DE102009000717A1 - Nature / plastic sheet - Google Patents

Abstract

The invention relates to natural / plastic fabrics containing linoxin and natural resin and organic and / or inorganic fillers, optionally applied to a carrier fabric, characterized in that the linoxin and / or natural resin are completely or partially replaced by water-redispersible polymer powder.

Description

The The invention relates to nature / plastic fabrics as well Process for their preparation and their use as covering materials.

When resilient floor coverings find PVC coverings, linoleum coverings and rubber flooring use. Especially the linoleum linings has risen steadily in recent years. Linoleum exists mainly from oxidatively polymerized linseed oil (Linoxin), natural resin such as rosin; besides these are organic fillers like cork or wood flour and / or inorganic fillers such as limestone powder and / or pigments (eg, titanium dioxide). As support materials are woven materials such as glass fiber fabric or jute fabric used. The Linoxin and the resins are the binders and make up as linoleum cement about 40% of the total mass.

linoleum is produced in a multi-level, very time-consuming process: The linseed oil is oxidized and mixed with the resin content to the linoleum cement, and this mixed with the fillers. Subsequently the mass formed is calendered and applied to the carrier fabric applied. The most time-consuming step is the multi-week Mature phase. These are the up to 30 meters long linoleum hanged in ripening rooms. The carrier fabric serves especially not, during this period of maturity which is not yet hardened and therefore unstable linoleum layer to stabilize.

From the WO 00/53841 A2 For example, a method for making strapless linoleum fabrics is known. For this purpose, the Linoleummasse is applied to a Mitläufergewebe, the linoleum so formed sheets are subjected to maturation and then pulled off the Mitläufergewebe again. As a follower fabric fabrics of synthetic fiber materials such as polyester fibers are used. In the WO 02/081812 A2 For example, a linoleum based flooring containing flame retardant from the group of expandable graphites is described.

adversely in the manufacture of linoleum materials is the long-lasting Ripening process to obtain dimensionally stable linoleum materials.

It Therefore, the task was to develop a method with which the process time can be shortened. Surprisingly This is succeeded by the linoleum cement or the individual Components of linoleum cement in whole or in part through in water be replaced with redispersible polymer powder.

object The invention contains plastic sheets Linoxin and natural resin as well as organic and / or inorganic fillers, optionally applied to a carrier fabric, characterized in that the linoxin and / or the natural resin is completely or partially replaced by water-redispersible polymer powder are.

As water-redispersible polymer powder (dispersion powder) is referred to powder compositions, which are accessible by drying the corresponding aqueous dispersions of the base polymers, in the presence of protective colloids. Due to this manufacturing process, the finely divided resin of the dispersion is coated with a water-soluble protective colloid of sufficient amount. During drying, the protective colloid acts like a shell, which prevents the particles from sticking together. When redispersing in water, the protective colloid dissolves again in water and an aqueous dispersion of the original polymer particles is present ( Schulze J. in TIZ, No. 9, 1985 ).

suitable Polymers are those based on one or more monomers from the group comprising vinyl esters, (meth) acrylic esters, Vinylaromatics, olefins, 1,3-dienes and vinyl halides and optionally further monomers copolymerizable therewith.

Suitable vinyl esters are those of carboxylic acids having 1 to 15 carbon atoms. Preference is given to vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids having 9 to 11 C atoms, for example VeoVa9 ^R or VeoVa10 ^R (trade name of the company Resolution). Particularly preferred is vinyl acetate.

suitable Monomers from the group of acrylic acid esters or methacrylic acid esters are esters of unbranched or branched alcohols with 1 to 15 C atoms. Preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, Propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate. Especially preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate.

When Vinylaromatics preferred are styrene, methylstyrene and vinyltoluene. Preferred vinyl halide is vinyl chloride. The preferred olefins are ethylene, propylene and the preferred dienes are 1,3-butadiene and isoprene.

