HUT62630A - Polyolefin shaped materials - Google Patents

Abstract

Polyolefin moulding materials containing, as essential ingredients, (A) 10 to 20 wt. % of apolar polyolefins, (B) 50 to 89 wt. % of an ethylene copolymerizate based on ethylene and unsaturated carboxylic acids and/or ionomers based on this type of ethylene copolymerizate, (C) 1 to 10 wt. % of a non-fibrous polymerizate, which is different from A and B, (D) 0 to 40 wt. % of conductive fillers, as well as (E) ordinary additives and processing aids.

Description

The present invention relates to polyolefin molding materials comprising:

A) 10% to 40% by weight of apolar polyolefin;

B) 50 to 89% by weight of ethylene copolymerate based on ethylene and unsaturated carboxylic acid and / or ionomer based on such ethylene copolymerate;

C) 1-10% by weight of a non-fibrous polymerate other than A and B;

D) 0-40% by weight of a conductive filler; as well as

(E) standard additives and processing aids.

The present invention relates to the use of the molding materials of the present invention for injection molding or extrusion molding and to the use of strip or sheet floor coverings made of the polyolefin molding materials of the invention.

Polyolefins are widely used in the industry, and a large number of products with different properties are used for different applications.

Vinyl halide copolymerate-based products are widely used in floor coverings, particularly those used in industrial areas, but they are not completely satisfactory in some respects.

Polyolefin-based, especially polypropylene-based floor coatings are used in the private sector, but these products are not suitable for industrial installations as they cannot withstand the high loads that occur there.

Highly crystalline polyolefin polymerizates exhibit improved mechanical stability but are extremely smooth and thus have a non-slip surface and are thus difficult to glue. In addition, they often have poor elasticity and are susceptible to rupture.

Flexibility can be improved by admixing impact-modified products such as ethylene / propylene copolymers or ethylene / propylene / diene terpolymers (EPDM rubbers). However, in this case, other valuable properties often deteriorate.

It is known from EP-A-309 674 that it reduces the elasticity of heavy coating masses used in crystalline polypropylene textile floor coverings and therefore replaces most of the polypropylene with polypropylene grafted with an unsaturated organic acid. However, the residual penetration depth of these products when applied to industrial floor coatings is too high.

U.S. Patent 4,387,188 discloses blends of linear polyolefins, acid copolymers of ethylene, and fibrous fillers and reinforcing materials, wherein the amount of fibrous additives is up to 50% by weight.

German Patent Publication No. 33 06 776 discloses a polyolefin molding material containing ethylene / vinyl acetate copolymerate as the main component. Ethylene / vinyl acetate copolymers have disadvantages for use in industrial floor coatings, in particular their relatively high shrinkage and

I because of their relatively low hardness.

SUMMARY OF THE INVENTION It is an object of the present invention to provide polyolefin molding materials which are particularly suitable for the production of industrial floor coatings and which have, for example, extremely high return elasticity (and associated residual indentation; defined by DIN 51 955)

- have bending strength and flexibility, low penetration depth, low rolling frictional resistance, high hot form resistance, high slip resistance and high abrasion resistance, good adhesion to many substrates, good chemical resistance.

The object of the present invention is achieved by the polyolefin molding materials as defined at the beginning of this specification.

Preferred materials are those known from the dependent claims.

The polyolefin molds according to the invention contain as component A) 10 to 40% by weight, preferably 11 to 35% by weight, in particular 12 to 25% by weight, of a non-polar polyolefin.

The polymers of component A) preferably have high degrees of crystallinity.

Polyethylene as well as polypropylene and mixtures thereof are preferred in terms of chemical structure.

The ethylene polymerate used as component A) preferably has a density of 0.94 to 0.97 g / cm ³ , in particular 0.945 to 0.965 g / cm ³ and a degree of crystallinity of at least 50%, preferably at least 60%.

