GB2163437A - Blends of thermoplastics and elastomeric materials - Google Patents
Blends of thermoplastics and elastomeric materials Download PDFInfo
- Publication number
- GB2163437A GB2163437A GB08518110A GB8518110A GB2163437A GB 2163437 A GB2163437 A GB 2163437A GB 08518110 A GB08518110 A GB 08518110A GB 8518110 A GB8518110 A GB 8518110A GB 2163437 A GB2163437 A GB 2163437A
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
-
- 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
- C08L23/0853—Vinylacetate
-
- 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
-
- 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A homogeneous blend suitable for the production of golf balls comprises a cured elastomeric component selected from cis-1,4-polybutadiene or cis-polyisoprene with a polymerisable metal salt monomer and has been cured and powdered prior to being mixed with a thermoplastics component which is a copolymer of ethylene with an alpha , beta -unsaturated carboxylic acid, a copolymer of ethylene with vinyl acetate, an elastomeric block copolymer, an ionic elastomer, a polyurethane or an elastomeric block copolyamide, the ratio of the cured elastomeric component to the thermoplastics component in the blend being in the range 85:15 to 50:50. The final properties of the blends depend on the properties of the thermoplastics and elastomeric components and the relative proportions of each in the blend. Thus, hardness and resilience may be varied by appropriate selection of each component and adjustment of the relative proportions. Scrap or waste material may be reprocessed to provide the elastomeric component of the blends.
Description
SPECIFICATION
Blends of thermoplastics and elastomeric materials
This invention relates to homogeneous blends of thermoplastics and cured elastomeric materials and to a method for their production. The blends of the present invention are particularly suitable for use in the manufacture of play balls, especially homogeneous one-piece golf balls and cores for two-piece and for multi-component golf balls, and are processible by thermoplastics moulding techniques such as injection-moulding and compression-moulding. Thus, the present invention also relates to golf balls and to golf ball cores, said balls and said cores comprising homogeneous blends of thermoplastics and cured elastomeric materials.
The blends of the present invention comprise one or more thermoplastics materials (hereinafter designated "thermoplastics component") and one or more cured elastomeric materials (hereinafter designated "cured elastomeric component").
Golf balls and golf ball cores can be made, according to the present invention, by blending the thermoplastics component, the cured elastomeric component and optionally a weighting filler to adjust the final specific gravity of the blend, at a temperature equal to or greater than the melting point of the thermoplastics component, by methods such as mill-blending, extrusion-blending or internal mixing in a
Banbury or similar mixer.
According to one aspect of the present invention there is provided a homogeneous blend comprising a thermoplastics component and a cured elastomeric component (both as hereinbefore defined) in which the cured elastomeric component is selected from cis - 1, 4-polybutadiene with a polymerisable metal salt monomer and cis polyisoprene with a polymerisable metal salt monomer and has been cured and powdered prior to being mixed with the thermoplastics component which is selected from a copolymer of ethylene with an (x,ss -unsaturated carboxylic acid, a copolymer of ethylene with vinyl acetate, an elastomeric block copolymer, an ionic elastomer, a polyurethane and an elastomeric block copolyamide, the ratio of the cured elastomeric component to the thermoplastics component in the blend being in the range 85:15 to 50:50.
According to a further aspect of the present invention there is provided a method of making a homogeneous blend of a thermoplastics component and a cured elastomeric component which comprises:
(i) curing either cis-1 4-polybutadiene or cispolyisoprene with a polymerisable metal salt monomer to form the cured elastomeric component, then
(ii) powdering the cured elastomeric component, and then
(iii) mixing the powdered cured elastomeric component with the thermoplastics component which is selected from a copolymer of ethylene with an size -unsaturated carboxylic acid a copolymer of ethylene with vinyl acetate, an elastomeric block polyester, an ionic elastomer, a polyurethane and an elastomeric block copolyamide, the ratio of the cured elastomeric component to the thermoplastics component being in the range 85:15 to 50::50, and the mixing taking place at a temperature equal to or greater than the melting point of the thermoplastics component.
The present invention further provides a moulded article, said article comprising a blend of a thermoplastics component and a cured elastomeric component (both as hereinbefore defined).
