WO2018117202A1 - Composition de caoutchouc et balle de golf - Google Patents

Composition de caoutchouc et balle de golf Download PDF

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Publication number
WO2018117202A1
WO2018117202A1 PCT/JP2017/045849 JP2017045849W WO2018117202A1 WO 2018117202 A1 WO2018117202 A1 WO 2018117202A1 JP 2017045849 W JP2017045849 W JP 2017045849W WO 2018117202 A1 WO2018117202 A1 WO 2018117202A1
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WIPO (PCT)
Prior art keywords
group
rubber composition
rubber
crosslinking agent
tetrazine
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PCT/JP2017/045849
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English (en)
Japanese (ja)
Inventor
佐藤　崇
宏昭 湯浅
慎也 中島
晃之 吉田
小島　正章
真希 武田
Original Assignee
大塚化学株式会社
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Application filed by 大塚化学株式会社 filed Critical 大塚化学株式会社
Priority to JP2018558061A priority Critical patent/JP7023862B2/ja
Publication of WO2018117202A1 publication Critical patent/WO2018117202A1/fr

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Classifications

    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • 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

Definitions

  • the present invention relates to a rubber composition and a golf ball.
  • the core of multi-piece golf balls such as one-piece golf balls, two-piece golf balls, and three-piece golf balls has a base rubber mainly composed of butadiene rubber as a rubber component, and an ⁇ , ⁇ -unsaturated carboxylic acid.
  • a vulcanized molded product of a rubber composition containing a metal salt and an organic peroxide is used.
  • the above metal salt of ⁇ , ⁇ -unsaturated carboxylic acid acts as a co-crosslinking agent and is introduced into the butadiene rubber main chain to form a complicated three-dimensional crosslinked structure, so that the resulting vulcanized molded article has an appropriate hardness.
  • the solid golf ball using the vulcanized molded product exhibits durability and resilience performance.
  • the main object of the present invention is to provide a rubber composition capable of imparting high resilience to a golf ball.
  • Another object of the present invention is to provide a golf ball excellent in high resilience.
  • the present inventors have found that a high rebound can be imparted to the rubber composition by blending a specific tetrazine compound into the rubber composition. As a result of further investigation based on such knowledge, the present inventors have completed the present invention.
  • the present invention provides the following rubber composition and golf ball.
  • Item 1 A rubber composition containing a rubber component, a tetrazine compound represented by the following general formula (1) or a salt thereof, a crosslinking agent, and a co-crosslinking agent.
  • X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an aralkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents.
  • Item 2. The rubber composition according to Item 1, wherein the tetrazine compound is a tetrazine compound in which X 1 and X 2 represent a heterocyclic group in the general formula (1).
  • a rubber composition comprising a rubber component, a modified polymer obtained by treating a tetrazine compound represented by the general formula (1) or a salt thereof, a crosslinking agent, and a co-crosslinking agent.
  • Item 4. Item 3. The rubber composition according to Item 1 or 2, comprising 0.1 to 10 parts by mass of the tetrazine compound represented by the general formula (1) or a salt thereof with respect to 100 parts by mass of the rubber component.
  • Composition. Item 6.
  • Item 6. Item 6.
  • Item 7. The rubber composition according to any one of Items 1 to 6, wherein the diene rubber is 50 parts by mass or more in 100 parts by mass of the rubber component.
  • Item 8. The rubber composition according to Item 7, wherein the diene rubber contains butadiene rubber.
  • Item 11. The rubber composition according to any one of Items 1 to 10, further comprising an inorganic filler.
  • Item 12. The rubber composition according to Item 11, containing 5 to 130 parts by mass of an inorganic filler with respect to 100 parts by mass of the rubber component.
  • Item 13 Item 13.
  • the rubber composition of the present invention can sufficiently disperse the co-crosslinking agent, the vulcanized molded product can form a highly crosslinked structure, thereby exhibiting high resilience.
  • the golf ball of the present invention is made of the rubber composition and has excellent high resilience.
  • the rubber composition of the present invention has excellent durability in addition to high resilience, a golf ball having high resilience and excellent durability can be provided.
  • the rubber composition of the present invention comprises a rubber component, a tetrazine compound represented by the following general formula (1) or a salt thereof (hereinafter sometimes referred to as “tetrazine compound (1)”), a crosslinking agent and a co-agent. Contains a crosslinking agent.
