Weld seam for ground coating

Abstract

The invention relates to a heat-fusible weld seam for joining ground coating members, comprising a copolymer selected from the group of polymers containing acrylic acid, methacrylic acid or maleic anhydride, a polyethylene and a copolyamide.

Claims

1. A hot-melt welding rod, for joining together elements of a floor covering, containing the following resins: from 12.5% to 25% by weight of at least one copolymer selected from the group consisting of acrylic acid-based, methacrylic acid-based and maleic anhydride-based copolymers, from 60% to 72.5% by weight of two polyethylene resins, one of which is a polyethylene wax having a Brookfield viscosity of less than 10000 cPoise (centipoise) at 140 C., 15% by weight of a copolyamide, wherein the copolyamide is the condensation product of a dimer of fatty acids with an aliphatic diamine, and wherein the amine index of the copolyamide is higher than its acid value.

2. The welding rod according to claim 1, wherein the copolymer selected from the group consisting of acrylic acid-based, methacrylic acid-based and maleic anhydride-based polymers, is partially or completely neutralized to form an ionomer.

3. The welding rod according to claim 1, wherein the at least one copolymer comprises acrylic acid-based or methacrylic acid-based copolymer having an acid concentration in the range from 10% to 20% by weight with respect to the other co-monomers.

4. The welding rod according to claim 3, wherein the at least one copolymer comprises acrylic acid-based or methacrylic acid-based copolymer having an acid concentration of 10% by weight with respect to the other co-monomers.

5. The welding rod according to claim 1, wherein the at least one copolymer comprises maleic anhydride-based copolymer having an anhydride concentration of between 1.3% and 3.1% by weight with respect to the other co-monomers.

6. The welding rod according to claim 1, comprising in addition camauba or paraffin wax.

7. A floor covering comprising floor covering elements joined together using the welding rod according to claim 1.

8. A floor covering as claimed in claim 7, wherein the floor covering elements are selected from the group consisting of floor coverings based on polyolefin, floor coverings based on PVC, floor coverings based on linoleum, and floor coverings based on rubber.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a hot-melt welding rod according to the invention, supplied in roll form.

(2) FIG. 2 shows various different hot-melt welding rods.

(3) FIG. 3 shows a hot-melt welding rod inside the welding nozzle of a hot-air welding device.

(4) FIG. 4 shows one of today's welding rods after a staining and cleaning test.

(5) FIG. 5 shows a welding rod according to the invention after a staining and cleaning test.

DETAILED DESCRIPTION OF THE INVENTION

(6) As mentioned above, a hot-melt welding rod for a floor covering, e.g. for the floor surface of any type of building or motor vehicle, has to reconcile numerous criteria which will differ depending on whether the priority is ease of application or easy subsequent upkeep.

(7) To enhance adhesion (which should ensure perfect sealing of elements of the floor covering) and ensure easy scraping off, it could be assumed that the welding rod material should contain low molecular weightor even very low molecular weight-polymers. In contrast, when it comes to resistance to physical damage (e.g. resistance to scratching), resistance to staining, and flexibility (or elasticity), it could be assumed that the welding rod should be based on higher molecular weight polymers.

(8) Moreover, in order to guarantee better adhesion, the composition of the welding rod should contain polar groups whereas to improve the material's behaviour vis--vis dirt and stains, a non-polar composition would be more desirable.

(9) Evaluation Tests

(10) Various compositions were evaluated in adhesion, staining, tar and scratching tests.

(11) The staining test involved depositing an abrasive powder on the scraped welding rod and then soiling the rod material by rubbing the powder in with a cotton cloth (10 passages back and forth) at a force of between 40 N and 50 N. Any excess abrasive powder was then removed. One part of the rod treated in this way was then cleaned without any solvent, using a clean cotton cloth. Another part was cleaned using a cotton cloth that had been dampened in water. The degree of staining of the rod was then evaluated on a scale going from 1 (meaning very heavy staining) to 10 (no staining at all). All the results obtained after cleaning without any solvent are presented side by side with the results obtained after cleaning with water.