The present invention yet further provides a moulded article, said article comprising a blend of a thermoplastics component and a cured elastomeric component (both as hereinbefore defined) together with a weighting filler.
The present invention still further provides a moulded article as described in the immediately preceding paragraph, said article being a homogeneous one-piece golf ball, a homogeneous core for a two-piece golf ball, or a core component for a multi-component golf ball.
The ratio of the cured elastomeric component to the thermoplastics component in the blend is preferably in the range 80:20 to 60:40.
The specific gravity of the final blend may be adjusted to the desired level by the addition of suitable weighting fillers, e g barium sulphate.
The major requirement for the selection of the thermoplastics materials suitable for the practice of the invention is that the melt temperature of the thermoplastics materials should be sufficiently low so that the cured powdered elastomeric material does not undergo degradation during the melt blending operation.
Thermoplastics materials which may be used in the present invention include copolymers of ethylene and asp -ethylenically unsaturated carboxylic acids.
Such materials include copolymers of ethylene-acrylic acid, ethylene-methacrylic acid and ethylenemaleic anhydride and terpolymers of ethylene with these acids and alkyl acrylates or methacrylates.
Thermoplastics materials which have been found especially useful in the invention are copolymers of ethylene and methacrylic acid or acrylic acid and terpolymers of ethylene with methacrylic acid or acrylic acid and alkyl methacrylates wherein a proportion of the acid groups have been neutralised by cation-supplying materials such as salts of metals from Groups I to IV of the Periodic Classification, e g sodium methoxide or zinc acetate. (Such materials are commonly termed 'ionomers'). Otherthermoplastics materials which have been found useful in the invention include copolymers of ethylene and vinyl acetate, elastomeric block copolymers, ionic elastomers (e g ionised sulphonated EPDM terpolymers), polyurethanes and elastomeric block copolyamides.Some examples of such suitable thermoplastics materials are shown in Table
TABLE I
Type of Thermoplastics Example Hardness
Material (ShoreD)* lonomer ) SURLYN 1605 67
SURLYN 1557 63
Ethylene/vinyl acetate) ALKATHENE 1802 38
Copolymer ) ALKATHENE 2805 27
Copolyester HYTREL 4056 40
Polyurethane TPU ST 444** 21
Poly(ether block amide) PEBAX 3533 35 * Manufacturers' data ** experimental material, believed to consist essentially of 1,4-butanediol with a polytetramethylene ether-4,4'-diphenylmethane dilsocyanate prepolymer.
SURLYN 1605, SURLYN 1557 and HYTREL 4056 are available from El Du Pont de Nemours; ALKATHENE 1802 and ALKATHENE 2805 are available from I C I; PEBAX 3533 is available from Atochem (UK) Ltd. The words SURLYN, ALKATHENE, HYTREL and PEBAX are Registered Trade Marks.
The cured elastomeric material from which the powdered component of the blend is obtained is generally required to have a high coefficient of restitution (as measured under conditions which simulate as far as possible the driving golf shot). Cured elastomeric materials which have been found useful in the present invention include those which are generally employed in the manufacture of solid homogeneous golf balls or cores of two-piece golf ball constructions. Preferably the elastomer is cis 1 ,4-polybutadiene with a polymerisable metal salt monomer. When cis-polyisoprene is used in the elastomeric component it may be as natural rubber. Compositions of this type can be cured by suitable peroxide initiators to produce thermosetting materials of extremely high cross-link density.Suitable polymerisable metal salt monomers include the mono- and di-salts of acrylic and methacrylic acid; zinc diacrylate (ZDA) and basic zinc monomethacrylate (BZM) being the preferred monomers. Cured elastomeric coknpositions including these polymerisable metal salt monomers are highly resilient materials which are eminently suitable for the production of the powdered elastomeric component of blends of the present invention.Typical cured elastomeric compositions which have been used in the practice of this invention are shown in TABLE II (below): TABLE II
Ingredient Formulation (parts by weight)
A B C D E
(a) High cis 1,4-polybuta dienerubber 100 100 100 100 100
(b) Basic zinc monometh
acrylate (BZM) 32 - - - - (c) Zinc diacrylate (ZDA) - 29 - 22 29
Zince oxide 37 35 60 55 55
(40% active) Dicumyl
peroxide 5 5 5 5 5
Stearic acid - - - - 2 (a) Available from the Japan Synthetic Rubber Company as JSR BR 01.
