EP3260589A1 - Needle-punching aid to be used in the production of needle-punched felts of mineral wool, and method of manufacturing needle-punched felts - Google Patents
Needle-punching aid to be used in the production of needle-punched felts of mineral wool, and method of manufacturing needle-punched felts Download PDFInfo
- Publication number
- EP3260589A1 EP3260589A1 EP17176317.0A EP17176317A EP3260589A1 EP 3260589 A1 EP3260589 A1 EP 3260589A1 EP 17176317 A EP17176317 A EP 17176317A EP 3260589 A1 EP3260589 A1 EP 3260589A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- needle
- graphite
- punching
- aid
- punched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004080 punching Methods 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000011490 mineral wool Substances 0.000 title description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002557 mineral fiber Substances 0.000 claims abstract description 8
- 239000011435 rock Substances 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims abstract 2
- 239000002893 slag Substances 0.000 claims abstract 2
- 239000006185 dispersion Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002671 adjuvant Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- -1 siloxanes Chemical class 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000004533 oil dispersion Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims 1
- 239000000080 wetting agent Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 description 29
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 8
- 235000019256 formaldehyde Nutrition 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 230000036541 health Effects 0.000 description 5
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NBXMJDVWESETMK-UHFFFAOYSA-N acetaldehyde Chemical compound CC=O.CC=O NBXMJDVWESETMK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- LCDFWRDNEPDQBV-UHFFFAOYSA-N formaldehyde;phenol;urea Chemical compound O=C.NC(N)=O.OC1=CC=CC=C1 LCDFWRDNEPDQBV-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- D04H1/44—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—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 the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of 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
- D04H1/42—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
- D04H18/00—Needling machines
- D04H18/02—Needling machines with needles
-
- 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
- D04H3/002—Inorganic yarns or filaments
Definitions
- the present invention relates to a needle-punching aid to be used in the production of needle-punched felts of mineral wool, and to a method of manufacturing needle-punched felts.
- Inorganic mineral fibers are manufactured by drawing, centrifugation, blowing or centrifugation/blowing processes of molten mineral masses.
- the resulting mat has poor mechanical and structural properties which impair the possible applications thereof as sound and heat insulator, fire-resistant material, filtering medium.
- mineral wool mats can be impregnated with organic resins, for example based on phenol-formaldehyde-urea, acrylates, natural or other starches (generally defined as ligands) which are meant to form junction points between the felt fibers, thus imparting strength and elasticity.
- organic resins for example based on phenol-formaldehyde-urea, acrylates, natural or other starches (generally defined as ligands) which are meant to form junction points between the felt fibers, thus imparting strength and elasticity.
- This process involves obtaining the physical interconnection of the fibers of the mats by mechanical twisting, which mechanically orients the fibers and fastens them together.
- Needle-punched felts are a combination of mineral fibers mechanically interconnected to form a non-woven fabric which does not contain any chemical binder. They provide an excellent and high thermal insulation and thermal protection and can be safely used without changing properties at the following temperatures: fiber C up to 500°C, fiber E up to 650°C, rock wool fiber up to 700°C, silica fiber up to 800°C, ceramic fiber up to 1000°C.
- Mineral fibers are however characterized by high fragility, and the mechanical stress induced by the action of the needles causes the fracture and the consequent breakage of the fibers, once again obtaining a product with inadequate mechanical properties.
- Another drawback of the needle-punching process is the production of a fine material which inevitably increases the dustiness of the article itself.
- the needle-punching process is therefore carried out by adding a so-called "needle-punching aid" on the fiber, i.e. a substance having an essentially lubricant function which is intended to improve the tribological properties of the system by reducing the friction between the needle and the surface of the fibers and thus limiting the breakage of the fibers themselves.
- a needle-punching aid i.e. a substance having an essentially lubricant function which is intended to improve the tribological properties of the system by reducing the friction between the needle and the surface of the fibers and thus limiting the breakage of the fibers themselves.
- the use of the needle-punching aid reduces the formation of dust and fine material, thereby reducing the emission thereof when using and handling the felt.
