JPH0436036B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a golf ball with a multilayer structure that provides durability, rebound resilience (flight characteristics), and excellent feel when hit. (Prior Art) Golf balls are required to have flight stability, long-distance flight performance, etc., and these characteristics require well-controlled rebound resilience, compressive strength, hardness, etc. Various proposals have been made for improving the quality of compositions. For example, it relates to a solid golf ball in which metal salt monomers of α,β-monoethylenically unsaturated carboxylic acids are added to a rubber composition, and these monomers are activated by a free radical initiator to form a rubber component. It is grafted onto the main chain of polybutadiene used as a polybutadiene and acts as a co-crosslinking agent, thereby giving the ball hardness, but a solid ball that is satisfactory in terms of durability and impact resilience has not been obtained. Further, the hardness of the golf ball can be adjusted by adjusting the amount of crosslinking agent, but if the amount is too large, the impact resilience will eventually decrease. Furthermore, various proposals have been made regarding fiber materials and fine particulate materials to improve the hardness, durability, and high resilience of rubber compositions, but at present, they all result in a decrease in durability and resilience, and little improvement can be expected. It was hot. Furthermore, although the fine fiber material is homogeneously dispersed in the rubber structure, it has poor wettability with the rubber material, and surface treatment of the fiber surface has been a major problem. Although it has been known that hydrolyzable silyl compounds are effective as a surface treatment technique for these, it requires a high degree of skill. Although it has been found that sulfur-containing silane compounds are excellent surface treatment agents with good compatibility with rubber components, these are all related to sulfur vulcanization systems, and conventionally, sulfur-containing compounds have been used for sulfur vulcanization systems. The curing mechanism inhibited vulcanization with non-sulfur-based vulcanizing agents, and it was thought to be impractical. (Problems to be Solved by the Invention) An object of the present invention is to provide a golf ball with excellent durability, rebound resilience, and hardness. Another object of the present invention is to provide a golf ball reinforced with a fibrous material surface-treated with a sulfur-containing compound that does not inhibit vulcanization even with non-sulfur vulcanizing agents. (Means for Solving the Problems) The present invention provides a golf ball having a multilayer structure in which an elastic rubber is used as a core material and a hard elastic material is used as a covering layer. A golf ball characterized by containing a fibrous alkali metal titanate surface treated with a surface treatment agent selected from mercapto group-containing silane compounds and silyl group-containing sulfide compounds shown in () and (). . Furthermore, the present invention uses elastic rubber as a core material and an intermediate layer,
In a golf ball having a multilayer structure with a hard elastic material as a coating layer, at least one component of the core material, intermediate layer, and coating layer contains fibrous alkali metal titanate that has been surface-treated by the above-mentioned surface treatment. The present invention relates to a characteristic golf ball. The multi-layer structure golf ball of the present invention includes, for example, a so-called two-piece ball in which an elastic rubber is used as a core material and a hard elastic material is used as a covering layer, and a core material portion is multi-layered (usually two layers), that is, an elastic rubber core material is used as a two-piece ball. One example is a so-called three-piece ball in which the surface of the ball is further provided with an intermediate layer coated with elastic rubber, and the outermost shell is coated with a hard elastic material. In the present invention, a core material in a golf ball,
By containing fibrous alkali metal titanate treated with a surface treatment agent in one or more of the intermediate layer and the coating layer, non-sulfur vulcanization can be achieved even if the surface treatment agent is a specific sulfur-containing silyl compound. It has been found that this method is effective in improving rubber compositions without causing vulcanization inhibition. Various known rubbers can be used as the rubber component of the present invention, such as natural rubber (NR),
Isoprene rubber (IR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), butadiene rubber (BR), chloropropylene rubber (CR), butyl rubber (IIR), acrylic rubber (AR), urethane rubber (UR), Silicone rubber (SiR), fluorocarbon rubber (FR), ethylene propylene rubber (EPR), chlorosulfonated polyethylene (CSM), ethylene acetate rubber (EVA), chlorinated polyethylene (CPE), polyisobutylene (PIB), Alfin rubber ( A.L.),
Examples include polyester rubber (ESR), epichlorohydrin rubber (ECR), chlorinated butyl rubber (CIR), and nitrile isobutylene rubber (NIR). Among these rubber components, cis-
It is particularly preferable to use a material containing 30% by weight or more of 1,4-structured polybutadiene because hardness and impact resilience are improved. The reason for this is not clear, but perhaps the sulfur component of the surface treatment agent for the fibrous alkali metal titanate reacts with the cis-1,4-structured polybutadiene, resulting in a reinforcing effect that effectively utilizes the fiber shape of the alkali metal titanate. This is thought to be due to the development of sulfur component-free surface treatment agents such as methyltrimethoxysilane, methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. Hardness and impact resilience are improved compared to those using an alkoxysilane surface treatment agent. In the present invention, the fibrous alkali metal titanate has a fiber length of 1 μm to 1 mm and an aspect ratio of 5 to 1 mm.
