Resin composition for golf ball and its cover or top coat
The use of plant-derived ultraviolet absorbers in golf ball covers and top coats addresses the environmental and health concerns of petroleum-based alternatives, ensuring effective UV protection and maintaining the ball's appearance.
Patent Information
- Application Number
- JP2020212550
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2020-12-22
- Publication Date
- 2024-12-25
- Estimated Expiration
- 2040-12-22
AI Technical Summary
Conventional ultraviolet absorbers used in golf balls are derived from petroleum resources, posing environmental and health risks, and they fail to effectively prevent yellowing due to ultraviolet rays while maintaining transparency and heat resistance.
A resin composition for golf ball covers and top coats utilizing plant-derived extracts such as ferulic acid, cinnamic acid, and linoleic acid, which absorb ultraviolet rays, ensuring a color difference of 10.0 or less under xenon lamp irradiation, and using oil-based paints and ester or ketone solvents for better solubility.
The use of plant-derived ultraviolet absorbers in golf ball covers and top coats maintains the ball's white appearance and prevents yellowing, being safe for the environment and human health, with effective UV protection.
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Figure 0007606345000001
Abstract
Description
[Technical field]
[0001] The present invention relates to a resin composition for a golf ball and its cover or top coat, and more particularly to a resin composition for a golf ball and its cover or top coat having an improved ultraviolet absorber. [Background technology]
[0002] Although golf balls with colorful or patterned exteriors are available, typical golf balls are white and have markings such as the golf ball manufacturer's name, brand name, logo, numbers, etc. White golf balls are usually manufactured by blending a white pigment into the resin of the cover in which the dimples are formed, and then forming a colorless and transparent top coat on the surface of this cover.
[0003] The resin of a golf ball cover is prone to yellowing when exposed to sunlight, so in order to prevent such yellowing, the cover or the top coat thereof may be compounded with an ultraviolet absorbing agent that absorbs the ultraviolet rays in sunlight, or, in order to make the white color stand out more, a fluorescent whitening agent that absorbs ultraviolet rays and emits visible light of a specified wavelength may be compounded.
[0004] As such an ultraviolet absorbing agent, JP 2009-050420 A describes the incorporation of a benzotriazole-based or triazine-based ultraviolet absorbing agent in both the cover and the top coat in order to effectively suppress discoloration of the urethane resin that constitutes the cover of a golf ball.
[0005] In addition, JP-T-2000-516521 describes that a UV light absorber having an absorption peak at wavelengths between about 330 nm and about 360 nm and having an absorbance of UV light at a wavelength of about 350 nm at least about three times that of UV light at about 370 nm is blended into a visible light-transmitting urethane top coat composition for golf balls in order to protect the top coat from both UV from the sun and UV light used to cure UV-curable inks and to reduce or prevent fading and yellowing. As a preferred UV absorber, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-1,3,5-triazine is described. [Prior art documents] [Patent documents]
[0006] [Patent Document 1] JP 2009-050420 A [Patent Document 2] Special Publication No. 2000-516521 Summary of the Invention [Problem to be solved by the invention]
[0007] The ultraviolet absorbing agents used in golf balls, including those described in the above-mentioned documents, are all made from petroleum-derived resources and are not friendly to the human body or the environment. There is a growing demand for golf balls to use natural resources instead of petroleum-derived resources, but the present inventor has found that there are problems with heat resistance, transparency, and discoloration prevention effect when using naturally derived substances known to have ultraviolet absorbing properties to actually suppress yellowing of golf balls due to ultraviolet rays.
[0008] In view of the above problems, the present invention has an object to provide a resin composition for a golf ball and its cover or top coat that is safe for the human body and the environment, and that is capable of suppressing yellowing of a golf ball due to ultraviolet light even when a naturally occurring substance is used as an ultraviolet absorbing agent. [Means for solving the problem]
[0009] In order to achieve the above object, one aspect of the present invention is a golf ball comprising at least a core, a cover, and a top coat, wherein the cover or the top coat contains a plant-derived extract that absorbs ultraviolet light, and in a color change test in which the cover or the top coat is irradiated with a xenon lamp, the color difference ΔE before and after the test according to the Lab color system is 10.0 or less.
[0010] The plant-derived extract is preferably ferulic acid, a ferulic acid compound, a cinnamic acid compound, linoleic acid, or a combination thereof.
