AU620264B2

AU620264B2 – Rubber composition for cover layer of golf ball
– Google Patents

AU620264B2 – Rubber composition for cover layer of golf ball
– Google Patents
Rubber composition for cover layer of golf ball

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Publication number
AU620264B2

AU620264B2
AU62476/90A
AU6247690A
AU620264B2
AU 620264 B2
AU620264 B2
AU 620264B2
AU 62476/90 A
AU62476/90 A
AU 62476/90A
AU 6247690 A
AU6247690 A
AU 6247690A
AU 620264 B2
AU620264 B2
AU 620264B2
Authority
AU
Australia
Prior art keywords
group
rubber
fibers
rubber composition
independently represents
Prior art date
1987-06-11
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)

Ceased

Application number
AU62476/90A
Other versions

AU6247690A
(en

Inventor
Takuo Morimoto
Kihachiro Nishiuchi
Masayoshi Suzue
Yasuyuki Tokui
Kenichi Wada
Syoji Yuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Otsuka Chemical Co Ltd

Asics Corp

Original Assignee
Asics Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
1987-06-11
Filing date
1990-09-13
Publication date
1992-02-13

1987-06-11
Priority claimed from JP62146019A
external-priority
patent/JPH0643526B2/en

1987-06-12
Priority claimed from JP62147218A
external-priority
patent/JPH0626627B2/en

1987-06-12
Priority claimed from JP62147221A
external-priority
patent/JPS63311973A/en

1987-06-12
Priority claimed from JP62147219A
external-priority
patent/JPS63311971A/en

1987-06-12
Priority claimed from JP62147220A
external-priority
patent/JPS63311972A/en

1990-09-13
Application filed by Asics Corp
filed
Critical
Asics Corp

1990-12-13
Publication of AU6247690A
publication
Critical
patent/AU6247690A/en

1992-02-13
Application granted
granted
Critical

1992-02-13
Publication of AU620264B2
publication
Critical
patent/AU620264B2/en

2008-06-09
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
Critical
Current

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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS

C08L21/00—Compositions of unspecified rubbers

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients

C08K7/00—Use of ingredients characterised by shape

C08K7/02—Fibres or whiskers

C08K7/04—Fibres or whiskers inorganic

A—HUMAN NECESSITIES

A63—SPORTS; GAMES; AMUSEMENTS

A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT

A63B37/00—Solid balls; Rigid hollow balls; Marbles

A63B37/0003—Golf balls

A—HUMAN NECESSITIES

A63—SPORTS; GAMES; AMUSEMENTS

A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT

A63B37/00—Solid balls; Rigid hollow balls; Marbles

A63B37/0003—Golf balls

A63B37/0023—Covers

A63B37/0024—Materials other than ionomers or polyurethane

A—HUMAN NECESSITIES

A63—SPORTS; GAMES; AMUSEMENTS

A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT

A63B37/00—Solid balls; Rigid hollow balls; Marbles

A63B37/0003—Golf balls

A63B37/0038—Intermediate layers, e.g. inner cover, outer core, mantle

A63B37/0039—Intermediate layers, e.g. inner cover, outer core, mantle characterised by the material

A—HUMAN NECESSITIES

A63—SPORTS; GAMES; AMUSEMENTS

A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT

A63B37/00—Solid balls; Rigid hollow balls; Marbles

A63B37/0003—Golf balls

A63B37/005—Cores

A63B37/0051—Materials other than polybutadienes; Constructional details

A—HUMAN NECESSITIES

A63—SPORTS; GAMES; AMUSEMENTS

A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT

A63B37/00—Solid balls; Rigid hollow balls; Marbles

A63B37/0003—Golf balls

A63B37/007—Characteristics of the ball as a whole

A63B37/0072—Characteristics of the ball as a whole with a specified number of layers

A63B37/0074—Two piece balls, i.e. cover and core

A—HUMAN NECESSITIES

A63—SPORTS; GAMES; AMUSEMENTS

A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT

A63B37/00—Solid balls; Rigid hollow balls; Marbles

A63B37/0003—Golf balls

A63B37/007—Characteristics of the ball as a whole

A63B37/0072—Characteristics of the ball as a whole with a specified number of layers

A63B37/0075—Three piece balls, i.e. cover, intermediate layer and core

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients

C08K9/00—Use of pretreated ingredients

C08K9/04—Ingredients treated with organic substances

C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS

C08L7/00—Compositions of natural rubber

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC

Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y10S524/00—Synthetic resins or natural rubbers — part of the class 520 series

Y10S524/908—Composition having specified shape, e.g. rod, stick, or ball, and other than sheet, film, or fiber