It is preferable to have a fiber shape of 1000, particularly preferably an average fiber length of 5 to 300 μm, and an aspect ratio of 10 to 300 μm.
300, and those in this range have excellent reinforcing properties and homogeneous dispersibility, and can obtain a homogeneous strength distribution.
Specific examples include sodium titanate fibers, potassium titanate fibers, lithium titanate fibers, etc., which have excellent reinforcing properties, heat resistance, whiteness, can be colored to the desired color tone, and have fine and uniform fiber length. Potassium titanate fiber is a particularly suitable material because it can be easily produced and has high homogeneous dispersibility as a composite material. Potassium titanate fiber has the general formula K ₂ O・nTiO ₂ or the general formula K ₂ O・nTiO ₂・1/2H ₂
O (in both formulas, n represents an integer from 2 to 8)
means a single crystal fiber represented by, specifically potassium tetratitanate fiber, potassium hexatitanate fiber,
Examples include potassium octatitanate fibers, which may be used alone or in combination of two or more. These potassium titanate fibers preferably have an average fiber diameter of 0.1 to 2 μm, an average fiber length of 5 to 100 μm, and a spectral ratio of 10 to 200. Here, the average fiber diameter and the average fiber length are the average values of the values measured for at least 10 or more fibers per field, examined using a scanning electron microscope in at least 5 or more fields of view, and the aspect ratio means the value obtained by dividing the average fiber length of such fibers by the average fiber diameter. In the present invention, examples of the surface treatment agent for treating the surface of the fibrous alkali metal titanate include sulfur-containing silane compounds such as mercapto group-containing silane compounds and silyl group-containing sulfide compounds. A typical example of the above mercapto group-containing silane compound is the general formula (R ¹ is a substituted or unsubstituted divalent hydrocarbon group having 2 to 6 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group, X is a hydrolyzable group, a is a 1 to 3 carbon number An integer, b is an integer of 0 to 2, and 1≦(a+b)≦3. Examples of R ¹ include an ethylene group, a trimethylene group, a tetramethylene group, a pantamethylene group, and a hexamethylene group, with an ethylene group and a trimethylene group being preferred, and a trimethylene group being particularly preferred. R ² is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl; alkenyl such as vinyl or allyl; phenyl group, aryl group such as tolyl group; aralkyl group such as benzyl group, β-phenylethyl group, β-phenylpropyl group; β-cyanoethyl group, γ-chloropropyl group, 3,3,
Substituted hydrocarbon groups such as 3-trifluoropropyl group and chlorophenyl group are exemplified, and various groups are selected depending on the type of rubber component and purpose of use. Aralkyl groups are added to rubber components containing aromatic rings,
Also, substituted hydrocarbon groups are effective for rubber components containing halogens, nitriles, and the like. X is a hydrolyzable group bonded to a silicon atom; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group; Alkoxy group; Enoxy group such as isopropenyloxy group; Ketooxymato group such as dimethylketooximato group, methylethylketooximato group; Amino group such as diethylamino group, dibutylamino group; Aminoxy group such as diethylaminoxy group; Acetoxy group, octa Examples include acyloxy groups such as a noyloxy group; and amide groups such as an N-methylacetamide group. Among these, lower alkoxy groups having 1 to 4 carbon atoms are preferred because they have excellent surface reactivity with fibrous alkali metal titanates, and among these, methoxy groups are particularly preferred because they have good reactivity. a is an integer of 1 to 3, preferably less than 2 on average, b is an integer of 0 to 2,
An average of 1 or less is preferable. If a and b are too large, the number of hydrolyzable groups will decrease and the reactivity with the fibrous alkali metal titanate will decrease, and if a is too small, the effect of the mercapto group on the rubber component will decrease. Preferably, the average value of a is adjusted to 1, and the average value of b is adjusted to less than 1. A typical example of a silyl group-containing sulfide compound is the general formula (R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is the same or different substituted or unsubstituted hydrocarbon group having 2 to 4 carbon atoms, Y is a hydrolyzable group , c is an integer of 0 to 2, and n is an integer of 1 to 6). R ³ is an alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group; alkenyl group such as vinyl group or allyl group; phenyl group group, aryl group such as tolyl group; aralkyl group such as benzyl group, β-phenylethyl group, β-phenylpropyl group; β-cyanoethyl group, γ-chloropropyl group, 3,3,
Substituted hydrocarbon groups such as 3-trifluoropropyl group and chlorophenyl group are exemplified, and various groups are selected depending on the type of rubber component and purpose of use. Aralkyl groups are added to rubber components containing aromatic rings,
Also, substituted hydrocarbon groups are effective for rubber components containing halogens, nitriles, and the like. Examples of R ⁴ include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group, with an ethylene group and a trimethylene group being preferred, and a trimethylene group being particularly preferred. Y is a hydrolyzable group bonded to a silicon atom, and includes alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; Alkoxy group; Enoxy group such as isopropenyloxy group; Ketooxymato group such as dimethylketooximato group, methylethylketooximato group; Amino group such as diethylamino group, dibutylamino group; Aminoxy group such as diethylaminoxy group; Acetoxy group, octa Examples include acyloxy groups such as a noyloxy group; and amide groups such as an N-methylacetamide group. Among these, lower alkoxy groups having 1 to 4 carbon atoms are preferred because they have excellent surface reactivity with fibrous alkali metal titanates, and among these, propoxy groups are particularly preferred because they are easily synthesized and are stable compounds. c is an integer of 0 to 2, and one molecule of the silyl group-containing sulfide compound represented by the general formula () has at least one, preferably two, hydrolyzable groups that react with the surface of the fibrous alkali metal titanate. Preferably, c is less than 2 on average. n is an integer from 1 to 6, with an average of 2 in view of ease of synthesis, affinity with rubber, and vulcanization inhibition.
-4 is preferred. In the present invention, the surface of the fibrous alkali metal titanate is treated with a surface treatment agent, and the amount of the surface treatment agent of the present invention used is generally about 0.05 to 10% by weight based on the fibrous alkali metal titanate. It is preferable to keep it in the range of . Within this range, the surface of the fibrous alkali metal titanate is sufficiently modified, and the physical properties of the rubber composition can be improved without inhibiting vulcanization during vulcanization, which will be described later. For the treatment method using the surface treatment agent of the present invention, any commonly used surface treatment method may be used. For example, the surface treatment agent of the present invention or its diluted solution is sprayed onto the fibrous alkali metal titanate surface. A method of homogeneous mixing with the fibrous alkali metal titanate or an impregnation treatment method can be adopted, and after the surface treatment agent of the present invention is uniformly adhered to the surface of the fibrous alkali metal titanate, the surface treatment agent is heated, dried, and hydrated. By performing decomposition or the like, the surface treatment agent of the present invention can be uniformly fixed to the surface of the fibrous alkali metal titanate. The surface treatment agent of the present invention contains a sulfur element in the molecule, and in particular, the terminal mercapto compound is a sulfur-containing compound that has been thought to inhibit vulcanization during peroxide-based vulcanization and deteriorate rubber physical properties. Although it is not clear by what mechanism of action the effect is expressed in the rubber composition, when fibrous alkali metal titanate is used, the effect is clearly expressed and the effect is achieved without inhibiting vulcanization. In addition to being homogeneously vulcanized, the fibrous alkali metal titanate and the rubber material are strongly bonded, and the sliding phenomenon at the interface between the fibrous filler and the rubber matrix, which is considered to be the cause of the decline in physical properties in composite materials, is eliminated. A rubber composition with high hardness and high compressive strength can be obtained. In the present invention, unsaturated carboxylic acids, salts thereof, other unsaturated vinyl compounds, etc. can be used as crosslinking monomers. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, 2-acetaminoacrylic acid, β,β-dimethacrylic acid, ethacrylic acid, α-chloroacrylic acid, cinnamic acid, acotic acid, 2-ethyl-3-propyl Acrylic acid, crotonic acid, aminocrotonic acid, acidophoshydroxyethyl (meth)acrylate, β
-Acryloxypropionic acid, 2-butene-
1,4-dicarboxylic acid, sorbic acid, acetylcarboxylic acid, N-butylmaleamic acid, fumaric acid,
Maleic acid, chlormaleic acid, di-n-butylmaleamic acid, N,N-dimethylmaleamic acid,
N-ethylmaleadic acid, N-phenylmaleadic acid, dichloromaleic acid, dihydroxymaleic acid, allylarsonic acid, chlorendeic acid,
Examples of other unsaturated vinyl compounds include vinyl compounds such as vinyl acetate, vinyl propionate, vinyl caproate, styrene, vinyltoluene, and divinylbenzene; acrylic acid, and methacrylic acid. Examples include alkyl esters such as; (meth)acrylic acid derivatives such as (meth)acrylonitrile, (meth)acrylamide, and glycidyl (meth)acrylate; and various compounds such as triallyl isocyanurate. Among these, acrylic acid,
