CA2052400A1

CA2052400A1 - High performance one-piece golf ball

Info

Publication number: CA2052400A1
Application number: CA002052400A
Authority: CA
Inventors: Duncan H. Pollitt
Original assignee: Dunlop Sport Group Americas Inc
Current assignee: Dunlop Sport Group Americas Inc
Priority date: 1990-10-24
Filing date: 1991-09-27
Publication date: 1993-03-28
Also published as: JPH06504688A; DE560798T1; WO1992007631A1; EP0560798A4; EP0560798A1; AU8917991A

Abstract

ABSTRACT
HIGH PERFORMANCE ONE-PIECE GOLF BALL
High performance one-piece golf balls and one-piece solid cores for golf balls are made by cure-molding a cis-1,4-polybutadiene rubber composition comprising, per 100 parts by weight of rubber, 0.1-3 parts by weight of free-radical initiator and 20-70 parts by weight of methacrylic acid zinc salt produced by reacting zinc oxide with methacrylic acid in the presence of sufficient oxygen to prevent substantial polymerization of the salt. The golf balls have outstanding performance and durability and are reproducable consistently and economically.

Description

2~2~

HIG~ PERFORMANCE ONE-PIECE GOLF BALL

~ he present invention relates to a one-piece solid golf ball and to a one-piece solid core for golf balls.

Golf balls are classi~ied as either wound or solid.
The traditional wound golf ball has a complex structure consisting of rubber threads wound around the center of the ball. The process for making such a ball is time-consuming f - and expensive.

Solid golf balls are classified as one-piece, two-piece or multi-layer. The one-piece golf ball consists of a single structure, the two-piece golf ball has a solid core covered with a cover and the multi-layer ball has three or more layers with an intermediate layer between the core and the cover.

There has been great technological advancement in the production of one-piece and two-piece golf balls; however, to date there is not in existence a one-piece golf ball g that embodies both performance and durability characteristics suitable for use by serious golfers in tournament play. The two-piece golf ball can be used to the satisfaction of an average golfer; but, a professional golfer would not use this type of ball since it lacks feel and controllability i.e. click of the ball and the ability to control spin, par~icularly on approach shots. Further, a high performance one-piece golf ball is not commercially practical in that it has not been possible to accurately reproduce it.

Most golf balls are formed from polymerized butadiene.
The polybutadiene elastomer is crosslin~ed by a crosslinking agent which is a rather large quan~ity of a -` 2052~

zinc salt of acrylic or methacrylic acid. An optimal crosslinker would increase hardness without decreasing resilience.

The zinc salts of methacrylic and acrylic acids have shown great promise as crosslinkers for butadiene in the manufacture of solid golf balls, but so far no suitable one-piece golf ball for play by tournament caliber golfers has been made from ~hese materials. Golf ball compounds crosslinked by acrylic acid zinc salts have generally demonstrated superior characteristics in terms of resilience but tend to be les~ durable. Ball forming compounds crosslinked by methacrylic acid zinc salts produce a ball of superior durability but at the expense of resilience. The following discussion of prior art illustrates these points.

Tominaga U.S.Patent No. 4,561,657 teaches that an improved golf ball can be made from a rubber composition containing zinc acrylate coated with a fatty acid such as stearic acid whereby the golf ball exhibits proper hardness, good impact resilience and good sound and feel when hit.
Another characteristic of this type of rubber composition is that it creates good roll workability and dipersability of rubber additives. -~ ' .
Isaac U.S.Patent No. 4,770,422 discloses an improved golf ball which is durable with good ~laying characteristics such as good initial velocity. The composition from which this ball is formed comprises polybutadiene crosslinked by zinc diacrylate whereby the amount of free-radical initiator is substantially below that typically used in the past.
This free-radical initiator is necessary to promote the crosslinking reaction.

Tominaga U-S.Patent No. 4,556,220 discloses a golf ball which shows mar~edly superior rebound performance, durability and flight carry characteristics. This is achieved by forming the ball from polysulfide type compounds ., ' 2~5~0 which regulate the molecular weight of the chains which result from crosslinking by regulating the length of such chains.

Llort U.S.Patent No. 4,71~,607 teaches that a better golf ball is made by using a small amount of zinc diacrylate to crosslink polybutadiene. Zinc diacrylate is used as a first crosslinker and zinc dimethacrylate is used as a second crosslinker. The result is a golf ball with higher initial velocity and higher compression. Natural rubber can be added to improve durability.

-3 Reiter U.S.Patent No. 4,688,801 teaches that a one-piece golf ball can be made with impro~ed compression and fracture strength while the desired rebound, click and feel characteristics are maintained. This is achieved by using a coasent comprising (i) admixture of a polyvalent metal salt of an unsaturated acid and a~ organic filler or (ii) a reaction product obtained by reac~ion of an unsaturated carboxylic acid with an organic filler followed by further reaction with a polyvalent metal compound in the presence of said unsaturated carboxylic acid where such coasent functions as a crosslinking agent with the polybutadiene elastomer.
'~
The above-noted prior art is directed to composltions for forming one-piece solid golf balls as well as rorming the cores of two-piece golf balls. Likewise, the compositions of the present invention are applicable to solid one-piece golf balls and the cores of two-piece golf balls.
It is an object of the present invention to provide a novel composition capable of producing a one~piece golf ball or a multi-piece golf baIl.
The presen~ invention is a composition for making a solid one-piece golf ball with a butadiene base which is crosslinked by a methacrylic acid zinc salt. The resulting product is a one-piece golf ball with outstanding 2~2~00 performance which possesses both resilience and durability and which can be reproduced accuratelY and economically.
This type of golf ball is suitable for play by tournament caliber golfers. In addition, the material comprising the composition can be used to form the core of a two-piece or multi-layer golf ball.

.
At the outset, the present invention is described in its broadest overall aspects with a more detailed description following. All embodiments of the invention involve a composition which includes a polybutadiene crosslinked with a methacrylic acid zinc salt manufactured under the tradename Z-Max MA. This zinc salt is present in the range of 20 to 70 parts by weight per 100 partC of rubber to be used in ~ormulating the solid one-piece golf ball and the core of the two-piece golf ball. The term rubber'is intended to include a major portion of polybutadiene and may include minor portions of other 2052~0~
.

polymers such as natural rubber, polylsoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber and nitrile elastomers. In all embodiments, the rubber com~onent must include at least 75% by weight of polybutadiene. A
table of the essential ingredients and their use ranges, in accordance with the present invention, appears below.

Essential Inqredients PPH

Rubber 100 (at leas~ 75% Polybutadiene by weight) Vul Cup R 0.1- 3 (a free-radical initiator) O~tional Inaredients Basic lead silicate 0 - 15 Titanium dioxide 0 - 15 Magnesium oxide3 0 - 5 Agerite Resin ~ 0 - 2 ~ part~ per 100 partsof polybutadiene 2 methacrylic acid zinc salt t-butyl cumyl peroxide 3 polymerized 1,2-dihydro-2,2,4-trimethylquinoline titanium IV, 2-propanolato, tris-(dodecyl) benzene sulfonato-o N,N~m-phenylene dimaleimide ~ he result of using the composition of the present invention in forming golf balls is a golf ball with outstanding performance. Such golf ball's improved characteristics include resilience, durability and economical reproducibility.

The key feature of the present invention is the methacrylic acid zinc salt used to crosslink the butadiene.

6 2 ~ 00 This zinc salt is unique in that its crosslinking energy is in the same order as or greater than the energy in commercially acceptable zinc salt made from acrylic acid, yet the golf ball produced from this salt cross-linked with polybutadiene is superior to commercially available balls. Suitably the zinc salt may have a crosslinking energy of at least about 180 Joules per gram and/or a xylene-solubility of at least 50~ by weight.
Methacrylic acid zinc salt is traditionally made by reacting methacrylic acid with zinc oxide. In accordance with the present invention, the reaction by which the zinc salt is produced is run in an abundance of air and suitably with more, e g 10% more, than the stoichiometric amount of zinc oxide. The introduction of oxygen into the reaction prevents polymerization of the methacrylic acid during mixing with polybutadiene rubber. Specifically, the zinc salt and the polybutadiene are blended in a roll mill producing a corrugated surface on one side of the product. This high radiating area keeps the temperature down and thus delays curing until the molding step. The temperature is preferably kept down to 75C
which is below polymerization temperature. As a result, polymerization and curing take place during the molding step and not during the mixing step.
In accordance with the present invention, the methacrylic acid zinc salt may be prepared by introducing a charge of 44 pounds of zinc oxide to 85 pounds of methacrylic acid along with 0.25 pound of stearic acid.
20 ml of sulfuric acid is added as a catalyst. Prior to reaction, the zinc oxide and the stearic acid are dispersed in a solvent which contains heptane and 1,1,1-trichloroethane in about equal parts by volume and has a specific gravity of about 0.98. During the reaction process, the methacrylic acid and sulfuric acid are added into a rotary vacuum drier and heated to 85-90C.
The solvents containing the zinc oxide are then added to the drier. A one-second blast of air is bled into the evacuated drier system at 30-second intervals to prevent polymerization of the zinc salt. After approximately 0.75 2 ~ 0 hour in the rotary vacuum drier, the solvents and water of reaction are substantially removed by vacuum and the resulting product is a solid methacrylic acid zinc salt.
The zinc salt is further dried and then reduced to particle size of 1-30 microns. This salt is currently manufactured by Yardley Ball Corporation, Milton, Florida, under the name Z-Max MA (Z-Max) and is referred to herein by that name.

