WO1997002317A1 - Compositions molles d'ionomeres, leurs melanges et leur utilisation en tant que materiaux de structure pour balles de golfe - Google Patents

Compositions molles d'ionomeres, leurs melanges et leur utilisation en tant que materiaux de structure pour balles de golfe Download PDF

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Publication number
WO1997002317A1
WO1997002317A1 PCT/US1996/010332 US9610332W WO9702317A1 WO 1997002317 A1 WO1997002317 A1 WO 1997002317A1 US 9610332 W US9610332 W US 9610332W WO 9702317 A1 WO9702317 A1 WO 9702317A1
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Prior art keywords
acid
ionomers
ionomer
soft
composition
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PCT/US1996/010332
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English (en)
Inventor
John Francis Hagman
Robert Joseph Statz
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E.I. Du Pont De Nemours And Company
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Priority to AU61772/96A priority Critical patent/AU6177296A/en
Publication of WO1997002317A1 publication Critical patent/WO1997002317A1/fr

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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0876—Neutralised polymers, i.e. ionomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof

Definitions

  • This invention relates to novel, soft, flexible ethylene copolymer ionomer compositions which have very high resilience.
  • the compositions are useful particularly as component materials in golf balls as well as other uses where high resilience is desirable.
  • the materials can be useful as a primary polymeric material for one-piece golf balls, for centers and cores, and as cover materials for golf balls.
  • the ionomers are copolymers of ethylene, a softening comonomer and (meth)acrylic acid, neutralized with magnesium or lithium.
  • golf ball materials possess a combination of flexibility and high resilience. This is an ideal property combination for materials used alone, in blends with other ionomers, or filled, for various parts of a golf ball.
  • metal ions disclosed as possible neutralizing ions included metals of groups I, II, III, IV-A and VIII of the Periodic Table, including Na, K, Li, Cs, Ag, Hg, Cu, Be, Mg, Ca, Sr, Ba, and many more.
  • Ionomers with a third monomer exemplified included ethylene/vinyl acetate/methacrylic acid neutralized with sodium and magnesium, and ethylene/methyl methacrylate/methacrylic acid neutralized with sodium.
  • Golf balls have certain measurable properties which, directly, strongly affect play characteristics. Most important of these are resilience and compressibility. High resilience increases the length a golf ball can be driven and compressibility increases the playability in terms of 'spin' and 'feel'.
  • Resilience and compressibility can be measured for the material itself, by testing a sphere of the material. These material properties can affect golf ball play characteristics when the material is used as a material in a one-piece ball, to form the center of a three-piece ball, the core of a two-piece ball, or to form the cover of a ball. For ionomers these two properties, resilience and
  • Balata covers impart very poor cut resistance to a ball.
  • Ionomers which generally impart better durability, soon began to take over a significant portion of the market, most particularly for cover materials.
  • blends show synergistic behavior over single ionomers.
  • Two distinct types of ionomer blends have been disclosed.
  • the first type of blend is that of ionomers neutralized with different metals
  • the second is that of blends of hard bipolymer ionomers with soft terpolymer ionomers.
  • the second type of blend may also include the first type of blend; that is to say the soft ionomer may use a different metal ion from the hard ionomer.
  • Interspersed with these combinations is the use of a particular acid as the acid comonomer, generally methacrylic acid or acrylic acid. In some cases, either of these acids has been disclosed as being preferred over the other for some particular utility.
  • the amount of acid comonomer may have preferred limits, with increasing emphasis on high levels of acid to achieve high resilience. Examples of these patents or publications include the following.
  • U.S. Patent No. 3,819,768 disclosed blends of sodium and zinc hard bipolymer ionomers as cover material. Zinc was shown to improve durability in terms of 'cold-crack' resistance. Sodium is generally particularly poor with regard to cold-crack durability.
  • the hard ionomers are disclosed as sodium or zinc ionomers, with lithium and magnesium also disclosed in the second patent.
