Patent Application
20220193502
The present invention relates to a golf ball, and particularly relates to a colored golf ball.
Conventionally, a golf ball is white. In case of bad weather conditions such as rainy, cloudy, foggy and dim conditions, it is difficult to follow the trajectory of the white golf ball and visually recognize where the golf ball falls. In addition, in a case that the white golf ball lies on dead grass, it is difficult to find the golf ball even if the golf ball is nearby. In addition, recently, golf players desiring a fashionable golf ball are also increasing. Under such circumstances, a colored golf ball has been proposed in order to satisfy the requirements such as the fashionable appearance and the visibility under bad weather conditions.
JP S63-38476 A discloses a method for producing a golf ball, comprising covering a first hemispherical shell and a core charged into a hemispherical concave portion of a lower mold having the hemispherical concave portion with a second hemispherical shell with a different color from the first hemispherical shell to form a sphere, covering an upper mold on the sphere, and heating and pressing the same to form a colored golf ball with two tones, wherein a protrusion for being horizontally locked to an edge of the concave portion of the lower mold is formed in the vicinity of an edge face of an opening of the first hemispherical shell.
JP 2013-183833 A discloses a golf ball comprising a core and a cover, wherein the cover consists of a first hemisphere and a second hemisphere, and the first hemisphere has a different style from the second hemisphere. JP 2013-183833 A further discloses the first hemisphere is formed from a first resin composition, the second hemisphere is formed from a second resin composition, and the first resin composition may have a different composition from the second resin composition.
JP 2017-118950 A discloses a golf ball comprising a core composed of at least one layer and a cover composed of at least one layer, wherein an outermost layer of the core has two hemispheres with color tones different from each other and formed from a rubber composition, a boundary between the hemispheres as a colored boundary line is formed along a great circle of the outermost layer of the core, at least one of the hemispheres contains a fluorescent coloring agent or a luminous agent, the cover is formed from a transparent or translucent thermoplastic resin composition, and at least one layer of the cover contains at least one of a fluorescent brightener, a fluorescent coloring agent, and a luminous agent.
JP S59-64165 U discloses a golf ball having a shell layer formed by covering a surface of a core with a plurality of shells with different colors, wherein an outer surface of the golf ball is comparted by the difference in the color of the shell layer.
U.S. Pat. No. 7,862,760 discloses a golf ball comprising a multi-color layer obtained by injection molding a first material and a second material respectively.
U.S. Pat. No. 8,915,802 discloses a golf ball comprising at least two layers, wherein each layer has at least two different color regions by which the golf ball shows an overall multi-color appearance.
U.S. Pat. No. 9,067,105 discloses a golf ball comprising a first hemispherical cover and a second hemispherical cover having a color tone different from each other.
An object of the present invention is to provide a golf ball having high visibility and excellent orientation at shot.
The present invention that has solved the above problem provides a golf ball comprising a core and a cover disposed outside of the core, wherein a surface of the golf ball has a first region with a first color and a second region with a second color, the first color has hue H1 represented by H value in HSL color space, the second color has hue H2 represented by H value in HSL color space, and the H1 and the H2 satisfy the following mathematical formula (1):
60<|H1−H2|<300 (1).
If the relationship of the mathematical formula (1) is satisfied, the first color of the first region and the second color of the second region have a complementary color relationship. As a result, the golf ball has excellent orientation at shot and is easily found on the rough.
According to the present invention, a golf ball having high visibility and excellent orientation at shot is obtained.
The present invention provides a golf ball comprising a core and a cover disposed outside of the core, wherein a surface of the golf ball has a first region with a first color and a second region with a second color, the first color has hue H1 represented b H value in HSL color space, the second color has hue H2 represented by H value in HSL color space, and the H1 and the H2 satisfy the following mathematical formula (1): 60<|H1−H2|<300 (1).
The surface of the golf ball according to the present invention has a first region with a first color, and a second region with a second color which is different from the first color. The first region and the second region are each preferably a region with a single color.
The first color of the first region has hue H1 represented by H value in HSL color space, the second color of the second region has hue H2 represented by H value in HSL color space, and the H1 and the H2 satisfy the following mathematical formula (1): 60<|H1−H2|<300 (1).
It is noted that, in the present invention, “the hue of the first color of the first region” is sometimes simply referred to as “the hue of the first region”, and “the hue of the second color of the second region” is sometimes simply referred to as “the hue of the second region”.
An absolute value |H1−H2| of a difference between the hue H1 of the first region and the hue H2 of the second region is preferably more than 60, more preferably 75 or more, and even more preferably 90 or more, and is preferably less than 300, more preferably 285 or less, and even more preferably 270 or less.
If the absolute value |H1−H2| falls within the above range, an effect of enhancing the visibility and the orientation at shot can be obtained.
The hue H1 of the first color of the first region is H value in HSL color space, The H1 is preferably 0 or more, more preferably 10 or more, and even more preferably 20 or more, and is preferably 360 or less, more preferably 350 or less, and even more preferably 340 or less
The saturation S1 of the first color of the first region is S value in HSL color space. The S1 is preferably 40 or more, more preferably 45 or more, and even more preferably 50 or more, and is preferably 100 or less, more preferably 95 or less, and even more preferably 90 or less.
The lightness L1 of the first color of the first region is L value in HSL color space. The L1 is preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more, and is preferably 100 or less, more preferably 97 or less, and even more preferably 94 or less.
The hue H2 of the second color of the second region is H value in HSL color space value. The H2 is preferably 60 or more, more preferably 65 or more, and even more preferably 70 or more, and is preferably 300 or less, more preferably 290 or less, and even more preferably 280 or less.
The saturation S2 of the second color of the second region is S value in HSL color space value. The S2 is preferably 40 or more, more preferably 45 or more, and even more preferably 50 or more, and is preferably 100 or less, more preferably 95 or less, and even more preferably 90 or less.
The lightness L2 of the second color of the second region is L value in HSL color space. The L2 is preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more, and is preferably 100 or less, more preferably 90 or less, and even more preferably 80 or less.
The first color of the first region is not particularly limited, but the first color is preferably a color selected from the group consisting of white, yellow, orange, blue, red, pink, green and black. The second color of the second region is not particularly limited, as long as the second color is a color different from the first color of the first region, but the second color is preferably a color selected from the group consisting of white, yellow, orange, blue, red, pink, green and black.
The area of the first region on the golf ball surface is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, and is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less, of the golf ball surface area.
The area of the second region on the golf ball surface is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, and is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less, of the golf ball surface area.
The area ratio of the first region to the second region is not particularly limited, but the area ratio is preferably 20/80 or more, more preferably 30/70 or more, and even more preferably 50/50 or more, and is preferably 80/20 or less, more preferably 70/30 or less.
The shape of the first region and the second region is not particularly limited, and examples thereof include a polygonal shape such as a triangular shape, quadrangular shape, pentagonal shape and hexagonal shape; a trapezoidal shape; a circle shape; and an elliptical shape, in a plan view. It is noted that a string of letters such as a trade name and a ball number usually formed on the golf ball surface is not qualified as the first region and the second region in the present invention.
The first region and the second region may be each formed only at one spot of the golf ball surface, or at a plurality of spots of the golf ball surface.
In the present invention, in the case that the golf ball surface consists of the first region and the second region, for example, when the first region has a specific shape, the second region is a region other than the first region. For example, if the first region has a polygonal shape such as a triangular shape, quadrangular shape, pentagonal shape and hexagonal shape, a trapezoidal shape, a circle shape, or an elliptical shape in a plan view, the second region is a region on the golf ball surface other the first region.
In addition, in a preferable embodiment according to the present invention, the first region and the second region are each a region surrounded by two boundary lines connecting the first pole and the second pole of the golf ball surface wherein the region continues from the first pole to the second pole. Herein, the first pole and the second pole are each an intersection point of the golf ball surface with the central axis passing through the center point of the golf ball. The first region and the second region are each preferably hemispherical.
