JPS6160735A - Blend of thermoplastic plastic and elastic material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to homogeneous blends of thermoplastic plastics and cured elastomeric materials and methods of making the same.

The formulations of the present invention are particularly suitable for the manufacture of recreational balls, particularly uniform monolithic Golua balls, bilayer golf ball centers and multilayer golf balls, and are suitable for injection molding and compression. Suitable for continuous molding techniques of thermoplastics such as molding. Accordingly, the present invention also relates to golf balls and golf ball cores, which golf balls and golf ball cores are comprised of a mixture of thermoplastic plastics and hardened elastomeric materials.

The composition of the present invention comprises one or more thermoplastic materials (hereinafter referred to as "thermoplastic component") and one or more cured elastic materials (hereinafter referred to as "cured elastic component"). It's getting better.

Bill 7 ball and golf ball h according to the present invention.

The core is prepared by adding a filler optionally measured to adjust the specific gravity of the thermoplastic component, the cured elastic component, and the final blend at a temperature at or above the melting point of the thermoplastic component. , by mixing in a mixer, mixing in an extruder, mixing in a Pampa+7-mixer, or using similar mechanical mixing methods.

In one example of the present invention, a homogeneous blend of thermoplastic components and cured components (both of which will be described below) is obtained in the following manner. That is, the cured elastic component is cis-1, which contains a polymerizable metal salt monomer.
cis-polyisoprene containing 4-polybutadiene and a polymerizable metal salt monoi-, and is cured into a powder before being mixed with the thermoplastic component, and the thermoplastic component is mixed with ethylene. A cured elastic component selected from copolymers with α,β-unsaturated carboxylic acids, copolymers of ethylene and vinyl acetate, Glock-type copolyester polymers, ionene elastomers, polyurethanes, and Zurok-type copolyamide P elastomers. The blending ratio of the thermoplastic component to the thermoplastic component is in the range of 85:15 to 5:50.

To further explain the invention, (1) Polymerizable gold IR salt monomer? Containing cis-
A hardened elastic component is produced by curing cis-polyisoprene containing 1,4-polygetadiene or a polymerizable metal salt monomer, and then the hardened elastic component is powdered and then (iiD!?t,'ytoα
, copolymers with β-unsaturated carboxylic acids, copolymers of ethylene and vinyl acetate, block polyester elastomers, ionene elastomers, polyurethanes and block copolyamide elastomers) and the curing of this powdered thermoplastic component. When mixing with the hardened elastic component, the blending ratio of the hardened elastic component to the thermoplastic plus snack component is 85:15 to 5.
0:50 range KL.

The present invention provides a method for forming a homogeneous blend of a thermoplastic component and a cured elastic component by mixing at a temperature equal to or higher than the melting point of the thermoplastic component.

The present invention further provides a molded article) comprising a formulation of a thermoplastic component and a cured elastomeric component (both of which will be described below).

The present invention further provides a molded article comprising a thermopolunable plastic component and a cured elastomeric component with the addition of an extender filler (both of which will be discussed below).

The present invention also provides the molded products described in the immediately preceding section, ie, a uniform one-piece golf ball, a two-layer uniform core of a golf ball, or a multilayer golf ball core.

The ratio of cured elastic component to thermoplastic component in the formulation is preferably 80:20 S6
It was 0:40.

The specific gravity of the final formulation may be adjusted as necessary with the addition of suitable extender fillers (eg sulfuric acid).

For purposes of practicing the present invention, the primary requirement in selecting a thermoplastic material is the melting temperature of the thermoplastic material, which melts the powdered, cured, elastic material. The temperature should be low enough so that the material does not undergo degradation during the melt compounding operation. Thermoplastic materials that can be used in the present invention include ethylene and α,β-
Includes copolymers with unsaturated carbons.