  • the soft ionomers in both are limited to sodium and zinc ionomers.
  • the preferred compositions are sodium zinc blends.
  • Patent publication WO 95/00212, published Jan. 5, 1995 is the published application of the parent case of the present application. It discloses other blends of hard and soft ionomers. It discloses that the ions used to neutralize soft ionomers may be sodium, zinc, magnesium and lithium. No magnesium or lithium soft ionomers are exemplified.
  • US. Patent No. 5,298,571 discloses blends of hard ionomers of zinc, lithium, sodium and magnesium. Blends of zinc and lithium hard ionomers of high acid copolymers are disclosed as having optimum resilience. The presence of magnesium was shown to be a disadvantage for obtaining the highest resiliency in any blend with any or all of zinc, lithium and sodium ionomers.
  • the polymers disclosed are very hard however, and do not generally fall within the range of flexibility or compressibility of interest for the polymers of the present invention.
  • Ionomers are disclosed for use as one polymer component of a filled three polymer blend useful for centers, cores and one-piece golf balls in U.S. Patent No. 5,155,157 (Statz et al.). Both terpolymer and bipolymer ionomers, with various metal ions, are disclosed for use as part of the polymer blend, but bipolymers are preferred in each type of use. Sodium and lithium hard bipolymers are the only polymers exemplified. The ionomers form only one polymer component of a three polymer blend which also included a non-ionomer thermoplastic and an ethylene glycidyl monomer copolymer which acts as a compatibilizing agent for the other two polymers.
  • lithium ionomers are harder than sodium or magnesium ionomers and zinc produces the softest ionomers.
  • Lithium and magnesium hard ionomers are known, and lithium is a preferred hard ionomer for certain uses.
  • ionomer compositions is possible, with any metal, either methacrylic or acrylic or other suitable carboxylic acid, at any level and, for terpolymer ionomers, almost every possible softening monomer. Also possible is an equally unlimited number of blend possibilities. The number of possible compositions, based on
  • the invention resides in the discovery that lithium and magnesium ions used as the ion in soft ionomers produce ionomers which can show a major increase in the level of compressibility for a given level of resilience or, conversely, a higher level of resilience for the same
  • composition comprising:
  • a soft, flexible ionomer having a neat-sphere PGA Compression below about 155 prepared from a terpolymer which is a first acid copolymer of a) ethylene, b) from 3 to 40 weight percent of an alkyl acrylate, the alkyl group having from 1 to 8 carbon atoms, and c) from 5 to 25 weight percent of methacrylic acid or acrylic acid, preferably acrylic acid, the ionomer being made by neutralizing 20 to 80 percent of the acid groups of the acid copolymer with magnesium or lithium ions.
  • the invention provides blends of as low as 10 weight percent of above ionomer, based on the blend, with a hard ionomer having a flexural modulus of from 40,000 to 110,000 psi, prepared from a bipolymer which is an acid copolymer of ethylene and from 5 to 25 weight percent of methacrylic acid or acrylic acid, the ionomer made by neutralizing 20 to 80 percent of the acid groups of the acid copolymer preferably with magnesium ions, but also with lithium or sodium ions, provided the neat-sphere PGA Compression of the blend does not exceeed 155.
  • sodium hard ionomers there is no more than 50% hard ionomer.
  • the invention provides a one-piece golf ball, or core or center made from the above ionomer or ionomer blend, having sufficient inorganic filler to provide a suitable density for the finished ball.
  • the invention provides a golf ball cover comprising either the above soft ionomer or blend of soft ionomer and hard ionomer.
  • Figure 1 is a plot of PGA Compression versus COR measured on neat-spheres, showing compositions within the invention compared with other compositions.
  • Figure 2 is a similar plot for the same properties, but measured on golf balls having the compositions as cover material.
  • copolymer is used to refer to polymers containing two or more monomers.
