DK2488596T3 - Limningssammensætning til mineraluld, der omfatter en reducerende sukkerart og et metalsalt af en uorganisk syre, og opnåede isoleringsprodukter - Google Patents
Limningssammensætning til mineraluld, der omfatter en reducerende sukkerart og et metalsalt af en uorganisk syre, og opnåede isoleringsprodukter Download PDFInfo
- Publication number
- DK2488596T3 DK2488596T3 DK10785105.7T DK10785105T DK2488596T3 DK 2488596 T3 DK2488596 T3 DK 2488596T3 DK 10785105 T DK10785105 T DK 10785105T DK 2488596 T3 DK2488596 T3 DK 2488596T3
- Authority
- DK
- Denmark
- Prior art keywords
- inorganic acid
- metal salt
- composition
- mineral
- reducing sugar
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 70
- 150000003839 salts Chemical class 0.000 title claims description 30
- 150000007522 mineralic acids Chemical class 0.000 title claims description 29
- 235000000346 sugar Nutrition 0.000 title claims description 23
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims description 3
- 239000011707 mineral Substances 0.000 title claims description 3
- 238000003466 welding Methods 0.000 title claims 2
- 238000004513 sizing Methods 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 16
- 239000011490 mineral wool Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- 229920001353 Dextrin Polymers 0.000 claims description 11
- 239000004375 Dextrin Substances 0.000 claims description 11
- 235000019425 dextrin Nutrition 0.000 claims description 11
- 150000004676 glycans Chemical class 0.000 claims description 10
- 229920001282 polysaccharide Polymers 0.000 claims description 10
- 239000005017 polysaccharide Substances 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002557 mineral fiber Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 239000004606 Fillers/Extenders Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 150000002772 monosaccharides Chemical group 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229920001542 oligosaccharide Polymers 0.000 claims description 4
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- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 150000008163 sugars Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
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- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 3
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- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
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- 210000002268 wool Anatomy 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011126 aluminium potassium sulphate Nutrition 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- DLRVVLDZNNYCBX-RTPHMHGBSA-N isomaltose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)C(O)O1 DLRVVLDZNNYCBX-RTPHMHGBSA-N 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229940050271 potassium alum Drugs 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 239000005569 Iron sulphate Substances 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- ZXRRHFSTAFVGOC-UHFFFAOYSA-N [AlH3].[K] Chemical compound [AlH3].[K] ZXRRHFSTAFVGOC-UHFFFAOYSA-N 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 claims 1
- 229910001848 post-transition metal Inorganic materials 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
- D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B1/7654—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only comprising an insulating layer, disposed between two longitudinal supporting elements, e.g. to insulate ceilings
- E04B1/7658—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only comprising an insulating layer, disposed between two longitudinal supporting elements, e.g. to insulate ceilings comprising fiber insulation, e.g. as panels or loose filled fibres
- E04B1/7662—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only comprising an insulating layer, disposed between two longitudinal supporting elements, e.g. to insulate ceilings comprising fiber insulation, e.g. as panels or loose filled fibres comprising fiber blankets or batts
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Architecture (AREA)
- Electromagnetism (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Acoustics & Sound (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Description
ADHESIVE COMPOSITION FOR MINERAL WOOL INCLUDING A REDUCING SUGAR AND A METAL SALT OF AN INORGANIC ACID, AND INSULATING PRODUCTS THUS OBTAINED
The present invention relates to the field of thermal and/or acoustic insulating products based on mineral wool, in particular of glass or of rock, and on a formaldehyde-free binder.
The invention more particularly relates to a sizing composition capable of crosslinking to form said binder, which includes at least one reducing sugar and at least one inorganic acid metal salt, to the process for the manufacture of thermal and/or acoustic insulating products and to the insulating products which result therefrom.
The manufacture of insulating products based on mineral wool generally comprises a stage of manufacture of the wool itself, which can be carried out by various processes, for example according to the known technique of fiberizing by internal or external centrifugation.
Internal centrifugation consists in introducing the molten material (generally glass or a rock) into a centrifugal device comprising a multitude of small orifices, the material being projected toward the peripheral wall of the device under the action of the centrifugal force and escaping therefrom in the form of filaments. On leaving the centrifugal device, the filaments are drawn and carried toward a receiving member by a gas stream having a high temperature and a high speed, in order to form a web of fibers (or mineral wool).