- the needle-punching aid is usually applied on the fibers output from the drawing machine using sprayers.
- the needle-punching aid should have low viscosity and low surface tension in order to facilitate the diffusion on the fibers.
- the aid should have a high viscosity to allow the weaving of the fibers and the stabilizing action.
- the needle-punching aids are based on mineral or natural oils, fatty acid derivatives, halogenated polyethers, fluorinated polyethers, fluoropolymers and mixtures thereof, and are in the form of emulsions, aqueous microemulsions and dispersions, solutions.
- the use of natural and mineral oils as a needle-punching aid requires the emulsification or dispersion in water thereof before use.
- particularly effective surfactants are generally used, such as ethoxylated or propoxylated alcohols and phenols, sorbitan esters, alkyl polyglucosides, phosphate esters.
- a drawback of these agents is the easy thermal decomposition when exposed to temperatures above 200°C.
- perfluoropolymers such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene polymers (FEP), polyvinylidene fluoride (PVDF) or fluoroelastomers such as vinylidene fluoride (VDF) and hexafluoropropylene copolymers, vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene terpolymers are applied as aqueous dispersion to substrates in order to obtain composites which are flexible and not brittle and show a low friction coefficient.
- PTFE polytetrafluoroethylene
- FEP fluorinated ethylene propylene polymers
- PVDF polyvinylidene fluoride
- VDF fluoroelastomers
- VDF vinylidene fluoride
- hexafluoropropylene and tetrafluoroethylene terpolymers are applied as aqueous dispersion to
- perfluoroethylene was produced by emulsion polymerization of tetrafluoroethylene.
- the surfactant of choice for this process was perfluorooctanoic acid ammonium salt.
- the use of PTFE dispersions therefore entailed the inevitable emission of perfluorooctanoic acid and salts thereof.
- the curing process of PTFE is currently carried out using alternative surfactants with a lower impact.
- An important advantage of using last-generation PTFE dispersions or perfluoropolyethers is the production of a fiberglass felt which does not release formaldehyde or PFOA and related compounds even if heated to about 500°C.
- MIC methyl isocyanate
- Methyl isocyanate is a highly toxic chemical and, therefore, very dangerous to human health.
- EP 1022260 proposes, in particular, the use of aqueous emulsions of alkylaryl silicones and diaryl silicones as useful needle-punching aid for mineral wool.
- EP2781635 B1 describes a needle-punching aid which does not release aldehydes (in particular formaldehyde), methyl isocyanate, perfluorooctanoic acid and salts thereof at temperatures above 350°C.
- the proposed needle-punching aid consists of an aqueous dispersion containing one or more perfluoropolyethers, one or more solvents and one or more alkaline metal salts. While this result represents a significant improvement over the prior art, it cannot ensure the absence of fluorinated compound emissions of any nature (including hydrofluoric acid) when the felt is exposed to temperatures greater than or equal to 350°C. It follows that a drawback common to needle-punching aids for the needle-punched felts described in the prior art is the release of toxic or irritant decomposition compounds when exposed to the typical temperatures of ovens, cookers and other domestic and industrial equipment.
- said objects are achieved by a method for manufacturing a needle-punched felt as described in claim 1.
- Graphite is known for its lubricating properties in the solid state, which thus allows to reduce the friction between two surfaces which slide relative to each other without requiring an oil or another liquid medium.
- Graphite consists of hexagonal planes essentially consisting of carbon whose relative distance is considerable and, therefore, the interaction strength between the planes is relatively low.
- the reduction in the friction coefficient is due precisely to this laminar structure in which the layers, held together by weak forces, can slide over each other without offering particular resistance.
- graphite can be used as a needle-punching aid both in solid form (for example in powder form), and in the form of an aqueous dispersion or dispersion in oil.
- Graphite as a needle-punching aid can be applied on the fibers output from the drawing machine by means of sprayers or at any point of the production chain which precedes the mechanical needle-punching step.