Preference is given to methacrylic acid, cinnamic acid, acotic acid, crotonic acid, itaconic acid and benzoyl acrylic acid. These compounds can be used alone or in a mixture of two or more. In the present invention, metal salts of the above-mentioned unsaturated carboxylic acids can also be used, and representative examples of the metals include lithium, sodium, potassium, strontium, zinc, magnesium, calcium, barium, cadmium, lead, zirconium, beryllium, copper, and aluminum. , tin, iron,
Any one type or a mixture of two or more of antimony, bismuth, molybdenum, tungsten, nickel, etc. can be used, and divalent or higher metal salts are preferred because they increase the crosslinking effect, are easily available, and have low toxicity. Among them, calcium, zinc, magnesium, zirconium, etc. are preferred. In addition to being used as metal salts of unsaturated carboxylic acids that have been previously reacted with unsaturated carboxylic acids, these metal species can also be used in combination with unsaturated carboxylic acids and these metals, metal oxides, hydroxides, and carbonic acids. Salt etc. are mixed separately into the rubber component,
It is also possible to react in a mixed system to form a metal salt. In the present invention, the amount of crosslinking monomer used is not particularly limited, but is 0.1 to 50 parts by weight, preferably 1 to 15 parts by weight, more preferably 3 parts by weight, based on 100 parts by weight of the rubber component.
~9 parts by weight, and within this range, durability is excellent and the hardness of impact resilience can be easily adjusted. Examples of the non-sulfur vulcanizing agent of the present invention include metal oxides such as magnesium oxide, lead oxide, and zinc oxide;
Crosslinkable resins such as phenolic resins, melamine formaldehyde resins, urethane resins, polyester resins, polyamide resins, and epoxy resins, and their low molecular weight products or modified products; diacetyl peroxide, dibenzoyl peroxide, dicapryl peroxide, di(p- chlorobenzoyl peroxide, didecanoyl peroxide, di(2,4-dichlorobenzoyl) peroxide, diisobutyl peroxide, diisononanoyl peroxide, dilauroyl peroxide, diperagonyl peroxide, diprovinyl peroxide , di(β-carboxypropinoyl) peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, dihydroxy-dimethyl-dioxacyclopentane, t-butyl peroxide, t-butyl peroxy (2-ethylhexanoate), t
-butyl peroxyisobutyrate, O, O-t
-butyl-O-isopropylmonoperoxycarbonate, t-butylperoxypivalate, dimethyl-di(benzoylperoxy)hexane,
t-butyl peroxy (2-ethyl butyrate),
Di-t-butyl peroxide, dicumyl peroxide, dimethyl-bis(t-butylperoxy)hexane, t-butyl hydroperoxide, walnut hydroperoxide, bis(t-butyl peroxide)
butylperoxy)trimethylcyclohexane,
Examples include organic peroxides such as n-butylbis(t-butylperoxy)valerate. Among these, dicumyl peroxide, cumyl hydroperoxide, t-butyl peroxide, dibutyl peroxide, bis(t-butylperoxy)trimethylcyclohexane, n-butylbis(t-butylperoxy)valylate, etc. It is suitable because vulcanization proceeds homogeneously due to the relationship between sulfur temperature and half-life. These non-sulfur vulcanizing agents can be used alone or as a mixture of two or more, and the amount used is arbitrarily selected depending on the type of rubber used, the purpose of use of the rubber composition, etc. Preferably, it is used in a range of about 0.1 to 15% by weight based on the ingredients. In the present invention, it is possible to add various known additives, such as vulcanization accelerators, vulcanization retarders, anti-aging agents, plasticizers, plasticizers, tackifiers, anti-blocking agents, blowing agents, A dispersant, powder, mold release agent, solvent, softener, etc. can be added as necessary. Furthermore, in the present invention, carbon black, magnesium carbonate, zinc oxide, calcium carbonate, barium sulfate, aluminum hydroxide, aluminum oxide, silica powder, titanium oxide, mica, talc,
Various inorganic fillers such as clay powders such as clay, diatomaceous earth, and kaolin, and arbitrary pigments and dyes as coloring agents can also be used in combination. Also, any resin commonly used as an organic modifier, such as coumaron indene resin, phenol resin, polystyrene resin, acrylic resin, polyamide resin,
Epoxy resin, elethane resin, polyolefin resin, etc. may be mixed and used. Furthermore, in the present invention, commonly used long fiber reinforcing agents such as glass fiber,
Inorganic fibers such as carbon fibers, metal fibers, quartz fibers, ceramic fibers; nylon fibers, vinylon fibers, polyester fibers, aromatic polyamide fibers,
Organic fibers such as polyimide fibers and aromatic polyetheramide fibers can also be used in combination. The golf ball of the present invention comprises a fibrous alkali metal titanate treated with the above-mentioned surface treatment agent, a rubber component, a vulcanizing agent, and various additives added as necessary.