The Melt index is generally 0.01 to 40 g / 10 min, preferably 0.1 g / 10 min, measured at 190 ° C under a load of 2.16 kg.

Suitable types of polyethylene are commercially available materials such as MDPE (Medium Density Polyethylene) or HDPE (High Density Polyethylene) such as BASF AG's Lopden ^R brand. Mixtures of different polyethylenes may also be used as component A).

Propylene polymerizates also useful as component A) are known to those skilled in the art and are commercially available.

Generally, isotactic propylene polymers having a high degree of crystallinity are suitable. Such products generally have a density of 0.88 to 0.92, especially from 0.89 to 0.91 g / cm ³ and a melt volume index (MVI) of the respective polypropylene depending on the molecular weight of from 0.1 to 100 cm ^3/10 min, preferably from 0.2 to 60 cm ^3/10 min, measured according to DIN 53 735 2.16 kg load at 230 ° C.

Examples of suitable polypropylenes are Novolen ^R 1100 and 1300, manufactured by BASF AG.

Suitable components A) are other copolymers of ethylene with 1-olefin, in particular propylene, and mixtures thereof with MDPE, HDPE and / or isotactic polypropylene.

In general, bulk and statistical copolymerizates are suitable, where the proportions of the individual monomers are not particularly limited.

Suitable copolymerizates are Novolen ^R 23, 25, and Novolen 32, and 35, respectively, which are manufactured by BASF AG.

«· · *: <Ί. *.:. · .. ·:: - 6 In general, the choice of the type of Component A influences the final properties of the molding material, when used at high processing temperatures and high shear rates of HDPE and / or MDPE has certain advantages over polypropylene and copolymerizates.

Component B, which comprises from 50 to 89% by weight, based on the total weight of components A) to C), in particular 57 to 87, particularly preferably 62 to 85%, of ethylene copolymer of ethylene and unsaturated carboxylic acid and / or ethylene copolymer thereof. Copolymerizate based ionomer.

The copolymerate is generally composed of 50 to 99% by weight of ethylene and 1 to 50% by weight of a carboxylic acid or derivative thereof and a minimal amount of units is derived from free carboxylic acid.

Suitable carboxylic acids are unsaturated mono- and dicarboxylic acids, preferably having from 3 to 12 carbon atoms, in particular acrylic acid, methacrylic acid, fumaric acid, and maleic acid, the first two of which are preferred. Maleic anhydride behaves like free maleic acid under processing conditions and is thus also classified in this group. The proportion of unsaturated carboxylic acids is generally 0.5 to 20% by weight, preferably 1 to 15% by weight, based on the total weight of the ethylene copolymer.

In addition to ethylene and the listed unsaturated carboxylic acids, the other comonomers are, in particular, the C 1 -C 18 alkyl esters of the listed acids, in particular the C 1 -C 18 (meth) alkyl acrylates. Their proportion is generally up to 45% by weight based on the total weight of the copolymer, preferably 2-40% by weight, in particular 6-35% by weight.

The density of the ethylene copolymerizates used as component B of the invention is generally 0.91 to 0.96 g / cm ³ , in particular 0.92 to 0.95 g / cm ³ , with a Melt index of 0.1 to 100, preferably 0.5 30 g / 10 min at 190 ° C measured at a load of 2.16 kg in accordance with DIN 53 735.

Suitable ionomers as component B are those which can be prepared by the partial or total neutralization of the carbonyl groups of the aforementioned ethylene copolymerizates using metal salts, in particular light or sodium salts. The preparation of such products, as well as the preparation of such products, are known, for example, from U.S. Patent No. 3,264,272 and are known to the person skilled in the art, so no further details are given. It will be understood that any mixture of ethylene copolymers and ionomers as component B may also be used as component B).

The corresponding ionomers preferably have a density of 0.92 to 0.97 g / cm ³ , in particular 0.93 to 0.95 g / cm ³ , with a Melt index of 0.5 to 30 g / 10 min, preferably 1.0 to 20 g / 10 min. At 190 ° C under a load of 2.16 kg. Suitable ethylene copolymers and ionomers are the Lucalene products of BASF AG.

