DE1578557A1 - Improvements in or in relation to play building - Google Patents

Description

Improvements in or regarding. Game balls

The invention relates to game balls and, more particularly, to balls that as golf balls are useful for general games and Practicing driving strokes

Golf balls used in golf courses and competitions, are in terms of durability, flight and playability of high quality. However, such golf balls are expensive. It is customary to use BU general game awakenings and sum Above, s.B «by Drift blows, use cheaper balls instead of tournament balls, see below. It is required of the cheaper ball that it Durability, plug-in and game-like properties that only exist differ little from those of a tournament ball · In particular, will Required of the exercise ball that he has a good sonic stability and

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The ball has good flight characteristics when it is hit with a golf club and covers almost the same distance as a tournament ball. In addition, when hitting the exercise ball you should have the same sluggishness as possible with the tournament ball and it should give the same "click ¹ *" as a tournament ball when you hit it.

Governed according to the present invention a game ball is prepared consisting of a 2-iisehung of (Α) Guaai and (B) a thermoplastic homopolymers of styrene or substituted Sty / ³ or a thermoplastic (/ © polymeric Xerpolymeren or interpolymers of styrene or substituted styrene with 1) acrylonitrile or substituted acrylonitrile and / or 2) an alkyl ester of acrylic or methacrylic acid and / or 3) a diene. The rubber portion of the mixture makes up 10 to 90% by weight of the mixture. The preferred diene is butadiene or isoprene. The rubber used can be natural or synthetic rubber, preferably the mixture contains both synthetic rubber, e.g. B ₀ cis-polybutadiene and natural rubber _o

Prevented copolymers of styrene are formed from butadiene, acrylonitrile or methyl methacrylate.

Kl «substituted styrenes can be alkylated, halogenated or be carboxylated styrenes. The substituted acrylonitrile

1098867033 6 bath original

can alky! substitutes leg

The preferred interpolates include butadiene, styrene and Methyl methacrylate or acrylonitrile · The latter are commercially available known as ABS polymers

A tetrapolymer can be used if smaller amounts of other polymer-soluble monomers such as monocarboxylic acids, e.g. acrylic acid, methacrylic acid or itaconic acid.

According to the present invention, there is also provided a method for producing a ball which can be used as a golf ball, wherein a mixture of the aforesaid composition is molded If desired, ice! filler is added to the calculated mixture, whereupon the mixture obtained is placed in a ball is shaped,

The amount of rubber is preferably 20 to 80% by weight and in particular 30 to 70% by weight of the mixture »

Examples of suitable synthetic Gusmiarten are polybutadiene (especially jcis-polybutadiene), copolymers of butadiene with Styrene and acrylonitrile, polybutylene, copolymers of ethylene with propylene or higher "olefins. Polyisoprene and polychloroprene. This means that mixtures or mixtures of

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synthetic rubber can include natural rubber and one or more types of synthetic rubbers. The rubber preferably consists of cis-polybutadiene or a mixture or mixtures of cis-polybutadiene with natural rubber. In this latter case, the ola polybutadiene should make up at least 50% by weight of the mixture or mixture. A high molecular weight cJB polybutadiene is preferred, eg _p B · a polymer which has a molecular weight of 2 10 ⁵ to 2 χ 10 ⁶ .

The mixture of the thermoplastic homopolymer or:

Together, meren and the rubber can by 'odsohen the two components in a mill or in an internal mixer at elevated temperature. The temperature can be 30 to 50 ⁰ G higher than the melting point of the thermoplastic component * Palis required »Fillers, dyes and antioxidants can be added to the mixture during mixing. The mixture can then be ^{cooled to 115 to 125 °} C. before the addition of a hardener, if desired, then the mixture can be cooled and chipped or granulated.

The mixtures are preferably cured and this is preferably achieved through the use of organic peroxide curing agents such as dicumyl peroxide, or, if so desired, curing can be carried out by irradiation. The use of sulfur has sur The consequence is that only the rubber component is crosslinked, which is why it is

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preferably a peroacyd hardener is used, which causes both or all of the components of the mixture to be revealed. This gives Han a highly elastic hall ₉ that is not deformed under the conditions of a golf club.