After kneading the auxiliary agents etc. in the usual manner, it is heated at about 80 to 180℃ for about 5 minutes.
It is obtained by molding the golf ball after being vulcanized for ~60 minutes, but the composition ratio of each component is adjusted depending on the type of rubber component and the purpose of use and cannot be specified, but it is possible to obtain a golf ball by vulcanizing it for ~60 minutes. The amount of compounding is usually about 2 to 100 parts by weight of the rubber component.
100 parts, particularly preferably about 10 to 50 parts; if too small, it will be soft but difficult to develop strength;
On the other hand, if the amount is too large, the strength will increase, but it will be too hard and the elongation rate will be insufficient, making it impractical. In the present invention, a core material made of the above-mentioned elastic rubber is used, the surface of which is covered with a normally used hard elastic material,
It can be obtained by molding into the shape of a golf ball with dimples or the like, or by treating its surface with a conventional coating material. As the hard elastic material covering the core material, for example, ionomer resin, transisoprene resin, etc. are suitable. The ionomer resin has the general formula R-CH=
A copolymer of an α-olefin represented by CH ₂ (wherein R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms, Examples include ionic copolymers obtained by reacting with metal compounds. The α-olefins include ethylene, propylene, butene-1, pentene-1, and hexene-1.
1, heptene-1,3-methylbutene-1,4-
Examples include methylpentene-1. Further, α-olefins having a large number of carbon atoms can also be used in the present invention, but they are difficult to obtain and lack practicality. These α-olefins may be used alone or in combination of two or more. The content of α-olefins in the copolymer is preferably at least 50 mol%, and preferably more than 80 mol% in terms of processability and physical properties. Examples of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, etc.; maleic acid, fumaric acid, etc., or monoesters of these dicarboxylic acids, such as maleic acid monomethyl ester. , fumaric acid monoethyl ester, and acid anhydrides of these dicarboxylic acids, such as maleic anhydride, but are not limited thereto. These α,β-unsaturated carboxylic acids may be used alone or in combination of two or more. α、β
- The content of unsaturated carboxylic acid in the copolymer is preferably 0.5 to 25 mol%, more preferably 1 to 10 mol%. In addition, as a component other than α-olefin and α,β-unsaturated carboxylic acid, monomers copolymerizable with these, such as styrene, vinyl chloride, vinyl acetate, acrylonitrile, and vinyl methyl ether, may be used as a part of α-olefin. It is also possible to replace and copolymerize. The copolymer consisting of α-olefin and α,β-unsaturated carboxylic acid is not limited to one obtained by directly copolymerizing a mixture of monomers, but can be obtained from α-olefin. It may be obtained by graft polymerizing an α,β-unsaturated carboxylic acid monomer onto a base polymer. An ionic copolymer is obtained by reacting (neutralizing) the thus obtained copolymer with a metal compound that generates metal ions. Metal ions suitable for producing the ionic copolymers include metal ions of Group 1 or Group 2 of the periodic table, namely Na, K, Li, Cs, Cu, Ag and Be,
Mg, Ca, Sr, Ba, Zn, Cd, Hg are listed,
These may be used alone or in combination of two or more. Using these metal ions,
Cross-linking is preferably formed in the formation of the ionic copolymer. Among these metal ions, Na and Zn are more preferred from the viewpoint of melt processability and physical properties in a solid state. The amount of ions used or the degree of neutralization of the copolymer cannot be determined unconditionally because it depends on the desired solid state properties and meltability of the ionic copolymer obtained. To effect a significant change in the solid state of the polymer, the amount is preferably such that it neutralizes at least 10% of the carboxyl groups in the copolymer, and can usually neutralize up to about 90%. . The degree of neutralization for optimizing the physical properties of ionic copolymers varies depending on the application, so
