Curable casting compound, molded body made therefrom and method for producing the molded body

Abstract

A curable casting compound, including a polymeric binder and at least one particulate filler incorporated therein, wherein the filler is ground fruit kernels and/or fruit shells, wherein either only the at least one filler composed of ground fruit kernels and/or fruit shells or additionally at least one further particulate inorganic filler is present.

Claims

1. A molded article formed as a kitchen sink or sanitary article, comprising a body made of a cured casting compound comprising a polymeric binder based on acrylic resin, polyester resin or a mixture of these resins, and at least one particulate filler incorporated therein, wherein the at least one particulate filler is composed of ground fruit kernels and/or fruit shells selected from the group consisting of olive kernels, apricot kernels, peach kernels, mango kernels, almond shells, pistachio shells, avocado kernels, argan shells, walnut shells, cherry shells and plum kernels, and additionally comprises at least one further particulate inorganic filler, and wherein the molded article has an impact resistance in a range of 2.5-4.5 mJ/mm.sup.2.

2. The molded article according to claim 1, wherein the at least one particulate filler is comprised of a mixture of multiple different ground fruit kernels or fruit shells.

3. The molded article according to claim 1, wherein the at least one particulate filler has a particle size of 0.001-2000 ?m.

4. The molded article according to claim 1, wherein the proportion of the polymeric binder is 11-56% by weight and the proportion of the at least one particulate filler has is 44-89% by weight.

5. The molded article according to claim 1, wherein the at least one further particulate inorganic filler is selected from SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, ZrO.sub.2, Fe.sub.2O.sub.3, ZnO, Cr.sub.2O.sub.5, carbon, metals or metal alloys and mixtures thereof.

6. The molded article according to claim 1, wherein the at least one further particulate inorganic filler particles have a particle size of 0.010 to 8000 ?m.

7. The molded article according to claim 1, wherein the ratio of the at least one particulate filler in the form of fruit kernels or fruit shells to the at least one further particulate inorganic filler is in the range from 99:1 to 1:99 by weight.

8. The molded article according to claim 1, wherein the casting compound prior to curing has a viscosity of 1000-20000 cPs which permits injection into a mold.

9. A process for producing a molded article according to claim 1, wherein the casting compound is introduced into a mold, the casting compound is polymerized to form the molded article, and the polymerized molded article is removed from the mold.

10. The molded article according to claim 3, wherein the at least one particulate filler has a particle size of 0.01 to 1000 ?m.

11. The molded article according to claim 10, wherein the at least one particulate filler has a particle size of 0.05 to 800 ?m.

12. The molded article according to claim 6, wherein the at least one further particulate inorganic filler particles have a particle size of 0.05 to 3000 ?m.

13. The molded article according to claim 12, wherein the at least one further particulate inorganic filler particles have a particle size of 0.1 to 1300 ?m.

14. The molded article according to claim 8, wherein the casting compound prior to curing has a viscosity of 1500-15000 cPs.

15. The molded article according to claim 14, wherein the casting compound prior to curing has a viscosity of 2000-12000 cPs.

Description

EXAMPLE 1

(1) TABLE-US-00001 TABLE 1 Composition of gray-colored kitchen sinks without and with ground olive stones in different concentrations (figures in % by weight) Comparative Molded articles according to the invention molded articles 1 2 3 4 5 6 7 8 9 Recycled acrylic resin* 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 Biobased methacrylate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 monomers** Quartz sand filler, 0.05-0.3 69.0 67.5 63.0 60.0 55.0 47.0 29.0 24.0 17.0 0.0 mm, Dorfner GmbH Olive kernel granules, 0.05- 1.5 6.0 9.0 14 22 40 45.0 52.0 69.0 0.8 mm, Schilling Ltd. Micronized biopolymer, 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 M?nzing GMBH Decane-1,10-diol 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 dimethacrylate, Arkema Peroxide, Pergan GmbH 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Natural pigment, Kreidezeit 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Naturfarben GmbH Biobased thixotropic additive, 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ashland *Recycled acrylic resin is a solution of recycled PMMA (Kunststoff- und Farben-GmbH) in recycled methyl methacrylate (Monomeros des Valles) with viscosity 120-155 cPs. **The mixture of biobased isobornyl methacrylate (Evonik Performance Materials GmbH) and biobased ethyl methacrylate (BCH Br?hl-Chemikalien Handel GmbH)