[0011] The plant-derived extract preferably has an absorbance peak at a wavelength between 320 nm and 360 nm.
[0012] When the plant-derived extract is contained in the top coat, the top coat preferably comprises an oil-based paint.
[0013] Furthermore, in another aspect, the present invention provides a resin composition for a cover or top coat of a golf ball, the resin composition comprising a resin for the cover or top coat of a golf ball and an extract derived from a plant that absorbs ultraviolet light, and in a color change test in which a film formed from the resin composition is irradiated with a xenon lamp, the color difference ΔE before and after the test according to the Lab color system is 10.0 or less.
[0014] The resin for the top coat preferably includes a urethane coating containing a base agent and a curing agent, and in this case, the content of the plant-derived extract is preferably within the range of 0.01 to 8.0 mass % relative to the total amount of the base agent including the solvent.
[0015] The solvent is preferably an ester-based solvent or a ketone-based solvent. Effect of the Invention
[0016] Thus, according to the present invention, by incorporating an ultraviolet ray absorbing plant-derived extract into the resin composition of a golf ball cover or top coat, it is possible for the golf ball cover or top coat to have a color difference ΔE of 10.0 or less before and after a color change test in which the cover or top coat is irradiated with a xenon lamp, according to the Lab color system. Therefore, even if a naturally occurring substance is used as the ultraviolet ray absorber, yellowing of the golf ball due to ultraviolet rays can be suppressed, making it possible to provide a golf ball that is kind to the human body and the environment.
[0017] In particular, ferulic acid compounds and cinnamic acid compounds, which are plant-derived extracts that absorb ultraviolet light, are poorly soluble in water but oil-soluble, and therefore can be incorporated into the top coat by using an oil-based paint such as a urethane paint containing a base agent and a hardener as the resin for the top coat. By using an ester-based solvent or a ketone-based solvent as the solvent for the resin for the top coat, rather than an aromatic solvent that is harmful to the human body and the environment, a golf ball that is more friendly to the human body and the environment can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the golf ball and the resin composition for the cover or top coat thereof according to the present invention will be described in detail.
[0019] The resin composition for a cover or top coat of the present embodiment contains a resin for a golf ball cover or top coat and a plant-derived extract (also called a "phytochemical") that absorbs ultraviolet light.
[0020] The resin for the cover may be, but is not limited to, for example, a thermoplastic polyurethane, an ionomer resin, or a mixture thereof as a main component.
[0021] The structure of the thermoplastic polyurethane material is composed of a soft segment made of a polymer polyol (polymeric glycol) and a chain extender and a polyisocyanate that constitute a hard segment. Here, the polymer polyol used as the raw material is not particularly limited, but in the present invention, polyester polyols and polyether polyols are preferred. Specific examples of polyester polyols include adipate polyols such as polyethylene adipate glycol, polypropylene adipate glycol, polybutadiene adipate glycol, and polyhexamethylene adipate glycol, and lactone polyols such as polycaprolactone polyol. Examples of polyether polyols include poly(ethylene glycol), poly(propylene glycol), and poly(tetramethylene glycol).
[0022] The chain extender is not particularly limited, but in the present invention, a low molecular weight compound having two or more active hydrogen atoms in the molecule capable of reacting with an isocyanate group and a molecular weight of 2,000 or less can be used, and among these, an aliphatic diol having 2 to 12 carbon atoms is preferred. Specific examples include 1,4-butylene glycol, 1,2-ethylene glycol, 1,3-butanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, and the like, and among these, 1,4-butylene glycol is particularly preferred.
[0023] The polyisocyanate compound is not particularly limited, but in the present invention, for example, one or more compounds selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate can be used. However, depending on the type of isocyanate, it may be difficult to control the crosslinking reaction during injection molding. Therefore, in the present invention, from the viewpoint of the balance between stability during production and the physical properties exhibited, the aromatic diisocyanate 4,4'-diphenylmethane diisocyanate is preferred.
[0024] The ionomer resin may be, but is not limited to, one having the following component (a) and / or component (b) as the base resin. Optionally, the following component (c) may be added to this base resin. The component (a) is an olefin-unsaturated carboxylic acid-unsaturated carboxylic acid ester ternary random copolymer and / or a metal salt thereof, the component (b) is an olefin-unsaturated carboxylic acid binary random copolymer and / or a metal salt thereof, and the component (c) is a thermoplastic block copolymer having a polyolefin crystalline block and a polyethylene / butylene random copolymer.
