Sizing composition for mineral wool comprising a saccharide, an organic polycarboxylic acid and a reactive silicone, and insulating products obtained

Abstract

A sizing composition for insulating products based on mineral wool, in particular on glass or on rock, includes: at least one saccharide, at least one organic polycarboxylic acid having a molar mass of less than or equal to 1000, and at least one reactive silicone. Furthermore, insulating products based on mineral fibers thus obtained and the process for the manufacture thereof are presented.

Claims

1. A sizing composition for insulating products based on mineral wool, the sizing composition consisting of: at least one saccharide, at least one organic polycarboxylic acid having a molar mass of less than or equal to 1000, wherein the polycarboxylic acid is a non-polymeric polycarboxylic acid selected from: (1) a dicarboxylic acid selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, optionally substituted phthalic acid, optionally substituted tetrahydrophthalic acid, isophthalic acid, terephthalic acid, mesaconic acid and citraconic acid; wherein optionally substituted phthalic acid comprises at least one boron or chlorine atom and optionally substituted tetrahydrophthalic acid comprises at least one chlorine atom; (2) a dicarboxylic acid precursor selected from the group consisting of maleic anhydride, succinic anhydride and phthalic anhydride; (3) a tricarboxylic acid selected from the group consisting of citric acid, tricarballylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, hemimellitic acid, trimellitic acid and trimesic acid; or (4) a tetracarboxylic acid selected from the group consisting of 1,2,3,4-butanetetracarboxylic acid and pyromellitic acid; wherein the non-polymeric polycarboxylic acid is present in an amount of at least 10% of the weight of the mixture of the saccharide plus the at least one polycarboxylic acid at least one reactive silicone; a catalyst chosen from Lewis acids and bases, phosphorus-containing compounds and compounds comprising fluorine and boron; wherein the catalyst is present up to 20% of the weight of the saccharide and organic polycarboxylic acid; additives, calculated on the basis of 100 parts by weight of saccharide and organic polycarboxylic acid: from 0 to 2 parts of silane, from 0 to 20 parts of oil, from 0 to 30 parts of urea and/or of glycerol, from 0 to 30 parts of an extender chosen from lignin derivatives, and animal or plant proteins; and water.

2. The composition as claimed in claim 1, wherein the saccharide is a monosaccharide, a polysaccharide or a mixture of these compounds.

3. The composition as claimed in claim 2, wherein the monosaccharide is chosen from monosaccharides including from 3 to 8 carbon atoms.

4. The composition as claimed in claim 3, wherein the monosaccharide is an aldose.

5. The composition as claimed in claim 4, wherein the aldose is a hexose.

6. The composition as claimed in claim 2, wherein the polysaccharide exhibits a weight-average molar mass of less than 1,000,000.

7. The composition as claimed in claim 6, wherein the polysaccharide is composed to more than 50% of glucose units.

8. The composition as claimed in claim 1, wherein the at least one saccharide is a mixture of monosaccharide(s) and/or of polysaccharide(s) chosen from dextrins and molasses.

9. The composition as claimed in claim 8, wherein the dextrin exhibits a dextrose equivalent of greater than or equal to 5.

10. The composition as claimed in claim 8, wherein the molasses comprises from 40 to 60% by weight of glucides.

11. The composition as claimed in claim 1, wherein the acid exhibits a molar mass of less than or equal to 750.

12. The composition as claimed in claim 1, wherein the organic polycarboxylic acid is a saturated or unsaturated and linear or branched alicyclic acid, a cyclic acid or an aromatic acid.

13. The composition as claimed in claim 1, wherein the saccharide represents from 10 to 90% of the weight of the mixture composed of the saccharide and the organic polycarboxylic acid.

14. The composition as claimed claim 1, wherein the reactive silicone has a molecular weight less than or equal to 50,000.

15. The composition as claimed claim 1, wherein the reactive silicone is constituted of a main chain composed of organosiloxane residues and optionally phenylsiloxane-residues.

16. The composition as claimed claim 1, wherein the reactive silicone bears at least one reactive hydroxyl, carboxyl or anhydride, amine, epoxy or vinyl functional group in a terminal position or on a pendent group.

17. The composition as claimed in claim 16, wherein the at least two terminal functional groups are hydroxyl functional groups.

18. The composition as claimed claim 1, wherein the proportion of reactive silicone varies from 0.1 to 5 parts by weight per 100 parts by weight of saccharide and of organic polycarboxylic acid.

19. An acoustic and/or thermal insulating product based on mineral wool sized using the sizing composition as claimed in claim 1.

