CN103923453A - Thermoplastic Polyurethane Resin Composition Used For Golfball Coverage Layer And Method For Manufacturing The Golfball Coverage Layer By Using Composition - Google Patents
Thermoplastic Polyurethane Resin Composition Used For Golfball Coverage Layer And Method For Manufacturing The Golfball Coverage Layer By Using Composition Download PDFInfo
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- CN103923453A CN103923453A CN201410019337.7A CN201410019337A CN103923453A CN 103923453 A CN103923453 A CN 103923453A CN 201410019337 A CN201410019337 A CN 201410019337A CN 103923453 A CN103923453 A CN 103923453A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- A—HUMAN NECESSITIES
- A63—SPORTS; GAMES; AMUSEMENTS
- A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
- A63B37/00—Solid balls; Rigid hollow balls; Marbles
- A63B37/12—Special coverings, i.e. outer layer material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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Abstract
The present invention provides a thermoplastic polyurethane resin composition used for a golfball coverage layer and a method for manufacturing the golfball coverage layer by using the composition. The thermoplastic polyurethane resin composition of the present invention, relative to 100 parts by weight of thermoplastic polyurethane resin, comprises 2-10 parts by weight of TPU color masterbatch, 0.1-10 parts by weight of organic peroxides and 0.1-10 parts by weight of isocyanate, wherein relative to 100 parts by weight of polymer resin containing 15-60 parts by weight of isocyanate, 5-40 parts by weight of chain extender and 30-70 parts by weight of polyhydric alcohols mixture, the thermoplastic polyurethane resin contains 0.1-5 parts by weight of montan class wax as a lubricant, so that the smooth performance at formation can be improved, and the cutting resistance and elasticity of the golfball can be improved.
Description
Technical field
The present invention relates to a kind of for golf ball tectum (Golf ball cover, coating layer, skin) thermoplastic polyurethane (Thermoplastic Polyurethane:TPU) resin combination and the tectal manufacture method of golf ball of utilizing said composition.In further detail, fairness (fairness) in the time of can improving ejection formation (injection molding), and can improve TPU(Thermoplastic polyurethanes) composition and the tectal manufacture method of golf ball of utilizing said composition for the cutting resistance of golf ball and elastic golf ball tectum.
Background technology
Generally, the outstanding golf ball of performance is should flying distance far away, and controlled should have outstanding spin rate (spin rate), iron shot time.Common golf ball manufacturing company's use ionomer resin (ionomer resine) or heat-curable urethane (thermosetting polyurethane) are as the tectal composition of golf ball.
Above-mentioned ionomer resin has outstanding weather resistance, therefore, and the most frequently used golf ball tectum composition of doing.But ionomer resin is too hard, reduce spin rate, when having the golf ball of outstanding performance, manufacture is subject to certain restrictions.
Thereby, in order to improve this problem, hold the golf ball manufacturing company of leading technology in order to improve cutting resistance, bounce-back property (rebound resilience), flying distance, ball-handling, use heat-curable urethane.Can regulate by the step with post-polymerization in two-pack type mode injection model the degree of crosslinking of above-mentioned thermosetting polyurethane resin, thereby can improve cutting resistance and bounce-back property etc., composition be manufactured to the laggard marketing of polyurethane golf ball by cast molding method and sell.
But, in this field, still wish to work out and not only there is outstanding cutting resistance and rebounding characteristic, the golf ball tectum composition of the fairness of improving while also thering is ejection formation.
For this reason, the present inventor studies the tectal TPU(Thermoplastic polyurethanes) composition of golf ball of the fairness of improving when not only having outstanding cutting resistance and rebounding characteristic but also having ejection formation, when selecting to have outstanding long durability as being used for the synthetic polyvalent alcohol of urethane, water tolerance and elastic ethoxylated polyhydric alcohol (ether polyol) are as main polyvalent alcohol, and, partial cross-linked in order to cause when the urethane polymerization, used the polyol blend that contains superbranched polyol (Hyper Branched polyol), and, when use contains after ejection formation thermal curable and has the chainextender (chain extension agent) of acrylate of hydroxy of two keys, fairness in the time of can guaranteeing ejection formation, and can obtain and improve cutting resistance, ball-handling property, directivity, flying distance, the golf ball tectum TPU(Thermoplastic polyurethanes) composition of rear rotation, thereby completed the present invention.