The first region and the second region may be each formed by the colored paint film, or may be each formed by the colored cover. Examples thereof include an embodiment that the first region and the second region are formed by the colored cover; an embodiment that the first region and the second region are formed by the colored paint film; and an embodiment that either one of the first region and the second region is formed by the colored cover, and the other one of the first region and the second region is formed by the colored paint film.
The golf ball according to the present invention may further have at least one intermediate layer between the core and the cover. The outermost layer of the intermediate layer has hue H0 represented by H value in HSL color space. Either one of |H0−H1| and |H0−H2| is preferably less than 10, and the other one of |H0−H1| and |H0−H2| is preferably 10 or more. In a case that the intermediate layer has a plurality of layers, the outermost layer is the layer of the intermediate layer closest to the cover. In a case that the intermediate layer is single layered, the outermost layer is the single layered intermediate layer.
Either one of |H0−H1| and |H0−H2| is preferably less than 10, more preferably 7 or less, and even more preferably 4 or less. If either one of |H0−H1| and |H0−H2| is less than 10, the golf ball has an appearance with better color development and inconspicuous dimple contour.
The other one of |H0−H1| and |H0−H2| is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, and is preferably 300 or less, more preferably 290 or less, and even more preferably 280 or less. If the other one of |H0−H1| and |H0−H2| is 10 or more, the first region and the second region are more distinguishable while keeping the color development.
The hue H0 of the outermost layer of the intermediate layer is H value in HSL color space. The H0 is preferably 0 or more, more preferably 10 or more, and even more preferably 20 or more, and is preferably 360 or less, more preferably 350 or less, and even more preferably 340 or less.
The saturation S0 of the outermost layer of the intermediate layer is S value in HSL color space. The S0 is preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more, and is preferably 100 or less, more preferably 97 or less, and even more preferably 94 or less.
The lightness L0 of the outermost layer of the intermediate layer is L value in HSL color space. The L0 is preferably 30 or more, more preferably 40 or more, and even more preferably 50 or more, and is preferably 100 or less, more preferably 97 or less, and even more preferably 94 or less.
In the present invention, the color of the golf ball surface and the outermost layer of the intermediate layer can be determined by L* value, a* value and b* value in CIELAB color coordinate system. L* value, a* value and b* value in CIELAB color coordinate system can be measured according to JIS-Z-8701 or JIS-Z-8728. In the measurement, suitably used is a color difference meter CM-350d available from Konica Minolta Co., in which a tristimulus values direct measuring method is adopted. Tristimulus values X, Y and Z are converted into L*, a* and b* as follows
L*=116(Y/YN)1/3−16
a*=500[(X/XN)1/3−(Y/YN)1/3]
b*=200[(Y/YN)1/3−(Z/ZN)1/3]
XN, YN and ZN are tristimulus values in the XYZ coordinate system of a perfect diffuse reflection surface.
In the present invention, the L* value, a* value and b* value obtained as above are converted into the H value (hue), S value (saturation) and L value (lightness) in HSL color space by using a color code conversion tool. As the color code conversion tool, for example, the tool described at the following website can be used.
https://syncer.jp/color-converter
The golf ball according to the present invention comprises a core, at least one intermediate layer covering the core, and a cover covering the intermediate layer. Next, materials constituting each constituent element of the golf ball will be explained.
The intermediate layer and/or cover of the golf ball according to the present invention is formed from a composition containing a resin component. It is noted that in the present invention, the resin composition for forming the intermediate layer is sometimes referred to as the intermediate layer composition, and the resin composition for forming the cover is sometimes referred to as the cover composition. Examples of the resin component include an ionomer resin, a thermoplastic polyurethane elastomer having a trade name of “Elastollan (registered trademark)” available from BASF Japan Ltd., a thermoplastic polyamide elastomer having a trade name of “Pebax (registered trademark)” available from Arkema K. K., a thermoplastic polyester elastomer having a trade name of “Hytrel (registered trademark)” available from Du Pont-Toray Co. Ltd., and a thermoplastic styrene elastomer having a trade name of “TEFABLOC (registered trademark)” available from Mitsubishi Chemical Corporation.
Examples of the ionomer resin include a product obtained by neutralizing at least a part of carboxyl groups of a binary copolymer composed of an olefin and an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms with a metal ion; a product obtained by neutralizing at least a part of carboxyl groups of a ternary copolymer composed of an olefin, an a,13-unsaturated carboxylic add having 3 to 8 carbon atoms and an a,3-unsaturated carboxylic acid ester with a metal ion; and a mixture thereof. The olefin is preferably an olefin having 2 to 8 carbon atoms. Examples of the olefin include ethylene, propylene, butene, pentene, hexene, heptene and octene, and ethylene is particularly preferable. Examples of the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms include acrylic acid, methacrylic acid, fumaric acid, maleic acid and crotonic acid, and acrylic acid or methacrylic acid is particularly preferable. In addition, as the α,β-unsaturated carboxylic acid ester, methyl ester, ethyl ester, propyl ester, n-butyl ester, isobutyl ester or the like of acrylic acid, methacrylic acid, fumaric acid, maleic acid or the like can be used, and acrylic acid ester or methacrylic acid ester is particularly preferable. Among them, as the ionomer resin, a metal ion-neutralized product of an ethylene-(meth)acrylic acid binary copolymer, or a metal ion-neutralized product of an ethylene-(meth)acrylic acid-(meth)acrylic acid ester ternary copolymer is preferable.
The resin composition constituting the intermediate layer or cover of the golf ball according to the present invention preferably contains the thermoplastic polyurethane elastomer or ionomer resin as the resin component. In case of using the ionomer resin, the thermoplastic styrene elastomer is also preferably used in combination. The amount of the polyurethane or ionomer resin in the resin component of the resin composition is preferably 50 mass % or more, more preferably 60 mass % or more, and even more preferably 70 mass % or more.
In a preferable embodiment according to the present invention, the intermediate layer is formed from a composition containing the ionomer resin, and the cover is formed from a composition containing the thermoplastic urethane elastomer.
[Dye and/or Pigment]
The intermediate layer and/or cover of the golf ball according to the present invention preferably contains a dye and/or a pigment, more preferably contains a fluorescent dye and/or a fluorescent pigment. The fluorescent dye may be organic or inorganic, and may be any commercially available fluorescent dye. Examples of the fluorescent dye include a thioxanthene derivative, a xanthene derivative, a perylene derivative, a perylene imide derivative, a coumarin derivative, a thioindigo derivative, a naphthalimide derivative, and a methine derivative.
In a preferable embodiment, the melting point of the fluorescent dye and/or fluorescent pigment is preferably 180° C. or less, more preferably 175° C. or less, and even more preferably 170° or less, and is preferably 135° or more, more preferably 140° or more, and even more preferably 145° C. or more. If the melting point of the fluorescent dye and/or fluorescent pigment falls within the above range, mixing and dispersing the fluorescent dye and/or fluorescent pigment in the resin component can be conducted at a relatively low temperature. Since the color change due to a high temperature during processing is not likely to occur, the desired color tone can be easily obtained,
The fluorescent dye is not particularly limited, and specific examples thereof include a yellow fluorescent dye such as Lumogen F Grange™ 240 (available from BASF Ltd.); Lumogen F Yellow™ 083 (available from BASF Ltd.); Hostasol Yellow™ 3G (available from Hoechst-Celanese Corp.); Oraset Yellow™ 8GF (available from Ciba-Geigy Ltd.); Fluorol 088™ (available from BASF Ltd.); Thermoplast F Yellow™ 084 (available from BASF Ltd.); Golden Yellow™ D-304 (available from DayGlo Color Corp.); Mohawk Yellow™ D-299 (available from DayGlo Color Corp,); Potomac Yellow™ D-838 (available from DayGlo Color Corp.); and Polyfast Brilliant Red™ SB (available from Keystone Corp.).