(12) The abrasive powder used in the staining test can be of any suitable composition. As an example the dust composition used for tests to compare different welding rod compositions was 38.85% dust, 17.45% Portland cement, 17.7% kaolin, 17.7% quartz, 6.2% Nujol Q14 mineral oil, 0.6% ferric oxide and 1.5% yellow pigment.

(13) The tar test involved bringing a drop of fluid tar into contact with the test surface. After an exposure time of thirty minutes, the tar was removed using a cloth and any excess was wiped away using a cloth soaked in isopropanol. The change in the colour of the welding rod was then scored on a scale of 1 (meaning no difference, i.e. restoration of the original colour), 2 (meaning discernible brown discolouration) (FIG. 5), 3 (meaning mild brown discolouration where the tar was in contact with the rod), 4 (dark brown) or 5 (black) (FIG. 4).

(14) Adhesion tests were conducted on a floor covering based on linoleum which is the most difficult to stick together because linoleum is not thermoplastic and adhesion depends entirely on mechanical fixation coupled with polar interactions through physical interactions or chemical interactions between the surface of the linoleum and the surface of the welding material.

(15) The adhesion test involved cutting a sample of the floor covering in two, using a holder fitted with a blade, through its entire thickness (including the jute backing in the case of linoleum). The two resultant test pieces of the floor covering were separated by about 3 millimeters, a gap which is kept constant to make comparison possible. The test welding rod (FIG. 1 and FIG. 2) was injected into this space using a Leister hot-air welding device (FIG. 3) to weld the two pieces of surface covering together. After the welding rod material had cooled down, the excess was scraped off and then the force required to pull the two joined pieces apart was measured using an extensometer. The force measurements were made on samples with an edge of 5 centimeters in length (i.e. 5 cm of welded seal) with the welded seal perpendicular to the direction of traction. Adhesion readings are expressed in Newtons per 50 mm length (N/50 mm).

(16) The scratch test or sclerometer test involved using a spring (calibrated in grams) to bring an abrasive pin with a well-defined diameter (of the order of 1 mm) into vertical contact with the surface to be tested for resistance to scratching. The pin was then displaced horizontally across the surface, after which the damage to the surface was evaluated. It is not always possible to evaluate the force at which the surface is first damaged which is why the decision was taken to measure the force at which the appearance of waves can first be observed. These waves correspond to the beginning of damage to the welding rod material in the form of superficial tearing. In practice, this wave threshold is far easier to determine and, in addition, the results of this type of test are highly reproducible.

(17) To be able to compare the performance of the welding rod according to the invention with that of current welding rods, we performed comparisons with various EVA (ethylenevinyl acetate)-based compositions. We then tested their resistance to scratches and staining. The proportion of additives in the various compositions (TiO.sub.2 in the examples) is given as a percentage with respect to the basic polymer(s) (pcr).

Composition of Welding Rods According to the Prior Art (Comparative Examples)

(18) TABLE-US-00001 TABLE 1 Composition of welding rods based on EVA according to the prior art Composition 1 2 3 4 5 6 7 8 EVA - 1 100 70 70 70 70 EVA - 2 100 85 85 PE - 1 wax 15 15 PE - 2 wax 15 15 15 15 Natural 15 15 tackifier Synthetic 15 15 tackifier TiO.sub.2 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5

(19) TABLE-US-00002 TABLE 2 Results of adhesion, scratching and staining tests for compositions based on EVA according to the prior art. Staining (dry/ Adhesion (N/ Prior art Test water) Tar 50 mm) Scratching (g) 1 4/5 5 150-190 500 2 4/4 5 160-210 350 3 4/5 5 270-300 300 EVA base 4 4/5 5 250-275 400 5 4/4 5 100-120 350 6 4/5 5 100-150 400 7 4/4 5 180-220 350 8 3/5 5 300-320 650 For the staining test (dry/water staining), 1 is very poor and 10 is very good. For the tar test, 5 is poor and 1 is good.

