DD158330A3 - Thermoplastic materials for flexible shoes - Google Patents

Abstract

The invention relates to thermoplastic molding compositions for flexible shoe materials, in particular for shoe sole materials and Vollplaststiefelschaeften with a compact or cell-shaped structure, which are preferably produced by the injection molding process. D. Shoematerials should have a high abrasion resistance and a good Keltbiegebestaendigkeit largely inde pendent of the set Haertegrad. The object of the invention is to develop modified PVC-soft mixtures with acrylonitrile-butadiene rubber and chlorinated polyethylene, which provide a significantly improved in its property values shoe material. According to the invention, the PVC-soft mixture consisting of PVC, plasticizers, acrylonitrile-butadiene rubber and optionally other plasticizers is from 1 to 10% by weight, preferably from 3 to 8% by weight, of a high-density chlorinated polyethylene having a chlorine content of about 38 to 45% and a glass transition temperature of below -10 degrees C, preferably below -20 degrees C, in the mixing ratio of 1: 3 to 1: 6 are added to the acrylonitrile-butadiene rubber.

Description

202 64 7

VEB CHEMIEKOITIBIBAT BITTERZELD Bitterfeld, 9 · 12

1889

Thermoplastic molding compounds for flexible shoe materials

Field of application of the invention

The invention relates to thermoplastic molding compositions for flexible shoe materials, in particular for shoe sole materials and Vollplaststiefelschäfte with compact and cell-shaped structure, which are preferably prepared by the Spritzgu method,

Characteristic of the known technical solutions

It is known to produce shoe materials, in particular shoe sole materials with a compact or cellular structure of PVC-soft mixtures by the injection molding process. The advantages of PVC-soft mixtures consist essentially in the fact that they are priced favorably and can be processed by productive processes. However, certain property values are sufficient. PVC soft-gauge compounds, in particular, the abrasion resistance and cold bending resistance, not the practical requirements «

  ·. ~ 2 J '2 0 2 6 Λ 7 1889

It is also known from FE-PS 1,502,145 and DE-ES 1,908,781 to prepare mixtures of PVG, steamers and acrylonitrile butadiene rubber. The addition of acrylonitrile butadiene rubber improves the oil and gasoline resistance of plasticized PVC «, Such mixtures are preferably used to seal elements, washers, container liners, packaging u * a. M # processed "DD-PS 40 182 describes mixtures which consist of PVC, acrylonitrile-butadiene rubber, monomer plasticizer and chlorinated polybutadiene." Our own experiments have shown that these mixtures are thermally unstable and also unsuitable for the production of shoe materials are.

French Patent Specification 1 135 902 discloses the use of acrylonitrile butadiene rubber modified PVG soft for shoe sole materials *. These molding compounds are characterized by a high hardness (Shore A hardness of at least 80) and a good abrasion resistance and bite resistance when bending while adhering to a specific ratio between PVC, plasticizer and acrylonitrile butadiene rubber. By changing the given ratio, however, products are obtained with unsatisfactory properties which, with a lower hardness setting, have a low abrasion resistance and, at an even greater hardness, a reduced bite resistance on iron. As is well known, however, the shoe soles made of soft PVC are suitable for the usual shoe ranges, e.g. Sports shoes, street shoes, work shoes, a much greater flexibility, so that the mixtures described in the latter patent are not suitable for use in the usual shoe materials »

British Patent Specification 1 175 903 discloses injection moldable, foamable compositions using polyvinyl chloride and polyester plasticizers and optionally

** 3

^; '-3-- 2.0264 7 1889

Acrylonitrile butadiene rubber "described" Although these compositions have good strength properties and abrasion values at normal temperatures, they are extremely difficult to process and have insufficient low - temperature behavior.

Object of the invention

The aim of the invention is to produce injection-moldable, flexible PVO-soft molding compositions for shoe materials with a compact or cellular structure, in particular shoe sole ("") materials and Stiefelschäfte, * have largely independent of the set hardness high abrasion resistance and resistance to cold bending.

Presentation of the essence, the invention

The object of the invention is to add PVC-soft mixtures modified with acrylonitrile-butadiene rubber with other components, so that one in its properties. According to the invention, the object is achieved by the fact that the polyvinyl chloride, plasticizers, acrylonitrile butadiene. , Rubber and optionally blowing agents, kickers, stabilizers, antioxidants, fillers and other plasticisers existing PVC soft mixture 1 to 10 Gewichtsstei preferably 3 to 8 parts by weight of a chlorinated polyethylene: high density with a chlorine content of about 38 to 45 % and a glass transition temperature of .lower -10 ⁰ C, preferably of below -20 ⁰ C, in a mixing ratio \ 1: 3 to 1 j 6 to acrylonitrile - will give rubber trains, £> ie operation of the chlorinated polyethylenes used in this invention in combination with acrylonitrile - - butadiene butadiene - Rubber is completely surprising in the novel compositions for .Schuhmaterialien is because it was fes that a sole addition of chlorinated polyethylene in PVC soft leads to any positive effects sense of the invention, ^ s was further found that daf

