COMPOSITIONS COMPRISING CURABLE RESIN FOR ANTI-STATIC FLOORING

Abstract

The invention relates to a composition for making flooring material comprising resin and particles comprising ammonium quaternary salt. The resin is generally an unsaturated polyester resin. The flooring materials, or engineered stone slabs from which the flooring materials or other material can be formed, are generally made from combining the resin, particles, inorganic particulate material and an initiator and allowing the resin to cure. The flooring material composition may be cobalt free. Metal catalysts may be used to cure the resin.

Claims

1. A flooring material composition comprising (A) an unsaturated polyester resin formulation comprising (i) an unsaturated polyester resin component; (ii) a metal catalyst capable of catalyzing curing of the unsaturated polyester resin component; (iii) a quaternary ammonium salt; and (iv) optionally, one or more additives selected from the group consisting of pigments, accelerators, co-promoters, dispersing agents, UV absorbers, stabilizers, inhibitors and rheology modifiers; (B) particles comprising ammonium quaternary salt; (C) an inorganic particulate material; and (D) an initiator.

2. The composition according to claim 1, wherein the ammonium quaternary salt that is comprised in the (B) particles is a N,N,N,N-tetraalkylammonium salt, a N-phenyl-N,N,N-trialkylammonium, a N-benzyl-N,N,N-trialkylammonium salt, a N,N-diphenyl-N,N-dialkylammonium salt, a N,N-dibenzyl-N,N-dialkylammonium salt, or a N-phenyl-N-benzyl-N,N-dialkylammonium salt.

3. The composition according to claim 1, wherein the ammonium quaternary salt that is comprised in the (B) particles differs from the (iii) quaternary ammonium salt that is comprised in the (A) unsaturated polyester resin formulation.

4. The composition according to claim 1, wherein the particles are encapsulated.

5. The composition according to claim 1, wherein the particles are encapsulated by an encapsulating material selected from the group consisting of polyurethane, polyurea, polyamide, polyester, polycarbonate, a urea/formaldehyde resin, a melamine resin, polystyrene, a styrene/methacrylate copolymer, a styrene/acrylate copolymer and a mixture of any of the foregoing.

6. The composition according to claim 5, wherein the encapsulating material selected from the group consisting of polyurethane, polyurea, polyamide, polyester, and polycarbonate.

7. The composition according to claim 1, wherein the content of the particles is up to about 3%, based on the weight of the flooring material composition.

8. The composition according to claim 1, wherein the particles have an average particle size of about 10 μm to about 250 μm.

9. The composition according to claim 1, wherein the unsaturated resin polyester resin component further comprises a reactive diluent.

10. The composition according to claim 9, wherein the reactive diluent is selected from the group consisting of styrene, substituted styrene, nono-, di- and polyfunctional esters of monofunctional acids with alcohols or polyols and mono-, di- and polyfunctional esters of unsaturated monofunctional alcohols with carboxylic acids or their derivatives.

11. The composition according to claim 1, wherein the unsaturated resin polyester resin component is cobalt free.

12. The composition according to claim 1, wherein the metal catalyst comprises zinc or copper.

13. The composition according to claim 1, wherein the (A)(iii) quaternary ammonium salt is a benzyl-N,N,N-trialkylammonium salt or a N,N,N,N-tetraalkylammonium salt.

14. The composition according to claim 1, wherein the unsaturated polyester resin component is obtained by reacting a mixture comprising a multicarboxylic acid component and a polyhydric alcohol component, wherein the multicarboxylic acid component and/or the polyhydric alcohol component comprises ethylenic unsaturation.

15. The composition according to claim 14, wherein the multicarboxylic acid component is selected from the group consisting of aliphatic dicarboxylic acids, aliphatic tricarboxylic acids, aliphatic tetracarboxylic acids, aromatic dicarboxylaic acids, aromatic tricarboxylic acids and aromatic tetracarboxylic acids; and the polyhydric alcohol component is selected from the group consisting of aliphatic diols, aliphatic triols, aliphatic tetraols, aromatic diols, aromatic triols and aromatic tetraols.