Summary of the invention
For this reason, the object of the present invention is to provide a kind of fairness while improving ejection formation, meanwhile, can improve cutting resistance and the elastic golf ball tectum TPU(Thermoplastic polyurethanes) composition of golf ball.
Another object of the present invention is to provide a kind of fairness while improving ejection formation and can improves cutting resistance and the tectal manufacture method of elastic golf ball of golf ball.
In order to realize the problems referred to above, the invention provides a kind of golf ball tectum TPU(Thermoplastic polyurethanes) composition, thermoplastic polyurethane (TPU) resin with respect to 100 weight parts, said composition comprises 2～10 weight part TPU colour batches (color master batch), 0.1～10 weight part organo-peroxide and 0.1～10 weight part isocyanic ester, wherein, 15～60 weight part isocyanic ester that comprise with respect to 100 weight parts, the polymer resin of 5～40 weight part mixture of chain extenders and 30～70 weight part polyol blends, described thermoplastic polyurethane (TPU) resin comprises 0.1～5 weight part and covers dawn class wax as lubricant.
Preferably, in composition according to the present invention, as above-mentioned isocyanic ester, comprise naphthalene-1,5 vulcabond (NDI; Naphthalene-1,5-diisocyanate), PPDI (PPDI; Paraphenylene diisocyanate), dimethyl diphenyl group diisocyanate (TODI; Tolidine diisocyanate), the sub-methane diisocyanate (MDI of phenylbenzene; Diphenyl methane diisocyanate), tolylene diisocyanate (TDI; Tolunene diisocyanate), hexamethylene diisocyanate (HDI; Hexamethylene diisocyanate), dicyclohexyl methane diisocyanate (H12MDI; Dicyclohexylmethane diisocyanate), isophorone diisocyanate (IPDI; Isoporone diisocyanate) or its two or more composition.
And, preferably, as above-mentioned mixture of chain extenders, comprise freely two or more in the following group forming of choosing: ethylene glycol (ethylene glycol), glycol ether (diethylene glycol), butyleneglycol (butane diol), hexylene glycol (hexane diol), TriMethylolPropane(TMP) (trimethylol propane), polytetramethylene ether diol (poly tetra methylene ether glycol), hexanediyl ester (salt) (Hexanediol diacrylate) and butylene glycol diacrylate (salt) (Butanediol diacrlate).
And, preferably, as above-mentioned polyol blends, the mixture that comprises ethoxylated polyhydric alcohol and superbranched polyol (Hyper branched polyol).
And, preferably, as above-mentioned organo-peroxide, comprise dialkyl peroxide (Dialkyl peroxide), ketal peroxide (Peroxy ketal), peroxy esters (Peroxy ester), peroxide list carbonate (Peroxy monocarbonate), peroxidation two acyls (Diacyl peroxide), diperoxyization two carbonic ethers (Diperoxy dicarbonate), hydrogen peroxide (Hydro peroxide), ketone peroxide (Ketone peroxide), dicumyl peroxide (Dicumyl peroxide) two (2-tert-butyl hydroperoxide sec.-propyl) benzene (Di-(2-t-butylperoxyisopropyl benzene) or its two or more composition.
In order to solve another above-mentioned problem, the invention provides the tectal manufacture method of golf ball, it comprises: mix isocyanic ester, mixture of chain extenders and polyol blends, by polyaddition reaction, manufacture polymer resin; In the polymer resin of above-mentioned manufacture, allotment is covered dawn class wax and is extruded, and obtains thermoplastic polyurethane (TPU) resin; In above-mentioned TPU(Thermoplastic polyurethanes), allocate TPU colour batch, organo-peroxide and isocyanic ester; And, by above-mentioned composite ejection formation (injection molding).