  • X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
  • the rubber composition of the present invention contains a modified polymer obtained by treating a rubber component and a tetrazine compound (1), a crosslinking agent and a co-crosslinking agent.
  • the compounding amount of the tetrazine compound (1) is usually 0.1 to 10 parts by mass, preferably 0.25 to 5 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is 0.5 to 2 parts by mass.
  • the compounding amount of the crosslinking agent is usually 0.1 to 10 parts by weight, preferably 0.2 to 7.5 parts by weight, based on 100 parts by weight of the rubber component.
  • the amount is preferably 0.5 to 5 parts by mass.
  • the compounding amount of the co-crosslinking agent is usually 5 to 60 parts by mass, preferably 7.5 to 50 parts by mass, more preferably 10 to 100 parts by mass of the rubber component. ⁇ 45 parts by mass.
  • the total amount of both components is usually 5 to 70 parts by weight, preferably 5.5 to 57.5 parts by weight with respect to 100 parts by weight of the rubber component. More preferably, it may be appropriately adjusted so as to be 10 to 50 parts by mass.
  • an inorganic filler may be blended for the purpose of improving the strength of the crosslinked molded product of the rubber composition, or for the purpose of adjusting the weight and strength of the golf ball produced from the rubber composition.
  • the amount of the inorganic filler is usually 5 to 130 parts by mass with respect to 100 parts by mass of the rubber component.
  • Rubber component The rubber component to be blended in the rubber composition of the present invention is not particularly limited.
  • natural rubber NR
  • synthetic diene rubber a mixture of natural rubber and synthetic diene rubber, and others Non-diene rubbers.
  • natural rubber examples include natural rubber latex, technically rated rubber (TSR), smoked sheet (RSS), gutta percha, Tochu-derived natural rubber, guayule-derived natural rubber, and Russian dandelion-derived natural rubber.
  • Modified natural rubbers such as modified epoxidized natural rubber, methacrylic acid-modified natural rubber, and styrene-modified natural rubber are also included in the natural rubber of the present invention.
  • Synthetic diene rubbers include styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene-propylene-diene ternary copolymer Polymer rubber (EPDM), styrene-isoprene-styrene terpolymer block copolymer (SIS), styrene-butadiene-styrene terpolymer block copolymer (SBS), ethylene- ⁇ -olefin copolymer rubber (SPO), ethylene Examples thereof include - ⁇ -olefin-diene copolymer rubbers, and modified synthetic diene rubbers thereof.
  • SBR styrene-butadiene copolymer rubber
  • BR butadiene rubber
  • IR isoprene rubber
  • NBR nitrile rubber
  • CR chloropre
  • the modified synthetic diene rubber includes a diene rubber by a modification technique such as main chain modification, one terminal modification, or both terminal modification.
  • examples of the modified functional group of the modified synthetic diene rubber include various functional groups such as an epoxy group, an amino group, an alkoxysilyl group, and a hydroxyl group, and one or more of these functional groups are modified synthetic diene series. It may be contained in rubber.
  • the method for producing the synthetic diene rubber is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, radical polymerization, anionic polymerization, and cationic polymerization. Further, there is no particular limitation on the glass transition point of the synthetic diene rubber.
  • the ratio of cis / trans / vinyl in the double bond portion of natural rubber and synthetic diene rubber is not particularly limited, and any ratio can be preferably used.
  • the number average molecular weight and molecular weight distribution of the diene rubber are not particularly limited.
  • the diene rubber preferably has a number average molecular weight of 500 to 3000000 and a molecular weight distribution of 1.5 to 15.
  • the rubber component used in the rubber composition of the present invention preferably contains a diene rubber, and preferably contains 50 parts by mass or more of diene rubber in 100 parts by mass of the rubber component, and 75 parts by mass or more. It is more preferable that it is contained, and it is particularly preferable that it is blended at a ratio of 80 to 100 parts by mass.
  • non-diene rubber known rubbers can be widely used.
  • the rubber component can be used alone or in combination (blend) of two or more.
  • a preferable rubber component is at least one rubber component selected from the group consisting of natural rubber, IR, SBR, BR, and EPDM, or a mixture of two or more, and more preferably BR.
  • Tetrazine compound (1) The rubber composition of the present invention contains a tetrazine compound represented by the following general formula (1) or a salt thereof.