  • bipolymer or terpolymer refers to monomers containing only two or three monomers respectively.
  • the phrase 'copolymer of (various monomers) means a copolymer whose units are derived from the various monomers.
  • the ionomers of this invention are prepared from 'direct' acid copolymers, that is to say copolymers polymerized by reacting all monomers simultaneously, as distinct from a graft copolymer, where a monomer or other unit is grafted onto an existing polymer, often by a subsequent polymerization reaction.
  • Methods of preparing ionomers are well known, and are described in
  • the materials of this invention while useful for other purposes are particularly useful as materials for use in golf balls.
  • This disclosure emphasizes the particular properties of interest in that end use, the excellent properties so revealed showing the uniqueness of these ionomers.
  • the present invention is directed to softer materials and softer golf balls with high resilience.
  • COR Coefficient of Restitution
  • a good correlation of 'playability' or 'spin' of a ball may be made using a test referred to as 'PGA Compression', which is a standard industry test.
  • the soft ionomers or ionomer blends of this invention will have a PGA Compression value below about 155, based on neat-resin sphere determinations.
  • values above 155 are generally too high for the material to provide balls with good spin.
  • the materials have a PGA Compression value below about 140.
  • Resins of this invention, with PGA Compression in the 80 to 120 range show the biggest advantage compared with prior art materials. Materials with higher PGA Compression values are in general stiffer, higher modulus materials. While there is no precise correlation between flexural modulus and PGA Compression, resins with flexural modulus of 35,000 psi will have a PGA Compression in the 130 to 160 range. The increased resilience at a given PGA Compression value seen in the materials of this invention may diminish at PGA values above about 130, and above 155 there may be no advantage over conventional prior art ionomers and ionomer blends.
  • one other quality is always desirable, and often essential, and that is durability of the material in golf ball structures.
  • this is measured on a finished golf ball, having a cover made of the material, using a repeated impact test, including tests at low temperature. Determination of durability on a neat-sphere is generally not so definitive because of the inherent toughness of many neat resins. The durability measured on spheres consisting of neat resin and filler would, of course, be relevant for one-piece balls. Without at least some durability in a finished ball, high COR and low PGA Compression may be almost without value.
  • Soft lithium are generally preferred over soft magnesium ionomers in single ionomer compositions used for golf ball construction.
  • soft ionomers can also form part of a soft ionomer/hard ionomer blend provided the resulting PGA Compression of the ionomer blend remains below about 155. Typically, this will correspond to a flexural modulus below about 35,000, but the highest flexural modulus is not limited to this value, and may in some cases exceed it.. When either soft ionomers alone or soft/hard blends are used in golf ball construction, whether for cores, centers, or one-piece balls, and fillers are used to modify the density of the material to produce a ball with acceptable weight or density, the flexural modulus of the filled material may often exceed 35,000 psi. The PGA Compression of the unfilled material used in the blend however should be below about 155.
  • the acid copolymer precursors of the soft ionomers of this invention are copolymers of ethylene, from 3 to 40 weight percent of alkyl acrylate, whose alkyl group has from 1 to 8 carbons, and from 5 to 25 weight percent of methacrylic or acrylic acid, preferably from 5 to 15 weight percent.
  • the preferred alkyl acrylate is n-butyl acrylate. It is to be understood that there can be more than one alkyl acrylate and both acrylic and methacrylic acid present, provided the percent limits for alkyl acrylate and acid are met. For this reason, the generic term copolymer is used rather than terpolymer, in referring to the claimed compositions, because terpolymer implies just three monomers.
  • the acid copolymer may be a blend of different soft acid copolymers having differing levels and/or species of either the softening comonomer, the acid or both.
  • the total percent neutralization of the acid groups present for magnesium or lithium ions, or both, is from 20 to 80%. Preferably the level is from 25 to 65% and most preferably from 30 to 60%.
