CS231388B1 - Baros,anton,cs durian,jan,cs shoemaker's outsole material - Google Patents

Abstract

The invention relates to a thermoplastic material elastomer for the manufacture of the sole footwear. The purpose of the invention is to reduce the cost preparation of sole material by replacement parts of the original S-B-S elastomers secondary raw materials, but without deterioration of physical-mechanical properties the resulting soles. This purpose is achieved by having of the invention comprises a shoe sole composition material, in relation to total weight of base polymers, 5 to 30 % by weight of filler particles; the shape of spherical bodies and a diameter of 0.2 up to 1.7 mm of rubber made of butadiene styrene rubber, in which the styrene fraction the component is 40 to 50 weight percent and containing 15 to 30 weight percent milled silica.

Description

The present invention solves a shoe sole material based on 80-100 parts by weight of block copolymers of the Ax-Ey-Ax type, in which Ax consists of polystyrene blocks having an average molecular weight of 20,000 to 30,000 and their proportion in the total copolymers is 30 to 40% by weight. whereas By would form polybutadiene blocks having an average molecular weight of 35,000 to 150,000, wherein the basic polystyrene and polybutadiene block units are non-linearly arranged with each other by intersecting in space teleblocks, possibly replacing a maximum of 30-36 weight percent of linearly ordered block copolymers, 10-50 parts by weight of crystalline polystyrene thermoplastic having a molecular weight of 180,000 to 220,000, 10 to 35 parts by weight of extender, predominantly naphthenic oil, and also fillers, possibly coumarone resins, ethylene vinyl acetate copolymers, or / a blowing agents.

In recent years, block copolymers have been the subject of industrial use; among them the types of polystyrene-polyisoprene-polystyrene and polystyrene-polybutadiene-polystyrene. Indeed, when manufactured within a relatively limited range of molecular weights, these block copolymers exhibit the properties of elastomers without the need for vulcanization, and at the same time exhibit processing capability in thermoplastic machinery from temperatures above their softening point. In particular, these treatments include extrusion or injection molding, and it is also worth noting that they are reprocessable in this way, which means that they do not generate waste which would have to be recovered before reprocessing,

Due to the favorable flow properties of block copolymers, they are used for more demanding footwear applications, such as unit soles with heels for men's and especially women's footwear, where wall thickness and overall heel height play an important role, although they have sometimes been shown to collapse load, probably due to the linear configuration of the polystyrene block, s131388

- 2 to be faced with possible further addition of crystalline polystyrene filler.

In addition to a small proportion of polystyrene, which may fit into the so-called polystyrene domains of the base block copolymer, the major part of the polystyrene forms a reinforcement, which could be called a polystyrene skeleton. This part then influences the physico-mechanical properties, in particular the hardness of the produced soles and heels and their abrasion resistance, in a favorable sense. However, the spatial teleblocks of the block copolymers do not exclude the possibility of being exchanged for linearly arranged block copolymers, provided that their proportion does not exceed a maximum of 30 to 35% by weight.

However, it should be noted that the prices of the basic block copolymers are high and that economic reasons present the problem of the reduction of the content of these copolymers in the mixtures, generally as a rule by the use of so-called secondary raw materials. Generally, this tends to result in a deterioration in the physical properties of the sole material, but this is not desirable in terms of technical progress.

These unfavorable properties do not burden the shoe sole material based on 80-100 parts by weight of a block copolymer of the Ax-Jty-Ax type, in which Ax consists of polystyrene blocks having an average molecular weight of 20,000 to 30,000 and their proportion in the total copolymer is 30 to 40%. percent, while Ety consists of polybutadiene blocks having an average molecular weight of 35,000 to 150,000, wherein the basic polystyrene and polybutadiene block units are non-linearly arranged relative to one another by intersecting in space teleblocks, possibly replacing a maximum of 30-35 weight percent of linearly arranged block copolymers, 10 to 50 parts by weight of crystalline polystyrene thermoplastic having a molecular weight of 180,000 to 220,000, 10 to 35 parts by weight of extender, predominantly naphthenic oil, and also fillers or coumarone resins, ethylenvins A lacetate copolymer and / or a blowing agent according to the invention comprising, based on the total weight of the base polymers, 5 to 30% by weight of filler particles in the form of spherical bodies having a diameter of 0.2 to 1.7 mm, made of rubber, butadiene-styrene rubber in which the proportion of the styrene component is 40 to 50% by weight and contains 15 to 20% by weight of ground silica.

The shoe sole material according to the invention is passed through at the end of the day

- 3 have the following advantages: Above all, the abrasion resistance is maintained in the range of 80-82%, while even slightly reflecting the elasticity from the original 40% up to 44%, which increases the resistance of the outsole against penetration of foreign bodies, ie sand and stones wearing shoes. A hardness in the range of 60 to 65 ShA is also maintained. In addition, the shoe sole material according to the invention contributes significantly to the solution of ecological problems by utilizing a secondary raw material, i.e. rubber meal with precisely defined parameters.

The shoe sole material according to the invention is prepared and processed essentially by two processes, namely continuously or discontinuously. In a continuous process, the individual components are homogeneous in a kneader, for example 14 liters, whose chamber is heated to about 130 ° C, from where the material passes to a two-roll calender, with rolls heated to a temperature of 90 to 100 ° C. From there, the web of material is conveyed to a granulating machine consisting of an extruder with a roller temperature of 90 to 100 ° C and a granulating head with a temperature of 85 to 95 ° C. From there, the granules pass to the cooling device and to the packaging.

In discontinuous production, the individual components of the material are homogenized in a kneader and then transferred to a two-roll calender, possibly also processed on a three-roll calender, from which the strip-shaped material is transferred to a multi-stage gourmet refrigerator. Subsequently, the material strips arrive at a heating calender with a temperature of 90 ° C and into an extruder piston machine, for example of the Homrich type, whose nozzle is adapted to extrude rods of 4 mm diameter and the arm is adapted to carry the chopping knives. This is again followed by a device for cooling the granules and packing the material, for example in sacks.

For both processes, the components are homogenized in two phases.

In the first phase, the teleblock copolymer S-B-S is homogenized in the kneading space with crystalline polystyrene, respectively with a high-styrene resin or a high-styrene rubber. At this stage, a proportion of the spherical body filler particles 0.2 to 1.7 mm in diameter made of butadiene-styrene rubber is added to the rubber polymers in which the proportion of the styrene component is 40 to 50% by weight and comprises 15% by weight. up to 20% by weight of ground silica, a so-called rubber meal, which is used in the description in some places for simplicity. The temperature of these components during mixing reached 231,388

- 4 is 150 ° C. An antioxidant, an ultraviolet absorbing agent and optionally a stabilizer are added thereto. The total homogenization time is 2 to 5 minutes. At the end of the first mixing phase, the heating of the agitator is interrupted in both processes, especially since a blowing agent is added to the material for the lightweight soles at the end of the mixing so that it decomposes at a temperature of 160 ° C.

^R 'in the second stage mix are added to the mixtures of pigments, fillers and oil. The addition of oil to the shoe sole component according to the invention is gradual, preferably with simultaneous addition of filler, taking into account the high oil content. The low-setting oil used is characterized by low evaporation at higher mixing temperatures and processing in extruders.

The filler, especially based on silica, whose total content is reduced compared to conventional processes used in the shoe sole according to the invention, binds with its large surface area ng oil during mixing and thus substantially shortens the mixing process. In addition to siliceous fillers, for example, for mixtures of the sole soles, combinations based on silica and calcium carbonate are used.

To illustrate the invention in greater detail, several exemplary embodiments are described, which also describe the industrial application of the sole material of the invention in the shoe industry and some of its physical and mechanical properties.

Example 1

Shoe material intended for the production of colored unit soles and the production of soles by direct injection.

Teleblock copolymer S-B-S (bu: sty = 60: 40; 50 dsp oil set) 85 parts by weight Teleblock copolymer S-B-S (bu: sty = 7O: 3O) 15 Dec »1 H Ethylene vinyl acetate copolymer 1 H ¹ n Crystalline polystyrene, clear 30 H tt • 'Rubber meal No.8O 15 Dec 1 » <1

(spherical bodies 0.2 to 1.7 mm in diameter made of butadiene-styrene rubber; bu-sty = 50O-6O: 40-50 + 15 to 20% by weight of ground silica)

Antioxidant mercaptobenzthiazole 0.8

Dilauryldithiopropionate stabilizer 0.7

TPE dye béč 5

- 5 231 388

Blowing agent azodicarbonamide 0.3 parts by weight Extract resin 1 M Zinc oxide 1 II II Stearin III 0.6 tt Titanium dioxide 0.4 II ♦ 1 OLN-4 low-setting oil 32 II VI

The soles made by replastifying the granulate from this material exhibited the following physico-mechanical properties:

Melt Flow Index, g / 10 min, 180 ° C, 5 cp 4

Density, g / cm? 0.98

Hardness ° ShA 69 'Reflection elasticity,% (methoda Schob) 55

Elongation,% 560 'Crack resistance (Matthia method) 100 000 bends

Abrasion resistance (Bussen-Schlobach method),% 75

Example 2

Unit lightweight soles were prepared from several mixtures in which the content of the individual components varied as follows:

Teleblock copolymer S-B-S (bu-sty = 60: 40 + 50 dsp oil)

Crystalline polystyrene clear

Ethylene vinyl acetate copolymer (VAC content = 5-25 wt.%)

Low-setting naphthenic oil

Kumaron light, stiff

Phenolic antioxidant

UV absorber (benzothiazole derivative)

Silicon dioxide

Dyes

Blowing agent azodicarbonamide ‘'Rubber flour

Zinc oxide

90-100 parts by weight

20-30

1-6

20-30

1- 5 0.5

0,5 ”“

2- 5

0, 5-5, 3-1

10-25 0.51

Example 3

The composition of several doses of shoe sole material for compact unit soles and for direct injection soles, either in black or in a dark tint, varied between:

Tele-block copolymer S-B-S 76 parts by weight (bu-sty = 60: 40 + 50 dsp oil)

- 6 231 388

Teleblock coplymer S-B-S 10 parts by weight (bu-sty = 70:30)

rubber meal.60 5-30 ♦ t ff Crystalline polystyrene, clear 20-30 fl lt Ethylene vinyl acetate copolymer (VAC content = 5-25 parts by weight) 1-5 H fl Extract resin 1-3 f | fl Stabilizer dilauryldithiopropionate 0.4-0.6 ti tt Phenolic antioxidant 0,4-0,8 ti tt Zinc oxide 0, 5-1 tf tt TPE is carbon black P-1250 10-12 11 th Stearin III 0,3-0,6 th lt Aromatic plasticizer TRIUMF 10-30 tt th The soles of this material showed these physically mechanical Properties : “3 Density, g / cm 0.98 Hardness, ° SHA 60-70 Strength, MPa 6-7 Ductility,%. 550-650 Abrasion resistance,% 75-80 Resistance to cracking 100 000 bends

Melt Flow Index (g / 10 min), 180 ° C, 5 kg 2 Example 4

The shoe sole composition containing 9% by weight of rubber meal contained the following components in parts by weight:

Solpren 475 90 000 parts by weight Solpren 416 15 Dec 000 lt tt Krasten 127 G 32 000 tt tt Miraviten D-23 1 500 tt tt Rubber meal No. 80 18 000 tt tt Chemantox 500 tt tt Antioxidant MB-3 900 tt tt Stearin III 600 tt tt Zinc oxide 1 000 tt tf Coumarone resin, dark 2 000 w tt TPE beck 698 5 000 tt tt Titanium white 400 lt th Asphalt A0K-120 150 tt tt Azoplaston 300 tt tt

231 388

- 7 OLH-4 oil

Silicon dioxide

Physical-mechanical parameters

Hardness I.E.H.D * s

Density, g / ear

Abrasion resistance,%

Module 100%, MPa Strength, N Strength, MPa Elongation,%

Tear strength, N / mm Breaking, kc Reflection elasticity

000 weight l 8 250 *

0.98

2,0

115.4

6.8

600

25.5 100.000

Claims (1)

SUBJECT OF THE INVENTION 231 38B The shoe sole material based on 80-100 parts by weight of an Ax-Ey-Ax block copolymer in which it forms polystyrene blocks with an average molecular weight of 20,000 to 30,000 and their proportion in the total copolymer is 30 to 40% by weight, while E They form polybutadiene blocks having an average molecular weight of 35,000 to 150,000, the basic polystyrene and polybutadiene block units being non-linearly interconnected with each other by intersecting them into space teleblocks, possibly replacing a maximum of 30-35% by weight of linearly arranged block copolymers, 10 to 50 parts by weight of crystalline polystyrene thermoplastic having a molecular weight of 180,000 to 220,000, 10 to 35 parts by weight of extender, predominantly naphthenic oil, and also fillers, possibly coumarone resins, ethylene vinyl acetate copolymer and / or blowing agents, by containing, based on the total weight of the base polymers, 5 to 30 weight percent of spherical body-shaped filler particles having a diameter of 0.2 to 1.7 mm of rubber made of butadiene-styrene rubber in which the proportion of styrene component is 40 to 50 % by weight and containing 15 to 20% by weight of ground silica.