Cast-molded article

Abstract

A cast-molded article in a composite material comprising a cured polymeric binder incorporating embedded particles of filler, characterized in that the binder incorporates randomly distributed fibers of polyamide, wherein the fibers have a length of 5-20 mm and a diameter of 0.05-0.2 mm and the fibers comprise 0.02-0.5 wt % based on the overall mass of the cast-molded article.

Claims

1. A cast-molded article made of a composite material comprising a cured polymeric binder incorporating embedded particles of filler, wherein the binder incorporates randomly distributed fibers of polyamide, wherein the fibers have a length of 5-20 mm and a diameter of 0.05-0.2 mm and the fibers are present in an amount of 0.02-0.5 wt % based on the overall mass of the cast-molded article, wherein the fibers have a main alignment essentially parallel to the face side of the cast-molded article.

2. The cast-molded article according to claim 1, wherein the fibers are of nylon-6 or nylon-6,6.

3. The cast-molded article according to claim 1, wherein the fibers have a length of 5-15 mm.

4. The cast-molded article according to claim 1, wherein the fibers have a diameter of 0.075-0.175 mm.

5. The cast-molded article according to claim 1, wherein the fibers comprise 0.025-0.25 wt % based on the overall mass of the cast-molded article.

6. The cast-molded article according to claim 1, wherein the fibers have a breaking strength of not less than 250 N/mm.sup.2.

7. The cast-molded article according to claim 1, wherein the fibers are colorless or match the color of the cast-molded article.

8. The cast-molded article according to claim 1, wherein an edge region adjoining the face side of the cast-molded article is fiberless and it is only in the remaining volume of the article that the fibers are present in the form of a dispersion.

9. The cast-molded article according to claim 1, wherein the fibers form a homogeneous distribution away from any edge region.

10. The cast-molded article according to claim 1, wherein the fibers attach to the binder via surficial reactive groups.

11. The cast-molded article according to claim 1, wherein the fibers have a coating of adhesion promoter attaching them to the binder.

12. The cast-molded article according to claim 1, wherein the binder comprises a monomer and a polymer dissolved in the monomer.

13. The cast-molded article according to claim 12, wherein the monomer is methyl methacrylate and the polymer is poly(methyl methacrylate).

14. The cast-molded article according to claim 13, wherein the binder comprises a crosslinker.

15. The cast-molded article according to claim 14, wherein the crosslinker is trimethylolpropane trimethacrylate.

16. The cast-molded article according to claim 1, wherein the mass fraction of the filler particles is between 40-85% based on the mass of the cast-molded article.

17. The cast-molded article according to claim 1, wherein it contains inorganic types of filler particles.

18. The cast-molded article according to claim 1, wherein the filler particles are each between 0.01 mm and 2 mm in size.

19. The cast-molded article according to claim 18, wherein filler particles in two or more different size fractions are present.

20. The cast-molded article according to claim 1, wherein it is a sink, a wash-basin, a shower tray or a worktop.

21. A process for producing a cast-molded article according to claim 1, wherein not only filler particles but also polyamide fibers having a length of 5-20 mm and a diameter of 0.05-0.2 mm are mixed into a curable polymeric solution of a binder to form a homogeneous casting composition wherein the fibers comprise 0.02-0.5 wt % based on the overall mass of the casting composition and then the casting composition is poured into a casting mold wherefrom the cast-molded article is demolded after the binder has cured.

22. The process according to claim 21, wherein fibers of nylon-6 or nylon-6,6 are used.

23. The process according to claim 21, wherein fibers having a length of 5-15 mm and/or having a diameter or 0.075-0.175 mm are used.

24. The process according to claim 21, wherein the admixed proportion of fibers comprises 0.025-0.25 wt based on the overall mass of the casting composition.

25. The process according to claim 21, wherein fibers having a breaking strength of not less than 250 N/mm.sup.2 are used.

26. The process according to claim 21, wherein the fibers used are colorless or match the color of the cast-molded article.

27. The process according to claim 21, wherein the fibers used have been plasma treated on the surface to form reactive groups or in that the fibers have a coating of adhesion promoter.

