EP0000056A1 - Incombustible insulating material - Google Patents
Incombustible insulating material Download PDFInfo
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- EP0000056A1 EP0000056A1 EP78100098A EP78100098A EP0000056A1 EP 0000056 A1 EP0000056 A1 EP 0000056A1 EP 78100098 A EP78100098 A EP 78100098A EP 78100098 A EP78100098 A EP 78100098A EP 0000056 A1 EP0000056 A1 EP 0000056A1
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- European Patent Office
- Prior art keywords
- weight
- phenol
- binder
- insulating material
- alkylphenol
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/12—Condensation polymers of aldehydes or ketones
- C04B26/122—Phenol-formaldehyde condensation polymers
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/92—Fire or heat protection feature
- Y10S428/921—Fire or flameproofing
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
Definitions
- the invention relates to non-combustible insulation materials with a long fire resistance and reduced water absorption for construction and insulation purposes from inorganic light particles which are connected to one another by temperature-resistant, highly polymeric organic binders.
- the insulating material contains 0.2 to 4, preferably 0.5 to 2% by weight, based on the mixture, of an alkylphenol / phenol / formaldehyde condensation product as additional binder C '.
- Such phenolic resins based on alkyl phenol act hydro- p hobierend to the insulating materials.
- the insulation materials according to the invention are non-combustible according to DIN 4102 and thus belong to building material class A; with an insulation thickness of 5 cm and planking on both sides with 3 mm asbestos cement, they have a high fire resistance duration and thus belong to resistance class W 90. They have a relatively low density, which is between 80 and 230, preferably between 120 and 180 g / l; this gives them very good thermal insulation properties.
- the inorganic light particles A used have an average particle diameter between 0.05 and 3 mm, preferably between 0.2 and 2 mm. Their bulk density is between 30 and 150, preferably between 40 and 80 g / l.
- Silicate materials are preferably used, such as water-insoluble alkali silicates with an SiO 2: Me 2 O 3 ratio of greater than 4.5: 1 or silicates of the 2nd and 3rd main group of the periodic table. Expanded pearlite or vermiculite are particularly preferred; However, expanded foam glass, fly ash or expanded plaster are also suitable.
- Perlite is a hydraulic aluminum silicate that is derived from rhyolite lava. It contains essentially 70 to 85% Si0 2 , 12 to 14% A1 2 0 3 and 2 to 3% water. Vermiculite is a hydraulic magnesium aluminum silicate with certain structure with a content of 8 to 12% MgO, 60 'to 65% Si0 2 , 6 to 12% A1 2 0 3 and 1 to 4% water.
- the insulation materials can optionally contain up to 40% by weight of fibrous or granular inorganic additives B.
- Fibrous additives improve the elastic modulus of the building materials.
- the fibers should have a length of 2 mm to 3 cm. Glass fibers which are used in amounts of 2 to 10% by weight and rock or mineral wool which are used in amounts of 5 to 30% by weight, based in each case on the total mixture, are preferred.
- Granular additives improve the strength of the building materials.
- the grains should have a diameter of ⁇ 100 / um. Talc or gypsum are preferred, which are used in amounts of 15 to 30% by weight, based on the total amount.
- the particles A and B are connected to one another by 1 to 20, preferably 8 to 20% by weight of a temperature-resistant, organic, high-molecular binder.
- the binders have a limiting temperature according to DIN 53 446 of greater than 100 o C, preferably of more than 150 ° C.
- the limit temperature is the temperature at which the substance in question can be stored in air for 25,000 hours without its properties changing noticeably.
- curable binder precursors are expediently used in the form of aqueous dispersions or solutions which, if appropriate, can contain small amounts of conventional dispersion stabilizers, crosslinking agents, catalysts, leveling agents or other additives.
- Organic polycondensates or poly- Adducts are used which harden at elevated temperatures, possibly in the presence of crosslinking agents or crosslinking catalysts with further condensation or crosslinking to give the high-temperature-resistant high-molecular binder. Since the curing of resins based on alkylphenol should only exceed temperatures of 200 ° C for a short time, binders with low curing temperatures are particularly suitable.
- polyesterimides polyurethanes, polyesters, melamine / formaldehyde resins and in particular phenol / formaldehyde resins are particularly suitable.
- the starting materials can - preferably in the presence of solvents - either be condensed together or pre-condensates can be used, e.g. Diimide dicarboxylic acids from 2 moles of trimellitic anhydride and 1 mole of a diprimeric aromatic amine.
- the polyesterimides are present in the aqueous dispersions in particle form with average particle diameters below 50, preferably below 5 / um. They generally contain 0.01 to 5, preferably 0.1 to 3,% by weight of dispersing aids, in particular high-polymer organic substances containing polar groups, such as, for example, polyvinyl alcohol, cellulose ethers, polyvinylpyrrolidone, polyacrylic acid, partially saponified copolymers of acrylic esters and acrylonitrile ; copolymers of vinyl pyrrolidone and vinyl propionate are preferred. They also contain crosslinking catalysts in amounts of 0.5 to 5% by weight, for example oxotitenates, triethanolamine titanate, titanium lactate or titanium oxalate. They can also contain leveling agents, thickeners, antithioxotropic agents and neutralizing agents. During curing, further condensation and crosslinking of the polyester imides occurs.
- Polyurethanes are also suitable as binders.
- Polyurethanes are polyadducts made from polyisocyanates and hydroxyl-containing polyesters or polyethers. Aqueous dispersions of starting materials forming polyurethanes are described in DT-OS 2 537 207. The raw materials are
- Aromatic polyisocyanates which are capped with a phenol or a lactam are particularly suitable.
- the dispersed particles have a diameter between 0.05 and 2 / ⁇ m; the dispersion again preferably contains dispersing agents. When hardening, the capping agent is split off and the released polyisocyanate can crosslink with the hydroxyl groups of the polyester or polyether with a polyurethane bond.
- Crosslinked polyesters are also suitable, preferably those based on aromatic dicarboxylic acids.