(b) Available from Berk Spencer Acids Limited (c) Available from Sartomer Inc. as CHEMLINK RT (CHEMLINK is a Registered Trade Mark)
The cured elastomer may be powdered by any convenient grinding or milling process. In practice, suitable powders have been prepared, both by cryogenic grinding and by traditional comminution methods, with particle sizes in the range 1 - 1000 microns. The maximum amount of powder compoundable in, and the processability of, the final blend are at least partly dependent on the powder particle size. Thus, whilst mouldable blends containing up to 85% by weight of powdered elastomeric material of particle size less than 100 microns have been achieved, the maximum achieveable loading with larger particle sizes is reduced to levels which vary according to the nature of the thermoplastics material.Additionally, cured powder particle size and loading can also determine the moulding process most applicable to forming the golf ball or core.
thus, whilst blends containing low loadings of fine particle size powder may readily be injection-moulded, those containing high loadings of coarser powders might only be thermoformable by compression moulding.
The final properties of a golf ball or core made from a blend according to the present invention are derived from the sum of the properties of both the thermoplastics and the elastomeric components and from the relative proportions of each in the blend. Thus, hardness and resilience may be varied as required by appropriate selection of each component and adjustment oftheir relative proportions.
The present invention will be illustrated, merely by way of examples, as follows:
In the Examples, two physical properties of the golf balls or cores are given to illustrate the performance of the blends of the present invention. These properties are:
(i) Compression - a measure of ball or core hardness. Quoted values are in units of 0.001 inch (0.0254mm) and represent the deformation of the ball or core, under a load of 87.5 Ibs (39.69 Kg) for cores and 91.5 Ibs (41.5 Kg) for balls, applied across a diameter.
(ii) Resilience - determined as Newton's coefficient of restitution (E) and calculated from photoelectronic measurement of the momentum of the ball or core and of a pneumatically-projected missile, before and after impact. The speed of impact is 180 ft.s-l (54.9 m.s.
Examples 1 to 4
The zinc monomethacrylate containing elastomer, formulation A of Table II, was prepared on a cold twinroll mill and cured in thick sheets in a press for 20 minutes at a temperature of 1 60"C. The cured material was then reduced to powder having a range of particle sizes by a cryogenic grinding process.
To 60 g of the ionomer available as SUR LYN 1605 (Registered Trade Mark) (believed to be a copolymer of ethylene and methacrylic acid containing 15% by weight of acid of which approx 30% is present in the form of its sodium salt) banded on a twin-roll mill at 160"C, was added 225 g of the aforementioned powdered cured material. Also added was 12 g of barium sulphate as a weighting filler. These ingredients were thoroughly mixed then removed from the mill, formed into 1.50" (38.10 mm) diameter golf ball cores by compression moulding at 170"C for 1-2 minutes, and cooled to ambient temperature.
A "control" composition, comprising a moulded core made from the formulation used to produce the
elastomeric component, was cured for 20 minutes at 1 600C and tested for compression and resilience. The
results are given in TABLE Ill: TABLE III
EXAMPLE # CONTROL 1 2 3 4
ELASTOMERIC COMPONENT
Formulation (a) A A A A A
Particle size (microns) - 0-100 100-200 200-300 300-500
Amount (g) - 225 225 225 225
THERMOPLASTICS COMPONENT
Type - SURLYN 1605 SURLYN 1605 SURLYN 1605 SURLYN 1605
Amount (g) - 60 60 60 60
FILLER barium barium barium barium
Type - sulphate sulphate sulphate sulphate
Amount (g) 12 12 12 12
RATIO ELASTOMERIC TO
THERMOPLASTICS - 79/21 79/21 79/21 79/21
COMPONENT
CORE PROPERTIES
Compression 55 52 44 52 47
Resilience 0.687 0.647 0.664 0.668 0.669
Notes to TABLE III (a) See TABLE II Thus, the blends of Examples 2,3 and 4 have good levels of resilience in comparison to the Control. The compositions of Examples 1 to 4 have the advantage that scrap or waste material can be reprocessed.
