when molded as a sphere, has a coefficient of restitution (COR) of at least 0.785 (the thermoplastic plastic sphere is at an initial rate of 125 feet per second on a steel plate located 3 feet away from the determination point of the initial velocity). It relates to a thermoplastic that fires and bounces back from the steel sheet (as determined by dividing the rebound velocity by the initial velocity), and has an Atti compression of 100 or less.

Such copolymers are useful for the production of molded articles, such as golf ball parts, thermoplastic soles of cleated footwear, and elastic foams for sporting goods. They are particularly useful for the manufacture of one-piece, two-piece and three-piece, and multi-layered golf balls. The present invention relates in particular to spherical parts (core, seam, one-piece holes) having a COR of 0.785 or more and an Arti hardness of 100 or less (measured at an initial rate of 125 feet / second).

Typical high-end golf balls include three-piece, two-piece and multi-layer golf balls. “Three-piece” balls typically include a spherical shim, a rubber seal-like material wound around this shim, and a thermoplastic or thermoset cover. A "two piece" ball typically comprises a spherical core covered with a thermoplastic material. A "multilayer" ball typically comprises a spherical core and one or more interlayers or mantles between the core and the cover.

The cores of three-piece balls and the cores of two-piece balls and multi-layer balls have traditionally been made of thermosetting rubber such as polybutadiene rubber. If thermoset rubber is used, the production of shims and cores requires a complex multi-step process and the debris cannot be recycled. To solve this problem, thermoplastics have been used instead of thermosets, but they have been less successful. In addition, attempts to manufacture the finest dress ball were unsuccessful. See US Patent No. 5,155,157 and UK Patent Application No. 2,164,342A and WO 92/12206. Balls, cores and shims made with reference to these documents are expensive and lack properties such as durability, ductility (low arterial hardness) and elasticity to be used in the manufacture of the finest balls.

One of the thermoplastics that has long been proven useful for golf ball parts and other applications is the ionomer of alpha olefins, especially copolymers of ethylene and C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acids. US Patent No. 3,264,272 (Rees) discloses a process for making ionomers from "direct" acid copolymers. A "direct" copolymer is a polymer that is polymerized by adding all monomers simultaneously, unlike graft copolymers, most often made by grafting additional monomers on a polymer already made by free radical reaction. Methods of making acid copolymers that are the parent of ionomers are described in US Pat. No. 4,351,931.

The acid copolymer may contain a third "softening" monomer that reduces the crystallinity of the polymer. Such acid copolymers in which the alpha olefin is ethylene can be represented as an E / X / Y copolymer wherein E is ethylene and X is an α, β-ethylenically unsaturated carboxylic acid, especially acrylic acid and methacrylic acid. And Y is a softening comonomer. Preferred softening comonomers are C ₁ -C ₈ -alkyl acrylate or methacrylate esters. X and Y may be present in a wide range of ratios, where X is typically up to about 35% by weight of the polymer and Y is typically up to about 50% by weight of the polymer.

Various cations are known which can neutralize the acid groups in the acid copolymer. The degree of neutralization is known to vary widely. Typical cations include lithium, sodium, potassium, magnesium, calcium, barium, lead, tin, zinc, aluminum and combinations thereof. Although a degree of neutralization of 90% or more, even up to 100%, is known, this high degree of neutralization results in loss of meltability or physical properties such as extensibility and toughness. There is therefore a particular need for copolymers having high acid levels and which can be neutralized with cations other than barium, lead and tin.

Summary of the Invention

The thermoplastic composition of the present invention, when molded into a sphere of 1.50 to 1.54 inches in diameter, has a COR of at least 0.785 (the sphere is fired at an initial rate of 125 feet per second on a steel plate located 3 feet away from the determination point of the initial velocity). , The rate of bounce back from the steel sheet (as determined by dividing the rate of bounce) by the initial rate), and the artis hardness of 100 or less.

The thermoplastic composition of the invention preferably comprises (a) an aliphatic monofunctional organic acid having less than 36 carbon atoms, and (b) ethylene with a C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acid. Copolymers and ionomers thereof, wherein all acids of (a) and (b) are neutralized to levels higher than 90%, preferably almost 100%, more preferably exactly 100%.