  • the modulus of the resulting ionomers will typically be about 5000 to 35,000 psi. The modulus will be higher for lithium than magnesium, and will increase with the level of acid. The modulus will be lower the higher the amount of alkyl acrylate.
  • the modulus of the soft lithium and magnesium ionomers prepared here ranged from about 5000 to 27000 psi, but it is readily possible to prepare magnesium and lithium terpolymer ionomers with a modulus up to 35,000 psi, and even higher.
  • Certain terpolymer ionomer compositions can be made, such as ones with very high acid, particularly acrylic acid, using lithium ions and with low amounts of alkyl acrylate which will give higher than 35,000 psi flexural modulus.
  • PGA Compression of neat-spheres of the ionomer is below about 155, it will be suitable. It is readily within the skill of the artisan to determine which combinations of monomers, neutralization level and acid type will produce ionomer within the required neat-sphere PGA Compression limits.
  • the terpolymer ionomers with a softening alkyl acrylate termonomer are still referred to as 'soft * even when the flexural modulus is much higher.
  • the soft ionomers of this invention can have a flexural modulus of 35,000, and even in some cases above this.
  • the modulus should be preferably above 10,000 psi. and more preferably above 15,000, irrespective of whether using a single soft ionomer or a soft/hard ionomer blend.
  • the soft ionomer has a modulus much below 10,000 psi, for cover materials it is therefore preferable to blend with a hard ionomer so the final modulus falls within the range 10,000 to 35,000 psi or even somewhat above.
  • soft ionomer When the soft ionomer is blended with hard ionomer, there should be at least 10 percent soft ionomer, preferably above 25 percent or the advantages of the particular soft ionomers of this invention will not be realized, or will be considerably diluted.
  • the hard ionomers which may be blended with the soft ionomers are derived from acid copolymers of ethylene and from 5 to 25 weight percent acid where the acid is methacrylic or acrylic acid, or both, preferably from 10 to 22 weight percent. It is to be understood that the hard ionomer may be a blend of more than one hard ionomer each having different levels of and/or different acids in them, just as for the soft ionomer.
  • the hard ionomer When the composition is a hard ionomer/soft ionomer blend, it is preferable for the hard ionomer to have a higher level of acid than the soft ionomer. Higher acid increases the hardness, so that to produce a blend having a specific final blend modulus, the higher the acid level in the hard ionomer, the less of it will be required in the blend.
  • the modulus may range from 40,000 to 110,000 psi.
  • the harder or higher modulus the hard ionomer whether due to acid level, acid type, neutralizing ion or degree of neutralization, the greater the amount of soft ionomer possible in the blend, for a given final blend modulus.
  • the neutralizing ion of any hard ionomer used in a blend is preferably magnesium or lithium but may also be sodium.
  • melt index of either the soft or hard ionomers can be from about 0.1 to 30 g/10 min., preferably 0.1 to 10 and most preferably from 0.1 to 6.
  • the melt index of the acid copolymers from which the ionomers are derived may be from about 20 to 350 g./10 min.
  • the preferred blends are lithium soft/magnesium hard. Magnesium/ magnesium and lithium/lithium blends are also attractive. Magnesium soft/lithium hard blends are generally less preferred, and one such blend showed a diminished resilience advantage compared with the reverse blend. It is not clear why this should be so.
  • the preferred soft resins, and those used in the examples have less acid than the hard resins. Therefore, for a given percent of acid groups neutralized they will have less equivalents of metal present.
  • the number of equivalents of lithium in magnesium soft/lithium hard blends will be higher, when there is more acid in the hard ionomer, than in lithium soft/magnesium hard blends. For blends containing both lithium and magnesium ions therefore, it seems that a higher level of magnesium equivalents is preferable.
  • the hard ionomer may also be a sodium ionomer.
  • Zinc ionomers have, in some instances, shown good properties in blends with lithium soft ionomer though, in general, zinc hard ionomer has not shown as great an advantage.