As component C, the polyolefin molds according to the invention contain from 1 to 10, preferably from 2 to 8, especially from 2 to 6% by weight of non-fibrous polymeric isates other than components A and B.

As component C, polyamides and polycarbonates and mixtures thereof are particularly preferred.

It is important that component C) is present in the mold material in a non-fibrous form such as granules or slices.

Component C may also be applied to the surface of component A) and incorporated into the mixture. Such products can be used in the production of films, and once used materials (recyclates) or milling waste can be properly used.

Examples of suitable polyamides are poly-ε-caprolactam (polyamide 6), polyhexamethylene adipic acid amide (polyamide-66), and polyamide-11 and polyamide-12.

The relative viscosity of said products is generally 1.2 to 5.0, preferably 1.8 to 4.0, 0.5%, 96% by weight in a solution of sulfuric acid, measured according to DIN 53727.

Instead of the polyamides, polycarbonates can also be used as component C), in particular polycarbonates based on bisphenol A or substituted derivatives thereof. Mixtures of polyamides and polycarbonates may also be used.

Suitable polyamides and polycarbonates are known to those skilled in the art, such as Ultramid ^R (product of BASF AG) and Lexan ^R (product of General Electric Co. Ltd.), which are commercially available, so no further details are given.

As mentioned above, the products used as component C) are preferably in the form of recyclates from production wastes or co-extrudates prepared with partially crystalline polyethylene, preferably in the form of granules up to 5 mm in size, in particular in the form of scales.

Incorporating said materials into the molded materials of the present invention in non-fibrous form confers on the molded materials properties which are not achievable with fibrous fillers.

The choice of the appropriate polyamides or polycarbonates depends on the properties to be achieved, and the advantage of each polyamide or polycarbonate is determined by the person skilled in the art.

An important advantage of the present invention is that the molded materials have optimum final properties without the addition of fiber reinforcing agents, i.e. they do not preferably contain such fillers. making processing much easier.

The molded materials according to the invention contain from 0 to 40% by weight of component D), preferably from 0.2 to 35% by weight, in particular from 0.5 to 25% by weight, of conductive filler in order to adjust the surface conductivity of the molded materials. In order to achieve a satisfactory increase in conductivity by the use of relatively small amounts of conductive fillers, these materials are preferably added during mixing of the components just prior to the production of the molds, thereby concentrating these materials on the surface with a poor dispersion. In particular, carbon black is used as a conductive filler.

In addition to Components A) to D), the formulation materials of the present invention contain conventional additives and processing aids known to those skilled in the art for processing polyolefins. Examples include additives added to improve burn properties, or pigments for coloring purposes, lubricants, and mold release agents.

The mold materials of the present invention are prepared by first partially coupling the phases together during mixing. This is done, for example, by mixing the components at elevated temperatures and / or using high shear forces. In a particularly preferred process, the components are blended in solid form and then thawed in an extruder for homogenization. The granules obtained during extrusion can then be used to produce molds.

The polyolefin molding materials according to the invention are particularly suitable for the production of industrial floor coatings, in particular for the production of tapes or sheets.

The floor coatings thus produced have the following advantages:

high residual elasticity measured according to DIN 51 955;

high impact bending strength at low temperatures;

low penetration depth, high heat resistance, high abrasion resistance,

- good slip resistance, good adhesion and weldability, and good chemical resistance.

The invention is illustrated by the following example.

Example

A polyolefin mixture according to the present invention consisting of the following components once without soot and once with 0.2% by weight of soot as mixture B after drying and mixing the compounds on an injection molding machine

A) to colorless sheets with a length of 400 x 500 mm and a thickness of 4 mm,

B) Converted into colored plates having a wind length of 400 x 400 mm and a thickness of 8 mm.