Description

IF
620264 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION (Original) FOR OFFICE USE Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority: Related Art: tei 4
I
Name of Applicant: Address of Applicant: ASICS CORPORATION and OTSUKA CHEMICAL CO., LTD.
1-1 Minatojima-Nakamachi 7-chome, Chuo-ku, Kobe-shi, Hyogo-ken, JAPAN; and Bungo-machi, Higashi-ku, Osaka-shi, Osaka-fu, JAPAN, respectively c Actual Inventor(s):
N
I
Syoji YUKI Yasuyuki TOKUI Kihachiro NISHIUCHI Kenichi WADA Masayoshi SUZUE Takuo MORIMOTO Address for Service: DAVIES COLLISON, Patent Attorneys, 1 Little Collins Street, Melbourne, 3000.
Complete Specification for the invention entitled: «RUBBER COMPOSITION FOR COVER LAYER OF GOLF BALL» The following statement is a full description of this ;nvention, including the best method of performing it known to us: -1- RUBBER COMPOSITION FOR COVER LAYER OF GOLF BALL Background of the Invention This invention relates to a rubber composition suitable for a cover layer of a golf ball.
For golf balls, required are flight stability, long flight distance characteristics and the like. The rubber compositions used in golf balls, therefore, are required to have well controlled properties such as bounce impact elasticity, Scompressive strength and hardness, and various rubber compositions having improved properties have been proposed.
t Particularly, an improvement of the rubber composition for cover layer of golf ball is important, since it is air.ctly hit with a .golf club.
S Hitherto, various compositions .comprising ionomer resin as a main component have been proposed, and we already proposed a rubber composition comprising ionomer resin and potassium I titanate fibers (Japanese Patent Application No. 60-202118).
Summary of the Invention The object of the invention is to provide a rubber composition suitable for molding a cover layer of a golf ball, hardness and which can give an excellent feeling upon hitting and a long flight distance when used in a golf ball.
We have now found that a rubber composition having further improved properties and suitable for cover laear of golf ball can be obtained by incorporating surface treated alkali metal S T i Ue o ~~Lrk, lb titanate fibers such as potassium titanate fibers with a sulfur-containing surface treating agent into a rubber component.
Accordingly, the present invention provides a rubber composition for a cover layer of a golf ball, which comprises an ionomer resin component and alkali metal titanate fibers having an average length of 1 pm to 1 mm and an aspect ratio of 5 to 1,000 and being treated with a sulfur-containing surface treating agent.
According to a further embodiment of the present invention there is provided a rubber composition for a cover layer of a golf ball, which comprises at least one natural and/or synthetic rubber component(s) and alkali metal titanate fibers having an average length of 1 pm to 1 mm and an aspect ratio of 5 to 1,000 and being treated with a sulfur-containing surface treating agent, and the composition being vulcanized, provided that said synthetic rubber component does not include an ionomer resin.
91124EAT.007,a:\624i6asLres,2 t J t titanate fibers such as potassium titanate fibers wi a sulfurcontaining surface treating agent into a rub r component.
Accordingly, the present inven n provides a rubber composition for a cover la of a golf ball, which comprises at least one natural /or synthetic rubber component(s) and alkali metal tit te fibers subjected to a surface treatment with a ur-containing surface treating agent.
t *r S #94
S.
**t Sr~ 19#1 4* 5
I
4* 9$o r C c
CC
f C Datailed Description of the Invention As the rubber component of the composition of the invention, any of the various known rubbers can be used. Examples of the rubber component include natural rubber isoprene rubber styrene-butadiene rubber (SBR), nitrile rubber (NBR), butadiene rubber chloroprene rubber butyl rubber (IIR), acrylic rubber urethane rubber silicone rubber (SiR), fluorocarbon rubber ethylene-propylene rubber (EPR), chlorosulphonated polyethylene (CSM), ethylene-vinyl acetate rubber (EVA), chlorinated polyethylene (CPE), polyisobutylene (PIB), alfin rubber polyester rubber (ESR), epichlorohydrin rubber (ECR), chlorinated isobutylene-isoprene rubber (CIR), nitrile-isobutylene rubber (NIR), ionomer resin, trans-polyisoprene resin and the like.
Among those rubber components mentioned above, ionomer resin and trans-polyisoprene resin are particularly preferable from the viewpoint of the high elasticity and wear resistance.
When ionomer resin is used as the rubber component of the present composition, the composition need not to be vulcanized with any vulcanizing agent since ionomer resin is thermoplastic and can have sufficient hardness without vulcanization.
r~ A Ar
O
A ti t
A*
Ve I r- y m a As an example of the ionomer resin, it can be mentioned an ionic copolymer which is obtained by reacting a copolymer of an a-olefin represented by the general formula of R-CH=CH 2 wherein R represents an alkyl group having 1 to 8 carbon atoms and an a,8-unsaturated carboxylic acid having 3 to 8 carbon atoms with a metal compound.
Examples of the a-olefin mentioned above include ethylene, propyrene, butene-1, pentene-1, hexene-1, heptene-1, 3-methylbutene-l, 4-methylpentene-1 and the like. Though a-olefins having larger numbers of carbon atoms than those mentioned above may be used in the present invention, they are unsuitable for the practical use because of their unavailability.
These a-olefins may be used alone or in any combination thereof.
The content of the a-olefins in the copolymer is preferably at least 50 molar particularly at least 80 molar from the view point of the moldability and. physical properties of the composition.
Examples of the a,8-unsaturated carboxylic acid having 3 to 8 carbon atoms include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, maleic acid, fumaric acid; monoester of dicarboxylic acid such as monomethyl maleate and monoethyl fumarate; and anhydride of dicarboxylic acid such as maleic anhydride, but it is not limited to those specific examples.
These a,8-unsaturated carboxylic acids may be used alone or in any combination thereof. The content of a,8-unsaturated carboxylic acid in the copolymer is preferably in the range of to 25 mole particularly in the range of 1 to 10 mole Further, the copolymer may contain any monomer component other than the a-olefin and a,8-unsaturated carboxylic acid, which is r a copolymerizable with the a-olefin and a,8-unsaturated carboxylic acid to replace a part of the a-olefin. Examples of such monomer include styrene, vinyl chloride, vinyl acetate, acrylonitrile vinyl methyl ether and the like.
The copolymer composed of the a-olefin and the a,8-unsaturated carboxylic acid is not limited to those obtained by directly copolymerizing a mixture of the monomers, and it also includes those obtained by graft polymerization where the a,8-unsaturated carboxylic acid monomers are grafted on a base polymer produced from the a-olefin.
The ionic copolymer can be obtained by reacting the copolymer obtained as above with a metal compound generating metal ions to neutralize the copolymer.
Examples of the metal ion suitable for the preparation of the ioniccopolymer include those of the metals of Group I and S*o Group II of the periodic table, Na, K, Li, Cs, Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd and Hg, and they can be used alone or in any combination thereof. Owing to the employment of those metal ions, cross-linkings are advantageously formed during the e formation of the ionic copolymer. Among those metal ions cited S above, Na and Zn are particularly preferable from the viewpoint cc c of the melt workability of the copolymer and the physical properties exhibited in the solid state of the copolymer. The amount of the ion to be used or the degree of the neutralization CCt CIC of the copolymer can not be specifically fixed, because they are variable depending on the desired properties in the solid state and melting property of the ionic copolymer. In order to significantly change the properties of the copolymer in the solid state, the amount of the ion is preferably enough to neutralize at least 10 of the carboxyl groups in the copolymer, and the neutralization can be generally effected up to about 90 of the carboxyl groups in the copolymer. The degree of neutralization for optimizing the physical properties of the copolymer is not also specifica2.ly fixed, because the optimum properties are variable depending on the use for which the copolymer is intended and further because the physical properties of the ionic copolymer are variable depending on the amount of the carboxylic group in the copolymer, the molecular weight of the copolymer and the like. However, it is generally preferable to neutralize at least 50 of the carboxyl groups in the copolymer.