28. The process according to claim 21, wherein the binder used comprises a monomer, a polymer dissolved in the monomer and optionally a crosslinker.

29. The process according to claim 28, wherein the monomer used is methyl methacrylate, the polymer used is poly(methyl methacrylate) and optionally trimethylolpropane trimethacrylate is used as crosslinker.

30. The cast-molded article according to claim 3, wherein the fibers have a length of 8-12 mm.

31. The cast-molded article according to claim 30, wherein the fibers have a length of 10 mm.

32. The cast-molded article according to claim 4, wherein the fibers have a diameter of 0.1-0.15 mm.

33. The cast-molded article according to claim 5, wherein the fibers comprise 0.03-0.2 wt % based on the overall mass of the cast-molded article.

34. The cast-molded article according to claim 33, wherein the fibers comprise 0.05-0.15 wt % based on the overall mass of the cast-molded article.

35. The cast-molded article according to claim 16, wherein the mass fraction of the filler particles is between 60-80% based on the mass of the cast-molded article.

36. The cast-molded article according to claim 35, wherein the mass fraction of the filler particles is between 65-75% based on the mass of the cast-molded article.

37. The cast-molded article according to claim 17, wherein it contains quartz sand, quartz meal, silicon dioxide, silicon carbide, glass, alumina or calcium carbonate.

38. The process according to claim 23, wherein fibers having a length of 8-12 mm are used.

39. The process according to claim 38, wherein fibers having a length of 10 mm are used.

40. The process according to claim 23, wherein fibers having a diameter of 0.1-0.15 mm are used.

41. The process according to claim 24, wherein the admixed proportion of fibers comprises 0.03-0.2 wt % based on the overall mass of the casting composition.

42. The process according to claim 41, wherein the admixed proportion of fibers comprises 0.05-0.15 wt % based on the overall mass of the casting composition.

43. A cast-molded article made of a composite material comprising a cured polymeric binder incorporating embedded particles of filler, wherein the binder incorporates randomly distributed fibers of polyamide, wherein the fibers have a length of 5-20 mm and a diameter of 0.05-0.2 mm and the fibers are present in an amount of 0.02-0.5 wt % based on the overall mass of the cast-molded article, wherein the fibers are colorless or match the color of the cast-molded article.

44. A cast-molded article made of a composite material comprising a cured polymeric binder incorporating embedded particles of filler, wherein the binder incorporates randomly distributed fibers of polyamide, wherein the fibers have a length of 5-20 mm and a diameter of 0.05-0.2 mm and the fibers are present in an amount of 0.02-0.5 wt % based on the overall mass of the cast-molded article, wherein an edge region adjoining the face side of the cast-molded article is fiberless and it is only in the remaining volume of the article that the fibers are present in the form of a dispersion.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) In the drawing:

(2) FIG. 1 shows a perspective view in the form of an in-principle depiction of a cast-molded article obtained according to the invention in the form of a kitchen sink,

(3) FIG. 2 shows an in-principle depiction of a sectional view through the cast-molded article of FIG. 1,

(4) FIG. 3 shows a table including impact strength measurements regarding a fiberless, comparative test-piece article and 48 test-piece articles comprising different admixtures of fibers, said fibers not having been surface treated,

(5) FIG. 4 shows a table featuring results of a visual inspection of the visible surface of the test-piece articles according to the above tables of FIG. 3,

(6) FIG. 5 shows a table featuring impact strength measurements for the fiberless, comparative test-piece article and 48 test-piece articles comprising different admixtures of fibers, said fibers having been surface activated via a plasma,

(7) FIG. 6 shows a table featuring results of a visual inspection of the visible surface of the test-piece articles according to the above tables of FIG. 5, and

(8) FIG. 7 shows a table concerning rheology measurements regarding the casting compositions used to produce the test-piece articles of FIG. 3.

DETAILED DESCRIPTION OF THE INVENTION

(9) FIG. 1 shows at 1 a perspective view of a cast-molded article as classified in the preamble, namely a cast-molded article in a composite material comprising a cured polymeric binder incorporating embedded particles of filler.