(20) As shown in Table 2, welding rods based on EVA have low adhesive power and their resistance to staining, tar and scratching is moderate. The addition of PE wax (compositions 5-7) and tackifiers (compositions 3, 4, 7 and 8) improves adhesion but does not affect their resistance to scratching or staining.

(21) Composition of Welding Rods According to the Invention

(22) Compositions according to the invention comprising one or more acid-based or anhydride-based polymers, in some cases partially neutralised to generate an ionomer, were produced and then tested for their resistance to physical damage and staining in the same conditions as those used to evaluate the EVA-based compositions according to the prior art.

(23) TABLE-US-00003 TABLE 3 Compositions of welding rods according to the invention with a base of approximately 60% polyethylene. Composition 9 10 11 12 13 LDPE - 1 57.5 57.5 45.0 45.0 65.0 PE wax - 1 15.0 15.0 15.0 15.0 15.0 Ionomer 12.5 25.0 5.0 EMAA - 2 12.5 25.0 PA - 1 15.0 15.0 15.0 15.0 15.0 TiO.sub.2 3.5 3.5 3.5 3.5 3.5

(24) TABLE-US-00004 TABLE 4 Compositions of welding rods according to the invention with acidic copolymers, either in totality or alternatively with 15% tackifier. Composition 14 15 16 17 18 19 EMAA - 1 100 85 EMAA - 2 100 85 EMAA - 3 100 85 Synthetic 15 15 15 tackifier TiO.sub.2 3.5 3.5 3.5 3.5 3.5 3.5

(25) TABLE-US-00005 TABLE 5 Compositions of welding rods according to the invention with 70% acidic copolymers combined with a PE wax and/or an ionomer and/or a tackifier and/or a copolyamide. Composition 20 21 22 23 EMAA - 2 70 70 70 EAA - 1 70 PE wax - 1 15 15 15 15 Synthetic 15 15 tackifier PA - 1 15 PA - 2 15 TiO.sub.2 3.5 3.5 3.5 3.5

(26) TABLE-US-00006 TABLE 6 Compositions of welding rods according to the invention of acidic or anhydride copolymers combined with the copolyamide (the polyamide is expressed as the fractional weight with respect to 100 parts in weight of the other polymers). Composition 24 25 26 27 28 29 30 31 32 33 EVA - 1 11.0 22.0 EMAA - 1 61.0 63.5 74.0 63.0 52.0 50.0 39.0 70.0 EMAA - 2 61.0 70.0 Acidic terpolymer 11.0 21.0 PE wax - 1 15.0 13.0 13.5 13.0 13.0 13.0 13.0 13.0 15.0 PE wax - 2 Ionomer 13.0 13.5 13.0 13.0 Natural tackifier 26.0 PA - 1 15.0 13.0 9.5 13.0 13.0 13.0 13.0 13.0 15.0 TiO.sub.2 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5

(27) TABLE-US-00007 TABLE 7 Compositions of welding rods according to the invention based on EMAA supplemented with terpolymers, polyethylene and waxes of an ionomer or a copolyamide. Composition MFI (g/10 min) Brookfield 190 C. viscosity 2.16 kg (cpoise) 34 35 36 EMAA - 1 450 40 40 40 PE wax - 1 180 (140 C.) 13 13 13 Acidic terpolymer 5 21 Anhydride 7 21 terpolymer - 1 Anhydride 35 terpolymer - 2 EVA - 1 20 21 Ionomer 80000 (190 C.) 13 13 13 PA - 1 18000 (200 C.) 13 13 13 TiO.sub.2 3.5 3.5 3.5
Examples of Polymers Used in the Tables Above

(28) For example, the EMAA1 could be Nucrel 599 from DuPont, EMAA2 Nucrel 699 from DuPont and EMAA3 Nucrel 2940 from DuPont.