Usually, the curable component of the mixture is cured by Erhitsen to a higher temperature in the presence of a curing agent, suitable temperatures are from 150 bit 250 ⁰ G. Since the Hasse au usually iron, at a temperature from 150 to 250 ° C a ball is formed, it is practically to perform forming and hardening at the same time. 3) The Hasse can be shaped into a ball using various shaping processes, for example by injection molding, compression molding or compression molding. When the hasse is hardened by heat, the time it takes for hardening is usually about 20 to. 60 minutes depending on the half-life of the ferocyd hardener used

In hates that are based on resins, in which one is unsaturated Carboxylic acid used as a comonomer can hate one Contain filler material which can be an active filler, i.e. one of the both as a thermolabile crosslinking agent and also acts as a filler. If an active filler is used it is not necessary to add a cross-linking agent, since part of the filler is in this redness

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works. Examples of active fillers are zinc oxide and magnesium oxide, while an example of a substantially inactive filler includes titanium dioxide. The incorporation of a filler improves the properties of hatred, especially in Besug the cut resistance, which is extremely important for golf balls. “The filler-containing hates are still thermoplastic. The amount of filler material is usually 30 to 70 wt. of the polymer and depends on the size and weight of the ball to be produced · Although most fillers can be used, those with a »very high level of fillers are specific Weight preferred to minimize the load required.

A ball of the present invention can be molded in one piece or a composite ball made up of 2 or more Consists of ropes, β, B. the ball can have a core and a shell to have. The core consists of a mixture of (A) rubber and (B) a thermoplastic homopolymer made from a styrene or substituted styrene, or a thermoplastic copolymer », Terpolymers or interpolation of styrene or substituted Styrene with (1) acrylonitrile or substituted acrylonitrile and / or (2) an alkyl ester of acrylic or methacrylic acid and / or (3) a service. The proportion of rubber in the mixture is 10 to 90 wt .- ^ of the mixture.

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The shell can have the same or a different composition as the core. The sheath may B. S ₉ from one or more of the following ingredients ■ consisting of: a mixture of the type he vie in the patents and ....... ...... * (patent application by the same applicant of the same date of filing with the internal machining line B 4164/4240 and D 4165); Balata; trans-P olTraerlBaten a conjugated diolefins, Sb _and trans-PolyiBopren, trans- Poiybutadien "(which is preferably min» deotens Jtrans having a polymer content of 90 f>); c £ "-Polymerisaten of conjugated diolefins, β · · Β cis-polyisoprene, cis polybutadiene (preferably with an OIS Polyoergebalt of at least 50 5έ) ϊ natural Gumai; Polyurethanes; Polyamides; MiBchpolyiaerieaten iron butadiene and styrene; Polymers and copolymers iron ethylene; Polymers and copolymers of propylene; Composition sets like those in patents ....... and ....... (patent application D 49 338 Ic / 77 a and D 51 068 Ic / 77 a) 5 copolymers of unsaturated olefins with esters and unsaturated acids « sB methyl methaorylate butadiene monohydrate polymers, especially those with a high (especially predominant) methyl methacrylic content, or keoprene, especially in crystalline form.

The envelope can be ordered from one or more of those elastomeric materials described in British Patent 1,057 has been described

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The shell material can contain a filler, e.g. "inorganic fillers such as silicon dioxide, lead carbonate or titanium" oxide, the latter is particularly suitable, 12m the ball a white Give the appearance of eu.

The term "copolymers" used in this application is inclusive Polymers made up of two, three or more reactants were obtained (the monomers or partially polymerized © materials can be), interpolymers, block polymers, and Mixtures thereof.