(10) The illustrated example is a kitchen sink 2 having, for the purposes of this example, two separate bowls 3, each bounded by sidewalls and a bottom surface. The upper rim 4 is continuous and relatively wide. The cast-molded article 1 has a face side 5, i.e., a surface that is visible in the installed position. This face side extends to all surfaces on the front, not only in the region of bowls 3 but also in the region of rim 4.

(11) The cast-molded article is produced using a closed casting mold whereinto the reaction composition, i.e., the casting composition, containing inter alia the polymeric binder and/or the binder solution and filler particles included therein and alsoin the example which is in accordance with the present inventionintroduced polyamide fibers is introduced. The casting composition has an adequate viscosity for filling into the casting mold. Inside the casting mold, the introduced casting composition is heated, using externally supplied energy, to effect polymerization and hence to cure the polymeric binder. The polymeric binder used is a corresponding binder solution, preferably of MMA as monomer and PMMA as polymer. The mass fraction of the MMA-PMMA solution which is attributable to the PMMA is preferably between 15-30%, while in general the ratio of the proportional parts by weight of the polymer to the monomer in the binder solution should be between 1:1 and 1:10, in particular between 1:2 and 1:7 and preferably between 1:3 and 1:5. The binder solution is preferably admixed with a crosslinker, preferably trimethylolpropane trimethacrylate (TRIM). The proportion of crosslinker may be below 10 wt % of the monomer fraction of the binder solution. However, it may also be preferable for it to be more than 10 wt %, preferably between 10-30 wt %, based on the monomer fraction in the binder solution.

(12) As described, the casting composition further includes filler particles, the level of the preferably inorganic types of filler particles being between 55-85 wt %, preferably between 60-80 wt % and particularly between 65 and 75 wt %, based on the reaction composition. Preference is given to using mineral inorganic fillers, in particular crystalline fillers, for example quartz sand. Alternatively, it is also possible to use glass, silicon carbide, alumina or carbon in the diamond allotrope or calcium carbonate. The filler particles should be between 0.01-1 mm in size and may optionally be present in different, distinguishable size fractions.

(13) The polyamide fibers admixed should have a length of 5-20 mm, in particular of 7-15 mm, particularly of 8-12 mm and more preferably of 10 mm, and a diameter of 0.05-0.2 mm, in particular of 0.075-0.175 mm, preferably of 0.1-0.15 mm. Their proportion should be between 0.02-0.5 wt % based on the overall mass of the casting composition, preferably between 0.025-0.3 wt %, in particular between 0.03-0.2 wt % and more preferably between 0.05-0.15 wt %, based on the overall mass of the casting composition (or of the molded article in its cured state).

(14) It is preferably nylon-6 or nylon-6,6 fibers which are used. The fibers used should have a breaking strength of not less than 250 N/mm.sup.2.

(15) FIG. 2 shows an in-principle depiction of a sectional view through the rim 4 of the cast-molded article 1 in FIG. 1. The thickness of the corresponding sections of the cast-molded article is typically between 5-15 mm.

(16) FIG. 2 shows firstly the cured polymeric binder 6, i.e., the binder matrix. This binder matrix incorporates the filler particles 7 in a substantially homogeneous distribution. The binder 6 similarly incorporates the polyamide fibers 8. Their main alignment, as shown by FIG. 2, is preferably essentially parallel to the face side 5 of the cast-molded article 1; that is, they extend approximately parallel thereto. This is to be understood as meaning that the angle formed by fibersor, for example, an approximated straight line placed against the particular polyamide fiber 8with the plane of the face side 5 is preferably below 15, more preferably below 10 and yet more preferably below 5. The polyamide fibers 8, as will be appreciated, do not just extend parallel to the plane of the drawing, but are at arbitrary angles to the same plane, i.e., they also extend into and out of the plane of the drawing. However, their primary, main alignment is determined by the local direction of flow of the casting composition within the casting mold.