- aqueous dispersions or solutions which contain the uncrosslinked or only slightly crosslinked polyester together with polyols as crosslinking agents. During curing, further condensation occurs with crosslinking.
- Crosslinked melamine / formaldehyde and phenol / formaldehyde resins are also suitable.
- Pre-condensates made of melamine, phenol or cresol with formaldehyde with molecular weights between approximately 400 and 800 are used here.
- Aqueous solutions of phenol / formaldehyde condensates are particularly advantageously used.
- the binders C 'to be added according to the invention are condensation products of an alkylphenol, phenol and formaldehyde. They are produced by base-catalyzed condensations of alkylphenol, phenol and formaldehyde in aqueous solution in the presence of an emulsifier and a protective colloid. A suitable manufacturing process is described, for example, in DT-OS 23 30 815. Alkylphenols having 2 to 12 carbon atoms in the alkyl radical are preferably used, octylphenol and nonylphenol are particularly suitable.
- the molar ratio of phenol to alkylphenol can vary n wide limits between 5: 1 and 1: 5, preferably between 2: 1 and 1: 2;
- the molar ratio of formaldehyde to the sum of phenol + alkylphenol can be higher than in DT-OS 23 30 815, it is preferably between 2.3: 1 and 1.6: 1.
- the method of production is somewhat different, depending on whether they contain fibrous additives or not.
- the light particles are sprayed with an approximately 1 to 50, preferably 2 to 10 percent by weight aqueous dispersion or solution of the binder precursor, the particles being kept in motion in conventional mixing machines. It is a particular advantage of using aqueous binder systems that a particularly fine and uniform distribution of light particles and binder is obtained.
- the product may become mechanical freed from part of the water and then pressed into plates in the moist state in conventional presses at pressures of about 1 to 10 kp / cm 2 . These are then heated further, with further condensation and crosslinking taking place with the formation of the temperature-resistant organic high-molecular binder.
- the fibers are first suspended in water, which contains surface-active substances dissolved as conventional disintegrants, with stirring. Then the binder dispersions or solutions and the light particles are added and mixed vigorously. The majority of the water is sucked off on a sheet former common in the paper industry. After pressing gently, the plate is dried and, if necessary, the crosslinking is carried out.
- the insulation materials according to the invention can be glued with conventional cover layers, such as asbestos cement, plasterboard or metal sheets, and processed into sandwich elements. They are suitable for the production of non-load-bearing walls, ceilings and floors; however, they can also be used to coat load-bearing walls, ceilings and floors or in warehouses or cold stores as a heat-insulating layer that prevents the passage of fire.
- cover layers such as asbestos cement, plasterboard or metal sheets
- 1035 parts of a 14% aqueous solution of polyvinyl 'alcohol are homogenised with 400 parts of water, 288 parts of an ethoxylated octylphenol, and 200 parts of 25% ammonia with stirring Then 846 parts of phenol, 1854 parts of octylphenol (molar ratio of formaldehyde to. Total phenol 2: 1) and 2700 parts of one 40% aqueous solution of formaldehyde was added and heated to reflux with vigorous stirring for about 4 hours. The mixture is then cooled to room temperature with further stirring. A homogeneous, stable dispersion is obtained with a dry content (2 hours at 120 ° C.) of 50%, a viscosity at 20 ° C. of 600 mPas and a pH of 8.0.
- the glued material is compressed in a conventional press apparatus with a pressure of about 2.5 to 3.0 kp / cm 3 to give a compact with a density of 200 g / l and then heated to a temperature of about 150 ° C., the binder hardening .
- a 50 mm thick insulation board shows a water absorption of 5 vol% in the 24 hour immersion test according to DIN 53 428.
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
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- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Building Environments (AREA)
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Abstract
Die Erfindung betriff nichtbrennbare Dämmstoffe mit hoher Feuerwiderstandsdauer und einer Dichte von 80 bis 230 g/1. Sie bestehen aus A. 99 - 80 Gew.% anorganischer Leichtpartikel, vorzugsweise geblähtem Perlit oder Vermiculit, B. 0 - 20 Gew.% faseriger oder körniger anorganischer Zusatzstoffe und C. 1 - 20 Gew.% eines temperaturbeständigen organischen hochmolekularen Bindemittels, vorzugsweise eines Phenol/Formaldehyd- kondensats. Zue Verhinderung der Wasseraufnahme enthalten sie als zusätzliche Bindemittel C' 0,2 - 4 Gew.% eines Alkylphenol/ Phenol/ Formaldehyd- Kondensationsproduktes. Die Dämmstoffe können als lsolier- oder Baumaterial verwendet werden.The invention relates to non-combustible insulating materials with a high fire resistance duration and a density of 80 to 230 g / 1. They consist of A. 99-80% by weight of inorganic light particles, preferably expanded perlite or vermiculite, B. 0-20% by weight of fibrous or granular inorganic additives and C. 1-20% by weight of a temperature-resistant organic high-molecular binder, preferably one Phenol / formaldehyde condensate. To prevent water absorption, they contain as additional binders C '0.2-4% by weight of an alkylphenol / phenol / formaldehyde condensation product. The insulation materials can be used as insulation or building material.
Description
Die Erfindung betrifft nichtbrennbare Dämmstoffe mit hoher Feuerwiderstandsdauer und verminderter Wasseraufnahme für Bau- und Isolierzwecke aus anorganischen Leichtpartikeln, die durch temperaturbeständige, hochpolymere organische Bindemittel miteinander verbunden sind.The invention relates to non-combustible insulation materials with a long fire resistance and reduced water absorption for construction and insulation purposes from inorganic light particles which are connected to one another by temperature-resistant, highly polymeric organic binders.