The method by which the shell is connected to the core depends on the nature of the material used for the shell. If thermoplastic material "is used it can be applied either in an injection molding process, for _e B" in a process in which molten material along the periphery of the core, which is arranged centrally in a Kugelechale is pressed or may for example be applied in the form of two hemispherical shells which enclose the core and are adapted to it, which are closed along their united edges and form a smooth, complete, spherical shell · The last-mentioned method can also be applied to a non-thermoplastic shell material «

The means used to attach the sheath to the core are highly dependent on the nature of the bull

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and core material. Where the shell around the core is manufactured by an injection molding process, no auxiliary means are normally required for fastening, since the molten shell material comes into close contact with the periphery of the core, which leads to a firm connection between the two parts of the ball. there however, before the shell is formed, B.B. at the pressure foundation two hemispherical shells, an aid for attaching may be necessary be * e.g. an adhesive. A corresponding aid for fastening is found in mechanical locks, e.g. by you shape the core so that it catches or depressions in its Has surface to which the shell can be firmly attached when it is applied to the core.

There is another in accordance with the present invention form of golf ball in which the core itself is made up of $ »$ £ or more Ropes consist “This setup is very useful when you want to concentrate the weight of the ball in the center, even though it is can also be used in other circumstances · In this case Structure, the core can consist of a spherical inner part or inner core (e.g. a glass or steel ball) surrounded by two or more outer core parts which together form a spherical shell. If, for example, one has two outer core parts, then know they be in the arrangement of hemisphere shells that are common enclose the inner core and thereby result in a structure of spherical shape. The material composition of the interior

109886/0336

Core and outer core parts can be the same or different be, and one or more of the inner or outer core parts can be made from the mixture of $ umml and a honey polyamide, mixed polymers, Consist of serpolymers or interpolation of styrene, as described above·

The appropriate dimensions of the components of a composite Golf balls according to the present invention are as follows;

Diameter of the ball

4 «11 cm (1.62 inches) 4 * 27 cm (1.68 inches]

Two-component balls

Core diameter

preferred area

Layer thickness of the shell

preferred area

particularly preferred area

Three-component tennis balls

1.9-4.06 cm (0.75b ~ 1.6 inches)

2.54-3.92 e »(1.00-1.54 inches)

0.05-1.1 cm (0.020-0.435 inch)

0.102-0.7? cm (0.040-0.31 inch)

0.152-0.318 <sm (0.060-0.125 inch)

Inner core diameter

whole core diameter

Layer thickness of the shell

0.635-2.54 cm (0.25 = 1.00 inch)

1.9-4.06 cm (0.75-1.6 inches) 1.9-4.16 cm (0.75-1.64 in.) inches)

2.54-4.06 cm (1 ₉ 00-1.60 inches)

0.05-1.18 cm (0.020-0.465 inch)

0.102-0.86 cm (0.040-0.34 inch)

0.152-0.318 cm (0 ₉ 06ol 0.125 inch)

0.635-2.54 cm (0.25-1.00 inches)

1.9-4.16 cm (0.75-1.64 inches)

like with the Zveikomponentenball

109886/0336

The present invention relates to a ball which can be manufactured more economically than conventional golf balls. Golf balls »used in tournaments and competitions exist usually consisting essentially of a core, which is a learning center contains, which consists of a spherical rubber bag filled with a paste, wrapped with rubber thread and / or Grunmib & M and a shell made from balata or the like and molded onto the core. Such balls have excellent durability, flight and playability, however they are expensive to manufacture, commensurate with the length of the manufacturing process. For general gaming purposes and above A cheaper ball is claimed. Commercial balls of this type have hitherto been common the same structure as a sumier ball, but they had one solid rubber center and a cover made of cheaper material (* «B. Polychloroprene) as the veneer ball. These obungsb & llt are permanent, but they are nonetheless still relatively expensive in production.

The present invention relates to a shaped ball of polymeric composition without a thread-wrapped core, which has good plugging properties.

The balls of the present invention, especially where to look Balls formed from one piece of uniform density

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is, can have with advantage a oberflSehenmuster in which the pits and grooves are less than in the usual OberflSchenmustern, for example can wells of a diameter of 0.32 cm (0 _£ l3 ") has a depth of less than 0.033 cm (0.0i ; 3 ") and the depressions in the mesh patterns can have a depth of less than 0.028 cm (O _t Q11 ⁿ ).