The metal ions mentioned above can be obtained by dissolving S€»c a metal compound generating such ions, for example, an inorganic metal compound such as sodium hydroxide and sodium carbonate and an organic metal compound. such as sodium methox’ide, sodium f oryrate and ‘sodium acetate in water or an organic solvent such as methanol.
The method for the production of the ionic copolymer from the aforementioned copolymer and the metal ion is not particularly limited, and any conventional method can be used for the production.
The molecular weight of the ionic copolymer can be conveniently expressed with the melt index which serves as S» a critorion of the melt viscosity and described in ASTM D 1238.
The MI of the ionic copolymer is advantageously in the range of 0.1 to 100 g/10 minutes (190 particularly in the range of to 20 g/10 minutes (190°C). The ionic copolymer of which MI is approximately in the range of 0.1 to 100 g/10 minutes has the excellent melt workability and exhibits high toughness, suitable ii iilil*—CC~- I elasticity and flexibility in the solid state.
The trans-polyisoprene resin used in the present invention occurs as a main component of natural resin such as balata and gutta-percha obtainable from natural plants and it has a molecular configuration of trans-1,4-polyisoprene. As a typical commercially available product of the resin, Kuraray Trans-Polyisoprene TP-301, Kuraray Isoprene Chemical Co.,Ltd. can be mentioned.
The terms of «alkali metal titanate fibers» in the present invention refers to alkali metal titanate fibers having an average length of 1 pm to 1 mm, preferably 5 to 300 and an aspect ratio of 5 to 1000, preferably 10 to 300. The alkali titanate fibers having an average length and aspect ratio in the range defined above exhibit an excellent reinforcing property and uniform dispersibility, and thereby they can produce an uniform Sg.» strength distribution of the composition. Examples of the alkali a metal titanate fibers include sodium titanate fibers, potassium titanate fibers, lithium titanate fibers and the like. Among those alkali metal titanate fibers exemplified above, the .i tc*t potassium titanate fibers are particularly preferable material, because they exhibit an excellent reinforcing effect and heat S resistance, permit the coloration of a desired hue owing to the outstanding whiteness thereof, ensure the easy production of fine S fibers of uniform length and show the uniform dispersibility in *e the composite material.
The terms «potassium titanate fibers» in the present invention refers to single crystal fibers represented by the formula: K 2 0OnTiO 2 or by the general formula: K 2 0*nTiO 2 1/2H 2 0 wherein n is an integer of 2 to 8. Examples of the potassium titanate fibers include potassium tetratitanate fibers, potasium hexatitanate fibers and potassium octatitanate fibers. These potassium titanate fibers can be used alone or in any combination thereof. The potassium titanate fibers preferably possess an average fiber-diameter in the range of 0.1 to 2 pm, average fiber length in the range of 5 to 100 Pm and aspect ratio in the range of 10 to 200. The average fiber diameter and the average fiber length are determined by measuring the values of each fiber by means of a scanning electron microscope and calculating the average of those values of at least 10 fibers per each of at least five fields of the view. The aspect ratio is obtained by dividing the average fiber length by the average fiber diameter.
As the surface treating agent for the alkali metal fibers of I the invention, sulfur-containing silane compounds such as a silane compound bearing one or more mercapto groups and a sulfide Scompound bearing silyl groups can be mentioned.
t Typical examples of the silane compound bearing one or more mercapto groups mentioned above are those compound represented by the general formula: r 1 2 (HS-R Si-R (I) 4-a-b 1 t wherein each R independently represents a substituted or unsubstituted divalent hydrocarbon group of. 2 tc b carbon atoms, C each R independently represents a substituted or unsubstituted Smonovalent hydrocarbon group, each X independently represents a hydrolyzable group, a is an integer of from 1 to 3, and b is an integer of from 0 to 2 with proviso of ls(a+b)13.
Examples of R 1 include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group i I- L i I -L I’ ttr Cr V C C C IC Cr V C
CC
r c C Ce I and the like. Among the examples mentioned above, R is preferably ethylene group or trimethylene group, particularly trimethylene group.
Examples of R include an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group and tolyl group; aralkyl group such as benzyl group, $-phenylethyl group and g-phenylpropyl group; and substituted hydrocarbon group such as 8-cyanoethyl group, y-chloropropyl group, 3,3,3-trifluoropropyl group and chlorophenyl group. The group of R 2 is selected depending on the kind of the rubber component and the purpose to which the product is intended. The group of R 2 of a long chain alkyl is suitable for a rubber component containing no aromatic ring, R of aryl group or aralkyl group is suitable for a rubber component containing aromatic rings and R of a substituted hydrocarbon group is suitable for a rubber component containing substituents such as halogen atoms or nitrile groups.
The symbol X represents a hydrolyzable group bonding to a silicon atom. Examples of the group X include an alkoxy group such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkoxy group such as’ -methoxyethoxy group, 8-ethoxyethoxy group and 8-butoxyethoxy group; enoxy group such as isopropenyloxy group; ketoximato group such as dimethyl ketoximato group and methylethyl ketoximato group; amino group such as diethylamino group and dibutylamino group; aminooxy group such as diethylaminooxy group; acyloxy group such as acetoxy group and octanoyloxy group; and amide group such as 1i
I
I
N-methylacetamide group. The group X is preferably selected from lower alkoxy groups of 1 to 4 carbon atoms from the view point of the reactivity with the surface of fine inorganic fibers, and methoxy group is most preferable because of its outstanding S reactivity.
The symbol a denotes an integer of from 1 to 3, preferably less than 2 in average, and b denotes an integer of from 0 to 2, preferably not more than 1 in average. If the value of a and b are unduly large, the number of the hydrolyzable groups become small and thereby the reactivity of the compound with the inorganic fibers is lowered. If the value of a is unduly small, the effect of the mercapto group on the rubber component is lowered. Accordingly, silane compound bearing mercapto group is S»t preferably controlled such that the average value of a is 1 and that the average value.of b is less than 1.
*I Typical examples of the sulfide compound bearing silyl V groups are those compounds represented by the following general formula; 3 4 4 3 I E R -Si-R -Si-R c n c (II) c Y 3-c 3-c wherein each R independently represents a substituted or S unsubstituted monovalent hydrocarbon group, each R independently represents a substituted» or unsubstituted hydrocarbon group of 2 S to 4 carbon atoms, each Y independently represents a hydrolyzable group, c is an integer of from 0 to 2 and n is an integer of from 1 to 6.
Examples of R include alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl ,i rZ 4 group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group and tolyl group; aralkyl group such as benzyl group, a-phenylethyl group and 8-phenylpropyl group; and substituted hydrocarbon group such as 8-cyanoethyl group, y-chloropropyl group, 3,3,3-trifluoropropyl group and chlorophenyl group. The group of R is selected depending on the kind of the rubber component and the purpose to which the product 3 is intended. The group of R of a long chain alkyl is suitable for a rubber component containing no aromatic ring, R of aryl group or aralkyl group is suitable for a rubber component 3 containing aromatic rings and R of a substituted hydrocarbon group is suitable for a rubber component containing substituents such as halogen atoms or nitrile groups.
4 SS Examples of R include ethylene group, trimethylene group, t cr tetramethylene group, pentamethylene group, hexamethylene group and the like. Among the examples mentioned above, R is preferably ethylene group or trimethylene group, particularly trimethylene group.
