(19)
(11)EP 3 492 150 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
10.06.2020 Bulletin 2020/24

(21)Application number: 18207243.9

(22)Date of filing:  20.11.2018
(51)International Patent Classification (IPC): 
A63B 37/00(2006.01)
C08G 83/00(2006.01)
C08G 18/79(2006.01)
C08G 18/48(2006.01)
C08G 18/64(2006.01)
C09D 175/04(2006.01)

(54)

GOLF BALL

GOLFBALL

BALLE DE GOLF


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 29.11.2017 JP 2017229720
29.11.2017 JP 2017229723
26.09.2018 JP 2018180088

(43)Date of publication of application:
05.06.2019 Bulletin 2019/23

(73)Proprietor: SUMITOMO RUBBER INDUSTRIES, LTD.
Kobe-shi, Hyogo-ken 651-0072 (JP)

(72)Inventors:
  • TARAO, Toshiyuki
    Kobe-shi, Hyogo 651-0072 (JP)
  • TANAKA, Mami
    Kobe-shi, Hyogo 651-0072 (JP)
  • INOUE, Hidetaka
    Kobe-shi, Hyogo 651-0072 (JP)

(74)Representative: Manitz Finsterwald Patent- und Rechtsanwaltspartnerschaft mbB 
Martin-Greif-Strasse 1
80336 München
80336 München (DE)


(56)References cited: : 
EP-A1- 2 671 619
JP-A- 2014 014 386
JP-A- 2014 014 384
US-A1- 2016 136 484
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF THE INVENTION



    [0001] The present invention relates to a technology for improving spin performance of a golf ball.

    DESCRIPTION OF THE RELATED ART



    [0002] A paint film is formed on a surface of a golf ball body. It has been proposed to improve properties of a golf ball by improving the paint film thereof.

    [0003] Japanese Patent Publication No. 2011-67595 A discloses a golf ball comprising a core, a cover disposed on an outer side of the core, and a paint layer disposed on an outer side of the cover, wherein the cover has a Shore D hardness of 61 or less, and the paint layer has a martens hardness of 2.0 mgf/µm2 or less. The golf ball disclosed in Japanese Patent Publication No. 2011-67595 A is excellent in spin performance, spin rate stability and paint layer durability.

    [0004] Japanese Patent Publication No. 2011-217820 A discloses a golf ball comprising a golf ball body and a paint film formed on a surface of the golf ball body, wherein the paint film has a martens hardness of 2.0 mgf/µm2 or less, and a ratio (50 % elastic modulus / 10 % elastic modulus) of 50 % elastic modulus to 10 % elastic modulus is 1.6 or more. The golf ball disclosed in Japanese Patent Publication No. 2011-217820 A has a high spin rate on approach shots under a wet condition and a rough condition.

    [0005] Japanese Patent Publications No. 2006-75209 A and No. 2006-75210 A have proposed a golf ball stopping quickly with an increased launch angle. Japanese Patent Publication No. 2006-75209 A discloses a golf ball comprising a golf ball body and a paint layer covering a surface of the golf ball body, wherein a resin component constituting the paint layer is cured by a polyamide based curing agent, and the golf ball has a static coefficient of friction of 0.22 or less. Japanese Patent Publication No. 2006-75210 A discloses a golf ball comprising a golf ball body and a paint film covering the golf ball body, wherein the paint film contains metal particles.

    [0006] Japanese Patent Publication No. 2000-288125 A has proposed a golf ball showing improved durability and abrasion resistance. The golf ball showing excellent durability comprises a core, a cover and at least one paint layer formed on the cover, wherein the cover has a Shore D hardness ranging from 50 to 65 and a bending flexural modulus ranging from 1,000 to 2,000 kgf/cm2, and at least an outermost layer of the paint has a 10 % elastic modulus ranging from 5 to 50 kgf/cm2.

    [0007] Japanese Patent Publication No. 2003-265650 A has proposed a golf ball showing improved spin retention ratio without sacrificing the properties required for a paint film. Japanese Patent Publication No. 2003-265650 A discloses a golf ball comprising a core, at least one cover layer covering the core and a paint film formed on an outer surface of the cover, wherein the paint film has a thickness falling within a range of 25 µm or more and 125 µm or less and a 50 % elastic modulus falling within a range of 5 MPa or more and 50 MPa or less, and R expressed by a following equation (1) falls within a range of 0.01 or more and 0.5 or less, when CL (mm) represents a thickness of an outermost layer of the cover, and PL (µm) represents the thickness of the paint film;



    [0008] Japanese Patent Publication No. 2014-14383 A has proposed a golf ball having high controllability on approach shots for less than 40 yards, a decreased spin rate on driver shots, and an excellent shot feeling. Japanese Patent Publication No. 2014-14383 A discloses a golf ball comprising a golf ball body and a paint film formed on a surface of the golf ball body, wherein the paint film has a storage modulus (E') of 1.00×107 dyn/cm2 or more and 1.00×108 dyn/cm2 or less in a temperature range from 120 °C to 150 °C, and a loss tangent (tan δ) of 0.050 or more at 10 °C, measured with a dynamic viscoelasticity measuring apparatus under the following measuring condition:

    Measuring mode: tensile mode

    Measuring temperature: from -50 °C to 150 °C

    Temperature rising rate: 4 °C/min

    Oscillation frequency: 10 Hz

    Measuring strain: 0.1%.


    SUMMARY OF THE INVENTION



    [0009] It goes without saying that not only the flight distance on driver shots but also the precision on second shots and third shots are important in making a good score when playing golf. Second shots and third shots are shots directly aiming at the green, and thus controllability is extremely important. In addition, the precision on approach shots around the green is also very important. Japanese Patent Publication No. 2014-14383 A has proposed a golf ball having enhanced controllability on approach shots of less than 40 yards, in particular, on approach shots of about 10 yards to 20 yards from around the green under a dry condition. However, for example, enhancement in the spin rate on approach shots from the rough was not discussed.

    [0010] On the other hand, if the paint film is softened for a purpose of increasing the spin rate on short iron shots and approach shots, there was a problem that the paint film is easily stained by grass juice, muddy water or the like.

    [0011] In one aspect of the present invention, an object of the present invention is to provide a golf ball having excellent controllability, shot feeling on short iron shots, and good stain resistance.

    [0012] In another aspect of the present invention, an object of the present invention is to provide a golf ball having enhanced controllability on approach shots from the rough, excellent stain resistance and shot feeling.

    [0013] In a preferable embodiment, the present invention provides a golf ball comprising a golf ball body and a paint film covering the golf ball body, wherein a 10% elastic modulus of the paint film is 75 kgf/cm2 or less, a storage modulus (E'150) at 150 °C of the paint film obtained by measuring dynamic viscoelasticities of the paint film is 1.0×107 Pa or more, an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is 1250 nm or more, a diameter of the golf ball ranges from 40 mm to 45 mm, and a compression deformation amount of the golf ball when applying a load from 98 N as an initial load to 1275 N as a final load to the golf ball is 3.0 mm or less.

    [0014] In another preferable embodiment, the present invention provides a golf ball comprising a golf ball body having a cover, and a paint film covering the golf ball body, wherein a 10% elastic modulus of the paint film is 75 kgf/cm2 or less, a storage modulus (E'150) at 150 °C of the paint film obtained by measuring dynamic viscoelasticity of the paint film is 1.0×107 Pa or more, an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is 1250 nm or more, and a material hardness of the cover is less than 50 in Shore D hardness.

    [0015] According to the preferable embodiment of the present invention, a golf ball having excellent controllability, shot feeling on short iron (for example, #8 iron, #9 iron) shots, and good stain resistance is obtained.

    [0016] According to another preferable embodiment of the present invention, a golf ball having enhanced controllability on approach shots from the rough, excellent stain resistance and shot feeling is obtained.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0017] 

    Fig. 1 is an explanatory drawing illustrating a molecular structure of one example of a polyrotaxane used in the present invention;

    Fig. 2 is a partially cutaway cross-sectional view of a golf ball according to one embodiment of the present invention;

    Fig. 3 is a schematic view showing one example of an embodiment for applying a paint with an air gun;

    Fig. 4 is a graph showing dynamic viscoelasticity of the paint film No. 1;

    Fig. 5 is a graph showing dynamic viscoelasticity of the paint film No. 2;

    Fig. 6 is a graph showing dynamic viscoelasticity of the paint film No. 3;

    Fig. 7 is a graph showing dynamic viscoelasticity of the paint film No. 4;

    Fig. 8 is a graph showing dynamic viscoelasticity of the paint film No. 5;

    Fig. 9 is a graph showing a relationship between a storage modulus (E') of the paint films No. 6 to No. 8 and a temperature;

    Fig. 10 is a graph showing a relationship between a loss modulus (E") of the paint films No. 6 to No. 8 and a temperature; and

    Fig. 11 is a graph showing a relationship between a loss tangent (tan δ) of the paint films No. 6 to No. 8 and a temperature.


    DESCRIPTION OF THE PREFERRED EMBODIMENT



    [0018] In a preferable embodiment, the present invention provides a golf ball comprising a golf ball body and a paint film covering the golf ball body, wherein a 10% elastic modulus of the paint film is 75 kgf/cm2 or less, a storage modulus (E'150) at 150 °C of the paint film obtained by measuring dynamic viscoelasticity of the paint film is 1.0×107 Pa or more, an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is 1250 nm or more, a diameter of the golf ball ranges from 40 mm to 45 mm, and a compression deformation amount of the golf ball when applying a load from 98 N as an initial load to 1275 N as a final load to the golf ball is 3.0 mm or less.

    [0019] In another preferable embodiment, the present invention provides a golf ball comprising a golf ball body having a cover, and a paint film covering the golf ball body, wherein a 10% elastic modulus of the paint film is 75 kgf/cm2 or less, a storage modulus (E'150) at 150 °C of the paint film obtained by measuring dynamic viscoelasticity of the paint film is 1.0×107 Pa or more, an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is 1250 nm or more, and a material hardness of the cover is less than 50 in Shore D hardness.

    [0020] The inventors of the present invention have found that when measuring the change of the storage modulus (E') of the paint film depending on the temperature with a dynamic viscoelasticity measuring apparatus, even if the paint film nearly has no difference in the storage modulus (E') in the low temperature region, the paint film has difference in the storage modulus in the high temperature region of 120 °C to 150 °C, and the storage modulus (E') in this temperature range of 120 °C to 150 °C affects the spin performance on approach shots of less than 40 yards and short iron shots.