In the tectal manufacture method of golf ball according to the present invention, preferably, after by the step of above-mentioned composite ejection formation, also comprise: at the temperature of 50 ℃～110 ℃, carry out the step of above aging annealing (Aging Annealing) in 2 hours.
Invention effect
According to golf ball tectum TPU(Thermoplastic polyurethanes) composition of the present invention, not only can carry out ejection formation, the fairness in the time that ejection formation can also being improved.
And, according to golf ball tectum TPU(Thermoplastic polyurethanes) composition of the present invention, the tough cutting resistance that the impact while making golf club have the shorter iron of utilization to knock golf ball brings, and, improve elasticity, increase the flying distance with a rod square stance.
Embodiment
According to structure and color golf ball, be divided into multiple, have by the centre of sphere (Core) and wrap the double-layer structure that the tectum of this centre of sphere forms double-deck ball, with the outer centre of sphere that wraps, three layers of ball of tectal three-decker are also installed in the above, are wrapped three layers, the centre of sphere, four layers of ball of four layers, five layers of ball, also have in addition tectum with versicolor colorful golf ball etc., golf ball develops into more kinds of structures and various ways gradually.
The present invention provides tectum (Cover) to use TPU(Thermoplastic polyurethanes) composition in the golf ball of these all structures, not only can carry out ejection formation, and the fairness while also improving ejection formation, improves cutting resistance and elasticity.
For this reason, according to golf ball tectum TPU(Thermoplastic polyurethanes) composition of the present invention, thermoplastic polyurethane (TPU) resin with respect to 100 weight parts, contain 2～10 weight part TPU colour batches, 0.1～10 weight part organo-peroxide and 0.1～10 weight part isocyanic ester, wherein, 15～60 weight part isocyanic ester that contain with respect to 100 weight parts, the polymer resin of 5～40 weight part mixture of chain extenders and 30～70 weight part polyol blends, above-mentioned thermoplastic polyurethane (TPU) resin contains 0.1～5 weight part and covers dawn class wax as lubricant.
After mixing 15～60 weight part isocyanic ester, 5～40 weight part mixture of chain extenders and 30～70 weight part polyol blends, pass through polyaddition reaction, manufacture polymer resin, the illiteracy dawn class wax of allocating 0.1～5 weight part in the polymer resin of 100 weight parts is prepared according to golf ball tectum TPU(Thermoplastic polyurethanes) of the present invention by extrusion moulding after as lubricant.
As the above-mentioned isocyanic ester for the preparation of polymer resin, can use and the same or similar isocyanic ester of isocyanic ester that is generally used for preparing urethane, preferably, can use aromatic isocyanate, aliphatic isocyanates or alicyclic isocyanate, more preferably, can adopt and be selected from naphthalene-1,5 vulcabond (NDI; 1,5naphthalene diisocyanate), PPDI (PPDI:paraphenylene diisocyanate), dimethyl diphenyl group diisocyanate (TODI; Tolidine diisocyanate), the sub-methane diisocyanate (MDI of phenylbenzene; Diphenyl methane diisocyanate), tolylene diisocyanate (TDI; Tolunene diisocyanate), hexamethylene diisocyanate (HDI; Hexamethylene diisocyanate), dicyclohexyl methane diisocyanate (H12MDI; Dicyclohexylmethane diisocyanate), isophorone diisocyanate (IPDI; Isoporone diisocyanate) material or in the group being formed by its two or more mixture.
And, preferably, as above-mentioned mixture of chain extenders, comprise glycolss such as selecting free ethylene glycol (ethylene glycol), glycol ether (diethylene glycol), butyleneglycol (butane diol) or hexylene glycol (hexane diol); Three alcohols such as TriMethylolPropane(TMP) (trimethylol propane); Two or more in the group that the esters of acrylic acid such as polytetramethylene ether diol, hexanediyl ester (salt) (hexanediol diacrylate) or butylene glycol diacrylate (salt) (butanediol diacrlate) forms.More preferably, mix butyleneglycol and diacrylate (diacrlate).