(2) The mixture for production of the polymer matrix is produced by dissolving the polymer in the monomers. For the moldings according to the invention, the appropriate amount of the ground olive kernels together with the crosslinker is additionally introduced with stirring for 30 min. Each finished casting compound is introduced into a casting mold for production of moldings in the form of simple kitchen sinks with a basin having a sink base and circumferential sidewalls, and a flat surface to the side, and polymerization is induced thermally. Proceeding from ambient temperature, the material is heated in a mold as described in patent application DE 10 2020 119 386.6, cured and demolded on completion of curing.

(3) TABLE-US-00002 TABLE 2 Mechanical & thermal properties of the comparative moldings and of the moldings made from samples 1-9. Comparative molded Sample Sample Sample Sample Sample Sample Sample Sample Sample PROPERTIES articles 1 2 3 4 5 6 7 8 9 Thermal cycling stability OK OK OK OK OK OK OK OK OK OK Impact resistance, 2.8 2.8 2.9 3 3.1 3.4 3.3 3.3 3.2 3.5 mJ/mm.sup.2 Scratch resistance OK OK OK OK OK OK OK OK OK OK Abrasion resistance OK OK OK OK OK OK OK OK OK OK Sink weight, kg 13.6 13.2 12.9 12.6 12.1 11.7 11.3 11 10.7 9.8 BCI content 7.6 11.8 22.2 27.8 35.6 45.1 58.8 61.4 64.6 77.6

(4) The tests were conducted as follows (this is also applicable to all further examples cited hereinafter, if the respective test was effected):

(5) Thermal cycling stability test based on test method DIN EN 13310, in which the sink is treated alternately with cold and hot water for 1000 cycles. Hot water (T=90? C.) flows into the sink for 90 seconds, followed by relaxation for 30 seconds, and with further flowing cold water (T=15? C.) for the next 90 seconds. The cycle is ended by relaxation for 30 seconds.

(6) For the impact resistance measurements, 12 samples of size 80?6 mm are cut out of the molded article. The measurements were conducted on the basis of test method DIN EN ISO 179-2 using the ZwickRoell HIT P pendulum impact tester.

(7) For the scratch resistance measurements, one sample (100?100 mm) was cut out of each corresponding molded article. Subsequently, the visible face is scratched by means of a diamond tip under a load of 1 N-6 N installed in an Erichsen scratch tester. The topography was measured before and after the scratching (Mitutoyo Surftest SJ 500P).

(8) For the abrasion resistance test, one sample (100?100 mm) was cut in each case. By means of a Taber abrasion tester from Frank, the test is conducted on the basis of test method DIN EN 13310, and abrasion is determined via the loss of weight after 100 rotations.

(9) The BCI (Bio Carbon Index, %) of the chemical components is calculated by the following formula:
BCI=100?(BRC/C)
where BCI=biologically renewable carbon index in % BRC=amount of biologically renewable carbon C=total amount of carbon

(10) Comminuted fruit kernels and fruit shells are organic substances in which cellulose, hemicellulose and lignin are the most important chemical constituents. There is a resultant carbon content of 100% in the stones. With the increase in the proportion of ground fruit kernels and fruit shells in the formulation, we thus increase the proportion of biobased carbon.

(11) In this test series, proceeding from a comparative molded article, the quartz sand content was increasingly replaced by olive kernel granules, while the other casting compound constituents remain the same.

(12) It is found that there is an increase in impact resistance as the proportion of ground olive kernels increases and the proportion of quartz sand correspondingly decreases. While the impact resistance for the comparative molded articles is 2.8 mJ/mm.sup.2, the impact resistance increases with an increasing proportion of olive kernel particles up to a maximum of 3.5 mJ/mm.sup.2; sample 9 in which the quartz sand has been fully replaced by fruit kernel granules shows the highest value.

(13) Likewise apparent is the decrease in weight with increasing content of ground olive kernels. While the comparative molded article has a weight of 13.6 kg, the weight of the molded article according to sample 9 is only 9.8 kg, meaning a decrease of 3.8 kg, with the same shape.

(14) All other test results are also positive.