  • the ions originally associated with the soft ionomer may, to some extent, tend to remain more associated with the soft ionomer in a blend, and this may produce blends with different properties than blends having the reverse ions in the soft and hard components.
  • the underlying acid copolymer when it is different, it may merely mean that higher intensity blending is required, such as very high shear extrusion blending, to achieve random distribution of ions throughout the whole composition.
  • higher intensity blending is required, such as very high shear extrusion blending, to achieve random distribution of ions throughout the whole composition.
  • metal oxides or other inert inorganic fillers will need to be added to achieve a density so that the ball weight is within a normal weight range for a golf ball. Fillers such as zinc oxide and barium sulfate are suitable, though any inert inorganic filler can be used.
  • the final density of a ball should be within the range 1.115 to 1.135 g/cc. For one-piece balls therefore, the amount of filler should produce about this density in the material. Cores and centers form only part of a ball. Centers may vary considerably in diameter, and even cores can vary in diameter
  • the amount of filler for cores and centers will vary depending on their size, and on the material used in the rest of the ball. It will be within the skill of the artisan to determine the amount of a given inorganic filler needed in a core or center to obtain the required ball density knowing the size of the core or center and the thickness and density of the other components, since this amount may be obtained by simple calculation.
  • the ionomer or ionomer blends of this invention may also contain conventional additives such as pigments, antioxidants, U.V. absorbers, brighteners and the like.
  • Flexural modulus is measured using ASTM D790-B, and is measured using a standard 'flex bar' and not on a sphere of material as for most other tests.
  • COR Coefficient of Restitution
  • COR of neat-spheres may fall anywhere between 0.50 and 0.70.
  • the range on useful covered balls of this invention is between about 0.67 and 0.74.
  • PGA Compression is defined as the resistance to deformation of a golf ball, measured using a standard industry ATTI machine. It was measured on a neat-sphere of resin and on balls having a cover of resin. For adequate spin of a ball, when the ionomer is used as a cover material, the PGA Compression, measured on a neat-sphere should be less than about 155, preferably less than 140 and most preferably less than 130.
  • the PGA Compression of a ball using the resin as a cover is, of course, dependent on the core of the ball. Generally, the PGA Compression of finished balls is much lower than the 155, and is typically in the 80 to 100 range.
  • the values of COR and PGA Compression fall in a different range than for values for neat-spheres of the material.
  • the desirable PGA Compression of a ball itself is typically in the 80 to 100 range.
  • the PGA Compression/COR correlation for balls is much more attractive than for neat-spheres, as indicated by a vast shift of the line to the right for finished balls. This range can be achieved however, using conventional cores, and cover material having neat-sphere PGA Compression values about in the 110 to 155 range.
  • a one-piece ball which is a sphere molded from resin and filler and minor quantities of typical additives, will not generally have as good a PGA Compression/COR relation as a ball made from a core and cover. While such one-piece balls would not have the same PGA Compression/COR relation as neat-spheres, because of the effect of filler, they would have a correlation more akin to that of neat-spheres than to balls with a core. While useful as 'range' balls, such one-piece balls will not have the superior properties of two and three-piece balls. Nevertheless, materials of this invention would still make superior balls having properties in the 'range' ball category. All the materials of the invention will be suitable for one piece balls. However, in view of the fact that filler will raise PGA Compression, it is clear that more flexible materials than for covers can be used. Melt Index (MI). was measured using ASTM D-1238, condition
  • Durability was measured using a repeat impact test on finished balls, with the material of the invention as the cover, on a Wilson Ultra ® conventional solid core.
  • cores are believed to be made of 1,4-cis polybutadiene, crosslinked with peroxides and co-crosslinking agents such as zinc (meth)acrylate.
  • Durability is meausred using the same machine as for COR, but using an initial velocity of 175 ft./sec. Durability values are the number of hits to break.