(29) The EAA1 could be Primacor 5980I from Dow Chemical or Nucrel 2806 from DuPont.

(30) The synthetic tackifier could be Escorez 5340 from ExxonMobil Chemical. The natural tackifier could be Sylvares TP300 from Arizona Chemical.

(31) LDPE1 could be Riblene MY00 from Polimeri Europa or Escorene LD 655 from ExxonMobil.

(32) The PE1 wax could be LD Wax 617 A or LD AC 16 wax or AC 617 wax from Honeywell. The PE2 wax could be an oxidised Wax AC 316 or AC 325 from Honeywell.

(33) The ionomer could be an ionomer of acrylic acid (Aclyn 285) from Honeywell. Alternatively, the ionomer could be the ionomer of EMAA1, of EMAA2 or of EAA1.

(34) The PA1 copolyamide could be Euremelt 2840 and the PA2 could be Euremelt 2140, from Huntsman.

(35) The EVA1 could be Escorene 2020 and the EVA2 Escorene 53019 from ExxonMobil Chemical, or alternatively Elvax 410 from DuPont or Evatane 18-500 from Arkema.

(36) The ethylene-acrylate-acid terpolymer could be Bynel 2022 from Dupont. It is mainly characterised by its 10% concentration in acrylic acid. The anhydride-1 terpolymer could be Lotader 3410 from Arkema which is mainly characterised by its 3.1% concentration in maleic anhydride and secondarily characterised by its 17% concentration in acrylate. The anhydride-2 terpolymer could be Lotader 4700 from Arkema which is mainly characterised by its 1.3% concentration in maleic anhydride and secondarily characterised by its 29% concentration in acrylate.

(37) As shown in Table 11, to reconcile the contradictory requirements for a welding rod which has to adhere strongly to a varnished floor covering and, at the same time, has to be resistant to physical damage and staining, the invention proposesin a novel fashionusing a composition containing one or more polymers selected from the group of polymers based on acrylic acid, methacrylic acid or maleic anhydride.

(38) The fluidity characteristics of a series of polymers used in this invention are shown in Table 10.

(39) TABLE-US-00008 TABLE 10 Characteristics of the constituents of the various welding rod compositions. Fluidity Viscosity (cps) Index Vinyl acetate/ Constituent 140 C. (g/10 min) or acid (%) EVA - 1 20 20 (VA) EVA - 2 530 19 (VA) LDPE - 1 200 0 PE wax - 1 180 0 PE wax - 2 8500 at 150 C. 0 Ionomer (sodium) - 1 80000 at 190 C. EAA - 1 60 18 (AA) Coplyamide (high 18000 at 200 C. 0 amine content) - 1 EMAA - 1 450 10 (MAA) EMAA - 2 95 11 (MAA) Terpolymer (ethylene- 35 10 (AA) acrylate-acrylic acid)

(40) Preferably, the fluidity of the copolymer selected from the group of polymers based on acrylic acid, methacrylic acid or maleic anhydride, has a fluidity index of over 100 g/10 min, advantageously 450 g/10 min or higher.

(41) Results of Measurements Made on the Rods According to the Invention

(42) TABLE-US-00009 TABLE 11 Results of tests of adhesion, and of resistance to scratching and staining, for acrylic acid-based, methacrylic acid- based or maleic anhydride-based compositions. Staining (dry/ Adhesion (N/ Composition water) Tar 50 mm) Scratching (g) 9 5/7 2.5 300-310 650 10 6/7 2 250-270 700 11 6/8 2.5 300-320 800 12 6/9 2 270-300 700 13 5/7 2 250-300 700 14 6/8 3 170-200 900 15 5/7 3 190-230 1000-1200 16 5/6 4 120-150 1000-1200 17 5/5 3.5 180-220 1000 18 5/7 3.5 290-300 1000 19 4/4 4 270-330 1200 20 6/8 3 250-260 1400 21 6/7 3.5 270-330 1400 22 6/8 2.5 330-375 1200 23 5/8 2.5 320-360 1300 24 5/9 3 180-210 1350-1500 25 5/8 3 300-320 1000-1200 26 8/9 2 300-310 1000-1100 27 9/9 2 300-310 10004/9 28 4/9 3.5 290-320 800 29 4/8 3.5 300-350 800 30 4/8 3.5 310-340 700 31 8/8 3 300-340 750 32 6/8 2.5 280-340 1000 33 5.5/8 2 330-360 850 34 4/7 3.5 200-250 450 35 7/8 2.5 350-375 850 36 6/8 2 320-350 800 For the staining test (dry/water staining), 1 is very poor and 10 is very good. For the tar test, 5 is poor and 1 is good.