Examples 5 to 8
The preparative procedure of Examples 1 to 4 was repeated using, as the elastomer, formulation B of Table
II. Test results show that the blends of Examples 5 to 8 have substantially higher levels of resilience than
those of Examples 1 to 4 and higher resilience than the conventionally cured control core based on the monomethacrylate monomer (formulation A of TABLE II).The results are given in TABLE IV: TABLE IV
EXAMPLE # CONTROL 5 6 7 8
ELASTOMERIC COMPONENT
Formulation (a) A B B B B
Particle size (microns) - 0.100 100-200 200-300 300-500
Amount (g) - 225 225 225 225
THERMOPLASTICS COMPONENT
Type - SURLYN 1605 SURLYN 1605 SURLYN 1605 SURLYN 1605
Amount (g) - 60 60 60 60
FILLER barium barium barium barium
Type - sulphate sulphate sulphate sulphate
Amount (g) 12 12 12 12
RATIO ELASTOMERIC TO
THERMOPLASTICS - 79/21 79/21 79/21 79/21
COMPONENT
CORE PROPERTIES
Compression 55 37 38 34 33
Resilience 0.682 0.688 0.698 0.715 0.711
Notes to TABLE IV (a) See TABLE II Examples 9 to ii These examples show how changes in the elastomeric component may be used to change the final properties of the blend.Thus, the reduced levels of zinc diacrylate monomer in elastomer formulations C and
D (see TABLE II) would be expected to soften and reduce the resilience of the cured elastomer and indeed these effects are apparent in the cores of examples 9 and 10. Similarly, the presence of a minor amount of stearic acid in formulation E (see TABLE II) produced slight core softening in example 11. Note also that extra amounts of weighting filler (zinc oxide) were already present in these elastomer formulations, thus obviating the need for later addition to the final blend. The results are given in TABLE V:
TABLE V
EXAMPLES CONTROL 9 10 11
ELASTOMERIC COMPONENT
Formulation (a) A C D E
Particle size (microns) - < 250 < 250 < 250
Amount (g) - 245 245 245 THERMOPLA S TICS COMPONENT
Type - SURLYN 1605 SURLYN 1605 SURLYN 1605
Amount (g) - 60 60 60
RATIO ELASTOMERIC TO
THERMOPLASTICS COMPONENT - 79/21 79/21 79/21
CORE PROPERTIES
Compression 55 78 54 37
Resilience 0.696 0.637 0.653 0.709
Notes to TABLE V
(a) See TABLE II
Examples 12 to 22 show how the properties of golf balls or cores of the invention may be varied as desired by the use of different thermoplastics or blends of thermoplastics or by varying the ratios of cured elastomer powder and thermoplastic.
The results are given in TABLE Vl: TABLE VI
EXAMPLE # CONTROL 12 13 14 15 16 17 18 19 20 21 22
ELASTOMERIC COMPONENT
Formulation (a) A B B B B B B B B B B B
Particle size (microns) - 200-300 200-300 200-300 200-300 200-300 200-300 < 250 < 250 < 250 < 250 < 250
Amount (g) - 225 225 225 180 180 225 225 225 225 125 225
THERMOPLASTICS COMPONENT (g)
SURLYN 1605 - 60 48 60 40 30 - 30 30 - -
ALKATHENE 2805 - - 12 - - - - - - - -
ALKATHENE 1802 - - - 60 - - - - - - -
HYTREL 4056 - - - - 20 30 60 - - - -
SURLYN 1557 - - - - - - - - - - - 60
PEBAX 3533 - - - - - - - 30 - 60 -
TPU ST 444 - - - - - - - - 30 - 60
FILLER
Barytes (g) - 20 20 20 20 20 20 - - - 20 20
RATIO ELASTOMERIC TO
THERMOPLASTICS COMPONENT - 79/21 79/21 65/35 75/25 75/25 79/21 79/21 79/21 67/33 79/21
CORE PROPERTIES
Compression 55 35 38 41 36 39 55 44 48 80 70 44
Resilience 0.696 0.698 0.679 0.632 0.688 0.671 0.653 0.687 0.657 0.657 0.647 0.634
Notes to TABLE VI (a) See TABLE II
Claims (20)
1. A homogeneous blend comprising a thermoplastics component and a cured elastomeric component (both as herein before defined) in which the cured elastomeric component is selected from cis-1,4polybutadiene with a polymerisable metal salt monomer and cispolyisoprene with a polymerisable metal salt monomer, and has been cured and powdered prior to being mixed with the thermoplastics component which is selected from a copolymer of ethylene with an oi,P os,ss -unsaturated carboxylic acid, a copolymer of ethylene with vinyl acetate, an elastomeric block copolyester, an ionic elastomer, a polyurethane and an elastomeric block copolyamide, the ratio of the cured elastomeric component to the thermoplastics component being in the range 85:15 to 50:50.