    [0021] In the golf ball according to the present invention, if the paint film having a storage modulus (E'150) at 150 °C of 1.00×107 Pa or more obtained by measuring the dynamic viscoelasticity of the paint film is used, the launch angle can be lowered and the spin rate can be increased on approach shots of less than 40 yards and short iron shots. As a result, the golf ball according to the present invention has enhanced controllability on approach shots of less than 40 yards and short iron shots. In light of this, the storage modulus (E'150) at 150 °C is preferably 1.20×107 Pa or more, more preferably 1.50×107 Pa or more. In addition, the storage modulus (E'150) at 150 °C is preferably 1.00×108 Pa or less, more preferably 9.00×107 Pa or less, and even more preferably 8.00×107 Pa or less.

    [0022] In the golf ball according to the present invention, a flat region in which the storage modulus (E') obtained by measuring the dynamic viscoelasticity of the paint film almost keeps constant preferably exists in the region of 120 °C to 150 °C. In light of this, the storage modulus (E'120) at 120 °C measured with a dynamic viscoelasticity measuring apparatus is preferably 1.00×107 Pa or more, more preferably 1.20×107 Pa or more, and even more preferably 1.50×107 Pa or more. In addition, the storage modulus (E'120) at 120 °C is preferably 9.00×107 Pa or less, more preferably 8.00×107 Pa or less.

    [0023] In the golf ball according to the present invention, the peak temperature of the loss tangent tan δ of the paint film obtained by measuring the dynamic viscoelasticity of the paint film is preferably 60 °C or less, more preferably 58 °C or less, and even more preferably 56 °C or less, and is preferably -40 °C or more, more preferably 0 °C or more, even more preferably 40 °C or more, and most preferably 44 °C or more. If the peak temperature of the loss tangent (tan δ) falls within the above range, viscosity becomes predominant on approach shots and short iron shots, and thus the shot feeling is good.

    [0024] In the golf ball according to the present invention, the peak height of the loss tangent tan δ of the paint film obtained by measuring the dynamic viscoelasticity of the paint film is less than 0.8, preferably 0.70 or less, more preferably less than 0.60, and even more preferably 0.55 or less. If the peak height of the loss tangent (tan δ) is less than 0.8, the shear force becomes higher and the spin performance becomes better since efficiency of energy transfer becomes better. The peak height of the loss tangent tan δ is preferably 0.3 or more, more preferably 0.31 or more, and even more preferably 0.32 or more. If the peak height of the loss tangent (tan δ) of the paint film is 0.3 or more, the launch angle can be lowered and the spin rate can be increased on approach shots of less than 40 yards and short iron shots.

    [0025] The 10% elastic modulus of the paint film covering the golf ball body of the present invention is preferably 75 kgf/cm2 or less, more preferably 60 kgf/cm2 or less, and even more preferably 30 kgf/cm2 or less. If the 10% elastic modulus of the paint film is 75 kgf/cm2 or less, the paint film is soft, and the spin rate on approach shots and short iron shots is high. The lower limit of the 10% elastic modulus of the paint film is not particularly limited, but it is preferably 2 kgf/cm2, more preferably 8 kgf/cm2, even more preferably 10 kgf/cm2, and most preferably 12 kgf/cm2. If the 10% elastic modulus is excessively low, the paint film becomes so soft that a tacky feel is remained, and the feeling becomes bad.

    [0026] The dynamic viscoelasticity and the 10% elastic modulus of the paint film are obtained by preparing a measuring film from the paint composition for forming the paint film under the predetermined conditions, and measuring the dynamic viscoelasticity and the 10% elastic modulus of the measuring film. The preparation method and measuring method of the measuring film will be described later.

    [0027] The golf ball according to the present invention comprises a golf ball body and a paint film formed on a surface of the golf ball body, wherein an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is preferably 1250 nm or more, more preferably 1800 nm or more, and even more preferably 2000 nm or more. The upper limit of the indentation depth of the paint film measured with the nanoindenter is not particularly limited, but the upper limit is preferably 4000 nm or less, more preferably 3000 nm or less, and even more preferably 2800 nm or less. The indentation depth of the paint film measured with the nanoindenter is an index directly showing the physical property of the paint film formed on the golf ball body. If the indentation depth of the paint film measured with the nanoindenter is 1250 nm or more, the spin rate on approach shots from the rough is increased, and the shot feeling on approach shots and short iron shots becomes better as well. In addition, if the indentation depth of the paint film measured with the nanoindenter exceeds 4000 nm, the deformation is so large that tackiness is excessively remained.

    [0028] The resin component of the paint film of the golf ball according to the present invention preferably contains a polyurethane, wherein the polyurethane comprises, as a constituent component, (A) a polyisocyanate component, and (B) a polyol component containing a polyrotaxane. In addition, the resin component of the paint film of the golf ball according to the present invention more preferably contains a polyurethane obtained by a reaction between (A) the polyisocyanate component, and (B) the polyol component containing the polyrotaxane.

    [0029] Examples of (A) the polyisocyanate include an aromatic polyisocyanate such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 3,3'-bitolylene-4,4'-diisocyanate (TODI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (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 derivates of these polyisocyanates. In the present invention, as the polyisocyanate, two or more of the polyisocyanates may be used.

    [0030] Examples of the derivative of the polyisocyanate include an isocyanurate of diisocyanate; an adduct obtained through a reaction between a diisocyanate and a low molecular weight triol such as trimethylolpropane or glycerin; an allophanate-modified product; and a biuret-modified product. It is preferable that a free diisocyanate is removed from the derivative of the polyisocyanate. The allophanate-modified product is, for example, a trifunctional polyisocyanate obtained by further reacting a diisocyanate with a urethane bond formed through a reaction between a diisocyanate and a low molecular weight diol. The biuret-modified products is, for example, a trifunctional polyisocyanate having a biuret bond and represented by the following formula (1). The isocyanurate of diisocyanate is, for example, a trifunctional polyisocyanate represented by the following formula (2).

    [0031] It is noted that in the formulae (1) and (2), R represents a residue where the isocyanate group is removed from the diisocyanate.





    [0032] In the present invention, as the polyisocyanate, a derivative of hexamethylene diisocyanate and a derivative of isophorone diisocyanate are preferably used. As the derivate of hexamethylene diisocyanate, an isocyanurate of hexamethylene diisocyanate is preferably used. As the derivate of isophorone diisocyanate, an isocyanurate of isophorone diisocyanate is preferably used.

    [0033] The mixing ratio (derivate of HDI/derivate of IPDI) of the derivate of hexamethylene diisocyanate to the derivate of isophorone diisocyanate is preferably 90/10 or less, more preferably 80/20 or less, and even more preferably 75/25 or less, and is preferably 10/90 or more, more preferably 30/70 or more, and even more preferably 45/55 or more in a mass ratio.

    [0034] The content (NCO %) of the isocyanate group in (A) the polyisocyanate is preferably 0.5 mass % or more, more preferably 1 mass % or more, and even more preferably 2 mass % or more, and is preferably 45 mass % or less, more preferably 40 mass % or less, and even more preferably 35 mass % or less. It is noted that the content (NCO %) of the isocyanate group in the polyisocyanate can be represented by 100 X [mole number of isocyanate group in polyisocyanate x 42 (molecular weight of NCO)] / [total mass (g) of polyisocyanate].

    [0035] Specific examples of the polyisocyanate include Burnock D-800, Burnock DN-950, and Burnock DN-955 available from DIC corporation; Desmodur N75MPA/X, Desmodur N3300, Desmodur L75 (C), and Sumidur E21-1 available from Sumika Bayer Urethane Co., Ltd; Coronate HX, and Coronate HK available from by Nippon Polyurethane Industry Co., Ltd; Duranate 24A-100, Duranate 21S-75E, Duranate TPA-100, and Duranate TKA-100 available from Asahi Kasei Chemicals Corporation; and VESTANAT T1890 available from Degussa Co., Ltd.

    [0036] Next, (B) the polyol component containing the polyrotaxane will be explained. The polyrotaxane comprises 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 cyclic molecule. The polyrotaxane is viscoelastic, since the cyclodextrin molecule is movable along the linear molecule that penetrates the cyclodextrin in a skewerring manner (pulley effect). Even if a tension is applied to the polyrotaxane, the tension can be uniformly dispersed due to the pulley effect. It is noted that in the present invention, the polyol component is not particularly limited as long as it has multiple hydroxyl groups, and the polyrotaxane is the polyol component since multiple hydroxyl groups reactive with the isocyanate group exist on the cyclic structure of the cyclodextrin.

    [0037] 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 α-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.

    [0038] The linear molecule is preferably a linear molecule capable of piercing through the cyclic structure of the cyclodextrin so that the cyclic structure of the cyclodextrin is 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 easily penetrates the cyclic structure of the cyclodextrin in a manner of piercing through the cyclic structure of the cyclodextrin.

    [0039] 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.

    [0040] The linear molecule preferably has a functional group at both terminals thereof. If 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, carboxyl group, amino group, and thiol group.

    [0041] The blocking group is not particularly limited, as long as it is 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 of the cyclodextrins penetrated by the linear molecule preferably ranges from 0.06 to 0.61, more preferably ranges from 0.11 to 0.48, and even more preferably ranges from 0.24 to 0.41, when the maximum number thereof is deemed as 1. If the number of the cyclodextrins is less than 0.06, the pulley effect may not be exerted, and if the number of the cyclodextrins exceeds 0.61, the cyclodextrins are very densely located, so that the movability of the cyclodextrin may decrease.

    [0042] The polyrotaxane used in the present invention is preferably a polyrotaxane having at least a part of hydroxyl groups of the cyclodextrin being modified with a caprolactone chain. If the modification with the caprolactone is performed, the compatibility with the polyurethane is enhanced. Further, if the modification with the caprolactone is performed, the polyrotaxane has enhanced flexibility, and thus the spin performance on approach shots is enhanced.

    [0043] As the above modification, for example, the hydroxyl groups of the cyclodextrin are treated with propylene oxide to hydroxylalkylate 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 a -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 the other terminal of the caprolactone chain, a hydroxyl group is formed through the ring-opening polymerization.

    [0044] 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, and 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 polyrotaxane has enhanced flexibility, and thus the spin performance under a wet condition is further enhanced.

    [0045] Fig. 1 is an explanatory drawing illustrating a molecular structure of one example of the polyrotaxane used in the present invention. The polyrotaxane 200 comprises a cyclodextrin 212, a linear molecule 214 piercing through the cyclic structure of the cyclodextrin 212, and blocking groups 216 located at both terminals of the linear molecule 214 to prevent disassociation of the cyclic molecule, and a caprolactone chain 218 is linked to the exterior side of the cyclic structure of the cyclodextrin via a -O-C3H6-O- group (not shown).