  • X 1 and X 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkylthio group, an aralkyl group, an aryl group, an arylthio group, a heterocyclic group, or an amino group. Each of these groups may have one or more substituents. ]
  • alkyl group is not particularly limited and includes, for example, a linear, branched or cyclic alkyl group, and specifically includes, for example, a methyl group, an ethyl group, and an n-propyl group.
  • the preferred alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or n -Pentyl group, particularly preferably a methyl group or an ethyl group.
  • alkylthio group is not particularly limited and includes, for example, a linear, branched or cyclic alkylthio group, and specifically includes, for example, a methylthio group, an ethylthio group, and an n-propylthio group.
  • the preferred alkylthio group is a methylthio group, an ethylthio group, an isopropylthio group, or an isobutylthio group, and more preferably a methylthio group or an ethylthio group.
  • the “aralkyl group” is not particularly limited, and examples thereof include benzyl group, phenethyl group, trityl group, 1-naphthylmethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl group). ) And the like.
  • a more preferred aralkyl group is a benzyl group or a phenethyl group, more preferably a benzyl group.
  • aryl group is not particularly limited, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a dihydroindenyl group, and a 9H-fluorenyl group.
  • a more preferred aryl group is a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • arylthio group is not particularly limited, and examples thereof include a phenylthio group, a biphenylthio group, and a naphthylthio group.
  • the “heterocyclic group” is not particularly limited, and examples thereof include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 3-pyridyl group, 4-pyridazyl group, 4- (1,2,3-triazyl group), 5- (1,2,3-triazyl group), 2- (1,3,5- Triazyl) group, 3- (1,2,4-triazyl) group, 5- (1,2,4-triazyl) group, 6- (1,2,4-triazyl) group, 2-quinolyl group, 3- Quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6- Isoquinolyl group, 6-
  • a preferable heterocyclic group is a pyridyl group, a furanyl group, a thienyl group, a pyrimidyl group or a pyrazyl group, and more preferably a pyridyl group.
  • the “amino group” includes not only an amino group represented by —NH 2 but also, for example, a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, an n-butylamino group.
  • alkyl groups, alkylthio groups, aralkyl groups, aryl groups, arylthio groups, heterocyclic groups, and amino groups may each have one or more substituents.
  • the “substituent” is not particularly limited, and examples thereof include halogen atoms, amino groups, aminoalkyl groups, alkoxycarbonyl groups, acyl groups, acyloxy groups, amide groups, carboxyl groups, carboxyalkyl groups, formyl groups, and nitrile groups.
  • the substituent may preferably have 1 to 5, more preferably 1 to 3.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom, a bromine atom, and an iodine atom are preferable.
  • aminoalkyl group is not particularly limited, and examples thereof include aminoalkyl groups such as aminomethyl group, 2-aminoethyl group, and 3-aminopropyl group.
  • alkoxycarbonyl group is not particularly limited, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
  • acyl group is not particularly limited, and examples thereof include a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms such as an acetyl group, a propionyl group, and a pivaloyl group.
  • acyloxy group is not particularly limited, and examples thereof include an acetyloxy group, a propionyloxy group, and an n-butyryloxy group.
  • the “amide group” is not particularly limited, and examples thereof include carboxylic acid amide groups such as acetamido group and benzamide group; thioamide groups such as thioacetamido group and thiobenzamide group; N-methylacetamido group, N -N-substituted amide group such as benzylacetamide group; and the like.
  • the “carboxyalkyl group” is not particularly limited, and examples thereof include a carboxymethyl group, a carboxyethyl group, a carboxy-n-propyl group, a carboxy-n-butyl group, a carboxy-n-pentyl group, and a carboxy group.
  • a carboxy-alkyl group such as an -n-hexyl group (preferably an alkyl group having 1 to 6 carbon atoms having a carboxy group).
  • hydroxyalkyl group is not particularly limited, and examples thereof include hydroxy-alkyl groups such as hydroxymethyl group, hydroxyethyl group, hydroxy-n-propyl group, hydroxy-n-butyl group (preferably And an alkyl group having 1 to 6 carbon atoms having a hydroxy group).
  • alkoxy group is not particularly limited and includes, for example, a linear, branched or cyclic alkoxy group, and specifically includes, for example, a methoxy group, an ethoxy group, an n-propoxy group.
  • aryloxy group is not particularly limited, and examples thereof include a phenoxy group, a biphenyloxy group, and a naphthoxy group.