Optionally, from 0.1 to 5 wt .-%, based on the total weight of the monomer mixture, auxiliary monomers are copolymerized. Preference is given to 0.5 to 2.5 wt .-% Hilfsmo nomere used. Examples of auxiliary monomers are ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and nitriles, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid such as diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or their salts, preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid. Further examples are precrosslinking comonomers such as polyethylenically unsaturated comonomers, for example diallyl phthalate, divinyl adipate, diallyl maleate, allyl methacrylate or triallyl cyanurate, or post-crosslinking comonomers, for example acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylol methacrylamide, N Methylolallyl carbamate, alkyl ethers such as isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate. Also suitable are epoxide-functional comonomers such as glycidyl methacrylate and glycidyl acrylate. Further examples are silicon-functional comonomers, such as acryloxypropyltri (alkoxy) and methacryloxypropyltri (alkoxy) silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, where as alkoxy groups, for example, ethoxy and ethoxypropylene glycol ether radicals may be present. Mention may also be made of monomers having hydroxyl or CO groups, for example methacrylic acid and acrylic acid hydroxyalkyl esters such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate, and also compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate. Preferably, no auxiliary monomers are used.

The monomer selection or the selection of the weight fractions of the comonomers is carried out so that in general a glass transition temperature Tg of <120 ° C, preferably -40 ° C to + 120 ° C, particularly preferably -20 ° C to + 80 ° C results. The glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC). The Tg can also be approximated by the Fox equation. To Fox TG, Bull. Physics Soc. 1, 3, Page 123 (1956) where: 1 / Tg = x1 / Tg1 + x2 / Tg2 + ... + xn / Tgn, where xn is the mass fraction (wt% / 100) of the monomer n, and Tgn is the glass transition temperature in Kelvin of the homopolymer of the monomer n is. Tg values for homopolymers are in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) listed.

Prefers are homopolymers or copolymers which contain one or more monomers from the group vinyl acetate, vinyl esters of α-branched monocarboxylic acids with 9 to 11 carbon atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, Ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene contain. Particularly preferred are copolymers with vinyl acetate and ethylene; with vinyl acetate, ethylene and a vinyl ester of α-branched Monocarboxylic acids having 9 to 11 C atoms; with n-butyl acrylate and 2-ethylhexyl acrylate and / or methyl methacrylate; with styrene and one or more monomers from the group of methyl acrylate, ethyl acrylate, Propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; with vinyl acetate and one or more monomers from the group methyl (meth) acrylate, Ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; with 1,3-butadiene and styrene and / or Methyl methacrylate and optionally further acrylic acid esters; wherein the mixtures mentioned optionally one or more may contain the above auxiliary monomers.

At the Most preferred are water-redispersible polymer powder compositions containing Vinylacetathomopolymerisate, copolymers with vinyl acetate and Ethylene, copolymers with vinyl acetate and ethylene and a Vinyl esters of α-branched monocarboxylic acids with 9 to 11 carbon atoms, copolymers with vinyl acetate and ethylene and (meth) acrylic acid ester, in each case as a film-forming base polymer, and in each case partially hydrolyzed polyvinyl alcohol as a protective colloid.

The preparation of the water-redispersible polymer powder is carried out in an aqueous medium and preferably by the emulsion polymerization process. The polymers are obtained in the form of aqueous dispersions and can be converted by conventional drying processes to corresponding water-redispersible polymer powder. This procedure is used for example in the WO 2007/093518 A1 whose details are part of the application (incorporated here by reference).

The Linoxin and / or natural resin is completely or partially dissolved in water redispersible polymer powder replaced. Preference is given to 50 to 100 wt .-%, preferably 90 to 99.5 wt .-%, of the Linoxinanteils and / or the natural resin portion by water-redispersible polymer powder replaced. It can also be the entire Linoxin and the entire share of natural resin, that is the total content of linoleum cement, be replaced by water-redispersible polymer powder. in the In general, the proportion of water-redispersible Polymer powder 10 to 80 wt .-%, preferably 20 to 50 wt .-%, respectively based on the total weight of the plastic sheet.