20. A veil of mineral fibres sized using the sizing composition as claimed in claim 1.

21. The composition as claimed in claim 1, wherein the mineral wool is based on rock or glass.

22. The composition as claimed in claim 3, wherein the monosaccharide includes from 5 to 7 carbon atoms.

23. The composition as claimed in claim 5, wherein the hexose is glucose, mannose or galactose.

24. The composition as claimed in claim 6, wherein the polysaccharide exhibits a weight-average molar mass of less than 50 000 and greater than 180.

25. The composition as claimed in claim 9, wherein the dextrin exhibits a dextrose equivalent of greater than or equal to 10 and less than 100.

26. The composition as claimed in claim 10, wherein the molasses comprises from 45 to 50% by weight of glucides.

27. The composition as claimed in claim 1, wherein the organic polycarboxylic acid comprises at most four carboxyl functional groups.

28. The composition as claimed in claim 11, wherein the acid exhibits a molar mass of less than or equal to 500.

29. The composition as claimed in claim 13, wherein the saccharide represents from 20 to 85% of the weight of the mixture composed of the saccharide and the organic polycarboxylic acid.

30. The composition as claimed claim 14, wherein the reactive silicone has a molecular weight less than or equal to 10,000.

31. The composition as claimed claim 15, wherein the reactive silicone is constituted of a main chain composed of alkylsiloxane residues and optionally methylphenylsiloxane residues.

32. The composition as claimed claim 18, wherein the proportion of reactive silicone varies from 0.3 to 3 parts by weight per 100 parts by weight of saccharide and of organic polycarboxylic acid.

33. The composition as claimed in claim 1, wherein the catalyst represents up to 10% of the weight of the saccharide and organic polycarboxylic acid.

34. A sizing composition for insulating products based on mineral wool, the sizing composition consisting of: at least one saccharide, at least one organic polycarboxylic acid having a molar mass of less than or equal to 1000, the at least one organic polycarboxylic acid is a non-polymeric polycarboxylic acid selected from the group consisting of a dicarboxylic acid, a dicarboxylic acid precursor, a tricarboxylic acid, and a tetracarboxylic acid; at least one reactive silicone, wherein the composition is provided in a form suitable for the formation of one or more ester bonds between the at least one organic polycarboxylic acid and the saccharide; a catalyst chosen from Lewis acids and bases, phosphorus-containing compounds and compounds comprising fluorine and boron; wherein the catalyst is present up to 20% of the weight of the saccharide and organic polycarboxylic acid; additives, calculated on the basis of 100 parts by weight of saccharide and organic polycarboxylic acid: from 0 to 2 parts of silane, from 0 to 20 parts of oil, from 0 to 30 parts of urea and/or of glycerol, from 0 to 30 parts of an extender chosen from lignin derivatives, and animal or plant proteins; and water.

Description

EXAMPLES 1 TO 3

(1) Sizing compositions are prepared which comprise the constituents appearing in Table 1, the proportions being expressed as parts by weight.

(2) The sizing compositions are prepared by successively introducing, into a vessel containing water, the saccharide followed by the other constituents with vigorous stirring until the constituents have completely dissolved.

(3) A conventional sizing composition is also prepared including a phenol-formaldehyde resin and urea (Reference) in accordance with Example 2, Test 1, of WO 01/96254 A1.

(4) The sizing compositions are used to form insulation products based on glass wool.

(5) The glass wool is manufactured continuously on a 2.4 m wide production line. The glass wool is formed by the internal centrifugation technique in which the molten glass composition is converted into fibres by means of a tool, referred to as centrifuging disc, comprising a basket forming a chamber for receiving the molten composition and a peripheral band pierced by a multitude of orifices: the dish is rotated about its vertically positioned axis of symmetry, the composition is ejected through the orifices under the effect of the centrifugal force and the material escaping from the orifices is drawn into fibres with the assistance of a drawing gas stream.

(6) Conventionally, a size spraying ring is positioned beneath the fiberizing disc so as to uniformly distribute the sizing composition over the glass wool which has just been formed.

(7) The mineral wool, thus sized, is collected on a belt conveyor equipped with internal extraction boxes which hold the mineral wool in the form of a felt or web at the surface of the conveyor. The felt or the web is cut up and then placed in an oven maintained at 290 C. (260 C. for the Reference product) where the constituents of the size polymerize to form a binder.

(8) The insulating product obtained at the outlet of the oven exhibits a thickness of the order of 82 mm, a density equal to 17.5 kg/m.sup.3 and a loss on ignition equal to 5%.

(9) The properties of the insulating products are given in Table 1 below.

(10) TABLE-US-00001 TABLE 1 Example 1 2 3 Ref. Sizing composition Saccharide.sup.(1) 62.0 62.0 62.0 Citric acid 38.0 38.0 38.0 Sodium hypophosphite 5.0 5.0 5.0 -aminopropyltriethoxysilane 1.0 1.0 1.0 Mineral oil 8.0 8.0 8.0 Reactive silicone.sup.(2) 1.5 Reactive silicone.sup.(3) 1.5 2.0 Insulating product Thickness (mm) 1 hour 78.1 78.0 79.2 78.3 24 hours 76.8 77.0 77.0 74.0 30 days 72.9 n.d. n.d. 72.2 90 days 73.1 n.d. n.d. 73.8 Water absorption (kg/m.sup.2) 0.66 1.00 0.10 0.97 n.d.: not determined .sup.(1)dextrin derived from corn starch; weight-average molecular weight: 3510; dextrose equivalent DE: 30; sold under the reference Roclys C3072S by ROQUETTE FRERES. .sup.(2)polydimethylsiloxane with terminal reactive hydroxyl functional groups; sold under the reference DOW CORNING 1581 by DOW CORNING. .sup.(3)reactive polydimethylsiloxane; sold under the reference SILRES BS 10421581 by WACKER SILICONES.

(11) It is observed that the insulating products in accordance with the invention have, in particular, a low water absorption, comparable to that of the product obtained with the reference phenol-formaldehyde sizing composition for Example 2 and reduced by 32% and 90% for Examples 1 and 3, respectively.

EXAMPLES 4 TO 8

(12) Sizing compositions are prepared under the conditions of Examples 1 to 3 from constituents appearing in Table 2, in the proportions indicated, expressed as parts by weight.

(13) These compositions are used to manufacture insulating products based on mineral wool under the conditions described in Examples 1 to 3. The products obtained have a variable nominal thickness (60, 100 or 160 mm), and a density equal to 19 kg/m.sup.3.

(14) The properties of the insulating products are given in Table 2.

(15) The products according to the invention which contain a reactive silicone have a water absorption at most equal to 0.6 kg/m.sup.2.

(16) The products from Examples 4 and 5 have a lower capacity to absorb water than the products from Comparative examples 1 and 2 which contain a non-reactive silicone.

(17) TABLE-US-00002 TABLE 2 Example Comparative Comparative 4 example 1 Ref. 5 example 2 6 7 8 Sizing composition Saccharide.sup.(1) 62.0 62.0 62.0 62.0 62.0 62.0 62.0 Citric acid 38.8 38.8 38.8 38.8 38.8 38.8 38.8 Sodium hypophosphite 5.0 5.0 5.0 5.0 5.0 5.0 5.0 -aminopropyltriethoxysilane 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Mineral oil 8.0 8.0 8.0 8.0 8.0 8.0 8.0 Reactive silicone.sup.(2) 1.5 1.5 1.0 1.5 1.5 Non-reactive silicone.sup.(4) 1.0 1.0 Insulating product Thickness (mm) Nominal 60 60 60 160 160 100 100 120 Measured Initial (wound-unwound) 71.6 64.2 66.3 176.9 175.7 108.1 120.6 133.8 15 days 69.3 63.2 66.6 170.2 171.7 107.1 115.3 121.7 30 days 70.0 61.4 65.8 162.3 165.9 108.0 111.1 116.5 60 days 67.5 62.6 63.9 157.9 167.9 n.d. 112.6 116.1 Compression ratio 2.0 2.5 2.5 2.9 2.4 2.5 2.5 2.6 Tensile strength (gf/g) Before ageing 407 351 407 413 413 361 351 303 After ageing 376 302 376 384 384 306 302 253 Loss (%) 8 14 8 7 7 15 14 17 Water absorption (kg/m.sup.2) 0.28 4.30 0.10 0.30 1.20 0.60 0.28 0.16 n.d.: not determined .sup.(1)dextrin derived from corn starch; weight-average molecular weight: 3510; dextrose equivalent DE: 30; sold under the reference Roclys C3072S by ROQUETTE FRERES .sup.(2)polydimethylsiloxane with reactive hydroxyl functional groups; sold under the reference DOW CORNING 1581 by DOW CORNING. .sup.(4)polydimethylsiloxane; sold under the reference DOW CORNING 346 by DOW Corning