- Graphite is characterized by the absence of toxicity and its use both in powder form and as an aqueous dispersion or in solvent base allows to obtain an article which, in use, does not release substances potentially harmful to health in such concentrations as to be a hazard.
- Aqueous graphite dispersions generally consist of at least two phases: a continuous phase, which forms the dispersant, and one or more dispersed phases (dispersed phase consisting of graphite).
- adjuvants may be used in their preparation, including surfactants, dispersants, thickeners and protective colloids. The role of adjuvants is essential not only to ensure adequate stability of the dispersion but also to obtain the rheological characteristics needed to apply the same dispersion by spraying.
- the dispersion may contain a variable amount of graphite from a minimum of 0.05% by weight to a maximum dictated by the rheological characteristics of the dispersion itself which must, however, allow easy application thereof.
- dispersions containing 0.1% - 5% by weight of graphite have optimal rheological characteristics to ensure a uniform spraying process and a degree of fiber surface coverage sufficient to reduce friction.
- Both natural graphite and synthetic graphite may be used, and the graphite particles used may have an average particle size ranging from 0.1 to 500 microns and preferably from 0.1 to 50 microns.
- the viscosity of the aqueous dispersion ranges from 100 to 1000 mPa.s and preferably from 500 to 600 mPa.s.
- a composition was prepared for use as a needle-punching aid by diluting the dispersion TIMREX ® LB 1300 of MERYS GRAPHITE AND CARBON in water.
- the graphite diluted solution was then sprayed onto the glass fibers exiting the drawing machines.
- the fibers were conveyed in an oven heated at 130°C to facilitate evaporation of the water and any low-boiling products.
- the fibers mat thus formed was conveyed to the needle-punching process.
- the felt of mineral wool obtained had an apparent density of about 78 kg/m 3 and a thickness of 25 mm and it was tested by TUV LGA Rheinland at 350°C to verify the release of aldehydes and methyl isocyanate using the ceramic tube furnace method.
- a composition was prepared for use as a needle-punching aid by diluting the dispersion TIMREX ® LB 1300 of MERYS GRAPHITE AND CARBON in water.
- the graphite diluted solution was then sprayed onto the glass fibers exiting the drawing machines.
- the fibers were conveyed in an oven heated at 300°C to facilitate evaporation of the water and any low-boiling products.
- the fibers mat thus formed was conveyed to the needle-punching process.
- the felt of mineral wool obtained had an apparent density of about 78 kg/m 3 and a thickness of 25 mm and it was tested by TUV LGA Rheinland at 350°C to verify the release of aldehydes and methyl isocyanate using the ceramic tube furnace method.
- the felt of mineral wool obtained had density and thickness similar to those reported in the previous examples and was tested by TUV Rheinland LGA Products at 350°C for the release of aldehydes and methyl isocyanate using the ceramic tube furnace method.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Inorganic Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
- The present invention relates to a needle-punching aid to be used in the production of needle-punched felts of mineral wool, and to a method of manufacturing needle-punched felts.
- Inorganic mineral fibers are manufactured by drawing, centrifugation, blowing or centrifugation/blowing processes of molten mineral masses.
- The resulting mat has poor mechanical and structural properties which impair the possible applications thereof as sound and heat insulator, fire-resistant material, filtering medium.
- In order to improve the structural and mechanical properties thereof, mineral wool mats can be impregnated with organic resins, for example based on phenol-formaldehyde-urea, acrylates, natural or other starches (generally defined as ligands) which are meant to form junction points between the felt fibers, thus imparting strength and elasticity.
- However, this solution, which is optimal in low temperature applications (for example in the field of thermal insulation in construction), cannot be implemented in applications involving the use under conditions of high temperatures, such as in home stoves and for communities, junction boxes, heaters, insulation of equipment.
- One of the basic requirements demanded for the inorganic fiber felts used for such applications is the substantial chemical stability at high temperatures to prevent or minimize the emission of substances which are potentially harmful to health. If the above-listed applications involve exposing the insulating felt to temperatures above 200°C-250°C, any organic binder would undergo an inevitable degradation process resulting in the formation of potentially toxic by-products, such as nitrogen oxides, isocyanates and aldehydes.