Examples of the fluorescent pigment include a pigment having a fluorescent dye dispersed in a polymer material, and a pigment having a fluorescent dye formed into a particle shape. The fluorescent pigment is not particularly limited, and examples thereof include ZQ-11, ZQ-12, ZQ-13, ZQ-14, ZQ-15, ZQ-16, ZQ-17-N, ZQ-18, ZQ-19, ZQ-21, GPL-11, GPL-13, GPX-14, GPL-15, GPX-17, GPL-19 and GPL-21 available from DayGlo Color Corp., and FZ-2000 series, FZ-5000 series, FZ-6000 series, FZ-3040 series and FX-300 series available from Sinloihi Co., Ltd.
Examples of the polymer material in which the fluorescent dye is dispersed include a benzoguanamine resin, an acrylic resin, and a polyester resin.
In a preferable embodiment, the amount of the dye and/or pigment contained in the cover and at least one layer of the intermediate layer is preferably 0.5 part by mass or more, more preferably 0.6 part by mass or more, and even more preferably 0.7 part by mass or more, and is preferably 7 parts by mass or less, more preferably 6 parts by mass or less, even more preferably 5 parts by mass or less, and most preferably 4 parts by mass or less, with respect to 100 parts by mass of the resin component. If the amount is too large, the color of the golf ball is so deep that the golf ball has a dark color tone, and if the amount is too small, the desired color tone is not obtained.
Since the fluorescent dye and/or fluorescent pigment has low light stability, an ultraviolet absorber or light stabilizer is preferably used. The ultraviolet absorber or light stabilizer is not particularly limited, and may be any commercially available product. Examples of the ultraviolet absorber or light stabilizer include an ultraviolet absorber such as a salicylic acid derivative, a benzophenone derivative, a benzotriazole derivative, a cyanoacrylate derivative, a triazine derivative and a nickel complex; and a light stabilizer such as a hindered amine derivative.
Examples of the salicylic acid derivative ultraviolet absorber include phenyl salicylate, p-t-butylphenyl salicylate, and p-octylphenyl salicylate. Examples of the benzophenone derivative ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone, 2,2-dihydroxy-4,4′-methoxybenzophenone. Examples of the benzotriazole derivative ultraviolet absorber include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-5′-t-butylphenyl)benzotriazole, 2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-[2-hydroxy-3,5-bis(α,α′-dimethlbenzyl)phenyl]-2H-benzotriazole, and 2-(5-methyl-2-hydroxyphenyl)benzotriazole. Examples of the cyanoacrylate derivative ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, and ethyl-2-cyano-3,3′-diphenylacrylate. Examples of the triazine derivative ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5[(hexyl)oxy]-phenol, 2,4-bis(2-hydroxy-4-butyloxyphenyI)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and 2-(4-{[2-hydroxy-3-(2′-ethyl)hexyl]oxy}-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. Specific examples include “Sumisoap 130” and “Sumisoap 140” (both of which are benzophenone-based ultraviolet absorber) available from Sumitomo Chemical Co., Ltd.; “TINUVIN 234”, “TINUVIN 900”, TINUVIN 326″ and “TINUVIN P” (all of which are benzotriazole-based ultraviolet absorber) available from Ciba Specialty Chemicals plc.; “Uvinul N-35” (cyanoacrylate-based ultraviolet absorber) available from BASF Ltd.; and “TINUVIN 1577”, “TINUVIN 460” and “TINUVIN 405” (triazine-based ultraviolet absorber) available from Ciba Specialty Chemicals plc. These ultraviolet absorbers may be used solely, or two or more of them may be used in combination, It is noted that the ultraviolet absorber that can be used in the present invention is not limited to the above examples, and any conventional ultraviolet absorber can be used.
Examples of the light stabilizer such as the hindered amine derivative include bis(1,2,2,6,6-pentamethyl-4-piperidyl){[3,5-bis(1,1′-dimethylethyl)-4-hydroxyphenyl]methyl}butyl malonate, and 1-{2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl}-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine. Specific examples include “Sanol LS-2626” and “TINUVIN 144” available from Ciba Specialty Chemicals plc.
The amount of the ultraviolet absorber or light stabilizer is preferably 0.02 part by mass or more, more preferably 0.04 part by mass or more, and is preferably 2 parts by mass or less, more preferably 1 part by mass or less, with respect to 100 parts by mass of the resin component of the intermediate layer or cover. If the amount of the ultraviolet absorber or light stabilizer falls within the above range, the color change due to the exposure to sunlight can be effectively suppressed.
The intermediate layer and/or cover may contain titanium oxide. The combination of the fluorescent pigment with a small amount of titanium oxide can provide a translucent cover with a vivid color, Since titanium oxide provides high opacity, the amount of titanium oxide is preferably 0.001 part by mass or more, more preferably 0.002 part by mass or more, and even more preferably 0.005 part by mass or more, and is preferably 0.7 part by mass or less, more preferably 0.5 part by mass or less, and even more preferably 0.4 part by mass or less, with respect to 100 parts by mass of the resin component. If the amount of titanium oxide is 0.001 part by mass or more, a translucent cover with a vivid color is obtained, and if the amount of titanium oxide is more than 0.7 part by mass, the cover tends to be opaque.
In case of increasing the opacity of the intermediate layer and/or cover and increasing the degree of the white color, the amount of titanium oxide can be increased. In this case, the amount of titanium oxide is preferably more than 0.7 part by mass, more preferably 1 part by mass or more, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, with respect to 100 parts by mass of the resin component constituting the intermediate layer and/or the cover. If the amount of titanium oxide is more than 0.7 part by mass, the intermediate layer and/or cover has enhanced opacity. In addition, if the amount of titanium oxide is more than 10 parts by mass, the obtained intermediate layer and/or cover may have lowered durability.
In addition to the above described components, the intermediate layer and/or cover may contain a mass adjusting agent such as zinc oxide, calcium carbonate and barium sulfate, a dispersant, an antioxidant, a fluorescent brightener, a lubricant, a light stabilizer, or the like, as long as they do not impair the performance of the intermediate layer and/or cover,
The golf ball according to the present invention preferably has a paint film covering the cover. In the case that the golf ball according to the present invention has the paint film, the color of the golf ball surface can be obtained by measuring the surface of the paint film formed on the golf ball surface. Examples of the paint film include a clear paint film that is colorless and transparent, a nontransparent colored paint film, and a matte paint film.
In the case that the golf ball has a dear paint film that is colorless and transparent, the first color of the first region and the second color of the second region on the golf ball surface reflect the color of the cover. In the case that the golf ball has a nontransparent colored paint film or a matte paint film, the color tone of the golf ball surface is affected by the paint film.
The nontransparent colored paint film preferably contains, for example, a resin component and the dye and/or pigment. The matte paint film preferably contains, for example, a resin component and a filler.
The resin component constituting the paint film is not particularly limited, an acrylic resin, epoxy resin, polyurethane, polyester, cellulose-based resin or the like can be used, and a two-component curing type polyurethane which will be described later is preferably used. If the two-component curing type polyurethane is used, the obtained paint film has further enhanced durability.
The polyurethane is preferably a polyurethane (two-component curing type polyurethane) obtained by a reaction between a polyol composition and a polyisocyanate composition.
The polyol composition contains a polyol compound. Examples of the polyol compound include a compound having at least two hydroxy groups in the molecule. Examples of the polyol compound include a compound having a hydroxy group at a terminal of the molecule, and a compound having a hydroxy group at a position other than the terminal of the molecule. The polyol compound may be used solely, or two or more of the polyol compounds may be used in combination.