Comparative Examples 1-6 and 8-12 further describe and define the present invention. Z-Max, Z-Max crosslinked with polybutadiene as well as two other commercially available salts, alone and crosslinked with polybutadien~, were analyzed and compared. The analysis was performed by Arthur D. Little Laboratories (ADL) of Cambridge, Massachusetts.
The salts compared with Z-Max axe Sartomer 365 manufactured under this tradename by Sartomer Co., Inc., Exton, Pennsylvania and ReactRite manufactured under this tradename by Rockland React-Rite, Inc., Cartersville, Georgia. Two different samples of Z-Max were analyzed; one sample was manufactured in the old Yardley Ball Corporation plant in Pennsylvania and the other sample was manufactured in the new, currently operating,Florida plant. The Pennsylvania sample represents Z-Max which has aged before curing and thus golf balls produced from it would be less resilient and thus less desirable. Z-Max should preferably be used, i.e., cross-linked with polybutadiene, within a week of production.

Examples 1-6 and 8-12 show that many features distinguish Z-Max and the polybutadiene cured with it from other commercially available zinc methacrylate. To begin with, Z-Max has a higher zinc content and ~resh Z-Max has a higher exothermic heat of polymerization. The X-raY
diffraction pattern of Z-Max shows a stronger peak between 11 and 12 degrees and the particle sizes of Z-Max are the smallest of the group analyzed. The FTIR spectrum of Z-Max has more prominent CO crystalline peaks and the Z-Max samples had the highest solubility in xylene. The heat of 2~2~

curing is highest for the fresh Z-Max sample and polybutadiene cured with Z-Max has the highest Shore Hardness. Finally, Z-Max samples have lower swell lndices than the other samples tested.

~ xamples 1-6, shown below, provide the results of: 1) elemental analysis 2) differential scanning calorimetry 3) X-ray diffraction 4) microscopic examination 5) Fourier transform in~rared spectroscopy and 6) xylene solubility.

EXAMPLE l f'`
The analysis for zinc content in the samples was carried out by plasma analysis. The samples were also vacuum dried and analyzed for zinc, carbon and hydrogen at Galbraith Laboratories, Inc., (GLI) in Knoxville, Tennessee.
The results are shown below. 'N.A.' = Not Applicable.
WEIGET % ELEMENT IN ZINC S~LTS
Salt % Zn %C %H %O by GLI ADL difference Theoretical Zinc 27.8 N.A. 40.8 4.3 27.2 Methacrylate PA Z-Max 1-91 30.6 N.A 35.8 3.9 29.7 PA Z-Max 10-90 N.A. 29 37.8 4.0 29 PL Z-Max 28.2 N.A. 38.3 4.1 29-.4 Sartomer 3~5 29.g 29 37.7 3.8 29.1 ReactRite 27.0 27 39.5 4.5 29.0 All samples, except ReactRite, contained more than the theoretical proportion of zinc; especially the FL Z-Max sample.
All samples, especially the PL Z-Max, contained more than the theoretical proportion of oxygen and less than the theoretical proportion of carbon. These results are consis~ent with known addition of excess zinc oxide in the production of Z-Max and indicate that the salts had been oxidized; especially the FL
Z-Max. In hydrogen content, the Z-Max and Sartomer samples 20~2~0 .

were below that calculated by ~heory, but the React~ite hydrogen content was high. This result suggests tha~ React~ite contained unxeacted methacrylic acid or its polymer.

EX~MPLE 2 .