- In order to avoid these drawbacks, a so-called "needle-punching" process is used, which allows to provide felts with satisfactory mechanical properties without having to resort to the use of organic binders.
- This process involves obtaining the physical interconnection of the fibers of the mats by mechanical twisting, which mechanically orients the fibers and fastens them together.
- The mechanical interconnection and the relevant link between the fibers are produced by needles with barbs which alternately pass through the mat. Needle-punched felts are a combination of mineral fibers mechanically interconnected to form a non-woven fabric which does not contain any chemical binder. They provide an excellent and high thermal insulation and thermal protection and can be safely used without changing properties at the following temperatures: fiber C up to 500°C, fiber E up to 650°C, rock wool fiber up to 700°C, silica fiber up to 800°C, ceramic fiber up to 1000°C.
- Mineral fibers are however characterized by high fragility, and the mechanical stress induced by the action of the needles causes the fracture and the consequent breakage of the fibers, once again obtaining a product with inadequate mechanical properties. Another drawback of the needle-punching process is the production of a fine material which inevitably increases the dustiness of the article itself.
- In order to obviate such a drawback, the needle-punching process is therefore carried out by adding a so-called "needle-punching aid" on the fiber, i.e. a substance having an essentially lubricant function which is intended to improve the tribological properties of the system by reducing the friction between the needle and the surface of the fibers and thus limiting the breakage of the fibers themselves.
- With the needle-punching aid, when the needle penetrates inside the mat, it slides freely on the surface of the fibers, twisting them without breaking them.
- Additionally, the use of the needle-punching aid reduces the formation of dust and fine material, thereby reducing the emission thereof when using and handling the felt.
- The needle-punching aid is usually applied on the fibers output from the drawing machine using sprayers. In this step, the needle-punching aid should have low viscosity and low surface tension in order to facilitate the diffusion on the fibers. On the contrary, when the felt is subject to a needle-punching process, the aid should have a high viscosity to allow the weaving of the fibers and the stabilizing action.
- In order to take into account all the requirements mentioned above, the needle-punching aids are based on mineral or natural oils, fatty acid derivatives, halogenated polyethers, fluorinated polyethers, fluoropolymers and mixtures thereof, and are in the form of emulsions, aqueous microemulsions and dispersions, solutions.
- Although some of the needle-punching aids described in the prior art have limited the emission of substances which are potentially harmful to health, the release of aldehydes (in particular formaldehyde), isocyanates (in particular methyl isocyanate) and fluorinated substances (in particular perfluorinated and polyfluorinated acids, perfluoroisopropene, hydrofluoric acid) is not completely excluded.
- Moreover, the use of natural and mineral oils as a needle-punching aid requires the emulsification or dispersion in water thereof before use. In order to obtain a sufficiently homogeneous and stable emulsion or dispersion, particularly effective surfactants are generally used, such as ethoxylated or propoxylated alcohols and phenols, sorbitan esters, alkyl polyglucosides, phosphate esters.
- A drawback of these agents is the easy thermal decomposition when exposed to temperatures above 200°C.
- Another approach is based on the use of aqueous dispersions of fluoropolymers. According to
US 4654235 , perfluoropolymers such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene polymers (FEP), polyvinylidene fluoride (PVDF) or fluoroelastomers such as vinylidene fluoride (VDF) and hexafluoropropylene copolymers, vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene terpolymers are applied as aqueous dispersion to substrates in order to obtain composites which are flexible and not brittle and show a low friction coefficient. - Historically, perfluoroethylene (PTFE) was produced by emulsion polymerization of tetrafluoroethylene. The surfactant of choice for this process was perfluorooctanoic acid ammonium salt. The use of PTFE dispersions therefore entailed the inevitable emission of perfluorooctanoic acid and salts thereof. As a result of the growing concern associated with the toxicity and persistence features and bioaccumulation of perfluorooctanoic acid and salts thereof, the curing process of PTFE is currently carried out using alternative surfactants with a lower impact.