    [0046] The hydroxyl value of the polyrotaxane is preferably 10 mg KOH/g or more, more preferably 15 mg KOH/g or more, and 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, and most 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 hydroxyl value can be measured according to JIS K 1557-1, for example, by an acetylation method.

    [0047] The total molecular weight of the polyrotaxane is preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more, and is preferably 3,000,000 or less, more preferably 2,500,000 or less, and 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 the approach performance of the golf ball is enhanced. It is noted that the weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard substance, tetrahydrofuran as an eluant, and an organic solvent GPC column (e.g., "Shodex (registered trademark) KF series" available from Showa Denko K.K.) as a column.

    [0048] Specific examples of the polyrotaxane modified with the polycaprolactone include SeRM (registered trademark) super polymer SH3400P, SH2400P, and SH1310P available from Advanced Softmaterials Inc.

    [0049] (B) The polyol component may further contain other polyol components. The other polyol components are not particularly limited as long as the other polyol components have multiple hydroxyl groups, and examples thereof include a low molecular weight polyol and a high molecular weight polyol.

    [0050] Examples of the low molecular weight polyol include a diol such as ethylene glycol, diethylene glycol, triethylene glycol, propane diol (e.g. 1,2-propane diol, 1,3-propane diol, 2-methyl-1,3-propane diol), dipropylene glycol, butane diol (e.g. 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 2,3-butane diol, 2,3-dimethyl-2,3-butane diol), neopentyl glycol, pentane diol, hexane diol, heptane diol, octane diol, 1,4-cyclohexane dimethylol, aniline type diol, and bisphenol A type diol; a triol such as glycerin, trimethylol propane, and hexane triol; and a tetraol or hexaol such as pentaerythritol and sorbitol.

    [0051] 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.

    [0052] The number average molecular weight of the high molecular weight polyol is not particularly limited, but it is, for example, preferably 400 or more, more preferably 1,000 or more. The upper limit of the number average molecular weight of the high molecular weight polyol is not particularly limited, but it is preferably 10,000, more preferably 8,000. If the number average molecular weight of the high molecular weight polyol falls within the above range, the obtained paint film has enhanced adhesion to the golf ball body. It is noted that the number average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, tetrahydrofuran as an eluant, and two columns of TSK-GEL SUPERH2500 (available from Tosoh Corporation) as a column.

    [0053] In a preferable embodiment of the present invention, (B) the polyol component contains at least one member selected from the group consisting of a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, and an acrylic polyol, in addition to the polyrotaxane.

    [0054] In a more preferable embodiment of the present invention, (B) the polyol component contains a polycaprolactone polyol (poly-ε-caprolactone (PCL)), in addition to the polyrotaxane. Specific examples of the polycaprolactone polyol include Placcel 308 and Placcel 312 available from Daicel Chemical Industries, Ltd., and Capa 4101 and Capa 4801 available from Perstorp Co., Ltd.

    [0055] Examples of the embodiment of (B) the polyol component include an embodiment where (B) the polyol component consists of the polyrotaxane; an embodiment where (B) the polyol component contains the polyrotaxane and the high molecular weight polyol; an embodiment where (B) the polyol component contains the polyrotaxane and the low molecular weight polyol; and an embodiment where (B) the polyol component contains the polyrotaxane, the low molecular weight polyol and the high molecular weight polyol. In addition, two or more of the low molecular weight polyol or the high molecular weight polyol may be used in combination.

    [0056] In the case that (B) the polyol component contains the polyrotaxane and another polyol, the amount of the polyrotaxane in (B) the polyol component is preferably 10 mass % or more, more preferably 15 mass % or more, even more preferably 20 mass % or more, and most preferably 50 mass % or more. In addition, the amount of the polyrotaxane in (B) the polyol component is preferably 100 mass % or less, more preferably 90 mass % or less, and even more preferably 80 mass % or less. If the amount of the polyrotaxane falls within the above range, the flexibility which is the property of the polyrotaxane is sufficiently exerted.

    [0057] The polyurethane used in the present invention may comprise a polyamine as a constituent component, in addition to (A) the polyisocyanate component and (B) the polyol component. The polyamine is not particularly limited as long as it has at least two amino groups. Examples of the polyamine include an aliphatic polyamine, an alicyclic polyamine, and an aromatic polyamine. Examples of the aliphatic polyamine include ethylene diamine, propylene diamine, butylene diamine, and hexamethylene diamine. Examples of the alicyclic polyamine include isophorone diamine and piperazine.

    [0058] The aromatic polyamine is not particularly limited, as long as it has at least two amino groups directly or indirectly bonded to an aromatic ring. Here, "indirectly bonded to an aromatic ring" means the amino groups are bonded to the aromatic ring via, for example, a lower alkylene group. The aromatic polyamine may be, for example, a monocyclic aromatic polyamine having two or more amino groups bonded to one aromatic ring, or a polycyclic aromatic polyamine having two or more aminophenyl groups each having at least one amino group bonded to one aromatic ring.

    [0059] Examples of the monocyclic aromatic polyamine include a type having the amino groups directly bonded to the aromatic ring, such as phenylene diamine, toluene diamine, diethyltoluene diamine, and dimethylthiotoluene diamine; and a type having the amino groups such as xylylene diamine bonded to the aromatic ring via a lower alkylene group. In addition, the polycyclic aromatic polyamine may be a poly(aminobezene) having at least two aminophenyl groups directly bonded to each other, or an aromatic polyamine having at least two aminophenyl groups bonded to each other via a lower alkylene group or alkylene oxide group. Among them, diaminodiphenyl alkane having two aminophenyl groups bonded to each other via a lower alkylene group is preferred, 4,4'-diaminodiphenyl methane and a derivate thereof is particularly preferred.

    [0060] The constitutional embodiment of the polyurethane used in the present invention is not particularly limited, and examples thereof include an embodiment composed of the polyisocyanate component and the polyrotaxane; an embodiment composed of the polyisocyanate component, the polyrotaxane and the high molecular weight polyol component; and an embodiment composed of the polyisocyanate component, the polyrotaxane, the high molecular weight polyol component and the low molecular weight polyol component.

    [0061] The amount of the polyurethane in the resin component of the paint film is preferably 40 mass % or more, more preferably 50 mass % or more, and even more preferably 55 mass % or more, and is preferably 100 mass % or less, more preferably 95 mass % or less, and even more preferably 90 mass % or less.

    [0062] The resin component of the paint film according to the present invention may further contain a fluorine resin, an acrylic resin or a vinyl chloride-vinyl acetate copolymer and/or a modified product thereof. Among them, the resin component of the paint film according to the present invention preferably contains the vinyl chloride-vinyl acetate copolymer and/or the modified product thereof. If the vinyl chloride-vinyl acetate copolymer and/or the modified product thereof is contained, the tackiness can be adjusted while maintaining abrasion resistance, and moderate tacky feeling is obtained. Examples of the modification method include a method of copolymerizing a monomer (e.g., vinyl alcohol, hydroxyalkyl acrylate) copolymerizable with vinyl chloride and vinyl acetate; and a method of partially or completely saponifying a vinyl chloride-vinyl acetate copolymer to introduce hydroxyl groups therein.

    [0063] The amount of the vinyl chloride component in the vinyl chloride-vinyl acetate copolymer and/or the modified product thereof is preferably 1 mass % or more, more preferably 20 mass % or more, and is preferably 99 mass % or less, more preferably 95 mass % or less. In the present invention, as the vinyl chloride-vinyl acetate copolymer and/or the modified product thereof, a hydroxyl group-modified vinyl chloride-vinyl acetate copolymer is preferably used. Specific examples of the vinyl chloride-vinyl acetate copolymer and/or the modified product thereof include Solbin (registered trademark) A, Solbin AL, Solbin TA2, and Solbin TA3 available from Nissin Chemical Industry Co., Ltd.

    [0064] Further, the amount of the vinyl chloride-vinyl acetate copolymer and/or the modified product thereof in the resin component constituting the paint film is preferably 4 mass % or more, more preferably 8 mass % or more, and is preferably 50 mass % or less, and more preferably 45 mass % or less.

    [Paint composition]



    [0065] The paint film of the golf ball according to the present invention is preferably formed from a curing type paint composition including a base material consisting of a polyol composition containing (B) the polyrotaxane, and a curing agent consisting of a polyisocyanate composition containing (A) the polyisocyanate component. In the present invention, in order to distinguish the polyol composition containing the polyrotaxane and the polyisocyanate composition containing the polyisocyanate component, as a matter of convenience, the polyol composition containing the polyrotaxane is referred to as the base material, and the polyisocyanate composition containing the polyisocyanate component is referred to as the curing agent. In addition, the base material may also be referred to as the A agent, and the curing agent may also be referred to as the B agent. Furthermore, the polyol composition containing (B) the polyrotaxane may also be referred to as the curing agent, and the polyisocyanate composition containing (A) the polyisocyanate component may also be referred to as the base material.

    [0066] In the curing type paint composition used in the present invention, the base material preferably contains a compound having reactivity with the isocyanate group included in the curing agent. Specifically, the base material preferably contains (B) the polyol component containing the polyrotaxane. Further, the base material of the curing type paint composition preferably contains the vinyl chloride-vinyl acetate copolymer and/or the modified product thereof.

    [0067] In the curing reaction of the curing type paint composition, the molar ratio (NCO group/OH group) of the isocyanate group (NCO group) of (A) the polyisocyanate component to the hydroxyl group (OH group) included in (B) the polyol component containing the polyrotaxane is preferably 0.95 or more, more preferably 1.05 or more, and even more preferably 1.10 or more. If the molar ratio (NCO group/OH group) is less than 0.95, the curing reaction may become insufficient. Further, if the molar ratio (NCO group/OH group) is too large, the amount of the isocyanate group is excessive, and the obtained paint film may become hard and fragile as well as the appearance of the obtained paint film may deteriorate. Thus, the molar ratio (NCO group/OH group) is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.5 or less. It is noted that the reason why the appearance of the obtained paint film deteriorates if the amount of the isocyanate group in the paint becomes excessive is considered as follows: an excessive amount of the isocyanate group may promote a reaction between the moisture in air and the isocyanate group, thereby generating a lot of carbon dioxide gas. It is noted that, when the NCO/OH molar ratio in the curing reaction is taken into account, the hydroxyl group of the base material includes the hydroxyl groups of the polyrotaxane and the polyol, but excludes the hydroxyl groups of the modified product of the vinyl chloride-vinyl acetate copolymer, the modified silicone which will be described later, and the like.

