WO2012076462A1 - Method of reducing the formaldehyde emission of a mineral fibre product, and mineral fibre product with reduced formaldehyde emission - Google Patents
Method of reducing the formaldehyde emission of a mineral fibre product, and mineral fibre product with reduced formaldehyde emission Download PDFInfo
- Publication number
- WO2012076462A1 WO2012076462A1 PCT/EP2011/071732 EP2011071732W WO2012076462A1 WO 2012076462 A1 WO2012076462 A1 WO 2012076462A1 EP 2011071732 W EP2011071732 W EP 2011071732W WO 2012076462 A1 WO2012076462 A1 WO 2012076462A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dextrose
- formaldehyde
- binder composition
- phenol
- mineral fibre
- Prior art date
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 69
- 239000011707 mineral Substances 0.000 title claims abstract description 69
- 239000000835 fiber Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 96
- 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 abstract description 95
- 239000008121 dextrose Substances 0.000 claims abstract description 89
- 239000000203 mixture Substances 0.000 claims abstract description 69
- 229920003987 resole Polymers 0.000 claims abstract description 52
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical class O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims description 54
- 239000011347 resin Substances 0.000 claims description 54
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 37
- 229920001568 phenolic resin Polymers 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000002516 radical scavenger Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 description 49
- 239000002253 acid Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000011490 mineral wool Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 235000000346 sugar Nutrition 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002772 monosaccharides Chemical class 0.000 description 4
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- 229920002748 Basalt fiber Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- -1 amine compounds Chemical class 0.000 description 2
- 150000001414 amino alcohols Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- XDIYNQZUNSSENW-UUBOPVPUSA-N (2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O XDIYNQZUNSSENW-UUBOPVPUSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002245 Dextrose equivalent Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 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 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002480 mineral oil Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Chemical class 0.000 description 1
- 235000020374 simple syrup Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
-
- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
-
- 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
-
- 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
-
- 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
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/12—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with filaments or yarns secured together by chemical or thermo-activatable bonding agents, e.g. adhesives, applied or incorporated in liquid or solid form
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
Definitions
- the present invention relates to a method of reducing formaldehyde emission of a mineral fibre product, and to bonded mineral fibre products having low formaldehyde emission.
- Mineral fibre products generally comprise man-made vitreous fibres (MMVF) such as, e.g., glass fibres, ceramic fibres, basalt fibres, slag wool, mineral wool and stone wool, which are bonded together by a cured thermoset polymeric binder material.
- MMVF man-made vitreous fibres
- bonded mineral fibre mats are generally produced by converting a melt made of suitable raw materials to fibres in conventional manner, for instance by a spinning cup process or by a cascade rotor process. The fibres are blown into a forming chamber and, while airborne and while still hot, are sprayed with a binder solution and randomly deposited as a mat or web onto a travelling conveyor. The fibre mat is then transferred to a curing oven where heated air is blown through the mat to cure the binder and rigidly bond the mineral fibres together.
- MMVF man-made vitreous fibres
- Phenolic binders in particular phenol-formaldehyde resole resins are frequently used in the manufacture of mineral fibre insulation materials, such as insulative batts for walls, roof boards, ceiling tiles, insulative coverings for pipes, and the like.
- a significant amount of formaldehyde is released into the environment during cure.
- Formaldehyde also can be released subsequently from the cured resin.
- formaldehyde emission is undesirable, particularly in enclosed spaces, because it is hazardous to human health and to the environment.
- Formaldehyde has been classified as carcinogenic to humans by The International Agency for Research on Cancer (IARC) of the World Health Organization (WHO); see the iARC Monograph on Formaldehyde, Volume 88 (2006). It is therefore desirable to reduce the release of formaldehyde into the environment.
- IARC International Agency for Research on Cancer
- WHO World Health Organization
- urea acts as a formaldehyde scavenger both at, and subsequent to, the manufacture of bonded mineral fibre products.
- Urea is typically added directly to the phenol-formaldehyde resin to produce a urea- modified phenol-formaldehyde resole resin.
- a mixture of phenol and formaldehyde is reacted with a suitable basic catalyst in one or more steps.
- reaction conditions, temperature, amount of catalyst, etc. are adjusted to favour phenol methy!olation reactions over condensation reactions.
- Urea is then added before or after inactivating the resin just prior to use of the resin.
- Such a resin is typically referred to as a PUF resin, or PUF binder.
- ammonia Another commonly used formaldehyde scavenger is ammonia which binds formaldehyde with formation of amine compounds such as hexamethylene tetramine.
- WO 96/26164 describes a phenol-formaldehyde resin composition for use as a binder in mineral wool products wherein the emission of phenol is reduced by using a stoichiometric excess of formaldehyde over phenol, wherein the emission of the excess formaldehyde is reduced by adding ammonia as a formaldehyde scavenger and wherein the emission of ammonia is reduced by reacting the ammonia with a sugar compound.
- thermosetting phenol-formaldehyde resole resin-type mineral wool binder systems that contain a sugar component are known in the art.
- WO 2006/136614 discloses a binder system similar to that of WO 96/26164 but substituting hydroxylamine or an amino alcohol for ammonia.
- US-A-4339361 discloses phenol-formaldehyde resole resins which are suitable for use in binder systems for bonding mineral fibre products and which are extended with an amide or amine such as urea and a sugar as inexpensive extenders.
- the sugar component may be selected from mono- and oligosaccharides and water- soluble polysaccharides.
- WO 2009/136106 discloses mineral wool binders comprising a liquid phenolic resin having a free formaldehyde content of less than or equal to 0.1% and an extender.
- the extender may be chosen from carbohydrates, including monosaccharides, oligosaccharides and polysaccharides.
- US-A-5795934 discloses a urea-modified phenol-formaldehyde resole resin composition which comprises an alkanolamine alone or preferably in combination with a monosaccharide or disaccharide in an amount sufficient to improve the storage stability of the urea-modified phenolic resole resin.
- WO 2008/127936 discloses composite Maillard-resole binder compositions comprising a phenol-formaldehyde resole resin or urea-modified phenol- formaldehyde resole resin and so-called Maillard reactants which comprise a mixture of a monosaccharide and an ammonium salt of a polycarboxylic acid.
- the present invention is based on the discovery that dextrose acts as a formaldehyde scavenger in the manufacture of mineral fibre products bonded with a urea-modified phenol-formaldehyde resole resin-type binder.
- the present invention relates to a method of reducing the formaldehyde emission of a mineral fibre product bonded with a urea-modified phenol-formaldehyde resol resin-type binder, said method comprising the step of adding dextrose to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
- the dextrose is added to the binder composition after the preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
- the present invention relates to a mineral fibre product having reduced formaldehyde emission and bonded with a cured urea-modified phenol- formaldehyde resol resin-type binder composition, the non-cured binder composition comprising dextrose in an amount of 15 wt% or more, and up to 70 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
- the present invention relates to the use of dextrose as a formaldehyde scavenger in a urea-modified phenol-formaldehyde resol resin-type binder composition for mineral fibre products.
- the dextrose used may be pure dextrose or in the form of a dextrose preparation having a DE equivalent of about 70 to 100, preferably about 90 to 100.
- the phenol may be reacted with molar excess formaldehyde in aqueous solution in a molar ratio of from 1 :2.5 to 1 :6; preferably from 1 :3 to 1 :5, in the presence of a base catalyst.
- the urea used may be in an amount of from 20 to 60 wt%, preferably 30 to 50 wt%, based on total dry solids of the phenol-formaldehyde resol resin and urea.
- the dextrose used may be in an amount of 15 to 70 wt%, preferably 20 to 50 wt%, based on total dry solids of urea- modified phenol-formaldehyde resol resin and dextrose.
- the use is preferably carried out with a step of adding dextrose to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
- the present invention relates to an apparatus for making a mineral fibre product having reduced formaldehyde emission and bonded with a cured urea-modified phenol-formaldehyde resol resin-type binder composition with dextrose added to the binder composition, said apparatus comprising
- a curing oven for curing the mixed binder composition and dextrose applied to the mineral fibres to form a cured web
- the confectioning of the mineral wool cured web is in the conventional meaning of cutting and packaging the web into products.
- the dextrose used may be pure dextrose or in the form of a dextrose preparation having a DE equivalent of about 70 to 100, preferably about 90 to 100.
- the phenol may be reacted with molar excess formaldehyde in aqueous solution in a molar ratio of from 1 :2.5 to 1 :6; preferably from 1 :3 to 1 :5, in the presence of a base catalyst.
- the urea used may be in an amount of from 20 to 60 wt%, preferably 30 to 50 wt%, based on total dry solids of the phenol-formaldehyde resol resin and urea.