  • the “salt” of the tetrazine compound represented by the general formula (1) is not particularly limited, and includes all kinds of salts.
  • examples of such salts include inorganic acid salts such as hydrochlorides, sulfates and nitrates; organic acid salts such as acetates and methanesulfonates; alkali metal salts such as sodium salts and potassium salts; magnesium salts and calcium Examples include alkaline earth metal salts such as salts; ammonium salts such as dimethylammonium and triethylammonium.
  • preferred compounds are those in which X 1 and X 2 are the same or different and may have a substituent, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. It is a compound which is an aryl group which may have a group, or a heterocyclic group which may have a substituent.
  • X 1 and X 2 are the same or different and have an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is a compound that is an optionally substituted heterocyclic group.
  • X 1 and X 2 are the same or different and each may be an optionally substituted 2-pyridyl group or an optionally substituted 3-pyridyl group. Compounds are particularly preferred.
  • tetrazine compound (1) for example, 1,2,4,5-tetrazine, 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine, 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine, 3,6-bis (4-pyridyl) -1,2,4,5-tetrazine, 3,6-diphenyl-1,2,4,5-tetrazine, 3,6-dibenzyl-1,2,4,5-tetrazine, 3,6-bis (2-furanyl) -1,2,4,5-tetrazine, 3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine, 3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine, 3,6-bis (2-thienyl) -1,2,4,5-tetrazine, 3-methyl-6- (2-pyridyl) -1,2,4,5-tete
  • preferred tetrazine compounds (1) are 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine and 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine.
  • more preferred tetrazine compound (1) is 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine, And 3,6-bis (3-pyridyl) -1,2,4,5-tetrazine.
  • High resilience can be imparted to the rubber composition by adding the tetrazine compound (1) to the rubber component.
  • a golf ball made (manufactured) from such a rubber composition containing the tetrazine compound (1) can have high hardness and high strength, and energy loss is reduced. As a result, high durability and high resilience performance are achieved. To express.
  • a modified polymer is produced by treating the modified polymer rubber component with the tetrazine compound (1). This is because the reverse electron request type Aza-Diels-Alder reaction proceeds between the double bond of the diene rubber in the rubber component and the tetrazine compound (1).
  • the rubber component and the tetrazine compound (1) are kneaded under heating conditions.
  • the compounding amount of the tetrazine compound (1) is not particularly limited, and is usually 0.1 to 10 parts by mass, preferably 0.25 to 5 parts by mass with respect to 100 parts by mass of the rubber component, More preferably, it may be appropriately adjusted to be 0.5 to 2 parts by mass.
  • the heating temperature is not particularly limited, and for example, the upper limit of the temperature of the rubber composition is preferably 80 to 190 ° C., more preferably 90 to 160 ° C., and preferably 100 to 150 ° C. Further preferred.
  • the mixing time or kneading time is not particularly limited, and is preferably, for example, 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 60 seconds to 7 minutes.
  • the rubber component is liquid (liquid)
  • a method of mixing the rubber component solution or emulsion (suspension) and the tetrazine compound (1) under heating conditions liquid mixing method and the like can be mentioned.
  • the compounding amount of the tetrazine compound (1) in this case may be the same as described above, and is usually 0.1 to 10 parts by mass, preferably 0.25 to 5 parts by mass with respect to 100 parts by mass of the rubber component. Yes, and more preferably 0.5 to 2 parts by mass.
  • the heating temperature is not particularly limited, and the upper limit of the temperature of the liquid rubber composition is preferably 80 to 190 ° C, more preferably 90 to 160 ° C, and further preferably 100 to 150 ° C. preferable.
  • the mixing time or kneading time is not particularly limited, and is preferably, for example, 10 seconds to 60 minutes, more preferably 30 seconds to 40 minutes, and further preferably 60 seconds to 30 minutes.
  • the solvent in the mixture can be removed (removed) under reduced pressure, and the solid rubber composition can be recovered.
  • the obtained modified polymer can be blended with a crosslinking agent, a co-crosslinking agent and the like to obtain a rubber composition of the present invention, and an inorganic filler can be blended as necessary.
  • Crosslinking agent The rubber composition of the present invention is blended with a known crosslinking agent used in rubber compositions for golf balls.
  • a known crosslinking agent used in rubber compositions for golf balls.
  • organic peroxides are preferably used.