    [0068] A conventionally known catalyst can be employed for the curing reaction. Examples of the catalyst include a monoamine such as triethyl amine and N,N-dimethylcyclohexylamine; a polyamine such as N,N,N',N'-tetramethylethylene diamine and N,N,N',N", N"-pentamethyldiethylene triamine; a cyclic diamine such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and triethylene diamine; a tin catalyst such as dibutyl tin dilaurate and dibutyl tin diacetate. These catalysts may be used solely, or two or more of the catalysts may be used in combination. Among them, the tin catalyst such as dibutyl tin dilaurate and dibutyl tin diacetate is preferred, and in particular, dibutyl tin dilaurate is preferably used.

    [Solvent]



    [0069] The curing type paint composition is preferably a solvent based paint containing an organic solvent as a dispersion medium. The polyrotaxane is insoluble in water, and thus the organic solvent is preferably used. Examples of the preferable solvent include toluene, isopropyl alcohol, xylene, methylethyl ketone, methylisobutyl ketone, ethylene glycol monomethyl ether, ethylbenzene, propylene glycol monomethyl ether, isobutyl alcohol, and ethyl acetate. It is noted that the solvent may be added in either of the base material and the curing agent, and in light of uniformly performing the curing reaction, the solvent is preferably added in the base material and the curing agent, respectively.

    [0070] The curing type paint composition preferably further contains a modified silicone. If the modified silicone which is used as a leveling agent is contained, unevenness of the coated surface can be reduced, and thus a smooth coated surface can be formed on the surface of the golf ball. Examples of the modified silicone include a modified silicone having an organic group being introduced to a side chain or an end of a polysiloxane skeleton, a polysiloxane block copolymer obtained by copolymerizing a polyether block and/or a polycaprolactone block, etc. with a polysiloxane block, and a modified silicone having an organic group being introduced to a side chain or an end of the polysiloxane block copolymer. The polysiloxane skeleton or the polysiloxane block is preferably linear, and examples thereof include dimethyl polysiloxane, methylphenyl polysiloxane, and methyl hydrogen polysiloxane. Examples of the organic group include an amino group, epoxy group, mercapto group, and carbinol group. In the present invention, as the modified silicone oil, a polydimethylsiloxane-polycaprolactone block copolymer is preferably used, and a terminal carbinol-modified polydimethylsiloxane-polycaprolactone block copolymer is more preferably used. This is because these block copolymers have excellent compatibility with the caprolactone-modified polyrotaxane and the polycaprolactone polyol. Specific examples of the modified silicone used in the present invention include DBL-C31, DBE-224, and DCE-7521 available from Gelest, Inc.

    [0071] The modified silicone is remained in the paint film formed from the paint composition. The amount of the modified silicone in the paint film and the curing type paint composition is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, with respect to 100 parts by mass of the resin component constituting the paint film.

    [0072] The curing type paint composition may further include additives generally included in the paint for a golf ball, such as a filler, ultraviolet absorber, antioxidant, light stabilizer, fluorescent brightener, anti-blocking agent, leveling agent, slip agent, and viscosity modifier, where necessary.

    [0073] Next, the method of applying the curing type paint composition of the present invention will be described. The method of applying the curing type paint composition is not limited, a conventionally known method can be adopted, and examples thereof include a spray coating and electrostatic coating.

    [0074] In the case of performing the spray coating with an air gun, the base material and the curing agent 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 base material and the curing agent 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.

    [0075] The curing type paint applied to the golf ball body can be dried, for example, at a temperature ranging from 30 °C to 70 °C for 1 hour to 24 hours to form the paint film.

    [0076] The thickness of the paint according to the appended claims is 1250 nm or more. The thickness of the paint film after drying is preferably, without limitation, 5 µm or more, more preferably 6 µm or more, even more preferably 10 µm or more, and most preferably 15 µm or more. If the thickness is less than 5 µm, the paint film is likely to wear off due to the continued use, and thickening the paint film increases the spin rate on approach shots. The thickness of the paint film is preferably 50 µm or less, more preferably 45 µm or less, and even more preferably 40 µm or less. If the thickness of the paint film is thicker than 50 µm, the dimple effect is lowered, and thus the flying performance of the golf ball tends to be lowered. The thickness of the paint film can be measured, for example, by observing a cross section of the golf ball using a microscope (VHX-1000 available from Keyence Corporation). In the case of overpainting the paint, a total thickness of the formed paint film preferably falls within the above range.

    [0077] The paint film of the golf ball according to the present invention may have a single-layered construction or a multiple-layered construction, and preferably has the single-layered construction.

    [Golf ball body]



    [0078] The golf ball according to the present invention is not particularly limited, as long as it is a golf ball comprising a golf ball body and a paint film covering the golf ball body, and wherein the ball body further comprises a cover. The construction of the golf ball body is not particularly limited, and the golf ball body may be a two-piece golf ball, a three-piece golf ball, a multi-piece golf ball such as a four-piece golf ball and a golf ball comprising more than four pieces, or a wound golf ball. The present invention can be applied suitably to any one of the above golf balls.

    [0079] The golf ball body according to the present invention preferably comprises a core and a cover covering the core. An intermediate layer may be further comprised between the core and the cover.

    [0080] Fig. 2 is a partially cutaway cross-sectional view showing a golf ball 100 according to one embodiment of the present invention. The golf ball 100 comprises a spherical core 104, an intermediate layer 106 covering the spherical core 104, a cover 112 covering the intermediate layer 106. On the surface of the cover 112, a plurality of dimples 114 are formed. On the surface of the golf ball, a part other than the dimples 114 is a land 116. The golf ball further comprises a paint layer and a mark layer on the outer side of the cover, but these layers are not depicted.

    [0081] In the preferable embodiment of the present invention, the material hardness of the cover of the golf ball body is 30 or more, preferably 40 or more, more preferably 50 or more, and even more preferably 55 or more in Shore D hardness. In addition, the material hardness of the cover is preferably 90 or less, more preferably 80 or less, and even more preferably 70 or less in Shore D hardness. The obtained golf ball has better shot feeling and durability by suitably adjusting the cover hardness. The material hardness of the cover is a slab hardness obtained by measuring a cover composition molded into a sheet form.

    [0082] In the other preferable embodiment of the present invention, the material hardness of the cover of the golf ball body is preferably less than 50, more preferably 45 or less, even more preferably 40 or less, and most preferably 35 or less in Shore D hardness. If the hardness of the cover is 50 or less in Shore D hardness, the spin rate on approach shots for a distance of about 40 yards to about 100 yards becomes higher, and thus controllability is enhanced. The lower limit of the hardness of the cover is not particularly limited, but it is preferably 18, more preferably 20, and even more preferably 25 in Shore D hardness. The material hardness of the cover is a slab hardness obtained by measuring a cover composition molded into a sheet form. It is noted that the material hardness of the cover is the material hardness of the outermost cover of the golf ball body.

    [0083] In the present invention, the thickness of the cover of the golf ball is not particularly limited, but it is preferably 4 mm or less, more preferably 2 mm or less, and even more preferably 1 mm or less. If the thickness of the cover is 4 mm or less, the outer diameter of the core can be increased, and thus the resilience performance can be enhanced. The lower limit of the thickness of the cover is not particularly limited, but it is preferably 0.3 mm, more preferably 0.4 mm, and even more preferably 0.5 mm. If the thickness of the cover is less than 0.3 mm, the molding of the cover may become difficult.

    [0084] The cover material constituting the cover of the golf ball according to the present invention is not particularly limited, and examples thereof include various resins such as an ionomer resin, a polyester resin, a urethane resin like a thermoplastic urethane resin or a two-component curing type urethane resin, and a polyamide resin; and a thermoplastic polyamide elastomer having a trade name of "Pebax (registered trademark) (e.g. "Pebax 2533")" available from Arkema Inc., a thermoplastic polyester elastomer having a trade name of "Hytrel (registered trademark) (e.g. "Hytrel 3548" and "Hytrel 4047")" available from Du Pont-Toray Co., Ltd., a thermoplastic polyurethane elastomer having a trade name of "Elastollan (registered trademark) (e.g. "Elastollan XNY97A")" available from BASF Japan Ltd, and a thermoplastic styrene elastomer having a trade name of "Rabalon (registered trademark)" and a thermoplastic polyester elastomer having a trade name of "Primalloy" available from Mitsubishi Chemical Corporation. In the present invention, as the cover material, a thermoplastic polyurethane elastomer is preferably used. These cover materials may be used solely, or two or more of these cover materials may be used in combination.

    [0085] The cover may include a pigment component such as a white pigment (e.g. titanium oxide), a blue pigment and a red pigment, a weight adjusting agent such as calcium carbonate and barium sulfate, a dispersant, an antioxidant, an ultraviolet absorber, a light stabilizer, a fluorescent material or a fluorescent brightener, or the like, in addition to the above resin component, as long as they do not impair the performance of the cover.

    [0086] The embodiment for molding the cover from the cover composition is not particularly limited, and examples thereof include an embodiment comprising injection molding the cover composition directly onto the core; and an embodiment comprising molding the cover composition into hollow shells, covering the core with a plurality of the hollow shells and compression molding the core with a plurality of the hollow shells (preferably an embodiment comprising molding the cover composition into half hollow-shells, covering the core with two of the half hollow-shells and compression molding the core with two of the half hollow-shells). After the cover is molded, the obtained golf ball body is ejected from the mold, and as necessary, the golf ball body is preferably subjected to surface treatments such as deburring, cleaning, and sandblast. If desired, a mark may be formed.

    [0087] 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. If the total number 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 formed dimple includes, for example, without limitation, 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 another irregular shape. The shape may be employed solely, or two or more of the shapes may be employed in combination.

    [0088] The golf ball preferably has a diameter ranging from 40 mm to 45 mm. In light of satisfying a regulation of US Golf Association (USGA), the diameter is preferably 42.67 mm or more. In light of prevention of the air resistance, the diameter is preferably 44 mm or less, more preferably 42.80 mm or less. The golf ball preferably has a mass of 40 g or more and 50 g or less. In light of obtaining greater inertia, the golf ball more preferably has a mass of 44 g or more, even more preferably 45.00 g or more. In light of satisfying a regulation of USGA, the golf ball preferably has a mass of 45.93 g or less.

    [0089] In the preferable embodiment of the present invention, when the golf ball has a diameter ranging from 40 mm to 45 mm, the compression deformation amount (shrinking amount along the compression direction) of the golf ball when applying a load from 98 N as an initial load to 1275 N as a final load to the golf ball is preferably 3.0 mm or less, more preferably 2.9 mm or less, and even more preferably 2.7 mm or less. If the compression deformation amount is 3.0 mm or less, a low launch angle and a high spin rate can be achieved, and thus the controllability on short iron shots is further enhanced. The lower limit of the compression deformation amount is not particularly limited, but it is preferably 2.3 mm or more, more preferably 2.4 mm or more, and even more preferably 2.5 mm or more. If the compression deformation amount is 2.3 mm or more, the golf ball has better shot feeling.