Suitable inorganic fillers are limestone powder or inorganic pigments such as titanium oxide. Suitable organic fillers are particulate natural materials on a vegetable or animal basis as well as synthetic fibers. Examples of natural materials are wood fibers, wood flour, wood chips, cork particles, cotton fibers, jute fibers, sisal fibers, hemp fibers, flax fibers, grass, rice husks, nut shells and leather fibers. Examples of synthetic fibers are polyester fibers. Particulate natural materials based on plants or animals are preferred as fillers. Particularly preferred are wood fibers, wood flour, wood chips, cork particles and in particular leather fibers. Embodiments in which only inorganic fillers and no organic fillers are contained or vice versa are also preferred. Embodiments in which no starch is used as natural material are also preferred.

Of the Proportion of fillers is 20 to 90 wt .-%, preferably 50 to 80 wt .-%, each based on the total weight of the plastic fabric.

For the setting of certain properties can be even more Plastic additives or natural product additives, such as synthetic resins, biodegradable polymers such as biopolyesters, or also additives for the production of electrically conductive fabrics, for example, graphite powder, or flame retardant additives, be added. It can also be recycled materials as Additives are used. The data in wt .-% for the individual Components of the plastic fabric add up in each case to 100 wt .-%.

The Plastic sheet may optionally be a fabric material as a carrier fabric included. Examples of this are fabrics of synthetic fibers, such as polyester fiber or glass fiber, or Fabrics made of natural materials, such as jute fibers. Due to the minimum share of 20 wt .-% of water-redispersible polymer powder one also in the production of the plastic sheet at high levels of linoxin and / or natural resin, up to 40 % By weight, even before the maturation of the linoleum cement, Fabrics with sufficient mechanical strength, so that a carrier made of fabric material is also dispensed with can.

at The production of plastic sheet can therefore on the characteristic for linoleum production Ripening step are dispensed with, which brings enormous benefits in terms the production time brings.

to Production of the plastic sheets are the individual Ingredients of the recipe, for example in a kneader, rolling mill or hot mixers, mixed together, and by means of the usual thermoplastic forming techniques to sheet processed. The processing preferably takes place by means of calendering, wherein the roll spacing is adjusted so that the sheet receives the desired layer thickness. The processing temperature is generally from 20 ° C to 195 ° C, preferably 90 ° C to 160 ° C. Preferably worked at elevated pressure, preferably at pressures from 10 to 600 bar abs. The production of the fabrics can also be done via the granule stage. The calendering can also be designed so that a multilayer sheet results or is pressed onto a carrier fabric. Surprisingly you get a much lower calendering Thermal damage of the product at high processing temperature as in extrusion. Especially with fibrous fillers is the flexibility in processing with calendering higher than with extrusion process.

To The calendering may optionally change the surface of the Fabrics are further processed, for example by printing, embossing, modifying with decorative Carriers or marbling with broken granules of plastic or rubber.

The Plastic fabrics are suitable in the form of webs or tiles as coverings, for example as a floor covering or Wall covering, as well as coverings for the most diverse Substrates like flexible fixtures, decorative surfaces for z. B. picture frames, book covers, writing pads, Electric switch surfaces, door panels. Further examples are interior surfaces for automobiles, Shoe surfaces, clothing or veneers for furniture.

The The following examples serve for further explanation the invention:

Example 1:

In a kneader the following components were mixed:
37 parts by weight of dispersion powder (Vinnex LL2501, Wacker Chemie)
20 parts by weight limestone powder (Omya 95T from Omya)
38 parts by weight of wood flour (Arbocel C32-10 from Rettenmaier)
2 parts by weight cork flour (MF4 from Amorim)
5 parts by weight of titanium dioxide (Kronos 2220 from Kronos)

Out this mixture was placed on a calender at 150 ° C Rolled and manufactured this at a pressure of 189 bar and a Temperature of 175 ° C to a 2.5 mm thick press plate pressed.

Comparative Example 2:

Linoleum plate linoleum-Marmorette-blue the company Armstrong

Application testing

Strain:

The elongation of the plates was in each case in the tensile test according to DIN EN ISO 527 1-3 with standard body 5A at a test speed of 50 mm / min.