The invention is illustrated by the following examples In Examples 1 to 5, the manufacture and testing of Solfbllen from one piece, and Examples 6 and 7 the fabrication describe and test two-component balls,

example 1

30 parts of a polystyrene of 2.1 ο viscosity to 2.25 centipoise, with a softening point 89-92 ⁰ C, both in accordance with BS 1493 were 52,5Teilen of ice - at polybutadiene (cis-content 97 $ i MII 4 100 ° 0 · 50) and 17 »5 parts of natural rubber ^{mixed in an internal mixer at 150 to 170 0} O until a homogeneous mixture was obtained, 40 parts of lead carbonate, 3 parts of titanium dioxide and 1 part of red pigment (for identification) added and mixed until a homogeneous mixture was obtained. • The mixture was cooled to 120 ⁰ C and 3.5 parts of dicumyl peroxide eugefügt _e

The mixture was then transferred to a film on a Walswerk and quickly cooled to room temperature Foil was 0.305 cm (0.120 inch) thick "

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Strips of 7 * 62 by 2.54 cm (3 by 1 inch) were cut from the film, these were compression molded and cured in the mold ^{at a temperature of 160 ° C. for 45 minutes} conventional Deckverhindungen for golf balls you -verglichene: Schnittfeetigkeit is given in arbitrary numbers, "said an earlier number anseigt better resistance · The results are further provided below in table I. · Sin ball ⁿ ° a 4 ₁ 11 cm diameter (1.62! inches) was formed from the hat and hardened, its cut resistance at play and its flight characteristics were beatismt, the values are further below in! Table I given

Example 2

42.5 ropes of an interpolate, consisting essentially of acrylonitrile butadiene and styrene (commercially available as Cycolao H) ₉ were mixed with 43 »1 parts of oia polybutadlene (of the same type as used in Example 1) and 14» 4 ropes of natural rubber was mixed in an internal mixer at 150 to 170 ⁰ C, obtained until a homogeneous mixture · 39 parts of lead carbonate, 3 ropes Sitandioxyd and 1 rope of a red pigment (but identification) were added and as long as mixed was obtained until a homogeneous mixture. The mixture was then cooled to 120 ⁰ C and 3.25 · ropes dicumyl peroxide eugefügt then was prepared from

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the mongrel a ball "B * with a diameter of 4.11 cm (1.62 inches) and strips molded and cured as described in Example 1 above. The measurement results obtained from the ball and the strip are given in Table X below?

Example 5

27.5 polystyrene ropes (of the same type as in the example ▼ was used) were used with 54 »! Haste jcis-polybutadiene (des same sypes as used in example 1) and 18 ropes Natural rubber mixed in an internal mixer at 130 to 170 ° C until a homogeneous mixture was obtained. 45 cables lead carbonate, 3 Sitandioxyd ropes and rope 1 of a red pigment (jsur identification) were sugefügt and mixed until a homogeneous mixture was formed "The mixture was abgekehlt to 120 ⁰ C and 3.5 gugefügt ropes dicumyl peroxide"

A ball * C * of A ₉ 11 cm in diameter (1.62 inches) and strips were then formed from the mixture and cured as described in Example 1. The measurement results obtained on the ball and strip are given in Table I below.

Example 4

A mixture was prepared as in Example 3 is described, with the change that the 27.5 ropes of poly-

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styrene has been replaced by 27 _v 5 ropes of a copolymer of styrene and acrylonitrile, available as Tyril 767 »supplied by Dow Chemical Company Limited ·

The mixture became a ball "D" 4.11c »in diameter (1.62 inches) and strips formed and mapped to the bottom, as described in the previous example. The measurement results obtained from the ball and the strips are given in Table I below.

Example 5

Its mixture was prepared as described in Example 3, with the change that the 27.5 polystyrene ropes were replaced by 27.5 parts of a copolymer of methyl methaorylate and Styrene containing 85% methylmetbaorylate, available as Series 150 supplied by Dow Chemical Company Limited.