Also, since the physical properties of ionic copolymers vary depending on the carboxyl group concentration in the copolymer and the molecular weight of the copolymer, it cannot be determined unconditionally, but it is usually possible to neutralize at least 50% of the carboxyl groups. desirable. The above-mentioned metal ions can be obtained by hydrating metal compounds that generate such metal ions, such as inorganic compounds such as sodium hydroxide and sodium carbonate, or organic metal compounds such as sodium methoxide, sodium formate, and sodium acetate. Alternatively, it can be obtained by dissolving it in an organic solvent such as methanol. There is no particular limitation on the method for obtaining the ionic copolymer from the copolymer and metal ions, and any known method may be used. The molecular weight of the ionic copolymer thus obtained is appropriately expressed by MI (melt index), which is a measure of melt viscosity described in ASTM D 1238. The range of MI of useful ionic copolymers is about 0.1 to 100 g/10 minutes (190°C), more preferably about 0.5 to 20 g/10 minutes (190°C). ionic copolymer
If MI is about 0.1 to 100g/10 minutes (190℃),
It has excellent melt processability and is extremely tough in the solid state, with appropriate elasticity and flexibility. In the present invention, these ionomer resins may be used in combination with commonly used fillers such as titanium oxide, talc, calcium carbonate, and silica. It is effective to utilize the technology related to JP-A-60-202142 using acid potassium fibers. In the present invention, the trans polyisoprene resin exists as a main component of naturally occurring balata and gutta percha, and has a molecular structure of trans-1,4-polyisoprene. Kuraray Trans Polyisoprene TP is a typical example of a commercially available product.
-301 [Clarei Soprene Chemical Co., Ltd.]. In the present invention, the fibrous alkali metal titanate treated with the above-mentioned surface treatment agent of the present invention, a rubber component, a vulcanizing agent, and various additives and auxiliary agents added as necessary are kneaded in a conventional manner. A two-piece golf ball can be obtained by molding into a core shape and simultaneously vulcanizing it, coating it with the coating layer of the present invention, molding it, and, if necessary, vulcanizing it. In addition, in the case of a three-piece golf ball, a core material obtained by the same method is coated with the rubber composition of the present invention as an intermediate layer and molded, and then the core material is re-vulcanized and coated with the coating layer of the present invention, molded, and as necessary. It can be created by vulcanization. Furthermore, it can be obtained by performing these steps in one step, that is, by providing a core material and, if necessary, an intermediate layer, coating the outermost shell with a coating layer, and then molding and vulcanizing. still,
In the present invention, the surface may be treated with a commonly used coating agent. (Example) Examples and comparative examples will be described below. Examples 1 to 4 and Comparative Examples 1 to 6 All components listed in Table 1 were added to a kneader, except for the vulcanizing agent, and heated at 60 to 100°C for 10 minutes.
After kneading for minutes, the contents were cooled to 60 to 70°C, a vulcanizing agent was added, and the mixture was kneaded, followed by vulcanization at 150±5°C for 30 minutes in a regular golf ball core mold. The material was coated with a mixture of 100 parts of ionomer resin and 10 parts of titanium oxide so that each ball weighed 45 g, and injection molded using an injection machine.
The resulting golf balls were measured for their rebound resilience, durability, compression, and actual impact. The results are shown in Table 1. In addition, in the table *1 Nippon Synthetic Rubber BR-11 *2 Nippon Synthetic Rubber STEREON 720 *3 Nippon Synthetic Rubber IR-2200 *4 Seido Kagaku No. 3 Zinc White *5 Nippon Silica Nipseal VN3AQ Potassium titanate (untreated product) Otsuka Chemical Co., Ltd.
Processed product A is Teismo D treated with 1% bis(3-triethoxysilylpropyl)tetrasulfide, and Processed product B is Teismo D treated with 1% γ-mercaptopropyltrimethoxysilane. Processed product C is Teismo D treated with 1% γ-mercaptopropyltriethoxysilane, and Processed product D is Teismo D treated with 1% bis(3-trimethoxysilylpropyl)tetrasulfide. Treated product E is Teismo D treated with 1% γ-glycidoxypropyltrimethoxysilane. In addition, the durability index is expressed as an index by measuring the number of times until it breaks after applying compression that deforms it by 10 mm, and taking Example 1 as 100, and rebound resilience is based on JIS S7005.
It was dropped from a height of 120cm and the rebound height was measured at a measurement temperature of 20℃, and the compression showed the strength when compressed by 2.54mm. Examples 11-14 In Examples 1-4, potassium titanate (treated product A) was added to 100 parts of ionomer resin as a coating layer.