The thermoplastic composition is preferably (1) ethylene and C ₃ -C ₈ -α, β-ethylenically unsaturated whose crystallinity is reduced by the addition of softening monomers or by other methods (for example, raising the acid level). Highly neutralized (greater than 90%), including non-volatile non-moving materials such as copolymers with carboxylic acids and (2) organic acids (or salts) that can significantly or completely inhibit any remaining ethylene crystallinity. Degree of neutralization, preferably about 100% neutralization degree, more preferably 100% degree of neutralization) melt-processable polymer. Materials other than organic acids (or salts) can also be used.

It has been found that by modifying the acid copolymer or ionomer with a sufficient amount of a particular organic acid (or salt thereof), the acid copolymer can be neutralized to a high level without losing processability or physical properties such as extensibility and toughness. The organic acids used in the present invention are aliphatic monofunctional saturated or unsaturated organic acids, in particular organic acids having less than 36 carbon atoms, in particular ionic array plasticizing, or a ratio capable of inhibiting ethylene crystallinity. It is a volatile non-mobile organic acid.

By adding an amount of the organic acid in the acid copolymer that is the parent of the ionomer to a level higher than 90%, almost 100%, preferably 100%, the acid can be processed without compromising the processability and physical properties such as elongation and toughness. The copolymer can be neutralized.                 

In order to prepare highly neutralized melt processable acid copolymer ionomers, (1) copolymers of ethylene with α, β-ethylenically unsaturated C ₃ -C ₈ -carboxylic acids or their melt processible ionomers will not be Ion-unionized to an extent not neutralized) and (2) at least one aliphatic monofunctional saturated or unsaturated organic acid having less than 36 carbon atoms or salts thereof, at the same time or after that, (b) all acid groups (acids) A sufficient amount of cation source is added so that the degree of neutralization is higher than 90%, preferably almost 100%, more preferably 100%, based on both the acid groups in the copolymer and the acid groups in the organic acid.

Preferably, to prepare the highly neutralized thermoplastics of the present invention, (1) ethylene and α, β-ethylenically unsaturated C ₃ -C ₈ whose crystallinity is reduced by addition of softening monomers or by other methods Melt-blending a copolymer with a carboxylic acid or its meltable ionomer and (2) a sufficient amount of nonvolatile non-movable material capable of significantly removing residual ethylene crystallinity, and at the same time or afterwards, (b) all acid groups The degree of neutralization is higher than 90%, preferably almost 100%, more preferably 100%, based on (including both the acid groups in the acid copolymer and the acid groups in the organic acid when the nonvolatile non-moving material is an organic acid). Add sufficient amount of cation source to make.

As used herein, "copolymer" refers to a polymer containing two or more monomers. "Copolymers of various monomers" refers to copolymers having units derived from various monomers. "Consisting essentially of ..." Corresponding components are essential components, and other components may be present in a smaller amount so as not to impair the effects of the present invention. "(Meth) acrylic acid" refers to methacrylic acid and / or acrylic acid. Likewise "(meth) acrylate" refers to methacrylate and / or acrylate.

All references mentioned herein, including the documents mentioned in the "Background" and the priorities of this application, are incorporated by reference in their entirety.

Acid copolymer

The acid copolymers used to make the ionomers in the present invention are preferably "direct" acid copolymers. These are preferably copolymers of alpha olefins, in particular ethylene, with C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acids, in particular acrylic acid and methacrylic acid. This copolymer optionally contains a third softening monomer. "Softening" refers to reducing crystallinity (polymers become less crystalline). Suitable “softened” comonomers are monomers selected from alkyl acrylates and alkyl methacrylates (alkyl groups having from 1 to 8 carbon atoms).

Acid copolymers in which the alpha olefin is ethylene can be represented as an E / X / Y copolymer, where E is ethylene, X is an α, β-ethylenically unsaturated carboxylic acid, and Y is a softening comonomer . X is preferably present at 3 to 30% by weight of the polymer (preferably 4 to 25% by weight, most preferably 5 to 20% by weight), and Y is preferably 0 to 30% by weight of the polymer (and Alternatively 3 to 25 weight percent or 10 to 23 weight percent).