And, preferably, the mixture that comprises ethoxylated polyhydric alcohol and superbranched polyol (Hyper branched polyol) as above-mentioned polyol blends.
Above-mentioned superbranched polyol is to mix dendritic polymer (dendritic polymer), multiple functional radical polyvalent alcohol and polytetramethylene ether diol (PTMG; Polytetramethylene etherglycol) and make to obtain after its reaction, hydroxyl value is 11.22～224.11mg KOH/g.
Preferably, the montanin wax (montanin wax) (Esters of montanic acids with ethylene glycol) that selects the ester of free montanic acid and ethylene glycol to make as the above-mentioned illiteracy dawn class wax of above-mentioned lubricant, the montanin wax of being made by the ester of montanic acid and glycerol (Esters of montanic acids with glycerine), the montanate that comprises montanic acid calcium (calcium montanate containing montanic acid esters), take montanic acid as basic ester blended wax (complex ester of montanic acid) (complex ester of montanic acid).
The above-mentioned illiteracy dawn below the polymer resin with respect to 100 weight parts is used 0.1 weight part, while carrying out the demoulding after ejection formation, and the detachment between mould was poor during class wax, and the demoulding is difficulty comparatively.And when the usage quantity of the above-mentioned illiteracy of the polymer resin dawn class wax with respect to 100 weight parts surpasses 5 weight part, polymer comprises lubricant more than saturation concentration, thereby, the possibility that cannot get rid of frosting (blooming) or move (migration).
Above-mentioned TPU colour batch refers to and in above-mentioned TPU resin, mixes colored pigment (for example, white pigment (TiO
2)) and a small amount of thermo-stabilizer after the extrusion moulding resin that is particle, its usage quantity is preferably in the scope of 2～10 weight parts.When the usage quantity of above-mentioned TPU colour batch is less than 2 weight part, color is excessively shallow, is difficult to manufacture the good ball of color, and when surpassing 10 weight part, the color of ball is too deep, is difficult to manufacture the good ball of color.
Above-mentioned organo-peroxide can be used as and causes partial cross-linked linking agent, particularly, preferably comprise dialkyl peroxide (Dialkyl peroxide), ketal peroxide (Peroxy ketal), peroxy esters (Peroxy ester), peroxide list carbonate (Peroxy monocarbonate), peroxidation two acyls (Diacyl peroxide), diperoxyization two carbonic ethers (Diperoxy dicarbonate), hydrogen peroxide (Hydro peroxide), ketone peroxide (Ketone peroxide), dicumyl peroxide (Dicumyl peroxide), two (2-tert-butyl hydroperoxide sec.-propyl) benzene (Di-(2-t-butylperoxyisopropyl benzene)) or its two or more composition.Preferably, the usage quantity of above-mentioned organo-peroxide is in the scope of 0.1～10 weight part, when above-mentioned organo-peroxide is less than 0.1 weight part, cannot react with TPU, there is significant deficiency in the tectal cutting resistance of golf ball, likely lose the function as golf ball, when surpassing 10 weight part, even fully react with TPU, also can residual reactive group, in ejection formation step, likely produce bad, and, the tectal hardness of golf ball is high, reduces touch, loses the function as golf ball.
And, as the isocyanic ester of other use, be also partial cross-linked for causing, the isocyanates that can use when manufacturing polymer resin, choice for use is identical or different, preferably uses naphthalene-1,5 vulcabond.Preferably, the usage quantity of the isocyanic ester of above-mentioned other use, in the scope of 0.1～10 weight part, when the usage quantity of above-mentioned other isocyanic ester is not during in above-mentioned scope, there will be the problem identical with organo-peroxide.