16. The composition according to claim 1, wherein the inorganic particulate material comprises quartz aggregates and/or quartz fillers.

17. The composition according to claim 16, wherein the quartz aggregate comprises about 25% to about 75%, by weight of the flooring material composition, of particles having a particle size of up to about 0.3 μm and about 5% to about 30%, by weight of the flooring material composition, of particles having a particle size of greater than about 0.3 μm and the quartz filler has a particle size of up to about 45 μm and the content of the quartz filler in the flooring material composition is about 15% to about 35% by weight of the flooring material composition.

18. The composition according to claim 1, wherein the initiator comprises peroxide.

19. The composition according to claim 18, wherein the peroxide comprises cumene hydroperoxide and/or methyl isobutyl ketone peroxide.

20. The composition according to claim 1, wherein the composition is cobalt free.

21. A flooring material composition comprising i) a resin selected from the group consisting of vinyl ester resin and epoxy resin and ii) particles comprising ammonium quaternary salt.

22. A flooring material comprising the flooring material composition according to claim 1 in cured form.

23. The flooring material according to claim 21 having electric resistivity values within the dissipative established zone.

24. A method for the making flooring material comprising the steps of (a) preparing a formable composition by mixing (A) an unsaturated polyester resin formulation comprising (i) an unsaturated polyester resin component; (ii) a metal catalyst capable of catalyzing curing of the unsaturated polyester resin component; (iii) a quaternary ammonium salt; and (iv) optionally, one or more additives selected from the group consisting of pigments, accelerators, co-promoters, dispersing agents, UV absorbers, stabilizers, inhibitors and rheology modifiers; (B) particles comprising ammonium quaternary salt; (C) an inorganic particulate material; and (D) an initiator; (b) forming the composition prepared in step (a) into a desired shape; and (c) allowing the composition formed in step (b) to cure.

25. The method according to claim 24, wherein the composition formed from steps (a), (b) and (c) is an engineered stone slab and comprising an additional step (d) of making a piece of flooring material from the engineered stone slab.

26. The method according to claim 24, wherein the unsaturated polyester resin formulation is cobalt free.

27. The method according to claim 24, wherein the metal catalyst comprises zinc or copper.

28. A piece of flooring material made by the method of claim 24.

Description

EXAMPLE 1

[0134] Tiles of three different types in accordance with the invention (size 300 mm×300 mm×10 mm) were prepared from unsaturated polyester resin (UPR), quartz, and encapsulated particles comprising ammonium quaternary salt [available under the trade name avanSTATIC from AVANZARE Innovacion].

[0135] Three samples in accordance with the invention were prepared. All samples had the following composition in common (UPR resin, filler, silica):

TABLE-US-00004 % % specific Volume weight weight weight Volume Mass/dm.sup.3 Ingredient [vol.-%] [wt.-%] [kg/dm.sup.3] [g] [cm.sup.3] [kg/dm.sup.3] UPR 20.8 10 1.12 400 357 0.233 resin filler 26.4 30 2.65 1200 453 0.699 0.1-0.3 30.8 35 2.65 1400 528 0.816 mm sillica 0.3-0.6 17.6 20 2.65 800 302 0.466 mm sillica 1-3 4.4 5 2.65 200 75 0.117 mm sillica total 100.0 100.0 4000 1716 2.33

[0136] Thus, the total weight amounted to 4000 g.

[0137] The UPR resin was in all cases the same, namely a reaction product of a mixture comprising one or more diols selected from the group consisting of propylene glycol, dipropylene glycol, ethylene glycol, and diethylene glycol; and one or more acids selected from the group consisting of maleic acid, isophthalic acid, phthalic acid, and adipic acid, or their acid anhydrides.

