JP2002284896A - Grip and golf club - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a grip 1 having excellent anti-slip properties in wet state. SOLUTION: The grip 1 for a golf club is formed by crosslinking of a rubber composition. A base polymer of the rubber composition contains >=5 mass% of a bromide of a copolymer of isobutylene and paramethylstyrene. The bromide improves the anti-slip properties in the wet state. The rubber composition contains carbon black of 10-60 nm in a particle diameter. A content of the carbon black is 3-50 pts.per 100 pts. of the base polymer. The carbon black improves wear resistance of the grip 1. Using the same rubber composition as the above, a tool such as a hammer or the like, bicycle handlebars, cultivator handlebars, and the grip of a tennis racket or the like may be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to tools such as hammers, bicycle handles, cultivator handles, tennis rackets, and golf clubs.

[0002]

2. Description of the Related Art As a grip mounted on a golf club or the like, a grip formed of rubber, synthetic resin, leather or the like is known. Typical rubber grips use natural rubber, styrene-butadiene rubber (SBR) or butadiene rubber (BR). An important required performance of the grip is that the grip and the hand holding the grip do not slip easily, that is, that the grip performance is high.

[0003] Various improvements have been made to grips with the aim of improving anti-slip performance. For example, Japanese Patent No. 303507
No. 5 discloses ethylene-propylene-diene rubber (E
(PDM) and natural rubber are used as a base rubber, and a grip formed from a rubber composition in which transpolyoctenemer and hydrous aluminum silicate powder are blended is disclosed. Japanese Patent No. 3035076 discloses a grip using EPDM and polyisobutylene having a predetermined molecular weight.

[0004]

In rainy weather, hands and grips may get wet with rainwater. Also, in the summer months, hands and grips may be wet by sweat. In a wet state of the hand or the grip, that is, in a wet state, slippage between the hands and the grip is likely to occur due to the presence of a water film between the hand and the grip. A grip with sufficient anti-slip performance even in the wet state has not yet been obtained.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a grip having excellent anti-slip performance, especially in a wet state.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that the use of a brominated copolymer of isobutylene and paramethylstyrene as a base polymer for a rubber grip significantly improves anti-slip performance. And completed the present invention. That is, in the invention made to achieve the above object, the rubber composition is formed by crosslinking, and the base polymer of the rubber composition is bromine of a copolymer of isobutylene and paramethylstyrene. And a bromide of a copolymer of isobutylene and paramethylstyrene in which the proportion of brominated compounds in the total base polymer is 5% by mass or more.

[0007] Preferably, carbon black is blended into the rubber composition. Brominated copolymers of isobutylene and paramethylstyrene are inferior in abrasion resistance, but the incorporation of carbon black compensates for this drawback and improves grip durability.

[0008] The preferred compounding amount of carbon black is 3 parts or more and 50 parts or less based on 100 parts of the base polymer. The preferred particle diameter of carbon black is 1
It is not less than 0 nm and not more than 60 nm. In addition, in this specification, the numerical value shown by "part" means a ratio based on mass.

[0009] This grip is particularly suitable for golf clubs.

[0010]

BRIEF DESCRIPTION OF THE DRAWINGS FIG.
The present invention will be described in detail based on preferred embodiments.

FIG. 1 is a perspective view showing a golf club grip 1 according to an embodiment of the present invention. The grip 1 has a cylindrical shape with its rear end closed, and its outer diameter gradually increases from the front end to the rear end.

FIG. 2 is a perspective view showing a golf club 2 using the grip 1 of FIG. As shown in this figure, the grip 1 has the vicinity of the rear end of the shaft 3 fitted therein. A head 4 is mounted near the front end of the shaft 3. The shaft 3 may be made of stainless steel or carbon fiber reinforced resin. The head 4 may be a wood type head or an iron type head. Examples of the material of the head 4 include stainless steel, aluminum alloy, titanium alloy, magnesium alloy, fiber-reinforced synthetic resin, and persimmon.

The grip 1 is formed by crosslinking a rubber composition. The base polymer of the rubber composition contains a bromide of a copolymer of isobutylene and paramethylstyrene. In this bromide, first, isobutylene represented by the following chemical formula (1) and paramethylstyrene represented by the following chemical formula (2) are copolymerized, and then the obtained copolymer is subjected to, for example, bromine (Br) or the like. It is manufactured by bromination. Specific examples of such a bromide include “EXPRO® 90-10” and “EXPRO89-”, trade names of Exxon Chemical Co., Ltd.
4 "and the like.

[0014]

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[0015]

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In this bromide, halogen such as bromine is
Mainly p of phenyl group of styrene part in copolymer
It is presumed that it is substituted with hydrogen of the methyl group substituted at the position. There are no particular restrictions on the various attributes of the bromide, but the copolymerization ratio of isobutylene and paramethylstyrene is preferably about 85/15 to 99/1 by mass. The content of halogen such as bromine is 0.3% by mass.
It is preferably at least about 2.0 mass%.

The base polymer may contain a polymer other than the bromide. Polymers that can be used include:
Natural rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, butyl rubber, chloroprene rubber, ethylene-propylene-diene rubber, ethylene-propylene rubber, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, urethane rubber, etc. Can be These rubbers may be used alone or in combination of two or more. Along with rubber,
The base polymer may be a synthetic resin or a thermoplastic elastomer having a soft segment and a hard segment.

Even when other polymers are used in combination, the ratio of brominated copolymer of isobutylene and paramethylstyrene to the entire base polymer is at least 5% by mass. Thereby, good anti-slip performance is imparted to the grip 1. From the viewpoint of anti-slip performance, the ratio of this bromide to the entire base polymer is more preferably 7% by mass or more, and particularly preferably 20% by mass or more. From the viewpoint of anti-slip performance, the larger the ratio is, the more preferable.
0% by mass. However, when importance is placed on improving the strength, wear resistance, and workability of the grip 1, it is preferable to use the grip 1 in combination with another base polymer as necessary.

The rubber composition is crosslinked by known means. As a cross-linking agent used, sulfur is typical,
Other examples include zinc oxide (ZnO), siamin, and phenol formaldehyde resin. These crosslinking agents may be used alone or in combination of two or more. When only a bromide of a copolymer of isobutylene and paramethylstyrene is used as the base polymer,
Crosslinking can be achieved using only zinc oxide. When sulfur is used as the cross-linking agent, the general amount of sulfur is from 0.3 part to 5.0 parts, especially from 0.1 part to 100 parts of the base polymer.
5 parts or more and 3.0 parts or less.

The rubber composition may contain a vulcanization accelerator together with a crosslinking agent. Suitable vulcanization accelerators include thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, and dicarbamate vulcanization accelerators. In particular, a thiazole vulcanization accelerator is suitable for the grip 1 of the present invention. The general compounding amount of the vulcanization accelerator is 0.5 part or more and 7.0 parts or less, especially 1.5 parts or more and 4.0 parts or less based on 100 parts of the base polymer. Further, a metal compound such as zinc oxide or a fatty acid such as stearic acid may be blended as a crosslinking aid.

For the purpose of improving the strength, it is preferable that a filler is added to the rubber composition. As the filler used,
Examples include carbon black, silica, calcium carbonate, clay and the like. Among them, carbon black having a relatively small diameter is preferable because it contributes to the reinforcing effect, particularly to the improvement of wear resistance. Brominated copolymers of isobutylene and p-methylstyrene have slightly lower abrasion resistance, but the incorporation of small diameter carbon black compensates for this disadvantage.

The particle diameter of carbon black is 10 nm.
The thickness is preferably 60 nm or less and 60 nm or less. When the particle diameter is less than 10 nm, workability may be deteriorated in the manufacturing process of the grip 1. From this viewpoint, the particle diameter is 15 nm.
More preferably, the thickness is 19 nm or more. If the particle diameter exceeds 60 nm, the wear resistance of the grip 1 may be insufficient. From this viewpoint, the particle diameter is 5
7 nm or less is more preferable, 48 nm or less is further preferable, and 23 nm or less is particularly preferable.

Specific examples of suitable carbon black include Super Abr having a particle size of 11 nm to 19 nm as measured according to "ASTM D1765".
asion furance (SAF), particle diameter 2
Intermediate from 0 nm to 25 nm
Super Abrasion Furnace (IS
AF), Hig with a particle diameter of 26 nm to 30 nm
h AbrasionFurnace (HAF) and the like.

In addition, silica, calcium carbonate, carbon black having a particle diameter of more than 60 nm, or the like may be used in combination with the above-mentioned small carbon black having a particle diameter of 10 to 60 nm.

The amount of carbon black is preferably 3 parts or more and 50 parts or less based on 100 parts of the base polymer. If the amount is less than 3 parts, the wear resistance of the grip 1 may be insufficient. In this respect, the amount is more preferably equal to or greater than 5 parts, more preferably equal to or greater than 10 parts, and particularly preferably equal to or greater than 25 parts. If the compounding amount exceeds 50 parts, the grip 1 may have high hardness and the feeling of grip may be deteriorated.
In this respect, the amount is more preferably equal to or less than 45 parts and is preferably 4 parts or less.
0 parts or less are more preferable. In addition, all the carbon blacks to be blended are in the above-mentioned range (10 nm to 60 nm).
It is particularly preferable that the particle diameter is as follows.

The rubber composition may optionally contain a softening agent. As a softener, paraffin oil,
Mineral oils such as naphthenic oil and aromatic oil; and plasticizers such as dioctyl phthalate, dibutyl phthalate, dioctyl sepate, and dioctyl adipate.

The rubber composition may contain an appropriate amount of an antioxidant, a silane coupling agent, a silylating agent, a coloring agent, a processing aid, and the like, if necessary.

Although not shown in FIG. 1, a predetermined pattern of grooves is formed on the outer peripheral surface of the grip 1.
Due to this groove, formation of a water film between the golfer's hand and the grip 1 is suppressed, and the anti-slip performance of the grip 1 in a wet state is enhanced. Further, a reinforcing cord may be provided on the grip 1 from the viewpoint of anti-slip performance and wear resistance. Furthermore, the surface roughness of the grip 1 may be adjusted by surface polishing for the purpose of improving the anti-slip performance.

In the manufacture of the grip 1, first, a base polymer, a crosslinking agent, various additives, and the like are kneaded by an internal mixer such as a Banbury mixer to obtain a rubber composition. Next, this rubber composition is put into a mold having a cavity having the same shape as the grip 1. Next, the rubber composition is heated and pressed to cause a crosslinking reaction. Thus, the grip 1 is formed. Of course, another molding method such as an injection molding method may be adopted.

[0030]

EXAMPLES Hereinafter, the effects of the present invention will be clarified based on examples, but the present invention should not be construed as being limited based on the description of the examples.

Example 1 100 parts of bromide of a copolymer of isobutylene and paramethylstyrene (trade name "EXPRO 90-10" of Exxon Chemical Co., Ltd.), carbon black having an average particle diameter of 23 nm (Mitsubishi Chemical Corporation) 25 parts of paraffin oil (trade name "PW380" of Idemitsu Kosan Co., Ltd.), 2.0 parts of 2,6-di-tert-butyl-4-methylphenol (antioxidant) 2.0 parts of Ouchi Shinko Kagaku Kogyo Co., Ltd.), 0.5 parts of other anti-aging agent (Ouchi Shinko Kagaku Kogyo Co., Ltd. product name of "San Nok N"), sulfur 1.0
Part, dibenzothiazyl disulfide as vulcanization accelerator (trade name “Noxeller DM” of Ouchi Shinko Chemical Co., Ltd.)
2.0 parts, zinc oxide 2.0 parts, and stearic acid 1.0
The mixture was kneaded with a Banbury mixer to obtain a rubber composition.
This rubber composition was charged into a mold having a known groove pattern on the cavity surface. And at a temperature of 160 ° C., 10
The rubber composition was allowed to undergo a crosslinking reaction over a period of
Golf club grip was obtained.

Comparative Example 1 A grip of Comparative Example 1 was obtained in the same manner as in Example 1 except that butadiene rubber (trade name “BR11” of Nippon Synthetic Rubber Co., Ltd.) was used as the base polymer.

Examples 2 and 3 and Comparative Example 2 As a base polymer, a bromide of a copolymer of isobutylene and paramethylstyrene (the above-mentioned trade name "Explo 90-
10 ") and butadiene rubber (the above-mentioned trade name" BR1
1 "), and grips of Examples 2 and 3 and Comparative Example 2 were obtained in the same manner as in Example 1 except that the mixing ratio was as shown in Table 1 below.

[Examples 4 to 7] The average particle diameter was 19 n.
A grip of Example 4 was obtained in the same manner as in Example 1 except that carbon black (diamond black A, trade name of Mitsubishi Kasei Co., Ltd.) was used. The average particle diameter is 48 nm.
A grip of Example 5 was obtained in the same manner as in Example 1, except that carbon black (trade name “Diablack E” of Mitsubishi Kasei Co., Ltd.) was used. Further, carbon black having an average particle diameter of 57 nm (trade name “NITERON #
A grip of Example 6 was obtained in the same manner as Example 1 except that 55U ") was used. Further, the average particle diameter is 72 nm.
A grip of Example 7 was obtained in the same manner as in Example 1 except that carbon black (trade name “Niteron # 75” of Nippon Steel Chemical Co., Ltd.) was used.

Examples 8 and 9 and 11 and 12 Examples 8 and 9 were carried out in the same manner as in Example 1 except that the amount of carbon black was varied as shown in Table 2 below.
And grips of 11 and 12 were obtained.

Example 10 A grip of Example 10 was obtained in the same manner as in Example 1 except that 5 parts of silica (trade name "Ultrasil VN3" manufactured by Degussa) was further added.

Example 13 30 parts of silica ("Ultrazil VN3") was used in place of carbon black, and bis- (3-triethoxysilylpropyl) tetrasulfene (Degussa) was used as a silane coupling agent. The grip of Example 13 was obtained in the same manner as in Example 1 except that 3.0 parts of the product name was “Si69”.

Example 14 As a base polymer, 20 parts of a bromide of a copolymer of isobutylene and paramethylstyrene (trade name "Explo 90-10") and butadiene rubber (trade name "BR11") ") A grip of Example 14 was obtained in the same manner as Example 13 except that 80 parts were used.

Comparative Example 3 Natural Rubber (RSS # 3) 10
0 parts, 5 parts of carbon black having an average particle diameter of 31 nm (Mitsubishi Kasei's trade name "Diablack H"), 30 parts of clay (South Eastern Clay Company's trade name "Crown Clay"), naphthenic oil (Idemitsu Kosan Company name "Diana Process Oil NS-100") 1
0.0 part, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as an antioxidant (trade name “Nocrack NS-6” of Ouchi Shinko Chemical Co., Ltd.)
0.5 parts, sulfur 2.0 parts, N-cyclohexyl-2-benzothiazolylsulfenamide as a vulcanization accelerator (trade name “Noxeller CZ” of Ouchi Shinko Chemical Co., Ltd.)
1.0 part, 1.0 part of tetramethylthiuram disulfide (trade name "Noxeller TT" of Ouchi Shinko Chemical Co., Ltd.) as another vulcanization accelerator, 5.0 parts of zinc oxide, and 1.0 of stearic acid The mixture was kneaded with a Banbury mixer to obtain a rubber composition. This rubber composition was crosslinked in the same manner as in Example 1 to obtain a grip of Comparative Example 3.

Comparative Example 4 Natural Rubber (RSS # 3) 70
Parts, 30 parts of styrene-butadiene rubber (trade name “SBR1502” of Nippon Synthetic Rubber Co., Ltd.), 5 parts of carbon black (trade name “Dia Black H” described above), and 30 parts of silica (trade name “Ultrasil VN3”) 30 Part, naphthenic oil (the above-mentioned trade name "Diana Process Oil NS-1
00 ") 20.0 parts, antioxidant (the above-mentioned trade name" Nocrack NS-6 ") 0.5 part, sulfur 2.0 parts, vulcanization accelerator (the above-mentioned trade name" Noxeller CZ ") 0 parts, other vulcanization accelerator (the above-mentioned trade name "Noxeller TT") 1.0
Parts, zinc oxide 5.0 parts and stearic acid 1.0 part were kneaded with a Banbury mixer to obtain a rubber composition. This rubber composition was crosslinked in the same manner as in Example 1 to obtain a grip of Comparative Example 4.

Comparative Example 5 Natural Rubber (RSS # 3) 60
Parts, 40 parts of ethylene-propylene-diene rubber (trade name “Esprene 505A” of Sumitomo Chemical Co., Ltd.), 5 parts of carbon black (trade name “diablack H” described above),
30 parts of clay (the above-mentioned trade name "crown clay"), 10.0 parts of naphthenic oil (the above-mentioned trade name "Diana Process Oil NS-100"), anti-aging agent (the above-mentioned trade name "Nocrack NS-6") 0.5 parts, sulfur 1.5 parts,
Vulcanization accelerator (the above-mentioned trade name "Noxeller CZ") 1.0
Part, another vulcanization accelerator (the above-mentioned trade name "Noxeller T
T ") 0.5 part, zinc oxide 5.0 parts and stearic acid 1.0 part were kneaded with a Banbury mixer to obtain a rubber composition. This rubber composition was crosslinked in the same manner as in Example 1,
The grip of Comparative Example 5 was obtained.

Comparative Example 6 Ethylene-propylene-diene rubber (the above-mentioned trade name "Esprene 505A") 100
Parts, 5 parts of carbon black (the above-mentioned trade name “Dia Black H”), 5 parts of clay (the above-mentioned trade name “Crown Clay”), and silica (the above-mentioned trade name “Ultrasil VN”)
3 ") 30 parts, antioxidant (the above-mentioned trade name" Nocrack NS-6 ") 0.5 part, sulfur 1.5 parts, vulcanization accelerator (the above-mentioned trade name" Noxeller CZ ") 1.0 part Then, 0.5 part of another vulcanization accelerator (the above-mentioned trade name “Noxeller TT”), 5.0 parts of zinc oxide and 1.0 part of stearic acid were kneaded with a Banbury mixer to obtain a rubber composition. This rubber composition was crosslinked in the same manner as in Example 1 to obtain a grip of Comparative Example 6.

[Evaluation of Anti-Slip Performance] A golf club was manufactured by attaching a grip to a shaft. The grip is dipped in water to make the golf club wet.
The anti-slip performance was evaluated on a five-point scale from “1” to “5” using a golfer of the same name. The one that caused the least slippage was “5”, and the one that was most likely to slip was “1”. 10
The average of the evaluation values of the first-name golfers is shown in Tables 1 and 2 below.
Is shown in

[Evaluation of Abrasion Resistance] The same rubber composition as that used for molding each grip was charged into a mold, and the rubber composition was added to the mold.
Pressing and heating were performed at 0 ° C. for 10 minutes to obtain a disc-shaped test piece having a thickness of 12.7 mm. This test piece was subjected to JIS-K-626.
The sample was subjected to an Akron abrasion test according to No. 4 to measure the abrasion capacity. The results are shown in Tables 1 and 2 below.

[Measurement of Hardness] The same rubber composition as that used for molding each grip was charged into a mold and heated at 160 ° C.
For 10 minutes to obtain a block-shaped test piece having a thickness of 12 mm. This test piece was subjected to a hardness test according to JIS-K-6251, and the hardness (Shore A) was measured. The results are shown in Tables 1 and 2 below.

[0046]

[Table 1]

[0047]

[Table 2]

As shown in Tables 1 and 2, the grips of the examples have excellent anti-slip performance in a wet state.
From the evaluation results, the superiority of the present invention is apparent.

As described above, the grip of the present invention has been described in detail by taking as an example the case of being used for a golf club. However, the grip of the present invention can be applied to tools such as hammers, bicycle handles, tiller handles, tennis rackets, and the like. Can be used.

[0050]

As described above, the grip of the present invention has excellent anti-slip performance. Tools and devices equipped with this grip are easy for the user to handle.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a golf club grip according to one embodiment of the present invention.

FIG. 2 is a perspective view showing a golf club using the grip of FIG. 1;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Grip 2 ... Golf club 3 ... Shaft 4 ... Head

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2C002 AA06 GG07 MM08 4F071 AA21X AA22X AA78 AB03 AD06 AE17 AF28 AG05 AH19 BA01 BB05 BC07 4J002 AC01X AC03X AC06X AC07X AC08X AC09X BB15X BB18X BB24W0X BB04 CHX04

Claims (5)

[Claims] 1. A rubber composition formed by crosslinking a rubber composition, wherein a base polymer of the rubber composition contains a bromide of a copolymer of isobutylene and paramethylstyrene, and isobutylene and paramethyl A grip in which a brominated product of a copolymer with styrene accounts for 5% by mass or more of the total base polymer. 2. The grip according to claim 1, wherein carbon black is compounded in the rubber composition. 3. The grip according to claim 2, wherein the compounding amount of the carbon black is 3 parts or more and 50 parts or less based on 100 parts of the base polymer. 4. The carbon black having a particle diameter of 10
The grip according to claim 2 or 3, wherein the thickness is not less than 60 nm and not more than 60 nm. 5. A shaft, a head mounted near a front end of the shaft, and a grip fitted near a rear end of the shaft, wherein the grip is formed by crosslinking a rubber composition. The base polymer of the rubber composition contains a bromide of a copolymer of isobutylene and paramethylstyrene, and the bromide of a copolymer of isobutylene and paramethylstyrene is used as the whole base polymer. A golf club having a proportion of 5% by mass or more.