External centrifugation consists, for its part, in pouring out the molten material at the external peripheral surface of rotating members, known as rotors, from where the melt is ejected under the action of the centrifugal force. Means for drawing by gas stream and for collecting on a receiving member are also provided.
In order to provide for the assembly of the fibers together and to make it possible for the web to have cohesion, a sizing composition comprising a thermosetting resin is projected onto the fibers, on the route between the outlet of the centrifugal device and the receiving member. The web of fibers coated with the size is subjected to a heat treatment, at a temperature generally of greater than 100°C, in order to bring about the polycondensation of the resin and to thus obtain a thermal and/or acoustic insulating product having specific properties, in particular dimensional stability, tensile strength, thickness recovery after compression and homogeneous color.
The sizing composition to be projected onto the mineral wool is generally provided in the form of an aqueous solution including the thermosetting resin and additives, such as a catalyst for the crosslinking of the resin, an adhesion-promoting silane, a dust-preventing mineral oil, and the like. The sizing composition is generally applied to the fibers by spraying.
The properties of the sizing composition depend largely on the characteristics of the resin. From the viewpoint of the application, it is necessary for the sizing composition to exhibit good sprayability and to be able to be deposited at the surface of the fibers in order to efficiently bind them.
The resin has to be stable for a given period of time before being used to form the sizing composition, which composition is generally prepared at the time of use by mixing the resin and the additives mentioned above.
At the regulatory level, it is necessary for the resin to be regarded as non-polluting, that is to say for it to comprise - and for it to generate during the sizing stage or subsequently - as little as possible in the way of compounds which may be harmful to human health or to the environment.
The thermosetting resins most commonly used are phenolic resins belonging to the family of the resols. In addition to their good crosslinkability under the abovementioned thermal conditions, these resins are soluble in water, have a good affinity for mineral fibers, in particular glass fibers, and are relatively inexpensive.
These resols are obtained by condensation of phenol and formaldehyde, in the presence of a basic catalyst, in a formaldehyde/phenol molar ratio of greater than 1, so as to promote the reaction between the phenol and the formaldehyde and to reduce the level of residual phenol in the resin. The condensation reaction between the phenol and the formaldehyde is carried out while limiting the degree of condensation of the monomers, in order to avoid the formation of long, relatively water-insoluble, chains which reduce the dilutability. Consequently, the resin comprises a certain proportion of unreacted monomer, in particular formaldehyde, the presence of which is undesirable because of its known harmful effects.
For this reason, resol-based resins are generally treated with urea, which reacts with the free formaldehyde by trapping it in the form of nonvolatile ureaformaldehyde condensates. The presence of urea in the resin in addition brings a certain economic advantage as a result of its low cost because it is possible to introduce it in a relatively large amount without affecting the operating qualities of the resin, in particular without harming the mechanical properties of the final product, which significantly lowers the total cost of the resin.
Nevertheless, it has been observed that, under the temperature conditions to which the web is subjected in order to obtain crosslinking of the resin, the ureaformaldehyde condensates are not stable; they decompose with restoration of the formaldehyde and urea, in its turn at least partially decomposed to give ammonia, which are released into the atmosphere of the factory.
Regulations with regard to environmental protection, which are becoming more restrictive, are forcing manufacturers of insulating products to look for solutions which make it possible to further lower the levels of undesirable emissions, in particular of formaldehyde.
Solutions in which resols are replaced in sizing compositions are known. A first solution is based on the use of a carboxylic acid polymer, in particular an acrylic acid polymer.
In US 5 340 868, the size comprises a polycarboxylic polymer, a β-hydroxy-amide and an at least trifunctional monomeric carboxylic acid.
Other sizing compositions have been provided which comprise a polycarboxylic polymer, a polyol and a catalyst, this catalyst being able to be a phosphorus-comprising compound (US 5 318 990, US 5 661 213, US 6 331 350, US 2003/0008978), a fluoroborate (US 5 977 232) or else a cyanamide, a dicyanamide or a cyanoguanidine (US 5 932 689).
The sizing compositions based on a polycarboxylic polymer and on a polyol can additionally comprise a cationic, amphoteric or nonionic surfactant (US 2002/0188055), a coupling agent of silane type (US 2004/0002567) or a dextrin as cobinder (US 2005/0215153). A description has also been given of sizing compositions comprising an alkanolamine including at least two hydroxyl groups and a polycarboxylic polymer (US 6 071 994, US 6 099 773, US 6 146 746) in combination with a copolymer (US 6 299 936). A second solution in which resols are replaced is based on the combination of a saccharide and a polycarboxylic acid.