    [0090] In the other preferable embodiment of the present invention, when the golf ball has a diameter ranging from 40 mm to 45 mm, the compression deformation amount (shrinking amount along the compression direction) of the golf ball when applying a load from 98 N as an initial load to 1275 N as a final load to the golf ball is preferably 2.0 mm or more, more preferably 2.2 mm or more, and is preferably 4.0 mm or less, more preferably 3.5 mm or less. If the compression deformation amount is 2.0 mm or more, the golf ball is not excessively hard, and thus the shot feeling thereof is better. On the other hand, if the compression deformation amount is 4.0 mm or less, the resilience of the golf ball becomes better.

    [0091] Next, the core used for a wound golf ball, two-piece golf ball and multi-piece golf ball, and the one-piece golf ball body will be explained.

    [0092] The core or the one-piece golf ball body may use a conventionally known rubber composition (hereinafter simply referred to as "core rubber composition" occasionally), and may be formed by heat pressing, for example, a rubber composition containing a base rubber, a co-crosslinking agent and a crosslinking initiator.

    [0093] As the base rubber, particularly preferred is a high cis-polybutadiene having a cis-bond in a proportion of 40 mass % or more, more preferably 70 mass % or more, and even more preferably 90 mass % or more in view of its advantageous 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 to be used 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. 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 to be used is preferably 0.2 part by mass or more, more preferably 0.3 part by mass or more, and is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the base rubber. In addition, the core rubber composition may further include an organic sulfur compound. As the organic sulfur compound, diphenyl disulfides, thiophenols or thionaphthols may be preferably used. The amount of the organic sulfur compound to be used 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 include 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 preferred. The amount of the carboxylic acid and/or the salt thereof to be used 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.

    [0094] The core rubber composition may further include a weight adjusting agent such as zinc oxide and barium sulfate, an antioxidant, or a colored powder, in addition to the base rubber, the co-crosslinking agent, the crosslinking initiator, and the organic sulfur compound. The molding conditions for heat pressing the core rubber composition may be determined appropriately depending on the rubber formulation. Generally, the heat pressing is preferably carried out at 130 °C to 200 °C for 10 to 60 minutes, or carried out in a two-step heating of heating at 130 °C to 150 °C for 20 to 40 minutes followed by heating at 160 °C to 180 °C for 5 to 15 minutes.

    [Golf ball]



    [0095] In the case that the golf ball according to the present invention is a three-piece golf ball, and a multi-piece golf ball such as a four-piece golf ball and a golf ball comprising more than four pieces, examples of the material for an intermediate layer disposed between the core and the outmost cover include a thermoplastic resin such as a polyurethane resin, an ionomer resin, a polyamide resin, and polyethylene; a thermoplastic elastomer such as a styrene elastomer, a polyolefin elastomer, a polyurethane elastomer, and a polyester elastomer; and a cured product of a rubber composition. Herein, examples of the ionomer resin include a product obtained by neutralizing, with a metal ion, at least a part of carboxyl groups in a copolymer composed of ethylene and an α,β-unsaturated carboxylic acid; and a product obtained by neutralizing, with a metal ion, at least a part of carboxyl groups in a terpolymer composed of ethylene, an α,β-unsaturated carboxylic acid and an α,β-unsaturated carboxylic acid ester. The intermediate layer may further include a weight adjusting agent such as barium sulfate and tungsten, an antioxidant, and a pigment. The intermediate layer may be referred to as an inner cover layer or an outer core depending on the construction of the golf ball.

    EXAMPLES



    [0096] Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the examples described below, and various changes and modifications without departing from the gist of the present invention are included in the scope of the present invention.

    [Evaluation method]


    (1) Material (slab) hardness (Shore D hardness)



    [0097] Sheets with a thickness of about 2 mm were produced by injection molding the intermediate layer composition or cover composition. The sheets were stored at 23 °C for two weeks. At least three of these sheets were stacked on one another so as not to be affected by the measuring substrate on which the sheets were placed, and the hardness of the stack was measured with an automatic hardness tester (Digitest II, available from Bareiss company) using a testing device of "Shore D" or "Shore A".

    (2) Measurement of dynamic viscoelasticity



    [0098] The storage modulus E' (Pa), loss modulus E" (Pa) and loss tangent (tan δ) of the paint film were measured under the following conditions.

    [0099] Apparatus: dynamic viscoelasticity measuring apparatus Rheogel-E4000 available from UBM Co. Ltd.

    [0100] Measuring sample: The base material and the curing agent were blended to prepare a paint, and the paint was dried and cured at 40 °C for 4 hours to prepare a paint film having a thickness ranging from 0.11 mm to 0.14 mm. A test piece having a width of 4 mm and a distance between the clamps of 20 mm was cut from the paint film.
    Measuring mode: tensile mode
    Measuring temperature: from -100 °C to 150 °C
    Temperature rising rate: 4 °C/min
    Measuring data capturing interval: 4 °C
    Oscillation frequency: 10 Hz
    Measuring strain: 0.1%

    (3) Indentation depth of paint film



    [0101] In the measurement of the indentation depth, the golf ball was cut to obtain a hemisphere. On the hemisphere, a cross section passing through the central point of the golf ball was exposed. The cross section includes a cross section of the paint film. The cross section of the hemisphere was made horizontal by a cryo-microtome. An indenter of a nanoindenter was brought into contact with the cross section of the paint film and pressed in a direction perpendicular to the cross section. The indenter advanced by the pressing. The load and the advancing distance of the indenter were measured. The measuring conditions were as follows.
    Nanoindenter: "ENT-2100" available from ELIONIX Inc.
    Temperature: 30 °C
    Indenter: Berkovich indenter (65.03° As (h) = 26.43 h2)
    Number of partitions: 500 steps, Step interval: 20 msec (100 mgf)

    [0102] The load of the indenter was gradually increased until the load of the indenter reached 50 mgf. The advancing distance (nm) of the indenter was measured as the indentation depth when the load was 30 mgf.

    (4) 10% Elastic modulus of paint film (kgf/cm2)



    [0103] The 10% elastic modulus of the paint film was measured according to JIS K7161 (2014). Specifically, the base material (polyol composition) and the curing agent (polyisocyanate composition) were blended to prepare a paint, and the paint was dried and cured at 40 °C for 4 hours to prepare a paint film (thickness: 0.05 mm). The paint film was punched into the Test Piece Type 2 (width of parallel part: 10 mm, gauge length: 50 mm) prescribed in JIS K7127 (1999) to prepare a test piece. The tensile test of the test piece was conducted using a precision universal tester (Autograph (registered trademark) available from Shimadzu Corporation) under testing conditions of a length between grips: 100 mm, a tensile speed: 50 mm/min and a testing temperature: 23 °C.

    (5) Thickness of paint film (µm)



    [0104] The golf ball was cut into two hemispheres, and the cross section of the paint film on the hemisphere was observed with a microscope (VHX-1000 available from Keyence Corporation) to obtain the thickness of the paint film.

    (6) Spin rate on short iron (#8 iron) shots (rpm)



    [0105] A #8 iron (Z-TX available from Dunlop Sports Co. Limited) was installed on a swing robot M/C available from Golf Laboratories, Inc. The golf ball was hit at a head speed of 38 m/sec, and the spin rate thereof right after hitting the golf ball was measured. This measurement was conducted twelve times for each golf ball, and the average value thereof was adopted as the measurement value for the golf ball. A sequence of photographs of the hit golf ball were taken for measuring the spin rate right after hitting the golf ball.

    (7) Spin rate on approach shots from the rough



    [0106] A sand wedge (trade name: "CG 15 forged wedge", loft angel: 52 °, available from Cleveland Golf) was installed on a swing machine available from Golf Laboratories, Inc. Two pieces of wild grass were attached to the surface of the golf ball. The golf ball was hit at a head speed of 16 m/sec. such that there was the wild grass between the club face and the golf ball, and the spin rate (rpm) thereof was measured. A sequence of photographs of the hit golf ball were taken for measuring the spin rate. The wild grass was attached by a cellophane tape on the position where the club face contacts the golf ball in a manner that the wild grass was perpendicular to the groove of the sand wedge. The measurement was conducted ten times for each golf ball, and the average value thereof was calculated respectively.

    (8) Shot feeling on short iron (#8 iron) shots



    [0107] An actual hitting test was carried out by ten amateur golfers (high skilled persons) using a #8 iron (Z-TX available from Dunlop Sports Co. Limited). In accordance with the number of people who answered the shot feeling was good (feeling like that the golf ball was lifted on the club face, feeling like that the golf ball gripped the club surface, feeling like that the spin was imparted, feeling like that the golf ball was stuck on the club face, etc.), the golf balls were evaluated as follows.
    E (Excellent): 8 or more
    G (Good): 5 to 7
    F (Fair): 3 to 4
    P (Poor): 2 or less

    (9) Shot feeling on approach shots



    [0108] An actual hitting test was carried out by ten amateur golfers (high skilled persons) using a sand wedge (CG 15 forged wedge (58°) available from Cleveland Golf). In accordance with the number of people who answered the shot feeling was good (feeling like that the golf ball was lifted on the club face, feeling like that the golf ball gripped the club surface, feeling like that the spin was imparted, feeling like that the golf ball was stuck on the club face, etc.), the golf balls were evaluated as follows.
    E (Excellent): 8 or more
    G (Good): 5 to 7
    F (Fair): 3 to 4
    P (Poor): 2 or less

    (10) Stain resistance



    [0109] The golf ball was immersed for 30 seconds in an aqueous solution of tincture of iodine obtained by diluting a tincture of iodine (an ethanol solution containing 6 mass % of iodine and 4 mass % of potassium iodide) to 40 times, and then taken out. After the extra aqueous solution of tincture of iodine adhered on the surface of the golf ball was wiped off, color tones (L, a, b) of the golf ball before and after the immersion were measured using a color difference meter (CM3500D available from Konica Minolta Inc.), and the color difference (ΔE) was calculated according to the following formula. It is noted that a larger color difference (ΔE) value means a larger color change extent.