Gegenstand der deutschen Patentanmeldung DT-OS 26 30 834 ist ein nichtbrennbarer Dämmstoff mit hoher Feuerwiderstandsdauer und einer Dichte von 80 bis 230 g/1 aus
- A) 99 bis 80 Gew.% anorganischer Leichtpartikel mit einem mittleren Partikeldurchmesser zwischen 0,05 und 3 mm und einer Schüttdichte zwischen 30 und 150 g/1,
- B) 0 bis 40 Gew.% faseriger oder körniger anorganischer Zusatzstoffe,
wobei die Partikel miteinander verbunden sind durch - C) 1 bis 20 Gew.% eines temperaturbeständigen organischen hochmolekularen Bindemittels mit einer Dauergebrauchstemperatur nach DIN 53 446 von mehr als 100o C.
- A) 99 to 80% by weight of inorganic light particles with an average particle diameter between 0.05 and 3 mm and a bulk density between 30 and 150 g / 1,
- B) 0 to 40% by weight of fibrous or granular inorganic additives,
whereby the particles are interconnected by - C) 1 to 20% by weight of a temperature-resistant organic high-molecular binder with a continuous use temperature according to DIN 53 446 of more than 100 o C.
Derartige Dämmstoffe haben den für manche Anwendungszwecke wesentlichen Nachteil, daß sie verhältnismäßig viel Wasser aufnehmen. Dies kann eine Verschlechterung der Wärmedämmeigenschaften zur Folge haben, außerdem ist die Frostbeständigkeit vermindert. Der Erfindung lag daher die Aufgabe zugrunde, bei Dämmstoffen nach der Patentanmeldung DT-OS 26 30 834 die Wasseraufnahme herabzusetzen.Such insulation materials have the essential disadvantage for some applications that they absorb a relatively large amount of water. This can result in a deterioration in the thermal insulation properties, in addition there is frost resistance reduced. The invention was therefore based on the object to reduce the water absorption in insulating materials according to patent application DT-OS 26 30 834.
Es wurde gefunden, daß dies erreicht wird, wenn der Dämmstoff als zusätzliches Bindemittel C' 0,2 bis 4, vorzugsweise 0,5 bis 2 Gew.%, bezogen auf die Mischung, eines Alkylphenol/Phenol/Formaldehyd-Kondensationsproduktes enthält. Derartige Phenolharze auf Basis Alkylphenol wirken hydro- phobierend auf die Dämmstoffe.It has been found that this is achieved if the insulating material contains 0.2 to 4, preferably 0.5 to 2% by weight, based on the mixture, of an alkylphenol / phenol / formaldehyde condensation product as additional binder C '. Such phenolic resins based on alkyl phenol act hydro- p hobierend to the insulating materials.
Die erfindungsgemäßen Dämmstoffe sind nach DIN 4102 nicht brennbar und gehören damit der Baustoffklasse A an ; sie weisen bei einer Dämmstoffdicke von 5 cm und beidseitiger Beplankung mit 3 mm Asbestzement eine hohe Feuerwiderstandsdauer auf und gehören damit zur Widerstandsklasse W 90. Sie haben eine verhältnismäßig niedrige Dichte, die zwischen 80 und 230, vorzugsweise zwischen 120 und 180 g/l liegt; dadurch haben sie ein sehr gutes Wärmedämmvermögen.The insulation materials according to the invention are non-combustible according to DIN 4102 and thus belong to building material class A; with an insulation thickness of 5 cm and planking on both sides with 3 mm asbestos cement, they have a high fire resistance duration and thus belong to resistance class W 90. They have a relatively low density, which is between 80 and 230, preferably between 120 and 180 g / l; this gives them very good thermal insulation properties.
Die verwendeten anorganischen Leichtpartikel A haben einen mittleren Teilchendurchmesser zwischen 0,05 und 3 mm, vorzugsweise zwischen 0,2 und 2 mm. Ihre Schüttdichte liegt zwischen 30 und 150, vorzugsweise zwischen 40 und 80 g/l. Bevorzugt werden silikatische Materialien verwendet, wie wasserunlösliche Alkalisilikate mit einem Si02:Me203-Verhältnis von größer als 4,5:1 oder Silikate der 2. und 3. Hauptgruppe des Periodensystems. Besonders bevorzugt sind geblähter Perlit oder Vermiculit; geeignet sind aber auch geblähtes Schaumglas, Flugasche oder geblähter Gips.The inorganic light particles A used have an average particle diameter between 0.05 and 3 mm, preferably between 0.2 and 2 mm. Their bulk density is between 30 and 150, preferably between 40 and 80 g / l. Silicate materials are preferably used, such as water-insoluble alkali silicates with an SiO 2: Me 2 O 3 ratio of greater than 4.5: 1 or silicates of the 2nd and 3rd main group of the periodic table. Expanded pearlite or vermiculite are particularly preferred; However, expanded foam glass, fly ash or expanded plaster are also suitable.
Perlit ist ein hydraulisches Aluminiumsilikat, das sich von Rhyolith-Lava ableitet. Es enthält im wesentlichen 70 bis 85% Si02, 12 bis 14% A1203 und 2 bis 3% Wasser. Vermiculit ist ein hydraulisches Magnesiumaluminiumsilikat mit un- bestimmter Struktur mit einem Gehalt von 8 bis 12% MgO, 60' bis 65% Si02, 6 bis 12% A1203 und 1 bis 4% Wasser.Perlite is a hydraulic aluminum silicate that is derived from rhyolite lava. It contains essentially 70 to 85% Si0 2 , 12 to 14% A1 2 0 3 and 2 to 3% water. Vermiculite is a hydraulic magnesium aluminum silicate with certain structure with a content of 8 to 12% MgO, 60 'to 65% Si0 2 , 6 to 12% A1 2 0 3 and 1 to 4% water.
