JP2009056309A - Golf tool formed from prescribed object having resilience equal to ionomer resin and casting aptitude - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a golf ball including the core and the cover. <P>SOLUTION: The golf ball includes the core and the cover. At least part of the golf ball is formed from the following component: a prepolymer formed from a reaction product of an isocyanate-containing component and an isocyanate-reactive component. Here, the isocyanate-containing component is trifunctional, and the isocyanate-reactive component is formed from a composition containing a curing agent containing a second diamine and a 3,3'-dimethyl-4,4'-bis(sec-butylamino)-dicyclohexyl methane. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composition comprising a castable formulation with improved resilience and recovery factor. The present invention further contemplates golf equipment formed from the castable formulation. In particular, the present invention contemplates a polyurea composition with castability having a recovery factor comparable to conventional ionomers.

  Golf balls are made from a variety of compositions that provide golf ball manufacturers and the like with the ability to change the feel and aerodynamic characteristics of a particular ball. For example, a golf ball cover made from balata allows highly skilled golfers to achieve a spin rate sufficient to accurately control the direction and distance of the ball, especially on short shots. To do. However, golf balls covered with balata are easily damaged, which precludes the average golfer from using such balls. In order to eliminate this durability problem, manufacturers typically use ionomer resins as the cover material. However, a golf ball covered with an ionomer resin has a cover that is virtually cutting resistant, but its spin properties and feel are inferior compared to balls covered with balata.

  Since the resulting golf balls are as durable as those made of ionomer resin, polyurethane and polyurea have been recognized as useful materials for golf ball covers, and soft golf balls covered with balata. Have a nice touch. U.S. Pat. No. 4,123,061 teaches a golf ball made from a polyurethane prepolymer made of polyether and diisocyanate that is cured with a polyol or amine-type curing agent. In addition, US Pat. No. 5,334,673 discloses the use of two classes of polyurethanes available on the market, namely thermosetting and thermoplastic polyurethanes, and in particular polyurethane prepolymers, and gradually to produce golf ball covers. A golf ball covered with a thermosetting polyurethane made from a composition comprising a reactive amine curing agent and / or a difunctional glycol is disclosed. U.S. Pat. No. 5,484,870 discloses a polyurea composition comprising a reaction product of an organic diisocyanate and an organic amine, each containing at least two functional groups. Once these two components are merged, the reaction rate is very fast and thus the ability to change the physical properties of the composition is limited.

  A golf ball covered with polyurethane and polyurea is softer than a golf ball covered with ionomer resin, but such a ball has the resilience or elastic rebound of the golf ball cover (impacted by the golf club). Regarding the later function of the golf ball's initial velocity), it does not completely match the ionomer resin golf ball. In addition, the polyurethanes and polyureas used to make such golf ball covers generally contain aromatic components such as aromatic diisocyanates, polyols or polyamines, so that they are light, particularly ultraviolet. It is easy to discolor when exposed to (UV) light. In order to prevent or slow down this discoloration, light and UV stabilizers such as Tinuvin 770, 765, and 328 are added to these aromatic polymer materials. In addition, to ensure that the cover formed from the aromatic polymer material does not discolor, the cover is painted with a white paint and then covered with a clear coat to maintain the whiteness of the golf ball. However, it is extremely difficult to apply a uniform white colored coat on the dimpled surface of the golf ball, and such a method requires a long production time and high cost to the golf ball manufacturer. The burden of.

  Thus, the ability to withstand golf equipment and, in particular, golf balls containing components made with a material that provides at least resilience comparable to that of ionomer resins without adversely affecting the overall performance characteristics of the golf ball. There is no request. Furthermore, it would be advantageous to provide a composition that combines improved discoloration resistance with cut and scratch resistance suitable for the manufacture of golf ball components and other golf-related devices.

  The present invention seeks to provide a golf ball comprising a core and a cover, wherein at least a portion of the golf ball comprises the reaction product of the following components: an isocyanate-containing component and an isocyanate-reactive component. A prepolymer formed from wherein the isocyanate-containing component is trifunctional and the isocyanate-reactive component comprises a secondary diamine; and 3,3′-dimethyl-4,4′-bis ( Manufactured from a composition containing a curing agent comprising sec-butylamino) -dicyclohexylmethane. In one embodiment, the composition consists essentially of a bond having the general formula:

In the general formula, x is a chain length and is about 1 or more, and R and R ₁ are alkyl groups, phenyl groups, cyclic groups containing about 1 to about 20 carbon atoms, Or a mixture of these.
In this aspect of the invention, the second diamine can have a molecular weight in the range of about 200 to about 3,000. In one embodiment, the second diamine has a molecular weight in the range of about 1,800 to about 2,200. The isocyanate-containing component can include NCO groups in the range of about 15% to about 25%. In one embodiment, the isocyanate-containing component comprises NCO groups in the range of about 20% to about 28%.
The present invention also includes a core, a layer disposed around the core to form an inner ball, and a cover cast on the inner ball, wherein at least a portion of the ball includes: Components: a prepolymer formed from the reaction product of at least one 3-functional isocyanate-containing component and at least one amine-terminated isocyanate-reactive component, wherein the prepolymer comprises about It also relates to a golf ball having an NCO content in the range of 10% to about 20%; and made from a composition comprising at least one amine-terminated curing agent.

In one embodiment, the amine-terminated curing agent comprises 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane. In another embodiment, the amine-terminated isocyanate-reactive component comprises a secondary diamine, a secondary triamine, or a combination thereof. In other embodiments, the prepolymer has an NCO content ranging from about 12% to about 16%. In yet another embodiment, the amine-terminated curing agent comprises 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane and the amine-terminated isocyanate- The reactive component includes a secondary diamine, a secondary triamine, or a combination thereof.
While the composition of the present invention can be incorporated into any part of the golf ball, in one embodiment the cover comprises the composition. In another embodiment, the ball intermediate layer is made of the composition. However, when molded into solid spheres, the composition will have a compressibility in the range of about 160 to about 200 atti, or about 170 to about 190 atti when molded into solid spheres. Has a compression ratio in the range. The composition can also have a coefficient of recovery (COR) of about 0.77 or greater when molded into a solid sphere.
The present invention also relates to a golf ball comprising a core; and a cover made of a castable polyurea material consisting essentially of a bond having the following general formula:

In the general formula, x is a chain length and is about 1 or more, and R and R ₁ are alkyl groups, phenyl groups, cyclic groups containing about 1 to about 20 carbon atoms, Or a polyurea material that represents and is castable is produced from the following components: at least one trifunctional isocyanate and at least one secondary diamine, secondary triamine, or mixtures thereof. Prepolymer, wherein the NCO content is in the range of about 12% to about 16%; and a curing agent comprising 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane In addition, the polyurea material having castability is molded into a solid sphere, the compression ratio in the range of about 170 to about 190 atti, and when molded into a solid sphere, Has a COR of about 0.77 or higher. The prepolymer can be made from at least one trifunctional isocyanate and a second diamine having a molecular weight in the range of about 1,800 to about 2,200.

Additional features and advantages of the present invention can be ascertained from the following detailed description, given in conjunction with the accompanying drawings.
The present invention also contemplates improved polyurea-based compositions for use in golf equipment such as golf balls, golf clubs, and the like, which have traditionally been harder resin materials such as ionomers. Have at least comparable resilience. In particular, the compositions of the present invention have at least comparable resilience compared to conventional ionomer compositions and have improved resilience over that of conventional polyurethane and polyurea compositions.
The compositions of the present invention can be used in various golf ball configurations, ie, one-piece, two-piece, or multi-layer balls, as well as golf club components, such as club head inserts. The composition of the present invention, when included in various golf ball components such as covers, is better than or equal to golf balls formulated with ionomers or conventional polyurethane or polyurea compositions, as well as physical and air. Generate golf balls with mechanical properties.

Compositions of the Invention The compositions of the present invention can comprise an isocyanate-containing component and at least one amine-terminated isocyanate-reactive component. In one embodiment, the polyurea-based composition of the present invention comprises an isocyanate-containing component, at least one amine-terminated isocyanate-reactive component, and at least one other isocyanate-reactive component. It is formed. As used herein, the terms “formed from (manufactured)” and “formed from (manufactured)” mean an open state, eg, “includes” in the terms of the claims. Thus, a series of listed components “formed from” or “formed with” means that the composition comprises at least one of these listed components, and further the preparation of the composition It is meant that other components not listed can be included therein. The at least one other isocyanate-reactive component can have an amine-terminus or a hydroxyl-terminus.

  In this aspect of the invention, the composition of the invention can be formed from a prepolymer and a curing agent. For example, the prepolymer made from the reaction product of an isocyanate-containing component and an amine-terminated isocyanate-reactive component is crosslinked with a curing agent. The curing agent is isocyanate-reactive and can be amine-terminated or hydroxyl-terminated. In one embodiment, the prepolymer is cured with at least one amine-terminated isocyanate-reactive component, the component being based on a primary amine, secondary amine, tertiary amine, or combinations thereof. It can be. For example, the amine-terminated isocyanate-reactive component can contain secondary amino groups.

The composition of the present invention may contain urea and / or urethane linkages. As is known to those skilled in the art, a composition formed from an isocyanate-containing component and an amine-terminated isocyanate-reactive component consists essentially of urea linkages, whereas the isocyanate-containing component, Compositions made from hydroxyl-terminated components consist essentially of urethane linkages. Furthermore, compositions formed from isocyanate-containing components and mixtures of amine-terminated and hydroxyl-terminated components contain both urea and urethane linkages. For example, a prepolymer formed from an isocyanate-containing component and an amine-terminated isocyanate-reactive component can be cured with a hydroxyl-terminated component to produce a hybrid polyurea / urethane composition. .
In this regard, in one aspect of the present invention, the composition of the present invention consists essentially of a urea bond, ie, a bond represented by the following formula:

In the general formula, x is a chain length of about 1 or more, and R and R ₁ are any containing about 1 to about 20, preferably about 1 to about 12 carbon atoms. Represents an alkyl group, a phenyl group, a cyclic group, or a mixture thereof. In one embodiment, at least one R and R ₁ is a straight or branched hydrocarbon chain containing about 1 to about 20 carbon atoms. In other embodiments, R and R ₁ are both straight or branched hydrocarbon chains containing from about 1 to about 20 carbon atoms. This aspect of the invention can be achieved by forming a composition based on an isocyanate-containing component and at least one amine-terminated isocyanate-reactive component. For the purposes of this disclosure, subscripts such as m, n, x, y, and z used herein in a generic structure indicate to those skilled in the art the degree of polymerization (i.e., continuous repeating units). To be understood). In the case of molecularly uniform products, these numbers are usually integers if not zero. In the case of molecularly heterogeneous products, these numbers are understood to be average numbers that are not limited to integers and average degrees of polymerization if not zero.
In other embodiments, the compositions of the present invention comprise urea linkages and also urethane linkages, ie linkages represented by the following formula:

In the general formula, x is the chain length, ie about 1 or more, and R and R ₁ are any containing about 1 to about 20, preferably about 1 to about 12 carbon atoms. Represents an alkyl group, a phenyl group, a cyclic group, or a mixture thereof. In one embodiment, at least one R and R ₁ is a straight or branched hydrocarbon chain containing about 1 to about 20 carbon atoms. In other embodiments, R and R ₁ are both straight or branched hydrocarbon chains containing from about 1 to about 20 carbon atoms.
These special components of the polyurea composition of the present invention are described in further detail below.

Isocyanate-Containing Component Any isocyanate available to those skilled in the art is suitable for use as the isocyanate-containing component according to the present invention. The isocyanate used in the present invention is aliphatic, cycloaliphatic, aromatic-aliphatic, aromatic, any derivative thereof, and combinations of these compounds having two or more isocyanate groups (NCO) per molecule. including. The isocyanate can be an organic polyisocyanate-terminated prepolymer, a low free isocyanate group-containing prepolymer, and mixtures thereof. The isocyanate-containing component can also include any isocyanate-functional monomer, dimer, trimer, or polymer adduct, prepolymer, quasi-prepolymer, or mixtures thereof. Isocyanate-functional compounds can include monoisocyanates or polyisocyanates containing two or more optional isocyanate functions. In one embodiment, the isocyanate functionality is from about 2 to about 3. For example, the isocyanate functionality can be in the range of about 2.1 to about 3.1. In other embodiments, the isocyanate functionality is 3.1, in other words, the isocyanate is trifunctional.

  Suitable isocyanate-containing components include diisocyanates represented by the generic structure: O = C = NRN = C = O, where R is preferably a cyclic group, an aromatic group, or about carbon atoms. 1 to about 20 linear or branched hydrocarbon moieties. The isocyanate can also contain one or more cyclic groups or one or more phenyl groups. When multiple cyclic or aromatic groups are present, straight and / or branched hydrocarbon chains having from about 1 to about 10 carbon atoms can be present as spacers between the cyclic or aromatic groups. In some cases, the cyclic or aromatic group may be substituted at its 2-, 3- and / or 4-position, or at the o-, m- and / or p-position, respectively. . Substituents include, but are not limited to, halogen atoms, primary, secondary, or tertiary hydrocarbon groups, or combinations thereof.

Examples of isocyanates that can be used in the present invention are substituted and isomeric mixtures such as 2,2'-, 2,4'-, and 4,4'-diphenylmethane diisocyanate (MDI); 3,3'-dimethyl-4, 4'-biphenylene diisocyanate (TODI); toluene diisocyanate (TDI); polymer MDI; carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate; p-phenylene diisocyanate (PPDI); m-phenylene diisocyanate (MPDI); triphenylmethane -4,4'- and triphenylmethane-4,4 "-triisocyanate;naphthylene-1,5-diisocyanate;2,4'-,4,4'- and 2,2-biphenyl diisocyanate; polyphenylene polymethylene Polyisocyanate (PMDI) (also known as polymeric PMDI); a mixture of MDI and PMDI; a mixture of PMDI and TDI; ethylene diisocyanate; propylene-1,2-diisocyanate Tetramethylene-1,2-diisocyanate; tetramethylene-1,3-diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate (HDI); octamethylene diisocyanate; decamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate; cyclohexane-1, 3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4'-dicyclohexyl diisocyanate 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate; 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isocyanatoethylcyclohexane isocyanate Bis (isocyanatomethyl) -cyclohexane diisocyanate; 4,4'-bis (isocyanatomethyl) -dicyclohexane; 2,4'-bis (isocyanatomethyl) -dicyclohexane; isophorone diisocyanate (IPDI); Isocyanate; triisocyanate of 2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI); 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI); 2,4-hexahydrotoluene diisocyanate; Hexahydrotoluene diisocyanate; 1,2-, 1,3- and 1,4-phenylene Diisocyanates; aromatic aliphatic isocyanates such as 1,2-, 1,3- and 1,4-xylene diisocyanates; m-tetramethylxylene diisocyanate (m-TMXDI); p-tetramethylxylene diisocyanate (p-TMXDI); Trimerized isocyanurate of any polyisocyanate, such as isocyanurate of toluene diisocyanate, trimer of diphenylmethane diisocyanate, trimer of tetramethylxylene diisocyanate, isocyanurate of hexamethylene diisocyanate, and mixtures thereof; dimerized uretdione of any polyisocyanate ( uretdione), such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and mixtures thereof; the above isocyanates and polyisocyanates Are al induced, modified polyisocyanates, and including mixtures thereof, without limitation.

  The compounds listed above that can be used in the present invention include unsaturated diisocyanates, i.e. aromatic compounds such as substituted and isomeric mixtures, e.g. 2,2'-, 2,4'-, and 4 , 4'-diphenylmethane diisocyanate (MDI), 3,3'-dimethyl-4,4'-diphenyl diisocyanate (TODI), toluene diisocyanate (TDI), polymer MDI, carbodiimide-modified liquid 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate (PPDI), m-phenylene diisocyanate (MPDI), triphenylmethane-4,4'- and triphenylmethane-4,4 "-triisocyanate, naphthylene-1,5-diisocyanate, 2,4 ' -, 4,4'-, and 2,2-biphenyl diisocyanate, polyphenylene polymethylene polyisocyanate (PMDI) (also known as polymeric PMDI), and mixtures thereof The use of unsaturated compounds is preferably combined with the use of light stabilizers or pigments, as discussed below.

In one embodiment, saturated or aliphatic isocyanates, ie isocyanate-containing components that do not contain carbon-carbon double bonds, are used to produce the compositions of the present invention. Suitable saturated isocyanates are: ethylene diisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate; tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate (HDO); octamethylene diisocyanate; decamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; 2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate; dicyclohexylmethane diisocyanate; cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate; -1,3-diisocyanate; cyclohexane-1,4-diisocyanate; methylcyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexane diisocyanate; 2,6-methylcyclohexanedii 4,4'-dicyclohexyl diisocyanate; 2,4'-dicyclohexyl diisocyanate; 1,3,5-cyclohexane triisocyanate; isocyanatomethylcyclohexane isocyanate; 1-isocyanato-3,3,5-trimethyl-5-isocyanato Isocyanatoethylcyclohexane isocyanate; bis (isocyanatomethyl) -cyclohexane diisocyanate; 4,4'-bis (isocyanatomethyl) -dicyclohexane; 2,4'-bis (isocyanatomethyl) -dicyclohexane; isophorone Diisocyanate (IPDI); HDI triisocyanate; 2,2,4-trimethyl-1,6-hexane diisocyanate (TMDI) triisocyanate; 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI); 2,4-hexa Hydrotoluene diisocyanate; 2,6-hexahydrotorue Diisocyanates; and mixtures thereof, but are not limited to these.

  In particular, the isocyanate-containing component of the present invention can be a low viscosity aliphatic polyisocyanate based on 1,6-hexamethylene diisocyanate (HDI) with a relatively high NCO content. Thus, in one embodiment, the isocyanate-containing component has an NCO content in the range of about 15% to 30%, preferably an NCO content in the range of about 18% to about 25%, and Including general structure:

Examples of such ingredients available commercially include, but are not limited to, Desmodur ^™ XP2410 and Desmodur XP2580 available from Bayer Material Science LLP, Pittsburgh, PA. These have an NCO content of 24% and 20% respectively.
When the isocyanate-containing component is aromatic in nature, the isocyanate-containing component may range from about 15% to 35%, preferably from about 20% to about 33%, more preferably from about 24% to It can be based on diphenyl diisocyanate (MDI) with an NCO content in the range of 32%. Examples of these isocyanates that are commercially available include, but are not limited to, Desmodur ^™ XP2619 and Desmodur XP7144 available from Bayer Material Science LLP, Pittsburgh, PA. They have an NCO content of 31.5% and 24% respectively.
As briefly discussed above, aromatic-aliphatic isocyanates can also be used in the compositions of the present invention. As used herein, an aromatic-aliphatic compound is to be understood as such a compound comprising an aromatic ring, wherein the isocyanate group is not directly bonded to the ring. Thus, while not intending to be bound by any particular theory, the indirect binding of the NCO group to the aromatic ring inhibits or delays the discoloration of the material typically associated with aromatic compounds. . An example of an aromatic-aliphatic compound is 1,3-bis-isocyanato-1-methyleneethylenebenzene (TMXDI), which has the following general structure:

Both m-tetramethylxylene diisocyanate (m-TMXDI); p-tetramethylxylene diisocyanate (p-TMXDI) are intended for use in the present invention as suitable aromatic-aliphatic isocyanates. Further non-limiting examples of aromatic-aliphatic isocyanates are 1,2-, 1,3- and 1,4-xylene diisocyanates; trimerized isocyanurates of any polyisocyanate, such as isocyanates of toluene diisocyanate Nurate, diphenylmethane diisocyanate trimer, tetramethylxylene diisocyanate trimer, hexamethylene diisocyanate isocyanurate, and mixtures thereof; dimerized isocyanurate of any polyisocyanate, such as uretdione of toluene diisocyanate, uretdione of hexamethylene diisocyanate, and these A modified polyisocyanate derived from the above isocyanates and polyisocyanates; and mixtures thereof. The aromatic-aliphatic isocyanate can be mixed with any of the unsaturated or saturated isocyanates listed above for the purposes of the present invention.
The NCO content of the isocyanate can be in the range of about 15% to about 35%. In one embodiment, the NCO content of the isocyanate is in the range of about 20% to about 33%, and more preferably in the range of about 24% to about 32%. In other embodiments, the isocyanate has an NCO content in the range of about 22% to about 26%.

Isocyanate-Reactive Component Any amine-terminated compound available to those skilled in the art is suitable for use as the isocyanate-reactive component. The amine-terminated compounds include amine-terminated hydrocarbons, amine-terminated polyethers, amine-terminated polyesters, amine-terminated polycarbonates, amine-terminated polycaprolactones, and the like. Mixtures can be included. The amine-terminated segment can be in the form of a primary amine (NH ₂ ) or a secondary amine (NHR). Further, the amine can be a diamine or a triamine.
The molecular weight of suitable amine-terminated compounds for use in the present invention can be in the range of about 100 to about 10,000. In one embodiment, the amine-terminated compound is about 200 or more, preferably about 300 or more, and even more preferably about 500 or more. In other embodiments, the molecular weight of the amine-terminated compound is about 5,000 or less, preferably about 3,000 or less, and more preferably about 2,500 or less. For example, in one embodiment, the molecular weight of the amine-terminated compound is in the range of about 300 to about 3,000.