More specifically, at golf ball tectum according to the present invention, with in TPU(Thermoplastic polyurethanes) composition, TPU(Thermoplastic polyurethanes) is prepared by the method comprising the following steps.
I) by 30～70 weight part polyol blends (for example, 10～20 weight part superbranched polyols and 20～50 weight part ethoxylated polyhydric alcohols) and 5～40 weight part mixture of chain extenders are (for example, 4～35 weight part butyleneglycols and 1～5 parts by weight of acrylic acid diol ester (diol acrylate)) at 80～100 ℃, stir the first mixing step mixing 30～60 minutes;
Ii) in the mixture obtaining, mix 10～30 weight part isocyanic ester (for example, MDI) in the first mixing step, at 50～60 ℃, with 300～1,000rpm speed polymerization, second mixing step of 10～30 minutes;
Iii) until the resultant obtaining at above-mentioned the second mixing step reaches 120～130 ℃ of temperature of reaction, make 5～30 weight part isocyanic ester (for example, naphthalene-1,5 vulcabond) with 300rpm～1,, until there is the 3rd mixing step of muddy (gonorrhoea) phenomenon in the polymerization of 000rpm speed;
While there is research of chaotic phenomenon in the resultant iv) obtaining in above-mentioned the 3rd mixing step, in aggregation container, insert split pin, in the temperature range of 60～140 ℃, the aging step of aging 1～48 hour;
V) the pulverising step of the resultant obtaining in above-mentioned aging step being pulverized in the temperature below 0 ℃;
Vi) in the crushed material obtaining, allocate the adaptation step of the exterior lubricant of 0.1～5 weight part in the above-mentioned pulverising step of 100 weight parts;
Vii) the step of the composite obtaining in above-mentioned adaptation step being extruded in the temperature range of 150～300 ℃.
Above-mentioned the first mixing step is the step of mixing first equably two or more polyol compounds and two or more chainextender, thereby above-mentioned second step mixing step is isocyanate compound and polyol blend polymerization to be prepared in fact to the step of urethane.According to observations, above-mentioned isocyanate compound and above-mentioned polyol blend immediate response after mixing.
Especially, in the present invention, the urethane of the resultant of reaction as obtaining at above-mentioned the second mixing step is carried out aging, thereby can regulate the molecular weight etc. of urethane.Wherein, in baking box, according to the time, adjust and to carry out agingly, at 120 ℃ of baking boxs, in the time of aging 4 hours, can draw best molecular weight, digestion time is longer, and molecular weight is larger, this be because the arrangement between molecule along with temperature increases.
Afterwards, as the urethane of above-mentioned resultant of reaction, by known pulverizing, lubricant allotment and extrusion step etc., be adjusted to suitable size etc.Be shaped to and can be processed into by such pulverizing and extrusion step the TPU(Thermoplastic polyurethanes) particle of product.
Then, manufacture and to there is good cutting resistance and the tectal method of elastic golf ball comprises the following steps.
1. in TPU(Thermoplastic polyurethanes) particle (TPU) 100 weight parts of above-mentioned acquisition, allocate TPU colour batch for 1～10 weight part toning, 0.1～10 weight part as organo-peroxide and 0.1～10 weight part isocyanic ester of linking agent, extrude, at 50～100 ℃, carry out the more than 2 hours steps that is dried, dehumidifies;
2. the hybrid resin obtaining is carried out to ejection formation (injection) step in above-mentioned drying step, with certain temperature and penetrate pressure and issuing velocity carries out ejection formation and cooling step;
3. the polishing of the golf ball cover surface of ejection formation (buffing, polishing) step;
4. in order to ensure the tectal tough and tensile weather resistance of golf ball and the outstanding bounce-back of ejection formation, at 50～110 ℃ of temperature, carry out more than 2 hours the aging annealing steps of maximum 72 hours;
5. basis paint (pigment, coating) sprays and drying step;
6. brand print steps; And,
7. top layer paint injection and drying step.