The mixture has the following composition:

(a) 28% by weight of non-polar HDPE / MDPE with a density of 950 kg / m ³ ,

Melt index 190 / 2.16 - 0.2 kg / 10 min.

b) Copolymer of 70% w / w with ethylene 8.2% w / w acrylic acid, density 0.937 g / cm ³ , melt index 15 - 19 g / 10 min (MFI 190 / 2.16) (Lucalen ^R A 3710S, BASF AG product).

c) 2% by weight of polyamide-6 which is coextruded with component a) and subsequently ground.

The results of the tests carried out on the products obtained are shown in the following tables. The tests carried out are as follows:

residual penetration depth and penetration depth

According to DIN 51 955

Shore The hardness according to DIN 53 505 Slip resistance, Stanley-Text Antiskidresistance building material standard Elastic modulus (tensile) DIN 53 445 Slip modulus according to DIN 53 445 Impact strength 23 ° / -40 ° C with PUR one-component sandblasted strength of bonding to a concrete surface

(a) shear strength

b) bark test thermal change according to DIN 51 962 abrasion resistance according to DIN 51 963

Table 1

Strength characteristics of A and B products

Product B is product

Penetration depth (mm)

150 min 0.0080,054

1500 min 0.0150.066

Residual penetration depth (mm) minutes after stopping the load 0.003-0.0090.02

150 minutes after stopping the load 0.001-0.0020,008

Shore Hardness 9896-97 * · «·

Table 1 (continued)

The product Product B. Impact strength 23 ° / -40 ° C It doesn't break It doesn't break E module (N / mm ² ) 650 520 Sliding modulus of elasticity 340 320 (N / mm ² ) Wear resistance (mm) 0,012 0,012

Table 2 Surface properties of products A) and B) The product Product B. Csúszásszilárdság 67-87 85 With PUR on concrete adhesive application a) Shear strength (N / mm ² ) 2.4 2.8 Fracture of concrete Fracture of concrete surface surface b) bark strength (N / mm) 4.5 4.8 According to DIN 53 278 Fracture of concrete Fracture of concrete surface surface Surface resistance (u ») 20 · 10 ¹¹ 20 · 10 ¹⁰

According to DIN 53 482

Claims (10)

Claims 1. Polyolefin molding materials which are essential constituents of A) 10% to 40% by weight of apolar polyolefin; B) 50 to 89% by weight of ethylene copolymerate based on ethylene and unsaturated carboxylic acid and / or ionomer based on such ethylene copolymerate; C) from 1% to 10% by weight of a non-fibrous polymer other than Components A and B; D) 0-40% by weight of a conductive filler; as well as (E) standard additives and processing aids. Polyolefin molding materials according to claim 1, characterized in that they contain from 0.2 to 35% by weight of component D). Polyolefin molding material according to claim 1 or 2, characterized in that component A) contains partially crystalline polyethylene having a density of 0.94 to 0.97 g / cm ³ . Polyolefin molding material according to claim 1 or 2, characterized in that it comprises as component A) partially crystalline polypropylene. Polyolefin molding material according to claim 1 or 2, characterized in that it comprises as component A) a statistical propylene / ethylene copolymer and / or a block copolymer of propylene and ethylene. 6. Polyolefin molding material according to any one of claims 1 to 3, characterized in that component B) comprises a copolymerate consisting of ethylene and acrylic acid and / or methacrylic acid and / or an ionomer based on such copolymerizate. 7. Polyolefin molding material according to any one of claims 1 to 3, characterized in that it comprises, as component C) thermoplastic polyamide and / or polycarbonate. 8. Use of a polyolefin molding material according to any one of claims 1 to 4 for the production of molding bodies by injection molding or extrusion. 9. Use of polyolefin molding materials according to any one of claims 1 to 11 for the production of floor coatings. 10. Floor coatings in the form of strips or sheets according to any one of claims 1 to 4.