The symbol Y represents a hydrolyzable group bonding to the c silicon atom. Examples of the group Y include an alkoxy group such as methoxy group, ethoxy group, propoxy group and butoxy group; alkoxyalkoxy group such as 8-methoxyethoxy group, S-ethoxyethoxy group and B-butoxyethoxy group; enoxy gry.p such as isopropenyloxy group; ketoximato group such as dimethyl c’ ketoximato group and methylethyl ketoximato group; amino group such as diethylamino group and dibutylamino group; aminooxy group such as diethylaminooxy group; acyloxy group such as acetoxy group and octanoyloxy group; and amide group such as N-methylacetamide group. The group Y is preferably selected from
I?
0 Si
I’
lower alkoxy groups of 1 to 4 carbon atoms from the view point of the reactivity with the surface of fine inorganic fibers, and propoxy group is particularly preferable because the compound having propoxy groups as the group of Y can be easily synthesized and have good stability.
The symbol c denotes an integer of from 0 to 2. The sulfide compound bearing silyl groups represented by the formla II preferably contains at least one, preferably two of the hydrolyzable groups reactive to the surface of the inorganic fibers. Therefore, the value of c is preferably less than 2 in average. The symbol n denotes an integer of from 1 to 6, and the average value of n is preferably 2 to 4 from the viewpoint of the ease of synthesis, affinity for the rubber and inability to inhibit the vulcanization of the compound.
Those surface treating agents defined above can be used alone or in any combination thereof.
In the present invention, the fine inorganic fibers are treated with aforementioned surface treating agent. The amount of the surface treating agent is preferably in the range of about 0.05 to 10 by weight based on the amount of the fibers. So long as the amount is in this range, the surface treating agent sufficiently imp.roves the surface property of the fine inorganic fibers, and consequently the physical properties of the rubber composition are improved without inhibiting the subsequent vulcanization.
The treatment with the surface treating agent can be effected according to any of the conventional methods. For example, the treatment can be carried out by spraying the surface treating agent or the dilution of the surface treating agent on the fine inorganic fibers, or mixing the agent with the fibers homogeneously, or impregnating the fibers with the agent to deposit the agent on the surface of the fibers uniformly. Then, the agent on the fibers are dried by heating or hydrolyzed to be immobilized on the fibers as a uniform. coating.
It was found that the rubber composition has a sufficient hardness and compressive strength with uniform vulcanization, without any inhibition of the vulcanization. In the rubber composition, the rubber component adheres tc the alkali metal titanate fibers strongly and the slippage at the interface between the fibrous filler and the rubber matrix is suppressed, the slippage being recognized to cause the deterioration of the S physical properties of the rubber composition.
jj The rubber composition of the present invention may be e t te incorporated with various known additives, for example, S’ vulcanization accelerator, vulcanization retarder, antioxidant, plasticizer, peptizer, tackifier, antitack agent, sponging agent, dispersant, dusting agent, mold release agent, solvent, softening agent and the like. Additionally, various inorganic fillers for S reinforcing the material and any desired pigment and dye for coloring the c< position may be also incorporated in the rubber Scomposition. Examples of the inorganic filler include clayish S powders of carbon black, magnesium carbonate, zinc oxide, calcium carbonate, barium sulfate, aluminium hydroxide, aluminium oxide, silica powder, titanium dioxide, mica, talc, clay, diatomaceous earth, kaolin and the like. The rubber composition of the present invention may also contain any of organic modifiers conventionally used, and examples of such organic modifier include cumarone-indene resin, phenol resin, polystyrern resin, 12 acrylic resin, polyamide resin, epoxy resin, urethane resin, polyolefin resin and the like. Further, the rubber composition of the invention may include long fiber reinforcing material, for example, inorganic fibers sjch as glass fibers, carbon fibers, metal fibers, quartz fibers and ceramic fibers, and organic fibers such as nylon fibers, vinylon fibers, polyester fibers, aromatic polyamide fibers, polyimide fibers and aromatic polyether amide fibers. The rubber composition of the invention can be produced by kneading one or more rubber components with the alkali metal titanate fibers of which surfaces are treated with the surface treating agent and optionally with various additives and auxiliaries by a conventional method. The vulcanization of the r r V rubber composition according to the present invention can be also S carried out in a conventional manner, and the vulcanization is Spreferably carried out at a temperature of from 80 0 C to 180 0 C for to 60 minutes. The mixing ratio of the each component is not specifically limited and can varied depending on the kind of the rubber Scomponent used in the composition. As concerns the amount of the surface treated alkali titanate fibers, it is preferable to S incorporate 1 to 100 parts by weight, particularly 10 to 50 parts by weight of the surface treated alkali titanate fibers into 100 j/ weight parts of the rubber component. When the content of the fibers is less than the lower limit of the range, it becomes difficult to obtain a sufficient strength of the composition though it has a sufficient flexibility, and when the content of the fibers exceeds the upper limit of the range, the composition becomes unsuitable for a practical use because it gets excessive 13 H i hardness and poor elongation ratio while the strength is enhanced. The rubber composition according to the present invetion can be used as a cover layer of various types of golf ball such as two-piece golf ball, three-piece golf ball and thread wound golf ball. A two-piece golf ball can be produced by covering a core of an elastic rubber with a layer of the composition according to the invention and molding the resultant composite in the shape of a golf ball having desired surface characteristics such as dimples. A three-p-ece golf ball can be produced by covering a core c c e I £a of an elastic rubber with a intermediate layer, molding the c 'I intermediate layer, vulcanizing the resultant composite, then covering the intermediate layer with a cover layer of the 1| composition according tr.the invention, molding the resultant I p composite in the shape of-a golf ball and optionally further vulcanizing the molded golf ball. A three-piece golf ball can be I c c also produced by a single molding process, that is, by covering 1 c C. the core with the intermediate layer and the cover layer successively, then molding and vulcanizing the resultant i composite. c A thread wound golf ball can be produced by winding a core of elastic rubber with an elastic thread in a conventional manner, covering the thread wound core with the composition of the invention and molding the resultant composite in the shape of a golf ball having desired surface characteristics such as dimples. Any known elastic thread can be employed for the preparation, and the examples of the elastic thread include a 14 therad produced by a known process for the preparation of the rubber thread utilizing a rubber material such as natural rubber polyisoprene rubber (IR) and a blend material of these rubber materials. Examples Now, the present invention will be described more specifically with reference to working examples and comparative experiments hereafter, however, it should be noted that the present invention is not intended to be restricted within those specific examples. In the attached tables, *1 denotes a product of Japan Synthetic Rubber Co.,Ltd. marketed under product code of "BR-11", V *2 denotes a product of Seido Kagaku marketed under a product C C I c' code of "Zinc White No. and *3 denotes a product of Nippon Ca Silica Co.,Ltd. marketed under a trade name of "Nipseal VN 3AQ". ic The potassium titanate fine fibers (untreated) were obtained I from Otsuka Chemical Co., Ltd. as a commercially available product under a trade name of "Tismo D". The surface treated fibers A were obtained by treating V Tismo D with 1 of bis(3-triethoxysilylpropyl)tetrasulfide. V The surface treated fibers B were obtained by treating Tismo D with 1 of Y-mercaptopropyltrimethoxysilane. f The surface treated fibers C were obtained by treating c. Tismo D with 1 of Y-mercapcopropyltriethoxysilane. The surface treated fibers D were obtained by treating Tismo D with 1 of bis(3-trimethoxysilylpropyl)tetrasulfide. The surface treated fibers E were