The mixture made a ball "E" 4.11 cm in diameter (1.62 inches) and strips molded and cured as described in previous examples. The ones from the ball and the strips The measurement results obtained are given below in Table I.,

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Example 6

Was a hat made as described in Example 3? with the change that 42 parts · Bleicarbönat were added instead of 45 cables you · Hasse was transferred to a roll mill into a sheet and extruded onto a cold extruder, and thus produced a rod of 2.86 cm diameter C 1.125 inches). This plug Sxtrudates were formed bu spherical nuclei of 2.65 cm diameter (1.04 inches) and cured for 7 1/2 minutes at 150 ⁰ C ·

A seckoasse was made as follows:

47 "5 parts of a G © polymeric iron Ithylen and methacrylic acid, which contains 7 * Ί of the acid, of which 85 # present as Hatriumsals and which g / 10 has a Hinuten Schmelsflufiindex at 190 ⁰ C of OT5 were mixed with 52.5 parts of was obtained until a homogeneous mixture cig-polybutadiene of the type described in example .1 mixed in an internal "mixer at 150 to 17O ⁰ C. 42 parts of lead carbonate, 3.75 parts of titanium dioxide and 0.25 part of a pigment (for identification) were added and mixed until a homogeneous mixture was obtained again. The mixture was cooled, shredded in a granulator and 3.5 parts of dicumyl peroxide added by rocking the mixture. The mixture was then used

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- 17 - ■;

100 to 120 ⁰ C eu of a raw film compression molded and rapidly cooled to room temperature. The resulting film was 0.318 cm (0.125 inches) in size.

The film was cut into strips ,, (3 to 1 inch), compression-molded to a thickness of 0.305 cm (120 inches Og) and 45 minutes in the foxm at a temperature of 160 ⁰ C cured 7.63 to 2.54 cm " .

From the above-described Deokmasse hemispherical shells were prepared by heating at 100 to 110 ⁰ C in a porn and cooling before removing old for golf balls (pinch 1) an inner diameter of 2.54 cm and a wall thickness of 0.79 cm 0 "310 inches) shaped. The cores already produced were absorbed with a 20 £ solution of! Criphenvlaethantriisjocyanat in methylene chloride, the solvent was allowed to evaporate "Two half-shells have been placed around a thus treated core and formed in a dimpled shape at 160 ⁰ C 45 Hinuten long, then cooled before removal to obtain a golf ball ⁿ f ⁿ of 4.11 cm (1.62 inches) and weighing 45 g. The measurement results obtained from the ball and the strips are given in Table 1 below.

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Example 7

40 parts of an interpolation consisting essentially of acrylonitrile-butadiene and styrene (commercially available as Cycolac H) ₉ as used in Example 2 were mixed with 60% cta- polybutadlene (as used in Example 1) in an internal mixer 150 to 170 ° 0 mixed until a homogeneous mixture was obtained. 40 & ropes Bleicarboo t sragsfflgt were mixed and "Biter, until a homogeneous mixture formed, the mixture was cooled to 120 ⁰ C and 3.5 ropes oxide added *

The mixture was then transferred into a film on a mixing roller and the mass was extruded in a cold extruder with a length of 1.86 cm (1.125 inches) in diameter ) formed (7 1/2 minutes at 150 ^° C.).

Using the deodorant cup and the method "described in Example 6, 7.63 cm by 2.54 cm (3 by 1 inch) strips and bellows shells for golf balls were made" Then a golf ball * G <* was made by inserting m & n εν / A half-shell formed around the core of this example, using the method described in Example 6, "Ball ⁿ G" was 4 * 11 cm in diameter (1.62 inches) and weighed 44.7 g to the

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Measurement results obtained from the ball and the strip are given in Table I below.

For comparison purposes, an ordinary thread-wound serial ball "E" with a diameter of 4.11 cn (1.62 inches) was subjected to the same series of tests as the BSIe and strips "produced according to the procedure of Examples 1 to 7 (respectively, A to G) had been produced. .

In! Fabeile I the names of the various columns have the following Meaning:

OR (b) * stability of the ball.

CR (s) · Cut _{resistance of a strip of the mass o} H * BErte (Shore C).

Rebound a f> Rebound from a height of 2.54 »(100 inches) from a solid concrete base.