- An important advantage of using last-generation PTFE dispersions or perfluoropolyethers is the production of a fiberglass felt which does not release formaldehyde or PFOA and related compounds even if heated to about 500°C.
- In the reference cited, however, no reference is made to the possible emissions of methyl isocyanate (MIC) which may result, at high temperatures, from organic precursors and from the ammonium ion present in the needle-punching aid. Methyl isocyanate is a highly toxic chemical and, therefore, very dangerous to human health.
-
EP 1022260 proposes, in particular, the use of aqueous emulsions of alkylaryl silicones and diaryl silicones as useful needle-punching aid for mineral wool. - These emulsions are claimed for releasing amounts of formaldehyde of less than 50 mg/kg of mineral fiber when exposed to temperatures of 350°C. Although this result represents a considerable improvement as regards the use of mineral oil-based emulsions, it does not conform to the requirements of aldehydes emissions set forth in the LGA certification "tested for contaminants".
-
EP2781635 B1 describes a needle-punching aid which does not release aldehydes (in particular formaldehyde), methyl isocyanate, perfluorooctanoic acid and salts thereof at temperatures above 350°C. The proposed needle-punching aid consists of an aqueous dispersion containing one or more perfluoropolyethers, one or more solvents and one or more alkaline metal salts. While this result represents a significant improvement over the prior art, it cannot ensure the absence of fluorinated compound emissions of any nature (including hydrofluoric acid) when the felt is exposed to temperatures greater than or equal to 350°C. It follows that a drawback common to needle-punching aids for the needle-punched felts described in the prior art is the release of toxic or irritant decomposition compounds when exposed to the typical temperatures of ovens, cookers and other domestic and industrial equipment. - It is the object of the invention to prepare a needle-punching aid for producing a felt which does not release significant amounts of toxic or irritating decomposition product, especially formaldehyde, methyl isocyanate, fluorine compounds of any kind (including hydrofluoric acid) at temperatures greater than or equal to 350°C.
- According to the invention, said objects are achieved by a method for manufacturing a needle-punched felt as described in claim 1.
- The present invention will be further described hereinafter in a preferred embodiment thereof, in two illustrative and non-limiting examples.
- Graphite is known for its lubricating properties in the solid state, which thus allows to reduce the friction between two surfaces which slide relative to each other without requiring an oil or another liquid medium. Graphite consists of hexagonal planes essentially consisting of carbon whose relative distance is considerable and, therefore, the interaction strength between the planes is relatively low.
- The reduction in the friction coefficient is due precisely to this laminar structure in which the layers, held together by weak forces, can slide over each other without offering particular resistance.
- For the applications of the present invention, graphite can be used as a needle-punching aid both in solid form (for example in powder form), and in the form of an aqueous dispersion or dispersion in oil.
- Graphite as a needle-punching aid can be applied on the fibers output from the drawing machine by means of sprayers or at any point of the production chain which precedes the mechanical needle-punching step.
- Graphite is characterized by the absence of toxicity and its use both in powder form and as an aqueous dispersion or in solvent base allows to obtain an article which, in use, does not release substances potentially harmful to health in such concentrations as to be a hazard.
- Aqueous graphite dispersions generally consist of at least two phases: a continuous phase, which forms the dispersant, and one or more dispersed phases (dispersed phase consisting of graphite). In order to obviate the natural destabilization and coalescence tendency of graphite dispersions, adjuvants may be used in their preparation, including surfactants, dispersants, thickeners and protective colloids. The role of adjuvants is essential not only to ensure adequate stability of the dispersion but also to obtain the rheological characteristics needed to apply the same dispersion by spraying. When graphite is used in the form of an aqueous dispersion, this can be applied by spraying in a uniform and homogeneous manner on the surface of the fibers output from the drawing chamber. The dispersion may contain a variable amount of graphite from a minimum of 0.05% by weight to a maximum dictated by the rheological characteristics of the dispersion itself which must, however, allow easy application thereof. For example, dispersions containing 0.1% - 5% by weight of graphite have optimal rheological characteristics to ensure a uniform spraying process and a degree of fiber surface coverage sufficient to reduce friction.