As required, may be combined in the materials such as the normally used additive in this field, the anti-blushing agent such as a small amount of, thermo-stabilizer, UV light absorber, flow promoters, its usage quantity is within the normally used content in this area.
And, when TPU(Thermoplastic polyurethanes) composition according to the present invention is used as to the tectum of golf ball, external diameters (diameter) two-layer, all centre ofs sphere of three layers, four layers are 39.5mm～41.5mm, tectal thickness is 0.6mm～1.6mm, the Shao Shi-D(shore-D of tectum composition) hardness is 45～60.
And the weight of the centre of sphere (except crust, outside tectum) is 38.5gr～40.5gr.
Below, the preferred embodiments of the present invention and comparative example are described.The embodiment the following describes, for illustrating the present invention, is not for limiting scope of the present invention.
Embodiment 1～4
5 weight part superbranched polyols and 60 weight part ethoxylated polyhydric alcohols and 15 weight part butyleneglycols and 5 parts by weight of acrylic acid diol esters are stirred 45 minutes at 80 ℃, carried out mixing for the first time.To in the mixture of above-mentioned acquisition, mix 10 weight part MDIs, at 55 ℃, with 8000rpm speed, stir 20 minutes, make its polymerization.To drop into 5 weight part naphthalene-1 in the resultant of above-mentioned acquisition, 5 vulcabond, until temperature of reaction reaches 125 ℃, the speed with 8000rpm stirs polymerization afterwards, until there is research of chaotic phenomenon.When the resultant generation research of chaotic phenomenon of above-mentioned acquisition, to aggregation container, insert split pin, in the temperature range of 100 ℃ aging 24 hours, aging resultant is pulverized in the temperature below 0 ℃, in the crushed material of above-mentioned 100 weight parts, allocate the exterior lubricant of 0.1～5 weight part, composite in above-mentioned acquisition is extruded in the temperature range of 200 ℃, thereby be particulate state by thermoplastic polyurethane (TPU) resin forming.
Colour batch for toning below allocating in the TPU(Thermoplastic polyurethanes) particle (TPU) of the above-mentioned acquisition of 100 weight parts shown in table 1, as organo-peroxide and the isocyanic ester of linking agent, extrusion moulding, at 50 ℃, carry out more than 8 hours dehumidifying and be dried, then, dry hybrid resin is dropped into golf ball tectum Jet forming machine, with 220 ℃, 130Kg/cm
2pressure and the issuing velocity that penetrates 80% degree of pressure carry out ejection formation, cooling at normal temperatures.Then, the golf ball cover surface that grinding is penetrated, at the temperature of 90 ℃, aging annealing more than 2 hours, is sprayed basis paint, after being dried, printing brand, dry after spray skin layer paint, thus manufacture golf ball.
Comparative example 1
Used the golf ball (ProductName: BIGYARD DISTANCE) that replaces thermoplastic polyurethane (TPU) resin with sarin (surlyn) (ionic) resin.
Table 1
1. T.P.U. resin (Polyurethane Thermoplastic Elastomer: Thermoplastic Polyurethane Elastomer)=proportion (ASTM D792): 1.16, Shao Shi-D hardness (ASTM D2240): 45-51, tensile strength (ASTM D412): 476Kgf/cm
2, unit elongation (ASTM D412): 507%, tearing strength (tear strength) (ASTM D624): 168kgf/cm
2, melting index (melt index) (ASTM D1238): the resin of 5.0g/10min.
2. TPU colour batch: mixture of white pigment (TiO in above-mentioned T.P.U. resin 100 weight parts
2), high-visibility pigment 5 weight parts and thermo-stabilizer 1 weight part, the resin that extrusion moulding is particle.
3. DCP-99%: Holland produces the dicumyl peroxide (DICUMILPEROXIDE) of AKZO company, the two (1-methyl isophthalic acid-phenylethyl (PEROXIDE of superoxide, BIS(1-METHYL-1-PHENYLETHYL)) chemical name, CAS 80-43-3, organo-peroxide purity adds sulphur agent at more than 99% organo-peroxide.