(17) The final cast-molded article develops an edge region 9 directly adjoining the face side 5, this edge region 9 being very narrow at a width in the range of 0.1-2 mm and fiberless. This edge region 9 is only formed of the cured binder 6 and the filler particles 7. Since, therefore, no polyamide fibers 8 are present on the edge region side, they are logically also not visible on the face side 5. This edge region develops on using sufficiently thin and long fibers having the dimensions described above and choosing the fiber fraction as a proportion of the overall mass of the casting composition in the manner described.

(18) The tables shown in FIGS. 3-6 show impact strength measurements (FIGS. 3 and 5) and results of a visual inspection of the visible surface (FIGS. 4 and 6) of altogether 96 different test-piece articles and/or 96 different casting compositions and one comparative test-piece article and/or casting composition, while FIG. 7 shows rheology measurements for the test-piece articles in FIG. 3 and for the comparative test-piece article.

(19) The casting compositions produced were all the same with regard to the binder solution, the filler particles, the crosslinker and any additives etc., merely the type and amount of the polyamide fibers admixed varied from casting composition to casting composition and/or from test-piece article to test-piece article.

(20) The casting compositions produced were as follows, although the table hereinbelow does not include the particular specific admixtures of fiber:

(21) TABLE-US-00001 Material Amount used (wt %) MMA about 19.1 PMMA about 4.6 filler 1 (quartz sand 0.05-0.3 mm) about 52 filler 2 (cristobalite meal 0.01-0.05 mm) about 18 crosslinker (TRIM) about 4.2 additives, peroxide, pigment about 2.1 SUM TOTAL: 100

(22) The molded articles identified in FIGS. 3-6 as a-l, or to be more precise their casting compositions, were each admixed with different fibers, said fibers differing in diameter and also length.

(23) The casting compositions and/or the test-piece articles a-d were admixed with fibers 5 mm in length and respectively 0.075 mm, 0.1 mm, 0.15 mm and 0.2 mm in diameter.

(24) The casting compositions and/or the test-piece articles e-h were admixed with fibers 10 mm in length and respectively 0.075 mm, 0.1 mm, 0.15 mm and 0.2 mm in diameter.

(25) The casting compositions and/or the test-piece articles i-l were finally admixed with fibers 20 mm in length and respectively 0.075 mm, 0.1 mm, 0.15 mm and 0.2 mm in diameter.

(26) In addition, within each casting composition or test-piece article group a-d, e-h or i-l, the particular amount of fiber admixed varied as shown in the columns of the tables shown in FIGS. 3 and 5 (amount used in wt %).

(27) The first group of casting compositions or test-piece articles were admixed with a fiber quantity of 0.05 wt % based on the overall mass of the casting composition. A second group of casting compounds or test-piece articles were admixed with a fiber quantity of 0.1 wt % based on the overall mass of the molded article. A third group of casting compounds or test-piece articles were admixed with a fiber quantity of 0.2 wt % based on the overall mass of the molded article. A fourth group of casting compounds or test-piece articles were finally admixed with a fiber quantity of 0.4 wt % based on the overall mass of the casting compound.

(28) Altogether 48 casting compounds were prepared in this way, giving 12 test-piece articles differing in fiber type and four different levels of fiber admixture. Fiber admixture raised the viscosity of the particular casting composition, the increase in some cases being so considerable as to render the casting composition unprocessable, i.e., uncastable. Not all casting composition batches could therefore be converted into test-piece articles. The batches whence no test-piece articles were obtained are identified in the tables of FIGS. 3 and 5 as neg..

(29) In addition, one test-piece article was produced for comparison from purely the casting compound sans fiber admixture.

(30) The values measured in a DIN 53448 impact strength measurement are reported in mJ/mm.sup.2 in FIGS. 3 and 5. The a-l test-piece articles produced from the respective casting compositions and tested were DIN-compliant. The impact strength measurements were carried out using an HIT5P pendulum impact tester from Zwick/Roell.

(31) The fibers admixed to the casting compositions leading to the test-piece articles tested as per FIG. 3 had not been given a surface treatment; that is, they were nylon-6 fibers neither having surfaces activated by a plasma treatment nor having surfaces coated with an adhesion promoter.