- If graphite dispersions containing organic adjuvants are used, these can lead to the formation of by-products potentially hazardous to health once the article is in use at high temperatures. To prevent the emission of substances resulting from the thermal decomposition of additives in operation, it is possible to introduce, after the fiber spraying step, a heating step at temperatures above 150°C for a time sufficient to remove, by thermal decomposition, any organic residues employed as adjuvants for the preparation of the dispersion.
- By using graphite or dispersions thereof as a needle-punching aid, formaldehyde and methyl isocyanate are detected, in the finished article, in lower concentration, at 10 mg/kg of glass fiber and 5 mg/kg of rock fiber, respectively, as regards formaldehyde, and 0.02 mg/kg of fiber as regards formaldehyde at temperatures up to 350°C. In addition, the same felts, when exposed to the above working conditions, do not emit any fluorinated substance or of an organic (such as polyfluorinated acids, perfluoroisopropene) or inorganic (hydrofluoric acid and salts thereof) nature.
- Both natural graphite and synthetic graphite may be used, and the graphite particles used may have an average particle size ranging from 0.1 to 500 microns and preferably from 0.1 to 50 microns. The viscosity of the aqueous dispersion ranges from 100 to 1000 mPa.s and preferably from 500 to 600 mPa.s. Obtaining a uniform distribution of the graphite on the fiber surface is crucial in order to reduce the mutual friction between the fibers and thus promote their mechanical intertwining, thus reducing fractures and consequent increase of dustiness.
- The use of other additives such as stabilizer oils, silicones, dyes can be contemplated with the application of graphite in powder form and as an aqueous or oil dispersion.
- The following examples describe more in detail the invention without limiting the scope thereof.
- A composition was prepared for use as a needle-punching aid by diluting the dispersion TIMREX® LB 1300 of MERYS GRAPHITE AND CARBON in water.
- 35.00 kg of the dispersion TIMREX® LB 1300 were diluted with 290 kg water to obtain a solution having a graphite content of about 2.9% (by weight).
- The graphite diluted solution was then sprayed onto the glass fibers exiting the drawing machines. The fibers were conveyed in an oven heated at 130°C to facilitate evaporation of the water and any low-boiling products. The fibers mat thus formed was conveyed to the needle-punching process.
- The felt of mineral wool obtained had an apparent density of about 78 kg/m3 and a thickness of 25 mm and it was tested by TUV LGA Rheinland at 350°C to verify the release of aldehydes and methyl isocyanate using the ceramic tube furnace method.
- The release of aldehydes and methyl isocyanate (MIC) from the felt of mineral wool complied with the requirements for aldehydes and MIC according to the "LGA-schadstoffgepruft" certification (LGA-tested for contaminants). The test results are shown in Table 1.
- In addition, the hydrofluoric acid emissions determined by combustion with Wickbold method at 500°C followed by liquid ion chromatography according to DIN EN ISO 10304-1 remained below the detection limit.
Table 1. Test report for emissions at 350°C from mineral wool felt as described in example 1. Contaminant Unit of measure Value Limit value for the glass wool relating to the "LGA tested for contaminants" certification Methanal (formaldehyde) mg/kg 7.2 ≤ 10 Ethanal (acetaldehyde) mg/kg 2.9 ≤ 10 Propanal mg/kg 0.5 Total: ≤ 10 Butyraldehyde mg/kg 0.2 Pentanal mg/kg <0.1 Methyl isocyanate (MIC) mg/kg <0.01 ≤0.02 - A composition was prepared for use as a needle-punching aid by diluting the dispersion TIMREX® LB 1300 of MERYS GRAPHITE AND CARBON in water.
- 29.00 kg of the dispersion TIMREX® LB 1300 of IMERYS GRAPHITE AND CARBON were diluted with 290 kg water to obtain a solution having a graphite content of about 2.5% (by weight).
