JPH06504688A - High performance one piece golf ball - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] High performance one piece golf ball Background of the invention The present invention relates to a one-piece solid golf ball.

Golf balls are classified into two types: pincushion type and solid type.

Traditional wind-type golf balls have a complex structure, and the Rubber thread is wrapped around the center.

Manufacturing such balls is time consuming and costly.

Solid golf balls come in one-piece, two-piece, or multilayer types.

One-piece golf balls have a one-piece construction, while two-piece golf balls have a solid structure. It is a multilayer type golf ball with a hard core covered with a cover. The core has a three or four layer structure with an intermediate layer between the core and the cover.

Although manufacturing technology for one-piece and two-piece golf balls is very advanced, High performance alignment that can withstand use by serious golfers in golf tournaments. The one-piece golf ball that combines both high durability and high durability has been developed to this day. Not yet. Two-piece golf balls are suitable for golfers of average skill. Although it provides sufficient satisfaction, professional golfers prefer this type of golf ball. do not use the file. This is because two-piece golf balls have a different feel when hit and ball control. However, it has some drawbacks in its control. In other words, the sound of the ball being hit and the spin shot. The reason for spin shots, especially approach shots, is the One Piece Golf. This is because accurate continuous reproduction in the Ruffball manufacturing process was impossible.

Most golf balls are made of butadiene polymer. Made by Adiene). Polybutadiene elastomer is made of acrylic acid or meth Large amount of acrylic or methacrylic acid A crosslinking agent that is a zinc salt (zinc 5ait) agent). The best crosslinkers do not impair elasticity to increase hardness.

Zinc salts of methacrylic acid and acrylic acid are used in the manufacture of solid golf balls. Although it has been found to be a highly effective cross-linking agent for Tagene, to date One-piece golf balls are suitable for tournament-level golfers. Not manufactured from these materials. Cross-linked by zinc acrylate salt Golf ball formulations generally exhibit good resiliency but poor durability.

On the other hand, golf ball formulations cross-linked with zinc methacrylate salts showed superior It exhibits durability but poor elasticity. The description of the prior art described below will be based on these features. It is related.

U.S. Patent No. 4,561,657 to Tominaga et al. Golf balls are made of zinc alloy coated with fatty acids such as stearic acid. It is possible to manufacture golf balls from rubber compounds containing acrylate. The ball provides appropriate hardness, good impact elasticity, and good impact sound and feel. It is disclosed that Other properties of this type of rubber compound include ease of processing and good diffusibility of rubber additives.

U.S. Pat. No. 4,770,422 to Isaac, et al. An improved golf ball with excellent durability that provides good playing performance such as providing the desired initial velocity. 'Fubor' has been disclosed. The compound in this golf ball is zinc diacrylate. The polybutadiene is more cross-linked and the free radical detonator used is The amount of radical 1 initiator) is the amount that was common in the past. It is much less than that. The free radical priming agent promotes cross-linking reactions. is necessary.

U.S. Patent No. 4,556,220, issued to Tominaga et al. A golf ball with excellent rebound performance, durability, and aerial carry performance. is disclosed. This golf ball has an adjustable chain length. Polysulfide-type formulations (p manufactured from olysulfide type compounds).

U.S. Patent No. 4,714°60 issued to “Llort, et al.” No. 7 states that [a good golf ball contains a small amount of zinc dichloride that cross-links the polybutadiene]. This product is manufactured by using acrylate (zinc diacrylate). is disclosed. Zinc diacrylate is used as the first cross-linking agent, Zinc dimethacrylate (zinc dimethacrylate) Used as a differential binder. Golf balls manufactured in this way are excellent first It has high compression speed and excellent compression performance. Adding natural rubber to improve durability is also possible.

U.S. Patent No. 4,688゜8 granted to "Reiter, et al." No. 01 states, ``Excellent compression that maintains the desired rebound performance, batted ball sound, and feel characteristics. A method for manufacturing a one-piece golf ball with high performance and crack resistance is disclosed. Ru. This golf ball contains (i) an unsaturated acid; d) a mixture of a polyvalent metal salt and an organic ring agent (admixture of a pol yvalent metal 5alt) or (ii) unsaturated carboxy Unsaturated carboxylic acid and organic cyclic agent (organic filler) and the subsequent chemical reaction with the organic filler. With polyvalent metal compounds in the presence of saturated carboxylic acids using a coagent consisting of a reaction product obtained by a chemical reaction. Manufactured. The synergist acts as a cross-linking agent for polybutadiene elastomers. Function.

The above-mentioned prior art is used to manufacture one-piece golf balls and to manufacture two-piece golf balls. It concerns the compositions used in the manufacture of the core. Ru. The compounds of the present invention are also used in the production of one-piece golf balls and in two-piece golf balls. It can be applied in the manufacture of ball cores.

Summary of the invention The present invention is based on butadiene cross-linked by zinc methacrylate salts. The present invention provides a compound for producing a solid one-piece golf ball. manufacturing The golf balls made with this product have excellent elasticity and durability, allowing for accurate continuous This is an excellent golf ball that can be produced and is inexpensive to produce. genuine tie Our golf balls have sufficient playability for tournament-level golfers. are doing.