Examples of the compound having the hydroxy group at the terminal of the molecule include a low molecular weight polyol having a molecular weight less than 500, and a high molecular weight polyol having a number average molecular weight of 500 or more. Examples of the low molecular weight polyol include a diol such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol; and a triol such as glycerin, trimethylolpropane, and hexanetriol. Examples of the high molecular weight polyol include a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, an urethane polyol, and an acrylic polyol. Examples of the polyether polyol include polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG), and polyoxytetramethylene glycol (PTMG). Examples of the polyester polyol include polyethylene adipate (PEA), polybutylene adipate (PBA), and polyhexamethylene adipate (PHMA). Examples of the polycaprolactone polyol include poly-ε-caprolactone (PCL). Examples of the polycarbonate polyol include polyhexamethylene carbonate.
The polyol composition preferably contains a urethane polyol as the polyol component. The urethane polyol is synthesized by a reaction between a polyisocyanate and a polyol. The polyisocyanate for use in synthesis of the urethane polyol is not particularly limited, as long as the polyisocyanate has at least two isocyanate groups, and examples thereof include an aromatic polyisocyanate such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TEN), 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 3,3′-bitolylene-4,4′-diisocyanate (TODI), xylylene diisocyanate (XDI), tetramethylxylylenedilsocyanate (TMXDI), and para-phenylene diisocyanate (PPDI); and an alicyclic polyisocyanate or aliphatic polyisocyanate such as 4,4′-dicyclohexylmethane diisocyanate (H12MDI), hydrogenated xylylenediisocyanate (H6XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and norbornene diisocyanate (NBDI). These polyisocyanates may be used solely or as a mixture of at least two of them. Among them, from the viewpoint of weather resistance, the non-yellowing type polyisocyanate (TMXDI, XDI, HDI, H6DI, IPDI, H12MDI, NBDI, etc) is preferably used.
The polyol for use in synthesis of the urethane polyol is not particularly limited, as long as the polyol has a plurality of hydroxy groups, and examples thereof include a low molecular weight polyol and a high molecular weight polyol. Examples of the low molecular weight polyol include a diol such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol; and a trial such as glycerin, trimethylolpropane, and hexanetriol. Examples of the high molecular weight polyol include a polyether polyol such as polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG), and polyoxytetramethylene glycol (PTMG); a condensed polyester polyol such as polyethylene adipate (PEA), polybutylene adipate (PBA), and polyhexamethylene adipate (PHMA); a lactone polyester polyol such as poly-ε-caprolactone (PCL); a polycarbonate polyol such as polyhexamethylene carbonate; and an acrylic polyol. Among the above polyols, the polyol having a weight average molecular weight ranging from 50 to 2,000, particularly the polyol having a weight average molecular weight ranging from 100 to 1,000 is preferably used. These polyols may be used solely or as a mixture of at least two of them.
The urethane polyol is a polyol having a urethane bond formed by the reaction between the polyisocyanate and the polyol, and a hydroxy group at the terminal. Herein, the amount of the urethane bond in the urethane polyol preferably ranges from 0.1 mmol to 5 mmol in 1 g of the urethane polyol. The amount of the urethane bond is correlative with the rigidity of the formed paint film. If the amount of the urethane bond is less than 0.1 mmol/g, the concentration of the urethane in the formed paint film is low, and thus abrasion resistance may be insufficient. On the other hand, if the amount of the urethane bond is more than 5 mmol/g, the paint film is so hard that the paint film has lowered followability to the deformation of the golf ball body, and a small crack may easily occur.
In addition, the weight average molecular weight of the urethane polyol is preferably 4,000 or more, more preferably 4,500 or more, and is preferably less than 10,000, more preferably 9,000 or less. If the weight average molecular weight of the urethane polyol is less than 4,000, the drying time is longer, and thus workability and productivity may be lowered. On the other hand, if the urethane polyol has a high molecular weight of 10,000 or more, the urethane polyol has a relatively low hydroxy value, the reacting amount after applied is small, and thus the adhesion of the paint film to the golf ball body may be lowered. In addition, if the weight average molecular weight is 9,000 or less, a dense paint film (or clear paint layer) having little lowering of adhesion can be formed even in a state of being wetted by water.
The hydroxy value of the urethane polyol is preferably 15 mgKOH/g or more, more preferably 25 mgKOH/g or more, and is preferably 130 mgKOH/g or less, more preferably 120 mgKOH/g or less. If the hydroxy value of the urethane polyol is less than 15 mgKOH/g, the amount of the urethane polyol reacting with the curing agent is insufficient, and thus the adhesion strength of the paint film to the ball body may be hardly obtained. On the other hand, if the hydroxy value of the urethane polyol is more than 130 mgKOH/g, the productivity may be lowered because the time for the reaction between the urethane polyol and the curing agent is longer and the drying time is longer, and a crack may easily occur at impact.
The above urethane polyol is obtained by a reaction between the polyol and the polyisocyanate which are raw materials under a condition that the molar amount of the hydroxy group included in the polyol component is excessive to the molar amount of the isocyanate group included in the polyisocyanate component. In the above reaction, a solvent, or a conventional catalyst (dibutyl tin dilaurate, etc.) used in a reaction for synthesizing a urethane can be used. It is noted that the amount of the urethane bond can be controlled by adjusting the molecular weight of the polyol which is the raw material, the mixing ratio of the polyol to the polyisocyanate, or the like.
The polyol component contained in the polyol composition is preferably the above specific urethane polyol itself, but the polyol composition may contain a polyol having no urethane bond and being compatible with the urethane polyol, in addition to the urethane polyol. In this case, the polyol having no urethane bond is not particularly limited, and the above described raw material polyol for synthesizing the urethane polyol can be used. In addition, in the case that the polyol composition contains the polyol having no urethane bond, the amount of the urethane polyol in the polyol component contained in the polyol composition is preferably 50 mass % or more, more preferably 80 mass % or more. If the amount of the urethane polyol in the polyol component is less than 50 mass % the amount of the urethane polyol is relatively small, and thus the drying time is long.
Examples of the compound having a hydroxyl group at a part other than the terminal of the molecule include a modified polyrotaxane having a hydroxyl group and a hydroxyl group-modified vinyl chloride-vinyl acetate copolymer.
The modified polyrotaxane having a hydroxyl group has a cyclodextrin, a linear molecule piercing through the cyclic structure of the cyclodextrin, and having blocking groups located at both terminals of the linear molecule to prevent disassociation of the cyclic molecule. The polyrotaxane is viscoelastic, since the cyclodextrin molecule is movable along the linear molecule that penetrates the cyclodextrin in a skewering manner (pulley effect). Even if a tension is applied to the polyrotaxane, the tension can be uniformly dispersed due to the pulley effect. Thus, the polyrotaxane has an excellent property that a crack or flaw very hardly occurs, unlike a conventional crosslinked polymer.
The cyclodextrin is a general term for an oligosaccharide having a cyclic structure. The cyclodextrin is, for example, a molecule having 6 to 8 D-glucopyranose residues being linked in a cyclic shape via an α-1,4-glucoside bond. Examples of the cyclodextrin include a-cyclodextrin (number of glucose units: 6), β-cyclodextrin (number of glucose units: 7), and γ-cyclodextrin (number of glucose units: 8), and α-cyclodextrin is preferable. As the cyclodextrin, one type may be used solely, and two or more types may be used in combination.
The linear molecule is not particularly limited, as long as it is a linear molecule capable of piercing through the cyclic structure of the cyclodextrin so that the cyclic structure of the cyclodextrin is movable along and rotatable around the linear molecule. Examples of the linear molecule include polyalkylene, polyester, polyether, and polyacrylic acid. Among them, polyether is preferable, and polyethylene glycol is particularly preferable. Polyethylene glycol has less steric hindrance, and thus can be easily included in the cyclic structure of the cyclodextrin in a manner of piercing through the cyclic structure of the cyclodextrin.
The weight average molecular weight of the linear molecule is preferably 5,000 or more, more preferably 6,000 or more, and is preferably 100,000 or less, more preferably 80,000 or less.