[0025] In addition to the main component of the thermoplastic polyurethane or ionomer resin, the resin for the cover may contain a thermoplastic resin or elastomer other than the thermoplastic polyurethane. Specifically, one or more of polyester elastomers, polyamide elastomers, ionomer resins, styrene block elastomers, hydrogenated styrene butadiene rubber, styrene-ethylene / butylene-ethylene block copolymers or modified products thereof, ethylene-ethylene / butylene-ethylene block copolymers or modified products thereof, styrene-ethylene / butylene-styrene block copolymers or modified products thereof, ABS resins, polyacetals, polyethylene, and nylon resins may be used. In particular, polyester elastomers, polyamide elastomers, and polyacetals are preferably used because they maintain good productivity while improving resilience and abrasion resistance through reaction with isocyanate groups. When the above components are blended, the blending amount is appropriately selected depending on the adjustment of the hardness of the cover material, the improvement of the resilience, the improvement of the fluidity, the improvement of the adhesion, etc., and is not particularly limited, but is preferably 5 parts by mass or more per 100 parts by mass of the thermoplastic polyurethane component. In addition, the upper limit of the blending amount is also not particularly limited, but is preferably 100 parts by mass or less, more preferably 75 parts by mass or less, and even more preferably 50 parts by mass or less per 100 parts by mass of the thermoplastic polyurethane component. In addition, polyisocyanate compounds, fatty acids or derivatives thereof, basic inorganic metal compounds, fillers, etc. may be added.
[0026] The resin for the top coat is not particularly limited, but for example, a paint resin such as a urethane paint consisting of a polyol as a main agent and a polyisocyanate as a hardener, or a rubber-based paint can be used as the main component. These paint resins are oil-based paints that use organic solvents. In addition to the above main components, the material forming the top coat may contain a low surface energy composition such as silicone wax as an additive. Each component will be described below.
[0027] The polyol is not limited thereto, but it is preferable to use polycarbonate polyol or polyester polyol, and two kinds of polyester polyols, that is, polyester polyol (A) and polyester polyol (B), may be used. When using these two kinds of polyester polyols, the weight average molecular weights (Mw) are different, and it is preferable that the weight average molecular weight (Mw) of the (A) component is 20,000 to 30,000 and the weight average molecular weight (Mw) of the (B) component is 800 to 1,500. The weight average molecular weight (Mw) of the (A) component is more preferably 22,000 to 29,000, and even more preferably 23,000 to 28,000. The weight average molecular weight (Mw) of the (B) component is more preferably 900 to 1,200, and even more preferably 1,000 to 1,100.
[0028] The polyester polyol is obtained by polycondensation of a polyol and a polybasic acid. Examples of the polyol include diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, hexylene glycol, dimethylolheptane, polyethylene glycol, and polypropylene glycol, triols, tetraols, and polyols having an alicyclic structure. Examples of polybasic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, and dimer acid, aliphatic unsaturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, and citraconic acid, aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, dicarboxylic acids having an alicyclic structure such as tetrahydrophthalic acid, hexahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and endomethylenetetrahydrophthalic acid, and tris-2-carboxyethyl isocyanurate. In particular, polyester polyols having a cyclic structure introduced into the resin skeleton can be used as the polyester polyol of component (A), and examples thereof include polyester polyols obtained by polycondensation of a polyol having an alicyclic structure such as cyclohexanedimethanol with a polybasic acid, or polycondensation of a polyol having an alicyclic structure with a diol or triol with a polybasic acid. On the other hand, as the polyester polyol of component (B), a polyester polyol having a multi-branched structure can be used, and an example thereof includes polyester polyols having a branched structure such as "NIPPOLAN 800" manufactured by Tosoh Corporation.
[0029] In addition, when the above-mentioned polyester polyol is used, the weight average molecular weight (Mw) of the entire base agent is preferably 13,000 to 23,000, more preferably 15,000 to 22,000. In addition, the number average molecular weight (Mn) of the entire base agent is preferably 1,100 to 2,000, more preferably 1,300 to 1,850. If these average molecular weights (Mw and Mn) deviate from the above ranges, the abrasion resistance of the top coat may decrease. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured values (polystyrene equivalent values) by gel permeation chromatography (hereinafter abbreviated as GPC) measurement by differential refractometer detection. In the case where two types of polyester polyols are used, the Mw and Mn of the entire base agent are also within the above-mentioned ranges.