Additionally, materials comprising the compounds of the present invention may be used for two-piece balls or multilayer golf balls. It can also be used to make cores for plastics.

SUMMARY OF THE INVENTION Accordingly, a primary object of the present invention is to manufacture superior one-piece golf balls and to provide multi-piece golf balls. An object of the present invention is to provide new compounds that produce superior cores for golf balls.

Another object of the invention is to provide a one-piece golf ball with superior elasticity and durability. It is to be.

Another object of the present invention is to reduce the manufacturing cost of such golf balls, and to To provide a one-piece golf ball manufacturing method that stably and continuously manufactures high-quality balls. That is.

First, the outline of the present invention will be explained, and the details will be described later. of the present invention In all examples, the trade name was replaced with a zinc methacrylate salt called rZ-Max MAJ. It concerns compounds containing differentially bound polybutadiene. The meta Zinc acrylate salts are used in solid one-piece golf balls and two-piece golf balls. The weight range of 20 to 70% of the weight of the rubber used to form the core is 100%. It exists. The above-mentioned "rubber" refers to rubber containing polybutadiene as a main component. and small amounts of natural rubber and polyisoprene rubber. , styrene butadiene rubber, ethylene Propylene rubber and nitrile (n may contain some polymers such as elastomers) There is also. In all examples, the rubber component was small by weight. It must contain at least 75% polybutadiene. Main component according to the invention (ingredients) and amounts used are listed in the table below.

Table 1 Main component PPH* Rubber 100 (at least 75% polybradadiene by weight) Z-MaxMA (Note 1) 20 -70 Vul Cup R (Note 2) 0. 1-3 (Free radical detonator) Optional Ingredients Basic lead silicate (B asic 1ead 5ilicate) O-15 Titanium Dioxide (Tit anium dioxide) O-15 magnesium oxide um oxide) O-5 Agerite resin D (Note 3) O-2CAPOW KR9S/H+ (Note 4) O-2HVA-2 (Note 5) O- 2 *For polybutadiene 100 Note 1: Methacrylic acid zinc 5 alt) Note 2: t-butylcumyl peroxide e) Note 3 Polymerization 1,2-dihydro-2,2,4-trimethylquinoline (poly Merized　1.2-dihydro-2,2,4-trimetbylq uinoline) Note 4: Titanium IV, 2-propaturate (propa nolato).

Tris-(dodectyl)benzenesulfonate (sulfonato) -0 Note 5: N,Nn-dimaleimide This invention Golf balls obtained using this compound have excellent properties. That is, excellent It offers excellent elasticity, durability, economy, and continuous reproducibility.

The main feature of the invention is the use of zinc methacrylate salt to cross-link butadiene. . This zinc methacrylate salt is noteworthy. That is, the cross-coupling energy is Commercially acceptable zinc salts obtained from acrylic acid similar in energy, but produced from the salt cross-linked with polybutadiene. The resulting golf balls will be superior to currently commercially available golf balls. ing.

Zinc methacrylate salt is traditionally made by converting methacrylic acid to zinc oxide (zinc oxide). It has been produced by chemical reaction with e). According to the invention, the production of zinc salt The chemical reaction required for stoichiometric zinc oxide It is carried out in a large volume of air, 10% more than what is used. Oxygen in reaction action Feeding interferes with polymerization of methacrylic acid during mixing with polybutadiene rubber . Zinc salt and polybutadiene are mixed in a roll mill. , a corrugated surface is provided on one side. get good Radiant heat dissipating surface keeps internal temperatures low and delays curing until sent to molding process exert an effect. The temperature is lower than the polymerization temperature. It is desirable that the temperature be maintained at a low temperature of 75 degrees Celsius. As a result, polymerization and curing The phenomenon will occur during the molding process and not during the mixing process.

In accordance with the present invention, the zinc methacrylate salt is prepared using a 44 lb. zinc oxide charge (charg. e) with 0.25 bonds of stearic acid at 85% Produced by supplying 1,000 pounds of methacrylic acid. 20 ml of sulfuric acid (s Add ulfuric acid). Zinc oxide and Stearic acid was mixed with heptane and 1.1.1-trichloroethane ( trichloroethane) in approximately the same volume, and has a specific gravity of approximately 0°98. Diffuses in solvent. Rotary vacuum drying of methacrylic acid and sulfuric acid while the chemical reaction is in progress. Add to dryer and heat to 85 to 90 degrees Celsius.

Thereafter, the solvent containing zinc oxide is introduced into the dryer. Prevents polymerization of zinc salts Air blasts of 1 second each are performed at 30 second intervals to achieve this. said rotation After about 0.75 hours in the vacuum dryer, the solvent and water produced by the reaction were removed under vacuum. Substantially removed by equipment to obtain solid zinc methacrylate salt. The zinc salt further dried and then ground to a particle size of 1 to 30 microns. . This salt is from Yardley Ba1 in Milton, Florida. l) The product name is Z-Max MA (Z-Max) by Corporation. The product name is used in this specification.