In US 5 895 804, a description is given of an adhesive composition based on heat-crosslinkable polysaccharides which can be used as size for mineral wool. The combination includes a polycarboxylic polymer having at least two carboxylic acid functional groups and a molecular weight at least equal to 1000, and a polysaccharide having a molecular weight at least equal to 10 000.
In WO 2009/080938, the sizing composition comprises a monosaccharide and/or a polysaccharide and an organic polycarboxylic acid with a molar mass of less than 1000. A formaldehyde-free aqueous sizing composition which comprises a Maillard reaction product, in particular combining a reducing sugar, a carboxylic acid and aqueous ammonia (WO 2007/014236), is also known. In WO 2009/019232 and WO 2009/019235, the proposal is made to substitute, for the carboxylic acid, an acid precursor derived from an inorganic salt, in particular an ammonium salt, which exhibits the additional advantage of being able to replace all or part of the aqueous ammonia.
The latter sizing compositions nevertheless comprise nitrogen-including compounds which are capable of decomposing, in particular to give ammonia, during the heat treatment employed in order for the mineral fibers to be able to be bonded to one another and to form the final insulating product.
An aim of the present invention is to provide a sizing composition for insulating products based on mineral wool, in particular of glass or of rock, which is devoid of formaldehyde and other nitrogenous compounds.
In order to achieve this aim, the present invention provides a sizing composition consisting of: at least reducing sugar, and at least one inorganic acid metal salt chosen from inorganic acid alkali metal, alkaline earth metal, transition metal or poor metal salts, said inorganic acid metal salt representing from 1 to 30% by weight of the total weight of the mixture of the reducing sugar and the inorganic acid metal salt, and - the additives below in the following proportions, calculated on the basis of 100 parts by weight of reducing sugar and of inorganic acid metal salt: from 0 to 2 parts of silane, from 0 to 20 parts of oil, from 0 to 20 parts of glycerol, from 0 to 5 parts of a silicone, from 0 to 30 parts of an “extender” selected from organic or mineral fillers soluble or dispersible in the aqueous sizing composition.
The reducing sugar in accordance with the present invention is a monosaccharide, an oligosaccharide, a polysaccharide or a mixture of these compounds.
Mention may be made, as example of monosaccharide, of glucose, galactose, mannose and fructose.
The term “oligosaccharide” is understood to mean a saccharide including from 2 to 10 saccharide units, preferably at most 5.
Mention may be made, as example of oligosaccharide, of lactose, maltose, isomaltose and cellobiose.
The polysaccharides in accordance with the invention are chosen from the polysaccharides having a number-average molar mass of less 100 000, preferably of less than 50 000 and advantageously of less than 10 000.
Mention may be made, as example of preferred polysaccharide, of dextrins. Dextrins are compounds corresponding to the general formula (C6HioOs)n obtained by partial hydrolysis of starch. The processes for the preparation of dextrins are known. For example, dextrins can be prepared by heating or by drying to dryness a starch, generally in the presence of an acid catalyst, which results in the constituent amylose and amylopectin molecules of said starch being ruptured to give products of lower molar mass. Dextrins can also be obtained by treating the starch enzymatically with one or more amylases, in particular microbial amylases, capable of hydrolyzing the bonds of the starch. The nature of the treatment (chemical or enzymatic) and the hydrolysis conditions have a direct effect on the average molar mass and the distribution of the molar masses of the dextrin.
The dextrins according to the present invention exhibit a dextrose equivalent (DE) of greater than or equal to 5, preferably of greater than or equal to 15.
Conventionally, the dextrose equivalent DE is defined by the following relationship:
The dextrins in accordance with the invention can be obtained from starch or starch derivatives of varied plant origin, for example resulting from tubers, such as potato, cassava, maranta and sweet potato, resulting from seeds, such as wheat, corn, rye, rice, barley, millet, oats and sorghum, resulting from fruit, such as horse chestnut, sweet chestnut and hazelnut, or resulting from leguminous plants, such as peas and
beans.
Preferably, the reducing sugar is chosen from glucose, polysaccharides composed predominantly (to more than 50% by weight) of glucose units and mixtures of these compounds.
The inorganic acid metal salt acts as inorganic acid precursor, which acid reacts with the reducing sugar under the effect of the heat to form a polymeric network constituting the final binder. The polymeric network thus formed makes it possible to establish bonds at the junction points of the fibers in the mineral wool.
