Sizing composition for fibers, in particular mineral fibers, based on humic and/or fulvic acid, and resulting insulating products

Abstract

A formaldehyde-free sizing composition for products based on fibers, in particular mineral fibers, such as glass or rock fibers, which includes at least one humic acid and/or one fulvic acid or a salt of these acids, at least one saccharide, and at least one inorganic acid ammonium salt.

Claims

1. A formaldehyde-free sizing composition for fibers comprising: at least one humic acid and/or one fulvic acid or a salt of these acids, at least one saccharide, and at least one inorganic acid ammonium salt.

2. The composition as claimed in claim 1, wherein the at least one humic and/or fulvic acid is in the form of a potassium, sodium or ammonium salt.

3. The composition as claimed in claim 1, wherein the at least one saccharide is a monosaccharide or an oligosaccharide including at most 50 saccharide units.

4. The composition as claimed in claim 3, wherein the at least one saccharide is chosen from a monosaccharide, a disaccharide, a trisaccharide, a tetrasaccharide, and a pentasaccharide.

5. The composition as claimed in claim 4, wherein the monosaccharide is glucose, galactose or mannose, wherein the disaccharide is fructose, lactose, maltose, isomaltose, cellobiose, trehalose, isotrehalose, sucrose or isosucrose, wherein the trisaccharide is melezitose, gentianose, raffinose, erlose or umbelliferose, wherein the tetrasaccharide is stachyose, and wherein the pentasaccharide is verbascose.

6. The composition as claimed in claim 1, wherein the at least one saccharide is present in a proportion of 10 to 95parts by weight per 100 parts by weight of the mixture of the at least one humic and/or fulvic acid or of the salts thereof.

7. The composition as claimed in claim 1, wherein the at least one inorganic acid ammonium salt is an ammonium sulfate, an ammonium phosphate, an ammonium nitrate or an ammonium carbonate.

8. The composition as claimed in claim 7, wherein the at least one inorganic acid ammonium salt is an ammonium sulfate.

9. The composition as claimed in claim 1, wherein the at least one inorganic acid ammonium salt represents from 1to 30% by weight of the total weight of the mixture consisting of the at least one humic and/or fulvic acid or the salt thereof and the at least one saccharide.

10. The composition as claimed in claim 9, wherein the at least one inorganic acid ammonium salt represents from 3 to 20% by weight of the total weight of the mixture consisting of the at least one humic and/or fulvic acid or the salt thereof and the at least one saccharide.

11. The composition as claimed in claim 10, wherein the at least one inorganic acid ammonium salt represents from 3 to 16% by weight of the total weight of the mixture consisting of the at least one humic and/or fulvic acid or the salt thereof and the at least one saccharide.

12. The composition as claimed in claim 11, wherein the at least one inorganic acid ammonium salt represents from 5 to 15% by weight of the total weight of the mixture consisting of the at least one humic and/or fulvic acid or the salt thereof and the at least one saccharide.

13. The composition as claimed in claim 1, additionally comprising the additives below in the following proportions, calculated on the basis of 100 parts by weight of a mixture consisting of the at least one humic and/or fulvic acid or the salt thereof and the at least one saccharide: from 0 to 2 parts of silane, from 0 to 20 parts of oil, from 0 to 20 parts of urea, from 0 to 5 parts of a silicone, from 0 to 30 parts of an extender.

14. The composition as claimed in claim 1, wherein the composition exhibits a pH which varies from 7 to 9.

15. A product based on fibers sized using the sizing composition as claimed in claim 1.

16. The product as claimed in claim 15, wherein the product is a thermal and/or acoustic insulating product, the fibers of which are in the form of mineral wool.

17. The product as claimed in claim 16, wherein the fibers are composed of a glass which comprises the constituents below in the following proportions, expressed as percentages by weight: TABLE-US-00010 SiO.sub.2 39-55% Al.sub.2O.sub.3 16-27% CaO 3-35% MgO 0-15% Na.sub.2O 0-15% K.sub.2O 0-15% R.sub.2O (Na.sub.2O + K.sub.2O) 10-17% P.sub.2O.sub.5 0-3% Fe.sub.2O.sub.3 0-15% B.sub.2O.sub.3 0-8% TiO.sub.2 .sup.0-3%, the MgO content being between 0 and 5% when the R.sub.2O content is less than or equal to 13.0%.

18. The product as claimed in claim 17, wherein the glass comprises the constituents below in the following proportions (as % by weight): TABLE-US-00011 SiO.sub.2 39-44% Al.sub.2O.sub.3 16-27% CaO 6-20% MgO 1-5% Na.sub.2O 0-15% K.sub.2O 0-15% R.sub.2O (Na.sub.2O + K.sub.2O) 10-14.7% P.sub.2O.sub.5 0-3% Fe.sub.2O.sub.3 1.5-15% B.sub.2O.sub.3 0-2% TiO.sub.2 0-2%.

19. A process for the manufacture of an acoustic and/or a thermal insulating product as claimed in claim 16, according to which the mineral wool is manufactured, the process comprising applying a sizing composition to said wool and treating said wool at a temperature which makes possible the crosslinking of the size and the formation of an infusible binder, wherein the sizing composition comprises at least one humic acid and/or one fulvic acid or a salt of these acids, at least one saccharide, and at least one inorganic acid ammonium salt.

20. The composition as claimed in claim 1, wherein the fibers are in the form of mineral wool.

21. The composition as claimed in claim 20, wherein the mineral wool is made from glass or rock.

Description

EXAMPLES 1 TO 17

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

(2) These compositions are prepared by introducing the constituents into a vessel containing water with stirring until the constituents have completely dissolved.

(3) The sizing compositions exhibit a solids content (dry extract) equal to 30%.

(4) The crosslinking start temperature (T.sub.c) of examples 1 to 17 is at most equal to 167 C., a temperature which remains compatible with the conditions for the manufacture of thermal and/or acoustic insulating products based on mineral wool.

(5) The crosslinking start temperature is virtually identical, whatever the nature of the humic acid salt (K or Na) used (examples 2, 3, 5, 6 and 8 compared with examples 9, 10, 12, 13 and 15, respectively). Examples 16 and 17, comprising a humic acid and fulvic acid mixture, exhibit a crosslinking start temperature also comparable to the abovementioned examples.

(6) Examples 2 and 9, which include ammonium sulfate, are preferred as they exhibit a lower crosslinking start temperature than that of examples 3 and 10, comprising diammonium phosphate.

EXAMPLES 18 TO 20

(7) These examples illustrate the manufacture of insulating products on an industrial-scale line.

(8) Use is made of the sizing compositions comprising the constituents appearing in table 2, in amounts expressed as parts by weight, to form products based on mineral wool exhibiting a nominal density equal to 10.6 kg/m.sup.3 and a nominal thickness equal to 144 mm. By way of comparison, use is also made of a sizing composition comprising a premix containing 80 parts by weight of a phenol-formaldehyde-monoethanolamine resin (example 1 of WO 2008/043960) and 20 parts by weight of urea, and the additives mentioned in table 2 (Reference 1).

(9) Glass wool is manufactured on a pilot line by the internal centrifugation technique in which the molten glass composition is converted into fibers by means of a tool, referred to as centrifuging disk, comprising a basket forming a chamber for receiving the molten composition and a peripheral band pierced by a multitude of orifices: the disk 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 fibers with the assistance of a drawing gas stream.

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

(11) 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 web at the surface of the conveyor. The web is placed in an oven at 230 C. for 10 minutes.

(12) The glass comprises the constituents below in the following proportions, expressed as % by weight:

(13) TABLE-US-00004 SiO.sub.2 65.40 Al.sub.2O.sub.3 2.05 CaO 8.05 MgO 2.55 Na.sub.2O 16.80 K.sub.2O 0.23 B.sub.2O.sub.3 4.65 Others (Fe.sub.2O.sub.3, ZrO.sub.2, Cr.sub.2O.sub.3, TiO.sub.2, MnO) 0.27

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

EXAMPLES 21 TO 23

(15) The procedure is carried out under the conditions of examples 18 to 20, modified in that use is made of the sizing compositions as defined in table 3 and of a glass having a high alumina content.

(16) The sizing composition used by way of comparison (Reference 2) comprises a premix including 60 parts by weight of a phenol-formaldehyde resin (example 2 of WO 01/96254) and 40 parts by weight of urea, and the additives mentioned in table 3.

(17) The glass comprises the constituents below in the following proportions, expressed as % by weight:

(18) TABLE-US-00005 SiO.sub.2 41.50 Al.sub.2O.sub.3 23.30 CaO 14.10 MgO 2.00 BaO 0.30 SrO 0.38 Na.sub.2O 5.50 K.sub.2O 5.40 MnO 0.20 Fe.sub.2O.sub.3 5.35 TiO.sub.2 0.70 P.sub.2O.sub.5 0.80

(19) The properties of the insulating products obtained are given in table 3.

EXAMPLES 24 AND 25

(20) These examples illustrate the manufacture of insulating products on an industrial line.

(21) Use is made of the sizing compositions comprising the constituents appearing in table 4, in amounts expressed as parts by weight, in order to form products based on mineral wool. By way of comparison, use is also made of a sizing composition comprising a premix including 80 parts by weight of a phenol-formaldehyde-monoethanolamine resin (example 1 of WO 2008/043960) and 20 parts by weight of urea, and the additives mentioned in table 4 (Reference 1).

(22) Glass wool is manufactured on an industrial line with a width of 2.4 m by the internal centrifugation technique using a glass having the composition given in examples 18 to 20.

(23) Conventionally, the molten glass composition is converted into fibers by means of a tool, referred to as centrifuging disk, comprising a basket forming a chamber for receiving the molten composition and a peripheral band pierced by a multitude of orifices: the disk 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 fibers with the assistance of a drawing gas stream.

(24) A size spraying ring is positioned beneath the fiberizing disk so as to uniformly distribute the sizing composition over the glass wool which has just been formed.

(25) 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 of a web at the surface of the conveyor. The conveyor subsequently moves through an oven maintained at 250 C., where the constituents of the size polymerize to form a binder. The product obtained has a nominal density equal to 17.5 kg/m.sup.3 and a nominal thickness equal to 75 mm.

(26) The properties of the insulating products obtained are given in table 4.

(27) TABLE-US-00006 TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Sizing composition Humin-P 775.sup.(1) 40 40 40 50 40 20 80 20 Humin-S 775 .sup.(2) 40 40 50 40 20 40 20 SHB Hydro Nectar.sup.(3) 40 20 Glucose 60 60 60 60 60 Sucrose 50 60 80 50 60 80 60 80 Fructose 20 80 60 80 Ammonium sulfate 10 10 7.5 10 10 15 10 10 10 10 15 10 15 Diammonium phosphate 10 15 10 15 Urea 10 10 8 5 20 10 10 10 10 8 5 10 10 10 5 Properties Crosslinking start temp. 130 132 144 150 160 156 156 131 126 145 162 167 163 144 135 153 146 T.sub.C ( C.) pH.sup.(4) 8.2 8.2 8.4 8.4 8.6 8.3 8.4 7.3 8.7 8.7 9.0 8.6 8.6 8.0 7.6 8.5 8.3 .sup.(1)Sold by Humintech; Potassium humate; 100% water-soluble powder .sup.(2) Sold by Humintech; Sodium humate; 100% water-soluble granules .sup.(3)Sold by Boisvalor; mixture of humic acid (55% by weight) and fulvic acid (45% by weight); liquid .sup.(4)solids content: 30%

(28) TABLE-US-00007 TABLE 2 Example 18 19 20 Ref. 1 Sizing composition Humin-P 775.sup.(1) 40 Humin-S 775 .sup.(2) 40 20 Sucrose 60 60 80 Ammonium sulfate 10 10 15 Urea 10 5 -Aminopropyltriethoxysilane 1 1 1 0.5 Mineral oil 9 9 9 9 Properties of the product Tensile strength (N/g) Initial 1.2 1.1 1.3 3.1 After aging (TS15) 1.3 1.2 1.5 2.9 Loss on ignition (%) 3.2 4.0 3.8 5.1 .sup.(1)Sold by Humintech; Potassium humate; 100% water-soluble powder .sup.(2) Sold by Humintech; Sodium humate; 100% water-soluble granules

(29) TABLE-US-00008 TABLE 3 Example 21 22 23 Ref. 2 Sizing composition Humin-S 775 .sup.(2) 10 10 10 Sucrose 90 Glucose 90 Roclys C 3072 S.sup.(5) 90 Ammonium sulfate 14 14 14 Urea 2 2 2 -Aminopropyltriethoxysilane 0.5 0.5 0.5 0.5 Mineral oil 9 9 9 9 Properties of the product Tensile strength (N/g) Initial 1.6 2.1 1.1 3.3 After aging (TS15) 1.1 1.4 1.1 2.7 Loss on ignition (%) 4.5 3.7 5.0 4.5 .sup.(1) Sold by Humintech; Potassium humate; 100% water-soluble powder .sup.(2) Sold by Humintech; Sodium humate; 100% water-soluble granules .sup.(5)Sold by Roquette; corn starch dextrins; Dextrose equivalent (DE):

(30) TABLE-US-00009 TABLE 4 Example 24 25 Ref. 1 Sizing composition SHB 105.sup.(6) 22.7 11.6 Sucrose 77.3 88.4 Ammonium sulfate 13.6 15.6 -Aminopropyltriethoxysilane 0.5 0.5 0.5 Mineral oil 9.5 9.5 9.5 Properties of the product Tensile strength (N/g) Initial 2.8 3.5 4.5 After aging (TS15) 2.7 3.4 4.4 Loss on ignition (%) 4.4 5.0 4.4 .sup.(6)Sold by Boisvaloir; mixture of humic acid (55% by weight) and fulvic acid (45% by weight); liquid