[0030] The blending amounts of the above two types of polyester polyols (A) and (B) are not particularly limited, but it is preferable that the blending amount of the (A) component is 20 to 30 mass % based on the total amount of the base material including the solvent, and the blending amount of the (B) component is 2 to 18 mass % based on the total amount of the base material.
[0031] The polyisocyanate is not particularly limited, but may be a commonly used aromatic, aliphatic, alicyclic, or other polyisocyanate, specifically, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, naphthalene diisocyanate, trimethylhexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1-isocyanato-3,3,5-trimethyl-4-isocyanatomethylcyclohexane, etc. These may be used alone or in combination.
[0032] Examples of the modified hexamethylene diisocyanate include polyester modified hexamethylene diisocyanate and urethane modified hexamethylene diisocyanate. Examples of the derivatives of hexamethylene diisocyanate include nurate (isocyanurate), biuret, and adduct of hexamethylene diisocyanate.
[0033] In the urethane coating material consisting of polyol and polyisocyanate as main components, the molar ratio (NCO group / OH group) of the hydroxyl group (OH group) of the polyol to the isocyanate group (NCO group) of the polyisocyanate is preferably 0.6 or more as a lower limit, more preferably 0.65 or more. The upper limit of this molar ratio is preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.9 or less. If this molar ratio is below the above lower limit, unreacted hydroxyl groups may remain, which may deteriorate the performance and water resistance of the top coat. On the other hand, if the molar ratio exceeds the above upper limit, the isocyanate group becomes excessive, which will react with water to produce urea groups (brittle), which may result in a deterioration of the performance of the top coat.
[0034] As the curing catalyst (organometallic compound) that promotes the reaction between polyol and polyisocyanate, an amine catalyst or an organometallic catalyst can be used. As this organometallic compound, metal soaps such as aluminum, nickel, zinc, tin, etc., which have traditionally been blended as curing agents in two-component curing urethane paints, can be suitably used.
[0035] The polyol, which is the main agent, and the polyisocyanate, which is the curing agent, can be mixed with various organic solvents depending on the coating conditions. Examples of such organic solvents include aromatic solvents such as toluene, xylene, and ethylbenzene, ester solvents such as ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, and propylene glycol methyl ether propionate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dipropylene glycol dimethyl ether, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, and ethylcyclohexane, and petroleum hydrocarbon solvents such as mineral spirits.
[0036] Among these, aromatic solvents such as toluene and xylene are not good for the human body and the environment, so it is preferable to use ester solvents or ketone solvents.Especially, ester solvents such as butyl acetate and ethyl acetate are more preferable from the viewpoint of easily dissolving plant-derived extracts.In addition, among plant-derived extracts, ferulic acid compounds and cinnamic acid compounds are oil-soluble and difficult to dissolve in water.
[0037] Examples of plant-derived extracts that absorb ultraviolet rays include, but are not limited to, ferulic acid, ferulic acid compounds, cinnamic acid compounds, linoleic acid, etc. It is known that some plant-derived extracts have the effect of absorbing ultraviolet rays, but the effect of ultraviolet absorption varies greatly depending on the plant-derived extract. The wavelength range that is effective as an ultraviolet absorbing agent used for golf balls is preferably 200 to 400 nm, more preferably 280 to 360 nm, and even more preferably 320 to 360 nm. In other words, it is preferable to use one that absorbs more in the UVA wavelength range.
[0038] Examples of plant-derived extracts that absorb in this wavelength range include ferulic acid, ferulic acid compounds, cinnamic acid compounds, and ricinoleic acid. Ferulic acid and ferulic acid compounds are contained in grains such as rice, wheat, rye, and barley, and in seeds such as coffee, apples, artichokes, peanuts, oranges, and pineapples, and are particularly extracted from rice bran. Ferulic acid and ferulic acid compounds have an absorbance peak in the wavelength range of 320 to 360 nm. Examples of ferulic acid compounds include ferulic acid esters such as γ-oryzanol.