    Evaluation Standard



    [0110] E (Excellent): ΔE is 15 or less
    G (Good): ΔE is more than 15 and 20 or less
    P (Poor): ΔE is more than 20

    (11) Compression deformation amount (mm)



    [0111] The deformation amount of the core or golf ball along the compression direction (shrinking amount of the core or golf ball along the compression direction), when applying a load from 98 N as an initial load to 1275 N as a final load to the core or golf ball, was measured.

    [Production of three-piece golf ball]


    (1) Production of spherical core



    [0112] The core rubber compositions having the formulations shown in Table 1 were kneaded, and heat-pressed in upper and lower molds, each having a hemispherical cavity, at 170 °C for 20 minutes to obtain the spherical cores having a diameter 39.7 mm.
    Table 1
    Core composition No.ABCDE
    Polybutadiene rubber 100 100 100 100 100
    Zinc acrylate 35.5 38.5 27.5 30.5 33.5
    Zinc oxide 5 5 5 5 5
    Barium sulfate Appropriate amount* Appropriate amount* Appropriate amount* Appropriate amount* Appropriate amount*
    Diphenyl disulfide 0.5 0.5 0.5 0.5 0.5
    Dicumyl peroxide 0.8 0.8 0.8 0.8 0.8
    Diameter (mm) 39.7 39.7 39.7 39.7 39.7
    Surface hardness (Shore D) 56 58 52 54 55
    Center hardness (Shore D) 41 42 40 41 41
    Compression deformation amount (mm) 2.7 2.5 3.6 3.3 2.9
    *) Adjustment was made such that the golf ball had a mass of 45.3 g. Polybutadiene rubber: "BR730 (high cis-polybutadiene)" available from JSR Corporation
    Zinc acrylate: ZN-DA90S (product of 10 % zinc stearate coating) available from Nihon Jyoryu Kogyo Co., Ltd.
    Zinc oxide: "Ginrei R" available from Toho Zinc Co., Ltd.
    Barium sulfate: "Barium Sulfate BD" available from Sakai Chemical Industry Co., Ltd.
    Diphenyl disulfide: available from Sumitomo Seika Chemicals Co., Ltd.
    Dicumyl peroxide: "Percumyl (register trademark) D" available from NOF Corporation

    (2) Preparation of intermediate layer composition and cover composition



    [0113] According to the formulations shown in Tables 2, 3, the materials were mixed with a twin-screw kneading extruder to prepare the intermediate layer composition and cover composition in a pellet form. The extruding conditions 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 200 °C to 260 °C at the die position of the extruder.
    Table 2
     Intermediate layer composition No. I
    Himilan 7337 50
    Himilan AM7329 50
    Slab hardness (Shore D) 65
    Formulation: parts by mass
    Himilan 7337: zinc ion neutralized ethylene-methacrylic acid copolymer ionomer resin available from Du Pont-Mitsui Polychemicals Co., Ltd.
    Himilan AM7329: sodium ion neutralized ethylene-methacrylic acid copolymer ionomer resin available from Du Pont-Mitsui Polychemicals Co., Ltd.
    Table 3
    Cover composition No.abcdef
    Elastollan XNY84A 100 - - - - -
    Elastollan XNY88A - 100 - - - -
    Elastollan XNY92A - - 100 - - -
    Elastollan XNY97A - - - 100 - -
    Elastollan XNY57D - - - - 100 -
    Elastollan ET164D - - - - - 100
    Ultramarine blue 0.08 0.08 0.08 0.08 0.08 0.08
    Titanium dioxide 4 4 4 4 4 4
    Slab hardness (Shore D) 32 40 44 47 57 64
    Formulation: parts by mass
    Elastollan XNY84A: thermoplastic polyurethane elastomer with a Shore D hardness of 32 available from BASF Japan Ltd.
    Elastollan XNY88A: thermoplastic polyurethane elastomer with a Shore D hardness of 40 available from BASF Japan Ltd.
    Elastollan XNY92A: thermoplastic polyurethane elastomer with a Shore D hardness of 44 available from BASF Japan Ltd.
    Elastollan XNY97A: thermoplastic polyurethane elastomer with a Shore D hardness of 47 available from BASF Japan Ltd.
    Elastollan XNY57D: thermoplastic polyurethane elastomer with a Shore D hardness of 57 available from BASF Japan Ltd.
    Elastollan ET164D: thermoplastic polyurethane elastomer with a Shore D hardness of 64 available from BASF Japan Ltd.

    (3) Production of intermediate layer



    [0114] The intermediate layer composition obtained above was directly injection molded on the spherical core obtained as described above to produce the intermediate layer. Upper and lower molds for molding have a hemispherical cavity and a retractable hold pin holding the spherical core. When molding the intermediate layer, the hold pins were protruded to hold the spherical core after the spherical core was charged, and the intermediate layer composition heated to 260 °C was charged for 0.3 second into the mold held under a pressure of 80 tons, and cooled for 30 seconds to mold the intermediate layer (thickness: 1 mm).

    (4) Molding of half shell



    [0115] The compression molding of the half shells was conducted by charging a pellet of the cover composition into each of the depressed part of the lower mold for molding half shells, and applying pressure to mold half shells. The compression molding was conducted under the conditions of a molding temperature of 170 °C, a molding time of 5 minutes and a molding pressure of 2.94 MPa.

    (5) Molding of cover



    [0116] The spherical body having the intermediate layer covered thereon and obtained in (3) was concentrically covered with two of the half shells obtained in (4), and the spherical body and two of the half shells were compression molded to obtain the cover (thickness: 0.5 mm). The compression molding was conducted under the conditions of a molding temperature of 145 °C, a molding time of 2 minutes and a molding pressure of 9.8 MPa. The constructions of the obtained golf ball bodies were shown in Tables 4-5.
    Table 4
    Golf ball body12345
    Core composition No. A B E D C
    Diameter of core (mm) 39.7 39.7 39.7 39.7 39.7
    Compression deformation amount of core (mm) 2.7 2.5 2.9 3.3 3.6
    Intermediate layer composition No. I I I I I
    Thickness of intermediate layer (mm) 1.0 1.0 1.0 1.0 1.0
    Cover composition No. a a a a a
    Thickness of cover (mm) 0.5 0.5 0.5 0.5 0.5
    Slab hardness of cover (Shore D) 32 32 32 32 32
    Compression deformation amount (mm) 2.26 2.06 2.46 2.86 3.16
    Table 5
    Golf ball body1678910
    Core composition No. A A A A A A
    Diameter of core (mm) 39.7 39.7 39.7 39.7 39.7 39.7
    Compression deformation amount of core (mm) 2.7 2.7 2.7 2.7 2.7 2.7
    Intermediate layer composition No. I I I I I I
    Thickness of intermediate layer (mm) 1.0 1.0 1.0 1.0 1.0 1.0
    Cover composition No. a b c d e f
    Thickness of cover(mm) 0.5 0.5 0.5 0.5 0.5 0.5
    Slab hardness of cover (Shore D) 32 40 44 47 57 64
    Compression deformation amount (mm) 2.26 2.23 2.21 2.19 2.13 2.08

    (6) Preparation of paint



    [0117] According to the formulations shown in Tables 6-7, the materials were mixed to prepare the paint compositions No. 1 to No 8. The surface of the golf ball body obtained above was subjected to a sandblast treatment, and a mark was formed thereon. Then, the paint was applied to the golf ball body with a spray gun, and the paint was dried in an oven at 40 °C for 24 hours to obtain the golf ball having a diameter of 42.7 mm and a mass of 45.3 g. The paint film had a thickness of 18 µm. The golf ball body was placed in a rotating member shown in Fig. 3, 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 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 °C to 27 °C, and an atmosphere humidity: 65 % or less. Results evaluating the spin performance of the obtained golf balls are shown in Tables 6-7. It is noted that the paint film was formed from each of the paints, and the results measuring the dynamic viscoelasticity of the paint film are shown in Fig. 4 to Fig. 11.
    Table 6
    Golf ball No.123456789101112
    Golf ball body 1 1 1 1 1 1 1 1 2 3 4 5
    Compression deformation amount of golf ball body (mm) 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.26 2.06 2.46 2.86 3.16
    Paint formulation No. 1 2 3 4 5 6 7 8 8 8 8 8
    Base material formulation (parts by mass) Polyrotaxane - - - - - 50 50 50 50 50 50 50
    Polycaprolactone polyol - - - - - 28 28 28 28 28 28 28
    Modified product of vinyl chloride-vinyl acetate copolymer - - - - - 22 22 22 22 22 22 22
    Modified silicone - - - - - 0.1 0.1 0.1 0.1 0.1 0.1 0.1
    Dibutyl tin dilaurate - - - - - 0.01 0.01 0.01 0.01 0.01 0.01 0.01
    Solvent - - - - - 100 100 100 100 100 100 100
    Polyn #950 100 100 100 100 100 - - - - - - -
    Curing agent formulation (parts by mass) HDI biuret-modified product 30 30 30 30 30 - - - - - - -
    HDI isocyanurate 30 30 30 30 30 50 50 70 70 70 70 70
    IPDI isocyanurate 40 40 40 40 40 50 50 30 30 30 30 30
    Solvent 100 100 100 100 100 100 100 100 100 100 100 100
    Mixing ratio of curing agent/base material (NCO/OH molar ratio) 1.2/ 1.0 0.7/ 1.0 0.61/ 1.0 0.5/ 1.0 0.38/ 1.0 1.3/ 1.0 1.1/ 1.0 1.2/ 1.0 1.2/ 1.0 1.2/ 1.0 1.2/ 1.0 1.2/ 1.0
    10 % Elastic modulus of paint film (kgf/cm2) 187 100 65 40 8 60 30 20 20 20 20 20
    Storage modulus E'120 at 120 °C of paint film (x 107 Pa) 1.3 0.8 0.5 0.4 0.2 1.6 1.3 1.7 1.7 1.7 1.7 1.7
    Storage modulus E'150 at 150 °C of paint film (x 107 Pa) 1.1 0.8 0.5 0.4 0.2 1.6 1.4 1.8 1.8 1.8 1.8 1.8
    Peak temperature of loss tangent (tan δ) of paint film (°C) 88 72 68 60 52 56 48 44 44 44 44 44
    Peak height of loss tangent (tan δ) of paint film 0.74 0.86 0.93 0.91 1.02 0.47 0.53 0.56 0.56 0.56 0.56 0.56
    Indentation depth of paint film (nm) 390 1000 1500 1600 2950 1550 1800 2200 2200 2200 2200 2200
    Physical properties of golf ball Spin rate on I#8 shot (38m/s, rpm) 6650 6825 7000 7175 7350 7175 7350 7525 7788 7438 7350 7000
    Stain resistance E G F P P E G G G G G G
    Shot feeling on I#8 shot P F G G G G G G F G E E
    Table 7
    Golf ball No.13141516171819202122232425
    Golf ball body 1 1 1 1 1 1 1 1 6 7 8 9 10
    Cover composition No. a a a a a a a a b c d e f
    Cover material hardness (Shore D) 32 32 32 32 32 32 32 32 40 44 47 57 64
    Paint formulation No. 1 2 3 4 5 6 7 8 8 8 8 8 8
    Base material formulation (parts by mass) Polyrotaxane - - - - - 50 50 50 50 50 50 50 50
    Polycaprolactone polyol - - - - - 28 28 28 28 28 28 28 28
    Modified product of vinyl chloride-vinyl acetate copolymer - - - - - 22 22 22 22 22 22 22 22
    Solvent - - - - - 100 100 100 100 100 100 100 100
    Polyn #950 100 100 100 100 100 - - - - - - - -
    Curing agent formulation (parts by mass) HDI biuret-modified product 30 30 30 30 30 - - - - - - - -
    HDI isocyanurate 30 30 30 30 30 50 50 70 70 70 70 70 70
    IPDI isocyanurate 40 40 40 40 40 50 50 30 30 30 30 30 30
    Solvent 100 100 100 100 100 100 100 100 100 100 100 100 100
    Mixing ratio of curing agent/base material (NCO/OH molar ratio) 1.2/ 1.0 0.7/ 1.0 0.61/ 1.0 0.5/ 1.0 0.38/ 1.0 1.3/ 1.0 1.1/ 1.0 1.2/ 1.0 1.2/ 1.0 1.2/ 1.0 1.2/ 1.0 1.2/ 1.0 1.2/ 1.0
    10 % Elastic modulus of paint film (kgf/cm2) 187 100 65 40 8 60 30 20 20 20 20 20 20
    Storage modulus E'120 at 120 °C of paint film (x 107 Pa) 1.3 0.8 0.5 0.4 0.2 1.6 1.3 1.7 1.7 1.7 1.7 1.7 1.7
    Storage modulus E'150 at 150 °C of paint film (x 107 Pa) 1.1 0.8 0.5 0.4 0.2 1.6 1.4 1.8 1.8 1.8 1.8 1.8 1.8
    Peak temperature of loss tangent (tan δ) of paint film (°C) 88 72 68 60 52 56 48 44 44 44 44 44 44
    Peak height of loss tangent (tan δ) of paint film 0.74 0.86 0.93 0.91 1.02 0.47 0.53 0.56 0.56 0.56 0.56 0.56 0.56
    Indentation depth of paint film (nm) 390 1000 1500 1600 2950 1550 1800 2200 2200 2200 2200 2200 2200
    Physical properties of golf ball Spin rate at rough (rpm) 3800 3900 4000 4100 4200 4100 4200 4300 4100 3800 3600 3300 3000
    Stain resistance E G F P P E G G G G G G G
    Shot feeling on approach shot P F G G E G E E G F P P P