(32) The comparative test-piece article produced from the casting composition sans fiber admixture gives an impact strength measurement of 1.98 mJ/mm.sup.2.

(33) The measured values shown in the table of FIG. 3 exhibit an improvement, i.e., increase, in impact strength on using the fibers without surface treatment, particularly in the case of the comparatively long fibers, i.e., the fibers 10 mm or 20 mm in length, and an admixed fiber quantity of 0.05 or 0.1 wt %, only in some instances also at higher admixtures. A fiber quantity of 0.4 wt % did not in general lead to any improvement over the comparative test-piece article having a measured impact strength of 1.98 mJ/mm.sup.2 for the short fibers at 5 mm, while the 10 mm fibers usually led to defective specimens due to excessive viscosity, and with the 20 mm fibers there was no longer any processability.

(34) FIG. 4 shows a table reporting data from a visual inspection of the surface of the test-piece articles which corresponds to the face side 5 on the final molded article. A 0 in this table indicates when the inspected test-piece surface was flawless, while 1 indicates that fibers were visible at the surface or the lack of processability had led to other defects such as, for example, cracks or holes.

(35) When fibers were 10 mm in length and admixed at a high level of 0.1 wt %, visible defects in the form of holes or cracks developed due to excessive viscosity particularly in the case of the thinner fibers used at 0.075 mm in diameter.

(36) As expected, casting compositions comprising fibers 20 mm in length were in some instances no longer processable (high viscosity and entanglement) in the case of thin fibers and a high amount used, and/or gave rise to defects on the visible surfaces of the specimens.

(37) A comparison with FIG. 3 and the impact strength measurements shows that, when untreated fibers are used, it should be preferable to admix fibers 10 mm in length and between 0.075 and 0.15 mm in diameter at an admixture rate of 0.05-0.2 wt %. Particularly the test-piece articles e and f exhibited in some instances marked improvements in impact strength measurements.

(38) Fibers having a length of 20 mm can also be admixed, albeit only at a low rate of 0.05 wt % if there are to be no visible defects on the visible surface.

(39) FIG. 5 shows a corresponding table, again featuring the test-piece articles a-e although this time, as already described, admixed with fibers surface activated via a plasma. The fibers admixed, as already described, again varied in length and diameter, and the amounts used also varied as already described with regard to FIG. 3. The comparative test-piece article corresponds to that of FIG. 3, since the same casting compound was used, and it gave an impact strength value of 1.98 mJ/mm.sup.2.

(40) As can be seen, even test-piece articles a-d exhibit significant increases in impact strength measurements, particularly at the admixture amounts of 0.05, 0.1 and 0.2 wt %, the maximum value here being 2.4 mJ/mm.sup.2 in the case of test-piece article c at a fiber quantity of 0.1 wt %. It is again observed that, depending on the test-piece article, the impact strength measurements will in some instances go back down as the fiber quantity increases. The explanation for this effect is that as fiber length decreases and fiber cross section increases, the dislocatory action of the fibers in the composite increases faster with the increasing fiber content than the forces of adherence do.

(41) The increase in the impact strength measurements is even more significant with test-piece articles e-h. Test-piece article f here exhibited the highest impact strength value of 3.05 mJ/mm.sup.2 at a fiber quantity of 0.4 wt %. Overall, however, test-piece articles e-h are all found to exhibit distinctly higher impact strength measurements than the comparative test-piece article.

(42) This also applies to test-piece articles i-l. They likewise exhibit significant increases in impact strength measurements.

(43) The explanation for the distinct improvement in impact strength measurements, including with regard to the FIG. 3 measurements for untreated fibers, is that the plasma activation of the surface has given rise to reactive groups there which lead to a distinctly stronger bond of the fibers to the binder matrix; that is, the reactive groups of the fiber surface have formed a bond with the binder.

(44) FIG. 6 shows the results of a visual examination of the surface of test-piece articles a-l as per FIG. 5. These results correspond to those already apparent from FIG. 4. It transpires that as fiber length, the diameter and the amount admixed all increase, the number of test-piece articles where there were visible defects in the face side also increases. A comparison with FIG. 5 shows that it is therefore particularly the test-piece articles f and g with add amounts of 0.05, 0.1 and 0.2 wt % that are useful for providing outstanding results not only with regard to improved impact strength but also with regard to the possibility of producing an impeccable face side. They deliver distinctly increased impact strength values in some cases.

(45) Even fibers having a length of 20 mm have proved to be perfectly usable not only with regard to an improved impact strength but also with regard to the production of a visually impeccable face side. This only at relatively low admixtures, however.

(46) FIG. 7 finally shows a table reporting rounded rheology measurements regarding the different casting compositions. The reported measurements indicate the dynamic viscosity. For each casting composition a-l comprising untreated nylon-6 fibers (i.e., in accordance with FIG. 3), 160 ml of casting composition were tested. The rheology measurement was carried out in accordance with DIN EN ISO 3219 by using an R/S Rheometer SST dynamic viscometer from Brookfield. The reported measurements are in mPas. The measured rheology value is obtained from three measured ranges at a rotation of 10 l/min. The measured values are determined from the second measured interval, and the intervals reside in a time range of 40-50 seconds, 80-90 seconds and 120-130 seconds.

(47) The comparative casting composition sans admixed fiber gave a dynamic viscosity of 5500 mPas. Casting compositions having distinctly different viscosities are also workable, but it transpired on corresponding admixture of fibers that the viscosity increase resulting therefrom will again, from a certain value onward, lead to the aforementioned defects in the surface and/or an end to the processability of the composition.

(48) The table reveals that for virtually every casting composition tested, the dynamic viscosity increases with increasing fiber quantity. It is further apparent that the dynamic viscosity decreases with increasing fiber diameter for the same amount of fiber admixed. This is because total fiber surface area decreases with increasing fiber diameter for the same amount of fiber admixed, and this has a positive effect on the viscosity value.

(49) From a manufacturing viewpoint, a casting compound whose viscosity has doubled or more as a consequence of fiber admixture, as compared with the viscosity of the casting compound sans fiber admixture, turned out to be no longer workable. Having regard to the results of the visual inspection as per FIGS. 4 and 6, it transpires that, again, particularly the test-piece articles f and g and admixtures of 0.05, 0.1 and 0.2 wt % still exhibit sufficiently good viscosity values to permit the production of test-piece articles and hence cast-molded articles having not only a distinctly improved impact strength but also visually impeccable face areas. Within the group of test-piece articles comprising fibers 20 mm in length, it is only the casting compositions j and k at admixed fiber quantities of 0.05 wt % which permit a technically impeccable process for producing test-piece articles of improved impact strength and hence of cast-molded articles having a visible surface that is impeccable.

(50) The rheology measurements regarding casting compounds a-l comprising the plasma-treated fibers of FIG. 5 are not presented separately because they correspond to those in FIG. 7.

(51) The measured results show overall that it is preferably fibers that have been surface activated, in particular by a plasma treatment, which deliver particularly distinct improvements in the impact strength of a cast-molded article. With regard to the production of a visually impeccable face area and the possibility of maintaining adequate viscosity for the casting compound for straightforward processing despite fiber admixture, fibers having an average length of about 7-15 mm, in particular 8-12 mm and more preferably of 10 mm should be used, while the fiber diameter should be between 0.075 and 0.175 mm, preferably between 0.1-0.15 mm.

(52) Since, in impeccable cast-molded articles, the fibers cannot be seen at the surface, they logically do not affect the mechanical properties of the surface and visible area; that is, these continue to exhibit the high level of scratch resistance as conferred particularly by the casting composition batch underlying the test-piece articles.

(53) Particular preference is given to producing cast-molded articles from binder batches as described in DE 10 2004 055 365 A1 or DE 10 2010 046 627 A1, which with regard to the binder solutions/casting compositions described therein are hereby fully incorporated in the disclosure of the present application by reference. That is, all the features disclosed therein fully form part of the disclosure of the present application.

(54) While specific embodiments of the invention have been shown and described in detail to illustrate the inventive principles, it will be understood that the invention may be embodied otherwise without departing from such principles.