Rttekpr & llelastiBität restoration coefficient, determined,

by firing a projectile at the ball and noting the time it takes for the ball and projectile to surf a certain distance _c

CH s compression hardness.

"Click" s that through the contact between the golf club and noise produced by the ball »

"Air flight" indicates the distance that the ball has covered from the tee point to the first landing point. ■ ' ^y ' - '■ ■ ■

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"Total distance" gives the total of the ball from the tee point to its rune position on the Ground covered distance again.

"Pluglienie" represents an arbitrary scale for comparing the heights to which the balls reach during the plug rise, with a higher number indicating a higher flight altitude «

The values are as follows Table I.

OR (b)

CR (s)

H rebound rebound elasticity

did

A good 330 75 67 0.528 B good 340 65 62 0.499 C siemlioh good 330 70 73 0.628 S pretty good 300 65 70 0.560 S good 305 66 75 0.578 P very good 340 73 69 0.588 G very good 340 71 72 0.603 H good 320 70 60 0.550

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Table I (Porte © tBung)

3SS

ABC D

CH Click

76

87

91

100

109

94

67

100

Air flight, m (yards;

quite

quite

quite

quite

quite

Well

Well

Well

good 171 (187)

good 171 (187)

good 197 (216)

good 190 (207)

good 191 (209)

174 (190)

191 (209)

1t2 (Ϊ88)

Cresamtent · "Plug line fernung. M, (yards)

224 (245) 21 3/4

231 (253) 18 1/4

230 (252) 22

216 (236) 22

218 (238) 22

222 (243) 23

239 (261) 23

234 (256) 21 1/2

From the table above it can be seen that the balls produced according to the invention have in some respects similar properties to the usual series balls and in some respects are superior to them "

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Claims (1)

- 22 - Claims A game ball such as a golf ball which contains rubber, characterized in that the game ball is made from a mixture of (A) rubber and (B) a thermoplastic homopolymer of a styrene or substituted styrene, or a thermoplastic copolymer, xerpolymer or interpolating one Styrenes or substituted styrenes with (1) acrylonitrile or substituted acrylonitrile and / or (2) an alkyl ter d @ r Acryl «or methacrylic acid and / or (3) a diene, and the gum present in the mixture, 10 to 90% by weight the mix 2 · game ball according to claim 1, characterized in that the Dien is butadiene or isoprene. 3 »game ball according to claim 1, characterized in that the Alkyl ester of methacrylic acid methyl methacrylate is « 4 · game ball according to claim 1, characterized in that the Contains interpolymers of styrene, butadiene and methyl methacrylate or acrylonitrile 109886/0336 5 * game ball according to one of the preceding claims, characterized in that it is a golf ball 6. Game ball according to one of the preceding claims, characterized in that it is a ball formed from a »piece. 7V game ball according to one of claims 1 to 5, characterized in that it is a ball formed together, consisting of two or more ropes, at least one of which consists essentially of the mixture of claim 1. 8 · game ball according to claim T · characterized in that it consists of a core, which Ib essentially consists of the mixture of claim 1 and is surrounded by a brace, 9 «game ball according to claim 8, characterized in that the Core consists of two or more ropes, 10. game ball according to any one of the preceding claims, characterized characterized in that the gum is 30 to 70% by weight of the mixture matters « 11 «Match ball avenge one of the preceding claims, thereby characterized in that the rubber is a polybutadiene. / ·; '■ 109886/0336 12 · Play ball according to one of the preceding claims _9, characterized in that the rubber is a bond of cis-poly butadiene with natural rubber and / or one or more types of synthetic rubber. 13 »Play ball according to one of claims 1 to 10, characterized in that the rubber is an copolymer of butadiene with styrene and acrylonitrile 1st 14 "Game ball according to one of claims 1 to ₉ characterized 1O, DAFL the rubber polybutylene, polychloroprene or polyisoprene · 15 · Play ball according to one of claims 1 to 10, characterized in that the rubber is an elastomeric copolymer des Ithylena with propylene or with a higher «« -olefin is · 109886/0336