In one embodiment, the amine-terminated compound comprises an amine-terminated hydrocarbon having the following general structure:
H ₂ N— [C _n H _2n ] _x —NH ₂ ;
H ₂ N- [C _n H _2n ] _x -NHR; or
RHN- [C _n H _2n ] _x -NHR
Where x is the chain length, ie about 1 or more, n is preferably about 1 to about 12, and R is about 1 to about 20, preferably about 1 to about Represents any alkyl group containing 12 carbon atoms, a phenyl group, a cyclic group, or a mixture thereof.
The amine-terminated compound may also be an amine-terminated polyether having the following general structure:
_{H 2 N- [C n H 2n} O] x -C n H 2n -NH 2;
_{H 2 N- [C n H 2n} O] x -C n H 2n -NHR; or
RHN- [C _n H _2n O] _x -C _n H _2n -NHR

Where x is the chain length, ie about 1 or more, n is preferably about 1 to about 12, and R is about 1 to about 20, preferably about 1 to about Represents any alkyl group containing 12 carbon atoms, a phenyl group, a cyclic group, or a mixture thereof. An example of an amine-terminated polyether is a polyetheramine. As used herein, the term “polyetheramine” means a polyoxyalkyleneamine containing a primary amino group bonded to the end of the polyether main chain. However, due to the rapid reaction of isocyanates with amines and the insolubility of many urea products, the choice of diamines and polyetheramines is limited to those that allow successful formation of polyurea prepolymers. In one embodiment, the polyether backbone is based on tetramethylene, propylene, ethylene, trimethylolpropane, glycerin, and mixtures thereof.
In one embodiment, the polyetheramine has the following general structure:

Wherein the repeating unit x has a value in the range of about 1 to about 70, and R is any alkyl group, phenyl group containing about 1 to about 20, preferably about 1 to about 12 carbon atoms. Represents a cyclic group, or a mixture thereof, and R ₃ represents a hydrogen atom, a methyl group, or a mixture thereof. Even more preferably, the repeat unit x is in the range of about 5 to about 50, and even more preferably in the range of about 12 to about 35.
In another embodiment, the polyetheramine has the general structure:

Where repeat units x and z have a combined value in the range of about 3.6 to about 8, and repeat unit y has a value in the range of about 9 to about 50, and R is about 1 Represents an alkyl group containing from about 20 carbon atoms, a phenyl group, a cyclic group, or mixtures thereof, and R ₁ represents — (CH ₂ ) _a —, where “a” is about 1 It may be a repeating unit in the range of about ˜10, a phenylene group, a cyclic group, or a mixture thereof, and R ₃ is a hydrogen atom, a methyl group, or a mixture thereof.
In yet another embodiment, the polyetheramine has the following general structure:
H ₂ N- (R ₁ ) -O- (R ₁ ) -O- (R ₁ ) -NH ₂ ;
H ₂ N- (R ₁ ) -O- (R ₁ ) -O- (R ₁ ) -NHR; or
RHN- (R ₁ ) -O- (R ₁ ) -O- (R ₁ ) -NHR
Where R represents an alkyl group containing from about 1 to about 20 carbon atoms, a phenyl group, a cyclic group, or a mixture thereof, and R ₁ represents — (CH ₂ ) _a —, where “A” can be a repeating unit in the range of about 1 to about 10, a phenylene group, a cyclic group, or a mixture thereof.

Suitable polyetheramines include: methyldiethanolamine; polyoxyalkylene diamines such as polytetramethylene ether diamine, polyoxypropylene triamine, polyoxyethylene diamine, and polyoxypropylene diamine; poly (ethylene oxide capped oxypropylene) ether diamine; propylene oxide , Triethylene glycol diamine; trimethylol propane-based triamine; glycerin-based triamine; and mixtures thereof, but are not limited thereto. In one embodiment, the polyetheramine used to make the prepolymer is Jeffamine ^™ D2000 (manufactured by Huntsman Corporation, Austin, Texas).

The molecular weight of the polyetheramine used in the present invention can be in the range of about 100 to about 5,000. In one embodiment, the polyetheramine has a molecular weight of about 200 or more, preferably about 230 or more. In other embodiments, the polyetheramine has a molecular weight of about 4,000 or less. In yet another embodiment, the polyetheramine has a molecular weight of about 600 or greater. According to yet another embodiment, the polyetheramine has a molecular weight of about 3,000 or less. In yet another embodiment, the molecular weight of the polyetheramine is in the range of about 1,000 to about 4,000, preferably in the range of about 1,000 to about 4,000, and more preferably in the range of about 1,500 to about 2,500. Lower molecular weight polyetheramines may tend to produce solid polyurea during prepolymer production, so higher molecular weight oligomers such as Jeffamine ^™ D2000 are preferred.
In addition, the amine-terminated compounds can include amine-terminated polyesters having the following general structure:
H ₂ N — [— R ₁ CO ₂ R ₂ CO ₂ —] _x —R ₁ —NH ₂ ;
H ₂ N-[-R ₁ CO ₂ R ₂ CO _2- ] _x -R ₁ -NHR; or
RHN-[-R ₁ CO ₂ R ₂ CO _2- ] _x -R ₁ -NHR

Where x is a chain length, i.e. a value in the range of about 1 or more, preferably about 1 to about 20, and R is about 1 to about 20, preferably about 1 to about 12 carbon atoms. Including any alkyl group, phenyl group, cyclic group, or mixtures thereof, and R ₁ and R ₂ are straight or branched hydrocarbon chains, such as alkyl or aryl chains.
Copolymers of polycaprolactone and polyamine can also be used as the isocyanate-reactive component of the present invention. Suitable copolymers include polycaprolactones initiated with bis (2-aminoethyl) ether, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) ethanol, polyoxyethylenediamine initiated poly Caprolactone, polycaprolactone initiated with propylenediamine, polycaprolactone initiated with polyoxypropylenediamine, polycaprolactone initiated with 1,4-butanediamine, triamine-initiated polycaprolactone based on trimethylolpropane, neo Examples include, but are not limited to, pentyldiamine-initiated polycaprolactone, hexanediamine-initiated polycaprolactone, polytetramethylene ether diamine-initiated polycaprolactone, and mixtures thereof. In addition, polycaprolactone polyamines having the following structure may also be useful as the isocyanate-reactive component used in the present invention:

Where x is a chain length, i.e. a value in the range of about 1 or more, preferably about 1 to about 20, and R is about 1 to about 20, preferably about 1 to about 12 carbon atoms. R ₁ is a linear or branched hydrocarbon chain containing from about 1 to about 20 carbon atoms.
Amine-terminated polycaprolactones also include those having the following structure:

Where x is a chain length, i.e. a value greater than or equal to 1, preferably in the range of about 1 to about 20, and R comprises about 1 to about 20, preferably about 1 to about 12 carbon atoms. One of an alkyl group, a phenyl group, or a cyclic group, and R ₁ is a straight or branched hydrocarbon chain containing from about 1 to about 20 carbon atoms.
In another embodiment, the amine-terminated compound can be an amine-terminated polycarbonate having one of the following general structures:

Wherein x is a chain length, preferably a value ranging from about 1 to about 20, and R is an alkyl containing from about 1 to about 20, preferably from about 1 to about 12 carbon atoms. One of a group, a phenyl group or a cyclic group, and R ₁ is a linear hydrocarbon or mainly a bisphenol A unit or a derivative thereof.
Amine-terminated polyamines can also be used as the isocyanate-reactive component of the present invention. Suitable amine-terminated polyamines include, but are not limited to, those having the following structures:

Where x is a chain length, i.e., a value greater than or equal to about 1, and R is an alkyl, phenyl, or cyclic group containing from about 1 to about 20, preferably from about 1 to about 12 carbon atoms. One of the groups, R ₁ is an alkyl, phenyl, or cyclic group containing from about 1 to about 12 carbon atoms, and R ₂ is from about 1 to about 12 carbons. An alkyl group containing an atom (straight or branched chain), a phenyl group, or a cyclic group. Accordingly, any of the above isocyanate-reactive components, as well as any of the polyamine telechelics taught in US Patent Publication No. 2007/0093317, are used as the isocyanate-reactive component according to the present invention. be able to.
Additional amine-terminated compounds that can be used as isocyanate-reactive components are poly (acrylonitrile-co-butadiene); poly (1,4-butanediol) bis (4-amino) in liquid or waxy solid form Benzoate); linear or branched polyethyleneimine; low molecular weight and high molecular weight polyethyleneimine having an average molecular weight in the range of about 500 to about 30,000; poly (propylene glycol) having an average molecular weight in the range of about 200 to about 5,000 ) Bis (2-aminopropyl ether); a compound with a polytetrahydrofuran bis (3-aminopropyl) end having an average molecular weight in the range of about 200 to about 2,000; and mixtures thereof (all of which are from Wisconsin, Including, but not limited to, Milwaukee, available from Aldrich.
Suitable poly (acrylonitrile-co-butadiene) compounds for use in the present invention have one of the structures listed below:

Where x is a chain length, i.e. a value greater than about 1, and R is any alkyl group, phenyl group, ring containing about 1 to about 20, preferably about 1 to about 12 carbon atoms. A formula group or a mixture thereof, R ₁ is a hydrogen atom, a methyl group, a cyano group, a phenyl group, or a mixture thereof; and R ₂ is a hydrogen atom, a methyl group, a chlorine atom, or a mixture thereof. It is. In one embodiment, the ratio: y: x ranges from about 82:18 to about 90:10. In other words, the poly (acrylonitrile-co-butadiene) can include acrylonitrile in the range of about 10% to about 18% by weight.
In another embodiment, the composition of the present invention comprises poly (1,4-butanediol) bis (4-aminobenzoate) having one of the structures listed below:

Where x is a chain length, i.e., a value greater than or equal to about 1, n is preferably a value in the range of about 1 to about 12, R and R ₁ are straight or branched hydrocarbon chains, about 1 Is an alkyl group, phenyl group, cyclic group, or a mixture thereof containing from about 20 to about 20, preferably from about 1 to about 12 carbon atoms, and R ₂ is a hydrogen atom, a methyl group, or a mixture thereof. It is. In one embodiment, R ₁ is a phenyl group, R ₂ is a hydrogen atom, and n is about 2.
In yet another embodiment, at least one linear or branched polyethyleneimine having one of the following structures is used as the isocyanate-reactive component:

Where x and y are chain lengths, i.e. values greater than about 1, and R is any alkyl group, phenyl group containing from about 1 to about 20, preferably from about 1 to about 12 carbon atoms. , A cyclic group, or a mixture thereof, and R ₁ is a hydrogen atom, a methyl group, or a mixture thereof. In one embodiment, R ₁ is a hydrogen atom. In another embodiment, the composition of the present invention comprises a mixture of linear or branched polyethyleneimines as the isocyanate-reactive component.
In yet another embodiment, the composition of the present invention comprises a compound with polytetrahydrofuran bis (3-aminopropyl) end having one of the following structures:

Here, m and n are chain lengths, i.e., a value of about 1 or more, n is preferably a value in the range of about 1 to about 12, and m is preferably about 1 to about 6. A value within the range, R is any one of alkyl groups, phenyl groups, cyclic groups, or mixtures thereof containing from about 1 to about 20, preferably from about 1 to about 12 carbon atoms. And R ₁ and R ₂ are a hydrogen atom, a methyl group, or a mixture thereof. In one embodiment, both R ₁ and R ₂ are hydrogen atoms, and both m and n are about 2.
By using an amine-terminated portion based on a hydrophobic segment, the polyurea composition of the present invention is more water resistant than a polyurea composition formed with an amine-terminated hydrophilic segment. obtain. Thus, in one embodiment, the amine-terminated compound comprises an amine-terminated compound based on a hydrophobic backbone, such as an unsaturated or saturated hydrocarbon. An example of an amine-terminated hydrocarbon is amine-terminated polybutadiene.

  Furthermore, as briefly mentioned above, diamines and triamines can be used as the isocyanate-reactive component. In one embodiment, aromatic diamines can be used when trying to incorporate UV stabilizers or whitening agents during post-treatment. US Pat. No. 5,484,870 provides suitable aromatic diamines suitable for use in the present invention, the entire disclosure of which is incorporated herein by reference. For example, useful aromatic polyamines include polymethylene-di-p-aminobenzoate, polyethylene glycol-bis (4-aminobenzoate), polytetramethylene ether glycol-di-p-aminobenzoate, polypropylene glycol-di-p-amino. Including benzoates, and mixtures thereof. Further, the triamines that can be used in preparing the prepolymers of the present invention include N, N, N ′, N′-tetramethyl-ethylenediamine, 1,4-diazobicyclo (2,2,2) -octane, N— Methyl-N'-dimethylaminoethylpiperazine, N, N-dimethylbenzylamine, bis- (N, N-diethylaminoethyl) -adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine N, N, N ′, N′-tetramethyl-1,3-butanediamine, N, N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, and 2-methylimidazole.

Non-limiting examples of triamines for use as the isocyanate-reactive component of the present invention include diethylenetriamine, dipropylenetriamine, N- (aminopropyl) ethylenediamine, N- (aminoethyl) butylenediamine, N- ( Aminopropyl) butylenediamine, N- (aminoethyl) hexamethylenediamine, N- (aminopropyl) hexamethylenediamine, 4-aminomethyloctane-1,8-diamine, triamine (aka propylene oxide) as the main component (aka Polyoxypropylene triamine), triamine based on trimethylolpropane, triamine based on glycerin, 3- (2-aminoethyl) aminopropylamine (ie, N- (2-aminoethyl) -1,3 - propylene diamine, N ₃ - amine), N, N-bis (2 - ((aminocarbonyl) amino) ethyl) urea, N, N ', N " - tris (2-A Noethyl) methanetriamine, N1- (5-aminopentyl) -1,2,6-hexanetriamine, 1,1,2-ethanetriamine, N, N ', N "-tris (3-aminopropyl) methanetriamine, N1- (2-aminoethyl) -1,2,6-hexanetriamine, N1- (10-aminodecyl) -1,2,6-hexanetriamine, 1,9,18-octadecanetriamine, 4,10,16, 22-tetrazapentacosane-1,13,25-triamine, N1- (3-((4-((3-aminopropyl) amino) butyl) amino) propyl) -1,2,6-hexanetriamine, di- -9-octadecenyl- (Z, Z) -1,2,3-propanetriamine, 1,4,8-octanetriamine, 1,5,9-nonanetriamine, 1,9,10-octane cantriamine, 1 , 4,7-heptanetriamine, 1,5,10-decanetriamine, 1,8,17-heptadecanetriamine, 1,2,4-butanetriamine, 1,3,5-pentanetriamine, N1- (4- ((3-Aminopropyl) amino) butyl) -1,2,6-triamine 2,5-dimethyl-1,4,7-heptanetriamine, N1-6-aminohexyl-1,2,6-hexanetriamine, 6-ethyl-3,9-dimethyl-3,6,9-undecantriamine, 1,5,11-undecantriamine, 1,6,11-undecantriamine, N, N-bis (aminomethyl) methanediamine, N, N-bis (2-aminoethyl) -1,3-propanediamine, methane Triamine, N1- (2-aminoethyl) -N-2- (3-aminopropyl) -1,2,5-pentanetriamine, N1- (2-aminoethyl) -1,2,6-hexanetriamine, 2 , 6,11-trimethyl-2,6,11-dodecanetriamine, 1,1,3-propanetriamine, 6- (aminomethyl) -1,4,9-nonanetriamine, 1,2,6-hexanetriamine, N2- (2-aminoethyl) -1,1,2-ethanetriamine, 1,3,6-hexanetriamine, N, N-bis (2-aminoethyl) -1,2-ethanediamine, 3- (amino Methyl) -1,2,4-butanetriamine, 1,1,1-ethanetriamine, N1, N1-bis (2-aminoethyl) -1,2-propanediamine, 1,2,3-propanetriamine, 2-methyl-1,2,3-propanetriamine, and mixtures thereof.

Non-limiting examples of tetramine include triethylenetetramine (i.e. bis (aminoethyl) ethylenediamine), tetraethylenetetramine, tripropylenetetramine, N, N'-bis (3-aminopropyl) ethylenediamine (i.e. aka N ₄ -amine, N, N'-1,2-ethanediylbis- (1,3-propanediamine), 1,5,8,12-tetrazadodecane), bis (aminoethyl) propylenediamine, bis (aminoethyl) Contains butylenediamine, bis (aminopropyl) butylenediamine, bis (aminoethyl) hexamethylenediamine, bis (aminopropyl) hexamethylenediamine. Illustrative examples of other higher polyamines include tetraethylenepentamine, pentaethylenehexamine, polymethylene-polyphenylamine, and mixtures thereof.
In one embodiment, the isocyanate-reactive component of the present invention is a secondary diamine or secondary triamine, where the amine end groups of these basic diamines or triamines are ketones such as acetone or other suitable React with solvent and reduce to produce hindered secondary amine end groups, represented by the following end structures:

Without being bound by any particular theory, one reactive hydrogen atom on each end group gives more selective reactivity and exhibits a slower intrinsic reactivity than primary amines. The secondary diamine or secondary triamine is produced. This is probably due to the higher steric hindrance, such as amines with a t-butyl group on the nitrogen atom, which have a lower reaction rate than amines that have no steric hindrance or only low levels of steric hindrance. .
In this regard, preferably the molecular weight of the second diamine is in the range of about 100 to about 5,000, preferably in the range of about 200 to about 2,500, and more preferably in the range of about 300 to about 2,100. . In one embodiment, the molecular weight of the second diamine isocyanate-reactive component is in the range of about 1,800 to about 2,100, preferably in the range of about 1,900 to about 2,075. When the isocyanate-reactive component is a secondary triamine, its molecular weight is in the range of about 50 to about 2,000, preferably in the range of about 100 to about 1,000, and more preferably in the range of about 300 to about 700. It can be a value. For example, the molecular weight of the secondary triamine suitable for use as the isocyanate-reactive component can range from about 500 to about 600.

The secondary diamine and secondary triamine preferably comprise a minor amount of primary amine, ie less than about 5%, preferably less than about 3%, and more preferably less than 2% primary amine. In addition, this type of isocyanate-reactive component has a relatively low kinematic viscosity compared to other amine-terminated components. For example, the kinematic viscosities of secondary diamines and secondary triamines suitable for use in the present invention can be in the range of about 5 cSt to about 500 cSt at 25 ° C. (77 ° F.). In one embodiment, the kinematic viscosity of the isocyanate-reactive component is in the range of about 180 cSt to about 250 cSt at 25 ° C. (77 ° F.). In another embodiment, the kinematic viscosity is in the range of about 5 cSt to about 50 cSt at 25 ° C. (77 ° F.).
Examples of commercially available suitable secondary diamines include JEFFAMINE ^™ XTJ-584, XTJ-585 and XTJ-576, available from Huntsman Corporation. JEFFAMINE ^™ XTJ-586, also available from Huntsman, is a commercially available secondary triamine that can be used as the isocyanate-reactive component.
In this aspect of the invention, the second diamine suitable for use as the isocyanate-reactive component is based on amine-terminated polypropylene glycol (PPG) having the following representative structure: Could be:

Here, x is a chain length, preferably a value within the range of about 1 or more, and more preferably about 1 to about 70. In one embodiment, x is a value within the range of about 2 to about 68. In another embodiment, x is a value in the range of about 25 to about 40, preferably in the range of about 30 to about 38. In yet another embodiment, x is a value within the range of about 2 to about 10. In yet another embodiment, x is a value in the range of about 60 to about 70, preferably in the range of about 65 to about 70. The molecular weight of the amine-terminated PPG can range from about 200 to about 4,500. In one embodiment, the molecular weight is in the range of about 210 to about 450. In other embodiments, the molecular weight is in the range of about 1,800 to about 4,200. In yet another embodiment, the molecular weight is in the range of about 1,900 to about 2,500. In yet another embodiment, the molecular weight is in the range of about 3,800 to about 4,200. Examples of commercially available base diamines suitable for use in the production of the second diamine are JEFFAMINE ^™ D-230, D-400, D, available from Huntsman Corporation. -Includes 2000 and D-4000X.
The above-mentioned secondary triamine is produced by reacting propylene oxide and a triol initiator and then aminating the terminal hydroxyl group, and is composed mainly of triamine and represented by the following representative structure. possible:

Where n can range from 0 to about 2, preferably from 0 to about 1, x, y, and z are chain lengths, preferably greater than or equal to 1 and R is It is a hydrogen atom or an alkyl group. The number of moles of propylene oxide is represented by x + y + z, which can range from about 4 to about 90. In one embodiment, x + y + z is in the range of about 5 to about 6. In other embodiments, x + y + z is in the range of about 40 to about 60, preferably in the range of about 45 to about 55, and more preferably in the range of 48 to about 52. In yet another embodiment, x + y + z is in the range of about 70 to about 95, preferably in the range of about 80 to about 90, and more preferably in the range of about 83 to about 88. Commercially available base triamines suitable for use in the production of the secondary triamines are JEFFAMINE ^™ T-403, T-3000 and T. available from Huntsman Corporation. Includes -5000.

  In addition to the amine-terminated isocyanate-reactive component, it is also possible to use hydroxyl-terminated isocyanate-reactive components in accordance with the invention. However, when using an isocyanate-reactive component having at least one hydroxyl-termination, the composition of the present invention is no longer required, even if the curing agent used thereafter is amine-terminated. It cannot be considered to consist essentially of urea bonds. Rather, this composition is considered a hybrid composition because it contains both urea and urethane linkages. Suitable hydroxyl-terminated components for use as the isocyanate-reactive component include, but are not limited to, any polyol available to those skilled in the art that is suitable for use in the polyurethane prepolymer. . Examples of polyols include, but are not limited to, polyether polyols, polycaprolactone polyols, polyester polyols, polycarbonate polyols, hydrocarbon polyols, and mixtures thereof. Both saturated and unsaturated polyols are suitable for use in the present invention.

Polyether polyols suitable for use in the present invention include polytetramethylene ether glycol (PTMEG); copolymers of polytetramethylene ether glycol and 2-methyl-1,4-butanediol (PTG-L); Poly (oxypropylene glycol); ethylene oxide capped (polyoxypropylene) glycol; poly (oxypropyleneoxyethylene) glycol; and mixtures thereof, including but not limited to.
Suitable polycaprolactone polyols are: diethylene glycol-initiated polycaprolactone; propylene glycol-initiated polycaprolactone; 1,4-butanediol-initiated polycaprolactone; trimethylolpropane-initiated polycaprolactone; neopentyl glycol-initiated polycaprolactone; 1,6-hexanediol-initiated poly Including, but not limited to: caprolactone; polytetramethylene ether glycol (PTMEG) initiated polycaprolactone; ethylene glycol initiated polycaprolactone; dipropylene glycol initiated polycaprolactone; and mixtures thereof.

Suitable polyester polyols include polyethylene adipate glycol; polyethylene propylene adipate glycol; polybutylene adipate glycol; polyethylene butylene adipate glycol; polyhexamethylene adipate glycol; polyhexamethylene butylene adipate glycol; o-phthalate-1,6-hexanediol polyester polyol Polyethylene terephthalate polyester polyols; and mixtures thereof, including but not limited to:
Examples of polycarbonate polyols that can be used in the present invention include, but are not limited to, poly (phthalate carbonate) glycol; poly (hexamethylene carbonate) glycol; polycarbonate polyol containing bisphenol A; and mixtures thereof.
Hydrocarbon polyols include hydroxyl-terminated liquid isoprene rubber (LIR); hydroxyl-terminated polybutadiene polyols; hydroxyl-terminated polyolefin polyols; hydroxyl-terminated hydrocarbon polyols; and mixtures thereof, It is not limited to these.

Other polyols that can be used as the isocyanate-reactive component of the present invention include castor oil and derivatives thereof; Polytail H; Polytail HA; Kraton polyol; Acrylic polyols; Carboxylic acid, sulfonic acid, or phosphoric acid Including, but not limited to, group-based acid functionalized polyols; dimer alcohols converted from saturated dimerized fatty acids; and mixtures thereof.
By using a polyol based on a hydrophobic backbone, the composition of the present invention can be even more water resistant than a composition comprising a polyol that does not have a hydrophobic backbone. Some non-limiting examples of polyols based on a hydrophobic backbone include hydrocarbon polyols, hydroxyl-terminated polybutadiene polyols, polyethers, polycaprolactones, and polyesters.
In one embodiment, at least two isocyanate-reactive components are used, wherein one of the isocyanate-reactive components is amino-terminated and the second is hydroxyl- It has a terminal. Any of the amino-terminated and hydroxyl-terminated components discussed above are suitable for use in this regard. However, as discussed above, once a hydroxyl-terminated isocyanate-reactive component is used, the resulting composition contains urethane linkages and is therefore no longer a pure polyurea for purposes of the present invention. If anything, the composition contains both urea and urethane linkages.

Curing Agent The curing agent used in the present invention includes, but is not limited to, a hydroxyl-terminated curing agent, an amine-terminated curing agent, and mixtures thereof. As is known to those skilled in the art, the type of curing agent used determines whether the resulting composition is polyurea / urethane or polyurea / urethane. A prepolymer containing only urea linkages, cured with a hydroxyl-terminated curing agent, is a polyurea / urethane. This is because any excess isocyanate groups react with the hydroxyl groups of the curing agent to form urethane bonds. In contrast, when an amine-terminated curing agent is used with a prepolymer that contains only urea linkages, the excess amount of isocyanate groups is linked to the amine groups of the amine-terminated curing agent. Reacts to produce more urethane bonds and give a pure polyurea composition.

  Thus, the curing agent is amine-terminated and thus the resulting composition contains only urea linkages. Suitable amine-terminated curing agents are ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane and its derivatives; 1,4-bis- (sec-butylamino) -cyclohexane; 1,2-bis- (sec-butylamino) -cyclohexane; 4,4'-dicyclohexylmethanediamine; 1,4-cyclohexane-bis (methylamine); 1,3-cyclohexane-bis (methylamine); diethylene glycol bis- (aminopropyl) ether; 2-methylpentamethylene-diamine; Diaminocyclohexane; diethylenetriamine; triethylenetetramine; tetraethylenepentamine; propylenediamine; 1,3-diaminopropane; dimethylaminopropylamine; Minopropylamine; imido-bis (propylamine); monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; isophoronediamine; 4,4'-methylene-bis (2-chloroaniline); 5-dimethylthio-2,4-toluenediamine; 3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine; 3,5-diethylthio-2,6-toluenediamine; 4,4'-bis- (sec-butylamino) -diphenylmethane and its derivatives; 1,4-bis- (sec-butylamino) -benzene; 1,2-bis- (sec-butylamino) -benzene; N , N'-dialkylamino-diphenylmethane; trimethylene glycol-di-p-aminobenzoate; polytetramethylene oxide-di-p-aminobenzoate; 4,4'-methylene-bis (2-chloro-2,6-diethylenea 4,4'-methylene-bis (2,6-diethylaniline); m-phenylenediamine; p-phenylenediamine; N, N'-diisopropylisophoronediamine; polyoxypropylenediamine; Triamines; 3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof. In one embodiment, the amine-terminated curing agent is 4,4′-bis- (sec-butylamino) -dicyclohexylmethane. In one embodiment, the amine-terminated curing agent can have a molecular weight of about 64 or greater. In other embodiments, the curing agent has a molecular weight of about 2,000 or less. In addition, any of the amine-terminated moieties listed above can be used as a curing agent to react with the polyurea prepolymer.

  Among the compounds listed above, the saturated amine-terminated curing agents suitable for use in the present invention are ethylenediamine; hexamethylenediamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine; 4,4'-bis- (sec-butylamino) -dicyclohexylmethane; 1,4-bis- (sec-butylamino) ) -Cyclohexane; 1,2-bis- (sec-butylamino) -cyclohexane; 4,4′-bis- (sec-butylamino) -dicyclohexylmethane derivative; 4,4′-dicyclohexylmethanediamine; -Cyclohexane-bis (methylamine); 1,3-cyclohexane-bis (methylamine); diethylene glycol bis- (aminopropyl) ether; 2-methylpentamethylene-diamine; diaminocyclohexane; diethylenetriamine; triethylenetetramine; 1,3-diaminopropane; dimethylaminopropylamine; diethylaminopropylamine; imido-bis (propylamine); monoethanolamine; diethanolamine; triethanolamine; monoisopropanolamine; diisopropanolamine; Isophoronediamine; and mixtures thereof, including but not limited to.

In connection with the use of secondary diamines or secondary triamines as isocyanate-reactive components, as briefly described above, many amines have their free NCO groups for reaction with the isocyanate. May be undesirable due to the rapid reactivity between the amine and the amine end groups. Similar problems exist when selecting a curing agent suitable for use with the prepolymer. For example, in general, a first diamine other than a hindered primary diamine reacts rapidly, so the selection of the primary diamine as the curing agent can be problematic depending on the processing conditions. Therefore, in one embodiment, a hindered secondary diamine can be used as the curing agent. For example, 4,4′-bis (sec-butylamino) -dicyclohexylmethane or 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane (both of which are respectively clear links ( Clearlink ^™ 1000 and Clearlink ^™ 3000, commercially available from UOP) are suitable for use in combination with isocyanates for the purpose of producing the polyurea prepolymers of the present invention. In addition, N, N′-diisopropyl-isophoronediamine, available from Huntsman under the trade name Jefflink ^™, can be used as the second diamine curing agent. Further, a second diamine mainly composed of methylene diamine can be used as a curing agent. For example, from UOP, Unilink ^™ 4200 is suitable for use as a curing agent.

Further, the polyurea prepolymer can be cured with a single hydroxyl-terminated curing agent or a mixture of hydroxyl-terminated curing agents. However, once a hydroxyl-terminated curing agent is used, an excess of isocyanate in the polyurea prepolymer reacts with hydroxyl groups in the curing agent to form urethane linkages, which are no longer pure. The result is a composition as a polyurea / urethane composition rather than a polyurea.
Suitable hydroxyl-terminated curing agents are: ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; dipropylene glycol; polypropylene glycol 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane; cyclohexyldimethylol; Triisopropanolamine; N, N, N ′, N′-tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol bis (aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol; -Bis (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis [2- (2-hydroxyethoxy) 1,3-bis {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} cyclohexane; polytetramethylene ether glycol, preferably having a molecular weight in the range of about 250 to about 3,900; resorcinol- Di- (β-hydroxyethyl) ether and derivatives thereof; hydroquinone-di- (β-hydroxyethyl) ether and derivatives thereof; 1,3-bis (2-hydroxyethoxy) benzene; 1,3-bis [2- ( 2-hydroxyethoxy) ethoxy] benzene; N, N-bis (β-hydroxypropyl) aniline; 2-propanol-1,1′-phenylaminobis; and mixtures thereof. The hydroxyl-terminated curing agent can have a molecular weight of at least about 50. In one embodiment, the hydroxyl-terminated curing agent has a molecular weight of about 2,000 or less.

  The saturated hydroxyl-terminated curatives included in the above list are preferred when preparing the photostable composition. These saturated hydroxyl-terminated curing agents are: ethylene glycol; diethylene glycol; polyethylene glycol; propylene glycol; 2-methyl-1,3-propanediol; 2-methyl-1,4-butanediol; Polypropylene glycol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; trimethylolpropane; Cyclohexyldimethylol; triisopropanolamine; N, N, N ′, N′-tetra- (2-hydroxypropyl) -ethylenediamine; diethylene glycol bis (aminopropyl) ether; 1,5-pentanediol; 1,6-hexanediol 1,3-bis (2-hydroxyethoxy) cyclohexane; 1,4-cyclohexyldimethylol; 1,3-bis [2- (2-hydro Xyloxy) ethoxy] cyclohexane; 1,3-bis {2- [2- (2-hydroxyethoxy) ethoxy] ethoxy} cyclohexane; polytetramethylene ether glycol having a molecular weight in the range of about 250 to about 3,900; and mixtures thereof Including, but not limited to.

  Thus, both of these types of curing agents, ie, hydroxyl-terminated and amine-terminated curing agents, can contain one or more saturated, unsaturated, aromatic, and cyclic groups. Furthermore, the hydroxyl-terminated and amine-terminated curing agents can contain one or more halogen atoms. In order to further improve the shear resistance of the resulting polyurea elastomer, a trifunctional curing agent can be used to assist and improve crosslinking. For example, a curing agent having a hydroxyl-terminus can be used. Preferably, a triol, such as trimethylolpropane or tetraol, such as N, N, N ′, N′-tetrakis (2-hydroxypropylethylenediamine) can be added to the formulation.

  In one embodiment, the curing agent is an improved curing agent blend disclosed in co-pending US Pat. No. 7,041,769. The entire contents of the patent are incorporated herein by reference. For example, the curing agent of the present invention can be improved with a freezing point depressant to delay the onset of solidification and produce a curing agent blend that includes a storage-stable pigment dispersion. Some amine-terminated curing agents have relatively high freezing points such as hexamethylenediamine (about 41 ° C. (105.8 ° F.)), diethanolamine (about 28 ° C. (82.4 ° F.)), triethanolamine ( About 21 ° C (69.8 ° F)), diisopropanolamine (about 23 ° C (73.4 ° F)), and triisopropanolamine (about 44 ° C (111.2 ° F)). Such amine-terminated curing agents can be improved with amine-terminated freezing point depressants or mixtures of amine-terminated freezing point depressants. Suitable amine-terminated freezing point depressants are ethylenediamine, 1,3-diaminopropane, dimethylaminopropylamine, tetraethylenepentamine, 1,2-propylenediamine, diethylaminopropylamine, 2,2,4-trimethyl- Including, but not limited to, 1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and mixtures thereof.

The freezing point depressant is preferably an amount sufficient to reduce the freezing point of the curing agent, and is an amount suitable to prevent loss of pigment dispersibility, and does not adversely affect the physical properties of the golf ball. Added in an amount. In one embodiment, the freezing point depressant is added to the hardener in an amount of about 5% by weight or more based on the weight of the hardener blend, ie, hardener, freezing point depressant. In other embodiments, the freezing point depressant is present in an amount greater than or equal to about 8% by weight, based on the weight of the hardener blend. In yet another embodiment, the freezing point depressant is present in an amount of about 10% by weight or more. In yet another embodiment, the curing agent blend contains the freezing point depressant in an amount of about 12% by weight or more, based on the weight of the curing agent blend. The hardener blend also contains the freezing point depressant in an amount of about 14% by weight or more, based on the weight of the hardener blend.
Further, after freezing and subsequent thawing, preferably the improved curative blend of the present invention is greater than 0, preferably about 1 or more, and more preferably about 2 or more on the Hegman scale. It has the above pigment dispersibility (degree). In one embodiment, the improved curative blend after a freeze / thaw cycle has a pigment dispersity of about 3 or greater on the Hegman scale. In another embodiment, the improved curative blend after freezing and thawing has a pigment dispersity of about 4 or more, preferably about 5 or more on the Hegman scale. In yet another embodiment, the improved curative blend, after freezing and thawing, has a pigment dispersion of about 6 or greater on the Hegman scale. In yet another embodiment, after freezing and thawing, has a pigment dispersity of about 7 or more on the Hegman scale.

Production of the Composition of the Invention There are two basic techniques used to treat the urea-based composition of the invention: the one-shot method and the prepolymer method. In the one-shot method, the isocyanate-containing compound, the isocyanate-reactive component, and the curing agent are reacted in one step, while the prepolymer method is used to produce the prepolymer. A first reaction between the compound and the isocyanate-containing compound and a subsequent reaction between the prepolymer and the curing agent are required. Either method can be used to produce the polyurea composition of the present invention, since the prepolymer method provides better control of the chemical reaction and results in more uniform properties of the resulting elastomer. This prepolymer method is preferred.
Accordingly, in one embodiment, the composition of the present invention comprises reacting at least one isocyanate-containing component with at least one isocyanate-reactive component to form a prepolymer, wherein the prepolymer chain. It can be produced by extending the length with a curing agent and curing the system. In particular, all of the isocyanate-containing components discussed above can be reacted with any of the isocyanate-reactive components discussed above to form a prepolymer. In one embodiment, the prepolymer is formed from an isocyanate-containing component and an amine-terminated isocyanate-reactive component and consists essentially of urea linkages. In another embodiment, the prepolymer is formed from an isocyanate-containing component and a second diamine.

  In another aspect of the present invention, the isocyanate-containing component used in the present invention can comprise an aromatic isocyanate hybridized with an aliphatic isocyanate. For example, an aromatic isocyanate can be reacted with an isocyanate-reactive component, such as an amine-terminated component, to produce an intermediate prepolymer, which is then combined with functional groups of the prepolymer. Heat at a temperature sufficient to allow further reaction with the aliphatic isocyanate added in excess. As a result, the prepolymer has aliphatic isocyanate groups at both ends. In one embodiment, the temperature sufficient to further react the functional groups of the intermediate prepolymer with the NCO groups in the aliphatic isocyanate is in the range of about 60 to about 90 ° C., preferably about 70. Within the range of ~ 80 ° C. For the purposes of this aspect of the invention, any of the previously discussed aromatic and aliphatic isocyanate-containing components can be used.

Once formed, the prepolymer preferably contains about 10% to 20% free isocyanate monomer (NCO groups). In one embodiment, the NCO content of the prepolymer is about 12% to 16%. The number of unreacted NCO groups in the prepolymer can be varied to adjust factors such as the rate of the reaction, the hardness of the resulting composition, and the like. For example, increasing the amount of unreacted isocyanate groups in weight percent increases its hardness in a somewhat linear fashion. Thus, if the NCO content is about 10.5% by weight, the hardness can be about 55 Shore A, whereas once the NCO content is increased to about 15% by weight, the hardness is about 80 Shore A. Over.
In this aspect of the invention, the prepolymer can be removed from the free isocyanate monomer. For example, after stripping, the prepolymer can contain about 1% or less of free isocyanate monomer. In other embodiments, the prepolymer comprises about 0.5% or less free isocyanate monomer.

Those skilled in the art recognize that various properties of golf balls and golf ball components, such as hardness, can be controlled by adjusting the ratio of prepolymer to curing agent. The ratio is a function of the NCO content of the prepolymer and the molecular weight of the curing agent as discussed above. For example, the ratio of a prepolymer cured with 1,4-butanediol and containing 6% unreacted NCO groups is 15.6: 1, while 4,4′-bis (sec-butylamino) dicyclohexylmethane The ratio of the same prepolymer cured with (Clearlink 1000) is 4.36: 1. For the purposes of the present invention, this ratio of prepolymer to curing agent is preferably in the range of about 0.5: 1 to about 16: 1. One skilled in the art will recognize that this ratio should be adjusted to minimize resilience, depending on the type of layer made from the composition of the present invention. For example, when making a cover from the composition of the present invention, the ratio of the prepolymer to the curing agent can be about 1: 0.95.
Similarly, the ratio of prepolymer to curing agent plays a role in determining whether the composition is thermoset or thermoplastic. For example, a 1: 1 stoichiometric ratio of a prepolymer crosslinked with a curing agent is thermoplastic in nature. On the other hand, thermosetting polyurethanes are generally produced when the ratio of prepolymer to curing agent is less than one. For example, the composition can be thermoset when the ratio of the prepolymer to the second diamine curing agent is 1: 0.95.

Since the selection of the curing agent determines whether the composition of the present invention is thermoset or thermoplastic, the method of molding the composition of the present invention on the ball also includes the composition of the composition. It will vary depending on the type. For example, the thermoplastic polyurea composition of the present invention can be used to produce thermoplastic pellets that can be molded on the balls by injection molding or compression molding. The thermosetting polyurea composition can be cast on the ball. Furthermore, both the thermosetting and thermoplastic polyurea compositions of the present invention can be molded around the core using reactive injection molding (RIM) and liquid injection molding (LIM) methods.
Additional materials conventionally formulated in polyurethane and / or polyurea compositions can be added to the prepolymers or cured compositions of the present invention. These additional materials, catalysts, wetting agents, coloring agents, fluorescent whitening agents, crosslinking agents, whitening agents, for example TiO _2, ZnO, UV absorbers, hindered amine light stabilizers, antifoaming agents, processing aids, Including but not limited to surfactants and other known additives. For example, wetting agents can be added to the improved curative blend of the present invention for the purpose of more effectively dispersing the pigment. Suitable wetting agents are available in particular from Byk-Chemle and Crompton Corporation.
Antioxidants, stabilizers, softeners, plasticizers including internally and externally added plasticizers, impact modifiers, foaming agents, density-controlling fillers, reinforcing materials and compatibilizers are also compositions of the present invention. Can be added to the product. Those skilled in the art will be aware of the purpose of adding these additives and the amount to be used to meet these purposes.

Catalyst A catalyst can also be used to control the reaction rate between the prepolymer and the curing agent. Suitable catalysts are bismuth catalyst; zinc octoate; stannous octoate; tin catalyst such as bis-butyltin dilaurate (DABCO ^™ T-12; Air Products and Chemicals, Inc.) Bis-butyltin diacetate (DABCO ^™ T-1); stannous octoate (DABCO ^™ T-9); tin (II) chloride, tin (IV) chloride Bis-butyltin dimethoxide (FASCAT ^TM -4211), dimethyl-bis [1- (oxondecyl) oxy] stannous salt (FORMEZ ^TM UL-28), di-n-octyltin Bis-isooctyl mercaptoacetate (FORMEZ ^™ UL-29); amine catalysts such as triethylenediamine (DABCO ^™ 33-LV), triethylamine, and tributylamine; organic acids such as oleic acid and acetic acid; Delayed catalyst such as polycarbonate Doo (POLYCAT ^TM) SA-1, Polycut (POLYCAT ^TM) SA-2, Polycut (POLYCAT ^TM) or the like; and including mixtures thereof, without limitation. In one embodiment, the catalyst is di-butyltin dilaurate.

The catalyst is preferably added in an amount sufficient to catalyze the reaction of the components in the reaction mixture. In one embodiment, the catalyst is present in an amount ranging from about 0.001 to about 5 weight percent, based on the weight of the composition. For example, when using a tin catalyst such as di-butyltin dilaurate, the catalyst is preferably present in an amount ranging from about 0.005 to about 1 weight percent. In other embodiments, the catalyst is present in an amount of about 0.05% by weight or more. In another embodiment, the catalyst is present in an amount of about 0.5% by weight or more.
The use of tin catalysts at low concentrations, typically in the range of about 0 to about 0.04 weight percent, based on the total composition, requires the use of high temperatures to achieve adequate reaction rates. However, this can lead to degradation of the resulting prepolymer. Increasing the amount of catalyst to a high concentration, which is unconventional, can reduce the processing temperature while maintaining a reasonable curing stage. The use of higher catalyst concentrations also makes it possible to reduce the mixing rate. Thus, in one embodiment, the tin catalyst is present in an amount ranging from about 0.01 to about 0.55% by weight of the composition. In other embodiments, an amount of tin catalyst in the range of about 0.05 to about 0.4 weight percent is present in the composition. In yet another embodiment, the tin catalyst is present in the composition in an amount ranging from about 0.1 to about 0.25% by weight.

While not intending to be bound by any theory, catalysts such as di-butyltin dilaurate inhibit or slow the cure rate when used with prepolymers containing urea linkages. However, when used with prepolymers containing urethane linkages, di-butyltin dilaurate accelerates the reaction rate. One skilled in the art will be able to select the type and amount of catalyst that is most appropriate for a particular type of composition made in accordance with the present invention.
Density-adjusting fillers can be added to the compositions of the present invention to affect their rheology and mixing characteristics, specific gravity (ie, density-adjusting filler), modulus, tear strength, degree of reinforcement, etc. . The fillers are generally inorganic and suitable fillers include many metals, metal oxides and salts, such as zinc oxide and tin oxide, and barium sulfate, tungsten carbide, a series of silicas, regrinds (typically , Recycled core material, ground to about 30 mesh particles), high Mooney viscosity rubber regrind, and mixtures thereof.

For example, the composition of the present invention comprises a wide range of density-adjusting fillers such as ceramics, glass spheres (solid or hollow, and filled or non-filled), and fibers, inorganic particles, as known to those skilled in the art. And by blending with metal particles such as metal flakes, metal powders, oxides, and derivatives thereof. The choice of such filler will depend on the type of golf ball desired, ie, one-piece, two-piece, multicomponent, spool, etc., as described in more detail below. Generally, the filler is an inorganic material having a density of greater than 4 g / cc and is present in an amount ranging from about 5 to about 65 weight percent, based on the total weight of the polymer component contained in the layer in question. . Examples of useful fillers include zinc oxide, barium sulfate, calcium oxide, calcium carbonate, and silica, and other known corresponding salts and oxides thereof.
The filler can also be used to adjust the mass of the core or at least one additional layer for a custom ball, for example, lower mass balls are preferred for athletes with lower swing speeds. .

Foaming agent The composition of the present invention can be foamed with the addition of at least one physical or chemical blowing agent. The use of the foamed polymer allows the golf ball designer to adjust the ball's density or mass distribution to adjust the angular momentum of inertia and consequently the spin speed and performance of the ball. Make it possible. Foamed materials also provide significant cost savings by reducing the amount of polymer material used.
Useful blowing agents are organic blowing agents such as azobisformamide, azobisisobutyronitrile, diazoaminobenzene, N, N-dimethyl-N, N-dinitrosotephthalamide, N, N-dinitrosopentamethylenetetramine , Benzenesulfonyl hydrazide, benzene-1,3-disulfonyl hydrazide, diphenylsulfone-3,3-disulfonyl hydrazide, 4,4'-oxybisbenzenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate, butylamine Nitrile, nitrourea, trihydrazinotriazine, phenylmethyl-uranthan, p-sulfone hydrazide, peracids, and inorganic blowing agents such as, but not limited to, ammonium bicarbonate and sodium bicarbonate. Gases such as air, nitrogen, carbon dioxide and the like can also be injected into the composition during injection molding of the composition of the present invention.

  Further, the foamed composition of the present invention can be produced by blending the composition and microspheres during or before the molding process. Polymers, ceramics, metal and glass microspheres are useful in the present invention, and these can be solid or hollow, and filled or non-filled. In particular, microspheres having a diameter of about 1,000 μm are useful. Furthermore, the use of liquid nitrogen for foaming, as described in US Pat. No. 6,386,992, which is hereby incorporated by reference, is a highly uniform foaming composition for use in the present invention. Allows manufacturing.

  Either injection molding or compression molding methods can be used to produce a layer or core containing foamed polymeric material. For example, the compositions of the present invention can be thermoformed and thus compression molded. For compression-molded grafted metallocene catalyst-containing polymer blend layers, a grafted metallocene catalyst-containing polymer sheet is injection molded or foamed in a conventional half-shell mold. The half shell can be manufactured by compression molding. The half shell is placed around a preformed center or core, cover, or mantle layer, and the assembly is introduced into a compression molding machine and ranges from about 121.1 to about 204.4 ° C (about 250 to about 400 ° F). Compression molding is performed at the internal temperature. The molded ball is then cooled while still in the mold, and finally the layer of the grafted metallocene catalyst-containing polymer blend is sufficiently hard to handle without deformation. Then, it is taken out from the mold. Additional core, mantle, and cover layers are then cast on the pre-molded layer, if necessary, until a complete ball is formed.

Light Stabilizer As discussed above, in order to obtain maximum light stability over time, the composition of the present invention preferably comprises only saturated components. However, a composition comprising a saturating component is resistant to discoloration, but is not immune to degradation in its mechanical properties when exposed outdoors. Therefore, the addition of UV absorbers and light stabilizers to any of the above compositions containing unsaturated components is recommended to prevent significant yellowing, and this addition is a composition containing only saturated components. It can assist in maintaining tensile strength, elongation, and color stability in the object. The use of light stabilizers also helps prevent cover surface breakage due to light degradation in both types of compositions. As used herein, the term “light stabilizer” can be understood to encompass hindered amine light stabilizers, ultraviolet (UV) absorbers, and antioxidants.

Suitable light stabilizers include TINUVIN ^™ 292, TINUVIN ^™ 328, TINUVIN ^™ 213, TINUVIN ^™ 765, TINUVIN ^™ 770 and TINUVIN ^™ 622. However, it is not limited to these. TINUVIN ^™ products are available from Ciba Specialty Chemicals, Tarrytown, NY. In one embodiment, the light stabilizer is TINUVIN ^™ 328, a UV absorber, which is useful for aromatic compounds. In another embodiment, TINUVIN ^™ 765, a hindered amine light stabilizer, is used with an aliphatic compound. Furthermore, TINUVIN ^™ 292 can also be used with the aromatic or aliphatic compositions of the present invention.
In addition, as discussed above, dyes and optical brighteners and fluorescent pigments can also be incorporated into golf ball covers made with polymers made in accordance with the present invention. Such additional ingredients can be added in any amount that will achieve its intended purpose.

Composition Blends The compositions of the present invention preferably comprise from about 1% to about 100% polyurea or polyurea-polyurethane, depending on the isocyanate-reactive component used and the type of curing agent used. The composition can also be blended with other materials. In one embodiment, the composition comprises from about 10% to about 90% polyurea or polyurea-polyurethane, preferably from about 10% to about 75% polyurea or polyurea-polyurethane, and from about 90% to Other polymers and / or other materials as described below in the range of 10%, more preferably in the range of about 90% to about 25%. Unless stated otherwise below, all percentages are given in weight percent, based on the weight of the total composition of the golf ball layer in question.
Other polymeric materials suitable for blending with the compositions of the present invention are castable thermoplastics, cationic and anionic urethane ionomers and urethane epoxy resins, polyurethane ionomers, polyurea ionomers, epoxy resins, polyethylene , Polyamides and polyesters, polycarbonates, polyacrylin, siloxanes and epoxy resins or blends thereof, and mixtures thereof. Those skilled in the art will be well aware of how to blend the polymeric material with the compositions of the present invention.

  Examples of suitable urethane ionomers are described in US Pat. No. 5,692,974. The entire disclosure of this patent is incorporated herein by reference. Other examples of suitable polyurethanes are described in US Pat. No. 5,334,673. The entire disclosure of this patent is incorporated herein by reference. Examples of suitable polyureas used to make the polyurea ionomers listed above are discussed in US Pat. No. 5,484,870. In particular, the polyureas described in U.S. Pat.No. 5,484,870 are produced by reacting a polyisocyanate and a polyamine curing agent to produce a polyurea, which is produced from a polyurea prepolymer and a curing agent. It is distinguished from the polyurea of the invention. Examples of suitable polyurethanes cured with an epoxy group-containing curing agent are described in US Pat. No. 5,908,358. The entire disclosure of the above patent is incorporated herein by reference.

Acid Functionalization of Compositions As described in US Pat. No. 6,610,812, the compositions of the present invention can also be acid functionalized to improve adhesion to other components or layers. The entire disclosure of the patent is hereby incorporated herein by reference. The acid functional groups are preferably based on sulfonic acid groups (HSO ₃ ), carboxylic acid groups (HCO ₂ ), phosphoric acid groups (H ₂ PO ₃ ) or combinations thereof. More than one type of acid functionality can be incorporated into the composition. In one embodiment, the acid functionalization is accomplished by incorporating the acid group into the isocyanate-containing component or the isocyanate-reactive component. For example, the isocyanate-containing component and acid functional group-containing compound, such as those described in US Pat. Nos. 4,956,438 and 5,071,578, can be reacted prior to preparation of the prepolymer. The entire disclosure of the above patent is incorporated herein by reference.

The acid groups can also be incorporated during the post-polymerization reaction. Here, the acid functional group can be introduced into or bonded to the cured polyurea or polyurea-polyurethane. Furthermore, the acid functional polyurea or polyurea-polyurethane produced by copolymerization as described above can further incorporate additional acid functional groups through such post-polymerization reactions. Suitable agents for incorporating acid functional groups into the polyurea or polyurethane and their preparation are described in US Pat. No. 6,207,784. The entire disclosure of this patent is incorporated herein by reference.
Those skilled in the art will recognize other methods for producing the acid functional polyurea or polyurethane. For example, combinations of the above embodiments can be utilized as described in US Pat. No. 5,661,207. The entire disclosure of this patent is incorporated herein by reference.

Golf Ball Composition Golf Ball Core Layer Golf ball cores made in accordance with the present invention are solid, semi-solid (semi-solid), hollow, fluid-filled or powder-filled, one-piece or It can be a multi-component core. As used herein, the term “semi-solid (semi-solid)” means paste, gel, and the like. Any core material known to those skilled in the art is suitable for use in the golf ball of the present invention. Suitable core materials include thermosetting materials such as rubber, styrene butadiene, polybutadiene, isoprene, polyisoprene, trans-isoprene, and thermoplastic materials such as ionomer resins, polyamides or polyesters, and thermoplastic and thermosetting polyurethane elastomers. including. As mentioned above, the composition of the present invention can be used to produce the core of a golf ball.

Alternatively, the golf ball core is formed from a composition comprising a base rubber (natural, synthetic, or a combination thereof), a crosslinker and a filler. In another embodiment, the golf ball core is formed from a reaction product comprising a cis-trans catalyst, an elastic polymer component comprising polybutadiene, a free radical source, and optional crosslinkers, fillers, or both. Using various combinations of polymers, cis-trans catalysts, fillers, crosslinkers, and free radical sources, such as those described in co-pending and assigned US Patent No. 6,998,445 A reaction product can be produced. The entire disclosure of this patent is incorporated herein by reference. While this polybutadiene reaction product is discussed in the section relating to the core composition, the present invention also contemplates using this reaction product to produce at least a portion of any part of a golf ball. .
As used herein, the terms “core and center” are generally used interchangeably to describe the innermost part of the ball. However, in some embodiments, the term “center” is used when there are multiple core layers, ie, the center and outer core layers.

In order to obtain higher resilience and lower compressibility, high molecular weight polybutadiene having a cis-isomer content of preferably greater than about 40% is converted to the trans-isomer at any point in the golf ball or part thereof. Convert to increase content. In one embodiment, the cis-isomer is present in an amount greater than about 70%, preferably greater than about 80%, and more preferably greater than about 90%, based on the total polybutadiene content. In yet another embodiment, the cis-isomer is present in an amount greater than about 95%, and more preferably greater than about 96%, based on the total polybutadiene content.
The presence of a small amount of 1,2-polybutadiene isomer (vinyl-polybutadiene) is desired in the initial polybutadiene and the reaction product. In one embodiment, the vinyl-polybutadiene isomer content is less than about 7%, preferably less than about 4%, and more preferably less than about 2%.
The polybutadiene material can have an absolute molecular weight greater than about 200,00. In one embodiment, the molecular weight of the polybutadiene is greater than about 250,000, and more preferably in the range of about 300,000 to 500,000. In other embodiments, the polybutadiene has a molecular weight of about 400,000 or greater. The polydispersity of this material is about 2 or less, more preferably 1.8 or less, and even more preferably 1.6 or less.

In one embodiment, the polybutadiene has a Mooney viscosity greater than about 20, preferably greater than about 30, and more preferably greater than about 40. Mooney viscosity is typically measured according to ASTM D-1646. In another embodiment, the polybutadiene has a Mooney viscosity of greater than about 35, and preferably greater than about 50. In yet another embodiment, the Mooney viscosity is about 120 or less. For example, the Mooney viscosity of the unvulcanized polybutadiene can be in the range of about 40 to about 120. In one embodiment, the Mooney viscosity can be in the range of about 40 to about 80. In other embodiments, the Mooney viscosity can be in the range of about 45 to about 60, more preferably in the range of about 45 to about 55.
In one embodiment, the central composition includes at least one rubber material having a resilience index of at least about 40. In another embodiment, the resilience index of the at least one rubber material is at least about 50.

Examples of desirable polybutadiene rubbers are commercially available from Bayer, Akron, Ohio, such as BUNA ^TM CB22 and BUNA ^TM CB23; UBE Industries, Tokyo, Japan UBEPOL ^™ 360L and UBEPOL ^™ 150L available commercially from CARIFLEX ^™ BCP820, CARIFLEX, commercially available from Shell, Houston, TX ^TM ) BCP824, CARIFLEX ^™ BR1220; and KINEX ^™ 7245 and KINEX ^™ 7665, commercially available from Goodyear, Akron, Ohio. If desired, the polybutadiene can also be mixed with other elastomers known in the art such as natural rubber, polyisoprene rubber and / or styrene butadiene rubber to improve the properties of the core.

While not intending to be bound by any particular theory, the cis-trans catalyst component is combined with the free radical source from the cis-conformation of the polybutadiene polymer component to the trans-conformation of the polymer component. It is thought to function to convert a certain percentage. Thus, the cis-trans conversion is preferably a cis-trans catalyst, such as organic sulfur or metal-containing organic sulfur compounds, sulfur or metal free, substituted or unsubstituted aromatic organic compounds, inorganic sulfide compounds, aromatic organic metals. Including the presence of a compound, or a mixture thereof.
As used herein, “cis-trans catalyst” means any component or combination thereof that converts at least a portion of the cis-isomer to the trans-isomer at a given temperature. The cis-trans catalyst component can include one or more cis-trans catalysts described herein, but typically includes at least one organosulfur compound, a Group VIA component, an inorganic sulfide. Or a combination thereof. In one embodiment, the cis-trans catalyst is a blend of an organic sulfur component and an inorganic sulfide component or a Group VIA component.

As used herein when referring to the present invention, the term “organic sulfur compound” or “organic sulfur component” means any compound containing carbon, hydrogen, and sulfur atoms. As used herein, the term “sulfur component” means elemental sulfur, polymeric sulfur, or a combination thereof. Furthermore, the term “elemental sulfur” means a ring structure of S ₈ , and the term “polymeric sulfur” means a structure containing at least one additional sulfur with respect to the elemental sulfur. It should be understood as meaning.
The cis-trans catalyst is typically present in an amount sufficient to produce the reaction product so as to increase the trans-polybutadiene isomer content, resulting in the entire elastomeric polymer component. And the content of trans-isomeric polybutadiene is within the range of about 5 to 70%. The cis-trans catalyst may be present in an amount sufficient to increase the trans-polybutadiene isomer content to at least about 15%, more preferably at least about 20%, and even more preferably at least about 25%. preferable.

  Accordingly, the cis-trans catalyst is preferably present in an amount in the range of about 0.1 to about 25 parts per 100 parts of the total elastomeric polymer component. As used herein, the term “parts per hundred”, also known as “pph”, is defined as the number of parts by weight of a particular component present in a mixture relative to 100 parts by weight of the total polymer component. The Mathematically, this is expressed as the mass of a component divided by the total mass of the polymer multiplied by a factor of 100. In one embodiment, the cis-trans catalyst is present in an amount ranging from about 0.1 to about 12 pph of the total elastomeric polymer component. In other embodiments, the cis-trans catalyst is present in an amount ranging from about 0.1 to about 10 pph of the total elastomeric polymer component. In yet another embodiment, the cis-trans catalyst is present in an amount ranging from about 0.1 to about 8 pph of the total elastomeric polymer component. In yet other embodiments, the cis-trans catalyst is present in an amount ranging from about 0.1 to about 5 pph of the total elastomeric polymer component. The value at the lower end of the above range can be increased if it becomes clear that 0.1 pph does not give a predetermined conversion. For example, the amount of the cis-trans catalyst present may be about 0.5 or more, 0.75 or more, 1.0 or more, or even 1.5 or more.

Suitable organic sulfur components for use in the present invention include at least one diphenyl disulfide; 4,4′-ditolyl disulfide; 2,2′-benzamido diphenyl disulfide; bis (2-aminophenyl) disulfide; 4-aminophenyl) disulfide; bis (3-aminophenyl) disulfide; 2,2'-bis (4-aminonaphthyl) disulfide; 2,2'-bis (3-aminonaphthyl) disulfide; 2,2'-bis (4-aminonaphthyl) disulfide; 2,2'-bis (5-aminonaphthyl) disulfide; 2,2'-bis (6-aminonaphthyl) disulfide; 2,2'-bis (7-aminonaphthyl) disulfide; 2,2'-bis (8-aminonaphthyl) disulfide; 1,1'-bis (2-aminonaphthyl) disulfide; 1,1'-bis (3-aminonaphthyl) disulfide; 1,1'-bis (3 -Aminonaphthyl) disulfide; 1,1'-bis (4-aminonaphthyl) disulfide 1,1′-bis (5-aminonaphthyl) disulfide; 1,1′-bis (6-aminonaphthyl) disulfide; 1,1′-bis (7-aminonaphthyl) disulfide; Bis (8-aminonaphthyl) disulfide; 1,2'-diamino-1,2'-dithiodinaphthalene;2,3'-diamino-1,2'-dithiodinaphthalene; bis (4-chlorophenyl) disulfide; (2-chlorophenyl) disulfide; bis (3-chlorophenyl) disulfide; bis (4-bromophenyl) disulfide; bis (2-bromophenyl) disulfide; bis (3-bromophenyl) disulfide; bis (4-fluorophenyl) disulfide Bis (4-iodophenyl) disulfide; bis (2,5-dichlorophenyl) disulfide; bis (3,5-dichlorophenyl) disulfide; bis (2,4-dichlorophenyl) disulfide; bis (2,6-dichlorophenyl) disulfide; Screw (2, 5-dibromophenyl) disulfide; bis (3,5-dibromophenyl) disulfide; bis (2-chloro-5-bromophenyl) disulfide; bis (2,4,6-trichlorophenyl) disulfide; bis (2,3, 4,5,6-pentachlorophenyl) disulfide; bis (4-cyanophenyl) disulfide; bis (2-cyanophenyl) disulfide; bis (4-nitrophenyl) disulfide; bis (2-nitrophenyl) disulfide; '-Dithiobenzoic acid ethyl; 2,2'-dithiobenzoic acid methyl; 2,2'-dithiobenzoic acid; 4,4'-dithiobenzoic acid ethyl; bis (4-acetylphenyl) disulfide; bis (2-acetyl Bis (4-formylphenyl) disulfide; bis (4-carbamoylphenyl) disulfide; 1,1'-dinaphthyl disulfide; 2,2'-dinaphthyl disulfide; 1,2'-dinaphthyl disulfide; 2,2'-bis (1-chlorodinaphthyl) disulfide; 2,2'-bis (1-bromonaphthyl) disulfide; 1,1'-bis (2-chloronaphthyl) disulfide; 2,2'-bis ( 1-cyanonaphthyl) disulfide; 2,2′-bis (1-acetylnaphthyl) disulfide and the like; or mixtures thereof. The most preferred organic sulfur component comprises diphenyl disulfide; 4,4′-ditolyl disulfide; or mixtures thereof, in particular 4,4′-ditolyl disulfide. In one embodiment, the at least one organic sulfur component is substantially free of metals. As used herein, the term “substantially metal free” means less than about 10% by weight, preferably less than about 5% by weight, more preferably less than about 3% by weight, even more preferably less than about 1% by weight, And most preferably means less than about 0.01% by weight. Suitable substituted or unsubstituted aromatic organic components that do not include sulfur and metals include, but are not limited to, diphenylacetylene, azobenzene, or mixtures thereof. The aromatic organic group is preferably in the size range C ₆ -C ₂₀ and more preferably C ₆ -C _{10 in} size.

In one embodiment, the organosulfur cis-trans catalyst is present in the reaction product in an amount of about 0.5 pph or greater. In other embodiments, the cis-trans catalyst comprising an organic sulfur component is present in the reaction product in an amount greater than about 0.6 pph. In yet another embodiment, the cis-trans catalyst comprising an organic sulfur component is present in the reaction product in an amount greater than about 1.0 pph. In yet other embodiments, the cis-trans catalyst comprising an organic sulfur component is present in the reaction product in an amount greater than about 2.0 pph.
Suitable metal-containing organosulfur components include, but are not limited to, cadmium, copper, lead, and tellurium analogs of diethyldithiocarbamate, diamyldithiocarbamate, and dimethyldithiocarbamate, or mixtures thereof. In one embodiment, the metal-containing organosulfur cis-trans catalyst is present in the reaction product in an amount greater than or equal to about 1.0 pph. In other embodiments, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount of about 2.0 pph or greater. In yet another embodiment, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount greater than about 2.5 pph. In yet other embodiments, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount of about 3.0 pph or more.
The organic sulfur component may also be a halogenated organic sulfur compound. Halogenated organosulfur compounds include, but are not limited to, compounds having the following general formula:

Here, R ₁ -R ₅ is a C ₁ -C ₈ alkyl group in any order; a halogen atom; a thiol group (—SH); a carboxylate group; a sulfonated group; and a hydrogen atom; 2-fluorothiophenol group; 4-fluorothiophenol group; 2,3-fluorothiophenol group; 2,4-fluorothiophenol group; 3,4-fluorothiophenol group 3,3,4-fluorothiophenol group; 3,3,4-fluorothiophenol group; 2,3,4,5-tetrafluorothiophenol group; 5,6-tetrafluorothiophenol group; 4-chlorotetrafluorothiophenol group; pentachlorothiophenol group; 2-chlorothiophenol group; 3-chlorothiophenol group; 4-chlorothiophenol group; Chlorothiopheno 2,4-chlorothiophenol group; 3,4-chlorothiophenol group; 3,5-chlorothiophenol group; 2,3,4-chlorothiophenol group; 3,3,4-chlorothiophenol group 2,3,4,5-tetrachlorothiophenol group; 2,3,5,6-tetrachlorothiophenol group; pentabromothiophenol group; 2-bromothiophenol group; 3-bromothiophenol group; 2,3-bromothiophenol group; 3,4-bromothiophenol group; 3,5-bromothiophenol group; 2,3,4-bromothio 2,3,4,5-bromothiophenol group; 2,3,5,6-tetrabromothiophenol group; pentaiodothiophenol group; 2- Thiophenol group; 3-thiophenol group; 4-thiophenol group; 2,3-iodothiophenol group; 4-iodothiophenol group; 3,4-iodothiophenol group; 3,5-iodothiophenol group; 2,3,4-iodothiophenol group; 3,4,5-iodothiophenol group; 2,4,5-tetraiodothiophenol group; 2,3,5,6-tetraiodothiophenol group; and salts thereof such as zinc, magnesium, lithium, calcium, potassium, manganese, nickel, etc. . Preferably, the halogenated organosulfur compound is pentachlorothiophenol, which is commercially available in pure form or under the trade name STRUKTOL ^™ ; and 45% (PCTP 2.4 And a carrier mainly composed of clay containing a sulfur compound pentachlorothiophenol. STRUKTOL ^™ is commercially available from the US Struktol Company, Stow, OH. PCTP is commercially available in pure form from eChinachem, Inc., San Francisco, CA, and is commercially available from the company in salt form. Most preferably, the halogenated organosulfur compound is a zinc salt of pentachlorothiophenol, which is commercially available from eChinachem, San Francisco, CA. The halogenated organosulfur compound of the present invention is preferably present in an amount greater than about 2.2 pph, more preferably in the range of about 2.3 pph to about 5 pph, and most preferably in the range of about 2.3 to about 4 pph. .

