DE1230560B - Production of floors and wall coverings - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 b -22/06

Number: 1230 560

File number: S 57542IV c / 39 b

Filing date: March 26, 1958

Opening day: December 15, 1966

The invention relates to the use of a molding compound composed of 1.50 to 92.5 percent by weight of fibrous and / or non-fibrous fillers and 2. 50 to 7.5 weight percent of a resinous binder from a) a soft, amorphous or a plasticized isotactic homopolymer or copolymer of propylene and, if appropriate, additionally b) a homo- or copolymers different from a) an unsaturated hydrocarbon monomer and / or c) a naphthalene-formaldehyde resin and / or d) a coumarone resin and / or e) asphalt-like bitumen and / or f) pitch, for production of floors and wall coverings.

The word "resinous" is used in a broad sense and denotes in connection with the polymers and copolymers of propylene both relatively soft polymers and copolymers that amorphous polypropylenes, which mostly have a rubbery consistency, as well as relatively hard polymers and copolymers, the isotactic polypropylenes and also polymers and Copolymers with intermediate physical properties. In general, they are proportionate soft polymers and copolymers have a low melting point and are advantageous used to toughen hard synthetic resin compositions. The relatively hard polymers and copolymers, on the other hand, are generally high-melting and are particularly used to stiffen softer synthetic resin compounds.

A specific mixture according to the invention contains fillers together with a resinous binder, which consists partly of an amorphous, soft, resinous propylene polymer or copolymer and partly of one or more additional resinous substances, such as petroleum resin, coumarone resin, polystyrene resin, resinous styrene -Butadiene copolymer with a high styrene content, resin-like polymers of oc-methylstyrene, resin-like polymers of cyclopentadiene, naphthalene-formaldehyde resin, asphalt-like bitumen and pitch. In general, it is desirable that a substantial proportion of the additional binder components are materials having a softening point in the range 65-145 ⁰ C.

The petroleum resins mentioned in the previous section are resins which are used in the polymerization of certain Mixtures of hydrocarbons are obtained from the cracking of petroleum or a Petroleum fraction or simply incurred in the fractional distillation of petroleum. Furthermore you can

Production of floors and wall coverings

Applicant:

Dunlop Semtex Limited, London

Representative:

Dipl.-Ing. R. Mertens, patent attorney,

Frankfurt / M., Neue Mainzer Str. 40-42

Named as inventor:

Walter Saul, Stanmore, Middlesex;

Ivor Mumford, Brynmawr, Breconshire

(Great Britain)

Claimed priority:

Great Britain March 26, 1957 (9800)

ao tall oil pitch and also coal tar pitch and 01-gasteer pitch be used.

Soft propylene polymers and / or copolymers in combination with polyethylene, in particular polyethylene with a high specific weight, are just as suitable as the resinous binder mixtures mentioned. Soft propylene polymers and / or copolymers can also be used in conjunction with a polyisobutylene or with a rubber-like isobutylene-butadiene copolymer, a rubber-like isobutylene-isoprene copolymer or a similar rubber-like mono-olefin-diolefin copolymer.
Other substances that can be used as constituents of the resinous binder, if it contains a soft propylene polymer or copolymer, are natural rubber and synthetic rubber of the styrene-butadiene copolymer type.

If a soft propylene polymer or copolymer is used, it is generally appropriate that the weight of the resinous binder is 50 to 10% of the total mixture weight and the weight of the fillers is correspondingly 50 to 90% of the total mixture weight. In some cases, however, the weight of the resinous binder can also be less than 10%> e.g. B. be about 7.5% of the total mixture weight.
The surprising fact was found that the binders mentioned can bind a significantly higher proportion of filler material than any other previously in connection with flooring

609 747/352

3 4

and wall covering mixtures for use instead of panels for floor or wall lengths flexible, resinous polymer. These own topping are produced, the mixtures become ebenschaft Can be of particular value in such mines prepared in an indoor mixer, on WaIzschungen its resinous binders are both milled, dimensioned and on the calender an amorphous, soft propylene polymer and / or 5 rolled up the cooled tape. -Mix polymer as well as a resinous material. . contain, its affinity for fillers, comparative example 1 wise low, such as low pressure poly- A thermoplastic blend is made by mixing ethylene. of the following components on a 2-roll roller

Even if the proportion of soft propylene works, one of which has a temperature of 140 ° C

Polymer and / or -Mischpolymerisats only slight and the other roll has a temperature of 160 ⁰ C.

is, one used according to the invention can be produced:

Mixture of flexural strength and impact strength Amorphous polypropylene 1 part

own that are much improved compared to Polvstvrol 4 parts

with mixtures that have an analogous structure, but 15

no soft polymer and / or mixed polymer Fetroleum resin / leüe

Contained by propylene. In addition to increasing coumarone resin 4 parts

the impact resistance is also a noticeable increase in tall oil pitch 11 parts

the hardness present. Asbestos fiber 28 parts

As already mentioned, the propylene poly- _{ao K} alksteinmehl can contain 43 parts

mensates and copolymers that are in the mixture _Ί

are processed, and isotactic, hard poly- iitandioxyd I ieüe

represent merisate or copolymers, z. B. The polypropylene is in the form of a concentrate, mixtures of soft and hard propylene with petroleum resin are processed, with V _{3 used} polypropylene polymers. The tough propylene poly 25 is. Likewise, the polystyrene is first made into a concentrate and copolymers are also processed in step with petroleum resin, the proportion of compound with another soft polymer of polystyrene being 50 percent by weight. Then or mixed polymer, such as a polyisobutyl, the concentrates are processed together with the other components, an isobutylene-butadiene mixed polymer, mixture components. Some mechanical and rubber-like isobutylene-isoprene mixture properties of this mixture are listed in the table below for polymer or a similar mono-olefin mixture. This mixture of olefin copolymers, or with an oil as a stretching agent, is used for the production of thermoplastic sheets or plasticizers. A typical used for flooring. Also the following isotactic polypropylene melts in approximately the examples relate to mixtures which are used for 162 ° C, whereby its immediate use as 35 has the same purpose. Component of a mixture of the type mentioned is unusable, since such mixtures are normally produced in example 2 machines in which essentially a thermoplastic mixture is used in the same lower temperatures, manner and with the same materials as in the case where the melting point is. This difficulty, the 40 game 1 produced, but with the difference that it results from the high melting point, but the proportion of amorphous polypropylene can be increased to 2 parts by adding an oil or by mixing it beforehand and the proportion of tall oil pitch accordingly a soft polymer or mixed 10 parts was lowered, polymer can be overcome. Some mechanical properties of the products

The following examples illustrate the invention. All 45 can be found in the table mentioned,

The amounts given in the examples are by weight. .

share. Examples 1, 2 and 3 relate to the examples

Turning soft propylene polymers into a thermoplastic mixture is made from the following

small portions to improve the usual additive ingredients in the same way as in

compositions of the mixtures for the preparation 50 Example 1 prepared:

of covering plates. Examples 4, 5 and 6 deal with Amorphous Polypropylene 3 parts

deal with the wide range of applications of Polvstvrol 4 parts

soft propylene polymers for the production of new ' ο τ -τ

like and improved products. Examples 7 and 8 petroleum resin 8 I rush

show the use of hard propylene-poly-55 coumarone resin 3 parts

merizaten and in particular isotactic polypropylene tall oil pitch 9 parts

lene for making useful mixtures. Asbestos fiber 28 parts

The mixtures, with or without pigments, are limestone powder '!.' "!. '".'. 'Υ !.' !. '.'. ' 43 parts

for making on a large scale, usually m a ο τ ί

Internal mixer to achieve a hot thermoplastic 60 Iitandioxyd 2 Ieile

processed mixture. The mechanical properties of the products are made of which can usually be seen on a rolling mill to a skin in the table below, rolled out and when passing through two calenders The table shows some mechanical properties reduced to the exact thickness. Finally, that of the mixture field used in the above three examples cut into sheets when hot. By 65 genes and a comparison mixture, which, as in the case of incorporation differently colored elements in the game 1 indicated, was made in the, however Fur during manufacture can be a marbling 1 part polypropylene by an additional part in effect can be achieved. Should from the mixtures tall oil pitch was replaced.

Tabel

exam on Comparison mixture Mix according to
example 1 Mix according to
Example 2 Mix according to
Example 3 Indentation depth 1 (mm)
Indentation depth 2 (mm)
Indentation depth 3 (mm)
Flexural strength in calendering
direction . . 0.23
0.30
0.40
6,400
4,100
1.8648 0.19
0.24
0.33
6,800
5,800
1.7984 0.20
0.25
0.33
7,000
6,400
2.268 0.20
0.25
0.33
11,000
9,300
3.8976 Flexural strength contrary to the
Calendering direction
Impact resistance

The indentation depths given in the table were determined with a McBurney indentation depth gauge. In case 1, the load acted at a temperature of 25 ° C and 1 minute on the test piece, in the case 2 at a temperature of 25 ⁰ C for 10 minutes and in the case 3 at a temperature of 46 ° C for 30 seconds. The indentation depths are given in mm. The flexural strengths given in the table were determined on samples with the dimensions 56-18-3 mm, which were initially heated at 25 ° C. for 15 minutes. Each of these samples was placed on a support device with the two support posts 37 mm apart, and the sample was loaded with a steel rod 30 mm in diameter in the middle between the two supports. The load was continuously increased until the sample was broken, the breaking load recorded, and the flexural strength from the formula

—— T ² · 0.142 calculated, where B is the load at the IUU ä5

Fraction in kg and T means the thickness of the specimen in cm.