As already indicated, the inorganic acid metal salt is chosen from inorganic acid alkali metal, alkaline earth metal, transition metal or poor metal salts. Preferably, it is a sodium, magnesium, iron, cobalt, nickel, copper, zinc or aluminum salt, advantageously an aluminum or copper salt.
The inorganic acid metal salt is advantageously chosen from sulfates, chlorides, nitrates, phosphates and carbonates and better still from sulfates and chlorides.
Preference is given to aluminum sulfate, copper sulfate, potassium aluminum sulfate (or potassium alum), iron sulfate, zinc sulfate and aluminum chloride, in particular to aluminum sulfate and copper sulfate.
In the sizing composition, the inorganic acid metal salt represents from 1 to 30% by weight of the total weight of the mixture composed of the reducing sugar and the inorganic acid metal salt, preferably from 3 to 20% and advantageously from 5 to 15%.
The sizing composition in accordance with the invention comprises the conventional additives below in the following proportions, calculated on the basis of 100 parts by weight of reducing sugar and of inorganic acid metal salt: from 0 to 2 parts of silane, in particular an aminosilane, from 0 to 20 parts of oil, preferably from 4 to 15 parts, from 0 to 20 parts of glycerol, preferably from 0 to 10 parts, from 0 to 5 parts of a silicone, from 0 to 30 parts of said “extender”.
The role of the additives is known and is briefly restated: the silane is an agent for coupling between the fibers and the binder, and also acts as antiaging agent; the oils are dust-preventing and hydrophobic agents; the glycerol acts as plasticizer and makes it possible to prevent pregelling of the sizing composition; the silicone is a hydrophobic agent having the role of reducing the absorption of water by the insulating product; the “extender” is an organic or inorganic filler, soluble or dispersible in the aqueous sizing composition, which makes it possible in particular to reduce the cost of the sizing composition.
The sizing composition exhibits a pH which varies to a large extent according to the nature of the inorganic acid metal salt used, generally from 2 to 10, advantageously acidic, in particular of less than or equal to 5.
The sizing composition is intended to be applied to mineral fibers, in particular glass or rock fibers.
Conventionally, the sizing composition is projected onto the mineral fibers at the outlet of the centrifugal device and before they are collected on the receiving member in the form of a web of fibers which is subsequently treated at a temperature which makes possible the crosslinking of the size and the formation of an infusible binder. The crosslinking of the size according to the invention takes place at a temperature of the order of from 100 to 200°C, generally at a temperature comparable to that of a conventional formaldehyde-phenol resin, in particular of greater than or equal to 110°C, preferably of less than or equal to 170°C.
The acoustic and/or thermal insulating products obtained from these sized fibers also constitute a subject matter of the present invention.
These products are generally provided in the form of a mat or felt of mineral wool, of glass or of rock, or of a veil of mineral fibers, also of glass or of rock, intended in particular to form a surface coating on said mat or said felt.
The following examples make it possible to illustrate the invention without, however, limiting it.
In these examples, the following are measured: - the crosslinking start temperature (Tc) and the crosslinking rate (R) by the Dynamic Mechanical Analysis (DMA) method, which makes it possible to characterize the viscoelastic behavior of a polymeric material. The procedure is as follows: a sample of Whatman paper is impregnated with the sizing composition (content of organic solids of the order of 40%) and is then fixed horizontally between two jaws. An oscillating component equipped with a device for measuring the stress as a function of the strain applied is positioned on the upper face of the sample. The device makes it possible to calculate the modulus of elasticity E’. The sample is heated to a temperature varying from 20 to 250°C at the rate of 4°C/min. The curve of variation in the modulus of elasticity E’ (in MPa) as a function of the temperature (in °C) is plotted from the measurements, the general appearance of the curve being given in figure 1. The values corresponding to the crosslinking start temperature (Tc), in °C, and the slope corresponding to the crosslinking rate (R), in MPa/°C, are determined on the curve.
Figure 1 - the viscosity, expressed in mPa.s, using a rheometer of plate/plate rotational type with shearing of 100 s'1 at 25°C. The sample has a solids content of 30% by weight. - the contact angle of the sizing composition on a glass substrate. - the tensile strength according to the standard ASTM C 686-71T on a sample cut out by stamping from the insulating product. The sample has the shape of a torus with a length of 122 mm, a width of 46 mm, a radius of curvature of the cut-out of the outer edge equal to 38 mm and a radius of curvature of the cut-out of the inner edge equal to 12.5 mm.