  • Durability at low temperatures is especially desirable, and for this reason, durability tests at -20 ° F were carried out. While good durability only at room temperature is adequate for golf balls used in some locales, low temperature durability values, preferably above at least 10, as tested under these conditions, is preferred for cold weather use. Durability at room temperature is almost invariably better than durability at -20°F, so that low temperature durability is a guide to the worst performance to be expected.
  • Good durability of a material may indicate good durability for use as a material in a one-piece ball.
  • Table 1 lists various ionomers used in the examples. The list includes soft ionomers which are part of the invention as well as soft ionomers which are not. It also includes hard ionomers which can be part of a blend of this invention as well as hard ionomers which are not. Flexural modulus is shown, if measured. Note that S8 has a modulus of almost 27,000 psi. This is stiff enough even to make a relatively stiff cover material by itself, i.e., without blending with a hard ionomer.
  • Table 2 lists values of COR and PGA Compression on neat-spheres for the compositions indicated. Comparative examples are numbered with a suffix C. The same values are plotted in Figure 1. Durability of balls which employed the compositions as a cover on a conventional solid core are also shown, if measured.
  • Figure 1 shows comparative examples, outside the invention, indicated by a circle, and examples by a cross.
  • a line is shown, correlating PGA Compression and COR values for prior art materials outside this invention, based on previous data (indicated by triangles), determined prior to this investigation, together with data on prior art materials measured during the present investigation (indicated by a circle).
  • the line is a 'visually best-fit' line, and is based on materials which differed in their ion or ions, their MI, the acid used (whether acrylic of methacrylic), the amount of acid and, in the case of soft ionomer, the amount of acrylate softening monomer.
  • the line is a good fit for data up to a PGA Compression of about 140.
  • Zinc has long been known to provide good durability at low temperatures, and compositions of comparative examples which contain zinc are clearly good in low temperature durability as seen from Table 2. Both zinc and sodium soft ionomers alone, generally will have a flexural modulus of 5,000 psi or less however. In general, this will be too flexible to be useful alone for use as materials of this invention. Zinc hard ionomer blended with lithium soft ionomer does seem to provide good compositions when the PGA Compression is above about 140. However, as noted above, the singularity of the correlation becomes less definite at high PGA values.
  • Sodium hard ionomer is known to provide poor low temperature durability (example 2C and blend 3C). However it can form the hard ionomer portion of blends (example 7), provided there is not more than 50 percent of it.
  • Lithium soft ionomer is not particularly durable at low temperatures (example 2) though not nearly as poor as sodium (2C). However its effect on increasing COR at a given PGA level in lithium soft ionomer or in blends of this invention can provide good compositions in this respect.
  • Magnesium ionomer as the hard segment provides excellent durability.
  • Magnesium soft/magnesium hard blends can thus provide excellent overall compositions (see Example 8).
  • the advantage can show up in the PGA Compression and COR of the resulting ball itself.
  • the PGA/COR improvment may be somewhat diminished in some cases.
  • Different cores provide somewhat different PGA Compression/COR correlations, so that manipulation of core alone can lead to improved balls.
  • Comparison of cover materials must be made on balls which use the same core.
  • the relationship between PGA Compression and COR for golf balls provides a line or lines which is shifted far from that observed for neat-spheres.
  • Table 3 shows PGA Compression and COR values measured on golf balls having a Wilson Ultra ® core, and a cover of the materials having the composition as indicated by the corresponding example number in Table 2.
  • the encircled crosses represent finished ball PGA Compression and COR values with prior art covers, and the crosses alone represent values using cover materials of the invention.
  • the line drawn is a 'visually-best' line, but there are insufficient data at low PGA values to establish the line with great certainty. It can be seen that, while covers made with soft ionomers alone, which give PGA values in the 78-81 range, appear to show only a small improvment, if any, when blends are tested, giving PGA in the 83-94 range, the improvement, for the most part is dramatic. It is not clear why examples 7 (PGA 94) shows such a low COR value, and why example 8 (also PGA 94) shows only a small improvment. Nevertheless, it is clear that a dramatic improvment is possible.

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Abstract

Cette invention se rapporte à des compositions nouvelles, molles, d'ionomères de copolymère d'éthylène, à faible module d'élasticité, contenant un monomère d'acrylate ramollisant, neutralisées avec des ions magnésium ou lithium et possédant un plus grand taux de résilience à un niveau donné de compressibilité PGA que les ionomères connus. L'avantage persiste dans certaines compositions de mélange avec des ionomères plus durs pour des mélanges ayant une compression PGA de sphère nette inférieure à 155 environ. Les compositions non mélangées et mélangées seront utiles toutes les deux en tant que balles de golf et en tant qu'éléments de balles de golf pour des balles d'un seul tenant, des centres, des noyaux et des enveloppes de balles.
PCT/US1996/010332 1995-06-30 1996-06-13 Compositions molles d'ionomeres, leurs melanges et leur utilisation en tant que materiaux de structure pour balles de golfe WO1997002317A1 (fr)

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WO2000073384A3 (fr) * 1999-06-01 2001-06-28 Du Pont Compositions ionomeres souples et leurs melanges pour enveloppe de balle de golf
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7479327B2 (en) 2003-05-27 2009-01-20 Exxonmobil Chemical Patents Inc. Tie-layer materials for use with ionomer-based films and sheets as skins on other materials
US7544420B2 (en) 2003-05-27 2009-06-09 Exxonmobil Chemical Patents Inc. Backing layers and substrates for articles formed from ionomer laminates
US8076000B2 (en) 2003-05-27 2011-12-13 Exxonmobil Chemical Patents Inc. Tie-layer materials for use with ionomer-based films and sheets as skins on other materials
WO2013016398A1 (fr) 2011-07-28 2013-01-31 Dow Global Technologies Llc Formulations de mélange polymère appropriées pour applications de cuir synthétique
US8404773B2 (en) 2008-03-17 2013-03-26 Dow Global Technologies Llc Coating composition, method of producing the same, articles made therefrom, and method of making such articles

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WO1995000212A1 (fr) * 1993-06-18 1995-01-05 E.I. Du Pont De Nemours And Company Melanges d'ionomeres pour revetements de balles de golf
WO1995011273A1 (fr) * 1993-10-21 1995-04-27 Dunlop Limited Materiau de couverture de balle de golf

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
WO1995000212A1 (fr) * 1993-06-18 1995-01-05 E.I. Du Pont De Nemours And Company Melanges d'ionomeres pour revetements de balles de golf
WO1995011273A1 (fr) * 1993-10-21 1995-04-27 Dunlop Limited Materiau de couverture de balle de golf

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000073384A3 (fr) * 1999-06-01 2001-06-28 Du Pont Compositions ionomeres souples et leurs melanges pour enveloppe de balle de golf
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7479327B2 (en) 2003-05-27 2009-01-20 Exxonmobil Chemical Patents Inc. Tie-layer materials for use with ionomer-based films and sheets as skins on other materials
US7544420B2 (en) 2003-05-27 2009-06-09 Exxonmobil Chemical Patents Inc. Backing layers and substrates for articles formed from ionomer laminates
US8076000B2 (en) 2003-05-27 2011-12-13 Exxonmobil Chemical Patents Inc. Tie-layer materials for use with ionomer-based films and sheets as skins on other materials
US8404773B2 (en) 2008-03-17 2013-03-26 Dow Global Technologies Llc Coating composition, method of producing the same, articles made therefrom, and method of making such articles
US8546477B2 (en) 2008-03-17 2013-10-01 Dow Global Technologies Llc Coating composition, method of producing the same, articles made therefrom, and method of making such articles
WO2013016398A1 (fr) 2011-07-28 2013-01-31 Dow Global Technologies Llc Formulations de mélange polymère appropriées pour applications de cuir synthétique

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