[0039] Cinnamic acid compounds are extracted from shea butter and coconut oil, and have an absorbance peak in the wavelength region of 280 to 320 nm. Examples of cinnamic acid compounds include cinnamic acid esters such as methyl cinnamate, ethyl cinnamate, methyl 2,4-diisopropylcinnamate, ethyl 2,4-diisopropylcinnamate, octyl paradimethylaminobenzoate, sodium paramethoxycinnamate, and potassium paramethoxycinnamate.
[0040] Ricinoleic acid is extracted from castor oil, soybean oil, corn oil, camellia oil, etc., and has an absorbance peak in the wavelength region around 230 nm.
[0041] In the case of a resin composition for a top coat, it is preferable to add the plant-derived extract that absorbs ultraviolet rays to the main agent for the top coat. The amount of the plant-derived extract is sufficient to make the color difference ΔE according to the Lab color system 10.0 or less in a color tone change test by irradiating a xenon lamp, which will be described in detail later, and is, for example, but not limited to, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total amount of the main agent including the solvent. In addition, the upper limit of the amount of the plant-derived extract is, for example, but not limited to, preferably 8.0% by mass or less, more preferably 7.0% by mass or less, even more preferably 6.0% by mass or less, and even more preferably 5.0% by mass or less, because some plant-derived extracts have low solubility in solvents and may affect the appearance and flight performance of a golf ball if they remain in the resin.
[0042] In the case of a resin composition for a cover, the amount of plant-derived extract to be blended is an amount sufficient to achieve a color difference ΔE of 10.0 or less in the Lab color system in a color change test in which a xenon lamp is irradiated as described above; for example, but not limited to, the amount is preferably 0.5% by mass or more and preferably 5.0% by mass or less with respect to the resin base material of the cover.
[0043] In addition, a white pigment, a pearl pigment, or the like may be added to the resin composition for the cover or top coat, if necessary.
[0044] In the resin composition for cover or top coat of the present embodiment, in a color change test in which a film formed from the resin composition is irradiated with a xenon lamp, the color difference ΔE according to the Lab color system is 10.0 or less. The color difference ΔE according to the Lab color system is measured in accordance with JIS Z 8730-1980. The smaller the color difference ΔE value, the less discoloration there is. By making this color difference ΔE 10.0 or less, it is possible to suppress color change due to sunlight. The color difference ΔE is preferably 8.0 or less, and more preferably 6.5 or less. The lower limit of the color difference ΔE is not particularly limited, but is preferably, for example, 0 or more.
[0045] The resin composition for the cover or top coat of the present embodiment preferably has a yellowing index ΔYI of 16 or less in a yellowing index change test in which a film formed from the resin composition is irradiated with a xenon lamp. The lower limit of the yellowing index ΔYI is not particularly limited, but is preferably 0 or more, for example. The yellowing index YI is measured in accordance with JIS Z 8722. The yellowing index ΔYI varies depending on the pigment blended into the resin composition for the cover or top coat, but also varies depending on the type and amount of the ultraviolet absorber blended. By setting the above range, the appearance of the golf ball can be made white. The plant-derived extract that absorbs ultraviolet rays of the present embodiment maintains transparency even when exposed to sunlight, so it can be blended into the cover or top coat without affecting the appearance of the golf ball.
[0046] Next, one embodiment of a method for producing a golf ball using this resin composition for the cover or top coat will be described.
[0047] The golf ball of the present embodiment may have a multi-piece structure, such as a two-piece structure consisting of a core and a cover, or a three-piece structure having an intermediate layer between the core and the cover.
[0048] The core can be mainly formed of a base rubber. As the base rubber, a wide variety of rubbers (thermosetting elastomers) can be used, including, but not limited to, polybutadiene rubber (BR), styrene butadiene rubber (SBR), natural rubber (NR), polyisoprene rubber (IR), polyurethane rubber (PU), butyl rubber (IIR), vinyl polybutadiene rubber (VBR), ethylene propylene rubber (EPDM), nitrile rubber (NBR), and silicone rubber. As the polybutadiene rubber (BR), for example, 1,2-polybutadiene, cis-1,4-polybutadiene, etc. can be used.
[0049] In addition to the base rubber as the main component, the core may optionally contain, for example, a co-crosslinking agent, a crosslinking agent, a filler, an antioxidant, an isomerizing agent, a mastication accelerator, sulfur, and an organic sulfur compound. Also, instead of the base rubber, a thermoplastic elastomer, an ionomer resin, or a mixture thereof may be used as the main component.