- 4- 202 6 4 7 1889

chlorinated polyethylenes whose characteristics do not correspond to those described above are unsuitable for shoe materials in the sense of the invention. As starting polyethylenes for the preparation of the chlorinated polyethylenes used according to the invention, products of homopolymers and copolymers with small proportions of propylene or butylene can be used. However, particularly preferred is high molecular weight high density polyethylene having a predominantly linear structure. , The chlorinated polyethylenes used according to the invention have a chlorine content of about 38 to about 45%. In particular, chlorination processes in solution are suitable for the preparation of these products known per se, as described, for example, in DDE Patent 78,372.

The acrylonitrile-butadiene rubber used is preferably an unvulcanized but vulcanizable product having an acrylonitrile content of about 20 to 40% by weight.

The sum of the two modifying components is. at least 6 wt. Tl. In general, however, gives the best results in an amount of 15 to 30 wt. Tl. In the specified mixing ratio.

Suitable vinyl chloride polymers are homopolymers and / or copolymers of vinyl chloride with small amounts of other unsaturated compounds, e.g. Propylene, vinyl acetate or vinylidene chloride. However, particularly preferred products are polyvinylchloride types having K values of 65 to 80, prepared by the bulk or suspension polymerization process.

As plasticizers, the usual phthalic acid esters, phosphoric acid esters, adipic acid esters, sebaiic acid esters, phenylalkylsulfensäureester u.a. individually or as a combination of two. or more plasticizers. "The molding compositions according to the invention can furthermore be used as plasticizers.

V " '

substances, such as Propellants, kickers, stabilizers, antioxidants, fillers and other processing aids containing * ^ der Mischling preparation of the modified PVC-soft mixtures according to the invention can by any method

2026Λ7 1889

the. Rubber or thermoplastic processing is carried out provided that a homogeneous distribution of the individual components of the mixture is ensured.

 The PVG-soft mixtures according to the invention can be molded by the usual methods of thermoplastic processing, preferably by the injection molding process. »The shoe materials produced from the PVC-soft-Mi fabric according to the invention have a Shore A hardness of from about 50 to about 80 high Abriebfestig speed and resistance to cold bending. These remarkable property values are almost independent of the respective hardness setting of the shoe materials and remain even with very flexible molding materials (Shore A of about 50). The PVC soft-Mi slings according to the invention are particularly suitable for the production of shoe soles with a compact or cellular structure for street shoes Children shoes, sports shoes, work shoes, work boots and full plastic boot shafts, but they are also suitable for the production of other injection molded articles as well as foils, cable compounds, etc., by calendering or extrusion techniques, by admixing blowing agents such as azodicarbonamide obtained foamed shoe sole materials with excellent properties, the density of which e 0 ,? to 1.0 g / cm ^.

Execution examples

The invention will be explained with reference to several examples. ,

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WP C 08 L / 202 647

example 1

In a heating-cooling mixer combination 6 different PVC-white hybrids are manufactured, the composition of which is shown in the following table. For comparison, an unmodified PVC-soft mixture (mixture 1), an acrylonitrile-butadiene-rubber-containing PVC-soft mixture (mixture 2) and a chlorinated polyethylene-containing PVC / soft mixture (mixture 3) are prepared.

The mixtures 4> 5 and .6 are inventive PVC-soft mixtures ·, which differ in the degree of hardness. The mixture preparation is carried out such that the solid mixture components are placed in the heating mixer, heated to 115 ⁰ C and at this temperature, the plasticizer mixture is added. Subsequently, the mixture is heated to 125 ⁰ C and added to the cooling mixer. The discharge of the ready-mixing occurs at about 40 ⁰ C. Thereafter, the mixtures according to TGX 20,427 zu.Prüfkörpern be processed The determined on the test specimens property values (Shore Α hardness, abrasion and cold bending resistance) are also seen from the following table:

Table 1

The recipes are given in steep weight.