Comparative Examples 1 to 6 and Comparative Examples 8 to 12 define the present invention in more detail. It is. Z-Max, Z-Max cross-linked with polybutadiene and alone or Two other commercially produced salts cross-linked by polybutadiene were analyzed and compared. The analysis was conducted at an office in Cambridge, Massachusetts. It was conducted by Sir Day Little Laboratories (ADL). Comparison with Z-Max The salts were manufactured by Sartomer, Exton, Pennsylvania. ), a product with the trade name "Saltomer 365", and Rockland React Light in Cartersville, Georgia The product name manufactured by React-Rite) is “Reactra”. It was a product called "Ito". Two different Z-Max samples were analyzed. Ta. One sample was from Yardley Pole Corporation in Pennsylvania. The sample was manufactured in an old factory, and the other sample is in a factory in Florida that is currently in operation. It was manufactured at a new factory in . Pennsylvania sample is representative of Z-Max which has undergone a long period of time before being hardened. Therefore, the manufactured rubber It is expected that the elasticity of golf balls will be poor and desirable golf balls will not be produced. Ru. Z-Max is cross-linked with polybutadiene within one week before manufacturing. It is desirable to do so.

Examples 1 to 6 and Examples 8 to 12 were cured using Z-Max and Z-Max. polybutadiene has over other commercially available zinc methacrylates. It shows many characteristics. First of all, Z-Max has a higher zinc content than others and has a fresh Z-Max has higher heat dissipation during polymerization than others. Z-Max X-ray circuit The fold pattern shows a stronger peak between 11 and 12 degrees than the others, indicating that Z- The particle size of Max is the smallest within the group analyzed. Z-Max FT The IR spectrum shows a more prominent CO crystalline peak. All Z-Max samples have the highest solubility in xylene. there was. The fresh Z-Max sample had the highest heat of cure, and the Z-Max cured pot had the highest heat of cure. Libutagene has the highest Shore hardness. Furthermore, all Z - The Max sample has a lower swelling index (swe) than the other tested samples. ll1ndices).

Examples 1 to 6 as shown below are 1) component analysis, 2) differential scanning 3) X-ray diffraction, 4) microscopic examination (microsc).

5) Fourier transform infrared spectroscope and 6) xylene solubility. The results of this analysis are presented.

Example 1 The zinc content in the sample was analyzed by plasma analysis.

Each sample was dried in a vacuum apparatus and albraith Institute (GLI) for zinc, carbon and hydrogen content. An analysis was conducted. The analysis results are as follows.

Weight % of constituents within zinc salt Salt %Zn %C%H%0 GLI ADL difference (difference) theoretical Zinc methacrylate 27.8 N, A, 40.8 4,3 27.2 (Th eoretical Zinc Methacrylate) PAZ-Maxi-9130, 6N, A, 35.8 3.9 29.7PAZ -MaxlO-90N, A, 29 37.8 4.0 29FLZ-Max 28.2 N, A, 38.3 4.1 29.4 Saltoma-36529,42 937,73,829,1 React Light 27.0 27 39.5 4,5 All samples except 29゜0 ReactRite (especially FL Z-Max sample) contained more zinc than the theoretical value. All samples (especially FLZ-Max sample) contains more oxygen than the theoretical value and less carbon than the theoretical value. Ta. These results are due to the well-known addition of excess zinc oxide in the manufacturing process of Z-Max. Consistent with the above, the salts (especially FLZ-Max) were oxidized. It shows. In terms of hydrogen content, the Z-Max sample and the Sartomer sample The hydrogen content of the Reactlite sample was lower than the theoretical value. It was higher than the value. From this result, Reactlite is a product of unreacted methacrylic acid or its It is estimated that it contained a polymer.

Example 2 The heat of reaction determined by thermal analysis has a correlation with the chemical reaction during curing of polybutadiene. What they are doing is well known in this field. Each sample at 10 degrees Celsius/min. DuPont 91 with oven lamp 0 Differential scanning calorimeter (DSC) is used and sealed. The analysis was conducted in a heated nitrogen atmosphere up to 300 degrees Celsius in a pan.

Each sample shows an exothermic peak due to heat generated during polymerization. Ta. Polymerization heat at those peak temperatures and Joule heat (17g) per duram was recorded. Older Z-Max samples also contain crystalline seeds, probably formed during storage ( crystalline 5 pecies), it has an endothermic property of dissolution ( Endothermic) fever. The structure of the cured polymer depends on the cooling rate. This is an important factor.

DSC results with ZN salt Characteristics/Salt PA Z-Max FL Z-Max React Saltmer/Rye G 365 Endothermic 28.617g None None None 130 degrees Celsius Heat dissipation 17g 138 170 61 73.9 Peak temperature (degrees Celsius) 140 217 115 225 Heat dissipation J/g 243 None N, A, 62 ．． 7 degrees Celsius 125 degrees for 15 minutes Quench and time After cooling with Peak temperature (degrees Celsius) 209 N, A, N, A, 218 dissolution, polymerization and by liquid nitrogen Cooling 17g 57.5 N, A, N, A, 70.9 Peak temperature (degrees Celsius) 213,248 260 N, A, N, A, 221 Example 3 To perform X-ray diffraction spectroscopy, each dry powder was placed in an aluminum frame. It was compressed inside. The diffraction pattern with CuK alpha radiation indicates that there is an acid in the sample. This shows that no zinc chloride remains.