- the dextrose used may be in an amount of 15 to 70 wt%, preferably 20 to 50 wt%, based on total dry solids of urea-modified phenol-formaldehyde resol resin and dextrose.
- the inventors have surprisingly found that by adding dextrose to a urea-modified phenol-formaldehyde resol resin-type binder composition, the formaldehyde emission of the bonded mineral fibre product after curing can be reduced down to values which cannot be explained by a mere dilution effect; i.e. by dextrose merely acting as an diluent or extender.
- the nature of the urea-modified phenol- formaldehyde resol resin is not critical, and any urea-modified phenol-formaldehyde resol resin known in the art may be used.
- UF urea- formaldehyde
- Suitable urea-modified phenol-formaldehyde resol resins are, for instance, those disclosed in EP-A-148050, EP-A-810981 , CA-A-1001788 and US- A-5371140; the emulsifiable phenolic resins disclosed in EP-A-1084167; the overcondensed phenolic resins disclosed in WO 99/03906 and WO 2009/136106, the disclosures of which are hereby incorporated by reference.
- the proportion of phenol to aldehyde is selected to yield a resol-type resin (stoichiometric excess of aldehyde), when phenol and formaldehyde are used, the mole ratio of phenol to formaldehyde preferably being from about 1 :2.5 to 1 :6, and more preferably from about 1 :3 to 1 :5.
- the catalyst used in the process of preparing the resol resin can include at least one basic alkali metal or alkaline earth metal compound or amine catalyst, such as triethyl amine (TEA).
- TAA triethyl amine
- alkali metal bases which can be used include the hydroxides of sodium, potassium and lithium.
- alkaline earth metal bases which can be used include the oxides and hydroxides of calcium, barium and strontium, such as calcium oxide and calcium hydroxide.
- an aqueous mixture of phenol and formaldehyde is maintained at a first temperature of, for instance, 40 to 50°C, as the basic catalyst is added.
- the temperature is then permitted to rise to a second reaction temperature of, for instance, 60 to 90°C.
- the reaction is carried out for a sufficient reaction time and at a suitable temperature to provide a resol resin having an acid tolerance of ⁇ 8, preferably within the range of 0.5 to 7, more preferably 3 to 5.
- the degree of conversion of phenol is preferably > 95%, more preferably > 97%.
- Acid tolerance is a measure of the reaction degree and is determined as follows: As acid is used a diluted solution of sulphuric acid (2,5 ml of concentrated sulphuric acid is added to 1 litre of ion-exchanged water). 5.0 ml of binder is transferred into an Erlenmeyer flask. Diluted acid is then added from a burette while keeping the binder in motion. The titration is continued until a slight cloud appears in the binder, which does not disappear when the binder is shaken. The acid tolerance is calculated by dividing the amount of acid in ml used for the titration with the amount of ml of the sample.
- the reaction mixture may be inactivated by addition of a latent acid such as ammonium sulphate or an acid such as sulfuric acid.
- a latent acid such as ammonium sulphate or an acid such as sulfuric acid.
- urea is preferably added and/or reacted in an amount of from about 20 to 60 wt%, preferably 20 to 50 wt%, based on total dry solids of phenol-formaldehyde resol resin and urea.
- the urea may be added to the resol resin during its preparation or in a post-reaction step.
- dextrose is added to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
- dextrose may be used as pure dextrose (glucose) or in the form of a dextrose preparation having a DE equivalent of about 70 to 100, preferably about 90 to 100.
- Dextrose is normally produced by subjecting an aqueous slurry of starch to hydrolysis by means of heat, acid or enzymes. Depending on the reaction conditions employed in the hydrolysis of starch, a variety of mixtures of glucose and intermediates is obtained which may be characterized by their DE number.
- pure dextrose or high DE glucose syrup are preferably used as formaldehyde scavengers.
- the non-cured binder composition according to the present invention generally contains dextrose in an amount of from 15 to 70 wt%, preferably 20 to 50 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
- Preferred lower concentrations of dextrose are 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt% and 45 wt%.
- Preferred higher concentrations of dextrose are 50 wt%, 55 wt%, 60 wt%, 65 wt% and 70 wt%.
- the skilled person will employ dextrose in appropriate concentration ranges between these values.
- the aqueous binder compositions according to the present invention may comprise one or more conventional binder additives.
- binder additives include, for instance, curing accelerators such as the free acid and salt forms of strong acids such as boric acid, sulphuric acid, nitric acid and p-toluenesulphonic acid which may be used either alone or in combination with guanidine carbonate.
- binder additives are, for example, silane coupling agents such as ⁇ -aminopropyltriethoxysilane; thermal stabilizers; UV stabilizers; emulsifiers; surface active agents, particularly nonionic surfactants; biocides; plasticizers; anti-migration aids; coalescents; fillers and extenders such as starch, clay, silicates and magnesium hydroxide; pigments such as titanium dioxide; hydrophobizing agents such as fluorinated compounds, mineral oils and silicone oils; flame retardants; corrosion inhibitors such as thiourea; antifoaming agents; antioxidants; and others.
- binder additives and adjuvants may be used in conventional amounts generally not exceeding 20 wt.% of the binder solids.
- the amount of curing accelerator in the binder composition is generally between 0.05 and 5 wt.%, based on solids.
- the final aqueous binder composition generally has a solids content of from 1 to 20 wt.% and a pH of 6 or higher.
- the binder composition according to the present invention preferably does not contain any one of the following components: hydroxylamine; amino alcohols; a!kanol amines; polycarboxylic acids and ammonium salts of polycarboxylic acids; sugar alcohols.
- the mineral fibres employed may be any of man-made vitreous fibres (MMVF), glass fibres, ceramic fibres, basalt fibres, slag fibres, rock fibres, stone fibres and others. These fibres may be present as a wool product, e.g. like a rock wool product.
- MMVF man-made vitreous fibres
- glass fibres ceramic fibres
- basalt fibres basalt fibres
- slag fibres rock fibres
- rock fibres e.g. like a rock wool product.
- Suitable fibre formation methods and subsequent production steps for manufacturing the mineral fibre product are those conventional in the art.
- the binder is sprayed immediately after fibrillation of the mineral melt on to the airborne mineral fibres.
- the aqueous binder composition is normally applied in an amount of 0.1 to 10 %, preferably 0.2 to 8 % by weight, of the bonded mineral fibre product on a dry basis.
- the spray-coated mineral fibre web is generally cured in a curing oven by means of a hot air stream.
- the hot air stream may be introduced into the mineral fibre web from below, or above or from alternating directions in distinctive zones in the length direction of the curing oven.
- the curing oven is operated at a temperature of from about 150 to 350°C.
- the curing temperature ranges from about 200 to about 300°C.
- the curing oven residence time is from 30 seconds to 20 minutes, depending on, for instance, the product density.
- the mineral wool web may be subjected to a shaping process before curing.
- the bonded mineral fibre products emerging from the curing oven may be cut to a desired format e.g., in the form of a batt.
- the mineral fibre products produced may, for instance, have the form of mats, batts, slabs, sheets, plates, strips, rolls, pipe sections, granulates, and other shaped articles.
- a specific type of bonded mineral fibre product is a horticultural growth substrate product.
- Such horticultural growth substrate products may be in any of the known forms for growth substrate products, such as those usually known as plugs, blocks, slabs and mats.
- the invention is beneficial in the case where the product is in a form generally known for use as a substrate for the propagation stage.
- the horticultural growth substrate product has a greater uniformity of environment across the set of seeds being grown, leading to greater uniformity of the end-product plants; this leads to generally improved plant quality.
- the growth substrate product may further comprise a wetting agent.
- a wetting agent This can be a conventional non-ionic surfactant but preferably the wetting agent is an ionic surfactant, more preferably an anionic surfactant.
- Particularly preferred wetting agents are anionic surfactants such as linear alkyl benzene su!phonates wherein the alkyl chain has from 5 to 20 carbon atoms.
- the amount (by weight) of ionic surfactant based on the weight of binder (dry matter) is in the range 0.01 to 5%, preferably 0.1 to 4%.
- This type of surfactant provides particularly beneficial water distribution properties for growth substrates of relatively large height and also provides excellent re-saturation properties and does not lead to foaming problems in the irrigation water.
- composite materials by combining the bonded mineral fibre product with suitable composite layers or laminate layers such as, e.g., metal, glass surfacing mats and other woven or non-woven materials.
- the mineral fibre products according to the present invention generally have a density within the range of from 5 to 250 kg/m 3 , preferably 20 to 200 kg/m 3 .
- a particular group of mineral fibre products according to the present invention are ceiling tiles having a density of from 50 to 220 kg/m 3 and manufactured using a non- cured binder composition comprising dextrose in an amount of 20 to 70 wt%, preferably 40 to 70 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
- Another group of mineral fibre products according to the present invention are roof boards having a density of from 100 to 250 kg/m 3 and manufactured using a non- cured binder composition comprising dextrose in an amount of 20 to 50 wt%, preferably 20 to 40 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
- the mineral fibre batts include an upper layer having a density of around 100 to 250 kg/m 3 and a lower layer with a density which is usually not more than 80% but usually more than 30% of the density of the upper layer, often around 40 to 70% of the density of the upper layer.
- the upper and lower layers in the final product have a total thickness of 30 to 300 mm.
- the lower layer is usually 25 to 275 mm thick and is usually at least 75 mm thick. Generally, it is at least 50%, and often 75 to 95%, of the combined thickness of the upper and lower layers.
- the mineral fibre products according to the present invention are light-coloured and often brownish to a varying degree, depending on the amount of dextrose.
- the mineral fibre products according to the present invention satisfy the formaldehyde emission requirements of international building industry standards.
- tests with mineral fibre products according to the invention showed that the formaldehyde emission requirements of Finnish Standard RTS-M1 (limit 50 ⁇ g/ m 2 h) for a roof board can be met by using > 20 wt% of dextrose.
- the Finnish Standard RTS-M1 standard determines the emission of the sample after 4 weeks in a testing chamber according to 1SO-16000-9, first edition, corrected version 2006-06- 15.
- Greenguard Children and Schools standard limit corresponds to a specific emission rate of approximately 35 pg/m 2 h.
- this standard is met for a building insulation product board or roll having a density of from 5 to 70 kg/m 3 and manufactured using a non-cured binder composition comprising dextrose in an amount of 10 to 50 wt%, preferably 20 to 40 wt%, based on total dry solids of phenol- formaldehyde resol resin and dextrose.
- solids content (dry matter) is herein determined at 200 °C, 1 hour and expressed as wt.%.
- a phenol-formaldehyde resin is prepared by reacting formaldehyde and phenol in a molar ratio of 3.7 to 1 in the presence of a catalyst (6 wt% KOH, relative to the amount of phenol) at a reaction temperature of 84°C. The reaction is continued until the acid tolerance of the resin is 4 and most of the phenol is converted. Urea is then added in an amount corresponding to 52 parts by weight of phenol-formaldehyde resin and 48 parts by weight of urea.
- a binder is made by addition of ammonium sulphate in equimolar amounts to the catalyst so as to inactivate the catalyst.
- the final PUF resin has a free formaldehyde content of ⁇ 0.5%, relative to the solids.
- PUF binder is mixed with a dextrose preparation, Sirodex® 431 from Syral (DE value 95), in the amounts indicated in Table 1 below.
- the binder is diluted with water to a solids content equal to 22%, and a commercial prehydrolysed aminosiiane is added in an amount corresponding to 0.5% of the solids.
- binder composition obtained is used for production of monolayer roof boards ("A- Tagplade"). Further details are given in the following table. Table 1 :
- the PUF binder content (%) and the dextrose content (%) are weight percentages based on total dry solids of phenol-formaldehyde resol resin and dextrose.
- the binder content of product (%) is defined as loss-on ignition (LOI) (%) - impregnation oil (%)
- a commercial resin PF-0415M from Hexion is used for the test.
- the resin is a phenol- formaldehyde resin modified with urea and ammonia. Free formaldehyde is ⁇ 0.3% based on the liquid resin. The amount of urea is 28% in relation to the solids content.
- the resin is mixed with a dextrose preparation, Sirodex® 431 (DE value 95) from Syral, in the amounts indicated in Table 2 below.
- a glucose syrup i.e. C Sweet® 01403 (DE value 30) from Cargill, is used in the amount indicated in Table 2 (Sample H).
- composition is diluted to 15% with water to provide a binder composition and further added with 0.5% of a commercial silane of the type pre-hydrolysed amino silane.
- the binder composition obtained is used for production of monolayer roof boards (DP-GF). Further details are given in the following table. Table 2:
- the PUF binder content (%) and the dextrose content (%) are weight percentages based on total dry solids of phenol-formaldehyde resol resin and dextrose.
- Binder content of product (%) LOI (%) - impregnation oil (%)
- the formaldehyde emission is measured for the products A-H of Examples 1 and 2 and stated in Table 3 below as formaldehyde emission in ⁇ g/m 3 .
- the emissions were measured in the climate chamber at the Danish Technological Institute (Tl) according to standard EN 717-1.
- the actually determined values are compared with the expected values (assuming a pure dilution effect of dextrose).
- the value of 80 for 100 parts of PUF is used as a reference and the expected values are calculated with reference to the value.
- Sample H is a comparative sample where the dextrose is substituted with a glucose syrup of low dextrose content having a DE-value of 30. Sample H using this sugar syrup does not show a significant reduction in formaldehyde emission compared to the high dextrose content syrups of Examples A-G. Instead, the measured value for the formaldehyde emission of Sample H is as expected when assuming a pure dilution effect.
Abstract
A method of reducing the formaldehyde emission of a mineral fibre product bonded with a urea-modified phenol-formaldehyde resol resin-type binder comprises the step of adding dextrose to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
Description
METHOD OF REDUCING THE FORMALDEHYDE EMISSION OF A MINERAL FIBRE PRODUCT, AND MINERAL FIBRE PRODUCT WITH REDUCED
FORMALDEHYDE EMISSION
Field of the Invention
The present invention relates to a method of reducing formaldehyde emission of a mineral fibre product, and to bonded mineral fibre products having low formaldehyde emission.
Background of the Invention
Mineral fibre products generally comprise man-made vitreous fibres (MMVF) such as, e.g., glass fibres, ceramic fibres, basalt fibres, slag wool, mineral wool and stone wool, which are bonded together by a cured thermoset polymeric binder material. For use as thermal and/or acoustical insulation products, bonded mineral fibre mats are generally produced by converting a melt made of suitable raw materials to fibres in conventional manner, for instance by a spinning cup process or by a cascade rotor process. The fibres are blown into a forming chamber and, while airborne and while still hot, are sprayed with a binder solution and randomly deposited as a mat or web onto a travelling conveyor. The fibre mat is then transferred to a curing oven where heated air is blown through the mat to cure the binder and rigidly bond the mineral fibres together.
Phenolic binders, in particular phenol-formaldehyde resole resins are frequently used in the manufacture of mineral fibre insulation materials, such as insulative batts for walls, roof boards, ceiling tiles, insulative coverings for pipes, and the like.
Typically, when a phenol-formaldehyde resole resin is used as a binder, a significant amount of formaldehyde is released into the environment during cure. Formaldehyde also can be released subsequently from the cured resin. Such formaldehyde emission is undesirable, particularly in enclosed spaces, because it is hazardous to
human health and to the environment. Formaldehyde has been classified as carcinogenic to humans by The International Agency for Research on Cancer (IARC) of the World Health Organization (WHO); see the iARC Monograph on Formaldehyde, Volume 88 (2006). It is therefore desirable to reduce the release of formaldehyde into the environment.
Various techniques have been used to reduce formaldehyde emission from formaldehyde-based resins. In particular, various formaldehyde scavengers have been used for that purpose. For instance, urea acts as a formaldehyde scavenger both at, and subsequent to, the manufacture of bonded mineral fibre products. Urea is typically added directly to the phenol-formaldehyde resin to produce a urea- modified phenol-formaldehyde resole resin. To obtain a typical urea-modified resole binder resin, a mixture of phenol and formaldehyde is reacted with a suitable basic catalyst in one or more steps. The reaction conditions, temperature, amount of catalyst, etc., are adjusted to favour phenol methy!olation reactions over condensation reactions. Urea is then added before or after inactivating the resin just prior to use of the resin. Such a resin is typically referred to as a PUF resin, or PUF binder.
Another commonly used formaldehyde scavenger is ammonia which binds formaldehyde with formation of amine compounds such as hexamethylene tetramine.
For instance, WO 96/26164 describes a phenol-formaldehyde resin composition for use as a binder in mineral wool products wherein the emission of phenol is reduced by using a stoichiometric excess of formaldehyde over phenol, wherein the emission of the excess formaldehyde is reduced by adding ammonia as a formaldehyde scavenger and wherein the emission of ammonia is reduced by reacting the ammonia with a sugar compound.