Such materials include ethylene-acrylic acid copolymers,
Included are ethylene-methacrylic acid copolymers and ethylene-maleic anhydride rR copolymers and ternary copolymers of ethylene and these acids with alkyl acrylates or argyl methacrylates. Thermofertilizable plastic materials found to be particularly useful in the present invention include copolymers of ethylene and methacrylic acid or tertiary copolymers of ethylene and acrylic acid and tertiary copolymers of ethylene and methacrylic acid and alkyl methacrylates or It is a ternary copolymer of acrylic acid and alkali methacrylate, and the acid group portion of these copolymers is a salt of a metal from group I to group II of the periodic table, such as sodium methoxy-P or zinc acetate. is neutralized with a substance that supplies cations. (Such substances are usually called "ionomers"). Other thermoplastic materials found to be useful in the present invention include copolymers of ethylene and vinyl acetate, elastomeric copolymers, ionic elastomers (i.e., ionized versions of sulfonated EPDM ternary copolymers), polyurethanes. and elastic block type copolyamide r. Some examples of such suitable thermoplastic materials are shown in Table IK: Table I Ionomer) t-phosphorus 1605
67 ionomer) Chilin 15
57 63 ethylene/hinyl acetate copolymer) Alcatene 1802 3B ethylene/INI” ternary copolymer) Alcatene 2805 27 copolyester Hytrel 4056 40 polyurethane TPU 5T444°“
21 Qin Trial product based on manufacturer's data, basically a repeat product of 1,4-butanediol
Chilin 1605, which is believed to consist of a polytetramethylene ether-4,4'-diphenylmethane diisocyanate prepolymer, -Lynn 1557 and /Uyo Itrel 4056 are obtained from IduPont Denemoers Ltd.; Alcatene 1802 and Alcatene 2805 are obtained from I7I Ltd.; P.I. Bassis 3533 is obtained from Atkego Ltd. (UK).

The names Chilin, Alcaten, Hytrel and Pibassis are registered trademarks.

The cured elastomeric material, which is the powder component of the formulation, is usually required to have a high coefficient of restoring force (as measured by simulating conditions as close as possible to driving a lure shot). Cured nine-elastic materials found useful in the present invention include those commonly used in the manufacture of solid, uniform golf ball or bilayer golf ball cores. Preferably - the elastic material is cis-1,4 containing a polymerizable metal salt monomer
- polybutadiene. When cis-polyisoprene is used as the elastic component, it will have the same performance as natural rubber. Compositions of the type ξ can be cured using suitable commercially available initiators to produce thermoset materials of very high crosslink density.

Suitable polymerizable gold salt monomers include mono- and di-salts of acrylic and methacrylic acids; zinc diacrylate (ZDA) and basic zinc monomethacrylate (
BZM) is a preferred monomer.

The cured elastomeric material compositions containing these polymerizable hexamers are materials with high resilience and are highly suitable for producing the powdered elastomeric components of the formulations of the present invention. . Examples of cured elastic components used in the practice of the present invention are shown in Table ■ (below): Table ■ (α) High cis L4-polybutadiene Im 10 (1
0)0(10)0(10)00 Zo.

(Kazoku Katsuki Monomethacrylate (BZM) 3
2 - - - -(C) Zinc diacrylic salt (Z
DA) -29-2229 Zinc oxide'
37 35 60 55 55 (active content outside 4σ) dicumyl peroxy) #5 5 5
5 5 (α) J, SRBR (10) Product of Japan Synthetic Rubber Co., Ltd.
Company A Product (C) Chemlink RT Sartomer Product This hardened elastic material can be easily ground into powder using any grinder or flour mill. Actually, frozen grinding or traditional grinding method? Powders with a particle size of 1 to 1000 microns are suitably produced using this method. The maximum amount of powder that can be incorporated into the final formulation and the blending process will depend to some extent on the particle size of the powder. Therefore, up to 85% by weight of a powdered elastic material with a particle size of 100 microns or less can be incorporated into a molding compound, but for larger particle sizes, the maximum amount that can be incorporated varies greatly depending on the nature of the thermoplastic material. do. In addition, the particle size and amount of cured elastomer powder added may also determine the most suitable molding method for making the golf ball or core. Thus, formulations containing less powder of fine particle size may be injection molded, whereas formulations containing more powder of coarse particle size may only be thermoformed by compression molding.

The final performance of a golf ball or core made of the compounded material of the present invention is determined by the sum of the properties of both the thermoplastic component and the elastic component and the blending ratio of the thermoplastic component and the elastic component in the compounded material. It will be done. Therefore,
The hardness and restoring force can be adjusted to the required performance by appropriately selecting each component and adjusting the relative proportions of each component.

The invention is illustrated by the following examples: In the examples, two physical properties of a golf ball or core are shown to demonstrate the performance of the compounded materials of the invention. What is this physical performance? (1) Compressibility - Measurement of the hardness of the ball or core The numbers shown are in units of 0.0 (10) inches (0,0254). Deformation when a load of 91.5 pounds (4), 5) is applied to the diameter of the core, and a load of 87.5 pounds (39,6 (#)) is applied to the core. represents.

(n) Determined by the = Neilton coefficient of restored car restoration (g). That is, it is calculated from the measured value of the photoelectric moment before and after impact is applied to the ball or core, and the measured value of the trajectory of the projection in the air.

Examples 1-4 Elastic materials containing zinc monomethacrylate were made in a two-blade mixer according to formulation A in Table 1, and cured under pressure at a temperature of 160°C for 20 minutes to form inch-thick pieces. I made it into a sheet. This hardened material was then processed into a powder having a range of particle sizes through a freeze-grinding process.

Surlyn 1605® (an ethylene/methacrylic acid copolymer containing 15 wt.% acid groups;
! R2fF (about 30% of which is believed to be in the form of sodium salt) was added in strips to a 605' trough-in-roll machine heated to 160°C, and 225g of the hardened powder material described above was added. Furthermore, 12 g of barium sulfate was added as an extender filler. These formulations were thoroughly mixed, taken out from the machine, and heated at 170°C for 1 to 2 hours.
51.50 inches (38,104I) by compression molding for 1 minute
f! ) diameter golf ball core and cooled to room temperature.

A core with the composition of "Formulation Example A (Table ■)" was molded with an elastic component, cured for 20 minutes at 160°C and tested for compression, modulus and restoring force. The results are shown in Table ■: Therefore, The formulations of Example 2, Example 3 and Example 4 are as follows: Table II
)K has good restoring power compared to K. The compositions of Examples 1 and 4 have the advantage that even if they are discarded and damaged, they can be reused.

Examples 5 to 8 The manufacturing method of Examples 1 to 4 was repeated by using the formulation example B in Table 1 for the elastic component, Example fi 15 to Example 8.
The test results with the formulations up to this point showed substantial K, a higher level of restoring power than the test results with the formulations in Examples 1 to 4. The core consists of the basic composition example A (Table ■))
It also shows high resilience2. The test results are shown in Table ffK: Examples 9-11 The examples herein demonstrate how the elastic components can be varied to alter the final performance of the formulation. Therefore, compositions C and C reduced the zinc diacrylate monomer in the elastic component.

(Refer to Table 3) can be expected to soften the hardened elastic component and weaken the restoring force, and in fact, such effects are evident in the core of Examples 9 and 10. Similarly 1
The presence of a small amount of stearic acid in composition E (see Table 1) K softens the core a little, as shown in Example 11. Keeping in mind that so much bulking agent phyto-(zinc oxide) is immediately present in the composition of these elastic components, there is no need to add more bulking agent to the final formulation. The test results are shown in Table VK: Examples 12 to 22 were tested by using different types of thermoplastics, by varying the blending amount of thermoplastics, or by using cured elastic component powders and thermoplastics. This figure shows how the properties of the golf ball or golf ball core of the present invention change by changing the proportion of the adhesive plastic. The results are shown in Table VIK:

Claims (19)

[Claims] (1) Copolymers of ethylene and α,β-unsaturated carboxylic acids, copolymers of ethylene and vinyl acetate, block copolyester elastomers, ionic elastomers,
Cis-1 containing a thermoplastic component selected from polyurethane and block copolyamide elastomers and a polymerizable metal salt monomer that is hardened and powdered before being mixed into the thermoplastic component.
, 4-polybutadiene and cis-polyisoprene containing polymerizable metal salt monomers, the ratio of the cured elastic component to the thermoplastic component being from 85:15 to 50. : A homogeneous compound material characterized in that it consists of a thermoplastic component in the range of 50 and a hardened elastic component. (2) A formulation according to claim 1, characterized in that the thermoplastic component consists of a copolymer of ethylene and acrylic acid, a copolymer of ethylene and methacrylic acid, or a copolymer of ethylene and maleic anhydride. . (3) A thermoplastic component comprising a copolymer of ethylene and methacrylic acid or a copolymer of ethylene and acrylic acid, in which the acid group portion is neutralized with a metal capable of supplying cations. A formulation according to claim 1 or 2. (4) The composition according to claim 3, wherein the material capable of supplying cations is a salt of a gold salt from Group I to Group IV of the periodic table. (5) The composition according to claim 3 or 4, characterized in that the metal capable of supplying cations is a sodium salt or a zinc salt. (6) A formulation according to claim 5, characterized in that the metal capable of supplying cations is sodium methoxide or zinc acetate. (7) The cured elastic component is cis-1,4-polybutadiene containing a polymerizable metal salt monomer, according to any one of claims 1 to 6. compound. (8) A composition according to any one of claims 1 to 6, characterized in that the cured elastic component is a natural rubber containing a polymerizable metal salt monomer. (9) A formulation according to any one of claims 1 to 8, characterized in that the polymerizable metal salt monomer is a mono- or di-salt of acrylic acid or methacrylic acid. (10) A formulation according to claim 9, characterized in that the polymerizable metal salt monomer is zinc diacrylate or basic zinc monomethacrylate. (11) The formulation according to any one of claims 1 to 10, characterized in that the ratio of the cured elastic component to the thermoplastic component is in the range of 80:20 to 60:40. thing. (12) A formulation according to any one of claims 1 to 11, characterized in that the hardened elastic component is a powder having a particle size in the range of 1 to 1000 microns. (13) A molded article made from the blend according to any one of claims 1 to 12. (14) A molded article, characterized in that it is made from a composition obtained by adding an extender to the blend according to any one of claims 1 to 12. (15) The molded product according to claim 13 or 14, which is a uniform, integrally molded golf ball. (16) The molded article according to claim 13 or 14, which is a uniform core of a two-layer golf ball. (17) The molded article according to claim 13 or 14, which is a core component of a golf ball having a multilayer structure. (18) (i) producing a cured elastic component by curing cis-1,4-polybutadiene containing a polymerizable metal salt monomer or cis-polyisoprene containing a polymerizable metal salt monomer; (ii) This cured elastic component is powdered; (iii) copolymers of ethylene and α,β-unsaturated carboxylic acids, copolymers of ethylene and vinyl acetate, block polyester elastomers, ionene elastomers, polyurethanes; When mixing the thermoplastic plastic component selected from block type copolyamide elastomer and this powdered hardened elastic component, the blending ratio of the hardened elastic component to thermoplastic component is 85:15.
A method of making a homogeneous blend of a thermoplastic component and a cured elastic component, characterized in that the mixture is in the range of ~50:50 and at a temperature equal to or above the melting point of the thermoplastic component. (19) The method according to claim 18, characterized in that the formulation according to any one of claims 2 to 12 above is used.