X-ray diffraction peak angle Angle PA PL React Saltoma-Z-Max Z-Max / Light 3657.3 Strong None None Weak 9.8 Strong Strong Strong Very strong 10.6 Medium Medium Slightly Strong Very Strong 11.6 Slightly strong Slightly strong Weak Medium crystal part Extent 2 3 4 (minimum) 1 (maximum) (Extent) The reactolite sample clearly has the largest amorphous phase and the other two types of samples It is one of multiple phases similar to , and has less crystalline phase than the others. Z-Max Sump The sulfur and saltomer samples appear to contain mostly crystals, and all samples The pull had at least four crystal planes. Sartomer samples are especially angular Strong binding force at peak angles of 9 to 10 degrees and 10 to 11 degrees. and showed the most complex crystal pattern. To confirm, take an X-ray spectrum Used on a well-known zinc acrylate and compared to that of a methacrylate sample. did.

PAZ-Max sample and Sartra-365 after treatment with ethyl alcohol The X-ray spectra of the samples were shown to be similar, with both having strong peaks. existed between angles 9 and 10 degrees and slightly below angle 11 degrees. Treatment with alcohol Rigo no Nori Actolite has its only crystalline peak at an angle slightly below 11 degrees; It had a wide range of amorphous peaks at the bottom.

Example 4 Microscope of various zinc methacrylate samples at 150x and 300x magnification Inspected using a mirror. Z-Max particles are the smallest and most rounded. , Sartomer particles were the largest and had crystalline, highly angular planes. tree Reactolite in silene exhibited birefringence. That is, amorphous phase and crystalline phase It is estimated that the shape is in the process of changing.

Microscopic examination Method PA PL React Saltoma-Z-Max Z-Max/Light 365 microscope Micron is 5-200 Diameter 3-10 up to 35 1-5 5-25 up to 200 Shape All irregular Irregular round & needle-like Crystal, some particles, rectangular crystal plate crystal & amorphous or incompletely crystallization Samples that are smaller than others in Z-Max have a larger surface area than others. It has the same meaning as , and the activity increases accordingly. Z-Max made in Florida is Sartoma It seemed to be an even more imperfect crystalline substance compared to -. Z-Max particle size Izu was much smaller than the other two salts. Sartomer sample is It appeared to be well crystalline as examined by X-ray. react try The sample had a mixture of needle-like crystals and irregular round amorphous particles. .

For confirmation, the well-known Sartomer zinc acrylate methacrylate) and methacrylate (methacrylate). ate).

Example 5 More than 40 scans using Bio-Rad FTS spectrophotometer The results were averaged. Infrared spectra vary from sample to sample. It had become. That is, in the Z-Max sample, carbon-oxygen bonds normally appear. Additional bands in 1090 reciprocal am ( band). Also, the Z-Max sample has more crystalline peas than the others. It showed. The crystal shape of Z-Max is clearly different from other salts analyzed. there was.

Results from infrared spectroscopy CO Peak PA PL React Sartomer-365Z-Max Z-Max /Light 1090 Co band Co band No surplus Co No surplus Co 1545 and 710 Yes More than Less Suggests less crystalline state Example 6 A large quantity of xylene was thoroughly mixed with the measured zinc salt sample. The remaining solvent is huge. removed. Before performing the measurement, dissolve the solubility using a heat lamp. xylene was volatilized from both the le) and insoluble portions. . The weight ratio of the collected amount (some of which disappears in the evaporation process) is below. It was as follows.

xylene solubility PA Z-Max FL Z-Max Reactlite Soluble Non-Soluble Dissolve Characteristic: Non-soluble Soluble: Non-soluble FLZ-Max is 10% lower than PAZ-Max. % of non-soluble substances. Contents of PAZ-Max ash corresponds to 29% to 30% zinc in the dissolved phase and insoluble part. It was. FLMax showed similar results. Regarding React Light, the soluble part The ash content in minutes corresponds to 32% zinc, and the undissolved part corresponds to 26%. there was.

Next, the core material of a solid one-piece golf ball or a two-piece golf ball. Let me explain about the usual compounds that serve as basic materials. In other words, it is as follows.