Other thermosetting phenol-formaldehyde resole resin-type mineral wool binder systems that contain a sugar component are known in the art. For instance, WO 2006/136614 discloses a binder system similar to that of WO 96/26164 but substituting hydroxylamine or an amino alcohol for ammonia.
US-A-4339361 discloses phenol-formaldehyde resole resins which are suitable for use in binder systems for bonding mineral fibre products and which are extended with an amide or amine such as urea and a sugar as inexpensive extenders. The sugar component may be selected from mono- and oligosaccharides and water- soluble polysaccharides.
WO 2009/136106 discloses mineral wool binders comprising a liquid phenolic resin having a free formaldehyde content of less than or equal to 0.1% and an extender. The extender may be chosen from carbohydrates, including monosaccharides, oligosaccharides and polysaccharides.
US-A-5795934 discloses a urea-modified phenol-formaldehyde resole resin composition which comprises an alkanolamine alone or preferably in combination with a monosaccharide or disaccharide in an amount sufficient to improve the storage stability of the urea-modified phenolic resole resin.
WO 2008/127936 discloses composite Maillard-resole binder compositions comprising a phenol-formaldehyde resole resin or urea-modified phenol- formaldehyde resole resin and so-called Maillard reactants which comprise a mixture of a monosaccharide and an ammonium salt of a polycarboxylic acid.
Summary of the Invention
The present invention is based on the discovery that dextrose acts as a formaldehyde scavenger in the manufacture of mineral fibre products bonded with a urea-modified phenol-formaldehyde resole resin-type binder.
Accordingly, in one aspect, the present invention relates to a method of reducing the formaldehyde emission of a mineral fibre product bonded with a urea-modified phenol-formaldehyde resol resin-type binder, said method comprising the step of adding dextrose to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres. Preferably, the dextrose is added to the binder composition after the
preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
In another aspect, the present invention relates to a mineral fibre product having reduced formaldehyde emission and bonded with a cured urea-modified phenol- formaldehyde resol resin-type binder composition, the non-cured binder composition comprising dextrose in an amount of 15 wt% or more, and up to 70 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
In a further aspect, the present invention relates to the use of dextrose as a formaldehyde scavenger in a urea-modified phenol-formaldehyde resol resin-type binder composition for mineral fibre products. The dextrose used may be pure dextrose or in the form of a dextrose preparation having a DE equivalent of about 70 to 100, preferably about 90 to 100. The phenol may be reacted with molar excess formaldehyde in aqueous solution in a molar ratio of from 1 :2.5 to 1 :6; preferably from 1 :3 to 1 :5, in the presence of a base catalyst. The urea used may be in an amount of from 20 to 60 wt%, preferably 30 to 50 wt%, based on total dry solids of the phenol-formaldehyde resol resin and urea. The dextrose used may be in an amount of 15 to 70 wt%, preferably 20 to 50 wt%, based on total dry solids of urea- modified phenol-formaldehyde resol resin and dextrose.
The use is preferably carried out with a step of adding dextrose to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
In still another aspect, the present invention relates to an apparatus for making a mineral fibre product having reduced formaldehyde emission and bonded with a cured urea-modified phenol-formaldehyde resol resin-type binder composition with dextrose added to the binder composition, said apparatus comprising
- means for fiberising a mineral melt to mineral fibres,
- separate tanks for the binder composition and dextrose;
- means for mixing the binder composition and the dextrose,
- means for applying the mixture of binder composition and dextrose to the mineral fibres,
- a collecting chamber for the mineral fibres with the applied mixed binder composition and dextrose,
- a curing oven for curing the mixed binder composition and dextrose applied to the mineral fibres to form a cured web, and
- means for confectioning the cured web to a mineral fibre product.
The confectioning of the mineral wool cured web is in the conventional meaning of cutting and packaging the web into products.
The dextrose used may be pure dextrose or in the form of a dextrose preparation having a DE equivalent of about 70 to 100, preferably about 90 to 100. The phenol may be reacted with molar excess formaldehyde in aqueous solution in a molar ratio of from 1 :2.5 to 1 :6; preferably from 1 :3 to 1 :5, in the presence of a base catalyst. The urea used may be in an amount of from 20 to 60 wt%, preferably 30 to 50 wt%, based on total dry solids of the phenol-formaldehyde resol resin and urea. The dextrose used may be in an amount of 15 to 70 wt%, preferably 20 to 50 wt%, based on total dry solids of urea-modified phenol-formaldehyde resol resin and dextrose.
The inventors have surprisingly found that by adding dextrose to a urea-modified phenol-formaldehyde resol resin-type binder composition, the formaldehyde emission of the bonded mineral fibre product after curing can be reduced down to values which cannot be explained by a mere dilution effect; i.e. by dextrose merely acting as an diluent or extender. For instance, with a mineral wool product bonded with 4,92% of a binder comprising a 43/57 (wt%) mixture of urea-modified phenol-formaldehyde resol resin and dextrose, a formaldehyde emission of 13 μg/m3 was determined instead of an expected value (assuming a pure dilution effect) of 40 μg/m3. Likewise, with a mineral wool product bonded with 3,59% of a binder comprising a 54/46 (wt%) mixture of urea-modified phenol-formaldehyde resol resin and dextrose, a formaldehyde emission of 7μg/m3 was measured instead of an expected value of 43 g/m3.
The notion of "reduced formaldehyde" is herein construed as a reduction in the formaldehyde emission, compared with an otherwise identical product in terms of binder content, urea content, ammonia content and product density.
Detailed Description and Preferred Embodiments
Urea-modified phenol-formaldehyde resol resin
In accordance with the present invention, the nature of the urea-modified phenol- formaldehyde resol resin is not critical, and any urea-modified phenol-formaldehyde resol resin known in the art may be used.
However, in accordance with the invention, preferably no substantive urea- formaldehyde (UF) resin formation is taking place, i.e. a dedicated UF formation giving the resin the character of a UF resin is preferably not aimed at.
Specific examples of suitable urea-modified phenol-formaldehyde resol resins are, for instance, those disclosed in EP-A-148050, EP-A-810981 , CA-A-1001788 and US- A-5371140; the emulsifiable phenolic resins disclosed in EP-A-1084167; the overcondensed phenolic resins disclosed in WO 99/03906 and WO 2009/136106, the disclosures of which are hereby incorporated by reference.
The proportion of phenol to aldehyde is selected to yield a resol-type resin (stoichiometric excess of aldehyde), when phenol and formaldehyde are used, the mole ratio of phenol to formaldehyde preferably being from about 1 :2.5 to 1 :6, and more preferably from about 1 :3 to 1 :5.
The catalyst used in the process of preparing the resol resin can include at least one basic alkali metal or alkaline earth metal compound or amine catalyst, such as triethyl amine (TEA). Examples of alkali metal bases which can be used include the hydroxides of sodium, potassium and lithium. Examples of alkaline earth metal bases which can be used include the oxides and hydroxides of calcium, barium and strontium, such as calcium oxide and calcium hydroxide.
The exothermic condensation reaction of the phenol and the aldehyde is initiated after mixing the phenol and the aldehyde by addition of the catalyst. In a preferred embodiment, an aqueous mixture of phenol and formaldehyde is maintained at a first temperature of, for instance, 40 to 50°C, as the basic catalyst is added. The temperature is then permitted to rise to a second reaction temperature of, for instance, 60 to 90°C. Preferably, the reaction is carried out for a sufficient reaction time and at a suitable temperature to provide a resol resin having an acid tolerance of < 8, preferably within the range of 0.5 to 7, more preferably 3 to 5. The degree of conversion of phenol is preferably > 95%, more preferably > 97%.
Acid tolerance is a measure of the reaction degree and is determined as follows: As acid is used a diluted solution of sulphuric acid (2,5 ml of concentrated sulphuric acid is added to 1 litre of ion-exchanged water). 5.0 ml of binder is transferred into an Erlenmeyer flask. Diluted acid is then added from a burette while keeping the binder in motion. The titration is continued until a slight cloud appears in the binder, which does not disappear when the binder is shaken. The acid tolerance is calculated by dividing the amount of acid in ml used for the titration with the amount of ml of the sample.
The reaction mixture may be inactivated by addition of a latent acid such as ammonium sulphate or an acid such as sulfuric acid.
For modification of the phenol-formaldehyde resol resin with urea, urea is preferably added and/or reacted in an amount of from about 20 to 60 wt%, preferably 20 to 50 wt%, based on total dry solids of phenol-formaldehyde resol resin and urea. The urea may be added to the resol resin during its preparation or in a post-reaction step.