1889 WP 0 08 L / 202 647

Mixing Stations I Ie

Mixture mixture mixture mixture mixture mixture 1 2 3 4 5 6

Suspension Po lyviny 1 chloride K value 70

Softener mixture (DOP / dioctyl adipate)

AcryInitri1-butadiene chewable AN content 33 # -

Chlorinated polyethylene Chlorine content 44 % Glass transition point - 21 C

solid Ba / Gd stabilizer abrasion resistance. (nmr)

Folding resistance at - 20 ⁰ C according to IPV of PIS ETr. 1,104

Shore A hardness

100

85

2.0 68th 2.0 183 142 35th 000 000 59 61

100

60

40 2.0 170

100 60

34

6 2.0

85

100 66

40

2.0 102

100 50

30

5. 2.0

77

56,000> 150,000 M50,000> 150,000 64 60 50 71

  -8- 2 0 2647 1889

, , · WP C 08 L / 202 647

It can be seen from Table 1 that the test specimens prepared from the mixtures according to the invention have markedly better abrasion resistance and resistance to cold bending in comparison to the mixtures 1, 2 and 3. Excellent property values remain even with the very flexible mixture 5 »

Example 2

The six PVC-soft mixtures according to Example 1 are processed into granules, which are deformed by means of an injection molding machine with screw plasticizing at cylinder temperatures of 165 ⁰ C to 180 ⁰ C and nozzle temperatures of 180 ⁰ C to 185 ⁰ C to soles »The on the soles of the shoe The tests performed gave the following values:

T abe lie 2

1889

WP C 08 I / 202 647

Shoe soles Shoe soles Shoe soles Shoe soles Shoe soles Shoe soles v · Blend of Mixture v, mixture v. Mixture of Mixture of mixture

; 1 2 __J 4__ 5_ 6

'Abrasion resistance'.

( ^J ) 205 .162 188 98 · 110 93

Resistant to cold bending at - 20 ⁰ C after. · ·

IPV of PIS Έτ, .1.104 3.1.000 66 · 000 52.000 '>150.000>150.000> 150.000

Shore A hardness' 61 63 65 61 52 .73

202 64 7 ₁₈₈₉

WP C 081/202 647

As expected, the test values show a slight decrease in abrasion resistance and resistance to cold bending in comparison to the test values determined in Example 1, while a slight increase in Shore hardness is observed. The measured values confirm the results of Example 1 _e

Example 3

Another part of the shoe soles produced by injection molding according to Example 2 is applied in the bonding process by means of PUR-KIebstoff on gezwickte men's low shoes carried out therewith wear results after a 'wearing time of about 1000 hours the following test result:

Carrying trial-Fri,

Wear time Assessment of sole wear and tear resistance

Shoe soles mixture 1 from 1000 H Shoe soles mixture 2 from 1000 H Shoe soles mixture 3 from 1000 H Shoe soles mixture 4 from 1000 H Shoe soles mixture 5 from 1000 H Shoe soles mixture 6 from 1000 H

Profile Bale expired crack on bale

Profile bales almost expired slight cracking on the bale

Profile bales almost expired slight cracking on the bale

Profile easily expired no cracking

Profile easily expired no cracking

Profile easily expired no cracking

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_ "_ .. 202647. ₁₈₈₉

WP C 08 1/202 647

The evaluation of the wearing cusps showed a clear superiority of those shoe soles which have been produced from the mixtures 4, 5 and 6 according to the invention.

Example 4

Six PYC-weioh-Mischungeη be prepared according to Example 1 with the difference that all mixtures each 0.4 parts by weight of the propellant azodicarbonamide is added and the mixtures are heated to only 115 ⁰ C during the mixing process.

The granules made from the mixtures v / earth processed on an injection molding machine at processing temperatures of 165 ⁰ C to 180 ⁰ C to foamed molded soles. The density of the mold soles is 0.78 to 0.85 g / cm. The abrasion resistance and cold bend resistance obtained are shown in Table 3 below.

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1889 WP C 08 1/202 647

Table 3

foamed foamed foamed foamed foamed foamed shoe soles shoe soles shoe soles shoe soles shoe soles shoe soles v »mixture v, mixture of v. Mixture v · Mixture v. Mixture of Mixture .__ ; 1 2 1_ 4. 5 6__

Abrasion resistance. 230 182 · 205 118 125 136

(mm ³ ).

Cold bending resistant- 25,000 48,000 28,000>100,000> 100,000 '> 100,000 at -20 ⁰ O.

, · - 13 - 2 0 2 647 _188g

WP C 08 L / 202 647

The test results obtained show that the shoe soles produced by injection molding from the mixtures 4, 5 and 6 according to the invention are clearly superior to the soles of the shoes from mixtures 1, 2 and 3.

Claims (1)

Thermoplastic molding compositions for flexible shoe materials, in particular shoe soles and boot shafts, using polyvinyl chloride, plasticizers, acrylonitrile-butadiene rubber and, if appropriate, propellants, kickers, stabilizers, antioxidants, fillers and other plastic auxiliaries, characterized in that the molding materials 1 to 10 Parts by weight, preferably 3 to 8 parts by weight, of a chlorinated polyethylene high density with a chlorine content of about 38 to about 45 percent and a glass transition temperature of below -10 ⁰ G, preferably below -20 ⁰ C, in the mixing ratio of 1: 3 to 1; 6 to the acrylonitrile butadiene rubber contained