The impact strengths given in the table are determined with a Hounsfield impact tester been. A description of this tester is in the book "Commercial Testing", Part II, by Leslie H. Hounsfield. The impact strengths are expressed in kg / m per cm width and per cm thickness and were out of the formula

45 impact energy in kg / m

Calculated the width of the pattern in cm times (thickness of the pattern in cm ² ).

From the figures given in the table it can be seen that the incorporation of the amorphous polypropylene causes significant improvements in flexural strength and impact strength. The improvements are particularly noticeable in the blend containing 3% polypropylene (Example 3).

Example 4

Thermoplastic mixtures made from the following components:

Amorphous polypropylene 6.4 parts

resinous styrene-butadiene copolymer with high
Styrene content 1.3 parts

Coumarone resin 1.3 parts

Chalk 34.0 parts

Asbestos fiber 57.0 parts

These ingredients were on a small laboratory 2-roll mill mixed with the temperature of each roller being 60 ° C. First, the polypropylene and the styrene-butadiene copolymer mixed together, then incorporated the coumarone resin and the chalk and finally the Asbestos added. The mixture was rolled out and flat patterns were formed by applying slight pressure. The result was a tough, usable mass which is particularly interesting because it only contains 9% binder with 91% fillers.

Example 5

Thermoplastic mixture, consisting of the following components:

Amorphous polypropylene 26.0 parts

Low pressure polyethylene in
Powder form 9.7 parts

Asbestos fiber 64.3 parts

The ingredients were mixed on a small laboratory 2-roll mill with the steam pressure in both rolls being 5 kg / cm ² . First the polypropylene was applied, then the polyethylene powder was added and these two materials were processed together until a translucent skin resulted on the rolling mill, after which the asbestos was added.

The resulting mixture was particularly advantageous because it was tough and light and yet it turned out to be was still very easy to process on the usual rubber and plastics machines.

55

Example 6

A thermoplastic blend was obtained from 15 parts of amorphous polypropylene and 85 parts of asbestos. These two ingredients were mixed on a small laboratory 2-roll mill, the temperature of each roller was 70 ° C. First the polypropylene was applied and then the asbestos incorporated.

The mixture according to Example 6 can optionally be replaced by a mixed polymer by replacing the polypropylene modified from amorphous propylene-ethylene copolymer in a ratio of 95: 5. It a product is obtained that is well suited for the production of wall and floor coverings.

Example 7

Thermoplastic mixture according to the following recipe:

Isotactic polypropylene 3.2 parts

Mineral oil 12.7 parts

Methyl styrene resin 11.1 parts

Asbestos fiber 46.0 parts

Limestone powder 15.9 parts

Titanium dioxide 11.1 parts

The hard polypropylene was mixed with mineral oil with stirring and heating to 100 ^° C. to form a gel. The methyl styrene resin and polypropylene gel were then mixed together on a small laboratory 2-roll mill and fillers and titanium dioxide were incorporated. Roller conditions were: rear roller 140 ^° C., front roller 160 ^° C. The mixture adhered to the front roller.

A hard, viscous mass was obtained, as did that is processed into the desired floor and wall coverings.

Example 8

A thermoplastic mixture was prepared from the following in the same manner as in Example 5 Components manufactured:

Amorphous polypropylene 20 parts

isotactic polypropylene 15 parts

Asbestos fiber 30 parts

Limestone powder 35 parts

The amorphous polypropylene was first placed on the roller, then the powdery isotactic Added polypropylene and roll milled until mixture was translucent; then the fillers were added.

The resulting mixture was hard and tough and easy to process into the desired products.

Claims (1)

Claim: Use of a molding compound composed of 1. 50 to 92.5 percent by weight of fibrous and / or non-fibrous fillers and 2. 50 to 7.5 percent by weight a resinous binder from a) a soft, amorphous or a plasticized one isotactic homo- or copolymers of propylene and optionally additionally b) one of a) different homopolymers or copolymers of an unsaturated hydrocarbon monomer and / or c) a naphthalene-formaldehyde resin and / or d) a coumarone resin and / or e) asphalt-like bitumen and / or f) pitch, for the production of floors and wall coverings.