Butadiene rubber, i.e., cis-1,4 polybutadiene rubber, is the main rubber. Although it is an elastomer component, it can also exist in small amounts in other elastomers. be. For example, to lower the modulus (a + odulus) and increase durability. You can add natural rubber to it. Components and free radicals of zinc methacrylate salt or solids with a number of other ingredients in addition to the peroxide priming agent. It can be added to golf ball formulations. The compounds of the present invention are usually Zinc oxide and barium sulfate (b) are used to control the weight of golf balls. fillers such as arium 5 ulfate), lead oxide, and basic lead silicate. or a combination thereof. Other possible additions include fillers and/or or magnesium oxide as acid acceptors; calcium carbonate, and silica , carbon black, clay, and other reinforcing fillers (mildly re informing fillers) and/or core drugs (nuclea ting agents), as well as bonding agents and/or diffusion agents. Silanes and/or titanium as dispersing agents titanates, and also during manufacturing process acceleration, heat and storage In order to prevent the quality deterioration of (shelf aging properties) There are antioxidants such as HVA-2, TMPTA and TMPTMA. co-curing agents, or even sulfur and sulfur Curing adjustment of sulfur bearing compounds, etc. granular or powdered high molecular weight polymerizing agent as an impact modifier, and It has various properties well known by experts in the field of rubber compounds for the production of rubber balls. There are pigments and other ingredients for the application.

Thereafter, the compound is mixed in a suitable wire mixer (k) such as a roll mill or a panberry mixer. (neader), mixer or blender. Next, the rubber compound A product is molded using, for example, a heat pressure molding method. one piece gol Fuball is made by heat-pre-sodching the rubber compound and forming it into a golf ball. Manufactured by appropriate size. On the other hand, two-piece golf balls are solid In order to mold the core, heat pressure molding is performed using a core molding mold of an appropriate size. , by covering the core with a cover of a suitable material. As for the cuckoo , for example, an ionomar resin as the main component and optionally carbon dioxide. Manufactured with fillers or pigments such as titanium or zinc oxide. Said sled The head core is covered with two covers pre-molded into a hemispherical shape, and the golf ball as a product is The two covers are bonded together by heat pressure molding to produce a . Injection molding is also used to cover the core. This is a possible means.

One important embodiment of the compounds of the invention is a high cis polyester as the primary elastomer. Butadiene, Z-Ma ranging from 20 to 70 per 100 elastomer weight xMA crosslinker, filler-for-we light) Basic lead silicate ranging from 5 to 15, dioxide ranging from 0 to 15 titanium pigment, magnesium oxide acid acceptor ranging from 0 to 5 (magn esium oxide acid acceptor), in the range of 0 to 2 Agerite resin antioxidant, CAP ranging from 0 to 2 OW KR9S/H titanate, 0. Vul Cup R in the range of 1 to 3 Contains peroxide initiator, HVA-2 curing synergist in the range of 0 to 2 It is something that The above-mentioned compounding agent was added to Panberry ( Banbury) Mix in a mixer or roll mill and heat at 175 degrees Celsius for 1. Mold for 20 minutes in a 72 inch golf ball mold.

The following are examples of preferred embodiments.

Example 7 High performance one piece golf ball Blend: GB-1 weight percentage Polybutadiene (high cis) 100Z-Max MA ( Note 1) 48 Basic lead silicate 6 Titanium dioxide 3 Magnesium oxide 1 Agierite Resin D (Note 2) 0.03 CAPOW KR9S/H (Note 3) 0 ．． 20Vul Cup R (Note 4) 0. 53HVA-2 (Note 5) 0.　 16 Total 158.98 Note 1 = Zinc methacrylate salt - Yardley Ball Corporation Note 2: Polymerization 1, 2-dihydro-2,2,4-)limethylquinoline-R,T, Panderbilt ( Vanderbilt Company) Note 3: Titanium IV, 2-propatz salt, tris-(dodectyl)benzenesulfonate-〇 -Kenrich Petrochemicals, Inc.

Note 4: t-butyl cumyl peroxide-vercules ink.

Note 5: N, N-n-Fini Dilene Dimaleimide-E, 1. Dupont de Nemor & Company (E, 1. DuPont do Nemours & 　Co,) Characteristic ball characteristics obtained Shore C93 Compression 122 CORO, 796° 1, V, ft/sec 254.6 Comparative Examples 8 to 12 below show conventional salt-polybutadiene compounds and Z-Max-polybutadiene compounds. Describes the differences between ribtagene compounds. The compound is prepared according to the teachings of the present invention. did.

The following analyzes were performed. Namely: 1) temperature of the rubber at which it crystallizes and cures; 2) curing. Exothermic recrystallization heat of the sample (heat), 3) Shore hardness, 4) Expansion index.

Example 8 The following components are equipped with an electric heater, air cooler, and variable speed 1 horsepower GP100 type drive machine. Eta PL-V2O3 type Brabender plastic corder Plasticorder (Product No. 177518).

Inert (1nert) for inspection by infrared spectrophotometry The pigment titanium dioxide was excluded.

Number of grams Ingredients 34.5 High cis polybutadiene Manufactured by Dunlops Radienger Greenville, South Carolina 0.138 Agierite resin D R, T, manufactured by Pandelbilt Poly(trimethyldihydroquinoline) antioxidant 0.3485 Magnesium oxide, 0.069 Capow K as a neutralizing agent R9S/H made by Kenritsu Betri Chemiru Co., Ltd. Monoalkoxytitanate coupling agent (m onoalkoxytitanate coupling agent on a hydroxylated silicon dfoxide carrier r) To dissolve the rubber, the said material is heated in a temperature range of 90 to 100 degrees Celsius. Mixed for 1 to 12 minutes. Then reduce the stirring speed and bring the mixture to about 96 degrees. The angle was set to 108 degrees. Next, the four zinc salts of methacrylic acid, namely sultomer 3 65, React Light, PA Z-Max or FLZ-Max. Only 5.962g was added. Take care not to let the temperature exceed 113 degrees Celsius. After stirring for a minute, reduce the stirring speed, reduce the temperature to approximately 102 degrees Celsius, and proceed as described below. Added hardener.

Number of grams Ingredients 0.1242 DiCup R Manufactured by Hercules, dicumyl peroxide 0.1242 Vul Cup R Manufactured by Hercules, t-butyl cumyl PE peroxide 0.0552 HVA-2 DuPont, N,N'-m-phenylene bismalei Mid (N, N'-m-phenylene bismaleimide) Rapid hardening In order to prevent these components from forming, the temperature is lowered from 100 to 102 degrees Celsius Mixed for 6 minutes. Using a press, press at 160 degrees Celsius with a 4-inch ram. A cylindrical shape of 6 mm thick and 32 mm wide was subjected to 10,000 pounds of pressure for 20 minutes A molded article was manufactured. The round molding had an outer diameter of about 2 inches.

Example 9 The sample in the formulation was cured in a DSC with the rubber, resulting in crystallization and hardening of the rubber. The heat at oxidation was measured. This critical heat dissipation was determined at 20 degrees Celsius/min.

Previous crystal heat dissipation was determined at both 5 and 20 degrees Celsius.

DSC heat of hardening and crystallization Zinc salt PA Z-Max FL Z-Max Sartomer React 365 /light 20 degrees Celsius/min dust Curing heat J/g Initial spike 5.50 8,78 6.14 17.28 Wide area 2nd temperature Mr. Se 46.21 95.80 46.93 22.96 1st beak: Onset 159.1 158.8 159.2 159.1 Peak 162 ．． 1 161.6 162.0 161.8 2nd beak: Peak 190.4 189.5 192.9 196.4 Celsius 5 degrees/min increase rate First peak: (159 degrees Celsius): Heat, 17g 5.48 6.93 6,37 5.49 The above results are FLZ-M The ax sample was cured with more than twice the activity compared to Sartomer-365. ing. The peak of react light is not only narrow in area but also wide. They were scattered. Curing heat was highest for FLZ-Max and lowest for Reactlight. .

When the uncured formulation is heated at 20 degrees Celsius/min, the heat after the first peak reaches the base line. It then moves to a second peak. Other rapid heat dissipation spikes are caused by uncured It occurs in cured rubber at the same temperature as in the compound, so the temperature increases at the same rate. When adding heat, the first heat dissipation peak is due to crystal restructuring, and the second heat dissipation peak is due to crystal restructuring. It is presumed that this is due to a curing reaction. The best results are determined by microscopic examination and X-ray examination. Reactlite samples, which appear to have low crystallinity, were heated at a heating rate of 20 degrees Celsius/minute. It had the highest crystal heat dissipation at 5 degrees Celsius/min, but the lowest heat dissipation at a heating rate of 5 degrees Celsius/min. Met. This difference means that the sample is not homogeneous. That's telling.

Example 10 The radiation recrystallization heat of the cured sample was measured. The curing process was carried out for 20 minutes. , the transformation process of the cured compound as described below is more physical than chemical. The conclusion was that there is. In all cases, the cured rubber spike heat dissipation is It started at 157.5 degrees Celsius and peaked at 158 to 159 degrees Celsius. this When the cured rubber is programmed into the DSC at a temperature increase rate of 5 degrees Celsius/minute, These slightly cured rubbers exhibited spike heat dissipation at approximately 159 degrees Celsius. This is a restructuring of the structure. This is thought to be due to the configuration.

heat dissipation process Zinc salt radiant heat, J/g 158 to 159 degrees Celsius PA Z-Max 15. 4 FL Z-Max 15.8 SR36519,0 React/Light 7.64 The above samples (with the exception of very low curing Reactolite) were similar. This is especially true when zinc methacrylate is absent or active. carbon-carbon bonds formed by peroxides when It is inferred that this is due to the form of cross-linking.

Example 11 Shore hardness measurements were performed on all samples. each molded product for at least 5 days It was measured after the elapsed time. According to ASTM standards, 5 samples should be at least 0. ．． Measured at a 5 inch point. The average of those measurements is listed below.

shore hardness Zinc salt hardness value average PA Z-Max 49 47 50 49 51 49. 2FL Z-Ma x 49 52 53 51 54 51.8 Saltoma-3654748484 84847,8 React Light 26 28 26 26 26 26. 4Z - The Max sample is harder than the other two samples, i.e. This indicates a high degree of cross-linking reaction with the reagent.