4.
770DF: the BASF(BASF that the Germany produces) thermo-stabilizer of company, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) (bis (2,2 for ester, 6,6-tetramethyl-4-piperidyl) sebacate) chemical name, CAS 52829-07-09, is called as Tinuvin770 as trade(brand)name.
5. sarin 9910: the product of Dupont (Dupont) company, to utilize zinc (Zn) metal ion to carry out the trade(brand)name of ionomer (ionomer) resin of copolymerization the randomcopolymer carboxyl of ethene and acrylate (methacrylate), proportion is 0.97, Shao Shi-D hardness is 64, and tensile strength is 253kg/cm
2, the resin that unit elongation is 290%.
6. sarin 8940: the product of du pont company, and utilize sodium (Na) metal ion to carry out the trade(brand)name of the ionomer resin of copolymerization ethene and acrylic acid randomcopolymer carboxyl, proportion is that 0.95, Shao Shi-D hardness is 65, tensile strength is 337kg/cm
2, the resin that unit elongation is 470%.
7. sarin masterbatch: sarin 8940 and sarin 9910 be take to weight and according to the ratio of 50:50, mix as benchmark, and mixture of white pigment (TiO therein
2) and high-visibility pigment 5 weight parts and thermo-stabilizer 1 weight part, extrusion moulding is granular resin.
8. Irganox1076: oxidation inhibitor and thermo-stabilizer that Switzerland vapour Ba-Jia Ji (Ciba-Geigy) company produces, its main component: 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl (octadecyl3 (3,5-di-tert butyl-4-hydroxy phenyl) propionate).
9. HRTDUR115: the trade(brand)name of ten thousand rich (JOHNSON FINE CHEMICAL) company is believed in the Chinese village, naphthalene-1,5 vulcabond (N D I:1.5Diisocyanate Naphthalene).
evaluation Example
The characteristic of having evaluated as follows the golf ball of above-described embodiment 1～4 and comparative example 1, has illustrated result in table 2.The experimental value separately that is used for the golf ball experiment slice of measurement is separately the mean value of 20 times.
hardness: the Shao Shi-D qualimeter that utilizes German Zi Weike (Zwinc) company to produce, according to the experimental technique of German standard specification DIN53505, numerical value is higher, represents that its hardness is higher, and surface is harder.
c.O.R(Coefficient of Restitution: bounce-back property coefficient, resilience factor): utilize U.S. ADC(Autometed Design Company) company ball, the centre of sphere COR/Durability experimental installation produced, speed with 125Ft/sec is got, the weather resistance of having measured bounce-back property and ball, the centre of sphere, the higher expression elasticity of its numerical value is relatively outstanding, and weather resistance is outstanding.
atti Comperssion(compression strength tester): the compression strength tester that U.S. ATTI company produces, while utilizing this trier to test, show numerical value, the higher expression ball of numerical value is relatively hard.
ball spin rate: utilize the robot rotary test rig that Japanese Miyamae company produces (trade(brand)name: MIYA ROBO-3) measured with the golf club of pole face (LOFT) angle 9.5 degree, rod, with the rotation number of the golf ball of 45m/sec bar head speed square stance, is scaled per minute rotation number (unit: value RPM).
Flying distance: utilize robot rotary test rig (trade(brand)name: MIYA ROBO-3), measured the numerical value of the flying distance of the ball while batting experiment under the condition identical with ball spin rate, numerical value is higher, the distance that is illustrated in general golf course ball flight is far away, is outstanding golf ball.
total flying distance: the flying distance of ball and the numerical value that rolling distance is added together while batting experiment under the condition identical with flying distance, numerical value is higher, and expression is the outstanding golf ball that distance is far away.
ball touch: 200 general linksmans (almost below 10) carry out the result of postevaluation touch reaction under battle conditions at golf course, are divided into general (△), good (zero), very good (◎).
cutting resistance: golf ball outward appearance is golf club PW(Pitching Wedge, pitching wedge), speed with bar head speed 35m/sec is knocked same area 1 time～6 times repeatedly, the evaluation result of more each tectal cutting resistance of golf ball, is divided into general (△), good (zero), very good (◎).