Die Dämmstoffe können gegebenenfalls bis zu 40 Gew.% faseriger oder körniger anorganischer Zusatzstoffe B enthalten. Faserige Zusätze verbessern den Elastizitätsmodul der Baustoffe. Die Fasern sollen eine Länge von 2 mm bis 3 cm aufweisen. Bevorzugt sind Glasfasern, die in Mengen von 2 bis 10 Gew.%, und Stein- oder Mineralwolle, die in Mengen von 5 bis 30 Gew.%, jeweils bezogen auf die Gesamtmischung, eingesetzt werden. Körnige Zusätze verbessern die Festigkeit der Baustoffe. Die Körner sollen einen Durchmesser von <100/um aufweisen. Bevorzugt sind Talkum oder Gips, die in Mengen von 15 bis 30 Gew.%, bezogen auf die Gesamtmenge, eingesetzt werden.The insulation materials can optionally contain up to 40% by weight of fibrous or granular inorganic additives B. Fibrous additives improve the elastic modulus of the building materials. The fibers should have a length of 2 mm to 3 cm. Glass fibers which are used in amounts of 2 to 10% by weight and rock or mineral wool which are used in amounts of 5 to 30% by weight, based in each case on the total mixture, are preferred. Granular additives improve the strength of the building materials. The grains should have a diameter of <100 / um. Talc or gypsum are preferred, which are used in amounts of 15 to 30% by weight, based on the total amount.
In den erfindungsgemäßen Dämmstoffen sind die Partikel A und B durch 1 bis 20, vorzugsweise 8 bis 20 Gew.% eines temperaturbeständigen, organischen, hochmolekularen Bindemittels miteinander verbunden. Die Bindemittel weisen eine Grenztemperatur nach DIN 53 446 von mehr als 100oC, vorzugsweise von mehr als 150°C auf. Als Grenztemperatur ist die Temperatur definiert, bei welcher der betreffende Stoff 25 000 stunden an der Luft gelagert werden kann, ohne daß sich seine Eigenschaften erkennbar ändern.In the insulation materials according to the invention, the particles A and B are connected to one another by 1 to 20, preferably 8 to 20% by weight of a temperature-resistant, organic, high-molecular binder. The binders have a limiting temperature according to DIN 53 446 of greater than 100 o C, preferably of more than 150 ° C. The limit temperature is the temperature at which the substance in question can be stored in air for 25,000 hours without its properties changing noticeably.
Bei der Herstellung der erfindungsgemäßen Dämmstoffe werden zweckmäßigerweise härtbare Bindemittel-Vorläufer in Form von wäßrigen Dispersionen oder Lösungen eingesetzt, die gegebenenfalls übliche Dispergierstabilisatoren, Vernetzungsmittel, Katalysatoren, Verlaufsmittel oder andere Zusatzstoffe in geringen Mengen enthalten können.In the production of the insulation materials according to the invention, curable binder precursors are expediently used in the form of aqueous dispersions or solutions which, if appropriate, can contain small amounts of conventional dispersion stabilizers, crosslinking agents, catalysts, leveling agents or other additives.
Als Bindemittel-Vorläufer werden bei der Herstellung der Dämmstoffe bevorzugt organische Polykondensate oder Poly- addukte verwendet, die bei erhöhten Temperaturen, gege- benenfalls in Gegenwart von Vernetzungsmitteln oder Vernetzungskatalysatoren unter Weiterkondensation bzw. Vernetzung zum hochtemperaturbeständigen hochmolekularen Bindemittel aushärten. Da bei der Aushärtung von Harzen auf Basis Alkylphenol Temperaturen von 200°C höchstens kurzzeitig überschritten werden sollten, sind vor allem solche Bindemittel geeignet, die niedrige Aushärtetemperaturen aufweisen.Organic polycondensates or poly- Adducts are used which harden at elevated temperatures, possibly in the presence of crosslinking agents or crosslinking catalysts with further condensation or crosslinking to give the high-temperature-resistant high-molecular binder. Since the curing of resins based on alkylphenol should only exceed temperatures of 200 ° C for a short time, binders with low curing temperatures are particularly suitable.
Gut geeignet sind beispielsweise: Polyesterimide, Polyurethane, Polyester, Melamin/Formaldehyd-Harze und insbesondere Phenol/Formaldehyd-Harze.For example, polyesterimides, polyurethanes, polyesters, melamine / formaldehyde resins and in particular phenol / formaldehyde resins are particularly suitable.
Wäßrige Dispersionen von Polyesterimiden sind z.B. beschrieben in den DT-OS 2 210 484 und 2 351 077. Es sind Polykondensationsprodukte aus aromatischen Polycarbonsäuren, mehrwertigen Alkoholen und mehrwertigen Aminen. Sie enthalten im allgemeinen 0,5 bis 7, vorzugsweise 1 bis 5 Gew.% Imidstickstoff in Form von fünfgliedrigen Imidringen, die mit aromatischen Kernen anelliert sind. Zu ihrer Herstellung können folgende Ausgangsstoffe'eingesetzt werden:
- 10 Äquivalente aromatischer Tri- oder Tetracarbonsäuren, deren Anhydride oder Ester, z.B. Trimellithsäure, Pyromellithsäure oder deren Anhydride, gegebenenfalls zusammen mit aromatischen Dicarbonsäuren oder deren Estern, z.B. Terephthalsäure, Isophthalsäure oder Naphthalindicarbonsäure, sowie deren niedrige Alkylester;
- 5 bis 20 Äquivalente niederer aliphatischer Diole, gegebenenfalls zusammen mit 3- oder 4-wertigen Alkoholen, beispielsweise Äthylenglykol, Propylenglykol, Butandiol, zusammen mit Glycerin, Trimethylolpropan oder Trishydroxy- äthylisocyanurat;
- 1 bis 5 Äquivalente di- oder triprimärer Amine, beispiel's-' weise Äthylendiamin, Hexamethylendiamin, Benzidin, Diaminodiphenylmethan, Diaminodiphenylketon, Diaminodiphenyläther oder Diaminodiphenylsulfon, Phenylendiamin, Toluylendiamine, Xylylendiamine oder Melamin.