The linear molecule preferably has functional groups at both terminals thereof. When the linear molecule has the functional group, the linear molecule can easily react with the blocking group. Examples of the functional group include a hydroxyl group, a carboxyl group, an amino group, and a thiol group.
The blocking groups are not particularly limited, as long as they are located at both terminals of the linear molecule to prevent the cyclodextrin from disassociating from the linear molecule. Examples of the method for preventing the disassociation include a method of using a bulky blocking group to physically prevent the disassociation, and a method of using an ionic blocking group to electrostatically prevent the disassociation. Examples of the bulky blocking group include a cyclodextrin and an adamantyl group. The number (pierced amount) of the cyclodextrins pierced by the linear molecule preferably ranges from 0.06 to 0.61, more preferably ranges from 0.11 to 0.48, even more preferably ranges from 0.24 to 0.41, if the maximum pierced amount is deemed as 1. This is because if the pierced amount is less than 0,06, the pulley effect may not be exerted, and if the pierced amount exceeds 0.61, the cyclodextrins are very densely located, so that the movability of the cyclodextrin may decrease.
As the polyrotaxane, a polyrotaxane having at least a part of hydroxyl groups of the cyclodextrin being modified with a caprolactone chain, is preferred. This is because if at least a part of hydroxyl groups of the cyclodextrin of the polyrotaxane is modified with the caprolactone, steric hindrance between the polyrotaxane and the polyisocyanate is alleviated, so that the efficiency of a reaction with the polyisocyanate increases.
As the above modification, for example, the hydroxyl groups of the cyclodextrin are treated with propylene oxide to hydroxylpropylate the cyclodextrin, and then ε-caprolactone is added to perform ring-opening polymerization. As a result of this modification, the caprolactone chain —(CO(CH2)5O)nH (n is a natural number of 1 to 100) is linked to the exterior side of the cyclic structure of the cyclodextrin via —O—C3H6-O- group. “n” represents the degree of polymerization, and is preferably a natural number of 1 to 100, more preferably a natural number of 2 to 70, and even more preferably a natural number of 3 to 40. At another terminal of the caprolactone chain, a hydroxyl group is formed through the ring-opening polymerization. The terminal hydroxyl group of the caprolactone chain can react with the polyisocyanate.
The ratio of the hydroxyl groups modified with the caprolactone chain to all the hydroxyl groups (100 mole %) included in the cyclodextrin before the modification is preferably 2 mole % or more, more preferably 5 mole % or more, even more preferably 10 mole % or more. If the ratio of the hydroxyl groups modified with the caprolactone chain falls within the above range, the hydrophobicity of the polyrotaxane increases, and the reactivity with the polyisocyanate increases.
The hydroxyl value of the polyrotaxane is preferably 10 mg KOH/g or more, more preferably 15 mg KOH/g or more, even more preferably 20 mg KOH/g or more, and is preferably 400 mg KOH/g or less, more preferably 300 mg KOH/g or less, even more preferably 220 mg KOH/g or less, particularly preferably 180 mg KOH/g or less. If the hydroxyl value of the polyrotaxane falls within the above range, the reactivity with the polyisocyanate increases, and thus the durability of the paint film becomes more favorable.
The total molecular weight of the polyrotaxane is preferably 30,000 or more, more preferably 40,000 or more, even more preferably 50,000 or more, and is preferably 3,000,000 or less, more preferably 2,500,000 or less, even more preferably 2,000,000 or less, in a weight average molecular weight. If the weight average molecular weight is 30,000 or more, the paint film has sufficient strength, and if the weight average molecular weight is 3,000,000 or less, the paint film has sufficient flexibility and thus approach performance of the golf ball increases. It is noted that the weight average molecular weight of the polyrotaxane can be measured, for example, by gel permeation chromatography (GPO) using polystyrene as a standard substance, tetrahydrofuran as an eluant, and an organic solvent system GPC column (e.g., “Shodex (registered trademark) KF series” available from Showa Denko K.K.) as a column.
Specific examples of the polyrotaxane modified with the polycaprolactone include SeRM super polymer SH3400P, SH2400P, and SH1310P available from Advanced Softmaterials Inc.
The hydroxyl group modified vinyl chloride-vinyl acetate copolymer can adjust the tackiness of the paint film while maintaining the scuff resistance of the paint film. The hydroxyl group modified vinyl chloride-vinyl acetate copolymer is obtained, for example, by a method of copolymerizing vinyl chloride, vinyl acetate and a monomer having a hydroxyl group (e.g., polyvinyl alcohol, hydroxyalkyl acrylate), or by a method of partially or completely saponifying a vinyl chloride-vinyl acetate copolymer.
The amount of the vinyl chloride component in the hydroxyl group modified vinyl chloride-vinyl acetate copolymer is preferably 1 mass % or more, more preferably 20 mass % or more, even more preferably 50 mass % or more, and is preferably 99 mass % or less, more preferably 95 mass % or less. Specific examples of the hydroxyl group modified vinyl chloride-vinyl acetate copolymer include Solbin (registered trademark) A, Solbin AL, and Solbin TA3 available from Nissin Chemical Industry Co., Ltd.
Preferable embodiments of the polyol composition are an embodiment containing a urethane polyol, wherein the urethane polyol includes a polyether diol having a number average molecular weight in a range from 600 to 3000 as a constituent component (embodiment 1); and an embodiment containing a polyrotaxane, wherein the polyrotaxane has a cyclodextrin, a linear molecule piercing through the cyclic structure of the cyclodextrin, and blocking groups located at both terminals of the linear molecule to prevent disassociation of the cyclodextrin, and at least a part of hydroxyl groups of the cyclodextrin is modified with a caprolactone chain via —O—C3H6—O— group (embodiment 2).
Examples of the polyisocyanate component of the polyisocyanate composition include a compound having at least two isocyanate groups. Examples of the polyisocyanate include an aromatic polyisocyanate such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 3,3′-bitolyiene-4,4′-diisocyanate (TODI), xylylene diisocyanate (XDI), tetramethylxylylenediisocyanate (TMXDI), and para-phenylene diisocyanate (PPDI); an alicyclic polyisocyanate or aliphatic polyisocyanate such as 4,4′-dicyclohexylmethane diisocyanate (H12MDI), hydrogenated xylylenediisocyanate (H6XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and norbornene diisocyanate (NBDI); and derivatives of these polyisocyanates. In the present invention, as the polyisocyanate, two or more of polyisocyanates may be used.
Examples of the polyisocyanate derivative include an adduct-modified product obtained by a reaction between a diisocyanate and a polyhydric alcohol; an isocyanurate-modified product of a diisocyanate; a biuret-modified product; and an aliophanate-modified product. The polyisocyanate derivative from which a free diisocyanate has been removed is more preferable.
The amount of the dye and/or pigment contained in the colored paint film is preferably 0.5 part by mass or more, more preferably 0.6 part by mass or more, and even more preferably 0.7 part by mass or more, and is preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, even more preferably 2.2 parts by mass or less, and most preferably 2.0 parts by mass or less, with respect to 100 parts by mass of the resin component constituting the paint film. If the amount is too high, the color of the golf ball is so deep that the golf ball has a dark color tone, and if the amount is too small, the desired color tone is not obtained.
The nontransparent colored paint film may contain titanium oxide to enhance opacity. In this case, the amount of titanium oxide is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, with respect to 100 parts by mass of the resin component constituting the paint film. If the amount of titanium oxide is 0.5 part by mass or more, the paint film can be imparted with opacity. In addition, if the amount of titanium oxide is more than 10 parts by mass, the obtained paint film may have lowered durability,
The paint film of the golf ball according to the present invention preferably contains a filler. If the filler is contained, the appearance of the paint film may become matte.
As the filler, a filler conventionally used in a paint can be used. Examples of the filler include silica (e.g. fused silica, dry silica (fumed silica), and wet silica such as precipitated silica, silica gel and colloidal silica), diatomaceous earth, zeolite, perlite, mica, glass, wollastonite, potassium titanate, xonotlite, gypsum, aluminum borate, molybdenum disulfide, aramide, crystalline cellulose, alumina, carbon, metal particle, and metal oxide particle.
As the filler, a porous filler is also preferably used. The porous filler has many fine pores. The shape of the fine pores included in the porous filler is not particularly limited. The pore size of the fine pores included in the porous filler is not particularly limited, but the pore size thereof preferably ranges from 0.1 nm to 500 nm. The pore size of the fine pores included in the porous filler varies depending on the type of the porous filler. For example, zeolite has a pore size in a range from 0.1 nm to 2 nm, and diatomaceous earth has a pore size of about 300 nm.
Examples of the porous filler include diatomaceous earth, zeolite, and perlite. Diatom is a kind of plankton, dead bodies of diatom deposited on seabed or lake bed, and fossilized into Diatomaceous earth. Diatomaceous earth primarily contains silica and has many very fine pores in each particle thereof. Perlite is a porous material formed when water included in a glassy volcanic stone such as obsidian, pearlstone and pitchstone is evaporated by treating the glassy volcanic stone at a high temperature, Zeolite is a crystalline porous alumino-silicate. Examples of the structure of zeolite include type A, ferrierite, ZSM-5, mordenite, beta, type X and type Y. It is noted that zeolite also includes porous silicalite. The porous filler may be used solely, or two or more of them may be used in combination.
The volume average particle size of the filler is preferably 0.5 μm or more, more preferably 1.0 μm or more, and even more preferably 2.0 μm or more, and is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. It is noted that the volume particle size distribution is measured by a laser diffraction method, and the particle size of 50% accumulation (D50) on the volume particle size distribution is deemed as the volume average particle size.
The amount of the filler in the paint film is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 120 parts by mass or less, with respect to 100 parts by mass of the resin component. If the amount of the filler is parts by mass or more, the appearance is matte, and if the amount of the filler is 200 parts by mass or less, the appearance is better, and dirt adhesion can be lowered.
The paint film may further contain an additive that is conventionally contained in a golf ball paint, such as an ultraviolet absorber, antioxidant, light stabilizer, fluorescent brighter, and antiblocking agent. The ultraviolet absorber and light stabilizer exemplified as the components that can be added in the intermediate layer and/the cover can also be used in the paint film,
The core of the golf ball according to the present invention can be formed from a conventional rubber composition (hereinafter sometimes referred to as “core rubber composition”). For example, the core can be molded by heat pressing a rubber composition containing a base rubber, a co-crosslinking agent and a crosslinking initiator.
As the base rubber, particularly preferred is a high-cis polybutadiene having a cis bond in an amount of 40 mass % or more, preferably 70 mass % or more, and more preferably 90 mass % or more in view of its superior resilience. As the co-crosslinking agent, an α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms or a metal salt thereof is preferable, and a metal salt of acrylic acid or a metal salt of methacrylic acid is more preferable. As the metal constituting the metal salt, zinc, magnesium, calcium, aluminum or sodium is preferable, and zinc is more preferable. The amount of the co-crosslinking agent is preferably 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the base rubber. In a case that the α,β-unsaturated carboxylic acid having 3 to 8 carbon atoms is used as the co-crosslinking agent, a metal compound (e.g. magnesium oxide) is preferably added. As the crosslinking initiator, an organic peroxide is preferably used. Specific examples of the organic peroxide include dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, and di-t-butyl peroxide. Among them, dicumyl peroxide is preferably used. The amount of the crosslinking initiator is preferably 0.2 part by mass or more, more preferably 0.3 part by mass or more, and is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, with respect to 100 parts by mass of the base rubber.
In addition, the core rubber composition may further contain an organic sulfur compound. As the organic sulfur compound, diphenyl disulfides, thiophenols, and thionaphthols are preferably used. The amount of the organic sulfur compound is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, and is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, with respect to 100 parts by mass of the base rubber. The core rubber composition may further contain a carboxylic acid and/or a salt thereof. As the carboxylic acid and/or the salt thereof, a carboxylic acid having 1 to 30 carbon atoms and/or a salt thereof is preferable. The carboxylic acid may be either an aliphatic carboxylic acid or an aromatic carboxylic acid (benzoic acid, etc.). The amount of the carboxylic acid and/or the salt thereof is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the base rubber.
The core of the golf ball according to the present invention is molded, for example, by heat pressing the core rubber composition. The molding conditions for heat pressing the core rubber composition may be suitably determined depending on the rubber composition. Generally, the molding is carried out at a temperature in a range from 130° C. to 200° C. and a pressure in a range from 2.9 MPa to 11.8 MPa for 10 to 60 minutes. For example, it is preferable that the molding is carried out by heating the core rubber composition at a temperature ranging from 130° C. to 200 ° C. for 10 minutes to 60 minutes, or alternatively, by molding the core rubber composition in a two-step heating, i.e. heated at a temperature ranging from 130° C. to 150 ° C. for 20 minutes to 40 minutes and then heated at a temperature ranging from 160° C. to 180° C. for 5 minutes to 15 minutes.
The intermediate layer composition and the cover composition can be obtained, for example, by dry blending the resin component, dye and/or pigment, and optional additives, Further, the dry blended mixture may be extruded into a pellet form. In the dry blending, for example, a mixer capable of blending raw materials in a pellet form is preferably used, a tumbler type mixer is more preferably used. The extrusion can be carried out with a conventional extruder such as a single-screw extruder, a twin-screw extruder, and a twin-screw/single-screw extruder.
The method for molding the intermediate layer is not particularly limited, and examples thereof include a method of molding the intermediate layer composition into a hemispherical half shell in advance, covering the spherical core with two of the half shells, and compression molding the spherical core with two of the half shells; and a method of injection molding the intermediate layer composition onto the spherical core to cover the spherical core.
In case of injection molding the intermediate layer composition onto the spherical core to form the intermediate layer, it is preferred to use upper and lower molds, each having a hemispherical cavity. When molding the intermediate layer by the injection molding method, the hold pin is protruded to hold the spherical core, and the intermediate layer composition which has been heated and melted is charged and then cooled to form the intermediate layer.
When molding the intermediate layer by the compression molding method, the molding of the half shell may be performed by either a compression molding method or an injection molding method, and the compression molding method is preferable. Compression molding the intermediate layer composition into the half shell may be carried out, for example, under a pressure of 1 MPa or more and 20 MPa or less at a temperature of −20° C. or more and +70° C. or less relative to the flow beginning temperature of the intermediate layer composition, If the molding is carried out under the above conditions, the half shell having a uniform thickness can be formed. Examples of the method for molding the intermediate layer by using the half shell include a method of covering the spherical core with two of the half shells, and compression molding the spherical core with two of the half shells. Compression molding the half shells into the intermediate layer may be carried out, for example, under a pressure of 0.5 MPa or more and 25 MPa or less at a temperature of −20° C. or more and +70° C. or less relative to the flow beginning temperature of the intermediate layer composition. If the molding is carried out under the above conditions, the intermediate layer having a uniform thickness can be formed.
It is noted that the molding temperature means the highest temperature where the temperature at the surface of the concave portion of the lower mold reaches from closing the mold to opening the mold. In addition, the flow beginning temperature of the composition may be measured using the thermoplastic resin composition in a pellet form under the following conditions with “Flow Tester CFT-500” available from Shimadzu Corporation.
Measuring conditions: Plunger area: 1 cm2, Die length: 1 mm, Die diameter: 1 mm, Load: 588.399 N, Starting temperature: 30° C., and Temperature rising rate: 3° C./min.