Table 2
The result of summing up above-mentioned table 2 is known, use is compared with comparative example according to the golf ball of the embodiment 1～4 of TPU(Thermoplastic polyurethanes) composition of the present invention manufacture, can improve degree of crosslinking, has good cutting resistance, and, can improve the tactile feel of the ball, directivity and rear verticity.
Claims (7)
1. a golf ball tectum TPU(Thermoplastic polyurethanes) composition, wherein,
TPU(Thermoplastic polyurethanes) with respect to 100 weight parts, described composition comprises 2～10 weight part TPU colour batches, 0.1～10 weight part organo-peroxide and 0.1～10 weight part isocyanic ester, wherein, with respect to the polymer resin that comprises 15～60 weight part isocyanic ester, 5～40 weight part chainextenders and 30～70 weight part polyol blends of 100 weight parts, described TPU(Thermoplastic polyurethanes) comprises 0.1～5 weight part and covers dawn class wax as lubricant.
2. golf ball tectum TPU(Thermoplastic polyurethanes) composition according to claim 1, wherein,
As described isocyanic ester, comprise naphthalene-1,5 vulcabond, PPDI, dimethyl diphenyl vulcabond, the sub-methane diisocyanate of phenylbenzene, tolylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate or its two or more composition.
3. golf ball tectum TPU(Thermoplastic polyurethanes) composition according to claim 1, wherein,
As mixture of chain extenders, comprise freely two or more in the following group forming of choosing: ethylene glycol, glycol ether, butyleneglycol, hexylene glycol, TriMethylolPropane(TMP), polytetramethylene ether diol, hexanediyl ester and butylene glycol diacrylate.
4. golf ball tectum TPU(Thermoplastic polyurethanes) composition according to claim 1, wherein,
The mixture that comprises ethoxylated polyhydric alcohol and super cladodification polyvalent alcohol as described polyol blends.
5. golf ball tectum TPU(Thermoplastic polyurethanes) composition according to claim 1, wherein,
As described organo-peroxide, comprise dialkyl peroxide, ketal peroxide, peroxy esters, peroxide list carbonate, peroxidation two acyls, diperoxyization two carbonic ethers, hydrogen peroxide ketone peroxide, dicumyl peroxide two (2-tert-butyl hydroperoxide sec.-propyl) benzene or its two or more composition.
6. the tectal manufacture method of golf ball, it comprises:
Mix isocyanic ester, chainextender and polyol blends, by carrying out polyaddition reaction, prepare the step of polymer resin;
In prepared polymer resin, dawn class wax is covered in allotment, extrusion moulding, the step of acquisition TPU(Thermoplastic polyurethanes);
In described TPU(Thermoplastic polyurethanes), allocate the step of TPU colour batch, organo-peroxide and isocyanic ester; And
By the step of composite ejection formation.
7. the tectal manufacture method of golf ball according to claim 6, wherein,
After by the step of described composite ejection formation, also comprise:
At the temperature of 50～110 ℃, carry out the step of the aging annealing of 2 hours.
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| KR1020130004760A KR101437411B1 (en) | 2013-01-16 | 2013-01-16 | Thermoplastic Polyurethane Resin Composition for Golf Ball Cover and Method for Preparation of Golf Ball Cover Using the Same |
| KR10-2013-0004760 | 2013-01-16 |
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| US20210317332A1 (en) * | 2020-04-09 | 2021-10-14 | Acushnet Company | Method of making golf ball and resulting golf ball |
| JP2023531337A (en) | 2020-07-02 | 2023-07-24 | ネクセン コーポレーション | Resin composition for golf ball cover |
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| KR20140092575A (en) | 2014-07-24 |
| KR101437411B1 (en) | 2014-09-04 |
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