- 10 equivalents of aromatic tri- or tetracarboxylic acids, their anhydrides or esters, for example trimellitic acid, pyromellitic acid or their anhydrides, optionally together with aromatic dicarboxylic acids or their esters, for example terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid, and their lower alkyl esters;
- 5 to 20 equivalents of lower aliphatic diols, optionally together with trihydric or tetravalent alcohols, for example ethylene glycol, propylene glycol, butanediol, together with glycerol, trimethylolpropane or trishydroxy ethyl isocyanurate;
- 1 to 5 equivalents of di- or triprimeric amines, for example 'ethylenediamine, hexamethylene diamine, benzidine, diaminodiphenylmethane, diaminodiphenyl ketone, diaminodiphenyl ether or diaminodiphenyl sulfone, phenylenediamine, toluenediamines, xylylenediamines.
Die Ausgangsstoffe können - vorzugsweise in Gegenwart von Lösungsmitteln - entweder zusammen kondensiert werden, oder man kann Vorkondensate einsetzen, z.3. Diimiddicarbonsäuren aus 2 Mol Trimellithsäureanhydrid und 1 Mol eines diprimären aromatischen Amins.The starting materials can - preferably in the presence of solvents - either be condensed together or pre-condensates can be used, e.g. Diimide dicarboxylic acids from 2 moles of trimellitic anhydride and 1 mole of a diprimeric aromatic amine.
In den wäßrigen Dispersionen liegen die Polyesterimide in Teilchenform mit durchschnittlichen Teilchendurchmessern unter 50, vorzugsweise unter 5/um vor. Sie enthalten im allgemeinen 0,01 bis 5, vorzugsweise 0,1 bis 3 Gew.% Dispergierhilfsmittel, wobei vor allem polare Gruppen enthaltende hochpolymere organische Substanzen in Frage kommen, wie z.B. Polyvinylalkohol, Celluloseäther, Polyvinylpyrrolidon, Polyacrylsäure, teilverseifte Copolymerisate aus Acrylestern und Acrylnitril; bevorzugt sind Copolymerisate aus Vinylpyrrolidon und Vinylpropionat. Außerdem enthalten sie Vernetzungskatalysatoren in Mengen von 0,5 bis 5 Gew.%, z.B. Oxotitenate, Triäthanolamintitanat, Titanlaktat oder Titanoxalat. Darüber hinaus können sie Verlaufsmittel, Verdickungsmittel, Antithioxotropiermittel und Neutralisationsmittel enthalten. Beim Aushärten tritt eine Weiterkondensation und Vernetzung der Polyesterimide ein.The polyesterimides are present in the aqueous dispersions in particle form with average particle diameters below 50, preferably below 5 / um. They generally contain 0.01 to 5, preferably 0.1 to 3,% by weight of dispersing aids, in particular high-polymer organic substances containing polar groups, such as, for example, polyvinyl alcohol, cellulose ethers, polyvinylpyrrolidone, polyacrylic acid, partially saponified copolymers of acrylic esters and acrylonitrile ; copolymers of vinyl pyrrolidone and vinyl propionate are preferred. They also contain crosslinking catalysts in amounts of 0.5 to 5% by weight, for example oxotitenates, triethanolamine titanate, titanium lactate or titanium oxalate. They can also contain leveling agents, thickeners, antithioxotropic agents and neutralizing agents. During curing, further condensation and crosslinking of the polyester imides occurs.
Weiterhin sind als Bindemittel Polyurethane geeignet. Polyurethane sind Polyaddukte aus Polyisocyanaten und hydroxylgruppenhaltigen Polyestern oder Polyäthern. Wäßrige Dispersionen von Polyurethane bildenden Ausgangsstoffen sind in der DT-OS 2 537 207 beschrieben. Die Ausgangsstoffe sindPolyurethanes are also suitable as binders. Polyurethanes are polyadducts made from polyisocyanates and hydroxyl-containing polyesters or polyethers. Aqueous dispersions of starting materials forming polyurethanes are described in DT-OS 2 537 207. The raw materials are
Mischungen aus 70 bis 10 Gew.% eines Polyesters oder Polyäthers mit einer Hydroxylzahl oberhalb von 20 und 30 bis 90 Gew.% eines verkappten Polyisocyanats. Aromatische Polyisocyanate, die mit einem Phenol oder einem Lactam verkappt sind, sind besonders geeignet. Die dispergierten Teilchen haben einen Durchmesser zwischen 0,05 und 2/um; die Dispersion enthält wieder vorzugsweise Dispergierhilfsmittel. Beim Aushärten spaltet das Verkappungsmittel ab und das freigesetzte Polyisocyanat kann mit den Hydroxylgruppen des Polyesters oder Polyäthers unter Polyurethanbindung vernetzen.Mixtures of 70 to 10% by weight of a polyester or polyether with a hydroxyl number above 20 and 30 to 90% by weight of a blocked polyisocyanate. Aromatic polyisocyanates which are capped with a phenol or a lactam are particularly suitable. The dispersed particles have a diameter between 0.05 and 2 / µm; the dispersion again preferably contains dispersing agents. When hardening, the capping agent is split off and the released polyisocyanate can crosslink with the hydroxyl groups of the polyester or polyether with a polyurethane bond.
Geeignet sind ferner vernetzte Polyester, vorzugsweise solche auf Basis von aromatischen Dicarbonsäuren.Hier kann man wäßrige Dispersionen oder Lösungen herstellen, die den unvernetzten oder nur gering vernetzten Polyester zusammen mit Polyolen als Vernetzungsmittel enthalten. Beim Aushärten tritt Weiterkondensation unter Vernetzung ein.Crosslinked polyesters are also suitable, preferably those based on aromatic dicarboxylic acids. Here it is possible to prepare aqueous dispersions or solutions which contain the uncrosslinked or only slightly crosslinked polyester together with polyols as crosslinking agents. During curing, further condensation occurs with crosslinking.
Weiterhin sind vernetzte Melamin/Formaldehyd- und Phenol/ Formaldehyd-Harze geeignet. Hier werden Vorkondensate aus Melamin, Phenol oder Kresol mit Formaldehyd mit Molgewichten zwischen etwa 400 und 800 eingesetzt. Besonders vorteilhaft werden wäßrige Lösungen von Phenol/Formaldehyd-Kondensaten verwendet.Crosslinked melamine / formaldehyde and phenol / formaldehyde resins are also suitable. Pre-condensates made of melamine, phenol or cresol with formaldehyde with molecular weights between approximately 400 and 800 are used here. Aqueous solutions of phenol / formaldehyde condensates are particularly advantageously used.