Example 12 The swelling index was determined for each sample. This index is made of hardened rubber It represents the equilibrium weight of toluene absorbed in the rubber divided by the initial weight of the rubber. example For example, an absorption rate of 69% results in an expansion index of 0.69. of the above molded product Immediately after opening, place a portion in sufficient amount of scintillation grade toluene for 4 hours. Observed for days. Daily blot of swollen rubber sample L, g The number was measured. Error in blotting technique Therefore, the last digits of the numbers listed below are not necessarily accurate.

Weight of polybutadiene including toluene Zinc salt/days 0 1 23 4 PA Z-Max 2.267 3.652 3.693 3.755 3.8 28FL Z-Max 2.281 4.534 4.752 4.752 4 ．． 708 Saltoma-3651, 9923, 9894, 1364, 2434, 29 1 react/light 2.508 5.7?1 5.819 5.870 5. After 9324 days, the solvent absorption was 69% by weight for PAZ-Max and 69% by weight for FLZ-M. 106% against ax, 115% against Sartomer, against Reactlite. It was 136%. These differences are due to the polybutadiene cured by Z-MaX. Polybutylene is highly resistant to solvents and therefore This shows that the degree of cross-linking is higher than that of

The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. It would be possible to materialize it. Therefore, this example is for illustrative purposes only. is not intended to limit the scope of the invention, and the true scope of the invention is determined by the specification. It is indicated within the scope of the claim rather than the description, and includes equivalent forms. It is. Therefore, various modifications can be made within the scope of the present invention as defined in the claims. It goes without saying that it is possible.

Copy and translation of written amendment) Submission (Article 184-7 of the Patent Law, page 1, 1992, 06/06/2002 19th prisoner

Claims (14)