    [0118] The raw materials used in Tables 6-7 are shown below.

    Base material



    [0119] Polyrotaxane: "SeRM (registered trademark) super polymer SH3400P (a polyrotaxane having a cyclodextrin, at least a part of hydroxyl groups of the cyclodextrin being modified with a caprolactone chain via a -O-C3H6-O- group, a linear molecule of polyethylene glycol and a blocking group of an adamantyl group; the molecular weight of the linear molecule: 35,000; the hydroxyl value of the polyrotaxane: 72 mg KOH/g; the total molecular weight of the polyrotaxane: 700,000 in a weight average molecular weight)" available from Advanced Softmaterials Inc.
    Polycaprolactone polyol: Placcel 308 available from Daicel Chemical Industries, Ltd.
    Modified product of vinyl chloride-vinyl acetate copolymer: Solbin AL (hydroxyl-modified vinyl chloride-vinyl acetate copolymer) available from Nissin Chemical Industry Co., Ltd.
    Modified silicone: DBL-C31 available from Gelest, Inc.
    Solvent: mixed solvent of xylene/methylethyl ketone = 70/30 (mass ratio)
    Polin #950: urethane polyol having a hydroxyl value of 128 mg KOH/g and formed from a polyol component (trimethylolpropane and polyoxytetramethylene glycol) and a polyisocyanate component (isophorone diisocyanate), available from Shinto Paint Co., Ltd.

    Curing agent



    [0120] Isocyanurate of hexamethylene diisocyanate (HDI isocyanurate): Duranate TKA-100 (NCO content: 21.7 %) available from Asahi Kasei Chemicals Corporation
    Biuret-modified product of hexamethylene diisocyanate (HDI biuret-modified product): Duranate 21S-75E (NCO content: 15.5 %) available from Asahi Kasei Chemicals Corporation
    Isocyanurate of isophorone diisocyanate (IPDI isocyanurate): VESTANAT T1890 (NCO content: 12.0 %) available from Degussa Co., Ltd.

    Solvent: methylethyl ketone



    [0121] The golf ball according to the present invention is a golf ball comprising a golf ball body and a paint film covering the golf ball body, wherein a 10% elastic modulus of the paint film is 75 kgf/cm2 or less, a storage modulus (E'150) at 150 °C of the paint film obtained by measuring dynamic viscoelasticity of the paint film is 1.0×107 Pa or more, an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is 1250 nm or more, a diameter of the golf ball ranges from 40 mm to 45 mm, and a compression deformation amount of the golf ball measured by applying a load from 98 N as an initial load to 1275 N as a final load to the golf ball is 3.0 mm or less. It can be seen from the results shown in Table 6 that the golf ball according to the present invention has a high spin rate on short iron shots and is excellent in controllability. Further, the golf ball according to the present invention is excellent in stain resistance and shot feeling.

    [0122] The golf ball according to the present invention is a golf ball comprising a golf ball body having a cover, and a paint film covering the golf ball body, wherein a 10% elastic modulus of the paint film is 75 kgf/cm2 or less, a storage modulus (E'150) at 150 °C of the paint film obtained by measuring dynamic viscoelasticity of the paint film is 1.0×107 Pa or more, an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is 1250 nm or more, and a material hardness of the cover is less than 50 in Shore D hardness. It can be seen from the results shown in Table 7 that the golf ball according to the present invention has a high spin rate on approach shots from the rough and is excellent in controllability. Further, the golf ball according to the present invention is excellent in stain resistance and shot feeling.

    [0123] The present invention is suitably useful for painted golf balls.

    [0124] This application is based on Japanese patent application No. 2017-229720 filed on November 29, 2017, Japanese patent application No. 2017-229723 filed on November 29, 2017, Japanese patent application No. 2017-229723 filed on November 29, 2017, and Japanese patent application No. 2018-180088 filed on September 26, 2018.


    Claims

    1. A golf ball comprising a golf ball body having a cover, and a paint film covering the golf ball body, wherein a 10% elastic modulus of the paint film is 75 kgf/cm2 or less, a storage modulus (E'150) at 150 °C of the paint film obtained by measuring dynamic viscoelasticity of the paint film is 1.0×107 Pa or more, an indentation depth of the paint film measured with a nanoindenter in a state that the paint film is formed on the surface of the golf ball body is 1250 nm or more, and a material hardness of the cover is less than 50 in Shore D hardness, wherein for the measurement of the indentation depth,

    a) the golf ball was cut to obtain a hemisphere,

    b) on the hemisphere, a cross section passing through the central point of the golf ball was exposed, wherein the cross section includes a cross section of the paint film,

    c) the cross section of the hemisphere was made horizontal by a cryo-microtome,

    d) an indenter of a nanoindenter was brought into contact with the cross section of the paint film and pressed in a direction perpendicular to the cross section, and wherein the measuring conditions of the indentation depth of the paint film measured with the nanoindenter are:

    Nanoindenter: "ENT-2100" available from ELIONIX Inc.,

    Temperature: 30 °C,

    Indenter: Berkovich indenter (65.03° As (h) = 26.43 h2),

    Number of partitions: 500 steps, Step interval: 20 msec (100 mgf), and

    wherein the indentation depth is the advancing distance of the indenter in nm when the load is 30 mgf.


     
    2. The golf ball according to claim 1, wherein a loss tangent tan δ of the paint film obtained by measuring dynamic viscoelasticity of the paint film has a peak temperature of 60 °C or less.
     
    3. The golf ball according to claim 1 or 2, wherein a storage modulus (E'120) at 120 °C of the paint film is 1.0×107 Pa or more.
     
    4. The golf ball according to any one of claims 1 to 3, wherein the 10% elastic modulus of the paint film is 2 kgf/cm2 or more.
     
    5. The golf ball according to any one of claims 1 to 4, wherein the paint film contains a polyurethane as a resin component, wherein the polyurethane comprises, as a constituent component, (A) a polyisocyanate component and (B) a polyol component containing a polyrotaxane.
     
    6. The golf ball according to claim 5, wherein the polyurethane is a reaction product obtained under a reaction condition that a molar ratio (NCO/OH) of isocyanate group (NCO) of (A) the polyisocyanate component to hydroxyl group (OH) of (B) the polyol component is 0.95 or more and 2 or less.
     
    7. The golf ball according to claim 5 or 6, wherein the polyrotaxane comprises 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, wherein at least a part of the cyclodextrin hydroxyl groups is modified with a caprolactone chain via a -O-C3H6-O- group.
     
    8. The golf ball according to claim 7, wherein the linear molecule of the polyrotaxane is polyethylene glycol, and the blocking group of the polyrotaxane is an adamantyl group.
     
    9. The golf ball according to any one of claims 5 to 8, wherein (B) the polyol component further comprises at least one member selected from the group consisting of a polyether polyol, a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, and an acrylic polyol.
     
    10. The golf ball according to any one of claims 5 to 9, wherein (B) the polyol component contains the polyrotaxane in an amount ranging from 10 mass % to 100 mass %.
     
    11. The golf ball according to any one of claims 5 to 10, wherein a resin component of the paint film further contains a vinyl chloride-vinyl acetate copolymer and/or a modified product thereof.
     
    12. The golf ball according to any one of claims 5 to 11, wherein the paint film further comprises a modified silicone.
     
    13. The golf ball according to claim 12, wherein an amount of the modified silicone ranges from 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component constituting the paint film.
     
    14. The golf ball according to any one of claims 5 to 13, wherein (A) the polyisocyanate component contains an isocyanurate of hexamethylene diisocyanate and an isocyanurate of isophorone diisocyanate.
     


    Ansprüche

    1. Golfball, umfassend einen Golfballkörper mit einer Abdeckung und einem den Golfballkörper bedeckenden Lackfilm, wobei ein 10%-Elastizitätsmodul des Lackfilms 75 kgf/cm2 oder weniger beträgt, ein Speichermodul (E'150) bei 150 °C des Lackfilms, der durch Messen der dynamischen Viskoelastizität des Lackfilms erhalten wird, 1,0 x 107 Pa oder mehr beträgt, eine Eindringtiefe des Lackfilms, die mit einem Nanoindenter in einem Zustand gemessen wird, in dem der Lackfilm auf der Oberfläche des Golfballkörpers gebildet ist, 1250 nm oder mehr beträgt und eine Materialhärte der Abdeckung in Shore D-Härte weniger als 50 beträgt,
    wobei für die Messung der Eindringtiefe,

    a) der Golfball geschnitten wurde, um eine Halbkugel zu erhalten,

    b) auf der Halbkugel ein Querschnitt freigelegt wurde, der durch den Mittelpunkt des Golfballs verläuft, wobei der Querschnitt einen Querschnitt des Lackfilms einschließt,

    c) der Querschnitt der Halbkugel durch ein Kryo-Mikrotom horizontal gemacht wurde,

    d) ein Indenter eines Nanoindenters mit dem Querschnitt des Lackfilms in Kontakt gebracht und in einer Richtung senkrecht zu dem Querschnitt gepresst wurde, und

    wobei die Messbedingungen der mit dem Nanoindenter gemessenen Eindringtiefe des Lackfilms sind:

    Nanoindenter: "ENT-2100" erhältlich bei ELIONIX Inc.,

    Temperatur: 30 °C,

    Indenter: Berkovich-Indenter (65,03° As (h) = 26,43 h2),

    Anzahl der Unterteilungen: 500 Schritte, Schrittweite: 20 msec (100 mgf), und

    wobei die Eindringtiefe die Vorschubdistanz des Indenters in nm ist, wenn die Belastung 30 mgf beträgt.


     
    2. Golfball nach Anspruch 1, wobei ein Verlusttangens tan δ des Lackfilms, der durch Messung der dynamischen Viskoelastizität des Lackfilms erhalten wird, eine Spitzentemperatur von 60 °C oder weniger aufweist.
     
    3. Golfball nach Anspruch 1 oder 2, wobei der Speichermodul (E'120) des Lackfilms bei 120 °C 1,0×107 Pa oder mehr beträgt.
     
    4. Golfball nach einem der Ansprüche 1 bis 3, wobei der 10%-Elastizitätsmodul des Lackfilms 2 kgf/cm2 oder mehr beträgt.
     
    5. Golfball nach einem der Ansprüche 1 bis 4, wobei der Lackfilm ein Polyurethan als eine Harzkomponente enthält, wobei das Polyurethan als eine konstituierende Komponente (A) eine Polyisocyanatkomponente und (B) eine Polyolkomponente, die ein Polyrotaxan enthält, umfasst.
     
    6. Golfball nach Anspruch 5, wobei das Polyurethan ein Reaktionsprodukt ist, das unter einer Reaktionsbedingung erhalten wird, bei der das Molverhältnis (NCO/OH) der Isocyanatgruppe (NCO) von (A) der Polyisocyanatkomponente zu der Hydroxylgruppe (OH) von (B) der Polyolkomponente 0,95 oder mehr und 2 oder weniger beträgt, und
     
    7. Golfball nach Anspruch 5 oder 6, wobei das Polyrotaxan ein Cyclodextrin, ein lineares Molekül, das die cyclische Struktur des Cyclodextrins durchdringt, und Blockiergruppen umfasst, die an beiden Enden des linearen Moleküls angeordnet sind, um eine Dissoziation des Cyclodextrins zu verhindern, wobei mindestens ein Teil der Cyclodextrin-Hydroxylgruppen mit einer Caprolactonkette über eine -O-C3H6-O-Gruppe modifiziert ist.
     
    8. Golfball nach Anspruch 7, wobei das lineare Molekül des Polyrotaxans Polyethylenglykol ist und die Blockiergruppe des Polyrotaxans eine Adamantylgruppe ist.
     
    9. Golfball nach einem der Ansprüche 5 bis 8, wobei (B) die Polyolkomponente ferner mindestens ein Mitglied umfasst, das aus der Gruppe ausgewählt ist, die aus einem Polyetherpolyol, einem Polyesterpolyol, einem Polycaprolactonpolyol, einem Polycarbonatpolyol und einem Acrylpolyol besteht.
     
    10. Golfball nach einem der Ansprüche 5 bis 9, wobei (B) die Polyolkomponente das Polyrotaxan in einer Menge im Bereich von 10 Massen-% bis 100 Massen-% enthält.
     
    11. Golfball nach einem der Ansprüche 5 bis 10, wobei eine Harzkomponente des Lackfilms ferner ein Vinylchlorid-Vinylacetat-Copolymer und/oder ein modifiziertes Produkt davon enthält.
     
    12. Golfball nach einem der Ansprüche 5 bis 11, wobei der Lackfilm ferner ein modifiziertes Silikon umfasst.
     
    13. Golfball nach einem Anspruch 12, wobei eine Menge des modifizierten Silikons im Bereich von 0,01 Massenteilen bis 10 Massenteilen, bezogen auf 100 Massenteile der Harzkomponente, die den Lackfilm bildet, liegt.
     
    14. Golfball nach einem der Ansprüche 5 bis 13, wobei (A) die Polyisocyanatkomponente ein Isocyanurat von Hexamethylendiisocyanat und ein Isocyanurat von Isophorondiisocyanat enthält.
     


    Revendications

    1. Balle de golf comprenant un corps de balle de golf ayant un revêtement, et un film de peinture recouvrant le corps de balle de golf, dans laquelle un module élastique à 10 % du film de peinture est inférieur ou égal à 75 kgf/cm2, un module de conservation (E'150) à 150 °C du film de peinture obtenu en mesurant la viscoélasticité dynamique du film de peinture est égal ou supérieur à 1,0 x 107 Pa, une profondeur d'indentation du film de peinture mesurée par un nano indenteur dans un état dans lequel le film de peinture est formé sur la surface du corps de balle de golf est égale ou supérieure à 1250 nm, et une dureté du matériau du revêtement est inférieure à 50 en dureté Shore D,
    dans laquelle, pour la mesure de la profondeur de pénétration,

    a) la balle de golf a été coupée pour obtenir un hémisphère,

    b) sur l'hémisphère, une section transversale passant à travers le point central de la balle de golf a été exposée, dans laquelle la section transversale comprend une section transversale du film de peinture,

    c) la section transversale de l'hémisphère a été faite horizontalement par un cryo-microtome,

    d) un indenteur d'un nano indenteur a été mis en contact avec la section transversale du film de peinture et pressé dans une direction perpendiculaire à la section transversale, et

    dans laquelle les conditions de mesure de la profondeur d'indentation du film de peinture mesurée par le nano indenteur sont :

    nano indenteur : « ENT-2100 » disponible chez ELIONIX Inc.,

    température : 30 °C,

    indenteur : indenteur Berkovich (65,03° As (h) = 26,43 h2),

    nombre de partitions : 500 cycles, intervalle d'un cycle : 20 msec (100 mgf), et dans laquelle la profondeur d'indentation représente la distance d'avancement de l'indenteur en nm lorsque la charge est de 30 mgf.


     
    2. Balle de golf selon la revendication 1, dans laquelle une tangente de perte tan δ du film de peinture obtenue en mesurant la viscoélasticité dynamique du film de peinture a une température de pic inférieure ou égale à 60 °C.
     
    3. Balle de golf selon la revendication 1 ou la revendication 2, dans laquelle un module de conservation (E'120) à 120 °C du film de peinture est égal ou supérieur à 1,0 x 107 Pa.
     
    4. Balle de golf selon l'une quelconque des revendications 1 à 3, dans laquelle le module élastique à 10 % du film de peinture est égal ou supérieur à 2 kgf / cm2.
     
    5. Balle de golf selon l'une quelconque des revendications 1 à 4, dans laquelle le film de peinture contient un polyuréthane en tant que composant résine, dans laquelle le polyuréthane comprend, en tant que composant constitutif, un composant polyisocyanate (A), et un composant polyol (B) contenant un polyrotaxane.
     
    6. Balle de golf selon la revendication 5, dans laquelle le polyuréthane est un produit de réaction obtenu dans une condition réactionnelle dans laquelle un ratio molaire (NCO / OH) d'un groupement isocyanate (NCO) du composant polyisocyanate (A) sur un groupement hydroxyle (OH) du composant polyol (B) est égal ou supérieur à 0,95 et inférieur ou égal à 2,0.
     
    7. Balle de golf selon la revendication 5 ou la revendication 6, dans laquelle le polyrotaxane comprend une cyclodextrine, une molécule linéaire perçant à travers la structure cyclique de la cyclodextrine, et des groupements de blocage situés aux deux extrémités de la molécule linéaire pour empêcher une dissociation de la cyclodextrine, dans laquelle au moins une partie des groupements hydroxyles de la cyclodextrine est modifiée avec une chaîne caprolactone via un groupement -O-C3H6-O-.
     
    8. Balle de golf selon la revendication 7, dans laquelle la molécule linéaire de polyrotaxane est du polyéthylène glycol, et le groupement de blocage du polyrotaxane est un groupement adamantyle.
     
    9. Balle de golf selon l'une quelconque des revendications 5 à 8, dans laquelle le composant polyol (B) comprend en outre au moins un élément choisi dans le groupe constitué d'un polyol polyéther, d'un polyol polyester, d'un polyol polycaprolactone, d'un polyol polycarbonate, et d'un polyol acrylique.
     
    10. Balle de golf selon l'une quelconque des revendications 5 à 9, dans laquelle le composant polyol (B) contient le polyrotaxane dans une quantité allant de 10 % en poids à 100 % en poids.
     
    11. Balle de golf selon l'une quelconque des revendications 5 à 10, dans laquelle un composant résine du film de peinture contient en outre un copolymère chlorure de vinyle-acétate de vinyle et/ou un produit modifié de celui-ci.
     
    12. Balle de golf selon l'une quelconque des revendications 5 à 11, dans laquelle le film de peinture comprend en outre une silicone modifiée.
     
    13. Balle de golf selon la revendication 12, dans laquelle une quantité de silicone modifiée va de 0,01 partie en poids à 10 parties en poids par rapport à 100 parties en poids du composant résine constituant le film de peinture.
     
    14. Balle de golf selon l'une quelconque des revendications 5 à 13, dans laquelle le composant polyisocyanate (A) contient un isocyanurate d'hexaméthylène diisocyanate et un isocyanurate d'isophorone diisocyanate.
     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description