obtained by treating Tismo D with 1 of Y-glycidoxypropyltrimethoxysilane. i ~c ad~ F c C IC tC C C C t CC 'cCC C cC cC CC CI C CCL SC The surface treated fibers F were obtained by treating Tismo D with 1 of bis(mercaptopropyl)tetramethyldisiloxane. The durability index of a given samples was determined by cyclically exerting a compression enough to produce a deformation of 10 mm on the sample and taking count of the number of compression cycles upto the rupture of the sample, and reported as a relative value based on the durability index of Example 1 taken as 100. The bounce impact elasticity was determined by allowing a given sample to fall from a height of 120 cm iil an atomosphere kept at 20 0 C and measuring the height to which the sample bounced according to the specification of JIS (Japan Industrial Standard) S 7005. The compression was evaluated as the strength exhibited by a given sample compressed 2.54 mm in diameter. Examples 1 to *In a kneader, 100 parts of rubber (BR 10 parts of zinc acrylate, 15 parts of zinc oxide (STEREON 720, Japan Synthetic Rubber Co.,Ltd.) and 15 parts of potassium titanate fibers (untreated) were blended at 60*C to 100°C for 10 minutes. Then, the contents of the kneader were cooled to 60*C to 70*C, mixed with 5 parts of dicumyl peroxide, adjusted in weight, and further kneaded. The resultant mass was vulcanized in a conventional mold for golf ball at 150*C I 5"C for 30 minutes to produce a golf ball core. The resultant core was covered with a layer of the rubber composition according to the invention of which formulating ratio is indicated in Table 1 in parts by weight and each column corresponds to each Example (the same shall apply hereafter) to produce a two-piece golf ball. The same procedure was repeated for each Example. The properties of the obtained balls were tested and the results are also shown in Table 1. Examples 11 to 16 Two-piece golf balls were produced by repeating the procedure of Examples 1 to 10 excepting that cores of which formulating ratios are indicated in Table 2 were used and that a hard elastomer obtained by blending 100 parts of ionomer resin with 10 parts of the surface treated fibers A was used as the cover layers. The properties of the obtained balls were tested and the e rusults are also shown in Table 2. Comparative Experiments 1 to 8 Ott f lTwo-piece golf balls were produced by repeating the S procedure of Example 1 to 8 excepting that cover layers of which 0I formulating ratios are indicated in Table 3 were used. The properties of the obtained balls were tested and the results are shown in Table 3. Examples 17 to 25 and Comparative Experiments 9 to 16 SIn a kneader, 100 parts of rubber (BR 10 parts of zinc acrylate, 15 parts of zinc oxide (STEREON 720, Japan Synthetic Rubber Co.,Ltd), 4 parts of an antioxidant, 2 parts of stearic acid and 15 parts of potassium titanate fibers (untreated) were kneaded at 60"C to 100 0 C for 10 minutes. Then, the contents of the kneader were cooled to 60 0 C to 70°C, mixed with 5 parts of dicumyl peroxide, adjusted in weight and furter kneaded. The resultant mass was vulcanized in a conventional mold for golf ball core at 150'C 5 0 C for 30 minutes to form a golf ball core. Three-piece golf ball was produced by utilizing the above-obtained core, intermediate layer of the same composition as the core and cover layer of which formulating ratio is K indicated in Table 4 or Table 5. The same procedure was repeated I for each Example and Comparative Experiment. The properties of the obtained balls were tested and the V results are shown in Table 4 and Table Examples 26 to 35 and Comparative Experiments 17 to 24 In a kneader,'100 parts of rubber (BR 10 parts of zinc acrylate, 15 parts of zinc oxide (STEREON 720, Japan Synthetic Rubber Co.,Ltd), 10 parts of aerosolizable silica (IR-2200, Japan Synthetic Rubber Co.,Ltd) and 15 parts of potassium titanate fibers (untreated) were kneaded at 60°C to 100"C for 10 minutes. Then, the contents of the kneader were cooled to 60 0 C to 70 0 C, cc( mixed with 5 parts of dicumyl peroxide, adjusted in weight and cc 0, further kneaded. The resultant mass was vulcanized in a conventional mold for golf ball core at 150 0 C 5°C for minutes to form a golf ball core. The core was wound with a i NR-based rubber thread, then covered with a cover layer of which ccc S ,t formulating ratio is indicated in Table 6 or Table 7 and tinjection molded by means of a injection machine to produce a thread wound golf ball of 45 g in weight. The same procedure was I repeated for each Example and Comparative Experiment. I The properties of the obtained balls were tested and the c results are shown in Table 6 and Table 7. S18 18 Table 1 Formulating Ratios of Cover Layers Examples 1 2 3 4 5 6 7 8 9 lonomer resin 100 100 100 100 100 Trans-polyisoprene resin 100 100 100 BR rebber *1 100 100 Zinc oxide *2 10 Zinc acrylate 9 9 Sulfur 1 1 1 Vulcanization accelerator 15 15 15 Dicumyl peroxide 5 Antioxidant 4 4 Stearic acid 2 2 Surface treated fibers A 20 30 10 B 20 10 C 20 10 20 D 20 Durability index 100 101 102 103 105 101 104 107 103 105 Bounce impact elasticity 115 116 117 118 117 116 118 119 100 101 Compression 123 124 128 126 122 120 122 124 121 119 Feeling upon hitting** E E E E E E E E E E E: Excellent m Ii i- D Table 2 Formulating Ratios of Cores 4 Examples 11 12 13 14 15 16 Rubber (BR) *1 100 100 100 100 100 100 Zinc acrylate 10 10 10 10 10 Zinc oxide *2 15 15 15 15 15 Aerosolizable silica *3 10 10 10 10 10 Dicumyl peroxide 5 5 5 5 5 Antioxidant 4 4 4 4 4 4 Stearic acid 2 2 2 2 2 2 Potassium titanate fibers 10 15 20 25 (untreated) Surface treated fibers E Durability index 96 96 95 95 93 94 Bounce impact elasticity. 97 98 101 101 98 99 Compression 111 108 109 108 108 106 Feeling upon hitting** G G G G G G G: Good I 1 i L 7 p Table 3 Ratios of Cover Layers Formulating Comparative Experiments 1 2 3 4 5 6 7 8 Ionomer resin 100 100 100 100 100 Trans-polyisoprene resin 100 100 100 Sulfur 1 1 1 Vulcanization accelerator 15 15 Titanium dioxide 20 30 30 Potassium titanate fibers 20 30 30 (untreated) Surface treated fibers E 30 Durability index 90 92 91 93 94 82 84 78 Bounce impact elasticity 90 92 96 94 95 90 91 88 Compression 108 110 112 111 111 108 107 105 Feeling upon hitting** B B B B B B B B B: Bad of C Table 4 Formulating Ratios of Cover Layers Examples 17 18 19 20 21 22 23 24 lonomer resin Trans-polyisoprene resin BR rubber *1 Zinc oxide *2 Zinc acrylate Sulfur Vulcanization accelerator Dicumyl peroxide Antioxidant Stearic acid Surface treated fibers 100 100 100 100 0 100 100 100 100. 1 1 1 15 15 15 2 30 20 20 Durability index Bounce impact elasticity Compression Feeling upon hitting** 104 117 124 E 102 116 122 E 103 116 123 E 104 116 123 E 104 115 122 E 101 110 121 E 103 108 122 E 102 109 123 E 104 108 120 E E: Excellent It n f Table Formulating Ratios of Cover Layers Comparative Experiments 9 10 11 12 13 14 .15 16 Ionomer resin 100 100 100 100 100 Trans-polyisoprene resin 100 100 100 Sulfur 1 1 1 Vulcanization accelerator 15 15 Titanium dioxide 20 30 30 Potassium titanate fibers 20 30 30 (untreated)' Surface treated fibers E 30 Durability index 91 93 92 94 92 82 85 Bounce impact elasticity 89 91 90 92 91 90 92 Compression 109 111 113 113 112 108 107 103 Feeling upon hitting** B B B B B B B B B: Bad 4' ~7I Table 6 Formulating Ratios of Cover Layers Examples 26 27 28 29 30 31 32 33 34 Ionomer resin Trans-polyiSOprele resin BR rubber *1 Zinc oxide *2 Zinc acrylate Sulfur Vulcanization accelerator Dicumyl peroxide Antioxidant Stearic acid Surface treated fibers 100 100 100 100 100 1001 00 100IO 100 100 10 9 9 15 15 15 5 4 4 2 2 30 20 10 20 10 20 10 Durability index Bounce impact elasticity Compression Feeling upon hitting** 100 98 98 99 105 99 98 97 102 103 109 108 108 109 108 99 100 99 100 99 123 124 124 125 128 122 123 121 121 122 E E E E E E E E E E Excellent Table 7 Formnulating Ratios of Cover Layers Comparative 9%periments 18 19 2:0 21 22 .23 24 Ionorner resin 100 ion9 100. 100 100i TranA-polyi-soprene :esin 100 100 100 Sulfur 1 1 1 Vulcanization accelerator 15 15 Titanium dioxide 20 30 3 30 Potassium titanate fibers 20 30 30 (untreated) ,Surface treated fibers E 30 Durability index 78 79 76 80 72 73 74 Bounce impact elasticity 82 82 83 84 84 85 86 81 Compression 101 102 102 101 98 97 96 Feeling upon hitting** B B B B B D B B3 B: i3ad Claims (5) 1. A rubber composition for a cover layer of a golf int ball, which comprises an ionomer resin component and and alkali metal titanate fibers having an average length of 1 pm to 1 mm and an aspect ratio of 5 to 1,000 and being treated with a sulfur-containing surface treating agent. 