The method for molding the cover from the cover composition is not particularly limited, and examples thereof include a method of injection molding the cover composition directly onto the intermediate layer; and a method of molding the cover composition into hollow shells, covering the spherical body having the intermediate layer formed thereon with a plurality of the hollow shells and compression molding the spherical body with a plurality of the hollow shells (preferably a method of molding the cover composition into hollow half shells, covering the spherical body having the intermediate layer formed thereon with two of the half shells and compression molding the spherical body with two of the half shells). The golf ball body having the cover formed thereon is ejected from the mold, and as necessary, the golf ball body is preferably subjected to surface treatments such as deburring, cleaning, and sandblast. In addition, if desired, a mark may also be formed thereon.
In the present invention, the first region and the second region are formed on the golf ball surface, for example, by producing a hollow first shell with the first color and a hollow second shell with the second color, covering the spherical body having the intermediate layer formed thereon with the first shell and the second shell, and compression molding the spherical body with the first shell and the second shell. In addition, a hemispherical first region with the first color and the hemispherical second region with the second color can be formed on the golf ball surface by molding a hollow half shell with the first color and a hollow half shell with the second color, covering the spherical body having the intermediate layer formed thereon with two of the half shells, and compression molding the spherical body with two of the half shells.
Dimples are preferably formed on the cover of the golf ball according to the present invention. The total number of the dimples formed on the cover is preferably 200 or more and 500 or less. If the total number of the dimples is less than 200, the dimple effect is hardly obtained, and if the total number of the dimples exceeds 500, the dimple effect is hardly obtained because the size of the respective dimples is small. The shape (shape in a plan view) of the dimples includes, for example, but is not limited to, a circle; a polygonal shape such as a roughly triangular shape, a roughly quadrangular shape, a roughly pentagonal shape, and a roughly hexagonal shape; and other irregular shape. The shape of the dimples may be employed solely, or two or more of the shapes may be employed in combination,
The golf ball having the cover formed thereon is ejected from the mold, and as necessary, the golf ball is preferably subjected to surface treatments such as deburring, cleaning, and sandblast. In addition, if desired, a paint film or a mark may also be formed thereon.
The paint film of the golf ball according to the present invention can be formed by painting the paint on the surface of the golf ball body, The method of applying the paint is not particularly limited, a conventional method can be adopted, and examples thereof include a spray coating and electrostatic coating.
In the case that the first region with the first color or the second region with the second color is formed by the colored paint film, the paint film can be formed by applying the paint, for example, in the desired shape of the first region or the second region.
In case of spray coating a two-component curing type urethane paint as the paint, the polyisocyanate composition and the polyol composition are fed with respective pumps and continuously mixed with a line mixer located in the stream line just before the air gun, and the obtained mixture is air-sprayed. Alternatively, the polyol composition and the polyisocyanate composition are air-sprayed respectively with an air spray system provided with a device for controlling the mixing ratio thereof. The paint application may be conducted by spraying the paint one time or overspraying the paint multiple times.
The paint applied on the golf ball body is dried, for example, at a temperature in a range of from 30° C. to 70° C. for 1 hour to 24 hours, to form the paint film.
The construction of the golf ball according to the present invention is not particularly limited, as long as the golf ball comprises a core and a cover disposed outside of the core. In a preferable embodiment, the golf ball according to the present invention further comprises at least one intermediate layer between the core and the cover. Examples of the construction of the golf ball include a two-piece golf ball composed of a spherical core and a cover covering the spherical core; a three-piece golf ball composed of a spherical core, one intermediate layer covering the spherical core, and a cover covering the intermediate layer; and a multi-piece golf ball composed of a spherical core, at least two intermediate layers covering the spherical core, and a cover covering the intermediate layers.
In case of having a plurality of intermediate layers, the color tone of the outermost layer of the intermediate layers is measured.
The core of the golf ball according to the present invention is preferably spherical, The diameter of the spherical core is preferably 34.8 mm or more, more preferably 36.8 mm or more, and even more preferably 38.8 mm or more, and is preferably 42.2 mm or less, more preferably 41.8 mm or less, even more preferably 41.2 mm or less, and most preferably 40.8 mm or less. if the diameter of the spherical core is 34.8 mm or more, the cover is not too thick and thus the resilience is better. On the other hand, if the diameter of the spherical core is 42.2 mm or less, the cover is not too thin and thus the cover functions well.
The thickness of the intermediate layer is preferably 0.8 mm or more, more preferably 0.9 mm or more, and even more preferably 1.0 mm or more, and is preferably 2.2 mm or less, more preferably 2.0 mm or less, and even more preferably 1.8 mm or less. If the thickness of the intermediate layer is 0.8 mm or more, the intermediate layer is more easily molded, and if the thickness of the intermediate layer is 2.2 mm or less, the core has a relatively large diameter and thus the golf ball has enhanced resilience performance. In case of having a plurality of intermediate layers, the total thickness of the intermediate layers preferably falls within the above range.
The cover of the golf ball according to the present invention is preferably single layered. The thickness of the cover is preferably 0.3 mm or more, more preferably 0.4 mm or more, and even more preferably 0.5 mm or more, and is preferably 2.0 mm or less, more preferably 1.5 mm or less, and even more preferably 1.0 mm or less. If the thickness of the cover is 0.3 mm or more, the cover is more easily molded, and if the thickness of the cover is 2.0 mm or less, the core has a relatively large diameter and thus the golf ball has enhanced resilience performance.
The thickness of the paint film is not particularly limited, and is preferably 5 μm or more, more preferably 7 μm or more, and is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less. If the thickness is less than 5 μm, the paint film tends to be easily worn off due to the continued use of the golf ball, and if the thickness exceeds 50 μm, the dimple effect may be lowered, and the flight performance of the golf ball tends to be lowered.
The golf ball according to the present invention preferably has a diameter in a range from 40 mm to 45 mm. In light of satisfying the regulation of US Golf Association (USGA), the diameter is preferably 42.67 mm or more. In light of prevention of air resistance, the diameter is preferably 44 mm or less, more preferably 42.80 mm or less. In addition, the golf ball preferably has a mass of 40 g or more and 50 g or less. In light of obtaining greater inertia, the mass is preferably 44 g or more, more preferably 45.00 g or more. In light of satisfying the regulation of USGA, the mass is particularly preferably 45.93 g or less.
Next, the present invention will be described in detail by way of examples. However, the present invention is not limited to the examples described below. Various changes and modifications without departing from the spirit of the present invention are included in the scope of the present invention.
The color tone of the intermediate layer and the golf ball surface was measured with a color difference meter (“CM-350d” available from KONICA MINOLTA, INC.). The color tone of the golf ball was measured in a state that the paint film was formed on the golf ball body.
The golf balls were sunk in the rough (length of grass: 5 cm to 10 cm) at a distance of 1 m to 10 m from the tester with an interval of 1 m. The longest distance at which the tester correctly told the color combination of these balls was measured. Evaluation was conducted by twenty testers, and the average distance was calculated,
The golf ball was placed such that the boundary between the hemispherical first region and the hemispherical second region faces the tester, and twenty testers were allowed to address the golf balls with a driver. The number of people who answered that he or she clearly recognized the orientation of the boundary line between the first hemisphere and the second hemisphere was ccounted.
The rubber composition having the formulation shown in Table 1 was kneaded with a kneading roll, and heat-pressed at a temperature of 170° C. for 20 minutes in upper and lower molds, each having a hemispherical cavity, to obtain a spherical core having a diameter of 39.7 mm. It is noted that the amount of barium sulfate was adjusted such that the obtained golf ball had a mass of 45.3 g.
*1) Barium sulfate: the amount was adjusted such that the golf ball had a mass of 45.3 g.
The materials used in Table 1 are shown as follows.
Polybutadiene rubber: high-cis polybutadiene “BR730” (cis-1,4 bond amount=96 mass %, 1,2-vinyl bond amount=1.3 mass %, Moony viscosity (ML1+4 (100° C.))=55, molecular weight distribution (Mw/Mn)=3) available from JSR Corporation
Zinc acrylate: “ZNDA-90S” available from Nisshoku Techno Fine Chemical Co., Ltd.