[0138] The following pigment composition was employed for all three samples:

TABLE-US-00005 Pigments % on resin content resin weight total [g] Titan 5.000 400 20.000 Yellow 920 0.013 400 0.050 Yellow 960 0.025 400 0.100

[0139] The differences of compositions 1 to 3 were as follows:

TABLE-US-00006 Composition 1: 10% of antistatic material based on resin content: % on resin content resin weight Total [g] encapsulated particles [g] 10 400 40 peroxide [g] 2 400 8 silane 12 [g] 2 400 8

TABLE-US-00007 Composition 2: 12% of antistatic material based on resin content: % on resin content resin weight Total [g] encapsulated particles [g] 12 400 48 peroxide [g] 2 400 8 silane 12 [g] 2 400 8

TABLE-US-00008 Composition 3: 15% of antistatic material based on resin content: % on resin content resin weight Total [g] encapsulated particles [g] 15 400 60 peroxide [g] 2 400 8 silane 12 [g] 2 400 8

[0140] The electrical resistivity of the thus obtained tiles was determined according to UNE-EN-1081:2004, method A (R1) and method C (R3), respectively. Definitions that apply for the tests, according to the standard: [0141] Vertical electrical resistivity R1: The electrical resistivity measured between a tripod electrode on the surface of a test piece and an electrode attached to the underside of the test piece. [0142] Surface electrical resistivity R3: The electrical resistivity measured between two tripod electrodes, set up at a fixed distance of 100 mm.

[0143] Samples were kept under constant temperature and humidity conditions, specifically at 23° C. (2) and 50% (5) of relative humidity. Time spent: 115 hours. Test conditions: 49% humidity and 23° C. Load applied in both tests: 380N. Applied voltage: 500 V. Measurement taken 15 seconds after voltage connection. Five readings were taken of each sample.

[0144] The following results were obtained:

TABLE-US-00009 Composition 1 Composition 2 Composition 3 aver- aver- aver- [×10.sup.7Ω] age max min age max min age max min R1* 22.5 22.8 22.0 8.73 8.83 8.64 3.24 3.28 3.17 R3** 82.3 82.9 81.5 15.3 15.6 14.6 8.93 8.98 8.88 *method A **method C

[0145] It becomes clear from the above data that all samples had excellent electrical resistivity well below 1.Math.10.sup.9Ω.

[0146] Furthermore, the mechanical values measured on the tiles of the 3 compositions met the standards of the engineered stone market and are superior over conventional products:

TABLE-US-00010 Flexural [MPa] Impact [J] Standard Flex/Impact Composition 1 76.01 7.1 >50/>4 Composition 2 74.56 7 >50/>4 Composition 3 70.56 6.8 >50/>4

EXAMPLE 2 (COMPARATIVE)

[0147] In accordance with Example 1 a comparative composition was prepared that differed from compositions 1 to 3 in that the encapsulated particles were omitted and a cobalt containing material was added instead:

TABLE-US-00011 % on resin content resin weight Total (g) cobalt (6%) [g] 0.2 400 0.8 peroxide TBPB [g] 2 400 8 silane [g] 2 400 8

[0148] The measured value of electrical resistivity was 3.26×10.sup.11 Ohms.

EXAMPLE 3

[0149] Another representative sample of the material according to the invention was tested according to ASTM F150-Standard Test Method for Electrical Resistance of Conductive and Static Dissipative Resilient Flooring.

[0150] Testing was conducted in accordance with ASTM F150. One 12″ (304.8 mm) long by 12″ (304.8 mm) wide by ½″ (12.7 mm) thick specimen was provided for testing. The specimens were conditioned at 73.4±3.6° F. (23°±2° C.) and 50±5% relative humidity for not less than 24 hours prior to testing. #

[0151] Three measurements were made of each dimension using a sliding caliper gauge. The results are summarized in the table here below:

Test Results

[0152]

TABLE-US-00012 Surface to Surface Specimen Test Resistance Applied # number (Ohms, Ω) Voltage (V) Floor Tile 1 1.0 × 10.sup.8 100 #1 2 1.0 × 10.sup.7 100 3 1.0 × 10.sup.8 100 4 1.0 × 10.sup.7 100 5 1.0 × 10.sup.7 100