2. A blend according to claim 1 in which the thermoplastics component is a copolymer of ethylene and acrylic acid, methacrylic acid or maleic anhydride.
3. A blend according to claim 1 or 2, in which the thermoplastics component is a copolymer of ethylene and methacrylic acid or ethylene and acrylic acid wherein a proportion of the acid groups have been neutralised by a cation-supplying material.
4. A blend according to claim 3, in which the cation-supplying material is a salt of ametal from Groups I to
IV of the Periodic Classification.
5. A blend according to claim 3 or 4, in which the cation-supplying material is a sodium or zinc salt.
6. A blend according to claim 5 in which the cation-supplying material is sodium methoxide or zinc acetate.
7. A blend according to any preceding claim, in which the cured elastomeric component is cis-1 4-polybutadiene with a polymerisable metal salt monomer.
8. A blend according to any one of claims 1 to 6, in which the cured elastomeric component is natural rubber with a polymerisable metal salt monomer.
9. A blend according to any preceding claim, in which the polymerisable metal salt monomer is a monoor di- salt of acrylic acid or methacrylic acid.
10. A blend according to claim 9, in which the polymerisable metal salt monomer is zinc diacrylate or basic zinc monomethylacrylate.
11. A blend according to any preceding claim, in which the ratio of the cured elastomeric component to the thermoplastics component is in the range 80:20 to 60:40.
12. A blend according to any preceding claim, in which the cured elastomeric component is powdered so as to have a particle size in the range 1 to 1000 microns.
13. A moulded article made from a blend according to any preceding claim.
14. A moulded article made from a composition comprising a blend according to any one of claims 1 to 12, and a weighting filler.
15. A moulded article according to claim 13 or 14, which is a homogeneous one-piece golf ball.
16. A moulded article according to claim 13 or 14, which is a homogeneous core for a two-piece golf ball.
17. A moulded article according to claim 13 or 14, which is a core component for a multi-component golf ball.
18. A blend, substantially as hereinbefore described, with reference to any one of the Examples.
19. A method of making a homogeneous blend of a thermoplastics component and a cured elastomeric component which comprises:
(i) curing either cis-1 ,4-polybutadiene or cis- polyisoprene with a polymerisable metal salt monomer to form the cured elastomeric component, then
(ii) powdering the cured elastomeric component, and then
(iii) mixing the powdered cured elastomeric component with the thermoplastics component which is selected from a copolymer of ethylene with an a,p -unsaturated carboxylic acid, a copolymer of ethylene with vinyl acetate, an elastomeric block polyester, an ionic elastomer, a polyurethane and an elastomeric block copolyamide, the ratio of the cured elastomeric component to the thermoplastics component being in the range 85:15 to 50: :50, and the mixing taking place at a temperature equal to or greater than the melting point of the thermoplastics component.