Since monomers and polymers are easily phase-separated, it is difficult to produce ethylene-acid copolymers having high levels of acid (X) in a continuous polymerization reactor. However, this challenge can be solved by using the "co-solvent technique" described in US Pat. No. 5,028,674 or by using a pressure slightly higher than the pressure at which copolymers with lower levels of acid are produced.

Examples of acid copolymers include ethylene / (meth) acrylic acid copolymers. Also included here are ethylene / (meth) acrylic acid / n-butyl (meth) acrylate, ethylene / (meth) acrylic acid / iso-butyl (meth) acrylate, ethylene / (meth) acrylic acid / methyl (meth) acrylate, and Ethylene / (meth) acrylic acid / ethyl (meth) acrylate terpolymers.

Ionomer

The unmodified melt-processing ionomers used in the present invention are prepared from acid copolymers as described under the heading "acid copolymers made with ionomer production methods known in the art" (see "Background"). This includes partially neutralized acid copolymers, in particular ethylene / (meth) acrylic acid copolymers. Unmodified ionomers can be neutralized to any level such that they will not become non-melt polymers that do not have useful physical properties. Preferably, about 15 to about 80%, preferably about 50 to about 75%, of the acid groups of the acid copolymer are neutralized by alkali metal or alkaline earth metal cations. In the case of acid copolymers having a high level of acid (eg 15 wt% or more), the percent neutralization should be lower to maintain melt processability.

Useful cations for preparing unmodified ionomers are lithium, sodium, potassium, magnesium, calcium, zinc or combinations thereof.

Organic acids and salts

Organic acids used in the present invention are aliphatic monofunctional (saturated, unsaturated or polyunsaturated) organic acids, in particular organic acids having less than 36 carbon atoms. Salts of these organic acids can also be used. Salts vary, in particular including barium salts, lithium salts, sodium salts, zinc salts, bismuth salts, potassium salts, strontium salts, magnesium salts or calcium salts of organic acids.

When melt-blending an acid copolymer or ionomer with an organic acid (and salt), it may be useful to use a low volatility organic acid (and salt), but neutralize the blend at high levels, particularly at nearly 100% or 100%. It has been found that there is no need to limit volatility. For 100% neutralization (based on all acids in copolymers and organic acids), volatility is no longer a problem. Organic acids having less carbon atoms can also be used. However, it is preferred that the organic acid (or salt thereof) is nonvolatile and non-mobile. Preference is given to using a substance which effectively plasticizes or removes ethylene crystallinity of the copolymer of ethylene with C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acid or ionomer thereof. "Non-volatile" means that it does not volatilize at the melt-blend temperature with the acid copolymer. "Non-movable" means that it will not bounce on the surface of the polymer under normal storage conditions (room temperature). Particularly useful organic acids include less than C ₄ -C ₃₆ (eg C ₃₄ ), C ₆ -C ₂₆ , in particular C ₆ -C ₁₈ , especially C ₆ -C ₁₂ organic acids. Particularly useful organic acids in the present invention include caproic acid, caprylic acid, capric acid, lauric acid, stearic acid, behenic acid, erucic acid, oleic acid and linoleic acid.

filling

The optional filler component of the present invention is selected to add density to the blend of components described above, taking into account the type of golf ball (ie, one piece, two piece, three piece or interlayer) as will be described in the future. Generally, the filler is an inorganic material having a density greater than about 4 g / cc, preferably greater than 5 g / cc, and is present at 0 to about 60 weight percent based on the total weight of the composition. Examples of useful fillers include zinc oxide, barium sulfate, lead silicate, tungsten carbide and tin oxide, as well as corresponding known salts and oxides thereof. It is desirable for the filler to be non-reactive or almost non-reactive and not to enhance or increase hardness and to significantly reduce COR.