Die erfindungsgemäß zuzusetzenden Bindemittel C' sind Kondensationsprodukte aus einem Alkylphenol, Phenol und Formaldehyd. Sie werden hergestellt durch basisch katalysierte Kondensationen von Alkylphenol, Phenol und Formaldehyd in wäßriger Lösung in Gegenwart eines Emulgators und eines Schutzkolloids. Ein geeignetes Herstellungsverfahren ist z.B. in der DT-OS 23 30 815 beschrieben. Vorzugsweise werden Alkylphenole mit 2 bis 12 Kohlenstoffatomen im Alkylrest eingesetzt, besonders geeignet sind Octylphenol und Nonylphenol. Das Molverhältnis Phenol zu Alkylphenol kann n weiten Grenzen zwischen 5:1 und 1:5, vorzugsweise zwischen 2:1 und 1:2 schwanken; aas Molverhältnis Formaldehyd zu der Summe Phenol + Alkylphenol kann höher sein.als in der DT-OS 23 30 815, es liegt bevorzugt zwischen 2,3:1 und 1,6:1.The binders C 'to be added according to the invention are condensation products of an alkylphenol, phenol and formaldehyde. They are produced by base-catalyzed condensations of alkylphenol, phenol and formaldehyde in aqueous solution in the presence of an emulsifier and a protective colloid. A suitable manufacturing process is described, for example, in DT-OS 23 30 815. Alkylphenols having 2 to 12 carbon atoms in the alkyl radical are preferably used, octylphenol and nonylphenol are particularly suitable. The molar ratio of phenol to alkylphenol can vary n wide limits between 5: 1 and 1: 5, preferably between 2: 1 and 1: 2; The molar ratio of formaldehyde to the sum of phenol + alkylphenol can be higher than in DT-OS 23 30 815, it is preferably between 2.3: 1 and 1.6: 1.
Ein bevorzugtes Verfahren zur Herstellung der erfindungsgemäßen Dämmstoffe besteht aus folgenden Schritten:
- a) Leichtpartikel und Zusatzstoffe sowie eine 1 bis 50 gewichtsprozentige wäßrige Dispersion oder Lösung des härtbaren Bindemittel-Vorläufers werden vermischt;
- b) das Wasser wird - falls erforderlich - größtenteils mechanisch entfernt;
- c) die feuchte Mischung wird zu Platten einer Dicke von 1 bis 25, vorzugsweise 2 bis 8 cm, gepreßt;
- d) schließlich wird - vorzugsweise in Gegenwart von Katalysatoren, wie p-Toluolsulfonsäure - bei Temperaturen zwischen 80 und 200°C, insbesondere zwischen 100 und 160°C ausgehärtet.
- a) light particles and additives and a 1 to 50 percent by weight aqueous dispersion or solution of the curable binder precursor are mixed;
- b) if necessary, the water is largely removed mechanically;
- c) the moist mixture is pressed into sheets with a thickness of 1 to 25, preferably 2 to 8 cm;
- d) finally - preferably in the presence of catalysts such as p-toluenesulfonic acid - at temperatures between 80 and 200 ° C, in particular between 100 and 160 ° C cured.
Die Herstellungsweise ist etwas verschieden, je nachdem, ob sie faserige Zusatzstoffe enthalten oder nicht.The method of production is somewhat different, depending on whether they contain fibrous additives or not.
Bei Dämmstoffen, die keine Fasern enthalten, werden die Leichtpartikel mit einer etwa 1 bis 50, vorzugsweise 2 bis 10 gewichtsprozentigen wäßrigen Dispersion oder Lösung des Bindemittel-Vorläufers besprüht, wobei die Partikel in üblichen Mischmaschinen in Bewegung gehalten werden. Es ist ein besonderer Vorteil der Verwendung von wäßrigen Bindemittelsystemen, daß eine besonders feine und gleichmäßige Verteilung von Leichtpartikel und Bindemittel erhalten wird. Das Produkt wird gegebenenfalls mechanisch von einem Teil des Wassers befreit und dann im feuchten Zu-' stand in üblichen Pressen bei Drücken von etwa 1 bis 10 kp/cm2 zu Platten gepreßt. Diese werden dann weiter erhitzt, wobei Weiterkondensation und Vernetzung unter Ausbildung des temperaturbeständigen organischen hochmolekularen Bindemittels eintritt.In the case of insulating materials that do not contain fibers, the light particles are sprayed with an approximately 1 to 50, preferably 2 to 10 percent by weight aqueous dispersion or solution of the binder precursor, the particles being kept in motion in conventional mixing machines. It is a particular advantage of using aqueous binder systems that a particularly fine and uniform distribution of light particles and binder is obtained. The product may become mechanical freed from part of the water and then pressed into plates in the moist state in conventional presses at pressures of about 1 to 10 kp / cm 2 . These are then heated further, with further condensation and crosslinking taking place with the formation of the temperature-resistant organic high-molecular binder.
Bei Dämmstoffen, die Fasern enthalten, werden zunächst die Fasern in Wasser, welches oberflächenaktive Stoffe als übliche Aufschlußmittel gelöst enthält, unter Rühren aufgeschlämmt. Dazu werden dann die Bindemitteldispersionen oder -lösungen sowie die Leichtpartikel gegeben und kräftig vermischt. Auf einem in der Papierindustrie üblichen Blattbildner wird der Großteil des Wassers abgesaugt. Nach leichtem Anpressen wird die Platte getrocknet und gegebenenfalls die Vernetzung durchgeführt.In the case of insulating materials which contain fibers, the fibers are first suspended in water, which contains surface-active substances dissolved as conventional disintegrants, with stirring. Then the binder dispersions or solutions and the light particles are added and mixed vigorously. The majority of the water is sucked off on a sheet former common in the paper industry. After pressing gently, the plate is dried and, if necessary, the crosslinking is carried out.