20. A method according to claim 19 having the feature defined in any one of claims 2 to 12 or 18.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848421433A GB8421433D0 (en) | 1984-08-23 | 1984-08-23 | Blends of thermoplastics and elastomeric materials |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8518110D0 GB8518110D0 (en) | 1985-08-21 |
| GB2163437A true GB2163437A (en) | 1986-02-26 |
| GB2163437B GB2163437B (en) | 1987-07-15 |
Family
ID=10565737
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB848421433A Pending GB8421433D0 (en) | 1984-08-23 | 1984-08-23 | Blends of thermoplastics and elastomeric materials |
| GB08518110A Expired GB2163437B (en) | 1984-08-23 | 1985-07-18 | Blends of thermoplastics and elastomeric materials |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB848421433A Pending GB8421433D0 (en) | 1984-08-23 | 1984-08-23 | Blends of thermoplastics and elastomeric materials |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS6160735A (en) |
| GB (2) | GB8421433D0 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993016764A1 (en) * | 1992-02-28 | 1993-09-02 | E.I. Du Pont De Nemours And Company | Process for thermoplastic golf balls |
| EP0568332A2 (en) * | 1992-04-28 | 1993-11-03 | Sumitomo Rubber Industries, Co. Ltd | Solid golf ball |
| EP0646396A2 (en) * | 1993-08-05 | 1995-04-05 | Gencorp Inc. | Play balls, pressureless tennis balls and rubber compounds for making them |
| GB2296014A (en) * | 1994-12-14 | 1996-06-19 | Inventa Ag | Golf ball |
| US20130344994A1 (en) * | 2012-06-25 | 2013-12-26 | Acushnet Company | Golf ball compositions |
| US20130344992A1 (en) * | 2012-06-25 | 2013-12-26 | David A. Bulpett | Golf ball compositions |
| US8944937B2 (en) | 2011-12-27 | 2015-02-03 | Nike, Inc. | Method of recycling a ball and ball for use in recycling method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154235A (en) * | 2020-01-08 | 2020-05-15 | 科恒高分子(广东)有限公司 | Environment-friendly TPEE tackifying and reinforcing composite material and preparation method thereof |
-
1984
- 1984-08-23 GB GB848421433A patent/GB8421433D0/en active Pending
-
1985
- 1985-07-18 GB GB08518110A patent/GB2163437B/en not_active Expired
- 1985-08-23 JP JP18561585A patent/JPS6160735A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993016764A1 (en) * | 1992-02-28 | 1993-09-02 | E.I. Du Pont De Nemours And Company | Process for thermoplastic golf balls |
| EP0568332A2 (en) * | 1992-04-28 | 1993-11-03 | Sumitomo Rubber Industries, Co. Ltd | Solid golf ball |
| EP0568332A3 (en) * | 1992-04-28 | 1994-03-30 | Sumitomo Rubber Ind | |
| US5589546A (en) * | 1992-04-28 | 1996-12-31 | Sumitomo Rubber Industries, Ltd. | Solid golf ball |
| US5558325A (en) * | 1993-08-05 | 1996-09-24 | Gencorp Inc. | Play balls or pressureless tennis balls |
| EP0646396A3 (en) * | 1993-08-05 | 1995-08-09 | Gencorp Inc | Play balls, pressureless tennis balls and rubber compounds for making them. |
| EP0646396A2 (en) * | 1993-08-05 | 1995-04-05 | Gencorp Inc. | Play balls, pressureless tennis balls and rubber compounds for making them |
| GB2296014A (en) * | 1994-12-14 | 1996-06-19 | Inventa Ag | Golf ball |
| US8944937B2 (en) | 2011-12-27 | 2015-02-03 | Nike, Inc. | Method of recycling a ball and ball for use in recycling method |
| US20130344994A1 (en) * | 2012-06-25 | 2013-12-26 | Acushnet Company | Golf ball compositions |
| US20130344992A1 (en) * | 2012-06-25 | 2013-12-26 | David A. Bulpett | Golf ball compositions |
| CN103505849A (en) * | 2012-06-25 | 2014-01-15 | 阿库施耐特公司 | Golf ball compositions |
| US9248346B2 (en) * | 2012-06-25 | 2016-02-02 | Acushnet Company | Golf ball compositions |
| CN103505849B (en) * | 2012-06-25 | 2016-08-17 | 阿库施耐特公司 | Golf composition |
| US9457232B2 (en) * | 2012-06-25 | 2016-10-04 | Acushnet Company | Golf ball compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8421433D0 (en) | 1984-09-26 |
| GB8518110D0 (en) | 1985-08-21 |
| JPS6160735A (en) | 1986-03-28 |
| GB2163437B (en) | 1987-07-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |