DE3743980A1 - DIRT AND SCRATCH RESISTANT ELASTIC SURFACE COVERING - Google Patents

Abstract

Surface coverings, and in particular floor coverings, comprise a polyurethane wear layer carrying a coating comprising a urea-based aminoplast, optionally a vinyl modifier resin, a polyol, and an acid catalyst. This coating may be formed on a release surface and thermally cured. A crosslinkable wear layer composition is then cast on the cured layer and crosslinked, and the composite is transferred to a support surface. Surface coverings are produced which exhibit surprising resistance to common household stains, and also improved scratch resistance.

Description

The invention relates to surface coverings, in particular Surface coverings with improved scratch and dirt resistance.

Elastic surface coverings and especially elastic ones Floor coverings are generally known. The flooring, which are generally used nowadays are first Line of vinyl products. Although they are different Can be flexible, they are in proportion to common natural materials, such as ceramic tiles, elastic. A large number of such products are on the market have high wear resistance, available. However, such coverings also have certain disadvantages on. So z. B. vinyl floor coverings are durable and dirt-resistant, however, show the tendency due to wear losing their shine. Is glossy however often desirable for flooring. The manufacturers Such fabrics have therefore long since improved Looking for flooring with high gloss retention.

There is a method for improving gloss retention in the application of polyurethane or other wear layers on vinyl flooring. Such fabrics are permanent and relatively scratch resistant. They also keep her Glossy looks longer than vinyl flooring surface. Nevertheless, such wear layers also have and certain polyurethane tread layers in particular Disadvantage. So z. B. they are sensitive to dirt. Stay like that stains from polyurethane coatings  Ballpoint pens, lipsticks, mustard, shoe polish and similar things or substances as they usually do used in the household, easier back than on Vinyl coatings.

In the past few years, the coating industry significant effort made to new and different Types of coatings, including coatings based on aminoplast resin. To this Substances include ureas and melamine formaldehyde resins such as melamines (Triaminotriazines) which formaldehyde to form a methylolated or partially methylolated melamine has been N-alkylated. The methylol Groups are then achieved completely or partially etherified of a crosslinkable substance. Such substances have with coatings for cars, devices or devices and other rather inelastic types of surfaces as well as coatings for certain elastic Substrates, including paper, cardboard, metal foils, Cellophane u. a., widely used. So far, however, such substances have never been successful be used for floor coverings, especially for vinyl floor coverings or vinyl floor coverings with polyurethane tread layers.

An object of the invention is therefore to provide it of elastic surface coverings with protective layers with a thickness of 0.2 mils (0.005 mm) or more, which deform together with the surface coverings leave, but improved scratch and dirt resistance exhibit.

Another object of the invention is to provide of floor coverings built from composite materials Have tread surfaces, which creates the wear layer material improved scratch and dirt resistance  acquired.

The invention relates to surface coverings and in particular Floor coverings, treated polyurethane or other wear layers comprise coatings having a Urea aminoplast, at least partially with alkyl groups is etherified with 4 to 10 carbon atoms, a vinyl modifier resin, a polyol and an acid catalyst. This coating can be applied to a removable surface and undergo heat curing. After that becomes a cross-linkable wear layer on the hardened layer composition cast and crosslinked, after which the composite is transferred to a substrate. That way to provide surface coverings with surprising durability compared to stains used in the home Fabrics as well as with increased scratch resistance.

One embodiment of the invention relates to an elastic Surface covering that is an elastic substrate and comprises a cross-linked wear layer adhering to it, the top surface of the wear layer being one of one Mixture made protective layer is that

• a) a urea aminoplast,
• b) a vinyl modifier resin,
• c) a polyol and
• d) a suitable catalyst

includes, and the protective layer prevents the deflection of the wear layer can adapt, but compared to the untreated Wear layer improves scratch and dirt resistance having.

A second embodiment of the invention relates to a Process for making a wear layer for a elastic surface covering using this method comprises the following stages:

• 1) Providing a peelable carrier that has a Comprises substrate surface and a peelable coating,
• 2) applying a mixture to the peelable coating, the
  • a) a urea aminoplast,
  • b) a vinyl modifier resin,
  • c) a polyol and
  • d) comprises a suitable catalyst,
• 3) at least partially heat curing the mixture,
• 4) Applying a crosslinkable wear layer mixture on the aminoplast layer,
• 5) hardening the wear layer,
• 6) Pull the hardened wear layer on an elastic Substrate and
• 7) peeling off the backing from the wear layer,

after which the surface covering comprises a wear layer, which has a protective coating that is elastic as well as compared to the untreated wear layer, is scratch and dirt resistant.

The elastic surface coverings that can be produced according to the invention are among the currently well known Coverings. So they can have an elastic substrate, as is usually the case for the production of vinyl floor coverings is used. Substrates of this type can from base materials, plastisols, foamed plastisols, from arbitrary and from distributed with the help of templates Vinyl particles, etc. can be produced.

The surface coverings can also be constructed from composite materials Have wear layers. The main part of the Wear layer is allotted to substances that are generally known are, such as B. from urethanes, acrylate or Methacrylaturethanes, unsaturated polyesters, etc. networked wear layers. These have to go through  Moisture curing, thermally induced free radical curing, oxidative curing, radiation curing or a combination of these techniques can be networked.

The novelty of the invention is the presence a second protective layer on the usual wear layer components. This second material is made from a urea aminoplast resin, a polyol, an acid catalyst and a vinyl modifier resin and results in an elastic, but scratch and dirt-resistant outer surface.

The resins used to practice the invention can be referred to here as "aminoplasts". In connection with melamine-formaldehyde resins, these can Substances partially or practically completely methylolated be, the methylol groups partially or practically completely with methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl, nonyl and decyl groups, isomers and mixtures thereof can be etherified. The However, aminoplast is preferably at least partially with a relatively long chain alkyl group with approx. 4 etherified up to approx. 10 C atoms. These long chain parts of the aminoplast favor the elasticity of the hardened Vinyl products. As for the urea-based resins many of these aminoplastics are commercially available, such as B. the Resimene® resins (Monsanto Company).

The vinyl modifier resins used in the present invention are known or represent mixtures of known resins. Examples for such resins are vinyl chloride and vinyl acetate prepared copolymer solution vinyl resins. Resins of this type are from Union Carbides are sold and can be hydroxyl or other Functionalities included. One of those accessible resins  is the resin known under the trade name VAGH. Other resins are VAGD, VROH and VYES. Examples for other resins there are special resins such as polyvinyl acetals (e.g. polyvinyl butyral), alone or in a mixture with polyvinyl alcohol and / or polyvinyl acetate, and polyvinyl esters like polyvinyl acetate. Such substances are for their applicability generally known from the solution. So it's resins which differs from dispersion resins and resins for general Uses essentially in most conventional solvents are insoluble. The Modifier resins should essentially be suitable the elasticity and strength of the cured composition without negative effects on dirt resistance to improve.

The polyols used to practice the invention are alcohols with 2 or more Alcohol groups. So z. B. can implement the invention 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerin, Neopentyl glycol, tripropylene glycol, 1,4-butanediol, Trimethylolpropane, pentaerythritol and many other known ones Polyols or esters of such polyols as neopentyl glycol esters and the like and many other known ones Polyols are used.

The acid catalysts used to catalyze the thermal Hardening between the vinyl modifier resin, the Aminoplast, the polyol and the wear layer surface can also be used are also generally known. Examples of such catalysts are sulfonic acids such as methane and p-toluenesulfonic acid and others Acids such as citric, maleic, phthalic etc. The catalysts can be used as free acids however, they can also be stabilized, e.g. B. by using an amine for neutralization  the acid. Examples of such amines are ammonia, Diisopropanolamine and 2-amino-2-methyl-l-propanol. The only limitation is that the catalysts compatible with the other components of the system have to be. These catalysts are known to the person skilled in the art generally known and can by him accordingly to be chosen.

To carry out the invention is for the aminoplast composition a separation surface is provided. in the If the surface is very smooth, it can be polished Chrome plate or one with a polyalkylene, in particular with polypropylene, such as polypropylene matted by calendering, coated peelable paper can be used. With less shiny surfaces, others can Types of coated papers or tapes used be such. B. silicone papers or tapes and papers or bands that are treated with complex chrome and Methyl cellulose was obtained.

A layer of aminoplast composition is then applied to the peelable paper infused. Although the component ratio the composition can vary considerably, it is generally about 4 to 1 part modifier resin 1 to 4 parts of the aminoplast polyol Mixture. This contains about 5 to 1 part of aminoplast to 1 to 5 parts of polyol. However, preferably approx. 3.5 to 1 part modifier resin for 1 to 2 parts each of the aminoplast-polyol mixture, which has a ratio of has about 3 to 1 part of aminoplast to 1 to 3 parts of polyol. This composition is usually made up of one organic solvent applied, but can also be applied in aqueous form.  

After coating the peelable paper with the Aminoplast composition, this is dried and at least partially hardened at approx. 250 ° F (121 ° C).

Although it is possible, the laminate according to the invention to be formed with partially hardened aminoplast layers it is usually recommended to achieve high quality products, the aminoplast layer before application harden the urethane layer.

The crosslinkable wear layer coating can be used immediately applied to the aminoplast layer after it has hardened will. However, those skilled in the art may prefer the surface of the hardened aminoplast layer to improve the adhesion between the layers Glow discharge or application of an adhesion promoter Pre-treat layer. As adhesion-promoting compositions vinyl varnishes are usually used, the broad Find application and are generally known to those skilled in the art. Such compositions often contain vinyl chloride copolymer solution resins such as the VAGH resin described above.