The cis-trans catalyst can also include a Group VIA component. As used herein, the term “Group VIA component” or “Group VIA element” means a component that includes a sulfur component, selenium, tellurium, or a combination thereof. Elemental sulfur and polymer sulfur are commercially available from, for example, Elastochem, Inc., Chardon, OH. Elemental sulfur catalyst compounds include PB (RM-S) -80 elemental sulfur and PB (CRST) -65 polymer sulfur, each available from Elastchem. An exemplary tellurium catalyst under the trade name TELOY and an exemplary tellurium catalyst under the trade name VANDEX are commercially available from RT Vanderbilt, Inc., Norwalk, CT, respectively. Available as
In one embodiment, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount greater than about 0.25 pph. In other embodiments, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount greater than about 0.5 pph. In yet another embodiment, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount greater than about 1.0 pph.

  Suitable inorganic sulfide components include, but are not limited to, titanium sulfide, manganese sulfide, and sulfide analogs of iron, calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc, tin and bismuth. In one embodiment, the cis-trans catalyst comprising an inorganic sulfide component is present in the reaction product in an amount greater than about 0.5 pph. In yet another embodiment, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount of about 0.75 pph or more. In yet another embodiment, the cis-trans catalyst comprising a Group VIA component is present in the reaction product in an amount of about 1.0 pph or more. When the reaction product comprises a blend of cis-trans catalyst comprising an organic sulfur component and an inorganic sulfide component, the organic sulfur component is preferably about 0.5 pph or higher, preferably 1.0 pph or higher, and more preferably about 1.5 pph. present in an amount greater than or equal to pph, and the inorganic sulfide component is present in an amount greater than or equal to about 0.5 pph, preferably greater than or equal to 0.75 pph, and more preferably greater than or equal to about 1.0 pph.

Substituted or unsubstituted aromatic organic compounds can also be included in the cis-trans catalyst. In one embodiment, the aromatic organic compound is substantially free of metals. Suitable substituted or unsubstituted aromatic organic compound has the _{formula: (R 1) x -R 3} -MR 4 - (R 2) including components with _y, is not limited thereto. In the general formula, R ₁ and R ₂ are each a hydrogen atom, or a substituted or unsubstituted C _1-20 linear, branched, or cyclic alkyl, alkoxy, or alkylthio group, or a monocyclic, polycyclic Or a fused cyclic C ₆ -C ₂₄ aromatic group; x and y are each an integer in the range of 0 to 5; R ₃ and R ₄ are each a monocyclic, polycyclic, or fused ring It is selected from the formula C ₆ -C ₂₄ aromatic group; and M includes an azo group or a metal component. R ₃ and R ₄ are each preferably selected from C ₆ -C ₁₀ aromatic groups, more preferably selected from phenyl, benzyl, naphthyl, benzamide, and benzothiazyl groups. R ₁ and R ₂ are each preferably selected from a substituted or unsubstituted C _1-10 linear, branched, or cyclic alkyl, alkoxy, or alkylthio group, or a C ₆ -C ₁₀ aromatic group . When R ₁ , R ₂ , R ₃ , or R ₄ is substituted, the substitution can include one or more of the following substituents: a hydroxyl group and its metal salt; a mercapto group and Halogen atoms; amino, cyano, nitro, and amide groups; carboxyl groups including esters, acids and metal salts thereof; silyl; acrylates and metal salts thereof; sulfonyl or sulfonamido groups; and phosphates and phosphites. When M is a metal component, it can be any suitable elemental metal available to those skilled in the art. Typically, the metal is a transition metal, but preferably the metal is tellurium or selenium.

  A free radical source, often referred to as a free radical initiator, is preferably present in the rubber-based core composition. The free radical source is typically a peroxide and preferably an organic peroxide, which decomposes during the cure cycle. Suitable free radical sources include organic peroxide compounds such as di-t-amyl peroxide, di (2-t-butylperoxyisopropyl) benzene peroxide or bis (t-butylperoxy) diisopropylbenzene, 1,1- Bis (t-butylperoxy) -3,3,5-trimethylcyclohexane or 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, dicumyl peroxide, di-t-butyl Peroxide, 2,5-di (t-butylperoxy) -2,5-dimethylhexane, n-butyl-4,4-bis (t-butylperoxy) valerate, lauryl peroxide, benzoyl peroxide, t -Butyl hydroperoxide and the like, and any mixtures thereof.

Other examples are commercially available from Elf Atochem, Philadelphia, PA, VAROX ^™ 231XL and Varox ^™ DCP-R; Akzo Nobel, Chicago, IL. ) company commercially available from, Perkadox (PERKADOX ^TM) BC and Perkadox (PERKADOX ^TM) 14; available and, NJ from Reinkemi (Rhein Chemie), Inc. in Trenton (Trenton) commercially Elastochem (Elastochem ^TM ) including, but not limited to, DPC-70. It is well known that peroxides are available in various forms with various activities. The activity is typically defined by its “active oxygen content”. For example, PERKADOX ^™ BC peroxide is 98% active and has an active oxygen content of 5.8%, while PERKADOX ^™ DPC-70 is 70% active and active. It has an oxygen content of 4.18%. The peroxide is in an amount greater than about 0.1 parts per 100 parts of the total elastic polymer component, preferably in the range of about 0.1 to 15 parts per 100 parts of the total elastic polymer component, and more preferably about 100 parts per 100 parts of the total elastic polymer component. Present in an amount ranging from 0.2 to 5 parts. When the peroxide is present as pure, it is preferably in an amount of at least about 0.25 pph, more preferably in the range of about 0.35 pph to about 2.5 pph, and most preferably in the range of about 0.5 pph to about 2 pph. Exists.

The peroxide can also be obtained as concentrated as described above, as is well known to those skilled in the art. In this case, when a concentrated peroxide is used in the present invention, those skilled in the art will recognize that a suitable concentration for pure peroxide can be easily adjusted by dividing the concentrated peroxide by its activity. For example, 2 pph of pure peroxide is equivalent to 4 pph of concentrated peroxide with 50% activity (ie 2 ÷ 0.5 = 4).
In one embodiment, the amount of the free radical source is about 5 pph or less, but may be about 3 pph or less. In other embodiments, the amount of free radical source is about 2.5 pph or less. In yet other embodiments, the amount of free radical source is about 2 pph or less. In yet another embodiment, the amount of free radical source is about 1 pph or less, preferably about 0.75 pph or less.

One skilled in the art should understand that the presence of several cis-trans catalysts according to the present invention is more suitable for larger quantities of free radical sources as described herein compared to conventional crosslinking reactions. It is. Optionally or incidentally, the free radical source is one or more of an electron beam, UV or gamma radiation, X-rays, or any other high energy radiation source capable of generating free radicals. There may be. Those skilled in the art recognize that heat often facilitates the initiation of free radical generation.
In one embodiment, the ratio of the free radical source to the cis-trans catalyst is about 10 or less, and can be about 5 or less. Further, the ratio of the free radical source to the cis-trans catalyst is about 4 or less, but may be about 2 or less, or may be about 1 or less. In other embodiments, the ratio of the free radical source to the cis-trans catalyst is about 0.5 or less, preferably about 0.4 or less. In yet another embodiment, the ratio of the free radical source to the cis-trans catalyst is greater than about 1.0. In yet another embodiment, the ratio of the free radical source to the cis-trans catalyst is about 1.5 or higher, preferably about 1.75 or higher.

  A crosslinking agent can be blended to increase the hardness of the reaction product. Suitable crosslinking agents include one or more unsaturated fatty acids of 3 to 8 carbon atoms, such as metal salts of acrylic acid or methacrylic acid or monocarboxylic acids, such as zinc, calcium, or magnesium acrylate salts, and the like Including these mixtures. Examples include, but are not limited to, one or more metal salt diacrylates, dimethacrylates, and monomethacrylates, where the metal is magnesium, calcium, zinc, aluminum, sodium, lithium or Nickel. Preferred acrylates include zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof. In one embodiment, zinc methacrylate is used in combination with a zinc salt of pentachlorothiophenol. The crosslinking agent must be present in an amount sufficient to crosslink a portion of the polymer chain in the elastic polymer component. For example, the predetermined compression ratio can be obtained by adjusting the amount of crosslinking. This can be accomplished, for example, by changing the type and amount of crosslinker in a manner well known to those skilled in the art. The cross-linking agent is typically in an amount greater than about 0.1% of the polymer component, preferably in an amount ranging from about 10 to about 50% of the polymer component, more preferably from about 10 to about 40% of the polymer component. Present in an amount in the range of%.

In one embodiment, the cross-linking agent is present in an amount greater than about 10 parts per hundred parts of the base polymer (pph), preferably in an amount ranging from about 20 to about 40 pph, more preferably the base polymer. It is present in an amount ranging from about 25 to about 35 pph relative to the base polymer. If organic sulfur is selected as the cis-trans catalyst, zinc diacrylate can be selected as the cross-linking agent and is present in an amount less than about 25 pph.
It should be understood that when elemental or polymeric sulfur is included in the cis-trans catalyst, promoters can be used to improve the performance of the cis-trans catalyst. Suitable accelerators include sulfenamides such as N-oxydiethylene 2-benzothiazole sulfenamide, thiazoles such as benzothiazyl disulfide, dithiocarbamates such as bismuth dimethyldithiocarbamate, thiurams such as tetrabenzyl thiuram disulfide, xanthates such as zinc Isopropyl xanthate, thiadiazine, thiourea, such as trimethylthiourea, guanazine, such as N, N'-di-o-tolylguanazine, or aldehyde-amine, such as butyraldehyde-aniline condensation products, or mixtures thereof, It is not limited.

  Typically, an antioxidant is included in conventional golf ball core compositions because the antioxidant is contained in the material supplied by the manufacturer of the compound used in the golf ball core. Because it is included. While not intending to be bound by any theory, the presence of larger amounts of antioxidant in the reaction product may result in lower trans-isomer content. This is because the antioxidant consumes at least a portion of the free radical source. Thus, even when the free radical source is used in large amounts in the reaction products described above, for example, in an amount of about 3 pph, an amount of antioxidant greater than about 0.3 pph can be used to assist in cis-trans conversion. Therefore, the effective amount of free radicals that can actually be used is greatly reduced.

The presence of an antioxidant in the composition is believed to potentially inhibit the ability of the free radical to adequately support the cis-trans conversion, thus ensuring a sufficient amount of free radicals. The method is to increase the initial level of free radicals in the composition so that a sufficient amount of free radicals are left after interaction with the antioxidant in the composition. Accordingly, the initial amount of free radicals provided to the composition is increased by at least about 10%, and more preferably by at least about 25%, so that an effective amount of residual free radicals is sufficient for the predetermined cis- It can be sufficient to obtain trans conversion. Depending on the amount of antioxidant in the composition, the initial amount of free radicals can be increased by at least about 50%, 100%, or more, as needed. As discussed below, the selection of the amount of free radicals in the composition can be determined based on a predetermined ratio of free radicals to antioxidants.
Another way is to reduce the amount of antioxidant in the composition or to eliminate the antioxidant. For example, the reaction product of the present invention is substantially free of antioxidants, and as a result, higher availability of free radicals for the cis-trans conversion can be achieved. As used herein, the term “substantially free” generally means that the polybutadiene reaction product contains less than about 0.3 pph of antioxidant, preferably less than about 0.1 pph, more preferably about 0.05. Means including less than pph antioxidant, and most preferably less than about 0.01 pph antioxidant.

It was shown in the present invention that the amount of antioxidant is related to the trans-isomer content after conversion. For example, a polybutadiene reaction product containing 0.5 pph antioxidant, cured at about 335 ° F. for 11 minutes, is about 15% on the outer surface of the center after the conversion, and internal This gives a trans-isomer content of about 13.4% in the part. In contrast, this same polybutadiene reaction product, substantially free of antioxidants, has a trans-isomer content of about 32% on the outer surface and about 21.4% on the inner part after the conversion. give.
In one embodiment, the ratio of the free radical source to the antioxidant is greater than about 10. In other embodiments, the ratio of free radical source to antioxidant is greater than about 25, preferably greater than about 50. In yet another embodiment, the ratio of the free radical source to the antioxidant is about 100 or higher. In yet other embodiments, the ratio of the free radical source to the antioxidant is about 200 or higher, preferably about 250 or higher, and more preferably about 300 or higher.

When the reaction product is substantially free of antioxidants, the amount of free radical source is preferably about 3 pph or less. In one embodiment, the free radical source is present in an amount of about 2.5 pph or less, preferably about 2 pph or less. In yet another embodiment, the amount of free radical source in the reaction product is about 1.5 pph or less, preferably about 1 pph or less. In yet another embodiment, the free radical source is present in an amount of about 0.75 pph or less.
When the reaction product contains about 0.1 pph or more of antioxidant, the free radical source is preferably present in an amount of about 1 pph or more. In one embodiment, when the reaction product comprises about 0.1 pph or more of the antioxidant, the free radical source is present in an amount of about 2 pph or more. In other embodiments, when the antioxidant is present in an amount of about 0.1 pph or greater, the free radical source is present in an amount of about 2.5 pph or greater.

In one embodiment, when the reaction product includes an amount of antioxidant greater than about 0.05 pph, the free radical source is preferably present in an amount of about 0.5 pph or greater. In other embodiments, when the reaction product includes an amount of antioxidant greater than about 0.05 pph, the free radical source is present in an amount of about 2 pph or more. In yet other embodiments, the free radical source is present in an amount greater than about 0.05 pph and in the amount of about 2.5 pph or more when an antioxidant is present.
Additional materials conventionally included in golf ball compositions can be added to the core composition based on rubber. These additional materials include density-adjusting fillers, colorants, reaction accelerators, crosslinking agents, whitening agents, UV absorbers, hindered amine light stabilizers, antifoaming agents, processing aids, and other known additives. Including, but not limited to. Stabilizers, softeners, plasticizers including internal and external plasticizers, impact modifiers, foaming agents, excipients, reinforcements, and compatibilizers may also be added to any composition of the present invention. it can. All of these materials, well known in the art, are added in typical amounts for their normal purposes.

For example, the filler described above in connection with the composition of the present invention may be added to a rubber-based core composition to add rheology and mixing properties, specific gravity (ie, density-adjusting filler), modulus, tear strength. In addition, the degree of reinforcement can be affected. Fillers can also be used to adjust the mass of the core, for example, lower mass balls are preferred by athletes with slower swing speeds.
As discussed above, it may be preferable to convert the cis-isomer in the polybutadiene core material to the trans-isomer. Thus, in one embodiment, the trans-isomer content after conversion is at least about 10% or more, while in other embodiments, the content is about 12% or more. In another embodiment, the trans-isomer content is about 15% or more after conversion. In yet another embodiment, the trans-isomer content after conversion is about 20% or more, and more preferably about 25% or more. In yet other embodiments, the trans-isomer content after conversion is about 30% or more, and preferably about 32% or more. The trans-isomer content after conversion is also about 35% or more, and preferably about 38% or more, or even about 40% or more. In yet other embodiments, it is about 42% or more, or even about 45% or more.

  The cured portion of the component comprising the reaction product of the present invention includes a first amount of trans-isomer polybutadiene at an internal location and a second amount of trans-isomer polybutadiene at an external surface location. Can do. In one embodiment, the amount of trans-isomer at the outer surface location is greater than the amount of trans-isomer at the inner location. As further shown by the examples given herein, the difference in trans-isomer content between the outer surface and the internal position after conversion was used for the curing cycle and the conversion reaction. It can vary depending on the ratio of the substances. For example, these differences may reflect a central portion with an amount of trans-isomer in the inner portion that is greater than the amount of trans-isomer in the outer portion.

  The outer portion of the center may contain the trans-isomer after conversion, such as about 10% or more, about 12% or more, about 15% or more, etc., or about 45% or as described above. It can be included in the amounts already mentioned herein, including up to and beyond. For example, in one embodiment of the invention, the polybutadiene reaction product can include the trans-isomer at a content ranging from about 35% to 60% on the outer surface of the central portion. Another embodiment includes the trans-isomer at a content ranging from about 40% to 50% on the outer surface of the central portion. In one embodiment, the reaction product comprises the trans-isomer polybutadiene at a content of about 45% at the outer surface of the central portion. In one embodiment, therefore, the reaction product at the center of the solid central portion comprises the trans-isomer in an amount at least about 20% less than the amount present on the outer surface, preferably at least about The trans-isomer can be included in an amount of 30% less, or the trans-isomer can be included in an amount of at least about 40% less. In other embodiments, the amount of the trans-isomer at the inner location is at least about 6% less than the amount present on the outer surface, preferably at least about 10% less than the second amount.

The slope between the inner part of the central part and the outer part of the central part can be varied. In one embodiment, the difference in trans-isomer content between the outside and inside after conversion is about 3% or more, while in other embodiments, the difference is about 5% or more. It can be. In another embodiment, the difference between the outer surface and the inner position after conversion is about 10% or more, and more preferably about 20% or more. In yet another embodiment, this difference in trans-isomer content between the outer surface and the inner position after conversion is about 5% or less, about 4% or less, and even about 3%. Or less. In yet other embodiments, the difference between the outer surface and the inner location after conversion is less than about 1%.
Preferably, the material as the polybutadiene reaction product is at least about 15 Shore A, more preferably in the range of about 30 Shore A to 80 Shore D, and even more preferably in the range of about 50 Shore A to 60 Shore D. Has hardness. Further, the specific gravity is typically greater than about 0.7, preferably greater than about 1, for the golf ball polybutadiene material. Further, the polybutadiene reaction product preferably has a bending range of about 3.445 MPa (about 500 psi) to about 2067 MPa (about 300,000 psi), preferably about 13.78 MPa (about 2,000 psi) to about 1378 MPa (about 200,000 psi). Has elastic modulus.

The predetermined loss tangent of the polybutadiene reaction product should be less than about 0.15 at -60 ° C and less than about 0.05 at 30 ° C when measured at a frequency of 1 Hz and 1% strain. In one embodiment, the material as the polybutadiene reaction product preferably has a loss tangent of about 0.1 or less at -50 ° C and more preferably about 0.07 or less at -50 ° C.
In order to produce a golf ball having a predetermined compression stiffness, the dynamic stiffness of the material as the polybutadiene reaction product should be less than about 50,000 N / m at -50 ° C. Preferably, the dynamic stiffness should be in the range of about 10,000 to 40,000 N / m at -50 ° C, and more preferably the dynamic stiffness is about 20,000 to 30,000 N / m at -50 ° C. Should be a range.
In one embodiment, the reaction product has a first dynamic stiffness measured at −50 ° C. that is less than about 130% of the second dynamic stiffness measured at 0 ° C. In other embodiments, the first dynamic stiffness is less than about 125% of the second dynamic stiffness. In yet another embodiment, the first dynamic stiffness is less than about 110% of the second dynamic stiffness.

Golf Ball Intermediate Layer When the golf ball of the present invention comprises an intermediate layer, such as an inner cover layer or an outer cover layer, that is, any layer disposed between the inner core of the golf ball and its outer cover, The layer can comprise any material known to those skilled in the art, including thermoplastic and thermoset materials. In one embodiment, the interlayer is made at least in part from the composition of the present invention.
The intermediate layer can also comprise one or more homopolymer or copolymer materials as listed below:
(1) Vinyl resin, for example, a resin produced by polymerization of vinyl chloride or copolymerization of vinyl chloride with vinyl acetate, acrylate ester or vinylidene chloride;
(2) Manufactured using polyolefins such as polyethylene, polypropylene, polybutylene and copolymers such as ethylene methyl acrylate, ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylic acid or ethylene acrylic acid or propylene acrylic acid and single site or metallocene catalysts Copolymers and homopolymers;
(3) polyurethanes, such as those made from polyols and diisocyanates or polyisocyanates, and those described in US Pat. No. 5,334,673;
(4) Polyureas, such as those described in US Pat. No. 5,484,870;

(5) Polyamides such as poly (hexamethylene adipamide) and other diamines and dibasic acids, as well as those made from amino acids such as poly (caprolactam), and polyamides and Surlyn (SURLYN), polyethylene , Blends with ethylene copolymers, ethyl-propylene-non-conjugated diene terpolymers, etc .;
(6) Acrylic resins and blends of these resins with polyvinyl chloride, elastomers, etc .;
(7) thermoplastic resins such as urethane; olefinic thermoplastic rubbers such as blends of polyolefins with ethylene-propylene-non-conjugated diene terpolymers; block copolymers of styrene with butadiene, isoprene or ethylene-butylene rubber; or copoly ( Ether-amide), such as Pebax (PEBAX) marketed by Atofina Chemicals, Inc. of Philadelphia, PA, and U.S. Pat.No. 5,688,191 (see the entire disclosure of this patent for reference). The thermoplastic composition described in the above;
(8) Polyphenylene oxide resin or a blend of polyphenylene oxide and high impact polystyrene marketed under the trade name NORRYL by General Electric Company of Pittsfield, MA;

(9) Thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, glycol modified polyethylene terephthalate, and trade names by EI DuPont de Nemours & Co., Wilmington, DE. Elastomers marketed under HYTREL and marketed under the trade name Lomod by General Electric Company of Pittsfield, MA;
(10) Contains polycarbonate and acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomer, etc., and includes polyvinyl chloride and acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomers Blends and alloys; and
(11) Blends of thermoplastic rubber and polyethylene, propylene, polyacetal, nylon, polyester, cellulose ether, etc.