Other ingredients

Additional and optional additives useful in the practice of the present invention include acid copolymer waxes (e.g., ethylene / having a number average molecular weight of 2040) which may assist in preventing the reaction of fillers (e.g. ZnO) with acid groups in the ethylene copolymer. Allied wax AC143, a 16-18% acrylic acid copolymer, is included. Other optional additives include TiO ₂ used as a whitening agent; Optional brighteners; Surfactants; Processing aids;

Ductile High-COR Thermoplastics

The present invention relates to soft and elastic (soft high COR) thermoplastic polymers. The soft, high-COR thermoplastics, when molded into spheres of 1.50 to 1.54 inches in diameter, have a COR of 0.785 or greater (the sphere is fired at an initial rate of 125 feet / sec on a steel plate located 3 feet away from the initial point of determination, The Arti hardness is determined by dividing the rate of bounce back from the steel plate by the initial velocity. The present invention also relates to ductile high COR thermoplastics having COR of 0.790, 0.795, 0.800, 0.805, 0.810, 0.815, 0.820, 0.825, 0.830, 0.835 and Arti hardness of 95, 90, 85, 80, 75 or less.

Such soft high-COR thermoplastics preferably comprise (a) a melt-blended polymer (a) and (b) at least one of the above-mentioned acid copolymers or melt-processing ionomers and (b) the above-mentioned aliphatic monofunctional organic acids or salts thereof. All acids) are neutralized to levels above 90%). Preferably all of the acids of (a) and (b) are neutralized almost 100% or 100% by the cation source. Preferably, the acid of (a) and (b) is neutralized using a larger amount of cation source than necessary to neutralize all the acids of (a) and (b).

Preferably, the acid copolymer is an E / X / Y copolymer, where E is ethylene, X is an α, β-ethylenically unsaturated carboxylic acid and Y is a softening comonomer. X is preferably present at 3 to 30% by weight of the polymer (preferably 4 to 25% by weight, most preferably 5 to 20% by weight), and Y is preferably 0 to 30% by weight of the polymer (and Alternatively 3 to 25 weight percent or 10 to 23 weight percent). Organic acids are non-volatile non-mobile organic acids that effectively plasticize ions and / or inhibit crystallinity of an E / X / Y copolymer or ionomer.

Preferably, the crystallinity of the acid copolymer can be reduced by adding softening monomers or using other methods. If softening monomers are not available, another way to reduce crystallinity is to raise the acid level. For example, in the E / X / Y copolymer, X may be methacrylic acid present in an amount greater than 18% by weight or acrylic acid present in an amount greater than 15% by weight and Y is absent. Preferably, the organic acid is selected as significantly or completely inhibiting the ethylene crystallinity, which is melt-blended with an acid copolymer having low crystallinity and at a high level (higher than 90% based on all acids, almost 100%). Or 100%).

Selection of materials according to elasticity and hardness

In the practice of the present invention, elasticity and hardness are largely combined according to the type of golf ball (ie one piece, two piece, three piece or multilayer) and the desired performance of the golf ball as described below.

Preferred Embodiments of Three-Piece Golf Balls

Three-piece golf balls are made by well known methods, such as those described in US Pat. No. 4,846,910. In order to manufacture the three-piece seam shim to meet the object of the present invention, the density of the seam is about, depending on the diameter of the seam, the yarn wound on the seam, the thickness and composition of the cover so that the finished golf ball meets the PGA weight limit (45g) The spheres of the desired size are injection molded or compression molded from the above-mentioned soft high COR thermoplastics filled with a sufficient amount of filler to be 1.6 g / cc to about 1.9 g / cc.

Preferred Embodiments of Two-Piece Golf Balls

Two-piece golf balls are made by well known methods (the cover is injection molded or compressed onto the core). In order to manufacture the two-piece ball core to meet the object of the present invention, the core density is about 1.14 g / cc depending on the diameter of the core, the thickness of the cover and the composition so that the finished golf ball meets the PGA weight limit (45 g). The spheres of the desired size are injection molded or compression molded from the above-mentioned soft high-COR thermoplastics, filled with a sufficient amount of filler to be from about 1.2 g / cc.

Preferred Embodiments of Multilayer Golf Balls

Multi-layer golf balls are made by well known methods (the injection molded or compression molded cores are covered with one or more intermediate layers or membranes and the cover is injection molded or compression molded). To produce the core and / or interlayer, injection molding a sphere or layer of the desired size or thickness from the above described soft high COR thermoplastics filled with a sufficient amount of filler to provide a golf ball conforming to the PGA weight limit (45 g). Or compression molding. The amount of filler used in the core and the interlayer can vary from 0 to about 60 weight percent, depending on the size (thickness) of the components and the weight position in the golf ball, to the extent that the finished golf ball meets weight limits. The filler may be filled only in the core and not in the interlayer, only in the interlayer and not in the core, or both. This embodiment provides a composition comprising (1) a core comprising the same composition as used for the three-piece shim and an interlayer film made from any composition known in the art, and (2) the same composition as used for the two-piece core or three-piece shim. A core comprising, and an interlayer made of a composition of the present invention with or without a filler within the limits that the finished golf ball meets the weight limits, (3) any (including thermosetting compositions such as polybutadiene rubber) Cores made of the composition, and interlayers made of the composition of the present invention with or without fillers within the limit that the finished golf ball meets the weight limits, and combinations thereof.

cover

Golf ball covers comprising the soft, high-COR thermoplastics described above are also within the scope of the present invention. The method of making a cover includes the above described soft high COR thermoplastics (fillers, other components, and other ionomers) on the thermoplastic or thermoset core of a two piece golf ball, on a thermoplastic or thermoset core wound, or as an outer layer of a multilayer golf ball. Injection molding or compression molding, with or without other thermoplastics, including).

Preferred Embodiments of One Piece Golf Balls

The one-piece hole can be made by a known injection molding method or a compression molding method. The ball has a traditional dimple pattern and may be coated with urethane lacquer or painted for aesthetics, but such application and / or painting will not affect the performance of the golf ball.

In order to produce the dress ball of the present invention, a sphere of the desired size is injection molded or compression molded from the above-mentioned soft high-COR thermoplastics filled with a sufficient amount of filler to provide a golf ball conforming to the PGA weight limit (45 g). . Preferably a sufficient amount of filler is used so that the density of the balls is 1.14 g / cc.

Process for producing highly neutralized ionomer

The method of making the highly neutralized melt processable acid copolymer ionomer of the present invention comprises (a) a copolymer of ethylene with an α, β-ethylenically unsaturated C ₃ -C ₈ -carboxylic acid or an ionomer thereof Melt-blending one or more aliphatic monofunctional saturated or unsaturated organic acids or salts thereof having less than 36 carbon atoms with ionomers that are not neutralized to such an extent that they are (b) all acid groups (acid copolymerization) An amount of cation source sufficient to bring the neutralization degree to a level higher than 90%, preferably almost 100%, more preferably 100%, based on both the acid groups in the organic groups and the acid groups in the organic acid).

Preferably, aliphatic monofunctional saturated or unsaturated organic acids having less than 36 carbon atoms or salts thereof are copolymers of ethylene and α, β-ethylenically unsaturated C ₃ -C ₈ -carboxylic acids or ionomers thereof And from about 5 to about 150 pph (parts per hundred parts) (or about 25 to about 80 pph) based on the weight of the polymer.

This neutralization of the acid copolymer and organic acid (simultaneously or sequentially) is less than the degree of neutralization of the meltability and physical properties of the ionomer alone, without the loss of processability or physical properties such as toughness and elongation without the use of an inert diluent. It has been found to be the only way to neutralize the copolymer at high levels. For example, the acid copolymer can be neutralized to a level higher than 90%, preferably nearly 100% or 100%, without the loss of meltability that may occur when the acid copolymer is neutralized to a level higher than 90%. . In addition, when molding the mixture neutralized to less than 100%, it can be seen that organic acids are deposited in a mold vent, and if the neutralization is performed at almost 100% or 100%, this can be reduced.

Melt-blending an acid copolymer or an unmodified melt-processing ionomer with an organic acid or salt can be performed by any method known in the art. For example, the ingredients can be salt and pepper blended and melt-blended in an extruder.

The melt processable acid copolymer / organic acid or salt blend can be neutralized or further neutralized by methods known in the art. For example, Werner & Pfleiderer twin screw extruders can be used to neutralize acid copolymers and organic acids simultaneously.

Depending on the acid level of the copolymer or terpolymer, the level of organic acid controlling the processability can be determined in accordance with the teachings herein. The higher the acid level in the main chain of the copolymer or terpolymer, the higher the proportion of organic acid needs to be. For example, for E / 14-16% nBA / AA terpolymers, see Table 1 for a comparison of melt indices at various acid levels. Smaller amounts of lower molecular weight organic acids are needed to produce the same effect as higher amounts of higher molecular weight organic acids.

Methods of making highly neutralized melt processable ionomers include (a) (1) copolymers of ethylene with α, β-ethylenically unsaturated carboxylic acids or their melt processable ionomers (the ethylene crystallinity of the acid copolymer is reduced). And (2) melt an amount of a nonvolatile non-moving material sufficient to significantly or completely inhibit the remaining ethylene crystallinity of the copolymer of ethylene with an α, β-ethylenically unsaturated carboxylic acid or its meltable ionomer. Blending, and (b) at the same time or after this, all acid groups of the acid copolymer or its ionomer are higher than 90% (preferably such that the nonvolatile non-moving material retains its acid groups as is) Adding a sufficient amount of cation source to neutralize to about 100% or at least 100%).

Preferably the non-volatile non-moving material is about 5 to about 150 (or about 25 to about based on the weight of the copolymer or ionomer of ethylene with α, β-ethylenically unsaturated C ₃ -C ₈ -carboxylic acid 80) exists as pph.

Preferably, the amount of cation source is greater than the amount necessary to neutralize all acid groups in the acid copolymer or ionomer thereof such that the nonvolatile non-mobile material retains its acid groups as is.                 

Preferably, the process employs copolymers of ethylene and α, β-ethylenically unsaturated carboxylic acids, or melt processable ionomers thereof, wherein the acid copolymers or ionomers are E / X / Y copolymers or E / Expressed as a melt processable ionomer of the X / Y copolymer, where E is ethylene, X is C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acid, Y is a softening comonomer, X is About 4 to 25 weight percent of the E / X / Y copolymer, and Y is about 3 to 25 weight percent of the E / X / Y copolymer.

Preferably the nonvolatile nonionic material is an organic acid or salt thereof, more preferably oleic acid.

Comparison of Melt Index According to Stearic Acid Level and% AA Mountain level Melt Index of Base Resin Stearic acid levels 20% 30% 35% 40% 45% 8.1% AA 67.9 1.8 2 6 8.3% AA 62.5 1.08 1.13 2.25 10.1% AA 66.8 0.62 1.55 2.22 6.8% AA 75 1.25 1.92 6.52 4.9% AA 86 4.9 9.7 23.2

Thermoplastic

Highly neutralized melt process ionomer

The thermoplastic compositions of the present invention consist essentially of (a) aliphatic monofunctional organic acids having less than 36 carbon atoms; And (b) a copolymer of ethylene with C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acids or ionomers thereof, wherein all acids of (a) and (b) are higher than 90% Preferably it is neutralized at almost 100%, More preferably, 100%.

The final material can be made by melt-blending the highly neutralized melt processable acid copolymer of the present invention with other components. For example, melt-blended components and acid copolymers used in co-pending US patent application Ser. No. 09 / 422,142 may be used to dress one-piece, two-piece, three-piece and multi-layer golf balls, and footwear and other athletic balls (e.g., For example, you can create a useful form for a softball ball. In this case, the components used with the highly neutralized melt processable acid copolymer include thermoplastic polymer components and fillers selected from copolyetheresters, copolyetheramides, elastomeric polyolefins, styrene diene block copolymers and thermoplastic polyurethanes. .

Test Criteria Used in Examples

The coefficient of repulsion (COR) is measured by firing a complete sphere, injection molded from the resin into the size of a golf ball, from the air cannon at a rate determined by air pressure. Initial speed is typically 125 feet / second. The sphere hits a steel plate three feet away from the initial speed decision point and bounces back through a speedometer installed at the same point as the initial speed decision point. The bounce speed divided by the initial speed is COR.

PGA hardness is defined as the resistance to deformation of a golf ball, measured by an artie device.

Tensile properties (tensile at break, elongation at break, tensile yield and elongation yield) are determined according to ASTM D1708.                 