Dextrose
In accordance with the present invention, dextrose is added to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
For use as a formaldehyde scavenger, dextrose may be used as pure dextrose (glucose) or in the form of a dextrose preparation having a DE equivalent of about 70 to 100, preferably about 90 to 100.
Dextrose is normally produced by subjecting an aqueous slurry of starch to hydrolysis by means of heat, acid or enzymes. Depending on the reaction conditions employed in the hydrolysis of starch, a variety of mixtures of glucose and intermediates is obtained which may be characterized by their DE number. DE is an abbreviation for Dextrose Equivalent and is defined as the content of reducing sugars, expressed as the number of grams of anhydrous D-glucose per 100 g of the dry matter in the sample, when determined by the method specified in Internationa! Standard ISO 5377-1981 (E). This method measures reducing end groups and attaches a DE of 100 to pure glucose (= dextrose) and a DE of 0 to pure starch.
In accordance with the present invention, pure dextrose or high DE glucose syrup are preferably used as formaldehyde scavengers.
Binder Composition
The non-cured binder composition according to the present invention generally contains dextrose in an amount of from 15 to 70 wt%, preferably 20 to 50 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose. Preferred lower concentrations of dextrose are 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt% and 45 wt%. Preferred higher concentrations of dextrose are 50 wt%, 55 wt%, 60 wt%, 65 wt% and 70 wt%. Depending on the properties desired and on the type and amount of formaldehyde generators present, the skilled person will employ dextrose in appropriate concentration ranges between these values.
In addition to the urea-modified phenol-formaldehyde resole resin and dextrose, the aqueous binder compositions according to the present invention may comprise one or more conventional binder additives. These include, for instance, curing accelerators such as the free acid and salt forms of strong acids such as boric acid, sulphuric acid, nitric acid and p-toluenesulphonic acid which may be used either
alone or in combination with guanidine carbonate. Other suitable binder additives are, for example, silane coupling agents such as γ-aminopropyltriethoxysilane; thermal stabilizers; UV stabilizers; emulsifiers; surface active agents, particularly nonionic surfactants; biocides; plasticizers; anti-migration aids; coalescents; fillers and extenders such as starch, clay, silicates and magnesium hydroxide; pigments such as titanium dioxide; hydrophobizing agents such as fluorinated compounds, mineral oils and silicone oils; flame retardants; corrosion inhibitors such as thiourea; antifoaming agents; antioxidants; and others.
These binder additives and adjuvants may be used in conventional amounts generally not exceeding 20 wt.% of the binder solids. The amount of curing accelerator in the binder composition is generally between 0.05 and 5 wt.%, based on solids.
The final aqueous binder composition generally has a solids content of from 1 to 20 wt.% and a pH of 6 or higher.
The binder composition according to the present invention preferably does not contain any one of the following components: hydroxylamine; amino alcohols; a!kanol amines; polycarboxylic acids and ammonium salts of polycarboxylic acids; sugar alcohols.
Mineral fibre product
The mineral fibres employed may be any of man-made vitreous fibres (MMVF), glass fibres, ceramic fibres, basalt fibres, slag fibres, rock fibres, stone fibres and others. These fibres may be present as a wool product, e.g. like a rock wool product.
Suitable fibre formation methods and subsequent production steps for manufacturing the mineral fibre product are those conventional in the art. Generally, the binder is sprayed immediately after fibrillation of the mineral melt on to the airborne mineral fibres. The aqueous binder composition is normally applied in an amount of 0.1 to 10
%, preferably 0.2 to 8 % by weight, of the bonded mineral fibre product on a dry basis.
The spray-coated mineral fibre web is generally cured in a curing oven by means of a hot air stream. The hot air stream may be introduced into the mineral fibre web from below, or above or from alternating directions in distinctive zones in the length direction of the curing oven.
Typically, the curing oven is operated at a temperature of from about 150 to 350°C. Preferably, the curing temperature ranges from about 200 to about 300°C. Generally, the curing oven residence time is from 30 seconds to 20 minutes, depending on, for instance, the product density.
If desired, the mineral wool web may be subjected to a shaping process before curing. The bonded mineral fibre products emerging from the curing oven may be cut to a desired format e.g., in the form of a batt. Thus, the mineral fibre products produced may, for instance, have the form of mats, batts, slabs, sheets, plates, strips, rolls, pipe sections, granulates, and other shaped articles.
A specific type of bonded mineral fibre product is a horticultural growth substrate product. Such horticultural growth substrate products may be in any of the known forms for growth substrate products, such as those usually known as plugs, blocks, slabs and mats. In particular the invention is beneficial in the case where the product is in a form generally known for use as a substrate for the propagation stage.
The horticultural growth substrate product has a greater uniformity of environment across the set of seeds being grown, leading to greater uniformity of the end-product plants; this leads to generally improved plant quality.
The growth substrate product may further comprise a wetting agent. This can be a conventional non-ionic surfactant but preferably the wetting agent is an ionic surfactant, more preferably an anionic surfactant. Particularly preferred wetting agents are anionic surfactants such as linear alkyl benzene su!phonates wherein the
alkyl chain has from 5 to 20 carbon atoms. Preferably the amount (by weight) of ionic surfactant based on the weight of binder (dry matter) is in the range 0.01 to 5%, preferably 0.1 to 4%.
This type of surfactant provides particularly beneficial water distribution properties for growth substrates of relatively large height and also provides excellent re-saturation properties and does not lead to foaming problems in the irrigation water.
In accordance with the present invention, it is also possible to produce composite materials by combining the bonded mineral fibre product with suitable composite layers or laminate layers such as, e.g., metal, glass surfacing mats and other woven or non-woven materials.
The mineral fibre products according to the present invention generally have a density within the range of from 5 to 250 kg/m3, preferably 20 to 200 kg/m3.
A particular group of mineral fibre products according to the present invention are ceiling tiles having a density of from 50 to 220 kg/m3 and manufactured using a non- cured binder composition comprising dextrose in an amount of 20 to 70 wt%, preferably 40 to 70 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
Another group of mineral fibre products according to the present invention are roof boards having a density of from 100 to 250 kg/m3 and manufactured using a non- cured binder composition comprising dextrose in an amount of 20 to 50 wt%, preferably 20 to 40 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
There are essentially two types of roof boards: mono density and dual density roof boards such as disclosed, e.g., in EP-A-88998 and EP-A-1456444, the disclosure of which is incorporated herein by reference.
In preferred dual density roof boards, the mineral fibre batts include an upper layer having a density of around 100 to 250 kg/m3 and a lower layer with a density which is usually not more than 80% but usually more than 30% of the density of the upper layer, often around 40 to 70% of the density of the upper layer. Usually, the upper and lower layers in the final product have a total thickness of 30 to 300 mm. The lower layer is usually 25 to 275 mm thick and is usually at least 75 mm thick. Generally, it is at least 50%, and often 75 to 95%, of the combined thickness of the upper and lower layers.
The mineral fibre products according to the present invention are light-coloured and often brownish to a varying degree, depending on the amount of dextrose.
The mineral fibre products according to the present invention satisfy the formaldehyde emission requirements of international building industry standards.
For instance, tests with mineral fibre products according to the invention showed that the formaldehyde emission requirements of Finnish Standard RTS-M1 (limit 50 μg/ m2 h) for a roof board can be met by using > 20 wt% of dextrose. The Finnish Standard RTS-M1 standard determines the emission of the sample after 4 weeks in a testing chamber according to 1SO-16000-9, first edition, corrected version 2006-06- 15.
Similarly, the formaldehyde emission requirements of U.S. Standard CDHS (version 15 July 2004; limit 16.5 μg m3) for a roof board can be met by using > 30 wt% of dextrose, and the formaldehyde emission requirements of Japanese Standard JIS A 1901-2003 (E) (limit 12 μg/m3, the F*** limit) can be met by using about 47 wt% of dextrose.
Another standard that is met by the product according to the present invention is the Greenguard Children and Schools standard limit, which corresponds to a specific emission rate of approximately 35 pg/m2 h. Preferably, this standard is met for a building insulation product board or roll having a density of from 5 to 70 kg/m3 and
manufactured using a non-cured binder composition comprising dextrose in an amount of 10 to 50 wt%, preferably 20 to 40 wt%, based on total dry solids of phenol- formaldehyde resol resin and dextrose.
The following examples are intended to illustrate the invention without limiting its scope. Unless indicated otherwise, the solids content (dry matter) is herein determined at 200 °C, 1 hour and expressed as wt.%.
Example 1
A phenol-formaldehyde resin is prepared by reacting formaldehyde and phenol in a molar ratio of 3.7 to 1 in the presence of a catalyst (6 wt% KOH, relative to the amount of phenol) at a reaction temperature of 84°C. The reaction is continued until the acid tolerance of the resin is 4 and most of the phenol is converted. Urea is then added in an amount corresponding to 52 parts by weight of phenol-formaldehyde resin and 48 parts by weight of urea.
Using the urea-modified phenol-formaldehyde resin obtained, a binder is made by addition of ammonium sulphate in equimolar amounts to the catalyst so as to inactivate the catalyst. The final PUF resin has a free formaldehyde content of <0.5%, relative to the solids.
The thus obtained PUF binder is mixed with a dextrose preparation, Sirodex® 431 from Syral (DE value 95), in the amounts indicated in Table 1 below.
Further, the binder is diluted with water to a solids content equal to 22%, and a commercial prehydrolysed aminosiiane is added in an amount corresponding to 0.5% of the solids.
The binder composition obtained is used for production of monolayer roof boards ("A- Tagplade"). Further details are given in the following table.
Table 1 :
The PUF binder content (%) and the dextrose content (%) are weight percentages based on total dry solids of phenol-formaldehyde resol resin and dextrose.
*) The binder content of product (%) is defined as loss-on ignition (LOI) (%) - impregnation oil (%)
Example 2
A commercial resin PF-0415M from Hexion is used for the test. The resin is a phenol- formaldehyde resin modified with urea and ammonia. Free formaldehyde is <0.3% based on the liquid resin. The amount of urea is 28% in relation to the solids content.
The resin is mixed with a dextrose preparation, Sirodex® 431 (DE value 95) from Syral, in the amounts indicated in Table 2 below. For comparison, a glucose syrup, i.e. C Sweet® 01403 (DE value 30) from Cargill, is used in the amount indicated in Table 2 (Sample H).
The composition is diluted to 15% with water to provide a binder composition and further added with 0.5% of a commercial silane of the type pre-hydrolysed amino silane.
The binder composition obtained is used for production of monolayer roof boards (DP-GF). Further details are given in the following table.
Table 2:
The PUF binder content (%) and the dextrose content (%) are weight percentages based on total dry solids of phenol-formaldehyde resol resin and dextrose.
*) Binder content of product (%) = LOI (%) - impregnation oil (%)
Example 3
The formaldehyde emission is measured for the products A-H of Examples 1 and 2 and stated in Table 3 below as formaldehyde emission in μg/m3. The emissions were measured in the climate chamber at the Danish Technological Institute (Tl) according to standard EN 717-1.
The actually determined values are compared with the expected values (assuming a pure dilution effect of dextrose). The value of 80 for 100 parts of PUF is used as a reference and the expected values are calculated with reference to the value. For instance, the 50/50 PUF/dextrose expected value is (50 PUF/100 PUF) x 80 = 40.
Table 3:
As can be seen from Table 3, the use of dextrose results in a significant reduction of the formaldehyde emission of the bonded mineral fibre products which cannot be explained by a pure dilution effect.
Sample H is a comparative sample where the dextrose is substituted with a glucose syrup of low dextrose content having a DE-value of 30. Sample H using this sugar syrup does not show a significant reduction in formaldehyde emission compared to the high dextrose content syrups of Examples A-G. Instead, the measured value for the formaldehyde emission of Sample H is as expected when assuming a pure dilution effect.
Claims
1. A method of reducing the formaldehyde emission of a mineral fibre product bonded with a urea-modified phenol-formaldehyde resol resin-type binder, said method comprising the step of adding dextrose to the binder composition during and/or after preparation of the binder composition but before curing of the binder composition applied to the mineral fibres.
2. The method of claim 1 , wherein dextrose is used as pure dextrose or in the form of a dextrose preparation having a DE equivalent of about 70 to 100, preferably about 90 to 100.
3. The method of claim 1 or 2, wherein phenol is reacted with a molar excess formaldehyde in aqueous solution in a molar ratio of from 1 :2.5 to 1 :6; preferably from 1 :3 to 1 :5, in the presence of a base catalyst.
4. The method of any one of claims 1 to 3, wherein urea is used in an amount of from 20 to 60 wt%, preferably 30 to 50 wt%, based on total dry solids of the phenol- formaldehyde resol resin and urea.
5. The method of any one of claims 1 to 4, wherein dextrose is used in an amount of 15 to 70 wt%, preferably 20 to 50 wt%, based on total dry solids of urea- modified phenol-formaldehyde resol resin and dextrose.
6. A mineral fibre product having reduced formaldehyde emission and bonded with a cured urea-modified phenol-formaldehyde resol resin-type binder composition, the non-cured binder composition comprising dextrose in an amount of 15 wt% or more, and up to 70 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
7. A mineral fibre product according to claim 6, wherein the non-cured binder composition comprises 20 wt% or more, such as 30 wt% or more, 40 wt% or more, or 50 wt% or more, and up to 70 wt% of dextrose.
8. A mineral fibre product according to claim 6 or 7 which satisfies the formaldehyde emission requirements of Finnish Standard RTS- 1.
9. A mineral fibre product according to claim 6 or 7 which satisfies the formaldehyde emission requirements of US Standard CDHS.
10. A mineral fibre product according to claim 6 or 7 which satisfies the formaldehyde emission requirements of Japanese Standard JiS A 19012003 (E).
11. A mineral fibre product according to any one of claims 6 to 10 which is a ceiling tile having a density of from 50 to 220 kg/m3 and has been manufactured using a non-cured binder composition comprising dextrose in an amount of 20 to 70 wt%, preferably 40 to 70 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
12. A mineral fibre product according to any one of claims 6 to 10 which is a roof board having a density of from 100 to 250 kg/m3 and has been manufactured using a non-cured binder composition comprising dextrose in an amount of 20 to 50 wt%, preferably 20 to 40 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
13. A mineral fibre product according to any one of claims 6 to 10 which is a building insulation product board or roll having a density of from 5 to 70 kg/m3 and has been manufactured using a non-cured binder composition comprising dextrose in an amount of 10 to 50 wt%, preferably 20 to 40 wt%, based on total dry solids of phenol-formaldehyde resol resin and dextrose.
14. The use of dextrose as a formaldehyde scavenger in a urea-modified phenol- formaldehyde resol resin-type binder composition for mineral fibre products.
15. The use according to claim 14 wherein the mineral fibre product is selected from among a roof board having a density of from 100 to 250 kg/m3 and having been manufactured using a non-cured binder composition and dextrose in an amount of 20 to 50 wt%, preferably 20 to 40 wt%;
a ceiling tile having a density of from 50 to 220 kg/m3 and having been manufactured using a non-cured binder composition and dextrose in an amount of 20 to 70 wt%, preferably 40 to 70 wt%;
a building insulation product board having a density of from 5 to 70 kg/m3 and having been manufactured using a non-cured binder composition and dextrose in an amount of 10 to 50 wt%, preferably 20 to 40 wt%,
where the weight percentages are based on total dry solids of phenol- formaldehyde resol resin and dextrose.
16. Apparatus for making a mineral fibre product having reduced formaldehyde emission and bonded with a cured urea-modified phenol-formaldehyde resol resin- type binder composition with dextrose added to the binder composition, comprising means for fiberising a mineral melt to mineral fibres,
separate tanks for the binder composition and dextrose;
means for mixing the binder composition and the dextrose,
means for applying the mixture of binder composition and dextrose to the mineral fibres,
a collecting chamber for the mineral fibres with the applied mixed binder composition and dextrose,
a curing oven for curing the mixed binder composition and dextrose applied to the mineral fibres to form a cured web, and
means for confectioning the cured web to a mineral fibre product.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201180058662.9A CN103298859B (en) | 2010-12-06 | 2011-12-05 | The method reducing mineral fiber product Form aldehyde release, and there is the mineral fiber product reducing Form aldehyde release |
| RU2013130735/05A RU2591951C2 (en) | 2010-12-06 | 2011-12-05 | Method of reducing formaldehyde emission from mineral fibrous article and mineral fibrous article with reduced emission of formaldehyde |
| US13/884,758 US20130295813A1 (en) | 2010-12-06 | 2011-12-05 | Method of reducing the formaldehyde emission of a mineral fiber product, and mineral fiber product with reduced formaldehyde emission |
| BR112013013409A BR112013013409A2 (en) | 2010-12-06 | 2011-12-05 | "method of reducing formaldehyde emission from a mineral fiber product, and reduced formaldehyde emission mineral fiber product" |
| EP11790791.5A EP2649116A1 (en) | 2010-12-06 | 2011-12-05 | Method of reducing the formaldehyde emission of a mineral fibre product, and mineral fibre product with reduced formaldehyde emission |
| CA2820559A CA2820559C (en) | 2010-12-06 | 2011-12-05 | Method of reducing the formaldehyde emission of a mineral fibre product, and mineral fibre product with reduced formaldehyde emission |
| US17/643,453 US20220098855A1 (en) | 2010-12-06 | 2021-12-09 | Method of reducing the formaldehyde emission of a mineral fiber product, and mineral fiber product with reduced formaldehyde emission |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10193849.6 | 2010-12-06 | ||
| EP10193849 | 2010-12-06 | ||
| US42090610P | 2010-12-08 | 2010-12-08 | |
| US61/420,906 | 2010-12-08 |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/884,758 A-371-Of-International US20130295813A1 (en) | 2010-12-06 | 2011-12-05 | Method of reducing the formaldehyde emission of a mineral fiber product, and mineral fiber product with reduced formaldehyde emission |
| US17/643,453 Division US20220098855A1 (en) | 2010-12-06 | 2021-12-09 | Method of reducing the formaldehyde emission of a mineral fiber product, and mineral fiber product with reduced formaldehyde emission |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012076462A1 true WO2012076462A1 (en) | 2012-06-14 |
Family
ID=43858484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2011/071732 WO2012076462A1 (en) | 2010-12-06 | 2011-12-05 | Method of reducing the formaldehyde emission of a mineral fibre product, and mineral fibre product with reduced formaldehyde emission |
Country Status (7)
| Country | Link |
|---|---|
| US (2) | US20130295813A1 (en) |
| EP (1) | EP2649116A1 (en) |
| CN (1) | CN103298859B (en) |
| BR (1) | BR112013013409A2 (en) |
| CA (1) | CA2820559C (en) |
| RU (1) | RU2591951C2 (en) |
| WO (1) | WO2012076462A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015042266A1 (en) * | 2013-09-20 | 2015-03-26 | Georgia-Pacific Chemicals Llc | Modified phenolic resins for making composite products |
| EP2884259A1 (en) | 2013-12-11 | 2015-06-17 | Rockwool International A/S | Method for detecting curing of the binder in a mineral fibre product |
| EP2886522A1 (en) | 2013-12-23 | 2015-06-24 | Rockwool International A/S | Method for reducing emissions of formaldehyde and volatile organic compounds (VOCs) in a product made of mineral fibres |
| EP2947117A1 (en) | 2014-05-19 | 2015-11-25 | Rockwool International A/S | Analytical binder for mineral wool products |
| EP3309133A1 (en) | 2013-10-16 | 2018-04-18 | Rockwool International A/S | Man-made vitreous fibres |
| WO2021197628A1 (en) | 2020-04-03 | 2021-10-07 | Rockwool International A/S | Insulation products |
| WO2021197626A1 (en) | 2020-04-03 | 2021-10-07 | Rockwool International A/S | Acoustic products |
| IT202000012220A1 (en) | 2020-05-25 | 2021-11-25 | Stm Tech S R L | NEW BINDER COMPOSITION FOR MULTIPLE APPLICATIONS |
| US20220081553A1 (en) * | 2019-01-11 | 2022-03-17 | Saint-Gobain Isover | Method for manufacturing an insulation product based on mineral wool |
| WO2022144107A1 (en) | 2020-12-30 | 2022-07-07 | Rockwool International A/S | Insulation products |
| WO2024023125A1 (en) | 2022-07-25 | 2024-02-01 | Rockwool A/S | Mineral fibre panel and process of manufacture |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2013010448A (en) * | 2011-03-14 | 2013-11-01 | Rockwool Int | Use of stone fibres. |
| CA2844575C (en) * | 2011-09-06 | 2016-07-05 | Rockwool International A/S | Insulation element for a flat roof or a flat inclined roof, roofing system for a flat roof or a flat inclined roof and method for producing an insulation element |
| GB201120137D0 (en) * | 2011-11-22 | 2012-01-04 | Dynea Oy | Modified binder compositions |
| CN105597261A (en) * | 2015-12-31 | 2016-05-25 | 山东新港企业集团有限公司 | Biomass formaldehyde eliminating agent and preparing method thereof |
| JP7017896B2 (en) * | 2016-09-30 | 2022-02-09 | 群栄化学工業株式会社 | Binder composition for wood board, wood board and its manufacturing method |
| JP2019171746A (en) * | 2018-03-29 | 2019-10-10 | 群栄化学工業株式会社 | Binder composition for particle board, particle board and its manufacturing method |
| KR20220125298A (en) * | 2020-01-09 | 2022-09-14 | 쌩-고벵 이조베르 | How to make insulation products based on mineral wool |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1001788A (en) | 1972-06-08 | 1976-12-14 | Hendrik J. Deuzeman | Resin binder compositions |
| US4014726A (en) * | 1974-03-18 | 1977-03-29 | Owens-Corning Fiberglas Corporation | Production of glass fiber products |
| US4339361A (en) | 1980-07-28 | 1982-07-13 | Fiberglas Canada, Inc. | Phenol-formaldehyde resins extended with carbohydrates for use in binder compositions |
| EP0148050A2 (en) | 1983-11-29 | 1985-07-10 | Isover Saint-Gobain | Resin for a sizing composition, process for its preparation and the resulting sizing composition |
| US5371140A (en) | 1992-11-25 | 1994-12-06 | Georgia-Pacific Resins, Inc. | Emulsifiable phenolic resole resin |
| WO1996026164A1 (en) | 1995-02-21 | 1996-08-29 | Rockwool Lapinus B.V. | Method for manufacturing a mineral wool product |
| US5795934A (en) | 1997-05-20 | 1998-08-18 | Georgia-Pacific Resins, Jr. | Method for preparing a urea-extended phenolic resole resin stabilized with an alkanolamine |
| EP0889981A1 (en) | 1996-03-25 | 1999-01-13 | Rockwool International A/S | Process and apparatus for the production of a mineral fibreboard |
| WO1999003906A1 (en) | 1997-07-15 | 1999-01-28 | Isover Saint-Gobain | Phenolic resin for glue sizing composition, preparation method and glue sizing composition containing same |
| EP1084167A1 (en) | 1998-05-18 | 2001-03-21 | Rockwool International A/S | Stabilized aqueous phenolic binder for mineral wool and production of mineral wool products |
| EP1456444A1 (en) | 2001-12-21 | 2004-09-15 | Rockwool International A/S | Mineral fibre batts and their production |
| WO2006136614A1 (en) | 2005-06-24 | 2006-12-28 | Saint-Gobain Isover | Method for producing bonded mineral wool and binder therefor |
| DE102005063381A1 (en) * | 2005-11-28 | 2007-05-31 | Saint-Gobain Isover G+H Ag | Production of formaldehyde-free bound mineral wool or glass wool for e.g. insulating board uses aqueous curable phenol-formaldehyde resin binder dispersion containing hydroxy(alkyl)amine or diamine and activated silane |
| WO2008127936A2 (en) | 2007-04-13 | 2008-10-23 | Knauf Insulation Gmbh | Composite maillard-resole binders |
| WO2009136106A2 (en) | 2008-04-11 | 2009-11-12 | Saint-Gobain Isover | Sizing composition for mineral fibers and resulting products |
| EP2230222A1 (en) * | 2009-03-19 | 2010-09-22 | Rockwool International A/S | Aqueous binder composition for mineral fibres |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5837621A (en) * | 1995-04-25 | 1998-11-17 | Johns Manville International, Inc. | Fire resistant glass fiber mats |
| US20030044566A1 (en) * | 2001-09-06 | 2003-03-06 | Certainteed Corporation | Insulation containing a mixed layer of textile fibers and of natural fibers, and process for producing the same |
| FR2910481B1 (en) * | 2006-12-22 | 2009-02-06 | Saint Gobain Isover Sa | SIZING COMPSITION FOR MINERAL FIBERS COMPRISING A PHENOLIC RESIN, AND RESULTING PRODUCTS |
| FR2964105B1 (en) * | 2010-08-27 | 2012-09-28 | Saint Gobain Isover | PHENOLIC RESIN, PROCESS FOR PREPARATION, SIZING COMPOSITION FOR MINERAL FIBERS, AND RESULTING PRODUCT. |
-
2011
- 2011-12-05 US US13/884,758 patent/US20130295813A1/en not_active Abandoned
- 2011-12-05 RU RU2013130735/05A patent/RU2591951C2/en active
- 2011-12-05 WO PCT/EP2011/071732 patent/WO2012076462A1/en active Application Filing
- 2011-12-05 CA CA2820559A patent/CA2820559C/en active Active
- 2011-12-05 BR BR112013013409A patent/BR112013013409A2/en not_active IP Right Cessation
- 2011-12-05 CN CN201180058662.9A patent/CN103298859B/en active Active
- 2011-12-05 EP EP11790791.5A patent/EP2649116A1/en active Pending
-
2021
- 2021-12-09 US US17/643,453 patent/US20220098855A1/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1001788A (en) | 1972-06-08 | 1976-12-14 | Hendrik J. Deuzeman | Resin binder compositions |
| US4014726A (en) * | 1974-03-18 | 1977-03-29 | Owens-Corning Fiberglas Corporation | Production of glass fiber products |
| US4339361A (en) | 1980-07-28 | 1982-07-13 | Fiberglas Canada, Inc. | Phenol-formaldehyde resins extended with carbohydrates for use in binder compositions |
| EP0148050A2 (en) | 1983-11-29 | 1985-07-10 | Isover Saint-Gobain | Resin for a sizing composition, process for its preparation and the resulting sizing composition |
| US5371140A (en) | 1992-11-25 | 1994-12-06 | Georgia-Pacific Resins, Inc. | Emulsifiable phenolic resole resin |
| WO1996026164A1 (en) | 1995-02-21 | 1996-08-29 | Rockwool Lapinus B.V. | Method for manufacturing a mineral wool product |
| EP0810981A1 (en) | 1995-02-21 | 1997-12-10 | Rockwool Lapinus B.V. | Method for manufacturing a mineral wool product |
| EP0889981A1 (en) | 1996-03-25 | 1999-01-13 | Rockwool International A/S | Process and apparatus for the production of a mineral fibreboard |
| US5795934A (en) | 1997-05-20 | 1998-08-18 | Georgia-Pacific Resins, Jr. | Method for preparing a urea-extended phenolic resole resin stabilized with an alkanolamine |
| WO1999003906A1 (en) | 1997-07-15 | 1999-01-28 | Isover Saint-Gobain | Phenolic resin for glue sizing composition, preparation method and glue sizing composition containing same |
| EP1084167A1 (en) | 1998-05-18 | 2001-03-21 | Rockwool International A/S | Stabilized aqueous phenolic binder for mineral wool and production of mineral wool products |
| EP1456444A1 (en) | 2001-12-21 | 2004-09-15 | Rockwool International A/S | Mineral fibre batts and their production |
| WO2006136614A1 (en) | 2005-06-24 | 2006-12-28 | Saint-Gobain Isover | Method for producing bonded mineral wool and binder therefor |
| DE102005063381A1 (en) * | 2005-11-28 | 2007-05-31 | Saint-Gobain Isover G+H Ag | Production of formaldehyde-free bound mineral wool or glass wool for e.g. insulating board uses aqueous curable phenol-formaldehyde resin binder dispersion containing hydroxy(alkyl)amine or diamine and activated silane |
| WO2008127936A2 (en) | 2007-04-13 | 2008-10-23 | Knauf Insulation Gmbh | Composite maillard-resole binders |
| WO2009136106A2 (en) | 2008-04-11 | 2009-11-12 | Saint-Gobain Isover | Sizing composition for mineral fibers and resulting products |
| EP2230222A1 (en) * | 2009-03-19 | 2010-09-22 | Rockwool International A/S | Aqueous binder composition for mineral fibres |
Non-Patent Citations (1)
| Title |
|---|
| IARC MONOGRAPH ON FORMALDEHYDE, vol. 88, 2006 |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015042266A1 (en) * | 2013-09-20 | 2015-03-26 | Georgia-Pacific Chemicals Llc | Modified phenolic resins for making composite products |
| EP3309133A1 (en) | 2013-10-16 | 2018-04-18 | Rockwool International A/S | Man-made vitreous fibres |
| US10370285B2 (en) | 2013-10-16 | 2019-08-06 | Rockwool International A/S | Man-made vitreous fibres |
| EP2884259A1 (en) | 2013-12-11 | 2015-06-17 | Rockwool International A/S | Method for detecting curing of the binder in a mineral fibre product |
| US9976958B2 (en) | 2013-12-11 | 2018-05-22 | Rockwool International A/S | Method for detecting curing of the binder in a mineral fiber product |
| EP2886522A1 (en) | 2013-12-23 | 2015-06-24 | Rockwool International A/S | Method for reducing emissions of formaldehyde and volatile organic compounds (VOCs) in a product made of mineral fibres |
| EP2947117A1 (en) | 2014-05-19 | 2015-11-25 | Rockwool International A/S | Analytical binder for mineral wool products |
| WO2015177163A1 (en) | 2014-05-19 | 2015-11-26 | Rockwool International A/S | Analytical binder for mineral wool products |
| US20220081553A1 (en) * | 2019-01-11 | 2022-03-17 | Saint-Gobain Isover | Method for manufacturing an insulation product based on mineral wool |
| WO2021197626A1 (en) | 2020-04-03 | 2021-10-07 | Rockwool International A/S | Acoustic products |
| WO2021197628A1 (en) | 2020-04-03 | 2021-10-07 | Rockwool International A/S | Insulation products |
| IT202000012220A1 (en) | 2020-05-25 | 2021-11-25 | Stm Tech S R L | NEW BINDER COMPOSITION FOR MULTIPLE APPLICATIONS |
| WO2021239650A1 (en) | 2020-05-25 | 2021-12-02 | Stm Technologies S.R.L. | New binding composition for several applications |
| WO2022144107A1 (en) | 2020-12-30 | 2022-07-07 | Rockwool International A/S | Insulation products |
| WO2022144106A1 (en) | 2020-12-30 | 2022-07-07 | Rockwool International A/S | Acoustic products |
| WO2024023125A1 (en) | 2022-07-25 | 2024-02-01 | Rockwool A/S | Mineral fibre panel and process of manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2013130735A (en) | 2015-01-20 |
| RU2591951C2 (en) | 2016-07-20 |
| CN103298859B (en) | 2016-08-10 |
| CN103298859A (en) | 2013-09-11 |
| US20220098855A1 (en) | 2022-03-31 |
| EP2649116A1 (en) | 2013-10-16 |
| CA2820559A1 (en) | 2012-06-14 |
| BR112013013409A2 (en) | 2016-09-06 |
| CA2820559C (en) | 2019-11-12 |
| US20130295813A1 (en) | 2013-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20220098855A1 (en) | Method of reducing the formaldehyde emission of a mineral fiber product, and mineral fiber product with reduced formaldehyde emission | |
| CA2805563C (en) | Bonded mineral fibre product having high fire and punking resistance | |
| EP2059118B1 (en) | Aqueous binder composition for mineral fibres | |
| KR101838974B1 (en) | Phenolic resin, method for preparing same, sizing composition for mineral fibers and resulting product | |
| CA2842237C (en) | Urea-modified binder for mineral fibres | |
| JP6092851B2 (en) | Formaldehyde-free sizing composition for fibers, especially mineral fibers, and resulting products | |
| JP6625554B2 (en) | Sizing composition based on non-reducing sugar and hydrogenated sugar, and resulting insulating product | |
| EP2785809B1 (en) | Aqueous binder composition | |
| KR20090077774A (en) | Phenolic resin, preparation method, sizing composition for mineral fibres and resulting products | |
| KR101456163B1 (en) | Glue composition for mineral fibres containing a phenolic resin, and resulting products | |
| WO2012046761A1 (en) | Binder for production of inorganic fiber product, and process for production of inorganic fiber product | |
| RU2566777C2 (en) | Adhesive composition for mineral wool containing non-reducing sugar and metal salt and inorganic acid and insulation materials made therefrom | |
| DK2697327T3 (en) | ADHESIVE COMPOSITION FOR MANUFACTURING FIRE-RESISTANT MINERAL WOOL AND INSULATION PRODUCT | |
| WO2017036843A1 (en) | Mineral wool product | |
| US20140113123A1 (en) | Binder for mineral and/or organic fiber mat, and products obtained | |
| JP2024504004A (en) | solid binder | |
| JP5328988B6 (en) | Binder for manufacturing inorganic fiber products and method for manufacturing inorganic fiber products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11790791 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2820559 Country of ref document: CA |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 13884758 Country of ref document: US |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2011790791 Country of ref document: EP |
|
| ENP | Entry into the national phase |
Ref document number: 2013130735 Country of ref document: RU Kind code of ref document: A |
|
| REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112013013409 Country of ref document: BR |
|
| ENP | Entry into the national phase |
Ref document number: 112013013409 Country of ref document: BR Kind code of ref document: A2 Effective date: 20130529 |