(43) Compositions based on an acidic polymer, in particular based on EAA (ethylene-acrylic acid copolymer) or on EMAA (ethylene-methacrylic acid copolymer), or an anhydride, in particular maleic anhydride, are more resistant to tar, staining and scratches at the same time as being as adherent or slightly more so than those observed with compositions based on EVA according to the prior art, in the case of a composition containing only a polymer with an acid base (compositions 14-19). In any case, compositions based on an acidic or anhydride polymer which also comprise a PE wax and/or a tackifier, are substantially more adherent. Advantageously, the tackifier can be replaced with a copolyamide which enhances resistance to tar, staining and scratching. This improvement could not be obtained with EVA-based compositions. For the two polyamides tested, i.e. PA1 (amine index=13; acid value=2) and PA2 (amine index=9; acid value=2), the results are essentially identical.

(44) The acidic and ionic groups of the polymer(s) used in the composition of the welding rods according to the invention, promote adhesion of the composition at high temperature to elements of the surface covering. When the temperature of the material drops back down to room temperature, free acidic groups, i.e. those not involved in the adhesion process, can form hydrogen bonds between macromolecules of the polymer, bonds that are 5-10 times stronger than Van der Waals forces. Thus, at room temperature, these polymers have similar physical properties to those of higher molecular weight polymers. Binding energies for ionic bonds are 10-20 times higher than those for the above-mentioned hydrogen bonds.

(45) Thus, surprisingly, using acidic polymers and copolymers and/or their corresponding ionomers, makes it possible to fulfil the dual requirement of low viscosity in the molten state with enhanced resistance to staining and scratches.

(46) Using an acidic polymer or copolymer or an ionomer also has the advantage of conferring a degree of adhesive power equivalent to that obtained with compositions based on acetate polymers such as EVA, while introducing a smaller number of polar groups. Thus, polar groups like acetate residues can advantageously be replaced with acidic groups or ionomers. In practice, unlike an acetate group, an acidic group or an ionomer can strongly interact with the numerous functional acidic or ionic groups in molecules of the surface covering, or even with alkaline groups (e.g. mineral constituents). These bonds are stronger than the dipolar interactions that acetate groups mediate.

(47) Thus, hot-melt welding rods according to the invention are less susceptible to staining and have the advantage that they can be simply wiped clean with a dry cloth.

(48) Preferably, the composition of the rod according to the invention includes an acidic polymer with a concentration of acid of between 10% and 20%, advantageously 10%. In practice, as a general rule, the characteristics of a composition containing an acidic polymer with a concentration of acid of 10% are superior to those of a composition containing an acidic polymer with a concentration of acid of 20%, especially with respect to resistance to tar and staining.

(49) Anhydride or acidic polymerspossibly neutralised to generate the ionomerin the welding rod according to the invention represent between 12.5% and 70% by weight, polyethylene represents between 13% and 80% by weight, and the copolyamide represents between 9.5% and 15% in weight, with respect to the total weight of all the polymers used.

(50) The polymer(s) according to the invention can be generated in a metallocene-catalysed synthetic pathway.

(51) According to a particular embodiment of the invention, one of the constituents of the welding rod is a wax, i.e. a polymer with a Brookfield viscosity of less than 10000 cPoise (centipoises) at 140 C. Preferably, the constituent that is in the form of a wax is the polyethylene.