Percent bounce is determined by dropping the ball (or three-piece shim / two-piece core) at a height of 100 inches and measuring the degree of jumping from a hard, hard surface, such as a thick steel sheet or stone block. Acceptable values are about 65 to 85%.

In the table below, the numbers in parentheses indicate the weight percent of the components in the blend.

Using a Werner und Flyderer biaxial screw extruder, 4812 g of stearic acid were added to 7218 g of E / 23nBA / 9.6MAA polymer. A sufficient amount of magnesium hydroxide was added to this mixture to neutralize at least 90% and at least 95% of the soluble acids (see Examples 1a and 1b in Table 1).

Two other resins having the composition shown in Table 2 were reacted with stearic acid and magnesium hydroxide. In this case, however, a sufficient amount of magnesium hydroxide was added to neutralize 100% of the total soluble acid. These mixed anionic ionomer examples 1c and 1d are listed in Table 2.

Magnesium ionomer modified with magnesium stearate Example number Resin composition Cation type Organic acid (%) Neutralization degree (%) Melt Index (g / 10min) 1a E / 23nBA / 9.6MAA Mg Stearic Acid (40) 90 5.2 1b E / 23nBA / 9.6MAA Mg Stearic Acid (40) 95 3.6 1c E / 15nBA / 8.5AA Mg Stearic Acid (40) More than 100 1.15 1d E / 16nBA / 12AA Mg Stearic Acid (40) More than 100 0.09

The physical properties of the 100% neutralized resin of Example 1c are described in Table 3 below.                 

PGA Hardness COR Tensile strength at break (psi) Yield Tensile Strength (psi) Elongation at Break (%) Yield Elongation (%) 90 0.787 2802 2069 340 28

Thermoplastic

The following describes a method of making a blend to make a test sphere. The extrusion conditions used to make the blends described in Table 5 are listed in Table 4.

Extrusion Conditions for Preparing Blends of Table 5 Screw speed (rpm) Zone 1 temperature (℃) Band 2-3 temperature (℃) Zone 4-9 Temperature (℃) Die temperature (℃) Speed (lb / hour) Speed (inch) 100-300 75-100 125-150 140-240 200-230 15-25 28

Sample number Resin Type (%) Acid type (%) Cation (% Neutralization ^* ) Melt Index (g / 10min) 1A A (60) Oleic Acid (40) Magnesium (100) 1.0 2B A (60) Oleic Acid (40) Magnesium (105 ^* ) 0.9 3C B (60) Oleic Acid (40) Magnesium (100) 0.9 4D B (60) Oleic Acid (40) Magnesium (105 ^* ) 0.9 5E B (60) Stearic Acid (40) Magnesium (100) 0.85 A-ethylene, 14.8% n-butyl acrylate, 8.3% acrylic acid B-ethylene, 14.9% n-butyl acrylate, 10.1% acrylic acid * is an amount sufficient to neutralize 105% of all acids present in the resin and organic acid To indicate that it was.

The molding conditions used to make the spheres 1.53 inches in diameter to obtain the data described in Table 7 below are listed in Table 6.

Forming condition of sphere Temperature (℃)    Cylinder rear 183    Cylinder center 173    Cylinder all 173    Nozzle 177    Mold front / rear 10    Melt molding materials 195 Pressure (㎏ / ㎠)    1st injection pressure 130    2nd injection pressure 110    Injection Hold 13 Molding cycle (seconds)    Pack 10    Hold 480    Booster 10    Cure Time 15    Screw Retraction 5.35

Sample number Arti Hardness COR (125 feet / second) 1A 75 0.826 2B 75 0.826 3C 78 0.837 4D 76 0.837 5E 97 0.807

The results show that COR is much greater than 0.785 and Arti hardness is less than 100. Fill the resin with a dense filler such as zinc oxide and soften it with a polyetherester such as the one sold under the trademark Hytrel® by EIdu Pont de Nemours and Company. This makes it possible to make thermoplastic golf ball parts.