Die erfindungsgemäßen Dämmstoffe können mit üblichen Deckschichten, wie Asbestzement, Gipskarton oder Metallblechen, verklebt und zu Sandwichelementen verarbeitet werden. Sie eignen sich zur Herstellung von nichttragenden Wänden, Decken und Böden; sie können aber auch zur Beschichtung von tragenden Wänden, Decken und Böden oder in Lager- oder Kühlhäusern als wärmeisolierende und den Feuerdurchgang hemmende Schicht eingesetzt werden.The insulation materials according to the invention can be glued with conventional cover layers, such as asbestos cement, plasterboard or metal sheets, and processed into sandwich elements. They are suitable for the production of non-load-bearing walls, ceilings and floors; however, they can also be used to coat load-bearing walls, ceilings and floors or in warehouses or cold stores as a heat-insulating layer that prevents the passage of fire.
1035 Teile einer 14%-igen wäßrigen Lösung von Polyvinyl-" alkohol werden mit 400 Teilen Wasser, 288 Teilen eines äthoxylierten Octylphenols und 200 Teilen 25%-igem Ammoniak unter Rühren homogenisiert. Dann werden 846 Teile Phenol, 1854 Teile Octylphenol (Molverhältnis Formaldehyd zu Gesamtphenol 2:1) und 2700 Teile einer 40%-igen wäßrigen Lösung von Formaldehyd zugegeben und unter kräftigem Rühren etwa 4 Stunden zum Rückfluß erhitzt. Danach wird unter weiterem Rühren auf Raumtemperatur abgekühlt. Man erhält eine homogene, stabile Dispersion, mit einem Trockengehalt (2 Stunden bei 120°C) von 50%, einer Viskosität bei 20°C von 600 mPas und einem pH-Wert von 8,0.1035 parts of a 14% aqueous solution of polyvinyl 'alcohol are homogenised with 400 parts of water, 288 parts of an ethoxylated octylphenol, and 200 parts of 25% ammonia with stirring Then 846 parts of phenol, 1854 parts of octylphenol (molar ratio of formaldehyde to. Total phenol 2: 1) and 2700 parts of one 40% aqueous solution of formaldehyde was added and heated to reflux with vigorous stirring for about 4 hours. The mixture is then cooled to room temperature with further stirring. A homogeneous, stable dispersion is obtained with a dry content (2 hours at 120 ° C.) of 50%, a viscosity at 20 ° C. of 600 mPas and a pH of 8.0.
89 Teile einer 60%-lgen wäßrigen Phenolharz-Lösung (Molverhältnis Phenol zu Formaldehyd von 1:1,6), 3 Teile p-Toluolsulfonsäure und 8 Teile der 50%-igen wäßrigen Dispersion a) werden homogen vermischt. Blähperlit mit einem mittleren Teilchendurchmesser von 0,7 mm und einer Schüttdichte von 50 g/l wird in einem Mischwerk mit diesem Bindemittel so verleimt, daß die Mischung, bezogen auf Feststoff, 13,3% des Phenol-Harzes und 1% des Phenol-Alkylphenol/Formaldehyd-Kondensates enthält. Das beleimte Gut wird in einer üblichen Preßapparatur mit einem Druck von etwa 2,5 bis 3,0 kp/cm3 zu einem Preßling des Raumgewichts 200 g/l verdichtet und anschließend auf eine Temperatur von etwa 150°C aufgeheizt, wobei das Bindemittel aushärtet.89 parts of a 60% strength aqueous phenolic resin solution (molar ratio of phenol to formaldehyde of 1: 1.6), 3 parts of p-toluenesulfonic acid and 8 parts of the 50% strength aqueous dispersion a) are mixed homogeneously. Expandable perlite with an average particle diameter of 0.7 mm and a bulk density of 50 g / l is glued in a mixer with this binder so that the mixture, based on solids, 13.3% of the phenolic resin and 1% of the phenolic Contains alkylphenol / formaldehyde condensates. The glued material is compressed in a conventional press apparatus with a pressure of about 2.5 to 3.0 kp / cm 3 to give a compact with a density of 200 g / l and then heated to a temperature of about 150 ° C., the binder hardening .
Eine 50 mm starke Dämmplatte zeigt im 24 Stunden-Untertauchtest nach DIN 53 428 eine Wasseraufnahme von 5 Vol%.A 50 mm thick insulation board shows a water absorption of 5 vol% in the 24 hour immersion test according to DIN 53 428.
Im Vergleich dazu zeigt eine Dämmplatte gleichen Raumgewichts, die aber kein hydrophobierendes Bindemittel C' enthält, eine Wasseraufnahme von 33 Vol%.In comparison, an insulation board of the same density, but which contains no hydrophobic binder C ', shows a water absorption of 33% by volume.
Claims (4)
wobei die Partikel miteinander verbunden sind durch
dadurch gekennzeichnet, daß der Dämmstoff aus zusätzliches Bindemittel 0,2 bis 4 Gew.%, bezogen auf die Mischung, eines Alkylphenol/Phenol/Formaldehyd-Kondensationsproduktes C' enthält.