The Linoleum substitute from Example 1 showed an elongation of 7.8%, the linoleum of Comparative Example 2 has an elongation of 2.6%. With receives the nature / plastic fabrics according to the invention one obtains a significant improvement in the elongation property on fabrics. The application for individual applications is thereby increased.

Hardness:

The ball indentation hardness was according to EN-ISO 2039-1 determined with method H132 / 20 and a steel ball with 10 mm diameter. For the linoleum substitute from Example 1, a value of 25.8 N / mm ² and for the linoleum from Comparative Example 2, a value of 13.8 N / mm ^{2 was} determined. In addition, the residual impression immediately after loading 50 kg / cm ² and after a recovery time of 150 min according to DIN EN 433 measured. For the linoleum substitute from example 1, the values 0.08 mm / 0.04 mm and for the linoleum from comparative example 2 the values 0.09 mm / 0.05 mm were determined.

The Ball indentation hardness and the residual impression are characteristic Features for fabrics, especially in the floor area. This gives the resistance to a short-term load from the outside. A nearly doubling of the value with respect to ball indentation hardness in the inventive nature / plastic fabrics compared to linoleum opens up new market opportunities for Nature / Plastic floors z. B. in the object construction. The residual impression is an important value for a floor or Wall covering. This indicates how strong traces of use after a long-term load remain. The values for the natural / plastic fabric are comparable to linoleum linings respectively improved.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 00/53841 A2 [0004]
• - WO 02/081812 A2 [0004]
• WO 2007/093518 A1 [0017]

Cited non-patent literature

• - Schulze J. in TIZ, no. 9, 1985 [0008]
• - Fox TG, Bull. Physics Soc. 1, 3, Page 123 (1956) [0014]
• Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) [0014]
• - DIN EN ISO 527 1-3 [0030]
• - EN-ISO 2039-1 [0032]
• - DIN EN 433 [0032]

Claims (11)

Nature / plastic sheet containing Linoxin and natural resin and organic and / or inorganic fillers, optionally applied to a carrier fabric, characterized in that the linoxin and / or natural resin are completely or partially replaced by water-redispersible polymer powder. Nature / plastic sheet according to claim 1, characterized in that the water-redispersible polymer powder Base polymers of one or more monomers from the group comprising vinyl esters, (meth) acrylic esters, vinyl aromatics, Olefins, 1,3-dienes and vinyl halides and optionally further thus copolymerizable monomers. Nature / plastic sheet according to claim 1, characterized in that the water-redispersible polymer powder Vinylacetathomopolymerisate, copolymers with vinyl acetate and Ethylene, copolymers with vinyl acetate and ethylene and a Vinyl esters of α-branched monocarboxylic acids with 9 to 11 carbon atoms, copolymers with vinyl acetate and ethylene and (meth) acrylic esters, in each case as film-forming base polymers, and in each case partially hydrolyzed polyvinyl alcohol as a protective colloid, contains. Nature / plastic sheet according to claim 1 to 3, characterized in that 50 to 100 wt .-% of Linoxinanteils and / or the natural resin portion by water-redispersible polymer powder are replaced. Nature / plastic sheet according to claim 1 to 4, characterized in that as organic fillers Wood fibers, wood flour, wood chips, cork particles, cotton fibers, Jute fibers, sisal fibers, hemp fibers, flax fibers, grass, rice husks, Nut shells and leather fibers are included. Nature / plastic sheet according to claim 5, characterized in that as fillers only organic and no inorganic fillers are included. Nature / plastic sheet according to claim 1 to 4, characterized in that as fillers only inorganic and no organic fillers are. Process for the production of natural / plastic fabrics according to claim 1 to 7, wherein the individual components of the recipe of nature / plastic sheets in a kneader, rolling mill or hot mixers, mixed together, and by means of the usual thermoplastic forming techniques to sheet are processed. Process for the production of natural / plastic fabrics according to claim 8, wherein the processing takes place by means of calendering. Use of natural / plastic fabrics according to claim 1 to 7 as covering materials. Use of natural / plastic fabrics according to claim 10 as a floor covering, wall covering or as a covering for Pieces of furniture.