The heat of reaction by thermal analysis is known in the art to correlate with chemical reactivity in curing polybutadiene. Each sample was analyzed using a DuPont 910 Differential Scanning Calorimeter (DSC) with a 20 C/minute oven ramp, nitrogen atmosphere,to 300 C in hermetically sealed pans. Each sample showed an exothermic peak due to heat of polymerization. The peak temperature in degrees centigrade and the heat of polymerization in ~oules per gram (J~g) were recorded. The older Z-Mzx sample also showed an endothermic heat of melting, apparently of a crystalline species formed on storage. It is noted that the structure of the cured polym~r is influenced by the rate of cooling.
DSC RESULTS WITH æN SALTS
Property/Salt PA Z-Max FL Z-Max React Rite Sartomer 365 Endgtherm, 28.6 J/g None None None Exotherm, OJ/g 138 170 61 73.9 Peak Temp. C 140 217 115 225 i~.~3 Exotherm J/g 2~3 No N.A. 62.7 after anngaling at 125 C 15 min.
and slow cooling Peak O
Temp. C 209 N.A. N.A. 218 Melted, Polymerized and quench cooled with liquid nitrogen J/g 57.5 N.A. N.A. 70.9 Temp. Peaks C 213,248, 260 N.A. N.A. 221 ` ~ 2~2~00 To perform the X-ray diffraction spectroscopy, the dry powders were each pressed in an aluminium frame. The diffraction patterns with CuK alpha radiation show no zinc oxide left in the samples.
X-RAY DIPFRACTION PEAK ANGLES
Angle, PA Z-M æ FL Z-Max React Rite Sartomer 365 Degrees 7.3 Strong Absent Absent Weak 9.8 Strong Strong Strong Very Strong 10.6 Medium Medium Somewhat Very Strong Strong 11.6 Somewhat Somewhat Weak Medium Strong Strong Extent of 2 3 4(Least) l(Most) Crystalline Part The ReactRite sample clearly has the largest amorphous phase and fewer crystals of one of the phases shared by the other two samples. The Z-Max and Sartomer samples appeared to contain mostly crystals and all samples had at least four crystalline planes. The Sartomer sample had particularly strong bands in the peaks at 9 to 10 and at 10 to 11 degrees and showed the most complicated crystalline pattern. As a check, an X-ray spectrum was run o~ a known zinc acrylate and compared to a methacrylate sample.

After treatment with ethyl alcohol, the X-ray spectra of the PA Z-Max and the Sartomer 365 samples were shown to be similar, with strong peaks between 9 and 10 degrees and just below 11 degrees. After alcohol treatment, the ReactRite had only one crystalline peak just below 11 degrees and a broad amorphous peak just below that.

2~2'~0~

The various zinc methacrylate samples were examined under the microscope at 150 and 300 x magnification. The Z-Max particles were the smallest and most rounded, the Sartomer ~articles were the largest and constituted highly crystalline acicular ~lat planes. The ReactRite particles in xylene showed birefringence, suggesting a transition between amorphous and crystalline forms.
f ~ICROSCOPICAL EXAMINATION
~ethod P~ Z-Max FL Z-Max React Rite Sart~mer 365 Mlcroscopy Microns, Mostly 3-10 1-5 5-25 5-200 Dia. Up to 35 Up to 200 Shape All Irreg. Irreg. Round ~ Needles Needles Crystals Some particles Rectangular crystalline ~ Crystalline amorphous or Plates poorly crystallized The finer particle size of the Z-Max samples corresponds with larger surface area for increased reactivity. The Florida Z-Max appeared to be less completely crystalline than the Sartomer. The particle sizes of the Z-Max were much smaller than those of the two other salts. The Sartomer sample appeared to be highly crystalline, in agreement with X-raY
observation. The ReactRite sample had a mixture o~ acicular crystals and irregular roundish amorphous-looking particles.
As a check, a known Sartomer zinc acrylate was examined microscopically and compared to methacrylate.