[0050] The core has a substantially spherical shape. The upper limit of the outer diameter of the core is preferably about 42 mm or less, more preferably about 41 mm or less, and even more preferably about 40 mm or less. The lower limit of the outer diameter of the core is preferably about 5 mm or more, more preferably about 15 mm or more, and most preferably about 25 mm or more. The core may be solid or hollow. The core may be a single layer, or may be a core consisting of multiple layers such as a center core and a surrounding layer.
[0051] The core can be molded by a known method for molding a golf ball core. For example, but not limited to, a material containing a base rubber can be kneaded in a kneading machine, and then the kneaded mixture can be pressure-vulcanized and molded in a round mold to obtain a core having multiple layers. A known method for molding a multi-layered solid core can be used to mold a core having multiple layers. For example, a center core can be obtained by kneading a material in a kneading machine and pressure-vulcanizing and molding the kneaded mixture in a round mold, and then a surrounding layer can be obtained by kneading a material in a kneading machine, molding the kneaded mixture into a sheet, and covering the center core with the sheet and pressure-vulcanizing and molding the sheet in a round mold to obtain a multi-layered core.
[0052] Next, a cover is formed on the outer periphery of the core using a resin composition for the cover containing the plant-derived extract that absorbs ultraviolet light according to the present embodiment. Note that, when a resin composition for the top coat containing the plant-derived extract that absorbs ultraviolet light according to the present embodiment is used for forming the top coat, a resin composition that does not contain the plant-derived extract that absorbs ultraviolet light is used for forming the cover.
[0053] The method for forming the cover can be a known molding method for a golf ball cover. For example, but not limited to, the core can be placed in a mold and the resin composition for the cover can be injection molded to form a cover so as to cover the core. The plant-derived extract that absorbs ultraviolet light in this embodiment does not decompose under the temperature conditions when the cover is formed by injection molding, and therefore can function as an ultraviolet absorbent in the cover. The mold for molding the cover has a plurality of protrusions for forming dimples on the cover surface. The size, shape, number, etc. of the dimples formed on the cover surface can be designed appropriately according to the desired aerodynamic characteristics of the golf ball.
[0054] The thickness of the cover is not limited to these values, but the lower limit is preferably 0.2 mm or more, and more preferably 0.4 mm or more, and the upper limit is preferably 4 mm or less, more preferably 3 mm or less, and even more preferably 2 mm or less.
[0055] The material hardness of the cover is not limited to, but the upper limit is preferably about 60 or less, more preferably about 55 or less, and even more preferably about 50 or less, in Shore D. The lower limit is preferably about 35 or more, and more preferably about 40 or more, in Shore D. The material hardness of the cover is measured in accordance with the ASTM D2240-95 standard after the resin material for the cover is molded into a sheet having a thickness of 2 mm and allowed to stand for at least two weeks.
[0056] Furthermore, a top coat (also called a "coating") is formed on the outer periphery of the cover using a resin composition for the top coat containing an extract derived from a plant that absorbs ultraviolet light according to this embodiment. As described above, when a resin composition for the cover containing an extract derived from a plant that absorbs ultraviolet light according to this embodiment is used to form the cover, a composition that does not contain an extract derived from a plant that absorbs ultraviolet light is used to form the top coat.
[0057] The thickness of the top coat is not particularly limited, but the lower limit is preferably 7 μm or more, more preferably 10 μm or more, and even more preferably 13 μm or more, and the upper limit is preferably 22 μm or less, and more preferably 20 μm or less.
[0058] The method for forming the top coat on the surface of the cover is not particularly limited, and any known method for applying a golf ball paint to the surface of the cover can be used, such as an air gun coating method or an electrostatic coating method.
[0059] After the top coat is applied, a step of drying the coating film may be carried out. The drying conditions may be the same as known conditions for drying urethane paints, and in this embodiment, for example, the drying temperature may be about 40° C. or higher, particularly 40 to 60° C., and the drying time may be 20 to 90 minutes, particularly 40 to 50 minutes. The plant-derived extract that absorbs ultraviolet light in this embodiment does not decompose under such drying conditions, and therefore can function as an ultraviolet light absorber in the top coat.