whereby the particles are interconnected by
characterized in that the insulating material from additional binder contains 0.2 to 4% by weight, based on the mixture, of an alkylphenol / phenol / formaldehyde condensation product C '.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772726105 DE2726105A1 (en) | 1977-06-10 | 1977-06-10 | NON-COMBUSTIBLE INSULATION |
DE2726105 | 1977-06-10 |
Publications (2)
Publication Number | Publication Date |
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EP0000056A1 true EP0000056A1 (en) | 1978-12-20 |
EP0000056B1 EP0000056B1 (en) | 1980-04-30 |
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ID=6011132
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EP78100098A Expired EP0000056B1 (en) | 1977-06-10 | 1978-06-06 | Incombustible insulating material |
Country Status (5)
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US (1) | US4190547A (en) |
EP (1) | EP0000056B1 (en) |
AT (1) | AT367384B (en) |
DE (2) | DE2726105A1 (en) |
IT (1) | IT1104732B (en) |
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EP0087889A1 (en) * | 1982-03-03 | 1983-09-07 | Imperial Chemical Industries Plc | Production of vermiculite products and suspension for use therein |
FR2543536A1 (en) * | 1983-03-28 | 1984-10-05 | Inst Francais Du Petrole | MATERIAL OF HIGH MECHANICAL RESISTANCE AND DENSITY ABOUT THE UNIT, ITS MANUFACTURE AND USES |
DE3715487A1 (en) * | 1987-05-09 | 1988-11-17 | Walter Voest | METHOD FOR PRODUCING COMPONENTS |
FR2627177A1 (en) * | 1988-02-11 | 1989-08-18 | Lievremont Henri | |
CN108821673A (en) * | 2018-07-20 | 2018-11-16 | 张莉敏 | A kind of ceiling and preparation method thereof |
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JPS5610547A (en) * | 1979-07-04 | 1981-02-03 | Onomichi Kumika Kogyo Kk | Bulking filler for synthetic resin |
US4373005A (en) * | 1981-05-13 | 1983-02-08 | Inventure, Inc. | Insulation material |
DE4036792C1 (en) * | 1990-11-19 | 1991-12-19 | Dmt Marinetechnik Gmbh, 2000 Hamburg, De | |
DE4315088A1 (en) * | 1993-05-06 | 1994-11-10 | Wacker Chemie Gmbh | Process for producing a microporous body with thermal insulation properties |
US5445754A (en) * | 1994-03-28 | 1995-08-29 | P.S.A.M.S., Inc. | Water-based, thermal paint |
EP0961761B1 (en) | 1997-02-18 | 2002-10-23 | Windsor Technologies Limited | Method of treating a lignocellulosic material or an expanded mineral to form a finished product |
WO1998038229A1 (en) * | 1997-02-27 | 1998-09-03 | Borden Chemical, Inc. | Wood-product laminated composites |
FR2811661B1 (en) * | 2000-07-13 | 2003-05-02 | Saint Gobain Isover | MINERAL WOOL THERMAL / PHONIC INSULATION PRODUCT AND MANUFACTURING METHOD THEREOF |
KR20030061541A (en) * | 2002-01-14 | 2003-07-22 | 길애숙 | Incombustible insulating material and preparing method of the same |
CZ302465B6 (en) * | 2004-03-03 | 2011-06-01 | Moravské keramické závody, a. s. | Mixtures for producing thermally insulating shaped bricks from expanded mineral materials and process for producing thereof |
USRE44070E1 (en) | 2005-06-09 | 2013-03-12 | United States Gypsum Company | Composite light weight gypsum wallboard |
US9840066B2 (en) * | 2005-06-09 | 2017-12-12 | United States Gypsum Company | Light weight gypsum board |
US11306028B2 (en) | 2005-06-09 | 2022-04-19 | United States Gypsum Company | Light weight gypsum board |
US9802866B2 (en) | 2005-06-09 | 2017-10-31 | United States Gypsum Company | Light weight gypsum board |
US20110195241A1 (en) * | 2005-06-09 | 2011-08-11 | United States Gypsum Company | Low Weight and Density Fire-Resistant Gypsum Panel |
US11338548B2 (en) | 2005-06-09 | 2022-05-24 | United States Gypsum Company | Light weight gypsum board |
US7731794B2 (en) | 2005-06-09 | 2010-06-08 | United States Gypsum Company | High starch light weight gypsum wallboard |
FR2903398B1 (en) * | 2006-07-07 | 2009-06-12 | Saint Gobain Isover Sa | MINERAL WOOL, INSULATING PRODUCT AND PROCESS FOR PRODUCING THE SAME |
ES2331043B1 (en) * | 2008-03-31 | 2010-10-01 | Barbara Roman Alemañ | PLASTER MORTAR WITH EXPANDED AND ADDITIVE VERMICULITE, AND PROCEDURE FOR OBTAINING IT. |
US8323785B2 (en) | 2011-02-25 | 2012-12-04 | United States Gypsum Company | Lightweight, reduced density fire rated gypsum panels |
EP2814786A1 (en) | 2012-02-17 | 2014-12-24 | United States Gypsum Company | Gypsum products with high efficiency heat sink additives |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0087889A1 (en) * | 1982-03-03 | 1983-09-07 | Imperial Chemical Industries Plc | Production of vermiculite products and suspension for use therein |
US4485203A (en) * | 1982-03-03 | 1984-11-27 | Imperial Chemical Industries Plc | Production of vermiculite products and suspension for use therein |
FR2543536A1 (en) * | 1983-03-28 | 1984-10-05 | Inst Francais Du Petrole | MATERIAL OF HIGH MECHANICAL RESISTANCE AND DENSITY ABOUT THE UNIT, ITS MANUFACTURE AND USES |
DE3715487A1 (en) * | 1987-05-09 | 1988-11-17 | Walter Voest | METHOD FOR PRODUCING COMPONENTS |
FR2627177A1 (en) * | 1988-02-11 | 1989-08-18 | Lievremont Henri | |
WO1989007518A1 (en) * | 1988-02-11 | 1989-08-24 | Lievremont Henri G | Process for obtaining a construction material, installation for implementation of said process and construction material thus obtained |
CN108821673A (en) * | 2018-07-20 | 2018-11-16 | 张莉敏 | A kind of ceiling and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
DE2726105A1 (en) | 1978-12-21 |
AT367384B (en) | 1982-06-25 |
US4190547A (en) | 1980-02-26 |
ATA421078A (en) | 1981-11-15 |
DE2857615D1 (en) | 1980-06-12 |
IT7849771A0 (en) | 1978-06-08 |
IT1104732B (en) | 1985-10-28 |
EP0000056B1 (en) | 1980-04-30 |
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