over 40 scans were taken with a Bio-Rad FTS
spectrophotometer with the averages used to provide results.
The infrared spectra differed among the samples, in that the `` 20~2~0 Z-Max samples had an additional band at 1090 reciprocal cm where carbon-to-oxygen bonds generally appear. The Z-Max samples also showed a greater number of crystalline peaks. The crystal form of Z-Max is clearly different from that of the other salts analyzed.
RESULTS FRO~ INFRARED SPECTROSCOPY
CO Peaks PA Z-Max FL Z-Max React Rite Sartomer 365 1090 CO Band CO Band No extra CO No extra CO

and 710 Yes More Fewer Fewer ~i~ Suggesting Crystallinity Excess xylene was mixed thoroughly with a weighed sample of zinc salt. The excess of solvent was decanted off. A he~t lamp was used to evaporate xylene from both the soluble and insoluble portions ~efore weighing. The weight percentages recovered (some was lost on evaporation) are given below.
XYLENE SOLUBILITY
PA Z-Max FL Z-M~x React Rite Soluble Insoluble Soluble Insoluble Soluble Insoluble ., ~-~J 72 19 62 29 38 S7 The FL Z-Max had about-10~ more insoluble material than the PA Z-Max sample. The ash contents o~ PA Z-~ax corresponded to between 29 and 30% zinc for both the soluble and insoluble phases. The FL Z-Max had similar results. For ReactRite, the soluble portion ash content corresponded to 32% zinc and the insoluble portion to 26%.

At this point a discussion regarding the usual composition of the base of the solid one-piece golf ball or the core of the two-piece golf ball is appropriate. Such a descriPtiOn follows.

'''' ''`'''''''`''~'''''''''''' 20~24~0 .

Bu~ad~ene rubber, that is cis-1,4-polybutadiene rubber, is the primary elastomer component, but other elastomers may also be present in smaller quantities. Natural rubber,for example, may be added to lower modulus and improve durability.
In addltion to the methacrylic acid zinc salt constituent and the free-radical or peroxide initiator, numerous other ingredients may be incorporated into the solid ball compound.
The composition usually contains fillers such as zinc oxide, barium sulfate, lead oxide, basic lead silicate, or the like, used singularly or in combination, to control the weight of the ball. Other additives may include: magnesium oxide, calcium carbonate as fillers and/or acid acceptors; mildly reinforcing fillers and/or nucleating agents such as silicas, carbon blacks, clays and the like; silanes and/or titanates as co-plin~
and/or dispersing agents; antioxidants for improving process, heat and shelf aging properties; co-curing agents such as HVA-2, TMPTA, TMPTMA and the like; cure modifying agents such as sulfur and sulfur-bearing compounds; granular or powdered high molecular weight polymeric materials as im~act modifiers;
pigments and other ingredients for imparting various characteristics known by those skilled in the art of rubber compounding for golf balls.

This composition is then kneaded by a suitable kneader, mixer or blender such as a roll mill or a Banbury mixer. Next, the rubber composition is molded using, for instance, heat-pressure molding. A one-plece golf ball is prepared by heat-pressure molding the rubber composition into a ball having the size suitable for a golf ball. A two-piece golf ball is prepared by heat-pressure molding the rubber composltion in a core mold having a suitable size to from a solld core and covering the core with a suitable cover. The cover can be prepared from compositions comprising, for lnstance, an ionomer resin as a main component and optionally a filler or coloring agent such as a titanium dioxide or zinc oxlde. The solid core is covered with two covers previously molded in the form of a hemispherical shell and is then .
.

! ' ~ ' , 29~2~0~

heat-pressure molded to fuse the two shells together to give a finished golf ball. Injection molding is also used to introduce the covering material around the core.

One important embodiment of the composition of the present invention comprises high cis polybutadiene as the primary elastomer, Z-Max MA crosslinker in the range of between 20 to 70 parts, based on 100 parts of elastomer, basic leAd silicate as filler-for-weight in the range of 5 to 15 parts, titanium dioxide pigment in the range of 0 to 15 parts, magnesium oxide acid acceptor in the range of 0 to 5 parts, AgeRite Resin D
antioxidant in the range of 0 to 2 parts, CAPOW KR 9S/H
i titanate in the range of 0 to 2 parts, Vul Cup R peroxide initiator in the range of 0.1 to 3 parts, and HVA-2 co-curing agent in the range of 0 to 2 parts. The compound is mixed at a temperature of 20 to 150C in a Banbury mixer or a roll mill, then molded for 20 minutes at 175C in a 1.727-inch golf ball mold.

The following is an example of the preferred embodiment.