- The graphite diluted solution was then sprayed onto the glass fibers exiting the drawing machines. The fibers were conveyed in an oven heated at 300°C to facilitate evaporation of the water and any low-boiling products. The fibers mat thus formed was conveyed to the needle-punching process.
- The felt of mineral wool obtained had an apparent density of about 78 kg/m3 and a thickness of 25 mm and it was tested by TUV LGA Rheinland at 350°C to verify the release of aldehydes and methyl isocyanate using the ceramic tube furnace method.
- The felt of mineral wool obtained had density and thickness similar to those reported in the previous examples and was tested by TUV Rheinland LGA Products at 350°C for the release of aldehydes and methyl isocyanate using the ceramic tube furnace method.
- The release of aldehydes and methyl isocyanate (MIC) from the felt of mineral wool complied with the requirements for aldehydes and MIC according to the "LGA-schadstoffgepruft" certification (LGA-tested for contaminants). The test results are shown in Table 3.
- In addition, the hydrofluoric acid emissions determined by combustion with Wickbold method at 500°C followed by liquid ion chromatography according to DIN EN ISO 10304-1 remained below the detection limit.
Table 2. Test report for emissions at 350°C from mineral wool felt as described in example 2. Contaminant Unit of measure Value Limit value for the glass wool relating to the "LGA tested for contaminants" certification Methanal (formaldehyde) mg/kg 1.8 ≤ 10 Ethanal (acetaldehyde) mg/kg 1.7 ≤ 10 Propanal mg/kg 0.17 Total: ≤ 10 Butyraldehyde mg/kg 0.12 Pentanal mg/kg <0.1 Methyl isocyanate (MIC) mg/kg <0.01 ≤ 0.02 - From the foregoing it is apparent that the felt needle-punched with the needle-punching aid according to the invention has the following advantages, in particular:
- it complies with the emission requirements for aldehydes and MIC determined by the Criteria Catalog "LGA-tested for contaminants" for mineral fibers in cookers and ovens (2PfG S 0079/03:12),
- it has an emission of hydrofluoric acid below the combustion detection limit with Wickbold method at 500°C and determination with liquid ion chromatography according to DIN EN ISO 10304-1,
- it has an emission of PFOA, PFOS and other perfluorinated acids below the detection limit for the determination by LC-MS/MS even after heating at temperatures up to 500°C.
Claims (9)
- A method for manufacturing a mechanically needle-punched felt consisting of mineral fibers such as glass, rock, slag, characterized in that the mechanical needle-punching step is carried out with a needle-punching aid consisting of graphite.
- A method according to claim 1, characterized in that graphite is applied in powder form.
- A method according to claim 1, characterized in that graphite is applied in aqueous dispersion.
- A method according to claim 1, characterized in that graphite is applied in oil dispersion.
- A method according to claim 3, characterized in that the aqueous dispersion comprises a dispersed phase (graphite), a continuous phase (water), and any adjuvants such as surfactants, wetting agents, dispersing agents, thickeners and protective colloids, silicones, siloxanes and silanes, stabilizer oils, dyes.
- A method according to claim 1, characterized in that the felt is heated before or after the needle-punching step at temperatures above 150°C.
- A needle-punching aid for implementing the method according to claim 1, characterized in that it consists of graphite having dimensions in the range from 0.1 to 500 microns.
- An aid according to claim 7, characterized in that the dimensions of the graphite particles are in the range from 0.1 to 50 microns.