  • the organic peroxide is decomposed by heat to generate radicals, and the resilience can be improved by increasing the degree of crosslinking between the co-crosslinking agent and the rubber component.
  • organic peroxide examples include dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di- ( Examples thereof include t-butylperoxy) hexane, 1,3-bis (t-butylperoxy-isopropyl) benzene, and di-t-butylperoxide.
  • An organic peroxide can be used individually by 1 type or in combination of 2 or more types.
  • Co-crosslinking agent A co-crosslinking agent is blended in the rubber composition of the present invention.
  • the co-crosslinking agent itself has a function of cross-linking and also reacting with rubber molecules to cross-link and polymerize the whole.
  • the co-crosslinking agent is not particularly limited as long as it is a commonly used co-crosslinking agent in the rubber industry, and known ones can be widely used.
  • co-crosslinking agents include monovalent or divalent metal salts of ⁇ , ⁇ -unsaturated carboxylic acids, and more specifically, acrylic acid, methacrylic acid, itaconic acid, maleic acid.
  • metal salts such as fumaric acid, crotonic acid, sorbic acid, tiglic acid, cinnamic acid, and aconitic acid.
  • the metal salt include alkali metal salts such as lithium salt, sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; and other metal salts such as zinc salt.
  • these metal salts of ⁇ , ⁇ -unsaturated carboxylic acids zinc acrylate and zinc methacrylate can be preferably used.
  • these co-crosslinking agents can be used individually by 1 type or in combination of 2 or more types.
  • the metal salt of ⁇ , ⁇ -unsaturated carboxylic acid itself may be mixed with the rubber component or the like.
  • an ⁇ , ⁇ -unsaturated carboxylic acid is further added to the rubber composition kneaded with a metal oxide or metal hydroxide, and kneaded, whereby the ⁇ , ⁇ -unsaturated carboxylic acid is added to the rubber composition.
  • An acid and a metal oxide may be reacted to form a metal salt.
  • a divalent metal salt a completely neutralized type or a partially neutralized type may be used.
  • the inorganic filler is not particularly limited as long as it is an inorganic compound usually used in the rubber industry.
  • examples of inorganic compounds that can be used include silica; alumina such as ⁇ -alumina and ⁇ -alumina (Al 2 O 3 ); alumina monohydrate such as boehmite and diaspore (Al 2 O 3 .H 2 O); gibbsite Aluminum hydroxide [Al (OH) 3 ], such as bayerite; aluminum carbonate [Al 2 (CO 3 ) 2 ], magnesium hydroxide [Mg (OH) 2 ], magnesium oxide (MgO), magnesium carbonate (MgCO 3 ), Talc (3MgO ⁇ 4SiO 2 ⁇ H 2 O), attapulgite (5MgO ⁇ 8SiO 2 ⁇ 9H 2 O), titanium white (TiO 2 ), titanium black (TiO 2n-1 ), calcium oxide (CaO), hydroxylated Calcium [Ca (OH) 2 ], aluminum magnesium oxide (MgO
  • zinc oxide is preferable from the viewpoint of imparting strength to rubber, and zinc oxide is more preferable.
  • These inorganic fillers can be used singly or in combination of two or more.
  • the compounding amount of the inorganic filler is usually 5 to 130 parts by mass, preferably 7.5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the rubber component.
  • the rubber composition of the present invention includes compounding agents commonly used in the rubber industry, such as anti-aging.
  • Agents, lubricants such as stearic acid, sulfur, softeners, processing aids, waxes, resins, foaming agents, oils, vulcanization accelerators, vulcanization retarders, etc. are appropriately selected within a range that does not impair the purpose of the present invention Can be blended.
  • these compounding agents commercially available products can be used.
  • an organic sulfur compound can be blended with the rubber composition of the present invention.
  • organic sulfur compounds include thiophenol, thionaphthol, halogenated thiophenol, or metal salts thereof. More specifically, pentachlorothiophenol, pentafluorothiophenol, pentabromothiophenol, para Examples thereof include zinc salts such as chlorothiophenol and pentachlorothiophenol, diphenyl polysulfide having 2 to 4 sulfur atoms, dibenzyl polysulfide, dibenzoyl polysulfide, dibenzothiazoyl polysulfide, and dithiobenzoyl polysulfide. These organic sulfur compounds can be used singly or in combination of two or more.
  • the production method of the rubber composition of the present invention is not particularly limited and can be produced by a conventionally known method.
  • a rubber component, a tetrazine compound (1), a crosslinking agent, and Examples thereof include a method including a step (A) of kneading raw material components including a co-crosslinking agent.
  • step (A) a double bond portion of the rubber component (diene rubber) and the tetrazine compound (1) react to form a modified polymer, and a mixture in which the co-crosslinking agent and the inorganic filler are suitably dispersed is formed. Obtainable.
  • the rubber composition in the present invention is mixed or kneaded using a Banbury mixer, roll, intensive mixer, kneader, twin screw extruder or the like.
  • Golf ball cores golf ball cores, using said rubber composition can be obtained by using a known method such as vulcanized in a mold.
  • the vulcanization conditions at this time are not particularly limited, and it is usually carried out at 100 to 240 ° C. for 10 to 60 minutes, preferably 130 to 200 ° C. for 10 to 40 minutes.
  • the specific gravity of the golf ball core is preferably 0.9 to 1.5, and more preferably 1.0 to 1.3.
  • the hardness of the golf ball core is preferably 35 to 60, more preferably 40 to 50 in accordance with JIS-D hardness (JIS K6253).
  • the diameter of the golf ball core may be set as appropriate according to the form of the solid golf ball (two-piece golf ball, three-piece golf ball, etc.).
  • the golf ball of the present invention is a solid golf ball produced using a rubber composition containing a tetrazine compound (1) or a modified polymer, and can take various golf ball modes.
  • the use of the solid golf ball is not particularly limited, and examples thereof include a one-piece solid golf ball, a two-piece solid golf ball, and a multi-piece solid golf ball.
  • the golf ball of the present invention can be suitably used for these applications.
  • the golf ball of the present invention can be manufactured by a known vulcanization or curing method of the rubber composition of the present invention.
  • the rubber composition of the present invention can be made into a one-piece golf ball by a method of heat and pressure molding using a mold.
  • the vulcanization conditions are usually 100 to 240 ° C. for 10 to 60 minutes, preferably 130 to 200 ° C. for 10 to 40 minutes.
  • the multi-piece golf ball of the present invention can be produced by coating the golf ball core made from the rubber composition of the present invention with a cover resin mainly composed of a thermoplastic resin, an intermediate layer, and the like.
  • the covering method of the cover resin, the intermediate layer and the like can be generally performed using a known method and is not particularly limited. For example, a method in which the core is covered with two hemispherical shells obtained by molding a coating composition and then heat-press molding, or a method in which the coating composition is directly injected into the core and molded. be able to.
  • Dimples may be formed on the resulting golf ball, and a paint finish or logo may be printed as necessary.
  • the shape, structure, size and material of the golf ball of the present invention are not particularly limited and can be appropriately selected according to the golf regulations.
  • the strength and hardness of the golf ball are improved and energy loss can be reduced, a golf ball having high resilience and durability can be provided.
  • Hardness index ⁇ (Hardness of rubber composition not containing tetrazine compound (1)) / (Hardness of rubber composition of the present invention) ⁇ ⁇ 100
  • Tensile strength Tensile strength at break was measured according to ASTM-D412. It shows that tensile strength is so high that a numerical value is large.
  • a rubber composition reference
  • an index of tensile strength was calculated.
  • the tensile strength of each reference vulcanized rubber composition is 100.
  • Tensile strength index ⁇ (Tensile strength of rubber composition not containing tetrazine compound (1)) / (Tensile strength of rubber composition of the present invention) ⁇ ⁇ 100
  • Loss factor (tan ⁇ index)
  • tan ⁇ index For the rubber compositions of Examples 1 and 2 below, tan ⁇ was measured at a temperature of 40 ° C., a dynamic strain of 5%, and a frequency of 15 Hz using a viscoelasticity measuring device (manufactured by Metravib).
  • a rubber composition (reference) was prepared with the same blending contents and the same manufacturing method as in each example except that no tetrazine compound was added, and the reciprocal of tan ⁇ was set to 100, respectively.
  • an index of loss factor was calculated. In addition, it shows that it is a low energy loss and the resilience is so large that the value of the index of a loss coefficient is large.
  • the loss factor of each reference vulcanized rubber composition is 100.
  • Loss coefficient index ⁇ (tan ⁇ of rubber composition not containing tetrazine compound (1)) / (tan ⁇ of rubber composition of the present invention) ⁇ ⁇ 100
  • Production Example 1 Kneading of Modified Polymer Each rubber component and tetrazine compound listed in Production Table 1 were kneaded at a ratio (parts by mass) using a Banbury mixer. When the temperature of the mixture reached 130 to 150 ° C., the mixture was kneaded for about 2 minutes while maintaining the temperature, and then cooled with a roll mill to produce a modified polymer.
  • the rubber compositions of any of the examples exhibited high hardness, high tensile strength, and high resilience relative to the comparative rubber composition to which no tetrazine compound was added.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de caoutchouc qui contient : un constituant caoutchouteux ; un composé tétrazine représenté par la formule générale (1) ou son sel ; un agent de réticulation ; et un co-agent de réticulation. (Dans la formule générale (1), X1 et X2 peuvent être identiques ou différents et chacun représente un atome d'hydrogène, un groupe alkyle, un groupe aralkylthio, un groupe aralkyle, un groupe aryle, un groupe arylthio, un groupe hétérocyclique ou un groupe amino ; et chacun de ces groupes peut posséder un ou plusieurs substituants.)
PCT/JP2017/045849 2016-12-21 2017-12-21 Composition de caoutchouc et balle de golf WO2018117202A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020000653A (ja) * 2018-06-29 2020-01-09 ブリヂストンスポーツ株式会社 ゴルフボール
JP2020103580A (ja) * 2018-12-27 2020-07-09 ブリヂストンスポーツ株式会社 ゴルフボール及びその製造方法
WO2023163233A1 (fr) * 2022-02-28 2023-08-31 株式会社ブリヂストン Composition de caoutchouc et produit en caoutchouc

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4947439A (fr) * 1972-08-25 1974-05-08
JPH0679018A (ja) * 1992-09-03 1994-03-22 Asics Corp ソリッドゴルフボール
JP2000086816A (ja) * 1998-09-11 2000-03-28 Yokohama Rubber Co Ltd:The ゴム組成物およびゴルフボール
JP2001353233A (ja) * 2000-06-14 2001-12-25 Kasco Corp ゴルフボール
JP2015093928A (ja) * 2013-11-12 2015-05-18 東洋ゴム工業株式会社 インナーライナー用ゴム組成物及び空気入りタイヤ
WO2017057758A1 (fr) * 2015-09-30 2017-04-06 大塚化学株式会社 Additif pour conférer une faible accumulation de chaleur à un composant de caoutchouc
JP2018029879A (ja) * 2016-08-26 2018-03-01 ダンロップスポーツ株式会社 ゴルフボール

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4947439A (fr) * 1972-08-25 1974-05-08
JPH0679018A (ja) * 1992-09-03 1994-03-22 Asics Corp ソリッドゴルフボール
JP2000086816A (ja) * 1998-09-11 2000-03-28 Yokohama Rubber Co Ltd:The ゴム組成物およびゴルフボール
JP2001353233A (ja) * 2000-06-14 2001-12-25 Kasco Corp ゴルフボール
JP2015093928A (ja) * 2013-11-12 2015-05-18 東洋ゴム工業株式会社 インナーライナー用ゴム組成物及び空気入りタイヤ
WO2017057758A1 (fr) * 2015-09-30 2017-04-06 大塚化学株式会社 Additif pour conférer une faible accumulation de chaleur à un composant de caoutchouc
JP2018029879A (ja) * 2016-08-26 2018-03-01 ダンロップスポーツ株式会社 ゴルフボール

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020000653A (ja) * 2018-06-29 2020-01-09 ブリヂストンスポーツ株式会社 ゴルフボール
JP7068072B2 (ja) 2018-06-29 2022-05-16 ブリヂストンスポーツ株式会社 ゴルフボール
JP2020103580A (ja) * 2018-12-27 2020-07-09 ブリヂストンスポーツ株式会社 ゴルフボール及びその製造方法
US11097163B2 (en) * 2018-12-27 2021-08-24 Bridgestone Sports Co., Ltd. Golf ball and method of manufacture
JP7183783B2 (ja) 2018-12-27 2022-12-06 ブリヂストンスポーツ株式会社 ゴルフボール及びその製造方法
WO2023163233A1 (fr) * 2022-02-28 2023-08-31 株式会社ブリヂストン Composition de caoutchouc et produit en caoutchouc

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