  In one embodiment, the intermediate layer comprises a polymer, for example a homopolymer or copolymer based on ethylene, propylene, butene-1 or hexene-1, comprising functional monomers such as acrylic acid, methacrylic acid, etc., and completely Or partially neutralized ionomer resins and blends thereof, methyl acrylate, methyl methacrylate homopolymers and copolymers, imidization, amino group-containing polymers, polycarbonate, reinforced polyamide, polyphenylene oxide, high impact polystyrene, polyether ketone , Polysulfone, poly (phenylene sulfide), acrylonitrile-butadiene, acrylic acid-styrene-acrylonitrile, poly (ethylene terephthalate), poly (butylene terephthalate), poly (ethylene vinyl alcohol), poly ( Tetrafluoroethylene) and copolymers containing functional comonomer, and blends thereof.

As briefly mentioned above, the intermediate layer can comprise an ionomer material, such as an ionic copolymer of ethylene and an unsaturated monocarboxylic acid, which is an EI Dupont Duy, Wilmington, DE. Nemours & Co. (EI DuPont de Nemours & Co), available under the trade name Surlyn (SURLYN ^TM ), and from Exxon under the trade names IOTEK ( ^TM ) or Escor (ESCOR ^TM ). Available. These are copolymers or terpolymers of ethylene and methacrylic acid or acrylic acid, which are wholly or partially, ie about 1 to about 100%, zinc, sodium, lithium, magnesium, potassium, calcium, manganese, nickel, etc. Neutralized with salt. In one embodiment, the carboxylic acid group is neutralized within the range of about 10% to about 100%. The carboxylic acid group can also include methacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid. The salt is a reaction product of an olefin having 2 to 10 carbon atoms and an unsaturated monocarboxylic acid having 3 to 8 carbon atoms.

The intermediate layer can also include at least one ionomer, such as an acid-containing ethylene copolymer ionomer, wherein the ionomer includes an E / X / Y terpolymer, where E is ethylene, X Is a softening comonomer based on acrylate or methacrylate present in an amount ranging from about 0 to 50% by weight, and Y is acrylic acid present in an amount ranging from about 5 to 35% by weight. Or methacrylic acid. In other embodiments, the acrylic or methacrylic acid is present in an amount ranging from about 8 to 35% by weight, more preferably from 8 to 25% by weight, and most preferably from 8 to 20% by weight.
The ionomers can also include so-called “low acid” and “high acid” ionomers, and blends thereof. In general, ionic copolymers containing up to about 15% acid are considered “low acid” ionomers, while ionic copolymers containing more than about 15% acid are “high acid” ionomers. Conceivable. For example, US Pat. Nos. 6,506,130 and 6,503,156 define low acid ionomers as having an acid content of 16% by weight or less, while high acid ionomers contain more than about 16% by weight acid. It is defined as a thing.

  Low acid ionomers are thought to impart high spin. Thus, in one embodiment, the intermediate layer is present in the range of about 10-15% by weight of acid, and optionally a softening comonomer such as iso- or n-butyl to produce a softer terpolymer. Contains low acid ionomers, including acrylates. The softening comonomer comprises a vinyl ester of an aliphatic carboxylic acid whose acid contains 2 to 10 carbon atoms, a vinyl ether whose alkyl group contains 1 to 10 carbon atoms and an alkyl group containing 1 to 10 carbon atoms. It can be selected from the group consisting of containing alkyl acrylates or methacrylates. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like.

  In other embodiments, the intermediate layer comprises at least one highly acidic ionomer to achieve low spin speed and maximum flight distance. In this regard, the acrylic acid or methacrylic acid is present in an amount ranging from about 15 to about 35 weight percent, making the ionomer a high modulus ionomer. In one embodiment, the high modulus ionomer comprises about 16% by weight carboxylic acid, preferably about 17 to about 25% by weight carboxylic acid, more preferably about 18.5 to about 21.5% by weight carboxylic acid. Including. In some situations, additional comonomers, such as acrylate esters (eg, iso- or n-butyl acrylate, etc.) can also be included to produce a more flexible terpolymer. The additional comonomers include vinyl esters of aliphatic carboxylic acids where the acid contains 2-10 carbon atoms, vinyl ethers where the alkyl group contains 1-10 carbon atoms, and 1-10 carbon atoms where the alkyl group contains 1-10 carbon atoms. Can be selected from the group consisting of alkyl acrylates or methacrylates. Suitable softening comonomers include vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like.

As a result, some examples of copolymers suitable for use in producing the high modulus ionomer include ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / itaconic acid copolymers, ethylene / maleic acid copolymers High acid aspects such as, but not limited to, ethylene / methacrylic acid / vinyl acetate copolymer, ethylene / acrylic acid / vinyl alcohol copolymer.
In one embodiment, the intermediate layer can be made from at least one polymer containing α, β-unsaturated carboxylic acid groups, or a salt thereof, which is 100% neutralized with organic fatty acids. The organic acid is an aliphatic, monofunctional (saturated, unsaturated, or polyunsaturated) organic acid. These organic acid salts can also be used. The organic acid salt of the present invention is composed of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium. Salts, fatty acids, especially salts of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, or dimerized derivatives thereof are included. The organic acids and salts thereof of the present invention are relatively non-migrating (these do not cause bloom on the polymer surface under ambient temperature conditions) and are non-volatile (these are necessary for melt mixing) It is preferable that it does not volatilize at a temperature of

  The acid portion of the highly neutralized polymer (HNP), typically an ionomer based on ethylene, is preferably greater than about 70%, more preferably greater than about 90%, and most preferred. At least about 100% neutralized. The HNP can also be blended with a second polymer component, which, if it contains acid groups, can be neutralized by conventional methods, organic fatty acids, or both. it can. The second polymer component, which may be partially or fully neutralized, is preferably an ionomer copolymer and terpolymer, ionomer precursor, thermoplastic resin, polyamide, polycarbonate, polyester, polyurethane, polyurea, thermoplastic elastomer , Polybutadiene rubber, balata, metallocene-catalyzed polymers (grafted and non-grafted), single site catalyst polymers, highly crystalline acidic polymers, cationic ionomers and the like.

In this embodiment, the acidic copolymer can be described as an E / X / Y copolymer, where E is ethylene, X is an ethylenically unsaturated carboxylic acid, and Y is a softening comonomer. In preferred embodiments, X is acrylic acid or methacrylic acid, and Y is a C _1-8 alkyl acrylate or methacrylate ester. X is preferably an amount in the range of about 1-35% by weight of the polymer, more preferably in the range of about 5-30% by weight of the polymer, and most preferably in the range of about 10-20% by weight of the polymer. Exists. Y is present in an amount ranging from about 0-50% by weight of the polymer, more preferably from about 5-25% by weight of the polymer, and most preferably from about 10-20% by weight of the polymer. .
The organic acid is an aliphatic, monofunctional (saturated, unsaturated, or polyunsaturated) organic acid. These organic acid salts can also be used. The organic acid salt of the present invention is composed of barium, lithium, sodium, zinc, bismuth, chromium, cobalt, copper, potassium, strontium, titanium, tungsten, magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium. Salts, fatty acids, especially salts of stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, or dimerized derivatives thereof are included. The organic acids and salts thereof of the present invention are relatively non-migrating (these do not cause bloom on the polymer surface under ambient temperature conditions) and are non-volatile (these are necessary for melt mixing) It is preferable that it does not volatilize at a temperature of

Thermoplastic polymer components such as copolyetheresters, copolyesteresters, copolyetheramides, elastomeric polyolefins, styrene diene block copolymers and their hydrogenated derivatives, copolyesteramides, thermoplastic polyurethanes such as copolyetherurethanes, copolyesterurethanes, copolyesters Polyureaethane, polyurethane based on epoxy, polyurethane based on polycaprolactone, polyurethane filler based on polyurea and polycarbonate, and other components if necessary, before neutralizing the acid part, It can be blended during or after.
Examples of these materials are described in US Patent Application Nos. 2001/0018375 and 2001/0019971, the entire disclosures of which are incorporated herein by reference.

The ionomer composition can also include at least one grafted metallocene catalyst polymer. The blend of this embodiment comprises at least one grafted metallocene catalyst polymer ranging from about 1 pph to about 100 pph and at least one ionomer ranging from about 99 pph to 0 pph, preferably at least about 5 pph to about 90 pph. One grafted metallocene catalyst polymer, and at least one ionomer ranging from about 95 pph to about 10 pph, more preferably at least one grafted metallocene catalyst polymer ranging from about 10 pph to about 75 pph, and from about 90 pph to about At least one ionomer in the range of 25 pph, and most preferably at least one grafted metallocene catalyst polymer in the range of about 10 pph to about 50 pph, and at least one ionomer in the range of about 90 pph to about 50 pph. it can. If the layer is foamed, the grafted metallocene catalyst polymer blend can be foamed during molding by any known blowing agent.
In addition, polyamides, discussed in more detail below, can also be mixed with ionomers.

  In other embodiments, the intermediate layer comprises at least one native or fully non-ionomeric thermoplastic material. Suitable non-ionomeric thermoplastic materials include polyamide and polyamide blends, grafted and non-grafted metallocene-catalyzed polyolefins or polyamides, polyamide / ionomer blends, polyamide / non-ionomer blends, polyphenylene ether / ionomer blends, and the like Includes mixtures. Examples of grafted and non-grafted metallocene catalyzed polyolefins or polyamides, polyamide / ionomer blends, polyamide / non-ionomer blends are described in co-pending U.S. Patent No. 6,800,690, the entire disclosure of which is Incorporated here for reference.

  In one embodiment, polyamide homopolymers such as polyamide 6,18 and polyamide 6,36 are used alone or in combination with other polyamide homopolymers. In other embodiments, polyamide copolymers, such as polyamide 6,18 / 6,36, are used alone or in combination with other polyamide homopolymers. Other examples of suitable polyamide homopolymers and copolymers include Polyamide 4, Polyamide 6, Polyamide 7, Polyamide 11, Polyamide 12 (Atofina Chemicals, Inc., Philadelphia, PA). AMNO)), polyamide 13, polyamide 4,6, polyamide 6,6, polyamide 6,9, polyamide 6,10, polyamide 6,12, polyamide 6,36, polyamide 12,12, polyamide 13, 13, polyamide 6 / 6,6, polyamide 6,6 / 6,10, polyamide 6/6, T (where T represents terephthalic acid), polyamide 6 / 6,6 / 6,10, polyamide 6 , 10 / 6,36, polyamide 66,6,18, polyamide 66,6,36, polyamide 6 / 6,18, polyamide 6 / 6,36, polyamide 6 / 6,10 / 6,18, polyamide 6/6 , 10 / 6,36, Polyamide 6,10 / 6,18, Polyamide 6,12 / 6,18, Polyamide 6,12 / 6,36, Polyamide 6/66 / 6,18, Polya 6/66 / 6,36, polyamide 66 / 6,10 / 6,18, polyamide 66 / 6,10 / 6,36, polyamide 6 / 6,12 / 6,18, polyamide 6 / 6,12 / 6 36, and mixtures thereof.

As noted above, any of the above polyamide homopolymers, copolymers, and homopolymer / copolymer blends may optionally be non-ionomer polymers, such as non-ionomer thermoplastic polymers, non-ionomer thermoplastic copolymers, non-ionomer TPEs, And can be blended with these mixtures.
A specific example of a polyamide-non-ionomer blend is a polyamide-metallocene catalyst polymer blend. These blended compositions can include grafted and / or non-grafted metallocene catalyst polymers. Grafted metallocene catalyst polymers functionalized with pendant groups, such as maleic anhydride, are available in experimental quantities from DuPont. Grafted metallocene-catalyzed polymers are also commercially available non-grafted metallocene-catalyzed polymers that are subjected to a post-polymerization reaction involving monomers and organic peroxides and grafted with a given pendant group (s). It can also be obtained by producing a metallocene catalyst polymer.
Another example of a polyamide-non-ionomer blend is a polyamide and a non-ionic polymer made with a non-metallocene single site catalyst. As used herein, the term “non-metallocene catalyst” or “non-metallocene single site catalyst” means a single site catalyst other than a metallocene catalyst. Examples of suitable single site catalyst polymers are described in co-pending US patent application Ser. No. 09 / 677,871. The entire disclosure of this document is incorporated herein by reference.

  Non-ionomers suitable for blending with the polyamide include block copoly (ester) copolymers, block copoly (amide) copolymers, block copoly (urethane) copolymers, copolymers based on styrene, thermoplastic resins and elastomers. Blends (where the elastomer is not vulcanized (TEB)), and blends of thermoplastic resin and elastomer or rubber (where the elastomer is mechanically vulcanized (TED)). Including, but not limited to. Other non-ionomers suitable for blending with the polyamide to form the composition for the interlayer are polycarbonate, polyphenylene oxide, imidized amino group-containing polymers, high impact polystyrene (HIPS), Polyetherketone, polysulfone, poly (phenylene sulfide), reinforced engineering plastic, acrylic acid-styrene-acrylonitrile, poly (tetrafluoroethylene), poly (butyl acrylate), poly (4-cyanobutyl acrylate), poly (2-ethyl) Butyl acrylate), poly (heptyl acrylate), poly (2-methyl butyl acrylate), poly (3-methyl butyl acrylate), poly (N-octadecyl acrylamide), poly (octadecyl methacrylate), poly (4-dodecyl styrene), Poly (4-tetradecylstyrene), poly (ethylene Lenoxide), poly (oxymethylene), poly (silazane), poly (furantetracarboxylic diimide), poly (acrylonitrile), poly (methylstyrene), silicone, and the polymers to which they belong and their functional comonomers. Including but not limited to copolymers, and blends thereof.

In one embodiment, the non-ionomer material has a hardness of about 60 Shore D or higher and a flexural modulus of about 206.7 MPa (about 30,000 psi) or higher.
The intermediate layer can preferably be used as a major component of the polymer in the intermediate layer and include an elastic polymer component that imparts resilience in its cured state, and a reinforcing polymer component as a blend. Elastic polymers suitable for use in the intermediate layer include polybutadiene, polyisoprene, styrene-butadiene, styrene-propylene-diene rubber, ethylene-propylene-diene (EPDM), mixtures thereof, and the like, which are preferably at least Has a high molecular weight in the range of about 50,000 to about 1,000,000. In one embodiment, the molecular weight is in the range of about 250,000 to about 750,000, and more preferably in the range of about 200,000 to about 400,000.
The toughening polymer component preferably has a crystalline melting point (Tg) that is low enough to allow mixing, preferably in the range of about -35 ° C to 120 ° C, without initiating crosslinking. Further, the toughening polymer component preferably has a viscosity that is sufficiently low to allow proper mixing of the two polymer components at the mixing temperature when mixed with the elastic polymer component. The weight of the reinforcing polymer component relative to the total composition for forming the intermediate layer is generally in the range of about 5-25% by weight, preferably in the range of about 10-20% by weight.

Examples of polymers suitable for use in the reinforced polymer component include those listed below: trans-polyisoprene, block copolymer ether / ester, acrylic polyol, polyethylene, polyethylene copolymer, 1,2-polybutadiene (Syndiotactic), ethylene-vinyl acetate copolymer, trans-polycyclooctenamer, trans-isomer polybutadiene, and mixtures thereof. Particularly suitable reinforcing polymers include those listed below: HYTREL ^™ , a block copolymer ether / ester commercially available by DuPont, Wilmington, DE; trans-isomerism Polybutadiene, for example, under the name FUREN 88, obtained from Asahi Chemicals, Kawasaki City, Kawasaki-ku, Yako, Japan; Kuraray TP251, under the trade name Kuraray Trans-polyisoprene commercially available from (KURRARAY CO.); Ethylene commercially available under the trade name LEVAPREN 700HV from Bayer-Rubber Division of Akron, OH Vinyl acetate copolymer; and commercially available under the trade name VESTENAMER 8012 from Huls America Inc., Taramaj, OH That trans- poly cyclooctenyl Raw chromatography (polycyclooctenenamer). Some suitable reinforced polymer components are listed in Table 1 below, along with Tc and glass transition temperature (Tg):

Other polymers that are particularly suitable for use in the reinforced polymer component typically have a trans-isomer content of at least about 80%, with the balance being the cis-isomer 1,4-polybutadiene and vinyl-isomer. This is a stiffened polybutadiene component containing 1,2-polybutadiene. Accordingly, this is referred to herein as “high trans-isomer polybutadiene” or “stiffened polybutadiene”, which is used to produce the golf ball cores of the present invention as cis-isomer polybutadiene or low trans- A distinction can be made from polybutadienes with an isomer content, ie with an isomer content of typically less than 80%. The vinyl content of the stiffened polybutadiene component is preferably about 15% or less, preferably less than about 10%, more preferably less than about 5%, and most preferably less than about 3% of the polybutadiene isomer.
When used in the golf balls of the present invention, the stiffened polybutadiene component preferably has a polydispersity not exceeding about 4, preferably not exceeding about 3, and more preferably not exceeding about 2.5. The polydispersity (Pd) is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of a polymer.

Further, when used in the golf balls of the present invention, the stiffened polybutadiene component typically has a high Mw, as defined as at least about 100,000, preferably in the range of about 200,000 to 1,000,000. In one embodiment, the absolute average molecular weight ranges from about 230,000 to 750,000. In other embodiments, the absolute average molecular weight ranges from about 275,000 to 700,000. In any embodiment where the vinyl content is greater than about 10%, the absolute average molecular weight is preferably greater than about 200,000.
When Trans-polyisoprene or high trans-isomer polybutadiene is included in the reinforced polymer component, the former ranges from about 10 to 40% by weight of the polymer blend, ie the elastic and reinforced polymer. , Preferably about 15-30% by weight, more preferably about 15-25% by weight.

The same crosslinkers as described above in connection with the core can be used in this embodiment to achieve a predetermined modulus for the elastic polymer-reinforced polymer blend. In one embodiment, the cross-linking agent is in the range of about 1 to about 50 parts per 100 parts of the polymer blend, preferably in the range of about 20 to about 45 parts per 100 parts of the blend, and more preferably the polymer blend. It is added in an amount ranging from about 30 to about 40 parts per 100 parts.
The elastic polymer component, the reinforcing polymer component, the free radical initiator, and any other material used to form the intermediate layer of the golf ball core according to the present invention can be mixed in any type known to those skilled in the art. Can be merged.

Golf ball cover The cover provides an interface between the ball and the club. Desirable properties for the cover are particularly good moldability, high wear resistance, high impact resistance, high tear resistance, high resilience, and good release properties. The cover layer can be made at least in part from the composition of the present invention. In one embodiment, the composition of the present invention can be used to form at least one cover layer of the golf ball of the present invention. For example, the cover layer can be made using a reaction product of an isocyanate-containing component and an isocyanate-reactive component, which can be cured with a curing agent.
The cover composition can also be prepared from or include one or more homopolymer or copolymer materials, such as those listed below:

(1) Vinyl resin, for example, a resin produced by polymerization of vinyl chloride or copolymerization of vinyl chloride with vinyl acetate, acrylate ester or vinylidene chloride;
(2) Polyolefins such as polyethylene, polypropylene, polybutylene and copolymers such as ethylene methyl acrylate, ethylene ethyl acrylate, ethylene vinyl acetate, ethylene methacrylic acid or ethylene acrylic acid or propylene acrylic acid and copolymers made using single site catalysts and Homopolymer;
(3) Thermoplastic or thermoset, saturated or unsaturated, aliphatic or aromatic, acid functionalized polyurethanes such as those made from polyols or amines and diisocyanates or polyisocyanates, and US Pat. No. 5,334,673 And those described in US patent application Ser. No. 10 / 072,395;
(4) Thermoplastic or thermosetting, saturated or unsaturated, aliphatic or aromatic, acid functionalized polyureas such as those described in US Pat. No. 5,484,870 and US Patent Application No. 10 / 072,395;

(5) Polyamides such as poly (hexamethylene adipamide) and other diamines and dibasic acids, as well as amino acids such as poly (caprolactam), reinforced polyamides, and polyamides and ionomers, polyethylene , Blends with ethylene copolymers, ethyl-propylene-non-conjugated diene terpolymers, etc .;
(6) Acrylic resins and blends of these resins with polyvinyl chloride, elastomers, etc .;
(7) thermoplastic resins such as urethane; olefinic thermoplastic rubbers such as blends of polyolefins with ethylene-propylene-non-conjugated diene terpolymers; block copolymers of styrene with butadiene, isoprene or ethylene-butylene rubber; or copoly ( Ether-amides), such as PEBAX sold by Atofina Chemicals, Inc. of Philadelphia, PA or a thermoplastic composition described in US Pat. No. 5,688,191;
(8) Polyphenylene oxide resin or a blend of polyphenylene oxide and high impact polystyrene marketed under the trade name NORRYL by General Electric Company of Pittsfield, MA;

(9) Thermoplastic polyesters such as polyethylene terephthalate, polybutylene terephthalate, glycol modified polyethylene terephthalate, and trade names by EI DuPont de Nemours & Co., Wilmington, DE. An elastomer marketed under HYTREL and marketed under the trade name LOMOD by General Electric Company of Pittsfield, MA;
(10) Homopolymers or copolymers based on ethylene, propylene, 1-butene or 1-hexene, or fully or partially neutralized ionomer resins containing functional monomers such as acrylic acid or methacrylic acid And blends thereof, methyl acrylate, methyl methacrylate homopolymers or copolymers, low acid ionomers, acidophilic ionomers, and blends thereof;
(11) Contains polycarbonate and acrylonitrile butadiene styrene, polybutylene terephthalate, polyethylene terephthalate, styrene maleic anhydride, polyethylene, elastomers, etc., and includes polyvinyl chloride and acrylonitrile butadiene styrene or ethylene vinyl acetate or other elastomers Blends and alloys; and

(12) A blend of thermoplastic rubber and polyethylene, propylene, polyacetal, nylon, polyester, cellulose ether, or the like.
The cover can also be made from the polybutadiene reaction product discussed above in connection with the core.
As discussed throughout the present specification, the composition of the present invention is molded onto the golf ball by any known method, such as injection molding, compression molding, injection molding, reactive injection molding, and the like. be able to. One skilled in the art will appreciate that the molding method used can be determined at least in part by the properties of the composition. For example, injection molding is preferred when the material is thermoset, while compression molding or injection molding may be the preferred method for thermoplastic compositions.

Golf Ball Compositions The compositions of the present invention can be utilized with any type of golf ball construction, which can be one-piece, two-piece, three-piece, depending on the type of performance of the ball. And four-piece designs, including, but not limited to, dual core, double cover, intermediate layer, multilayer core and / or multilayer cover. That is, the compositions of the present invention can be used in golf ball cores, interlayers, and / or covers, each of which can comprise a single layer or multiple layers. As used herein, the term “multi-layer” means at least two layers.
As explained in the section on cores above, the cores can be one-piece cores or multilayer cores, both of which can be solid, semi-solid, hollow, fluid-filled, or powder-filled configurations. A multi-layer core is one that includes an innermost component that has an associated core layer or an associated core layer disposed thereon.

Further, if the golf ball of the present invention includes an intermediate layer, this layer may be incorporated with a single or multi-layer cover, single or multi-piece core, single layer cover and core, or both multi-layer cover and multi-layer core. it can. The intermediate layer can be an inner cover layer or an outer core layer of a golf ball, or any other layer provided between the inner cover layer and the outer core layer. In the context of the core, the intermediate layer can also include multiple layers. It will be appreciated that any number or type of intermediate layers may be used if desired.
For example, FIG. 1 shows a golf ball 1 that includes a core 2, at least one intermediate layer 3, and a cover 4. In one embodiment, the golf ball of FIG. 1 shows a cover 4 comprising a polybutadiene reactive material or other known material core 2 and a composition of the present invention. In other embodiments, the core 2 of FIG. 1 can be a liquid, wherein the hollow spherical core shell is filled with a liquid. The intermediate layer 3 is made of a known ionomer or a composition according to the invention.

  The intermediate layer can also be wound with a tensioned elastomeric material around a solid, semi-solid, hollow, fluid-filled or powder-filled center. As used herein, the term “fluid” refers to a liquid or gas, and the term “semi-solid” refers to a paste, gel, or the like. The wound layer can be described as a core layer or an intermediate layer for the purposes of the present invention. As an example, the golf ball 1 of FIG. 1 can include a core 2, a tensioned elastomer layer 3 wound thereon, and a cover layer 4. In particular, the golf ball 1 of FIG. 1 can have a core 2 made of a polybutadiene reactive material, an intermediate layer including a tensioned elastomer layer 3, and a cover 4 formed from the composition of the present invention. In this aspect of the present invention, the composition of the present invention can be formed using an isocyanate-reactive component having a hydrophobic backbone to create a golf ball with higher water resistance. The tensioned elastomeric material can be made of any suitable material known to those skilled in the art. In one embodiment, the composition of the present invention is used to produce the tensioned elastomeric material.

  At least one layer of the ball can be a moisture barrier layer, such as the layer described in US Pat. No. 5,820,488, which is hereby incorporated by reference. Any suitable film-forming material can be used that has a lower water vapor transmission rate than the other layers between the core of the ball and the outer surface, ie, the cover, primer layer, and clear coat layer. Examples include, but are not limited to, polybutadiene reactive materials, including fluorine gas, polyvinylidene chloride, and leechite. In one embodiment, the moisture barrier comprises the same type of core and cover without the moisture barrier when the ball is stored at about 37.8 ° C. (100 ° F.) and 70% relative humidity for 6 weeks. It has a water vapor transmission rate sufficient to reduce the loss of the golf ball's CRO by at least 5% as compared to the loss in the COR of the golf ball that is contained and stored under substantially identical conditions.

Prior to forming the cover layer, the inner ball, i.e., the core and all intermediate layers provided thereon, are surface treated to provide adhesion between the outer surface of the inner ball and the cover. Can be increased. Examples of such surface treatments can include mechanically or chemically eroding the outer surface of the subassembly. Further, the inner ball can be subjected to corona discharge treatment, plasma treatment, silane dipping treatment, or other chemical methods known to those skilled in the art before forming a cover around it. Other layers of the ball, such as the core and the cover layer, can also be surface treated. Examples of these and other surface treatment techniques can be found in US Pat. No. 6,315,915. This entire patent is incorporated herein by reference.
The core or cover may include a plurality of layers, for example, an inner cover layer provided near the center of the golf ball and an outer cover layer formed thereon. For example, FIG. 2 represents a golf ball 5 that includes a core 6, an outer core or intermediate layer 7, a thin inner cover layer 8, and a thin outer cover layer 9 disposed thereon. In particular, the core 6 and the intermediate layer 7 can be made of a polybutadiene reactive material, the inner cover layer 8 can be made of the composition of the present invention or a known ionomer material, and the outer cover layer 9 Can be made of the composition of the present invention or a known cover material.

Further, the composition of the present invention can be used to produce the golf ball 10 shown in FIG. In one embodiment, the large core 11 is made of a polybutadiene reactive material and the thin outer cover layer 12 is formed of the composition of the present invention.
Typically, a hardness gradient is used in a golf ball to achieve some properties, but the present invention also includes a golf ball that includes multiple cover layers having essentially the same hardness. It is also contemplated to use the inventive composition, wherein at least one layer has been modified in some way to change properties that affect the performance of the ball. Such a ball configuration is described in US patent application Ser. No. 10/10, filed Jun. 13, 2002, entitled “Golf Ball with Multiple Cover Layers”. No. 167,744. The entire disclosure of this patent application is incorporated herein by reference.

In one such embodiment, both cover layers can be made of the same material and have essentially the same hardness, but these layers are designed to have different coefficient of friction values. Is done. In another embodiment, the compositions of the present invention are used in golf balls comprising multiple layers that have essentially the same hardness but have different rheological properties under high deformation. Another aspect of this embodiment relates to a golf ball that includes multiple cover layers that have essentially the same hardness but different thickness and mimic a flexible outer cover on a hard inner cover ball. .
In another aspect of this concept, the cover layer of a golf ball has essentially the same hardness, but has different properties at higher or lower temperatures than ambient temperature. In particular, this aspect of the invention contemplates a golf ball having a multilayer cover layer, wherein the outer cover layer composition has a lower flexural modulus at lower temperatures than the inner cover layer, These layers, on the other hand, maintain the same hardness at ambient and low temperatures, which provides a feel that mimics the flexible outer cover layer on the hard inner cover layer. Some polyureas can have a more stable flexural modulus at various temperatures than ionomer resins, and as a result, more effectively “more than at ambient or higher temperatures. Can be used to create a “flexible” layer.

Yet another aspect of this concept relates to golf balls having multiple cover layers that have essentially the same hardness, but have different properties under wet conditions compared to those under dry conditions. The wettability of a golf ball layer can be affected by surface roughness, chemical heterogeneity, molecular orientation, swellability, and interfacial tension, among others. Thus, a non-destructive surface treatment of a golf ball layer can help increase the hydrophobicity of the layer, while a highly polished or smoothed golf ball layer can reduce wettability. . US Pat. Nos. 5,403,453 and 5,456,972 disclose methods of treating the surface of a polymeric material to affect wettability. The entire disclosure of these patents is incorporated herein by reference. Further, plasma etching, corona discharge treatment, and flame treatment can be useful surface treatments to change the wettability of the material surface to a desired state. A wetting agent can be added to the golf ball layer composition to adjust the surface tension of the layer.
Thus, the difference in wettability of the cover layer according to the present invention can be measured by the difference in contact angle. The contact angle of a layer can range from about 1 degree (low wettability) to about 180 degrees (very high wettability). In one embodiment, the cover layer has a contact angle that varies by about 1 degree or more. In other embodiments, the contact angle of the cover layer varies by about 3 degrees or more. In yet another embodiment, the contact angle of the cover layer varies by about 5 degrees or more.

Other non-limiting examples of suitable types of ball configurations that can be used in the present invention include U.S. Pat.Nos. 5,919,100, 5,965,669, 5,981,654, 5,981,658, and 6,149,535, and published patents US2001 / 0009310 A1, US2002 / 0025862, US2002 / 0028885 Including those described in. The entire disclosures of these patents and published patent applications are incorporated herein by reference.
Production of the above layerThe golf ball of the present invention comprises compression molding, flip molding, injection molding, retractable pin injection molding, reactive injection molding (RIM), liquid injection molding (LIM), injection molding, vacuum molding, powder coating, It can be manufactured using various application techniques such as spin coating, dipping and spraying. An injection molding process using split vent pins can be found in US Pat. No. 6,877,974. Examples of retractable pin injection molding methods can be found in US Pat. Nos. 6,129,881, 6,235,230, and 6,379,138. All references to these molding methods are incorporated herein by reference in their entirety.

One skilled in the art will appreciate that the molding method used can be determined, at least in part, by the properties of the composition. For example, injection molding, RIM or LIM methods may be preferred when the material is thermosetting, while compression molding or injection molding methods may be preferred for thermoplastic compositions. However, the compression molding method can also be used for thermoset inner ball materials. For example, when the core is made of a thermosetting material, the compression molding method is a particularly suitable method for forming the core, while the core is made of a thermoplastic material The core can be injection molded. Furthermore, the intermediate layer can also be produced using any suitable method known to those skilled in the art. For example, the intermediate layer may be manufactured by blow molding and covered with a cover layer having dimples formed by injection molding, compression molding, injection molding, vacuum molding, powder coating, or the like.
In addition, if the layer is made of a composition of the present invention or other known polyurea and / or polyurethane compositions, these materials can be applied to various application techniques such as spraying, compression molding, well known in the art. It can be applied on the inner ball using dipping, spin coating, injection molding, or flow coating methods. Examples of producing polyurea and polyurethane materials around the inner ball are described in US Pat. Nos. 5,733,428, 5,006,297, and 5,334,673. The entire disclosures of these US patents are incorporated herein by reference. In one aspect, a combination of injection molding and compression molding can be utilized to apply a polyurethane or polyurea composition on the inner ball. However, the method of forming the cover according to the present invention is not limited to the use of these techniques, and other methods known to those skilled in the art can also be used.

Prior to forming the cover layer, the inner ball, i.e. the core and any intermediate layer provided thereon, is surface treated to increase the adhesion between the outer surface of the inner ball and the cover. be able to. Examples of such surface treatments can include mechanically or chemically eroding the outer surface of the subassembly. Further, the inner ball can be subjected to corona discharge, plasma treatment, and / or silane dipping treatment before forming the cover layer therearound. Other layers of the ball, such as the core, can also be surface treated. Examples of these and other surface treatment techniques can be found in US Pat. No. 6,315,915. The entire disclosure of this patent is incorporated herein by reference.
The methods discussed herein and other methods of manufacturing the golf ball components of the present invention are also described in US Pat. Nos. 6,207,784 and 5,484,870. The entire disclosures of these patents are incorporated herein by reference.

Dimple The golf ball of the present invention is preferably designed in consideration of several flight characteristics. The various dimple pattern profiles provide a relatively effective way to adjust the aerodynamic characteristics of a golf ball. Therefore, the method of arranging dimples on the surface of the ball can be any available method. For example, the ball may be a icosahedron-based pattern as described in US Pat. No. 4,560,168, or an octahedral-based dimple pattern as described in US Pat. No. 4,960,281. Can have. Alternatively, the dimple pattern can be arranged according to a phylogenetic pattern, as described in US Pat. No. 6,338,684. The entire disclosure of this patent is incorporated herein by reference.
The dimple pattern may also be based on an Archimedean pattern that includes a truncated octahedron, a large rhombcuboctahedron, a truncated dodecahedron, and a large rhomboid dodecahedron. Here, the pattern has a non-linear dividing line as described in US Pat. No. 6,705,959. The entire disclosure of this patent is incorporated herein by reference. The golf ball of the present invention may also be covered with non-circular dimples, i.e., irregular dimples, as described in US Pat. No. 6,409,615.

Dimple patterns that provide high surface coverage are preferred and are known in the art. For example, U.S. Pat. . In one embodiment, the golf ball of the present invention has a dimple coverage of the cover layer surface area of at least 60%, preferably at least 65%, and more preferably at least 70% or more. Dimple patterns with higher dimple coverage values can also be used in the present invention. Accordingly, the golf balls of the present invention can have a dimple coverage of at least 75% or more, about 80% or more, or even about 85% or more.
In addition, tubular lattice patterns such as those described in US Pat. No. 6,290,615 (the entire disclosure of which is incorporated herein by reference) can also be used in the golf ball of the present invention. The golf ball of the present invention also includes a plurality of layers disposed on the intermediate layer of the ball as described in US Pat. No. 6,383,092, the entire disclosure of which is incorporated herein by reference. It can also have pyramidal protrusions. The plurality of pyramidal protrusions on the golf ball can cover a range of about 20% to about 80% of the surface of the intermediate layer.

  In another embodiment, the golf ball can have an uneven dividing line, which allows some of the pyramidal protrusions to be placed around the equator portion of the ball. Such a golf ball is disclosed in U.S. Patent Application No. 09 / 442,845, filed November 18, 1999, entitled "Mold For A Golf Ball." The whole can be produced using a mold such as that described in (incorporated herein by reference). This aspect makes it possible to make the pyramidal protrusions more uniform. Some additional non-limiting examples of dimple patterns with varying sized dimples are also found in US Pat. Nos. 6,358,161 and 6,213,898, the entire disclosures of which are incorporated herein by reference. Is given.

The total number of dimples or the number of dimples on the ball can vary depending on factors such as the size of the dimple and its pattern selected. Generally, the total number of dimples on the ball is preferably in the range of about 100 to about 1,000 dimples, but those skilled in the art will recognize that different numbers of dimples within this range can significantly change the flight characteristics of the ball. You will recognize. In one embodiment, the number of dimples is about 380 dimples or more, but more preferably it is about 400 dimples or more and even more preferably about 420 dimples or more. In one embodiment, the number of dimples on the ball is about 422 dimples. In some cases it may be desirable to have fewer dimples on the ball. Accordingly, one aspect of the present invention has about 380 dimples or less, and more preferably the number of dimples is about 350 dimples or less.
A dimple profile that pivots around a catenary curve about the axis of symmetry provides an advantageous way to change the dimple to increase aerodynamic efficiency, adjust the performance of the ball without changing the dimple pattern, and any swing It enables a golfer with speed to have an evenly increased flight distance. Accordingly, a catenary curve dimple pattern as described in US Pat. No. 6,796,912 (the entire disclosure of which is incorporated herein by reference) is intended for use with the golf ball of the present invention. is there.

Golf Ball Post Treatment The golf ball of the present invention can be painted, coated, or surface treated for further convenience. For example, the golf ball of the present invention can be treated with a raw resin coating composition, or the cover composition can include several additives to achieve a predetermined color. In one embodiment, the golf ball cover composition can include an optical brightener, such as a derivative of 7-triazinylamino-3-phenylcoumarin, for the purpose of providing improved weather resistance and whiteness. . Examples of such optical brighteners are disclosed in US Patent Application No. 2002/0082358, the entire disclosure of which is hereby incorporated by reference.
Decorative and protective coating materials and methods for applying such materials to the surface of golf ball covers are well known in the golf ball art. In general, such coating materials include urethanes, urethane hybrids, epoxy resins, polyesters and acrylic resins.

  The coating layer may be suitable by any suitable method known to those skilled in the art. For example, the coating layer may be applied to the golf ball cover in an in-mold coating process, such as the method described in US Pat. No. 5,849,168, the entire disclosure of which is incorporated herein by reference. Can do. Further, the golf ball of the present invention uses the methods and materials described in US Pat. Nos. 6,500,495, 6,248,804, and 6,099,415, the entire disclosures of which are incorporated herein by reference. And can be painted or coated with UV curable / processable inks. Any trademark or other indication that can be used in the present invention can be applied to the golf ball by a variety of methods known to those skilled in the art of golf ball manufacturing. In one embodiment, the indicia is stamped on the outer surface of the golf ball cover, i.e. pad-printed, and the stamped outer surface is then treated with at least one clearcoat to the ball, The glossy finish of the display stamped on the cover and its protection can be performed. In other embodiments, the indication can be applied to the intended layer by ink-jet printing. If necessary, two or more coating layers can be used.

Golf Ball Properties Various characteristics of the golf ball of the present invention, such as hardness, modulus, core diameter, intermediate layer thickness, and cover layer thickness, can be attributed to the competitive characteristics of the golf ball of the present invention, such as spin, initial speed and feel. Is known to affect For example, the flexural modulus and / or tensile modulus of the intermediate layer is considered to have an influence on the “feel” of the golf ball of the present invention. Here, it is to be understood that the range (s) are interrelated, i.e. the lower limit of one range can be combined with the upper limit of another range.
Part Dimensions The dimensions of a golf ball part, i.e. its thickness and diameter, can be varied according to predetermined characteristics. For the purposes of the present invention, any layer thickness can be used. Non-limiting examples of the various aspects outlined above are given here in relation to the layer dimensions.

The present invention relates to a golf ball of any size. The USGA specification limits the size of a golf ball for competition to a diameter exceeding about 1.27 inches (4.27 cm), but for leisure golf competitions, golf balls of any size may be used. it can. The preferred diameter of the golf ball is in the range of about 1.68 inches to about 1.8 inches. A more preferred diameter is in the range of about 1.68 inches to about 1.76 inches. A diameter in the range of about 4.27 cm (about 1.68 in) to about 4.42 cm (about 1.74 in) is most preferred, but any in the range of about 4.32 cm (about 1.7 in) to about 4.95 cm (about 1.95 in) A certain diameter can be used. Preferably, the overall diameter of the core and all intermediate layers is about 80% to about 98% of the overall diameter of the final ball.
The core may have a diameter in the range of about 2.29 mm (about 0.09 in) to about 4.19 cm (about 1.65 in). In one embodiment, the diameter of the core of the golf ball of the present invention is in the range of about 3.05 cm (1.2 in) to about 4.14 cm (about 1.630 in). In another embodiment, the core diameter ranges from about 1.3 inches to about 1.6 inches, preferably from about 1.39 inches to about 1.6 inches. ) And more preferably in the range of about 1.5 inches to about 1.6 inches. In yet another embodiment, the core has a diameter in the range of about 1.55 inches to about 1.65 inches.

The core of the golf ball can be significantly larger than the rest of the ball. For example, in one embodiment, the core comprises about 90% to about 98% of the ball, preferably about 94% to about 96% of the ball. In this embodiment, the core diameter is preferably about 1.54 inches or more, preferably about 1.55 inches. In one embodiment, the core has a diameter of about 1.59 inches or more. In yet another embodiment, the core has a diameter of about 1.64 inches or less.
Where the core includes an inner core layer and an outer core layer, the inner core layer is preferably about 0.9 inches or more, and the outer core layer is about 0.254 cm (about 0.14 cm). in) or more. In one embodiment, the inner core layer has a diameter ranging from about 0.09 inches to about 1.2 inches, and the outer core layer is about 0.1 inches to about 0.24 inches. It has a diameter in the range of about 2.03 cm (about 0.8 in). In yet another embodiment, the inner core layer has a diameter in the range of about 0.095 inches to about 1.1 inches, and the outer core layer is about 0.20 inches. ) To about 0.762 mm (about 0.03 in).

When the composition of the present invention is used as an outer core layer, the thickness of the layer after curing is preferably in the range of from about 0.0254 mm (about 0.001 in) to about 0.254 cm (about 0.1 in). In one embodiment, the thickness of the outer core layer after curing ranges from about 0.002 in to about 0.05 in. In another embodiment, the thickness of the outer core layer after curing ranges from about 0.0762 mm (about 0.003 in) to about 0.762 mm (about 0.03 in).
The cover typically has a thickness that provides sufficient strength, good performance characteristics, and durability. In one embodiment, the cover has a thickness in the range of about 0.02 inches to about 0.35 inches. In other embodiments, the cover preferably ranges from about 0.02 in to about 0.12 in, preferably about 0.1 in or less, and most preferably about 0.118. It has a thickness of cm (about 0.07in) or less. In yet another embodiment, the outer cover has a thickness in the range of about 0.02 inches to about 0.07 inches. In yet another embodiment, the cover has a thickness of about 0.127 cm (about 0.05 in) or less, preferably about 0.508 mm (about 0.02 in) to about 0.127 cm (about 0.05 in). For example, the outer cover may be in the range of about 0.008 inches to about 0.045 inches, preferably in the range of about 0.025 inches to about 0.04 inches. With thickness. In one embodiment, the outer cover has a thickness of about 0.03 inches.

  The range of golf ball interlayer thickness is large because of the great potential when using an interlayer, ie, an interlayer as an outer core layer, an inner cover layer, a wound layer, and a moisture / vapor barrier layer. When used in the golf ball of the present invention, the intermediate layer or inner cover layer can have a thickness of about 0.362 inches or less. In one embodiment, the thickness of the intermediate layer ranges from about 0.002 in to about 0.1 in, preferably about 0.01 in or more. In one embodiment, the intermediate layer has a thickness of about 0.09 inches or less, preferably about 0.06 inches or less. In other embodiments, the intermediate layer has a thickness of about 0.127 cm (about 0.05 in) or less, more preferably about 0.254 mm (about 0.01 in) to about 0.114 cm (about 0.045 in). In one embodiment, the thickness of the intermediate layer is in the range of about 0.02 inches to about 0.04 inches. In other embodiments, the intermediate layer has a thickness in the range of about 0.025 inches to about 0.035 inches. In yet another embodiment, the intermediate layer has a thickness of about 0.035 inches. In yet another embodiment, the thickness of the inner cover layer ranges from about 0.73 mm (about 0.03 in) to about 0.889 mm (about 0.035 in). Various combinations of these ranges for the intermediate layer and outer cover layer can be used in combination with other embodiments described herein.

The ratio of the thickness of the intermediate layer to the outer cover layer is preferably about 10 or less, more preferably about 3 or less. In another embodiment, the ratio of the thickness of the intermediate layer to the outer cover layer is about 1 or less. The core and intermediate layer together form an inner ball, which preferably has a diameter of about 1.48 inches or more for a ball of about 1.68 inches. In one embodiment, the inner ball of a ball of about 1.68 inches has a diameter of about 1.52 inches or more. In other embodiments, the inner ball of a ball of about 1.68 inches has a diameter of about 1.66 inches or less. In yet another embodiment, a ball of about 1.72 inches (or more) has an inner ball diameter of about 1.50 inches or more. In yet another embodiment, the inner ball diameter for a ball of about 1.72 inches is about 1.70 inches or less.
Hardness Most golf balls are composed of layers having different hardnesses, eg, gradients in hardness, in order to achieve predetermined performance characteristics. The present invention intends to provide a golf ball having a hardness gradient between layers, and a golf ball having a layer having the same hardness.

  In particular, those skilled in the art should understand that there is a fundamental difference between “hardness of material” and “hardness measured directly on a golf ball”. The hardness of the material is defined by the procedure shown in ASTM-D2240 and generally the process of measuring the hardness of a flat “slab” or “button” made from the material whose hardness is to be measured including. Hardness when measured directly on a golf ball (or other sphere surface) is a completely different measurement and therefore results in different hardness values. This difference includes a number of factors including, but not limited to, ball configuration (i.e., core type, number of core and / or cover layers, etc.), ball (or sphere) diameter, and adjacent layer material composition. Brought from. These two physical property measurement techniques are not in a linear relationship, so one hardness value cannot be easily correlated with the other hardness value.

The golf ball core of the present invention can have varying hardness depending on the particular golf ball configuration. In one embodiment, the hardness of the core is at least about 15 Shore A, preferably at least about 30 Shore A, as measured on a molded sphere. In other embodiments, the core has a hardness in the range of about 50 Shore A to about 90 Shore D. In yet another embodiment, the core has a hardness of about 80 Shore D or less. Preferably, the core has a hardness in the range of about 30 to about 65 Shore D, and more preferably, the core has a hardness in the range of about 35 to about 60 Shore D.
The hardness of the intermediate layer of the present invention can also vary depending on the particular configuration of the ball. In one embodiment, the intermediate layer has a hardness of about 30 Shore D or higher. In other embodiments, the intermediate layer has a hardness of about 90 Shore D or less, preferably about 80 Shore D or less, and more preferably about 70 Shore D or less. In yet another embodiment, the intermediate layer has a hardness of about 50 Shore D or higher, preferably about 55 Shore D or higher. In one embodiment, the intermediate layer has a hardness in the range of about 55 Shore D to about 65 Shore D. The intermediate layer may also be about 65 Shore D or higher.

When it is desired that the intermediate layer be harder than the core layer, the ratio of the intermediate layer hardness to the core hardness is preferably about 2 or less. In one embodiment, this ratio is about 1.8 or less. In yet another embodiment, the ratio is about 1.3 or less.
In relation to the core and intermediate layer, the hardness of the cover can vary depending on the configuration and predetermined characteristics of the golf ball. The hardness ratio of the cover to the inner ball is the main variable used to adjust the aerodynamic characteristics of the ball, in particular the spin of the ball. Generally, the harder the inner ball, the greater the driver's spin, and the softer the cover, the greater the driver's spin.

  For example, if the intermediate layer is desired to be the hardest part of the ball, such as the part having a hardness in the range of about 50 Shore D to about 75 Shore D, the cover material is measured as measured on the slab. , About 20 Shore D or higher, preferably about 25 Shore D or higher, and more preferably about 30 Shore D or higher. In another embodiment, the cover itself has a hardness of about 30 Shore D or greater. In particular, the hardness of the cover can range from about 30 Shore D to about 70 Shore D. In one embodiment, the cover has a hardness in the range of about 40 Shore D to about 65 Shore D, and in another embodiment, the hardness is in the range of about 40 Shore D to about 55 Shore D. is there. In another aspect of the invention, the cover has a hardness of less than about 45 Shore D, preferably less than about 40 Shore D, and more preferably in the range of about 25 Shore D to about 40 Shore D. In one embodiment, the cover has a hardness in the range of about 30 Shore D to about 40 Shore D.

In this embodiment, if the outer cover layer is more flexible than the intermediate layer or inner cover layer, the ratio of the hardness of the outer cover material to the Shore D hardness of the intermediate layer material is about 0.8 or more. Below, preferably about 0.75 or less, and more preferably about 0.7 or less. In other embodiments, the ratio is about 0.5 or less, preferably about 0.45 or less.
In yet another embodiment, the ratio is about 0.1 or less when the cover and interlayer material have substantially the same hardness. If the difference in hardness between the cover layer and the intermediate layer is not desired to be significant, the cover can have a hardness in the range of about 55 Shore D to about 65 Shore D. it can. In this embodiment, the Shore D hardness ratio of the outer cover to the intermediate layer is about 1.0 or less, preferably about 0.9 or less.

The hardness of the cover can also be defined by the Shore C hardness. For example, the cover can have a hardness of about 70 Shore C or higher, preferably about 80 Shore C or higher. In other embodiments, the cover has a hardness of about 95 Shore C or less, preferably about 90 Shore C or less.
In other embodiments, the cover layer is harder than the intermediate layer. In this design, the ratio of Shore D hardness of the cover layer to the intermediate layer is about 1.33 or less, preferably about 1.14 or less.
When building a two-piece ball, its core can be more flexible than its outer cover. For example, the hardness of the core can be in the range of about 30 Shore D to about 50 Shore D, and the hardness of the cover can be in the range of about 50 Shore D to about 80 Shore D. In this type of configuration, the ratio of the cover hardness to the core hardness is preferably about 1.75 or less. In other embodiments, the ratio is about 1.55 or less. For example, if the composition of the present invention is acid-functionalized, where the acid groups are at least partially neutralized, depending on the material, the cover to core hardness ratio Is preferably about 1.25 or less.

Compressibility The compressibility value depends on the diameter of the part being measured. In order to measure the compression rate of a golf ball, the Achch compression rate is typically used. As used herein, the term “Ach compression rate” or “compression rate” is defined as the deflection of an object (object) or material relative to a calibrated spring deflection as measured by an Atti Compression Gauge. Is done. The gauge is commercially available from Atti Engineering Corp., Union City, NJ.
The hatch compression ratio of solid spheres made from the composition of the present invention can be in the range of about 140 to about 210. In one embodiment, the compression ratio is in the range of about 150 to about 200. In other embodiments, the compression ratio is in the range of about 170 to about 190.

Golf balls prepared in accordance with the present invention preferably have an atch compression ratio of the core, or a portion of the core, of less than about 80, more preferably less than about 75. In other embodiments, the compression ratio of the core is in the range of about 40 to about 80, preferably in the range of about 50 to about 70. In yet another embodiment, the compression ratio of the core is about 50 or less, and more preferably about 25 or less. In another low compression ratio embodiment, the core is less than about 20, more preferably less than about 10, and most preferably zero. However, as is known to those skilled in the art, the core made in accordance with the present invention can be below the measurement limit of the compression compression gauge.
In one embodiment, the golf ball of the present invention preferably has an atch compression ratio in the range of about 55 or more, preferably about 60 to about 120. In another embodiment, the golf ball of the present invention has an atch compression ratio of at least 40, preferably in the range of about 50 to about 120, and more preferably in the range of about 60 to 100. In yet another embodiment, the compression ratio of the golf ball of the present invention is about 75 or higher and about 95 or lower. For example, preferred golf balls of the present invention have a compression ratio in the range of about 80 to about 95.

Initial speed and COR
In general, there is no USGA limit on golf ball COR, but the initial velocity of the golf ball exceeds about 76.25 ± about 1.53 m / s (m / s) (250 ± 5 ft / s (ft / s)). Must not. Thus, in one embodiment, the initial speed is about 74.7 m / s (about 245 ft / s) or higher, and about 89.3 m / s (about 255 ft / s) or higher. In another embodiment, the initial speed is about 76.3 m / s (about 250 ft / s) or more. In one embodiment, the initial speed is in the range of about 77.2 m / s (about 253 ft / s) to about 77.5 m / s (about 254 ft / s). In yet another embodiment, the initial speed is about 89.3 m / s (about 255 ft / s). The general rules regarding initial speed require that golf ball manufacturers remain within this range, but those skilled in the art will readily recognize that the golf ball of the present invention has a golf ball with an initial speed outside this range. You will understand that you can convert. For example, the golf ball of the present invention can be designed to have an initial velocity of about 67.1 m / s (about 220) or higher, preferably about 7.63 m / s (about 225 ft / s) or higher. .

  As a result, the ultimate goal for the initial speed limitation shown by the USGA is to maximize the COR without violating the limit of about 89.3 m / s (255 ft / s). The COR of the ball is measured by determining the ratio of the ball's outbound or rebound speed to the return or inbound speed. In a one-piece solid golf ball, the COR will depend on various properties, including the compressibility and hardness of the ball. For a given compression ratio, the COR will generally increase as the hardness increases. In two-piece solid golf balls, such as cores and covers, one purpose of providing the cover is to obtain a COR gain that exceeds the COR gain in the core. If the core's contribution to high COR is substantial, the contribution required for the cover is smaller. Similarly, if the cover contributes substantially to the high COR of the ball, a smaller contribution is required for the core.

The present invention contemplates a golf ball having a COR in the range of about 0.700 to about 0.850 at an inbound speed of about 38.1 m / s (about 125 ft / s). In one embodiment, the COR is about 0.750 or more, preferably about 0.780 or more. In another embodiment, the ball has a COR of about 0.800 or greater. In yet another embodiment, the golf ball of the present invention has a COR in the range of about 0.800 to about 0.815.
Further, the inner ball preferably has a COR of about 0.780 or higher. In one embodiment, the COR is about 0.790 or more. Furthermore, solid spheres made from the compositions of the present invention have a COR of about 0.65 or greater. In one embodiment, the COR is about 0.75 or more. In other embodiments, the solid sphere has a COR of about 0.76 or greater. In yet another embodiment, the solid sphere has a COR of about 0.77 or more. In yet other embodiments, the solid sphere has a COR of about 0.79 or more. For example, the solid sphere can have a COR of about 0.80 or more.

Spin Speed As is known to those skilled in the art, the spin speed of a golf ball will vary depending on the configuration of the golf ball. In multi-layer balls, such as the core, intermediate layer, and cover, where the cover is made from the polyurea or polyurethane composition of the present invention, the spin speed of the golf ball away from the driver (`` driver spin speed '') Is about 2,000 rpm or more. In one embodiment, the driver spin speed is in the range of about 2,000 rpm to about 3,500 rpm. In another embodiment, the driver spin speed is in the range of about 2,200 rpm to about 3,400 rpm. In yet another embodiment, the driver spin speed is less than about 2,700 rpm.
Two-piece balls made in accordance with the present invention can also have a driver spin speed of 1,500 rpm and higher. In one embodiment, the driver spin speed is in the range of about 2,000 rpm to about 3,300 rpm. The wound ball made according to the present invention preferably has a similar spin rate.
The method of measuring the spin rate should be well understood by those skilled in the art. Examples of methods for measuring the spin rate are described in US Pat. Nos. 6,500,073, 6,488,591, 6,286,364, and 6,241,622. The entire contents of these US patents are incorporated herein by reference.

Flexural Modulus Accordingly, the golf balls of the present invention preferably have a flexural modulus, measured according to ASTM D-6272-98, in the range of about 3.445 MPa to about 3445 MPa (about 500 psi to about 500,000 psi). More preferably, the flexural modulus of the intermediate layer is in the range of about 6.89 MPa to about 1723 MPa (about 1,000 psi to about 250,000 psi). Most preferably, the intermediate layer has a flexural modulus in the range of about 13.78 MPa to about 1378 MPa (about 2,000 psi to about 200,000 psi).
The flexural modulus of the cover layer is preferably about 13.78 MPa (about 2,000 psi) or more, and more preferably about 34.45 MPa (about 5,000 psi) or more. In one embodiment, the flexural modulus of the cover layer is in the range of about 68.9 MPa to about 1034 MPa (about 10,000 psi to about 150,000 psi). More preferably, the flexural modulus of the cover layer is in the range of about 103.4 MPa to about 826.8 MPa (about 15,000 psi to about 120,000 psi). Most preferably, the flexural modulus of the cover layer is in the range of about 124.0 MPa to about 757.9 MPa (about 18,000 psi to about 110,000 psi). In other embodiments, the flexural modulus of the cover layer is about 689 MPa (about 100,000 psi) or less, preferably about 551.2 MPa (about 80,000 psi) or less, and more preferably about 482.3 MPa (about 70,000). psi) or less. For example, the flexural modulus of the cover layer is in the range of about 68.9 MPa to about 482.3 MPa (about 10,000 psi to about 70,000 psi), in the range of about 82.68 MPa to about 413.4 MPa (about 12,000 psi to about 60,000 psi). Or about 96.46 MPa to about 344.5 MPa (about 14,000 psi to about 50,000 psi).

In one embodiment, when the cover layer has a hardness in the range of about 50 Shore D to about 60 Shore D, the cover layer is preferably about 379.0 MPa to about 447.9 MPa (about 55,000 psi to about 65,000 psi).
In one embodiment, the ratio of flexural modulus of the intermediate layer to the cover layer is in the range of about 0.003 to about 50. In another embodiment, the ratio of flexural modulus of the intermediate layer to the cover layer is in the range of about 0.006 to about 4.5. In yet another embodiment, the ratio of flexural modulus of the intermediate layer to the cover layer is in the range of about 0.11 to about 4.5.
In one aspect, the compositions of the present invention are used in golf balls with multiple cover layers that have essentially the same hardness but differ in flexural modulus. In this aspect of the invention, the difference between the flexural moduli of the two cover layers is preferably about 34.45 MPa (about 5,000 psi) or less. In another embodiment, the difference in flexural modulus is about 3.445 MPa (about 500 psi) or more. In yet another embodiment, the difference between flexural moduli between the two cover layers (where at least one is reinforced) is about 3.445 MPa to about 68.9 MPa (about 500 psi to about 10,000 psi). Within a range of about 3.445 MPa to about 34.45 MPa (about 500 psi to about 5,000 psi). In one embodiment, the difference between the flexural moduli of the two cover layers made of unreinforced or unmodified material is within the range of about 6.89 MPa to about 17.23 MPa (about 1,000 psi to about 2,500 psi). is there.

Specific gravity The specific gravity of the cover or intermediate layer is preferably at least about 0.7. In one embodiment, the intermediate layer or cover has a specific gravity of about 0.8 or higher, preferably about 0.9 or higher. For example, in one embodiment, the golf ball includes an intermediate layer having a specific gravity of about 0.9 or higher and a cover having a specific gravity of about 0.95 or higher. In other embodiments, the intermediate layer or cover has a specific gravity of about 1.00 or greater. In yet another embodiment, the intermediate layer or cover has a specific gravity of about 1.05 or higher, preferably about 1.10 or higher.
The core can have a specific gravity of about 1.00 or more, preferably 1.05 or more. For example, a golf ball of the present invention can include a core having a specific gravity of about 1.10 or higher and a cover having a specific gravity of about 0.95 or higher.

  The following non-limiting examples merely illustrate preferred embodiments of the invention and should not be construed as limiting the invention in any way, the scope of the invention being defined by the appended claims. Defined by range. In the following examples, “parts” means “parts by mass” unless otherwise specified.

Example 1: Solid spheres made using the composition of the present invention Solid spheres were produced using the composition of the present invention (sample # 1). As shown in Table 2 below, the modulus and recovery coefficient (COR) are higher than solid spheres made from ionomer materials. In particular, the composition is an excess of aliphatic polyisocyanate based on hexamethylene diisocyanate with an NCO content of 24% (Desmodur ^™ XP-2410; available from Bayer) And a secondary diamine having a molecular weight of 2050 (Jeffamine ^™ XTJ-576; commercially available from Huntsman) to produce a prepolymer having a free NCO content of 14%. Produced by producing. This prepolymer was then used with 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane (Clearlink ^™ 3000; available from UOP) 1: Crosslinking was carried out at a prepolymer to curing agent ratio of 0.95. The solid spheres of the comparative examples are manufactured using ionomer materials found in Titlelist golf balls, ie samples # 2 and # 3 are the covers used in NXT and DT Solo golf balls, respectively. The material is the main component and Sample # 4 is based on the material used in the Titleist Pro VI casing.

Example 2: Composition of the Invention As shown in Table 3 below, in addition to the formulation described in Example 1, the composition of the invention can be made using these various ingredients. .

A catalyst can be added to any of the above formulations to adjust the cure rate of the formulation. For example, dibutyltin dilaurate can be added in an amount ranging from about 0.005 to about 0.01% based on total resin solids.
As used herein, the term “about” is used in the context of one or more numbers or numerical ranges and refers to all such numerical values, including all numerical values within a range. Should be understood. All numerical ranges, amounts, values and percentages other than the examples or not specifically specified, e.g. material amounts, reaction times and temperatures, ratios between different amounts, molecular weight values (number average Molecular weight (Mn), weight average molecular weight (Mw), and other numbers in the following part of this specification are not explicitly indicated in that value, amount or range However, the term “about” can be read as preceding. Accordingly, even if the opposite is not indicated, the numerical parameters set forth in the following specification and appended claims will depend on the predetermined characteristics sought to be obtained by the present disclosure, It is an approximation that can vary. In any case, and not intending to limit the application of the principles equivalent to the claims, each numerical parameter is at least in light of the number of meaningful values reported and is subject to normal rounding techniques. It should be understood by applying.

Although the above numerical ranges and parameters indicating the broad scope of the disclosure are approximations, the numerical values shown in the specific examples are reported as accurate as possible. Any numerical value, however, inherently contains certain errors resulting from the standard deviation found in their respective testing measurements. Further, where a variable range of numerical values is presented herein, it is intended that any combination of these values can be used, including the values described.
The invention described and claimed herein is not to be limited in scope by the specific embodiments described herein. This is because these embodiments are illustrative of some aspects of the present invention. Any equivalent aspects are intended to be within the scope of this invention. For example, the compositions of the present invention can also be used in golf equipment such as putter inserts, golf club heads and portions thereof, golf shoe portions, and golf bag portions. In addition to those presented and described herein, various modifications of the present invention will become apparent to those skilled in the art from the foregoing description. Such improvements are also within the scope of the appended claims. The entire disclosures of all patents and patent applications cited in the above specification text are hereby expressly incorporated by reference.

1 is a cross-sectional view of a multi-component golf ball, wherein at least one layer is made of the composition of the present invention. 1 is a cross-sectional view of a multi-component golf ball including a core, a thin inner cover layer, and a thin outer cover layer disposed thereon, wherein at least one layer is made of the composition of the present invention. 1 is a cross-sectional view of a two-piece ball including a cover made of the composition of the present invention.

Explanation of symbols

1, 5, 10 .. Golf ball 2, 6 .. Core 3, 7 .. Intermediate layer 4 .. Cover 8 .. Thin inner cover layer 9, 12 .. Thin outer cover layer 11.

Claims (17)

A golf ball comprising a core and a cover, wherein at least a portion of the golf ball comprises the following components:
A prepolymer formed from the reaction product of an isocyanate-containing component and an isocyanate-reactive component, wherein the isocyanate-containing component is trifunctional and the isocyanate-reactive component comprises a second diamine ;and
A curing agent comprising 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane,
The golf ball according to claim 1, wherein the golf ball is formed from a composition comprising: The composition consists essentially of a bond having the following general formula:

In the general formula, x is a chain length and is about 1 or more, and R and R ₁ are alkyl groups, phenyl groups, cyclic groups containing about 1 to about 20 carbon atoms, 2. The golf ball according to claim 1, wherein the golf ball is a mixture thereof.   The golf ball of claim 1, wherein the second diamine has a molecular weight in the range of about 200 to about 3,000.   4. The golf ball of claim 3, wherein the second diamine has a molecular weight in the range of about 1,800 to about 2,200.   The golf ball of claim 1, wherein the isocyanate-containing component comprises NCO groups in the range of about 15% to about 25%.   The golf ball of claim 5, wherein the isocyanate-containing component comprises NCO groups in the range of about 20% to about 28%.   2. The golf ball according to claim 1, wherein the cover includes the composition.   2. The golf ball according to claim 1, wherein the composition has a compression ratio of about 170 to 190 atti when formed into a solid sphere. With the core;
A layer disposed around the core to produce an inner ball;
A cover cast on the inner ball, wherein at least a portion of the ball comprises the following components:
A prepolymer formed from the reaction product of at least one isocyanate-containing component and at least one isocyanate-reactive component, wherein the prepolymer has an NCO content ranging from about 10% to about 20% And at least one amine-terminated curing agent,
A golf ball characterized by being formed from a composition comprising:   The golf ball of claim 9, wherein the amine-terminated curing agent comprises 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane.   The golf ball of claim 9, wherein the amine-terminated isocyanate-reactive component comprises a secondary diamine, a secondary triamine, or a combination thereof.   10. The golf ball according to claim 9, wherein the at least part includes the cover.   The golf ball of claim 9, wherein the composition has at least one of a compressibility in the range of about 160 to about 200 atti and a recovery factor of about 0.77 or greater.   The golf ball of claim 9, wherein the prepolymer has an NCO content ranging from about 12% to about 16%.   The amine-terminated curing agent comprises 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane, and the amine-terminated isocyanate-reactive component comprises 13. The golf ball according to claim 12, comprising didiamine, secondary triamine, or a combination thereof. A core; and a cover made of a polyurea material with castability consisting essentially of a bond having the following general formula:

In the general formula, x is a chain length and is about 1 or more, and R and R ₁ are alkyl groups, phenyl groups, cyclic groups containing about 1 to about 20 carbon atoms, Or a polyurea material representing a mixture thereof and having the casting suitability is composed of the following components:
Prepolymers formed from at least one trifunctional isocyanate and at least one secondary diamine, secondary triamine, or mixtures thereof, wherein the NCO content is in the range of about 12% to about 16% ;and
A polyurea material containing 3,3′-dimethyl-4,4′-bis (sec-butylamino) -dicyclohexylmethane, containing a curing agent, and having the castability, is molded into solid spheres. Having a compression ratio in the range of about 170 to about 190 and a COR of about 0.77 or higher,
A golf ball characterized by that.   The golf ball of claim 16, wherein the prepolymer is formed from at least one trifunctional isocyanate and a second diamine having a molecular weight in the range of about 1,800 to about 2,200.

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