EXAMPLE 2

(15) TABLE-US-00003 TABLE 3 Composition of molded articles without and with ground olive kernel stones with different olive stone sizes (figures in % by weight) Comparative molded Inventive molded article articles Sample 10 Sample 11 Recycled acrylic resin* 23 23 23 Biobased methacrylate monomers** 4 4 4 Quartz sand filler 0.05-0.3 mm, Dorfner GmbH 69 57 57 Olive stone granules 0.01-0.1 mm, Schilling Ltd. 12 Olive kernel granules 0.3-0.6 mm, Schilling Ltd 12 Decane-1,10-diol dimethacrylate, Arkema 2.2 2.2 2.2 Micronized biopolymer, M?nzing GMBH 0.3 0.3 0.3 Peroxide, Pergan GmbH 0.6 0.6 0.6 Biobased pigment, Orion Engineering Carbon 0.8 0.8 0.8 Ethyl cellulose, Ashland 0.1 0.1 0.1 *Recycled acrylic resin is a solution of recycled PMMA (Kunststoff-und Farben-GmbH) in recycled methyl methacrylate (Monomeros des Valles) with viscosity 120-155 cPs. **The mixture of biobased isobornyl methacrylate (Evonik Performance Materials GmbH) and biobased ethyl methacrylate (BCH Br?hl-Chemikalien Handel GmbH)

(16) TABLE-US-00004 TABLE 4 Mechanical & thermal properties of the comparative molding and the inventive moldings Inventive molded Comparative article molded Sample Sample PROPERTIES article 10 11 Thermal cycling stability OK OK OK Impact resistance, mJ/mm.sup.2 3.0 3.6 4.5 Scratch resistance OK OK OK Abrasion resistance OK OK OK

(17) The test series shows that, irrespective of the size of the fraction of olive kernel filler added, an increase in impact resistance is recorded. However, it is found that impact resistance is also dependent on fraction size. While an increase in impact resistance of 0.6 mJ/mm.sup.2, namely from 3.0 mJ/mm.sup.2 for the comparative molded article including no olive kernel filler to 3.6 mJ/mm.sup.2 for sample 10, is found when olive kernel granules having a size of 0.01-0.1 mm are added, which replaces proportions of the quartz sand compared to the comparative molded article, there is an increase in impact resistance by 1.5 mJ/mm.sup.2, i.e. to 4.5 mJ/mm.sup.2, when olive kernel granules having a size of 0.3-0.6 mm are added.

(18) The reason for the elevated impact resistance of sample 11 compared to sample 4 having a similar composition lies in the somewhat altered proportions of recycled acrylic resin and of the methacrylate monomer. The addition of the crosslinker in sample 11 also has an impact resistance-increasing effect since the flexible crosslinker has very good affinity for the lignocellulose surface of the fruit kernel particles. And finally, sample 4 has a higher proportion of very fine fruit kernel granules beginning with a size of 0.05 ?m, compared to sample 11 containing granules having the smallest size of 0.3 ?m.

EXAMPLE 3

(19) In example 3, in the formulations of the applicant's known CRISTADUR? and CRISTALITE? brands, 10% by weight of the quartz filler in each case, based on the total weight of the sink, was replaced by ground olive kernels (0.1-600 ?m). Comparative sinks and sinks of the invention were produced under identical conditions and in the same forms in each case. CRISTADUR? kitchen sinks were produced in the Stone color and in the Mono D-100L form. CRISTALITE? was produced in the Bisques color and in the Primus D-100L form.

(20) TABLE-US-00005 TABLE 5 Mechanical & thermal properties of the comparative moldings and of the inventive moldings Inventive molding Sample 12 Sample 13 Comparative molding (CRISTALITE?- (CRISTADUR?- PROPERTIES CRISTALITE? CRISTADUR? based) based) Thermal cycling stability OK OK OK OK Impact resistance, mJ/mm.sup.2 2.0 2.4 2.8 2.5 Scratch resistance OK OK OK OK Abrasion resistance OK OK OK OK Sink weight, kg 15.4 16.2 14.3 15.0

(21) Two molded articles produced in accordance with the invention, each having different compositions, but each with a comparable proportion of quartz sand and olive kernel granules, were compared here with two molded articles produced according to figures in the prior art. It is found that the molded articles according to the invention have higher impact resistance values than the known molded articles.