Glow discharge treatment is also a well known technique for increasing surface energy by treating the surface in an arc. The amount of energy required to promote good adhesion can easily be determined by standard methods. So z. For example, the surface tension of the coating can be determined according to ASTM D 1331 and the surface energy of the surface to be coated essentially according to ASTM D 2578. The purpose of the glow discharge treatment is to increase the surface energy of the surface to be coated so that it can be wetted by the coating composition. Ideally, the energy resulting from the glow discharge treatment should be at least about 10 dynes / cm (about 10 ^-4 N / cm) above the surface tension of the coating composition.

The thickness of the wear layer to be applied can vary within a range of about 1 mil to about 8 mil (about 0.025 to about 0.20 mm), preferably between about 2.5 and Move approximately 4.5 mils (approximately 0.06 and 0.11 mm). The composition can be a moisture-curable solution of urethane based on polyether or polyester with low solids content (e.g. 40%) or a two-component system made of a polyester with a hydroxyl functionality and a diisocyanate. The hardening of the latter composition is carried out by reacting the diisocyanate with the hydroxyl groups of the polyester and through the Humidity. But it can also be radiation-curable or combined radiation and moisture curable Components are used. As for the aminoplast layers it is also advisable to ensure that the urethane layer before mounting on the elastic Surface covering is completely hardened.

When the fabrics are fully hardened and then put on the elastic surface coverings can be occasionally a little liability of the Determine the laminate on the surface covering. What it concerns the aminoplast and the wear layer desirable to separate layers by arrangement an adhesion-promoting layer between the unprotected Back surface of the wear layer and the elastic layer to prevent. To improve the adhesion of the coatings but you can also get the glow discharge treatment serve.  

After the application of an adhesion promoter, if applicable Layer or after glow discharge treatment, if applicable to connect the outer wear layer with the elastic substrate surface layer the composite body to ensure firm adherence treated with heat and pressure. The composite body can also be granulated in the same way or solidified, applied using a template Vinyl products.

After solidification, the peelable paper is removed from the hot sample peeled off, creating a decorative Preserves surface covering, the good scratch and dirt resistance having. These substances are therefore opposite Pollution from common household substances or items such as lipstick, shoe polish, mustard, food dyes and the like resistant.

example 1

From the following components, in parts by weight mixtures are prepared:  

Table I

Removable on any series of polypropylene coated Paper becomes a coating from the samples 1-1 to 1-5 in a thickness of approximately 2.5 to 3.5 mils (0.06 to 0.09 mm) when wet using a Reverse roller coater applied. The coated paper is then baked through an oven at a Temperature of 260 ° F (127 ° C).

Then a is used to coat the peelable papers moisture-curable polyurethane coating. The components are as follows:

Component Weight (grams)

Polyether diol (Union Carbide LHT 240) 40.80 Polyether diol (Union Carbide LHT 112) 14.20 Xylene (solvent) 110.00 Toluene (solvent) 46.00 Dimethyltin dienolodecanoate as a catalyst (Witco UL-28®) 0.55 Surfactant (Monsanto XA-677 Multiflow®) 0.30 Light stabilizer (American Cyanamid UV-5411) 0.20

These components are then used to stir Nitrogen-purged glass reactor is fed, after which one heated to 70 ° C for one hour. After that, 30 minutes long at a speed sufficient to maintain the temperature of the mixture at 70 ° C, 44.90 g of 4,4'-diisocyanate dicyclohexyl methane dropwise added. After stirring and heating at 70 ° C during the product is cooled for a further two hours.  Then a 1 to is added to each of the peelable papers 2.5 mils (0.003 to 0.06 mm) thick wet layer of one adhesion-promoting lacquer applied, the 18.54 wt .-% VAGH® resin, 0.37% Thermolite 31®, 0.0094% Uvitex OB® and Contains 81.08% methyl isobutyl ketone as solvent. After that, the coated sample is in the surrounding Air or with little heating to remove the Solvent dried. After drying is on each paper a 5 to 6.5 mils (0.13 to 0.17 mm) thick wet coating of the moisture-curable described above Applied polyurethane material. Then the coated samples are complete Drying through an oven with a temperature of Sent 250 ° F (121 ° C) with the dwell time in the oven Is 7 minutes.

The coatings of samples 1-6 to 1-9 were coated on polypropylene Paper by pulling with the help of a rod wrapped with a No. 30 wire which, after drying, yields 0.5 mil (0.013 mm) thick coatings were obtained. The samples were then Cured at 250 ° F (121 ° C) for 5 minutes. Samples 1-6 detached completely and were discarded. The remaining Samples were made with a moisture curable polyurethane coating composition as you can read above coated.