20~2~00 -HIGH PE~FORMANCE ONE-PIECE GOLF ~AL~
Com~ound: GB-1 Parts bv weight Polybuta~iene (high cis) 100 Z-Max MA 48 Basic lead silicate 6 Titanium dioxide 3 Magnesium oxide AgeRite Resin3D2 0.03 CAPOW KR 4S/H 0.20 Vul C~p R 0.53 HVA-2 0.16 Total158.98 2 methacrylic acid zinc salt - Yardley Ball Corp.
polymerized 1,2-dihydro-2,2,4-trimethylquinoline - R.T. Van 3derbilt Company titanium IV, 2-propanolato, tris-(dodecyl~ benzene ~ulfonato-O - Kenrich Petrochemicals, Inc.
t-butyl cumyl peroxide - Hercules, Inc.
N,N-m-phenylene dimaleimide - E.I. DuPont de Nemours & Co.
The resulting typical ball properties are:

Shore C 93 Compression 122 ~,~ COR 0.796.
I.V. ft/sec 254.6 Comparative Examples 8-12 which appear below show the differences between the conventional salt-polybutadiene compositions and the Z-Max-polybutadiene compositions. The compositions were prepared in accordance with the teachlngs of the present invention. The following analyses were performed: 1) heats of crystallizing and curing rubbers 2) exothermic recrystallization heat of cured samples 3) Shore hardness and 4) swell index.

' ~

2~52400 The below-listed ingredients were mixed with a Type PL-V302 Brabender PlastiCorder, Serial Number 177518, with electrical heating, air cooling and variable speed one horsepower Type GP 100 Drive. Titanium dioxide, an inert pigment, was omitted to facilitate examination by infrared spectrophotometry.

Grams Inqredients 34.5 High cis-polybutadiene from Dunlop Slazenger, Greenville, South Carolina 0.138 AgeRite Resin D, R. T. Vanderbilt,poly(~rimethyl dihydroquinoline) antioxidant 0.3485 Magnesium Oxide, to neutralize acid 0.069 Capow KR 9S/H, Kenrich Pe~rochemical,monoalkoxy titanate coupling agent on a hydroxylated silicon dioxide carrier These materials were mixed at a temperature in the 90 to 100 C range to masticate the rubber for 11 or 12 minutes. The mixture was then allowed to cool to about 96 - 108 C by reducing the s~irring speed. Next, 15.962 gof one of the four zinc salts of methacrylic acid was added: Sartomer 365, ReactRite, PA Z-Max or FL Z-Max. After a dozen minutes of stirring, during which time the temperature was not allowed to exceed 113 C, the stirrer was slowed and the temperature allowed to fall to about 102 C for the addition of the curing agents which are listed below.
Grams Inqredients 0.1242 Di Cup R from Hercules, dicumyl peroxide 0.1242 Vul Cup R from Hercules, t-butyl cumyl peroxide 0.0552 HVA-2 from DuPont, N.N'-m-phenylenebismaleimide ` 2~2~00 , These ingredients were blended for 6 mlnutes with the temperature keot down to 100 - 102 C to prevent premature curing. Cylindrical moldings about 6 mm thick and 32 mm wide were produced by curing at 160 C for 20 minutes in a press at 10,000 pounds on a 4-inch ram. The round mold was about 2 inches in outer diameter.

The samples in the compound with rubber were cured in the DSC and the heats of crystallizing and curing of the rubbers were measured. This important exothermic heat was determined at 20 C/mlnute. The preceding crystallization exotherms were determined at both 5 and 20 C.
DSC HEATS OF CURING AND CRYSTALLIZ~TION
Zinc Salt PA Z-Max PL Z-Max Sartomer 365 React Rite 20C/Minute Rate of Increase Heat of Curing J/g Initial Spike5.50 8.78 6.14 17.28 Broad Secondg6.21 95.80 46.93 22.96 Temperatures, C
Pirst Peak:
Onset 159.1 158.8 159.2 159.1 Peak 162.1 161.6 162.0 161.8 Second Peak:
Peak 190.4 189.5 192.2 196.4 5C/Minute Rate of Increase ~irst Pgak:
(at 159 C):
Heat, J/g 5.48 6.93 6.37 5.49 20~4~0 The above-shown results show that the FL Z-Max sample cured more ~han twice as energetically as the Sartomer 365.
The ReactRite peak was not only smaller in area but more spread out. The heat of curing is highest for FL Z-Max and lowest for Reac~Rite.

When the uncured compound is heat d at 20 C/minute, the heat flow after the first peak subsides to the base line followed by an excursion to the second peak. Because other sharp exothermic spikes occur at the same temperature in cured rubbers as in the uncured compound, when the temperature is increased at the same rate, the first exothermic peak is considered due to crystal reorganization and the second to the curing reaction. The ReactRite sample, which appeared least crystalline by microscope and X-ray, had the largest crystallization exotherm at the 20 C/minute heating rate but one of the lowest heats at the 5 C/minute rate. This difference suggests that the sample is not homogeneous.

ExAMæLE 10 The exothermic recrystallization heat of the cured samples was measured. Since curing had been carried on for 20 minutes, the transitions in the cured compounds as noted below are concluded to have been physical rather than chemical. In every case, spike exotherms of the cured rubbers began at 157.5 C
and peaked at 158 to 159 C. When the cured rubbers were ~rogrammed in the DSC at a 5 C/minute increase ln temperature, they revealed spike exotherms at about 159 C which are considered dtle to reorganization in structure.
EXOTHERMIC TRANSITION
zinc Salt Exothermic Heat, J/g at 158-159C
PA Z-Max 15.4 FL Z-Max 15.8 Sartomer 365 19 . O
React Rite 7.64 The samples were close in heat of crystallization except for cured ReactRite which was significantly lower. This may be due to a less desirable form of cross-linking, such as the carbon-carbon bonds formed by peroxides, especially when zinc methacrylate is absent or less active.

Shore hardness measurements were performed on all samples.
Each molding was measured after aging for at least five days.
The five measureme~ts were at least 0.5 inch in from the edge as prescribed by ASTM. Averages of the measurements were taken and are shown below.
S~ORE HARDN~SS
zinc Salt Hardness Readings Average PA Z-~ax 4g 47 50 49 51 49.2 FL Z-Max 49 52 53 51 54 51.8 Sartomer 365 47 48 48 48 48 47.8 React Rite 26 28 26 26 26 26.4 It is important to note that the Z-Max samples were harder than the other two samples,indicating a higher degree of cross-linking reaction for the same proportion of reagent.

The swell index was measured for each sample. This index represents the equilibrium weight of toluene absorbed by a cured rubber divided by the initial weight of the rubber. For example, an uptake of 69~ is a swell index of 0.69. Parts of the moldings described above were weighed into an excess of freshly opened scintillation grade toluene and obcerved over four days of aging. Each day the swollen rubber samples were blotted and weighed in grams. The following results may vary in the last figure due to variability in blotting technique.

~ ;
,.

2~52~
.~

WEIGHTS OF POLYBUTADIENE WIl~I TOLUENE
Zinc Salt/days 0 1 2 3 4 PA Z-Max 2.267 3.652 3.693 3.755 3.828 FL Z-Max 2.281 4.534 4.752 4.752 4.708 Sartomer 365 1.992 3.989 4.136 4.243 4.291 React Rite 2.508 5.771 5.819 5.870 5.932 After four days, the solvent up~ake was 69 weight percent toluene for the PA Z-Max, 106~ for the FL Z-Max, 115% for Sartomer and 136~ for ReactRite. This difference indicates ,. .
that the polybutadiene cured with Z-Max was more resistant to solvent and therefore more cross-linked than the polybutadiene cured with the other salts.

The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, ~nd there is no intention to exclude any equivalence thereof. Hence, it is recognized that various modifications are possible when within the scope of the present invention as claimed.
,

Claims

1. Composition for use in making a one-piece golf ball or a one-piece solid core for a golf ball, which comprises:
(i) rubber comprising at least 75 percent by weight of cis-1,4-polybutadiene;
(ii) methacrylic acid zinc salt in the range of 20 to 70 parts by weight per 100 parts by weight of rubber, said salt being the product of reacting zinc oxide with methacrylic acid in the presence of sufficient oxygen to prevent substantial polymerization of the zinc salt;
and (iii) free-radical initiator in the range 0.1 to 3 parts by weight per 100 parts weight of rubber.

2. Composition according to Claim 1 wherein the rubber consists essentially of cis-1,4-polybutadiene.

3. Composition according to Claim 1 wherein the methacrylic acid zinc salt has a crosslinking energy of at least about 180 Joules per gram.

4. Composition according to Claim 1 wherein the methacrylic acid zinc salt has a xylene-solubility of at least about 50 percent by weight.

5. Composition according to Claim 1 wherein the methacrylic acid zinc salt is the product of reacting methacrylic acid with zinc oxide in an amount greater than the stoichiometric amount required for reaction with the methacrylic acid.