The sample is positioned between two cylindrical mandrels of a test machine, one of which is movable and is moved at a constant rate. The breaking force F (in gramforce) of the sample is measured and the tensile strength TS, defined by the ratio of the breaking force F to the weight of the sample, is calculated.
The tensile strength is measured after manufacture (initial tensile strength) and after accelerated aging in an autoclave at a temperature of 105°C under 100% relative humidity for 15 minutes (TS 15). - the initial thickness of the insulating product and the thickness after compressing for 1 hour, 24 hours and 30 days with a degree of compression (defined as being the ratio of the nominal thickness to the thickness under compression) equal to 4.8/1. The thickness measurements make it possible to evaluate the good dimensional
behavior of the product. - the thermal conductivity coefficient λ according to the standard EN 13162, expressed in W/(m x °K). EXAMPLES 1 TO 8
Sizing compositions are prepared which comprise the constituents appearing in Table 1, expressed as parts by weight.
The sizing compositions are prepared by successively introducing, into a vessel containing water, the reducing sugar and the inorganic acid metal salt with vigorous stirring until the constituents have completely dissolved.
The following dextrins are used as reducing sugar: - glucose syrup 74/968®, which has a glucose content by weight of greater than 95% and exhibits a dextrose equivalent DE equal to 99 (sold by Roquette Fréres; solids content: 75%); - Flolys® B6080S, which has a weight-average molar mass of 1520 and a dextrose equivalent DE of 62 (sold under the reference by Roquette Fréres; solids content: 81%).
The properties of the sizing compositions which appear in table 1 are evaluated in comparison with a conventional sizing composition including a formaldehyde-phenol resin and urea (Reference) prepared in accordance with example 2, test 1, of WO 01/96254 A1 and with a composition comprising only the reducing sugar (C1).
The sizing compositions of examples 1 to 8 exhibit a crosslinking start temperature (Tc) which is lower than that of the Reference. These compositions also exhibit a crosslinking rate (R) close to that of the Reference, and even significantly higher (examples 2 and 3).
The sizing compositions of examples 1 to 8 additionally have a low viscosity, lower than that of the Reference at an identical solids content, which allows good application to the mineral fibers, in particular by spraying.
The sizing compositions according to the invention also exhibit a low contact angle on a glass substrate, which denotes a good ability to wet the fibers. EXAMPLE 9
This example illustrates the manufacture of insulating products on an industrial line. A sizing composition is prepared which comprises the following constituents (as parts by weight): glucose syrup 74/968®92.5 aluminum sulfate7.5 γ-aminopropyltriethoxysilane1.0 mineral oil8.0 silicone1.5
Glass wool is manufactured 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.
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.
The mineral wool, thus sized, is collected on a belt conveyor with a width of 2.4 m equipped with internal extraction boxes which hold the mineral wool in the form of a web at the surface of the conveyor. The web passes continuously through an oven maintained at 270°C, where the constituents of the size polymerize to form a binder. The final insulating product has a density of 17.5 kg/m3.
During the manufacture of the insulating product, the nitrogen emissions in the chimney remained at a minimal level.
The insulating product exhibits the following properties:
Tensile strength (gf/g) before aging206 after aging150 loss (%)27
Thickness (mm) after 1 hour83.5 after 24 hours81.6 after 30 days79.5
Loss on ignition (%)6.0 λ (W/(m x °K))0.035
The insulating product is stable in thickness and retains mechanical cohesion after aging. This product can be used in particular in applications where the mechanical stress is relatively unimportant, for example for the insulation of unoccupied attics. EXAMPLES 10 TO 14
These examples illustrate the manufacture of insulating products in an industrial plant employing different inorganic acid metal salts.
The procedure is carried out under the conditions of example 9, modified in that, in the sizing compositions, the glucose syrup 74/968® and the inorganic acid metal salts are present in the proportions shown in table 2 (as parts by weight).
The properties of the insulating products obtained are collated in table 2.