[0060] An intermediate layer may be provided between the core and the cover. The intermediate layer may be formed using the same material as the cover described above, i.e., thermoplastic polyurethane, ionomer resin, or a mixture thereof. In addition to the main components described above, the intermediate layer may contain other thermoplastic elastomers, polyisocyanate compounds, fatty acids or derivatives thereof, basic inorganic metal compounds, fillers, etc.
[0061] The material hardness of the mid layer is not limited to this, but the lower limit is preferably 50 or more, and more preferably 55 or more, in Shore D. The upper limit of the hardness of the mid layer 40 is preferably 70 or less, and more preferably 65 or less, in Shore D.
[0062] The thickness of the intermediate layer is not limited to this value, but is preferably 0.5 mm or more, and more preferably 1 mm or more. The upper limit of the thickness of the intermediate layer is preferably 10 mm or less, and more preferably 5 mm or less.
[0063] In this manner, a golf ball can be obtained having a cover or top coat that includes an ultraviolet ray absorbing plant-derived extract. EXAMPLES
[0064] Examples and comparative examples of the present invention will be described below.
[0065] In producing the golf balls of the examples and comparative examples, the top coat of the golf ball was produced using the coating composition shown in Table 1. The composition in Table 1 is expressed in parts by mass. The coating thickness of the top coat was 15 μm. The produced golf balls were subjected to a xenon color tone change test and a xenon yellowness change test.
[0066] As the main polyol of the coating composition in Table 1, a polyester polyol with a weight average molecular weight (Mw) of 28,000 was used. This was synthesized by the following method. In a reaction apparatus equipped with a reflux condenser, a dropping funnel, a gas inlet tube, and a thermometer, 140 parts by mass of trimethylolpropane, 95 parts by mass of ethylene glycol, 157 parts by mass of adipic acid, and 58 parts by mass of 1,4-cyclohexanedimethanol were charged, and the temperature was raised to 200 to 240°C while stirring, and the mixture was heated (reacted) for 5 hours. After that, a polyester polyol with an acid value of 4, a hydroxyl value of 170, and a weight average molecular weight (Mw) of 28,000 was obtained.
[0067] As the curing agent isocyanate, a nurate (isocyanurate) of hexamethylene diisocyanate (HMDI) available under the trade name Duranate TPA-100 (NCO content 23.1%, non-volatile content 100%) manufactured by Asahi Kasei Corporation was used.
[0068] As the ultraviolet absorbent in Table 1, the ferulic acid compound was used as the product name "UV Cut Rice Extract", which is rice powder manufactured by Mono. The ricinoleic acid was used as the product name "VELUS Castor Oil", which is castor oil manufactured by TORASOL Pharmaceuticals. Tinuvin 479 is a triazine-based ultraviolet absorbent manufactured by BASF. Both ultraviolet absorbents were blended into the base agent. Butyl acetate was used as the solvent for both the base agent and the curing agent. In addition, the dissolution of the ultraviolet absorbent in the solvent was observed and evaluated. The one that dissolved without leaving any precipitate was evaluated as ◎, and the one that dissolved almost completely but with some precipitate was evaluated as ◯. The evaluation results for the examples and comparative examples are shown in Table 1.
[0069] The covers of all the golf balls were made of ether-type thermoplastic polyurethane (trade name: Pandex) manufactured by DIC Covestro Polymer Co., Ltd. The material hardness of the covers was 47 on the Shore D scale.
[0070] The intermediate layer of each golf ball was formulated with 35 parts by weight of Himilan 1706 (trade name), an ionomer resin made of an ethylene-methacrylic acid copolymer manufactured by Dow Mitsui Polychemicals, 15 parts by weight of Himilan 1557 (trade name), 50 parts by weight of Himilan 1605 (trade name), and 1.1 parts by weight of trimethylolpropane.