Zinc oxide: “Ginrei R” available from Toho Zinc Co., Ltd.
Barium sulfate: “Barium sulfate BD” available from Sakai Chemical Industry Co., Ltd.
PBDS: bis(pentabromodiphenyl) disulfide available from Kawaguchi Chemical Industry Co., Ltd.
Dicumyl peroxide: “Percumyl (register trademark) D” available from NOF Corporation
According to the formulations shown in Table 2, the materials were mixed with a twin-screw kneading extruder to prepare the intermediate layer resin composition in a pellet form. The extruding conditions were a screw diameter of 45 mm, a screw rotational speed of 200 rpm, and a screw L/D=35, and the mixture was heated to 160° C. to 230° C. at the die position of the extruder. The obtained intermediate layer resin composition was injection molded onto the spherical core obtained above to form the intermediate layer having a thickness of 1 mm.
Himilan 1605: sodium ion-neutralized ethylene-methacrylic acid copolymer ionomer resin available from Dow-Mitsui Polychemicals Co,, Ltd,
Himilan AM7329: zinc ion-neutralized ethylene-methacrylic acid copolymer ionomer resin available from Dow-Mitsui Polychemicals Co,, Ltd.
Titanium oxide: “A-220” available from Ishihara Sangyo Kaisha, Ltd.
FX305: Lemon Yellow available from Sinloihi Co., Ltd.
GPX-17: Saturn yellow available from DayGlo Color Corp.
GPL-15: Blaze orange available from DayGlo Color Corp.
The materials shown in Table 3 were dry blended, and mixed with a twin-screw kneading extruder, to prepare the cover (half shell) composition in a pellet form. The extruding conditions of the cover (half shell) composition were a screw diameter of 45 mm, a screw rotational speed of 200 rpm, and screw L/D=35, and the mixtures were heated to 150° C. to 230° C. at the die position of the extruder,
The compression molding of half shells was conducted as follows. The obtained cover resin composition in the pellet form was charged one by one into each of the depressed part of the lower mold of a half shell molding mold, and pressed to mold half shells. The compression molding was conducted under the following conditions: a molding temperature of 170°, a molding time of 5 minutes, and a molding pressure of 2.94 MPa. The spherical core having the intermediate layer formed thereon was concentrically covered with two half shells, i.e. half shell A and half shell B which had a color tone different from each other, and compression molded to form the cover. The compression molding was conducted under the following conditions: a molding temperature of 150° C., a molding time of 2 minutes, and a molding pressure of 9.8 MPa, The cover has a thickness of 0.5 mm.
The materials used in Table 3 are shown as follows.
Urethane resin: Elastollan (registered trademark) NY80A: polyurethane elastomer (polyol component: polytetramethylene ether glycol, polyisocyanate component: dicyclohexylmethane-4,4′-diisocyanate, chain extender: 1,4-butanediol) (Shore A hardness: 80) available from BASF Japan Ltd.
JF-90: light stabilizer available from Johoku Chemical Co. Ltd.
Titanium oxide: “A220” available from Ishihara Sangyo Kaisha, Ltd.
EPO Color FP3000: fluorescent pigment having fluorescent dye dispersed and fixed in benzoguanamine resin (condensation product of benzoguanamine and formaldehyde) available from Ukseung Chemical Co., Ltd.
FX305: Lemon yellow available from Sinloihi Co., Ltd.
FX-327: Magenta available from Sinloihi Co., Ltd.
GPX-17: Saturn yellow available from DayGlo Color Corp.
GPL-15: Blaze orange available from DayGlo Color Corp.
ZQ-14: Fire orange (fluorescent pigment having fluorescent dye dispersed and fixed in polyester resin) available from DayGlo Color Corp.
ZQ-17: Saturn yellow (fluorescent pigment having fluorescent dye dispersed and fixed in polyester resin) available from DayGlo Color Corp.
ZQ-18: Signal green (fluorescent pigment having fluorescent dye dispersed and fixed in polyester resin) available from DayGlo Color Corp.
FP113: Red available from Ukseung Chemical Co., Ltd.
FP1050: Blue available from Ukseung Chemical Co., Ltd.
Polyoxytetramethylene glycol (PTMG, number average molecular weight: 650) and trimethylolpropane (TMP) were dissolved in a mixed solvent (mass ratio of toluene/methyl ethyl ketone: 15/85). The molar ratio (PTMG:TMP) was 1,8:1.0. Dibutyltin dilaurate was added as a catalyst into the solution in an amount of 0.1 mass % with respect to the total amount of the base agent. While keeping the temperature of the polyol solution at 80° C., isophorone diisocyanate (IPDI) was added dropwise and mixed. The molar ratio (NCO/OH) of the mixed liquid was 0.6. After the dropwise addition of isophorone diisocyanate was finished, stirring was continued until the isocyanate component in the mixed liquid disappeared. Then, the mixed liquid was cooled to a normal temperature to prepare the polyol composition No. 1 containing a urethane polyol as the base agent. In the polyol composition No. 1, the amount of the solid component was 30 mass %, the amount of PTMG was 67 mass %, the hydroxy value of the solid component was 67.4 mgKOH/g, and the weight average molecular weight of the urethane polyol was 4867. In the case that the filler was added, the filler was added in the polyol composition. The amount of the filler was 45 parts by mass with respect to 100 parts by mass of the polyol composition constituting the paint film.
The isocyanurate-modified product of hexamethylene diisocyanate (trade name “Duranate TKA-100” available from Asahi Kasei Chemicals Corporation, NCO amount: 21.7 mass %) in an amount of 30 parts by mass, the biuret-modified product of hexamethylene diisocyanate (trade name “Duranate 21S-75E” available from Asahi Kasei Chemicals Corporation, NCO amount: 15.5 mass %) in an amount of 30 parts by mass, and the isocyanurate-modified product of isophorone diisocyanate (trade name “Desmodur 24470” available from BAYER Corporation, NCO amount: 11.9 mass %) in an amount of 40 parts by mass were mixed. Methyl ethyl ketone, n-butyl acetate and toluene were added as a solvent in the above mixture and mixed to obtain the polyisocyanate composition No. 1 as the curing agent. The concentration of the polyisocyanate component in the composition was 60 mass %.
The polyol composition and the polyisocyanate composition were mixed in the mixing ratio shown in Table 4 to prepare the paint compositions. The surface of the golf ball bodies obtained above was treated with sandblast and marked. The paint was applied with a spray gun, and dried for 24 hours in an oven at a temperature of 40° C. to obtain golf balls having a diameter of 42.7 mm and a mass of 45.3 g.
Silica: CARPLEX FPS-1 (wet silica, volume average particle size: 7.0 μm) available from Evonik Industries AG
The golf ball body was placed in a rotating member provided with a prong, the rotating member was allowed to rotate at 300 rpm, and application of the paint was conducted by spacing a spray distance (7 cm) between the air gun and the golf ball body while moving the air gun in an up and down direction. The painting interval in the overpainting operation was set to 1.0 second, Application of the paint was conducted under the air gun spraying conditions of overpainting: two times, a spraying air pressure: 0.15 MPa, a compressed air tank pressure: 0.10 MPa, a painting time for one application: 1 second, an atmosphere temperature: 20° to 27°, and an atmosphere humidity: 65% or less. Evaluation results of the obtained golf balls are shown in Table 5.
It is apparent from Table 5 that a golf ball comprising a core and a cover disposed outside of the core, wherein a surface of the golf ball has a first region with a first color and a second region with a second color, the first color has hue H1 represented by H value in HSL color space, the second color has hue H2 represented by H value in HSL color space, and the H1 and the H2 satisfy 60<|H1−H2|<300, has high visibility and excellent orientation at shot.
This application is based on Japanese patent application No. 2020-214236 filed on Dec. 23, 2020, the contents of which are hereby incorporated by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-214236 | Dec 2020 | JP | national |