- A needle-punching aid for producing needle-punched felts according to claim 7, characterized in that the graphite content of the aid is in the range from 0.05% to 5% referred to the dry weight of the mineral fiber treated.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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SI201730099T SI3260589T1 (en) | 2016-06-24 | 2017-06-16 | Needle-punching aid to be used in the production of needle-punched felts of mineral wool, and method of manufacturing needle-punched felts |
PL17176317T PL3260589T3 (en) | 2016-06-24 | 2017-06-16 | Needle-punching aid to be used in the production of needle-punched felts of mineral wool, and method of manufacturing needle-punched felts |
Applications Claiming Priority (1)
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ITUA2016A004647A ITUA20164647A1 (en) | 2016-06-24 | 2016-06-24 | ANGLING ASSIST TO BE USED IN THE PRODUCTION OF FERTILIZED FELT IN MINERAL WOOL AND A METHOD FOR REALIZING FELT AGUGLIATI |
Publications (2)
Publication Number | Publication Date |
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EP3260589A1 true EP3260589A1 (en) | 2017-12-27 |
EP3260589B1 EP3260589B1 (en) | 2019-07-10 |
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EP17176317.0A Active EP3260589B1 (en) | 2016-06-24 | 2017-06-16 | Needle-punching aid to be used in the production of needle-punched felts of mineral wool, and method of manufacturing needle-punched felts |
Country Status (4)
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EP (1) | EP3260589B1 (en) |
IT (1) | ITUA20164647A1 (en) |
PL (1) | PL3260589T3 (en) |
SI (1) | SI3260589T1 (en) |
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DE102022126757A1 (en) | 2022-10-13 | 2024-04-18 | Saint-Gobain Isover G+H Aktiengesellschaft | Needle felt and use of a fatty acid amide amine in the manufacture of a needle felt |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2232785A1 (en) * | 1972-07-04 | 1973-10-31 | Bayerische Wollfilzfabriken Kg | Needled felting - of combined mineral and ceramic fibres with lubricant impregnation |
US5057173A (en) * | 1988-10-13 | 1991-10-15 | Grunzweig + Hartmann Ag | Process for the production of needle felt from rock wool |
US5671518A (en) * | 1992-01-24 | 1997-09-30 | Isover Saint-Gobain | Methods for producing a mineral wool needle-felt and a mineral wool product using a thixotropic additive |
EP0819788A2 (en) * | 1996-07-15 | 1998-01-21 | Isover Saint-Gobain | Needling aid for producing needle felts, a needle felt produced by using it, and a method for production thereof |
WO2001038220A1 (en) * | 1999-11-26 | 2001-05-31 | Timcal Ag | Method for producing graphite powder with an increased bulk density |
EP2781635A1 (en) * | 2013-03-18 | 2014-09-24 | EUROFIBRE S.p.A. | Aqueous dispersion used as needling aid for producing needle mineral fiber felts and use of an aqueous dispersion |
-
2016
- 2016-06-24 IT ITUA2016A004647A patent/ITUA20164647A1/en unknown
-
2017
- 2017-06-16 PL PL17176317T patent/PL3260589T3/en unknown
- 2017-06-16 EP EP17176317.0A patent/EP3260589B1/en active Active
- 2017-06-16 SI SI201730099T patent/SI3260589T1/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2232785A1 (en) * | 1972-07-04 | 1973-10-31 | Bayerische Wollfilzfabriken Kg | Needled felting - of combined mineral and ceramic fibres with lubricant impregnation |
US5057173A (en) * | 1988-10-13 | 1991-10-15 | Grunzweig + Hartmann Ag | Process for the production of needle felt from rock wool |
US5671518A (en) * | 1992-01-24 | 1997-09-30 | Isover Saint-Gobain | Methods for producing a mineral wool needle-felt and a mineral wool product using a thixotropic additive |
EP0819788A2 (en) * | 1996-07-15 | 1998-01-21 | Isover Saint-Gobain | Needling aid for producing needle felts, a needle felt produced by using it, and a method for production thereof |
WO2001038220A1 (en) * | 1999-11-26 | 2001-05-31 | Timcal Ag | Method for producing graphite powder with an increased bulk density |
EP2781635A1 (en) * | 2013-03-18 | 2014-09-24 | EUROFIBRE S.p.A. | Aqueous dispersion used as needling aid for producing needle mineral fiber felts and use of an aqueous dispersion |
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SI3260589T1 (en) | 2019-11-29 |
EP3260589B1 (en) | 2019-07-10 |
PL3260589T3 (en) | 2019-12-31 |
ITUA20164647A1 (en) | 2017-12-24 |
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