Table 1
(1) solution with a solids content of 30% (2) solution with a solids content of 40%
Table 2
Claims (12)
1. Limningssammensætning til isoleringsprodukter på basis af mineraluld, kendetegnet ved, at den består af følgende bestanddele: - vand - mindst en reducerende sukkerart og - mindst et metalsalt af en uorganisk syre valgt blandt alkalimetal-, jordalkalimetal-, overgangsmetal- eller post-overgangsmetalsalte afen uorganisk syre, hvilket metalsalt af en uorganisk syre repræsenterer 1 til 30 vægt-% af den samlede vægt af blandingen bestående af den reducerende sukkerart og metalsaltet af en uorganisk syre, og - nedenstående additiver i følgende forhold beregnet på basis af 100 vægtdele af reducerende sukkerart og metalsalt af en uorganisk syre: - 0 til 2 dele silan, - 0 til 20 dele olie, - 0 til 20 dele glycerol, - 0 til 5 dele silicone, - 0 til 30 dele af et "udstrækningsmiddel" valgt blandt de organiske eller uorganiske fyldstoffer, der er opløselige eller dispergerbare i limningssammensætningen.
2. Sammensætning ifølge krav 1, kendetegnet ved, at den reducerende sukkerart er et monosaccharid, et oligosaccharid, et polysaccharid eller en blanding af disse forbindelser.
3. Sammensætning ifølge krav 2, kendetegnet ved, at den reducerende sukkerart er glucose, galactose, mannose, fructose, lactose, maltose, isomaltose, cellobiose eller et dextrin.
4. Sammensætning ifølge et af kravene 1 til 3, kendetegnet ved, at den reducerende sukkerart er valgt blandt glucose, polysaccharider, der indeholder over 50 vægt-% glucosegentagelsesgrupper, og blandinger af disse forbindelser.
5. Sammensætning ifølge et af kravene 1 til 4, kendetegnet ved, at metalsaltet af en uorganisk syre er et natrium-, magnesium-, jern-, cobalt-, nikkel-, kobber-, zink- eller aluminiumsalt.
6. Sammensætning ifølge krav 5, kendetegnet ved, at metalsaltet afen uorganisk syre er valgt blandt sulfater, chlorider, nitrater, phosphater og carbonater.
7. Sammensætning ifølge krav 5 eller 6, kendetegnet ved, at metalsaltet af en uorganisk syre er aluminiumsulfat, kobbersulfat, kaliumaluminiumdobbeltsulfat (eller kalialun), jernsulfat, zinksulfat og aluminiumchlorid.
8. Sammensætning ifølge et af kravene 1 til 7, kendetegnet ved, at metalsaltet af en uorganisk syre repræsenterer 3 til 20 vægt-% af den samlede vægt af blandingen bestående af den reducerende sukkerart og metalsaltet af en uorganisk syre.
9. Sammensætning ifølge et af kravene 1 til 8, kendetegnet ved, at silanen er en aminosilan.
10. Akustisk og/eller termisk isoleringsprodukt på basis af mineraluld, der er limet ved hjælp af limningssammensætningen ifølge et af kravene 1 til 9.
11. Mineralfiberslør, der er limet ved hjælp af limningssammensætningen ifølge et af kravene 1 til 9.
12. Fremgangsmåde til fremstilling af et akustisk og/eller termisk isoleringsprodukt på basis af mineraluld ifølge krav 10 elleret mineralfiberslør ifølge krav 11, hvor mineralulden eller mineralfibrene fremstilles, en limningssammensætning sprøjtes på ulden eller fibrene, og ulden eller fibrene behandles ved en temperatur, der muliggør tværbinding af limningen og dannelse af et usmelteligt bindemiddel, kendetegnet ved, at limningssammensætningen har en sammensætning, der er som defineret i et hvilket som helst af kravene 1 til 9.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0957144A FR2951189B1 (fr) | 2009-10-13 | 2009-10-13 | Composition d'encollage pour laine minerale comprenant un sucre reducteur et un sel metallique d'acide inorganique, et produits isolants obtenus |
PCT/FR2010/052164 WO2011045531A1 (fr) | 2009-10-13 | 2010-10-13 | Composition d'encollage pour laine minerale comprenant un sucre reducteur et un sel metallique d'acide inorganique, et produits isolants obtenus |
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DK2488596T3 true DK2488596T3 (da) | 2018-10-29 |
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Application Number | Title | Priority Date | Filing Date |
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DK10785105.7T DK2488596T3 (da) | 2009-10-13 | 2010-10-13 | Limningssammensætning til mineraluld, der omfatter en reducerende sukkerart og et metalsalt af en uorganisk syre, og opnåede isoleringsprodukter |
Country Status (10)
Country | Link |
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US (1) | US8597532B2 (da) |
EP (1) | EP2488596B1 (da) |
DK (1) | DK2488596T3 (da) |
ES (1) | ES2690763T3 (da) |
FR (1) | FR2951189B1 (da) |
HR (1) | HRP20181634T1 (da) |
PL (1) | PL2488596T3 (da) |
PT (1) | PT2488596T (da) |
SI (1) | SI2488596T1 (da) |
WO (1) | WO2011045531A1 (da) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2974104B1 (fr) | 2011-04-15 | 2014-08-15 | Saint Gobain Isover | Composition d'encollage pour laine minerale resistant au feu et produit isolant obtenu |
FR2975689B1 (fr) * | 2011-05-25 | 2014-02-28 | Saint Gobain Isover | Composition d'encollage exempte de formaldehyde pour fibres, notamment minerales, et produits resultants. |
FR2976582B1 (fr) | 2011-06-17 | 2014-12-26 | Saint Gobain Isover | Composition d'encollage pour laine minerale a faible emission de composes organiques volatils, et produits isolants obtenus. |
FR2976584B1 (fr) | 2011-06-17 | 2014-12-12 | Saint Gobain Isover | Composition d'encollage pour laine minerale a base de sel d'acide lignosulfonique et d'oligosaccharide, et produits isolants obtenus. |
FR2981647B1 (fr) | 2011-10-20 | 2019-12-20 | Saint-Gobain Isover | Composition d'encollage a faible teneur en formaldehyde pour laine minerale resistant au feu et produit isolant obtenu. |
FR2985725B1 (fr) | 2012-01-17 | 2015-06-26 | Saint Gobain Isover | Composition d'encollage pour fibres, notamment minerales, a base d'acide humique et/ou fulvique, et produits isolants resultants. |
MX2016010192A (es) | 2014-02-07 | 2017-01-09 | Knauf Insulation Inc | Articulos no curados con estabilidad en almacen mejorada. |
FR3019816B1 (fr) * | 2014-04-10 | 2021-04-02 | Saint Gobain Isover | Composite comprenant une laine minerale comprenant un sucre |
FR3021651A1 (fr) * | 2014-05-28 | 2015-12-04 | Saint Gobain Isover | Composition de liant pour laine minerale |
CN109477267B (zh) | 2016-06-06 | 2022-11-22 | 欧文斯科宁知识产权资产有限公司 | 粘结剂体系 |
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GB191201937A (en) * | 1912-01-24 | 1913-01-23 | Louis Alexandre | Improved Composition for Preparing Porous Surfaces for the Reception of Coatings of Paint. |
GB116620A (en) * | 1917-09-06 | 1918-06-20 | Raymond Welch Tunnell | Improvements in Vegetable Glue or Adhesive. |
GB421456A (en) * | 1934-08-07 | 1934-12-20 | James Graham | Improvements in and relating to adhesives |
US2544714A (en) * | 1949-07-12 | 1951-03-13 | Stein Hall & Co Inc | Water-resistant adhesive |
US2657163A (en) * | 1951-03-06 | 1953-10-27 | Upson Co | Wallboard adhesive and method |
US4369173A (en) * | 1974-11-27 | 1983-01-18 | Wickhen Products, Inc. | Antiperspirant compositions |
GB2170208B (en) * | 1985-01-29 | 1988-06-22 | Enigma Nv | A formaldehyde binder |
DE4222444A1 (de) * | 1992-07-08 | 1994-01-13 | Helmut Schiwek | Verfahren und Anlage zur Herstellung von Glasfasern für Dämmstoffe |
US5661213A (en) | 1992-08-06 | 1997-08-26 | Rohm And Haas Company | Curable aqueous composition and use as fiberglass nonwoven binder |
US5340868A (en) | 1993-06-21 | 1994-08-23 | Owens-Corning Fiberglass Technology Inc. | Fibrous glass binders |
US5318990A (en) | 1993-06-21 | 1994-06-07 | Owens-Corning Fiberglas Technology Inc. | Fibrous glass binders |
EE9700180A (et) * | 1995-02-21 | 1998-02-16 | Rockwool Lapinus B.V. | Meetod mineraalvillast toote valmistamiseks |
DE19606392A1 (de) | 1996-02-21 | 1997-08-28 | Basf Ag | Formaldehydfreie Beschichtungsmittel für Formkörper |
DE19606393A1 (de) | 1996-02-21 | 1997-08-28 | Basf Ag | Formaldehydfreie Bindemittel für Formkörper |
DE19606394A1 (de) | 1996-02-21 | 1997-08-28 | Basf Ag | Formaldehydfreie, wäßrige Bindemittel |
TW408152B (en) | 1997-04-25 | 2000-10-11 | Rohm & Haas | Formaldehyde-free curable composition and method for bonding heat-resistant fibers of a nonwoven material by using the composition |
US5977232A (en) | 1997-08-01 | 1999-11-02 | Rohm And Haas Company | Formaldehyde-free, accelerated cure, aqueous composition for bonding glass fiber heat-resistant nonwovens |
DE19735959A1 (de) | 1997-08-19 | 1999-02-25 | Basf Ag | Verwendung thermisch härtbarer, wässriger Zusammensetzungen als Bindemittel für Formkörper |
US5895804A (en) | 1997-10-27 | 1999-04-20 | National Starch And Chemical Investment Holding Corporation | Thermosetting polysaccharides |
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FR2810031B1 (fr) | 2000-06-13 | 2003-03-07 | Saint Gobain Isover | Produit d'isolation, notamment thermique, et sa fabrication |
US6933349B2 (en) | 2001-03-21 | 2005-08-23 | Owens Corning Fiberglas Technology, Inc. | Low odor insulation binder from phosphite terminated polyacrylic acid |
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EP1382642A1 (en) * | 2002-07-15 | 2004-01-21 | Rockwool International A/S | Formaldehyde-free aqueous binder composition for mineral fibers |
DE102004011231A1 (de) * | 2004-01-27 | 2005-08-11 | Wtb Biotech Gmbh | Mehrkomponenten-Bindemittel und dessen Verwendung |
US20050215153A1 (en) | 2004-03-23 | 2005-09-29 | Cossement Marc R | Dextrin binder composition for heat resistant non-wovens |
US20050214519A1 (en) * | 2004-03-26 | 2005-09-29 | Clements Christopher J | Sugar as a binder for muffler preforms |
KR101963076B1 (ko) | 2005-07-26 | 2019-03-27 | 크나우프 인설레이션, 인크. | 접착제 및 이들로 만들어진 물질 |
WO2008089850A1 (en) * | 2007-01-25 | 2008-07-31 | Knauf Insulation Limited | Mineral fibre board |
GB0715100D0 (en) * | 2007-08-03 | 2007-09-12 | Knauf Insulation Ltd | Binders |
FR2924719B1 (fr) * | 2007-12-05 | 2010-09-10 | Saint Gobain Isover | Composition d'encollage pour laine minerale comprenant un monosaccharide et/ou un polysaccharide et un acide organique polycarboxylique, et produits isolants obtenus. |
PL2223941T3 (pl) | 2009-02-27 | 2019-04-30 | Rohm & Haas | Szybkoutwardzalna kompozycja węglowodanowa |
-
2009
- 2009-10-13 FR FR0957144A patent/FR2951189B1/fr active Active
-
2010
- 2010-10-13 ES ES10785105.7T patent/ES2690763T3/es active Active
- 2010-10-13 PT PT10785105T patent/PT2488596T/pt unknown
- 2010-10-13 DK DK10785105.7T patent/DK2488596T3/da active
- 2010-10-13 EP EP10785105.7A patent/EP2488596B1/fr active Active
- 2010-10-13 WO PCT/FR2010/052164 patent/WO2011045531A1/fr active Application Filing
- 2010-10-13 PL PL10785105T patent/PL2488596T3/pl unknown
- 2010-10-13 US US13/320,868 patent/US8597532B2/en active Active
- 2010-10-13 SI SI201031773T patent/SI2488596T1/sl unknown
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2018
- 2018-10-11 HR HRP20181634TT patent/HRP20181634T1/hr unknown
Also Published As
Publication number | Publication date |
---|---|
ES2690763T3 (es) | 2018-11-22 |
WO2011045531A1 (fr) | 2011-04-21 |
SI2488596T1 (sl) | 2018-11-30 |
PL2488596T3 (pl) | 2019-01-31 |
PT2488596T (pt) | 2018-11-07 |
US8597532B2 (en) | 2013-12-03 |
FR2951189B1 (fr) | 2011-12-09 |
EP2488596B1 (fr) | 2018-10-03 |
FR2951189A1 (fr) | 2011-04-15 |
US20120085962A1 (en) | 2012-04-12 |
EP2488596A1 (fr) | 2012-08-22 |
HRP20181634T1 (hr) | 2018-12-14 |
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