A two-piece golf ball was prepared in the same manner except that a hard elastic body containing 10 parts of the compound was used. The results are also shown in Table 2. Examples 21-24 and Comparative Examples 21-26 Two-piece golf balls were prepared in the same manner as Examples 1-4, except that the core material composition shown in Table 3 was used. The results are also shown in Table 3. Examples 31 to 34 In Examples 21 to 24, potassium titanate (treated product A) was added to 100 parts of ionomer resin as a coating layer.
A two-piece golf ball was prepared in the same manner except that a hard elastic body containing 10 parts of the compound was used. The results are also shown in Table 4. Examples 41 to 49 Core materials obtained using the same core material formulation as in Example 22 were coated with various coating layers shown in Table 5 to prepare two-piece golf balls. The results are also shown in Table 5. Examples 50 to 60 Two-piece golf balls were made using the core material formulations shown in Table 6. In addition, as a coating layer, Example 43 was used for Examples 50 to 52, and Example 43 was used for Examples 53 to 56.
47, Examples 57 to 60 used the same material as Example 44. The results are also shown in Table 6. Examples 71 to 79 and Comparative Examples 71 to 72 Core material composition: Listed in Table 7.

[Table] A three-piece golf ball was prepared using each layer having the above formulation. The results are also shown in Table 7. Examples 81 to 84 and Comparative Examples 81 to 86 Core material composition: Listed in Table 8.

[Table] A three-piece golf ball was prepared using each layer having the above formulation. The results are also shown in Table 8. Examples 91-94 In Examples 81-84, potassium titanate (treated product A) was added to 100 parts of ionomer resin as a coating layer.
A three-piece golf ball was prepared in the same manner except that a hard elastic material containing 10 parts of the hard elastic material was used. The results are also shown in Table 9. Comparative Examples 91 to 94 Comparative Example 81 except that the core material composition shown in Table 9 was used.
A three-piece golf ball was made in the same manner as ~86. The results are shown in Table 9. Examples 101 to 104 and Comparative Examples 101 to 104 Example 91 except that the core material composition shown in Table 10 was used.
Three-piece golf balls were prepared in the same manner as in Comparative Examples 91-94 and Comparative Examples 91-94. The results are shown in Table 10. Examples 111 to 119 Core materials obtained from the same core material formulation as in Example 82 were coated with various coating layers shown in Table 11 to prepare three-piece golf balls. The results are also shown in Table 11. Examples 120-130 Three-piece golf balls were made using the core material formulations shown in Table 12. As the coating layer, the same one as in Example 113 was used in Examples 120 to 122, the same as in Example 117 in Examples 123 to 126, and the same as in Example 114 in Examples 127 to 130. Also, as the middle layer, the example
For 120 to 122, the following formulation A was used in Example 123
In ~125, the following B formulation was used in Example 126~
For No. 130, the formulation of Example 71 was used. The results are also shown in Table 12.

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Claims (1)

[Scope of Claims] 1. A golf ball having a multi-layer structure in which an elastic rubber is used as a core material and a hard elastic material is used as a covering layer, wherein the core material and/or the covering layer contains the general formula (R ¹ is a substituted or unsubstituted divalent hydrocarbon group having 2 to 6 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group, X is a hydrolyzable group, a is a 1 to 3 carbon number an integer, b is an integer of 0 to 2, 1≦(a+b)≦3) and a mercapto group-containing silane compound and general formula (R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is the same or different substituted or unsubstituted hydrocarbon group having 2 to 4 carbon atoms, Y is a hydrolyzable group , c is an integer of 0 to 2, and n is an integer of 1 to 6. A two-piece golf ball characterized by: 2. The two-piece golf ball according to claim 1, wherein the core material is a mixture of one or more of fibrous alkali metal titanate and synthetic rubber and/or natural rubber whose surface has been treated with the surface treatment agent. . 3. The core material is (a) a fibrous alkali metal titanate surface treated with the above surface treatment agent, (b) one or a mixture of two or more of synthetic rubber and/or natural rubber,
(c) The two-piece golf ball according to claims 1 to 2, which is obtained by vulcanizing a mixture of a crosslinking monomer and a weight adjuster with a non-sulfur vulcanizing agent. 4 Synthetic rubber and/or natural rubber is cis-1,
The two-piece golf ball according to any one of claims 2 to 3, which contains 30% by weight or more of 4-structure polybutadiene. 5. The two-piece golf ball according to claims 3 to 4, wherein the crosslinking monomer is an unsaturated carboxylic acid, a salt thereof, or an unsaturated vinyl compound. 6 Covering layer is general formula (R ¹ is a substituted or unsubstituted divalent hydrocarbon group having 2 to 6 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group, X is a hydrolyzable group, a is a 1 to 3 carbon number an integer, b is an integer of 0 to 2, 1≦(a+b)≦3) and a mercapto group-containing silane compound and general formula (R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is the same or different substituted or unsubstituted hydrocarbon group having 2 to 4 carbon atoms, Y is a hydrolyzable group , c is an integer of 0 to 2, and n is an integer of 1 to 6. A two-piece golf ball according to any one of claims 1 to 5. 7. The two-piece golf ball according to claims 1 to 6, wherein the elastic body forming the coating layer is an ionomer resin. 8. The two-piece golf ball according to claims 1 to 6, wherein the elastic body forming the coating layer is a trans polyisoprene resin. 9 In a golf ball having a multi-layer structure in which an elastic rubber is used as a core material and an intermediate layer, and a hard elastic material is used as a covering layer, at least one component of the core material, intermediate layer and covering layer has the general formula (R ¹ is a substituted or unsubstituted divalent hydrocarbon group having 2 to 6 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group, X is a hydrolyzable group, a is a 1 to 3 carbon number an integer, b is an integer of 0 to 2, 1≦(a+b)≦3) and a mercapto group-containing silane compound and general formula (R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is the same or different substituted or unsubstituted hydrocarbon group having 2 to 4 carbon atoms, Y is a hydrolyzable group , c is an integer of 0 to 2, and n is an integer of 1 to 6. A three-piece golf ball featuring: 10 A fibrous alkali metal titanate whose core material has been surface-treated with the above-mentioned surface treatment agent, synthetic rubber, and/or
The three-piece golf ball according to claim 9, which is one type or a mixture of two or more types of natural rubber. 11 The core material is (a) a fibrous alkali metal titanate surface treated with the above surface treatment agent, (b) one or a mixture of two or more of synthetic rubber and/or natural rubber,
(c) The three-piece golf ball according to claim 9, which is obtained by vulcanizing a mixture of a crosslinking monomer and a weight adjuster with a non-sulfur vulcanizing agent. 12 Synthetic rubber and/or natural rubber is cis-
The three-piece golf ball according to claims 9 to 11, which contains 30% by weight or more of 1,4-structure polybutadiene. 13. The three-piece golf ball according to claims 9 to 12, wherein the crosslinking monomer is an unsaturated carboxylic acid, a salt thereof, or an unsaturated vinyl compound. 14 The middle layer is a general formula (R ¹ is a substituted or unsubstituted divalent hydrocarbon group having 2 to 6 carbon atoms, R ² is a substituted or unsubstituted monovalent hydrocarbon group, X is a hydrolyzable group, a is a 1 to 3 carbon number an integer, b is an integer of 0 to 2, 1≦(a+b)≦3) and a mercapto group-containing silane compound and general formula (R ³ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ⁴ is the same or different substituted or unsubstituted hydrocarbon group having 2 to 4 carbon atoms, Y is a hydrolyzable group , c is an integer of 0 to 2, and n is an integer of 1 to 6. The three-piece golf ball according to any one of claims 9 to 13, which is one type or a mixture of two or more types of natural rubber. 15 The intermediate layer comprises (a) a fibrous alkali metal titanate surface-treated with the above-mentioned surface treatment agent, (b) a mixture of one or more of synthetic rubber and/or natural rubber, (c) a crosslinkable monomer, and The three-piece golf ball according to claims 9 to 13, which is obtained by vulcanizing a mixture of weight adjusters with a non-sulfur vulcanizing agent. 16 Synthetic rubber and/or natural rubber is cis-
The three-piece golf ball according to claims 9 to 14, which contains 30% by weight or more of 1,4-structure polybutadiene. 17. The three-piece golf ball according to claims 9 to 15, wherein the crosslinking monomer is an unsaturated carboxylic acid, a salt thereof, or an unsaturated vinyl compound. 18. The three-piece golf ball according to claims 9 to 17, wherein the coating layer is a fibrous alkali metal titanate-containing elastic body whose surface has been treated with the above-mentioned surface treatment agent. 19. The three-piece golf ball according to claims 9 to 17, wherein the elastic body forming the coating layer is an ionomer resin. 20. The three-piece golf ball according to claims 9 to 17, wherein the elastic body forming the coating layer is a transpolyisoprene resin.