(52) Preferably, the welding rod according to the invention contains a so-called ionomer wax, i.e. a wax derived from ionomer precursors with a fluidity that is in line with the definition of a wax, containing acidic or anhydride groups which may be neutralised by metal cations. Once it has been neutralised by ions, the so-called ionomer wax can no longer be in line with the definition of a wax (a Brookfield viscosity of less than 10000 cPoise at 140 C.) because the neutralisation of ionomer precursors entails a loss in fluidity and therefore an increase in viscosity. The so-called ionomer wax is used to reinforce the polymer based on an acid or an anhydride and enhances the homogeneity of the composition of the welding rod according to the invention.

(53) In order to further enhance the adhesive power of the hot-melt welding rod according to the invention, rather than adding tackifiers (which substantially compromise a welding rod's resistance to physical damage and staining), a copolyamide can be added instead. Surprisingly, copolyamides can enhance the adhesive power of a composition based on an acidic polymer or an ionomer, vis--vis the sub-units of a floor covering, and this despite the fact that the amine groups can, in theory, be neutralised by the acidic groups of the acidic copolymers or ionomers. In consequence, the potential adhesive power contributed by the amine groups would be substantially curtailed because it would no longer be free to interact with the surface of the floor covering.

(54) Preferably, the copolyamide is the product of the polycondensation of a dimer of fatty acids and an aliphatic diamine. Advantageously, the copolyamide has an amine index which is higher than its acid value.

(55) Preferably, the welding rod according to the invention also contains a naturally-occurring wax, advantageously carnauba or paraffin wax. Preferably, the natural wax represents up to 20% extra weight with respect to the total weight of polymers used.

(56) The welding rod according to the invention can also contain additives at proportions in the welding rod (expressed by percentage weight vis--vis the rest of the composition) that are preferably below 25%. Such additives could be a lubricating agent, silicone, a mineral bulking agent, an antistatic agent, a UV filter, an antioxidant, a pigment or a mixture of more than one of these. Preferably, the welding rod contains at least one suitable pigment. Advantageously, this could be titanium dioxide (TiO.sub.2).

(57) Depending on the type of floor covering, priority can be given to either ease of application and scraping, or ease of upkeep, by adjusting the composition of the hot-melt welding rod.

(58) In a particular embodiment, the hot-melt welding rod according to the invention comprises both an acid-based polymer, a poly-olefin wax, an ionomer, a copolyamide and an acidic terpolymer. Advantageously, it corresponds to Composition N 31 (Table 6).

(59) The welding rod according to the invention could be produced using any suitable process. Preferably, it is manufactured by extrusion.

(60) The welding rod according to the invention can be used to join any type of surface covering, in particular floor coverings and, more specifically, floor coverings based on linoleum, a polyolefin, PVC or rubber.

(61) Preferably, polyolefin-based surface coverings are coverings whose nature and structures are described in Document EP1567336. In particular, they are coverings made up of multiple layers including a substrate layer based on an olefin polymer, an intermediate layer based on a polymer generated in a metallocene-catalysed synthetic pathway, and a superficial, wear layer based on an ionomer-type polymer; they may also have a top layer coating of polyurethane.

(62) Preferably, rubber-based surface coverings are coverings whose nature and structures are described in European Patent Application N 07000622.6. In particular, they are coverings based on a mixture of SBS (styrene butadiene styrene) with SBR (a copolymer of butadiene and styrene containing at least 40% styrene by weight) or NBR (nitrile butadiene rubber), and HSR (a copolymer of styrene and butadiene with a high styrene content); they can also contain an ionomeric polymer.

(63) The surface coverings, in particular the floor coverings, of any nature that are joined together with the hot-melt welding rod according to the invention may also contain additives and/or mineral bulking agents or a fire-retardant, e.g. chalk aluminium hydrate, calcite, kaolin, dolomite, silica, silicates or magnesium hydroxide.