2. A rubber composition for a cover layer of a golf ball, which comprises at least one natural and/or synthetic rubber component(s) and alkali metal titanate whex fibers having an average length of 1 pm to 1 mm and an unst aspect ratio of 5 to 1,000 and being treated with a ind sulfur-containing surface treating agent, and the hydi composition being vulcanized, provided that said ind synthetic rubber component does not include an ionomer inte resin. 6. 3. A rubber composition according to claim 1 or 2, I which comprises 100 parts by weight of said rubber 1 to I component(s) and 2 to 100 parts by weight of said alkali from metal titanate fibers. 4. A rubber composition according to any one of claims S1 to 3, wherein said surface treating agent is selected j from the group consisting of a silane compound i represented by the formula 16. 2 to poly f X S4-.ab 7. 1 to wherein sach R 1 independently represents a substituted or potas unsubst.tuted divalent hydrocarbon group having 2 to 6 carbon atoms, each R2 independently represents a substituted or unsubstituted monovalent hydrocarbon UTA 91204,EEDXMAT.CM,a:62476asLres,26 j -27- group, each X independently represents a hydrolyzable group, a is an integer of from 1 to and b is an integer of from 0 to 2 with a proviso of 1 5 (a b) 5 3; and a sulfide compound represented by the formula (II): 3 Si-R 4 4 S R 4 Si-R' I (I n Y Y 3-c wherein each K 3 independently represents a substituted or unsubstituted monovalent hydrocarbon group, each R 4 independently represents a substituted or unsubstituted hydrocarbon group having 2 to 4 carbon atoms, each Y independently represents a hydrolyzable group, c is an integer of from 0 to 2 and n is an integer of from 1 to 6. A rubber composition according to any one of claims 1 to 3, wherein said surface treating agent is selected from the group consisting of: bis(3-triethoxysilylpropyl)tetrasulfide; y-mercaptopropyltrimethoxysilane; I y-mercaptopropyltriethoxysilane; bis(3-trimethoxysilylpropyl)tetrasulfide; and bis(mercaptopropyl)tetramethyldisiloxane. 6. A rubber composition adcording to any one of claims I 2 to 4, wherein said rubber component is trans- polyisoprene resin. 7. A rubber composition according to any one of claims 1 to 6, wherein said alkali metal titanate fibers are potassium titanate fibers. 911204,EEDAT.007,a:\62476p5Lres,27 i -28 8. A rubber composition according to claim 1 and substantially as hereinbefore described with reference to the Examples. DATED this 4th day of December, 1991. ASICS CORPORATION and OTSUKA CHEMICAL CO., LTD. By Their Patent Attorneys DAVIES COLLISON CAVE Aw 911204,EEDAT.007,a:\62476asLres,28 AU62476/90A 1987-06-11 1990-09-13 Rubber composition for cover layer of golf ball Ceased AU620264B2 (en) Applications Claiming Priority (10) Application Number Priority Date Filing Date Title JP62146019A JPH0643526B2 (en) 1987-06-11 1987-06-11 Rubber composition JP62-146019 1987-06-11 JP62-147219 1987-06-12 JP62-147218 1987-06-12 JP62-147220 1987-06-12 JP62147218A JPH0626627B2 (en) 1987-06-12 1987-06-12 Solid Golf Ball JP62147221A JPS63311973A (en) 1987-06-12 1987-06-12 Coating composition for golf ball JP62147219A JPS63311971A (en) 1987-06-12 1987-06-12 Golf ball JP62-147221 1987-06-12 JP62147220A JPS63311972A (en) 1987-06-12 1987-06-12 Golf ball Related Parent Applications (1) Application Number Title Priority Date Filing Date AU17557/88A Division AU604915B2 (en) 1987-06-11 1988-06-09 Rubber composition and golf ball comprising it Publications (2) Publication Number Publication Date AU6247690A AU6247690A (en) 1990-12-13 AU620264B2 true AU620264B2 (en) 1992-02-13 Family ID=27527754 Family Applications (3) Application Number Title Priority Date Filing Date AU17557/88A Ceased AU604915B2 (en) 1987-06-11 1988-06-09 Rubber composition and golf ball comprising it AU62476/90A Ceased AU620264B2 (en) 1987-06-11 1990-09-13 Rubber composition for cover layer of golf ball AU62475/90A Ceased AU619131B2 (en) 1987-06-11 1990-09-13 Rubber composition Family Applications Before (1) Application Number Title Priority Date Filing Date AU17557/88A Ceased AU604915B2 (en) 1987-06-11 1988-06-09 Rubber composition and golf ball comprising it Family Applications After (1) Application Number Title Priority Date Filing Date AU62475/90A Ceased AU619131B2 (en) 1987-06-11 1990-09-13 Rubber composition Country Status (9) Country Link US (3) US4955966A (en) KR (1) KR920004891B1 (en) AU (3) AU604915B2 (en) CA (1) CA1331233C (en) DE (1) DE3819827A1 (en) FR (1) FR2616438A1 (en) GB (1) GB2206889B (en) HK (1) HK45392A (en) SG (1) SG111191G (en) Families Citing this family (144) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title GB2206889B (en) * 1987-06-11 1991-03-20 Asics Corp Rubber composition and golf ball comprising it DE4004781A1 (en) * 1990-02-16 1991-08-22 Degussa Modifying surface of natural or synthetic oxidic or silicate fillers - using organo:silicon cpds. useful in vulcanisable natural rubber mixts. to improve rubber properties JP2665991B2 (en) * 1990-10-18 1997-10-22 住友ゴム工業株式会社 Golf ball and manufacturing method thereof US5155157A (en) * 1990-12-27 1992-10-13 E. I. Du Pont De Nemours And Company Compositions useful in the manufacture of golfballs US5255922A (en) * 1991-07-26 1993-10-26 Wilson Sporting Goods Co. Golf ball with improved cover TW223025B (en) * 1991-07-26 1994-05-01 Wilson Sporting Goods US5314187A (en) * 1991-07-26 1994-05-24 Wilson Sporting Goods Co. Golf ball with improved cover US5298562A (en) * 1991-08-19 1994-03-29 Sartomer Company, Inc. Calcium di(meth)acrylate cured halogenated polyethylene polymers JP2916310B2 (en) * 1991-11-01 1999-07-05 住友ゴム工業株式会社 Two-piece golf ball JP3169287B2 (en) * 1992-06-09 2001-05-21 住友ゴム工業株式会社 Wound golf ball US5387637A (en) * 1992-08-20 1995-02-07 Lisco, Inc. Golf ball core compositions JP3552116B2 (en) * 1992-12-25 2004-08-11 住友ゴム工業株式会社 Rubber composition for golf balls US6213895B1 (en) * 1997-03-28 2001-04-10 Spalding Sports Worldwide, Inc. Dual cores for golf balls US6159110A (en) * 1997-03-28 2000-12-12 Spalding Sports Worldwide, Inc. Golf ball utilizing silicone materials US6162134A (en) * 1993-04-28 2000-12-19 Spalding Sports Worldwide, Inc. Low spin golf ball comprising silicone material US6193618B1 (en) 1993-04-28 2001-02-27 Spalding Sports Worldwide, Inc. Low spin golf ball comprising a mantle with a cellular or liquid core US6569035B2 (en) 1993-04-28 2003-05-27 Spalding Sports Worldwide, Inc. Golf ball comprising silicone material US6244977B1 (en) 1996-09-16 2001-06-12 Spalding Sports Worldwide, Inc. Golf ball comprising a metal mantle with a cellular or liquid core US6676876B2 (en) 1993-04-28 2004-01-13 The Top-Flite Golf Company Method of molding a low spin golf ball comprising silicone material US6142887A (en) * 1996-09-16 2000-11-07 Spalding Sports Worldwide, Inc. Golf ball comprising a metal, ceramic, or composite mantle or inner layer US6057403A (en) 1993-06-01 2000-05-02 Spalding Sports Worldwide, Inc Dual cores for golf balls US6204331B1 (en) 1993-06-01 2001-03-20 Spalding Sports Worldwide, Inc. Multi-layer golf ball utilizing silicone materials US6432000B1 (en) 1993-06-01 2002-08-13 Spalding Sports Worldwide, Inc. Multilayer golf ball with filled inner layer having dual core, liquid core, or wound core US6506130B2 (en) 1993-06-01 2003-01-14 Spalding Sports Worldwide, Inc. Multi layer golf ball US6695718B2 (en) 1993-06-01 2004-02-24 The Top-Flite Golf Company Golf ball with sulfur cured inner core component US6548618B2 (en) * 1993-06-01 2003-04-15 Spalding Sports Worldwide, Inc. Golf ball having dual core and thin polyurethane cover formed by RIM US6325731B1 (en) 1993-06-01 2001-12-04 Spalding Sports Wordwide, Inc. Multi-layer golf ball CA2116399C (en) * 1993-07-29 2004-04-20 Michael J. Sullivan Golf ball and method for making same US5558325A (en) * 1993-08-05 1996-09-24 Gencorp Inc. Play balls or pressureless tennis balls US5885172A (en) 1997-05-27 1999-03-23 Acushnet Company Multilayer golf ball with a thin thermoset outer layer JP3703107B2 (en) * 1995-03-09 2005-10-05 Ｓｒｉスポーツ株式会社 Solid golf balls US7153467B2 (en) * 1995-06-07 2006-12-26 Acushnet Company Method of making a golf ball with a multi-layer core US7131914B2 (en) * 1995-06-07 2006-11-07 Acushnet Company Method of making a golf ball with a multi-layer core US6056842A (en) 1997-10-03 2000-05-02 Acushnet Company Method of making a golf ball with a multi-layer core US7014573B2 (en) 1995-06-07 2006-03-21 Acushnet Company Method of making a golf ball with a multi-layer core US5971869A (en) * 1995-06-07 1999-10-26 Acushnet Company Golf ball composition US7594866B2 (en) * 1996-02-16 2009-09-29 Acushnet Company Method of making a golf ball with a multi-layer core US6395861B1 (en) 1996-03-01 2002-05-28 Spalding Sports Worldside, Inc. Quick-cure game ball coating system US6340503B1 (en) 1996-03-01 2002-01-22 Spalding Sports Worldwide, Inc. Method of coating a game ball with a solvent-based polyurethane cured with catalyst US20030050425A1 (en) * 1996-03-01 2003-03-13 Spalding Sports Worldwide, Inc. Quick-cure game ball coating system US5906491A (en) * 1996-03-27 1999-05-25 Berman; Robert J. Geography teaching apparatus US5962140A (en) * 1996-06-25 1999-10-05 Acushnet Company Golf ball comprising fluoropolymer US6309312B1 (en) 1996-09-16 2001-10-30 Spalding Sports Worldwide, Inc. Golf ball comprising a metal mantle having a hollow interior US6120393A (en) 1996-09-16 2000-09-19 Spalding Sports Worldwide, Inc. Low spin golf ball comprising a mantle having a hollow interior US5932661A (en) * 1996-10-02 1999-08-03 Wilson Sporting Goods Co. Golf ball core with titanate coupling agent JPH10137365A (en) * 1996-11-13 1998-05-26 Bridgestone Sports Co Ltd Golf ball US6384140B1 (en) 1996-12-10 2002-05-07 Spalding Sports Worldwide, Inc. Nylon compositions for golf ball constructions and method of making same US20030078116A1 (en) * 2001-04-18 2003-04-24 Spalding Sports Worldwide, Inc. Isophthalic acid polyamide polymer for use in golf ball covers or mantles AU757103B2 (en) * 1997-03-28 2003-01-30 Callaway Golf Company Low spin golf ball comprising a metal, ceramic, or composite mantle or inner layer US20030199338A1 (en) * 1997-03-28 2003-10-23 Nesbitt R. Dennis Multi-core, multi-layer cover golf ball GB2360221B (en) * 1997-03-28 2001-10-31 Spalding Sports Worldwide Inc Golf ball comprising a metal ceramic or composite mantle in inner Layer CA2283790A1 (en) * 1997-03-28 1998-10-08 Callaway Golf Company Improved multi-layer golf ball utilizing silicone materials AU761494B2 (en) * 1997-03-28 2003-06-05 Callaway Golf Company Golf ball comprising a metal, ceramic, or composite mantle or inner layer US20050070377A1 (en) * 1997-05-27 2005-03-31 Christopher Cavallaro Thin-layer-covered multilayer golf ball US6913547B2 (en) 1997-05-27 2005-07-05 Acushnet Company Thin-layer-covered multilayer golf ball US6486261B1 (en) * 1998-12-24 2002-11-26 Acushnet Company Thin-layer-covered golf ball with improved velocity US6849006B2 (en) 1997-05-27 2005-02-01 Acushnet Company Thin, thermoset, polyurethane-covered golf ball with a dual core US6634964B2 (en) 1997-05-27 2003-10-21 Acushnet Company Initial velocity dual core golf ball US6465578B1 (en) 1998-12-24 2002-10-15 Acushnet Company Low compression, resilient golf balls including an organosulfur catalyst and method for making same US6277037B1 (en) 1997-10-03 2001-08-21 Performance Dynamics Llc Golf ball with water immersion indicator US6358160B1 (en) * 1997-10-03 2002-03-19 Performance Dynamics Llc Golf ball with water immersion indicator US6093357A (en) 1998-03-26 2000-07-25 Acushnet Company Methods for making multi-layer golf balls using rigid uncrosslinked shells US6458895B1 (en) 1998-12-24 2002-10-01 Acushnet Company Low compression, resilient golf balls including elemental catalyst and method for making same US6417278B1 (en) 1998-03-26 2002-07-09 Acushnet Company Low compression, resilient golf balls including a cis-to-trans catalyst and method for making same US6998445B2 (en) 1998-03-26 2006-02-14 Acushnet Company Low compression, resilient golf balls with rubber core US6162135A (en) * 1998-12-24 2000-12-19 Acushnet Company Low compression, resilient golf balls including an inorganic sulfide catalyst and methods for making the same US6180722B1 (en) 1998-03-26 2001-01-30 Acushnet Company Dual core golf ball compositions US6291592B1 (en) 1998-12-24 2001-09-18 Acushnet Company Low compression, resilient golf balls including aromatic catalyst and method for making same AUPP395898A0 (en) 1998-06-05 1998-07-02 Waggle Pty. Ltd. Rubber compound AU744816B2 (en) * 1998-06-05 2002-03-07 Waggle Pty. Ltd. Rubber compound for golf ball and golf ball GB2378398B (en) * 1998-08-07 2003-04-02 Bridgestone Sports Co Ltd Multi-piece solid golf ball US6120390A (en) * 1999-03-01 2000-09-19 Acushnet Company Golf ball cores with improved durability US6193617B1 (en) 1999-03-10 2001-02-27 Purespin Golf Company, Inc. Golf ball and method of making same US6290797B1 (en) 1999-04-02 2001-09-18 Acushnet Company Process for making multi-layer core golf balls US6608127B1 (en) * 1999-07-07 2003-08-19 Sumitomo Rubber Industries, Ltd. Golf ball US6620061B1 (en) * 1999-07-07 2003-09-16 Bridgestone Sports Co., Ltd. Golf ball JP2001095948A (en) * 1999-09-29 2001-04-10 Sumitomo Rubber Ind Ltd Solid golf ball US6884181B1 (en) * 1999-11-09 2005-04-26 Talon Sports Golf ball and method of manufacture WO2001039843A1 (en) * 1999-12-06 2001-06-07 Spalding Sports Worldwide, Inc. One-piece golf ball US7148266B2 (en) 1999-12-23 2006-12-12 Callaway Golf Company Game balls with cover containing post crosslinkable thermoplastic polyurethane and method of making same EP1266214B1 (en) * 2000-03-20 2009-09-23 The Charles Stark Draper Laboratory, INC. Flexural plate wave sensor JP3629420B2 (en) * 2000-08-24 2005-03-16 住友ゴム工業株式会社 Golf ball JP3544174B2 (en) * 2000-09-20 2004-07-21 住友ゴム工業株式会社 Rubber thread for golf balls and golf balls US6726985B2 (en) 2000-11-03 2004-04-27 Nathan Amitai Shoe sole US6555627B2 (en) 2000-12-21 2003-04-29 Acushnet Company Golf balls including rigid compositions and methods for making same US6575848B2 (en) 2000-12-21 2003-06-10 Acushnet Company Low modulus golf ball compositions and methods for making same US6710114B2 (en) 2000-12-21 2004-03-23 Acushnet Company Golf balls including solution blended polymeric composite and method of making same US20080261722A1 (en) * 2001-09-13 2008-10-23 Bulpett David A Compositions for use in golf balls US7361711B2 (en) * 2001-09-13 2008-04-22 Acushnet Company Compositions for use in golf balls US7358308B2 (en) * 2001-09-13 2008-04-15 Acushnet Company Compositions for use in golf balls CN1305950C (en) * 2001-10-05 2007-03-21 株式会社普利司通 Rubber composition US20030069085A1 (en) * 2001-10-09 2003-04-10 Hogge Matthew F. Golf ball with vapor barrier layer and method of making same US7137908B2 (en) * 2001-12-10 2006-11-21 Sri Sports Limited Golf ball JP4043243B2 (en) * 2002-01-28 2008-02-06 Ｓｒｉスポーツ株式会社 Golf ball US6899642B2 (en) 2002-03-21 2005-05-31 Acushnet Company Golf ball with a layer including composite material and a method for making such a golf ball US7026399B2 (en) * 2002-09-27 2006-04-11 Taylor Made Golf Company, Inc. Golf ball incorporating a polymer network comprising silicone EP1572776B1 (en) * 2002-12-04 2009-03-25 Blue Goo L.L.C. Metal-acylates as curing agents for polybutadiene, melamine and epoxy compounds US20080176678A1 (en) * 2003-05-14 2008-07-24 Bulpett David A Compositions for Use in Golf Balls US7528196B2 (en) * 2005-01-24 2009-05-05 Taylor Made Golf Company, Inc. Polyalkenamer compositions and golf balls prepared therefrom US7819761B2 (en) 2005-01-26 2010-10-26 Taylor Made Golf Company, Inc. Golf ball having cross-core hardness differential and method for making it US7156755B2 (en) 2005-01-26 2007-01-02 Callaway Golf Company Golf ball with thermoplastic material US7175543B2 (en) 2005-01-26 2007-02-13 Callaway Golf Company Golf ball and thermoplastic material US7612134B2 (en) 2005-02-23 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material US7312267B2 (en) 2005-02-23 2007-12-25 Callaway Golf Company Golf ball and thermoplastic material US7358310B2 (en) * 2005-06-13 2008-04-15 Acushnet Company Compositions for use in golf balls US7358309B2 (en) 2005-06-13 2008-04-15 Acushnet Company Compositions for use in golf balls US7874940B2 (en) * 2005-07-13 2011-01-25 Taylor Made Golf Company, Inc. Extrusion method for making golf balls US8030411B2 (en) 2005-12-21 2011-10-04 Taylor Made Golf Company, Inc. Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture US7612135B2 (en) 2006-02-17 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material US7915348B2 (en) * 2006-03-13 2011-03-29 Taylor Made Golf Company, Inc. Method for making ionomers using amine compounds comprising salt functional groups, ionomers made by the method and sports equipment comprising such ionomers US8450397B2 (en) * 2007-09-25 2013-05-28 Dunlop Sports Co. Ltd. Golf ball US8211976B2 (en) 2007-12-21 2012-07-03 Taylor Made Golf Company, Inc. Sports equipment compositions comprising a polyurethane, polyurea or prepolymer thereof and a polyfunctional modifier US8932154B2 (en) 2007-12-28 2015-01-13 Taylor Made Golf Company, Inc. Golf ball with softer feel and high iron spin US8096899B2 (en) * 2007-12-28 2012-01-17 Taylor Made Golf Company, Inc. Golf ball comprising isocyanate-modified composition US8357060B2 (en) 2007-12-28 2013-01-22 Taylor Made Golf Company, Inc. Golf ball with soft feel US8047933B2 (en) 2008-02-19 2011-11-01 Taylor Made Golf Company, Inc. Golf ball US8236880B2 (en) * 2008-04-23 2012-08-07 Taylor Made Golf Company, Inc. Compositions comprising an amino triazine and ionomer or ionomer precursor US8809428B2 (en) 2008-12-23 2014-08-19 Taylor Made Golf Company, Inc. Golf ball US8357756B2 (en) 2008-12-23 2013-01-22 Taylor Made Golf Company, Inc. Compositions for sports equipment US20100304894A1 (en) * 2009-05-27 2010-12-02 Michael Michalewich Polyisobutylene-based compositions for golf balls US20110130216A1 (en) * 2009-12-01 2011-06-02 Taylor Made Golf Company, Inc. Golf ball constructs and related systems US8992341B2 (en) * 2009-12-23 2015-03-31 Taylor Made Golf Company, Inc. Injection moldable compositions and golf balls prepared therefrom US8680204B2 (en) * 2009-12-23 2014-03-25 Hyun J. Kim Crosslinked ionomer compositions US8629228B2 (en) 2009-12-31 2014-01-14 Taylor Made Golf Company, Inc. Ionomer compositions for golf balls US8674023B2 (en) 2009-12-31 2014-03-18 Taylor Made Golf Company, Inc. Ionomer compositions for golf balls US8575278B2 (en) 2009-12-31 2013-11-05 Taylor Made Golf Company, Inc. Ionomer compositions for golf balls US8979677B2 (en) 2010-11-24 2015-03-17 Taylor Made Golf Company, Inc. Golf ball with selected spin characteristics US8475297B2 (en) * 2011-02-23 2013-07-02 Nike, Inc. Golf ball with carbon dioxide absorbents US8480516B2 (en) 2011-02-23 2013-07-09 Nike, Inc. Methods for encouraging use of greenhouse gas reducing golf balls US20120231898A1 (en) * 2011-03-10 2012-09-13 Sullivan Michael J Golf ball comprising fluorinated silane-treated filler to promote moisture resistance US8758167B2 (en) * 2011-09-15 2014-06-24 Acushnet Company Compositions for golf balls based on oriented nanostructures US9108082B2 (en) 2011-12-19 2015-08-18 Taylor Made Golf Company, Inc. Golf ball composition US8858365B2 (en) 2011-12-23 2014-10-14 Taylor Made Golf Company, Inc. Multi-layer golf ball construction US20150375051A1 (en) 2014-06-30 2015-12-31 Dunlop Sports Co., Ltd. Golf ball resin composition and golf ball US10507363B2 (en) 2015-06-08 2019-12-17 Taylor Made Golf Company, Inc. Metallic monomer used as ionomeric additives for ionomers and polyolefins JP6516621B2 (en) * 2015-07-31 2019-05-22 住友ゴム工業株式会社 Golf ball CA3033410A1 (en) * 2016-08-11 2018-02-15 Jetson I.P. Pty Ltd Smart ball, locator system and method therefor US10682553B2 (en) 2018-04-18 2020-06-16 Acushnet Company Golf ball incorporating melt processable highly-crosslinked ethylene acid copolymer(s) and/or ionomer(s) US10773132B2 (en) 2018-04-18 2020-09-15 Acushnet Company Golf ball incorporating melt processable highly-crosslinked rubber-containing ionomer(s) JP7210980B2 (en) * 2018-09-28 2023-01-24 住友ゴム工業株式会社 Golf ball JP7215085B2 (en) * 2018-10-30 2023-01-31 住友ゴム工業株式会社 Golf ball JP7358733B2 (en) * 2018-12-26 2023-10-11 住友ゴム工業株式会社 Golf ball JP7358734B2 (en) * 2018-12-26 2023-10-11 住友ゴム工業株式会社 Golf ball JP7342357B2 (en) * 2018-12-26 2023-09-12 住友ゴム工業株式会社 Golf ball Citations (3) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title AU7097587A (en) * 1981-08-27 1987-07-16 Union Carbide Corporation Additive for filled thermoplastics US4715607A (en) * 1986-02-18 1987-12-29 Acushnet Company Golf ball composition AU604915B2 (en) * 1987-06-11 1991-01-03 Asics Corporation Rubber composition and golf ball comprising it Family Cites Families (19) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title US3992014A (en) * 1969-10-22 1976-11-16 Brunswick Corporation Molded solid golf ball comprising a silane for greater velocity GB1349853A (en) * 1970-07-10 1974-04-10 Dunlop Holdings Ltd Playballs US3997356A (en) * 1971-08-17 1976-12-14 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler Reinforcing additive FR2192560A5 (en) * 1972-07-11 1974-02-08 Gerdec GB1520254A (en) * 1974-12-30 1978-08-02 Uniroyal Ltd Golf balls US4008181A (en) * 1975-09-04 1977-02-15 Texaco Inc. Steam dealkylation catalyst and process for preparing it JPS572348A (en) * 1980-06-07 1982-01-07 Bridgestone Corp Reinforced rubber composition JPS5774342A (en) * 1980-10-29 1982-05-10 Bridgestone Corp Remarkably reinforced rubber composition US4400485A (en) * 1981-08-28 1983-08-23 Standard Oil Company (Indiana) Rubber composition JPS58168638A (en) * 1982-03-31 1983-10-05 Japan Synthetic Rubber Co Ltd High-modulus diene rubber composition FR2527620B1 (en) * 1982-05-28 1986-02-21 Rhone Poulenc Spec Chim COMPOSITION FOR MOLDING BASED ON THERMOPLASTIC POLYMERS REINFORCED BY MINERAL FILLERS JPS591550A (en) * 1982-06-29 1984-01-06 Bridgestone Corp Rubber composition having improved crack propagation resistance US4431755A (en) * 1982-07-16 1984-02-14 Standard Oil Company (Indiana) Rubber composition comprising phyllosilicate minerals, silanes, and quaternary ammonium salts JPS5991972A (en) * 1982-11-19 1984-05-26 三菱レイヨン株式会社 Solid golf ball US4546980A (en) * 1984-09-04 1985-10-15 Acushnet Company Process for making a solid golf ball JPH0680123B2 (en) * 1985-06-12 1994-10-12 ブリヂストンスポーツ株式会社 Rubber composition for solid golf ball JPS62156148A (en) * 1985-12-27 1987-07-11 Otsuka Chem Co Ltd Rubber composition JP2577207B2 (en) * 1986-02-14 1997-01-29 三菱電線工業株式会社 Flame-retardant flexible fluorine rubber composition US4792141A (en) * 1987-04-20 1988-12-20 Acushnet Company Golf ball cover composition 1988 1988-06-08 GB GB8813497A patent/GB2206889B/en not_active Expired - Fee Related 1988-06-09 US US07/204,310 patent/US4955966A/en not_active Expired - Fee Related 1988-06-09 AU AU17557/88A patent/AU604915B2/en not_active Ceased 1988-06-10 CA CA000569213A patent/CA1331233C/en not_active Expired - Fee Related 1988-06-10 DE DE3819827A patent/DE3819827A1/en not_active Ceased 1988-06-11 KR KR1019880007065A patent/KR920004891B1/en not_active IP Right Cessation 1988-06-13 FR FR8807869A patent/FR2616438A1/en active Pending 1990 1990-07-11 US US07/551,163 patent/US5150905A/en not_active Expired - Fee Related 1990-07-11 US US07/551,162 patent/US5141233A/en not_active Expired - Fee Related 1990-09-13 AU AU62476/90A patent/AU620264B2/en not_active Ceased 1990-09-13 AU AU62475/90A patent/AU619131B2/en not_active Ceased 1991 1991-12-31 SG SG1111/91A patent/SG111191G/en unknown 1992 1992-06-25 HK HK453/92A patent/HK45392A/en unknown Patent Citations (3) * Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title AU7097587A (en) * 1981-08-27 1987-07-16 Union Carbide Corporation Additive for filled thermoplastics US4715607A (en) * 1986-02-18 1987-12-29 Acushnet Company Golf ball composition AU604915B2 (en) * 1987-06-11 1991-01-03 Asics Corporation Rubber composition and golf ball comprising it Also Published As Publication number Publication date HK45392A (en) 1992-07-03 GB2206889A (en) 1989-01-18 GB2206889B (en) 1991-03-20 AU619131B2 (en) 1992-01-16 FR2616438A1 (en) 1988-12-16 AU6247590A (en) 1990-12-13 AU604915B2 (en) 1991-01-03 US5150905A (en) 1992-09-29 SG111191G (en) 1992-02-14 AU1755788A (en) 1988-12-15 AU6247690A (en) 1990-12-13 CA1331233C (en) 1994-08-02 DE3819827A1 (en) 1988-12-22 US4955966A (en) 1990-09-11 KR890000573A (en) 1989-03-15 KR920004891B1 (en) 1992-06-22 GB8813497D0 (en) 1988-07-13 US5141233A (en) 1992-08-25 Similar Documents Publication Publication Date Title AU620264B2 (en) 1992-02-13 Rubber composition for cover layer of golf ball US5019319A (en) 1991-05-28 Golf ball US4561657A (en) 1985-12-31 Golf ball US7402629B2 (en) 2008-07-22 Highly-neutralized acid polymers and their use in golf balls US5338610A (en) 1994-08-16 Golf ball compositions US6441095B1 (en) 2002-08-27 Multi-layer golf ball utilizing silicone materials US5330837A (en) 1994-07-19 Golf ball compositions US6245862B1 (en) 2001-06-12 Golf balls comprising sulfonated or phosphonated ionomers US6159110A (en) 2000-12-12 Golf ball utilizing silicone materials US4082288A (en) 1978-04-04 Method of making adjuvant for elastomeric composition GB2144130A (en) 1985-02-27 Composition for cover of golf balls GB2139101A (en) 1984-11-07 Three-piece solid golf ball GB2376637A (en) 2002-12-24 Golf ball rubber composition GB2239458A (en) 1991-07-03 Improved golf ball compositions GB2376638A (en) 2002-12-24 Golf ball JPH0679017A (en) 1994-03-22 Golf ball and production thereof US4145045A (en) 1979-03-20 Pressureless tennis ball JPH0696651B2 (en) 1994-11-30 Rubber composition for golf ball US4020054A (en) 1977-04-26 Impact resistant high vinyl polydiene thermosetting compositions containing fibrous sulfur-containing organic polymer JPH02297384A (en) 1990-12-07 Solid golf ball JP4336958B2 (en) 2009-09-30 Golf ball JP2724534B2 (en) 1998-03-09 Golf ball JPS60181161A (en) 1985-09-14 Preparation of polyamide resin composition JP3606641B2 (en) 2005-01-05 Ionomer composition and use thereof JP4390338B2 (en) 2009-12-24 Golf ball and method for manufacturing the same
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