[0071] The core of each golf ball was formulated as follows: 20 parts by weight of polybutadiene (product name BR51, manufactured by JSR Corporation) as a base rubber, 80 parts by weight of polybutadiene (product name BR-01, manufactured by JSR Corporation), 28.5 parts by weight of zinc acrylate (manufactured by Wako Pure Chemical Industries Co., Ltd.), 1.0 part by weight of dicumyl peroxide (product name Percumyl D, manufactured by Nippon Oil & Fats Corporation) as an organic peroxide, 0.1 part by weight of 2,2-methylenebis(4-methyl-6-butylphenol) (product name Nocrac NS-6, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) as an antioxidant, 33.0 parts by weight of barium sulfate (product name Precipitated Barium Sulfate #100, manufactured by Sakai Chemical Industry Co., Ltd.), 4.0 parts by weight of zinc oxide (product name Three-type Zinc Oxide, manufactured by Sakai Chemical Industry Co., Ltd.), and 0.5 part by weight of pentachlorothiophenol zinc salt (manufactured by Wako Pure Chemical Industries Co., Ltd.) as an organic sulfur compound.
[0072] [Xenon color change test] The xenon color change test was carried out using a Super Xenon Weather Meter (SX75) manufactured by Suga Test Instruments Co., Ltd., and the color change of the ball surface before and after xenon irradiation was measured using a color difference meter (model SC-P) manufactured by Suga Test Instruments Co., Ltd. Based on the Lab color display of JIS Z 8701, the discoloration of the ball before and after irradiation (color difference ΔE) was examined. The smaller the color difference ΔE value, the less discoloration there was. Yellowing was also evaluated from the color difference ΔE. The evaluation criteria were as follows: a color difference ΔE of 6.5 or less was evaluated as ◎, a color difference ΔE of more than 6.5 and less than 10.0 was evaluated as ○, and a color difference ΔE of more than 10.0 was evaluated as ×.
[0073] [Xenon yellowing test] The xenon yellowness change test was carried out using a color difference meter (spectrometer SC-P manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS Z 8722 "Method of measurement of reflective objects" (diffuse light illumination, optical system with 8-degree light reception: condition c), and was measured at d / 8 (measurement without including the regular reflection component of the sample: with light trap). The measurement hole diameter was φ30 mm. The ball surface before and after xenon irradiation was measured for L, a, b values and yellowness YI based on the Lab color table of JIS Z 8701, and the difference between before and after irradiation (yellowing degree ΔYI) was calculated.
[0074] [Table 1]
[0075] As shown in Table 1, Comparative Example 1, which did not contain any ultraviolet absorbent, had a high color difference ΔE of 11.0 in the xenon color change test, and noticeable yellowing occurred. On the other hand, Comparative Examples 2 and 3, which used petroleum-derived triazine Tinuvin 479 as the ultraviolet absorbent, had a very low color difference ΔE of 6.5 and hardly any yellowing occurred, even with a small amount of 0.3 to 0.5 parts by mass.
[0076] In addition, in Examples 1 to 5, which used a ferulic acid compound, which is a plant-derived extract, as an ultraviolet absorber, the color difference ΔE was 10.0 or less at any concentration, and it was confirmed that by incorporating a ferulic acid compound into the top coat of a golf ball, the yellowing of the golf ball can be prevented. In particular, the more the amount of ferulic acid compound incorporated, the lower the color difference ΔE, and the same effect as that of a petroleum-derived ultraviolet absorber can be obtained, but it was found that if the amount is too much, it does not completely dissolve in the solvent.
[0077] Furthermore, Example 6, which used ricinoleic acid, a plant-derived extract, also had a color difference ΔE of 10.0 or less, confirming that by incorporating ricinoleic acid into the top coat of a golf ball, yellowing of the golf ball can be prevented.
Claims
1. A resin for a cover or top coat of a golf ball; Plant-derived extracts that absorb UV rays A resin composition for a cover or top coat of a golf ball, comprising: In a color change test in which a film formed from the resin composition is irradiated with a xenon lamp, the color difference ΔE before and after the test according to the Lab color system is 10.0 or less, The resin composition for a cover or top coat of a golf ball includes a urethane paint containing a base agent and a curing agent, and the content of the plant-derived extract is within a range of 0.01 to 8.0 mass % based on the total amount of the base agent including the solvent.
2. 2. The golf ball according to claim 1, wherein the solvent is an ester-based solvent or a ketone-based solvent.
3. The golf ball of claim 1, wherein the plant-derived extract is ferulic acid, a ferulic acid compound, a cinnamic acid compound, linoleic acid, or a combination thereof.
4. The golf ball as described in claim 1, wherein the plant-derived extract has an absorbance peak at a wavelength between 320 nm and 360 nm.
Citation Information
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