Claims (27)

Coefficient of restitution (COR) when molded as a sphere with a diameter of 1.50 to 1.54 inches (fired at an initial rate of 125 feet / sec on a steel plate located 3 feet away from the determination of initial velocity) A melt processable thermoplastic polymer having a ratio of 0.785 or more and an Atti compression of 100 or less; The thermoplastic polymer (a) E / X / Y copolymers, where E is ethylene, X is C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acid, and Y is of E / X / Y copolymer Softening comonomer, X is 3-30% by weight of the E / X / Y copolymer or partially neutralized ionomer thereof, Y is 0-30% by weight of the E / X / Y copolymer), and (b) one or more aliphatic monofunctional organic acids having less than 36 carbon atoms or salts thereof, present in 25 to 150 parts per hundred parts (pph) based on the weight of the E / X / Y copolymer Contains as a main ingredient, All the acids of (a) and (b) are neutralized by the cation source to a level higher than 90%, melt processability is maintained when the acids of (a) and (b) are neutralized to a level higher than 90%, the neutralization is A melt processable thermoplastic composition, comprising adding a cation source together with melt blending of (a) and (b) or after melt blending of (a) and (b). The composition of claim 1 wherein the COR is at least 0.800. The composition of claim 2 wherein the COR is at least 0.810. The composition of claim 1 wherein the organic acid or salt thereof is a nonvolatile non-moving material. The composition of claim 4 wherein X is from 4 to 25% by weight of the E / X / Y copolymer and Y is from 3 to 25% by weight of the E / X / Y copolymer. The composition of claim 4 wherein X is 5-20% by weight of the E / X / Y copolymer and Y is 10-23% by weight of the E / X / Y copolymer. The composition of claim 4 wherein X is methacrylic acid present in an amount greater than 18% by weight or acrylic acid present in an amount greater than 15% by weight and Y is absent. The composition of claim 1, wherein 100% of the acids present in (a) and (b) are neutralized. 9. The composition of claim 8, wherein the acid of (a) and (b) is neutralized using a cation source in an amount greater than the amount necessary to neutralize the acid of (a) and (b) by 100%. The composition of claim 1, wherein the organic acid is at least one C ₆ -C ₂₆ organic acid. The composition of claim 10, wherein the organic acid is at least one C ₆ -C ₁₈ organic acid. The composition of claim 11, wherein the organic acid is at least one C ₆ -C ₁₂ organic acid. A golf ball comprising a cover comprising a composition according to claim 1. A two-piece golf ball comprising a core comprising a composition according to claim 1 and a cover surrounding the core. A three-piece golf ball comprising a shim comprising the composition of claim 1. A multi-layer golf ball comprising a core comprising the composition of claim 1. A one-piece golf ball comprising the composition of claim 1. A multi-layer golf ball comprising an interlayer comprising a composition according to claim 1. A multi-layer golf ball comprising a core, one or more interlayers or interlayers, and a cover, each of which comprises a composition according to claim 1. (a) melt-blending (1) at least one copolymer of ethylene with an α, β-ethylenically unsaturated carboxylic acid, or a melt processable ionomer thereof, and (2) a sufficient amount of nonvolatile non-moving material, And (b) Sufficient to neutralize all acid groups in the acid copolymer or its ionomer to a level higher than 90% such that, simultaneously with or after step (a), the nonvolatile non-moving material retains its acid groups intact. Adding a positive cation source, Herein, the copolymer of ethylene and an α, β-ethylenically unsaturated carboxylic acid or a melt processable ionomer thereof may be an E / X / Y copolymer or a melt processable ionomer of an E / X / Y copolymer (where E is Ethylene, X is C ₃ -C ₈ -α, β-ethylenically unsaturated carboxylic acid, Y is a softening comonomer, X is 3-30% by weight of the E / X / Y copolymer, Y Is from 0 to 30% by weight of the E / X / Y copolymer), and the nonvolatile non-moving material is at least one aliphatic monofunctional organic acid or salt thereof having less than 36 carbon atoms, Wherein the monofunctional organic acid is present at 25 to 150 pph based on the weight of the E / X / Y copolymer. 21. The method of claim 20, wherein the acid groups are 100% neutralized. The method of claim 20, wherein the amount of cation source is greater than the amount necessary to neutralize all acid groups. delete delete delete delete delete