For the production and consolidation of laminates for the Laboratory evaluation uses a press with the dimensions 12 inch × 12 inch (30.48 cm × 30.48 cm), making samples with the dimensions 9 inch × 9 inch (22.86 cm × 22.86 cm) be preserved. The top plate of the press is set to 310 ° F (154 ° C) heated while the bottom plate was at 300 ° F (149 ° C) is heated. The time spent in the press is 10 seconds at a press force of 250 pounds (1135 N) and then 10 seconds at 1200 pounds (5448 N).  

After the sample has been removed from the press, it becomes removable Peeled paper from the hot sample.

For the production of laminates using the mentioned Coatings can be both elastic substrates on the basis of vinyl applied with stencils as can also be used with gelled vinyl plastisol. The dirt resistance can usually be found in the household used and stain-forming substances evaluated will. Although samples 1-7 are significantly more sensitive to dirt than the rest of the samples, all show Samples better dirt resistance than the untreated Polyurethane material and also high scratch resistance.

According to Example 1, three groups of samples are produced, however, the above five coatings be used. In one group of samples the hardened coating is on a peelable Paper before coating with the polyurethane layer according to example 1 of a glow discharge treatment subjected. The second group of samples is between the hardened coating on the peelable Paper and the polyurethane layer an adhesive Layer arranged according to Example 1. The third Group of samples is neither between the melamine containing Layer and the polyurethane layer an adhesion-promoting Layer arranged, another glow discharge treatment carried out. In all cases it will be excellent Resistance to dirt found and it becomes a better one in the case of glow discharge treatment Adhesion of the melamine-containing layer to the polyurethane layer achieved.

Claims (15)

1. Elastic surface covering, which comprises an elastic carrier layer and a cross-linked tread layer adhering thereto, characterized in that the upper surface of the tread layer is a protective layer made of a mixture, the

• a) a urea aminoplast,
• b) a vinyl modifier resin,
• c) a polyol and
• d) a suitable catalyst

comprises, and the protective layer against the deflection of the Wear layer can adapt, but compared to the untreated Wear layer improves scratch and dirt resistance having.   2. Surface covering according to claim 1, characterized in that the wear layer is made from fabrics selected from the group of urethanes, acrylic urethanes, Methacrylate urethanes and unsaturated polyesters. 3. Surface covering according to claim 1 or 2, characterized in that the vinyl modifier resin Is copolymer solution vinyl resin. 4. Surface covering according to claim 3, characterized in that the resin of vinyl chloride and vinyl acetate is derived. 5. Surface covering according to one of claims 1 or 2, characterized in that the modifier resin is selected from the group polyvinyl acetal, polyvinyl ester and a mixture of a polyvinyl acetal and Polyvinyl alcohol or a polyvinyl ester. 6. Surface covering according to one of claims 1 to 5, characterized characterized that the composition 1 to approx. 4 parts of urea aminoplast / polyol mixture contains about 4 to about 1 part of modifier resin, this mixture being about 5 to about 1 part urea aminoplast to 1 to about 5 parts of polyol. 7. Surface covering according to claim 6, characterized in that the composition for each 1 up to approx. 2 parts urea aminoplast / polyol mixture approx. 3.5 contains up to about 1 part of modifier resin, this mixture about 3 to about 1 part urea aminoplast each Contains 1 to about 3 parts of polyol. 8. Surface covering according to one of claims 1 to 7, characterized  characterized that liability between the tread and the urea aminoplast layer an adhesion-promoting layer is improved. 9. Surface covering according to one of claims 1 to 7, characterized characterized that liability between the tread and the urea aminoplast layer by glow discharge treatment of the urea aminoplast layer is improved. 10. A method for producing a tread surface for an elastic surface covering according to one of claims 1 to 9, characterized in that it comprises the following steps:

• 1) providing a strippable carrier comprising a substrate surface and a strippable coating,
• 2) applying a mixture to the peelable coating, the
  • a) a urea aminoplast,
  • b) a vinyl modifier resin,
  • c) a polyol and
  • d) a suitable catalyst

includes

• 3) at least partially heat curing the mixture,
• 4) applying a crosslinkable wear layer mixture to the urea aminoplast layer,
• 5) hardening of the wear layer,
• 6) mounting the hardened wear layer on an elastic substrate and
• 7) Peeling off the backing from the wear layer, after which the surface covering comprises a wear layer which has a protective coating which is elastic and, compared to the untreated wear layer, is scratch and dirt-resistant.

11. The method according to claim 10, characterized in that between the tread and the urea aminoplast layer an adhesion-promoting layer is arranged is. 12. The method according to claim 10, characterized in that that the liability between the kick and the urea aminoplast layer by glow discharge treatment the urea aminoplast layer is improved. 13. The method according to claim 10, characterized in that that the urea aminoplast layer hardened first and then the wear layer mixture is applied to it.