6. Composition according to any one of the preceding Claims wherein the free-radical initiator is t-butyl cumyl peroxide.

7. Composition according to any one of Claims 1 to 5 comprising additionally up to 15 parts by weight of filler per 100 parts by weight of rubber.

8. Composition according to any one of Claims 1 to 5 comprising additionally up to 15 parts by weight of basic lead silicate per 100 parts by weight of rubber.

22.

9. Composition according to any one of Claims 1 to 5 comprising additionally basic lead silicate in the range of 5 to 15 parts by weight per 100 parts by weight of rubber.

10. Composition according to any one of Claims 1 to 5 comprising additionally up to 15 parts by weight of pigment per 100 parts by weight of rubber.

11. Composition according to any one of Claims 1 to 5 comprising additionally up to 15 parts by weight of titanium dioxide per 100 parts by weight of rubber.

12. Composition according to any one of Claims 1 to 5 comprising additionally up to 5 parts by weight of acid-acceptor per 100 parts by weight of rubber.

13. Composition according to any one of Claims 1 to 5 comprising additionally up to 5 parts by weight of magnesium oxide per 100 parts by weight of rubber.

14. Composition according to any one of Claims 1 to 5 comprising additionally up to 2 parts by weight of antioxidant per 100 parts by weight of rubber.

15. Composition according to any one of Claims 1 to 5 comprising additionally up to 2 parts by weight of polymerized 1,2-dihydro-2,2,4-trimethylquinoline per 100 parts by weight of rubber.

16. Composition according to any one of Claims 1 to 5 comprising additionally up to 2 parts by weight of coupling or dispersing agent per 100 parts by weight of rubber.

17. Composition according to any one of Claims 1 to 5 comprising additionally up to 2 parts by weight of titanium IV,-2-propanolato, tris-(dodecyl) benzene sulfonato-0 per 100 parts by weight of rubber.

18. Composition according to any one of Claims 1 to 5 comprising additionally up to 2 parts by weight of co-curing agent per 100 parts by weight of rubber.

19. Composition according to any one of Claims 1 to 5 comprising additionally up to 2 parts by weight of N,N-m-phenylene dimaleimide per 100 parts by weight of rubber.

23.

20. Composition according to Claim 1 comprising additionally: up to 15 parts of filler, up to 15 parts of pigment, up to 5 parts of acid-acceptor, up to 2 parts of antioxidant, up to 2 parts of coupling or dispersing agent and up to 2 parts of co-curing agent, all parts being parts by weight per 100 parts by weight of rubber.

21. Composition according to Claim 1 wherein the free-radical initiator is t-butyl cumyl peroxide and the composition comprises additionally: up to 15 parts of basic lead silicate, up to 15 parts of titanium dioxide, up to 5 parts of magnesium oxide, up to 2 parts of polymerized 1,2-dihydro-2,2,4-trimethylquinoline, up to 2 parts of titanium IV,2-propanolato, tris-(dodecyl) benzene sulfonato-0 and up to 2 parts of N,N-m-phenylene dimaleimide, all parts being parts by weight per 100 parts by weight of rubber.

22. Method of making a one-piece golf ball or a one-piece solid core for a golf ball, which comprises mixing together the ingredients of a composition defined in any one of Claims 1 to 5, 20 and 21 to form a reaction mixture, and heating the reaction mixture in a mold to cure the composition.

23. Method of making a one-piece golf ball or a one-piece solid core for a golf ball, which comprises mixing together the ingredients of a composition defined in any one of Claims 1 to 5, 20 and 21 at a temperature in the range of 20°C to 150°C to form a reaction mixture, and heating the reaction mixture in a mold to cure the composition.

24. One-piece golf ball when made from a composition according to any one of Claims 1 to 5, 20 and 21.

25. One-piece solid core for a golf ball when made from a composition according to any one of Claims 1 to 5, 20 and 21.

26. One-piece golf ball or one-piece solid core for a golf ball when made by a method which comprises 24.
mixing together the ingredients of a composition defined in any one of Claims 1 to 5, 20 and 21 to form a reaction mixture, and heating the reaction mixture in a mold to cure the composition.

27. One-piece golf ball or one-piece solid core for a golf ball when made by a method which comprises mixing together the ingredients of a composition defined in any one of Claims 1 to 5, 20 and 21 at a temperature in the range of 20°C to 150°C to form a reaction mixture, and heating the reaction mixture in a mold to cure the composition.