[Claims] 1. A method of manufacturing an improved high performance one-piece golf ball comprising: A manufacturing method comprising steps (a), (b) and (c). (a) A step of providing a golf ball forming compound having the following components. (i) At least 75% by weight of cis-1,4 polybutadiene (100%) ) (ii) zinc methacrylate salt ranging from 20 to 70 parts per 100 parts rubber; (It is the product of a chemical reaction between zinc oxide and methacrylic acid. The reaction reduces polymerization. It is carried out in the presence of oxygen. Sufficient acid to prevent polymerization of zinc salts element into the reaction process. ) (iii) basic lead silicate ranging from 0 to 15 parts per 100 parts rubber; (iv) titanium dioxide ranging from 0 to 15 parts per 100 parts rubber; (v) Magnesium oxide ranging from 0 to 5 to 100 parts of rubber (vi) 10 parts of rubber Polymerized 1,2-dihydro-2,2,4-trimethyl groups ranging from 0 to 2 relative to 0 Titanium IV. Lopanolate, tris-(dodectyl)benzenesulfonate-O (viii) a free radical initiator (init (iator) (ix) N,N-n-phenylene dimerey in the range of 0 to 2 per 100 rubber Mido (b) mixing the compounds of step (a) to form a reaction mixture; (c) molding the compound to form a golf ball; 2. 2. The method of claim 1, wherein in step (a)(ii) methacrylic The acid zinc salt has a cross-linking energy of at least 180 J/g. A method of manufacturing an improved high performance one-piece golf ball having the following characteristics. 3. 2. The method of claim 1, wherein in step (a)(iii) basic lead An improved version characterized in that the silicate content ranges from 5 to 15 parts per 100 parts rubber. A method of manufacturing a high performance one-piece golf ball. 4. 2. The method according to claim 1, wherein the free radicals in step (a)(viii) The detonator is t-butyl tamyl (cumyl) peroxide. A method of manufacturing an improved high performance one-piece golf ball. 5. 2. The method of claim 1, wherein step (b) Improved high-performance one-piece golf ball featuring performance in a temperature range of 0 degrees How to make a roll. 6. 2. The method of claim 1, wherein step (c) is carried out at 175 degrees Celsius. Manufactures an improved high-performance one-piece golf ball that is characterized by a 0 minute run time. how to. 7. A compound characterized by having the components described below. (a) Cis-type 1,4 polybutadiene rubber (assumed to be 100) (b) zinc methacrylate salt ranging from 20 to 70 parts per 100 parts rubber; (It is the product of a chemical reaction between zinc oxide and methacrylic acid. The reaction reduces polymerization. It is carried out in the presence of oxygen. Sufficient acid to prevent polymerization of zinc salts element into the reaction process. ) (c) basic lead silicate ranging from 5 to 15 parts per 100 parts rubber; (d) 10 parts rubber; Titanium dioxide (e) rubber ranging from 0 to 15 Magnesium oxide (f) ranging from 0 to 2 per 100 rubber 1,2-dihydro-2,2,4-trimethylquinoline (g) Titanium IV,2-propanol ranging from 0 to 2 parts per 100 parts rubber. acid salt, tris-(dodectyl)benzenesulfonate-O (h) t-butyl cumyl peroxide in a range of 0.1 to 3 per 100 rubber; (i) N,N-n-phenylene dimerium in the range of 0 to 2 per 100 rubber de 8. A high-performance one-piece golf ball containing the following components: A one-piece golf ball characterized by being formed from a material. (a) Rubber containing 75% cis-type 1,4 polybutadiene rubber (assumed to be 100) (b) zinc methacrylate salt ranging from 20 to 70 parts per 100 parts rubber; (It is the product of a chemical reaction between zinc oxide and methacrylic acid. The reaction reduces polymerization. It is carried out in the presence of oxygen. Sufficient acid to prevent polymerization of zinc salts element into the reaction process. ) (c) basic lead silicate ranging from 0 to 15 parts per 10 parts rubber; (d) 10 parts rubber; Titanium dioxide (e) rubber ranging from 0 to 15 Magnesium oxide (f) ranging from 0 to 2 per 100 rubber 1,2-dihydro-2,2,4-trimethylquinoline (g) Titanium IV,2-propanol ranging from 0 to 2 parts per 100 parts rubber. acid salt, tris-(dodectyl)benzenesulfonate-O (h) a free radical initiator ranging from 0.1 to 3 parts per 100 parts of rubber; (i) 100 parts of rubber; N,Nn-phenylene dimaleimide ranging from 0 to 2 for 9. 9. The golf ball of claim 8, wherein the basic lead silicate is rubber. Improved high performance one piece characterized by a range of 5 to 15 per 100 golf ball. 10. 9. The golf ball of claim 8, wherein the free radical initiator is a t-button. Improved high-performance one-piece golf characterized by being made of chircumyl peroxide ball. 11. A method of manufacturing an improved high performance one-piece golf ball, the method comprising: A manufacturing method comprising steps (a), (b) and (c). (a) A step of providing a golf ball forming compound having the following components. (i) 75% polybutadiene by weight (assumed to be 100) (ii) zinc methacrylate salt ranging from 20 to 70 parts per 100 parts rubber; (It is the product of a chemical reaction between zinc oxide and methacrylic acid. The reaction reduces polymerization. It is carried out in the presence of oxygen. Sufficient acid to prevent polymerization of zinc salts element into the reaction process. ) (iii) a filler ranging from 0 to 15 per 100 parts of rubber; (iv) a filler per 100 parts of rubber; Polymerized 1,2-dihydro-2,2,4-trimethylquinoline ranging from 0 to 2 (v) Titanium IV,2-propanol ranging from 0 to 2 parts per 100 parts rubber. acid salt, tris-(dodectyl)benzenesulfonate-O (vi) a free radical initiator ranging from 0.1 to 3 parts per 100 parts of rubber; (vii) rubber; N,Nn-phenylene dimaleimide ranging from 0 to 2 per 100 (b) mixing the compounds of step (a) to form a reaction mixture; (c) molding the compound to form a golf ball; 12. A compound characterized by having the components described below. (a) Cis-type 1,4 polybutadiene rubber (assumed to be 100) (b) zinc methacrylate salt ranging from 20 to 70 parts per 100 parts rubber; (It is the product of a chemical reaction between zinc oxide and methacrylic acid. The reaction reduces polymerization. It is carried out in the presence of oxygen. Sufficient acid to prevent polymerization of zinc salts element into the reaction process. ) (c) basic lead silicate ranging from 0 to 15 parts per 10 parts rubber; (d) 10 parts rubber; Titanium dioxide (e) rubber ranging from 0 to 15 Magnesium oxide (f) ranging from 0 to 2 per 100 rubber 1,2-dihydro-2,2,4-trimethylquinoline (g) Titanium IV,2-propanol ranging from 0 to 2 parts per 100 parts rubber. acid salt, tris-(dodectyl)benzenesulfonate-O (h) t-butylcumyl peroxide in a range of 0.1 to 3 per 100 parts rubber; (i) N,N-n-phenylene dimerium in the range of 0 to 2 per 100 rubber de 13. A method of manufacturing an improved high performance one-piece golf ball, the method comprising: A manufacturing method comprising steps (a), (b) and (c). (a) A step of providing a golf ball forming compound having the following components. (i) 75% polybutadiene by weight (assumed to be 100) (ii) zinc methacrylate salt ranging from 20 to 70 parts per 100 parts rubber; (It is the product of a chemical reaction between zinc oxide and methacrylic acid. The reaction reduces polymerization. It is carried out in the presence of oxygen. Sufficient acid to prevent polymerization of zinc salts element into the reaction process. ) (iii) a filler ranging from 0 to 15 per 100 parts of rubber; (iv) a filler per 100 parts of rubber; Antioxidant in the range of 0 to 2 (v) in the range of 0 to 2 per 100 parts of rubber. coupling agent or diffusing agent (vi) a free radical initiator ranging from 0.1 to 3 parts per 100 parts of rubber; (vii) rubber; Co-curing agent (co-curing agent) ranging from 0 to 2 in 100 ) (b) mixing the compounds of step (a) to form a reaction mixture; (c) molding the compound to form a golf ball; 14. Commercially available zinc methacrylate salts with xylene solubility of 50% or more. It has the same or higher cross-linking energy than the available zinc acrylate salt. A zinc methacrylate salt characterized by: