WO2007057342A1 - Glass laminates with thermoplastic polysiloxane-urea copolymers - Google Patents

Glass laminates with thermoplastic polysiloxane-urea copolymers Download PDF

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Publication number
WO2007057342A1
WO2007057342A1 PCT/EP2006/068285 EP2006068285W WO2007057342A1 WO 2007057342 A1 WO2007057342 A1 WO 2007057342A1 EP 2006068285 W EP2006068285 W EP 2006068285W WO 2007057342 A1 WO2007057342 A1 WO 2007057342A1
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Prior art keywords
layer
laminated glass
layers
glass
carbon atoms
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PCT/EP2006/068285
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German (de)
French (fr)
Inventor
Ernst Selbertinger
Oliver SCHÄFER
Uwe Scheim
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Wacker Chemie Ag
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Publication of WO2007057342A1 publication Critical patent/WO2007057342A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10908—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form
    • B32B17/10917—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form between two pre-positioned glass layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10935—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences

Definitions

  • the invention relates to glass laminates in which at least one layer of thermoplastic polysiloxane-urea
  • Glass laminates have been known for a long time and have a wide range of uses as laminated glasses in the automotive, vehicle and aircraft construction as well as in the construction industry.
  • Laminated glass is sandwiched and consists of at least one glass sheet and a polymeric layer thereon. Most commonly used as polymeric
  • Interlayer plasticized polyvinyl butyral (PVB) used in film form This technology has been used successfully for over 70 years and has been constantly refined and refined, both in terms of polymer films and processing technologies.
  • the intermediate layer can also consist of polyurethane or polyacrylate or of a combination of several different materials.
  • the laminated glass is different from ordinary glass
  • the polymeric layer binds the splinters, so that the risk of injury is considerably lower than with normal glass.
  • the advantage over toughened safety glass is that the laminate glass pane continues to be transparent after a breakage. Laminate glass also complicates the penetration of the disc structure by violence, such as burglary with Tools, projectiles, or hurricanes flying objects, such as larger pieces of wood.
  • laminated glass Due to the layered structure and with the help of suitable polymeric interlayers, laminated glass can achieve good sound and heat insulation in addition to the optical and safety aspects. Especially good
  • the document WO 2004/039581 Al describes a sound-damping laminated glass for vehicles, which consists of two glass panes and a single intermediate PVB layer.
  • the PVB layer combines both sound absorption and penetration resistance and adhesion.
  • good penetration resistance and soundproofing run counter to each other, which is why the material has limits for soundproofing if the safety aspect is to be additionally fulfilled.
  • Tg of the plasticized PVB which is usually set to about 16 ° C in the case of plasticized types.
  • polyurethanes polyurethanes
  • polyureas polyureas
  • polyvinyl chloride polyvinyl chloride
  • epoxides epoxides
  • Polyesters such as polyterephthalate, (meth) acrylates, silicones such as UV or hot-curing silicones, cold-curing 2-component silicones, moisture-crosslinking silicones, silicone resin polymers, modified silicone polymers, hot-melt adhesives, coatings and sealants, plastisols, polyethylene, polypropylene , PVC, polystyrene, polycarbonate and polyvinyl acetate. These materials may additionally contain plasticizers. Laminates of such materials are described, for example, in WO 99/62707.
  • thermoplastic silicone elastomers TPSE
  • TPSE thermoplastic silicone elastomers
  • US Pat. No. 6,156,417 describes polyurethanes which may also be modified by siloxanes.
  • the products can be obtained by reacting siloxanols with isocyanates, whereby silylurethanes are formed, which are also not resistant to hydrolysis.
  • the mechanical strengths that can be achieved with siloxane-containing polyurethanes are not sufficient for use in laminated glass. This is not changed by using hydrolysis-stable hydroxyalkyl-functional siloxanes as building blocks.
  • German Patent DE 1 596 960 describes laminated safety glass articles in which the intermediate layer consists of a silicon-containing polyurethane.
  • silicon-containing polyurethanes contain reaction products of polyols with silicone compounds containing silanol or alkoxysilane groups. This forms polymeric compounds containing Si-OC linkages, which are known to be not resistant to hydrolysis. In the course of use, therefore, laminate glasses with such polymers would lose their properties from the edges, as a gradual destruction of the polymers occurs. The function of the laminate glass is thus no longer given in these zones.
  • the polyurethanes of DE 1 596 960 may also contain silicon-containing compounds having Si-CH 2 -OH groups. However, such compounds are very difficult to access and therefore expensive to manufacture. Furthermore, it is stated that amino groups can be introduced via amino alcohols, which, however, lead to products which are likewise not resistant to hydrolysis and, moreover, tend to become discolored.
  • the requirements for the polymeric layers or intermediate layers are very large and should ideally in addition to high penetration resistance and very good sound-damping properties also have other properties such as little or no haze, high strength, very good UV stability, very good adhesion to glass and low Moisture absorption with very good moisture resistance.
  • a number of inventions also describe a combination of different polymer layers of partly different materials, of which at least one layer is a very good glass adhesion and / or penetration resistance on the one hand, another optimized for good soundproofing on the other hand.
  • the patent EP 0 457 190 Bl describes a sound-absorbing laminated glass, which consists of two glass sheets and at least two intermediate PVB layers.
  • One PVB layer primarily serves to absorb sound, while the other is responsible for the safety aspect.
  • the laminate described here has good sound absorption and safety properties at room temperature. At lower
  • the patent specification WO 98/26927 likewise describes sound-damping glass laminates of similar construction as in the patent EP 0 457 190 B1.
  • the laminates described here have good sound absorption and safety properties at room temperature, but at low temperatures these properties naturally decrease rapidly as a result of the freezing of the acrylate layer.
  • the vibration-damping acrylate layer is particularly sensitive to plasticizers or chemicals that diffuse from the adjacent PVB layers or especially from the edge area.
  • laminates are also described which have barrier layers of thin transparent layers between the individual polymer layers Have polymers that are plasticizer resistant. Disadvantage here is the higher cost of production and thus in the Hersteil emerge.
  • the patent document WO 2004/089616 A1 describes laminated glass which contains as a flexible and at the same time sound-damping layer a branched polysiloxane-urea-urethane copolymer which has a ratio of urea to urethane groups of at least 4: 1.
  • This object could be achieved by using a linear block copolymer as the sound-absorbing layer, which led to a substantial improvement in the sound-insulating properties of the glass laminate.
  • the invention therefore relates to a laminated glass comprising
  • R is a monovalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20 carbon atoms,
  • X is an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups - 0 -,
  • A is an oxygen atom or an amino group -NR ⁇ -
  • Z represents an oxygen atom or an amino group -NR ⁇ - ⁇ R is hydrogen or an alkyl radical having 1 to 10 carbon atoms
  • Y is a divalent, unsubstituted or fluorine, chlorine or oxygen-substituted or interrupted hydrocarbon radical having 1 to 20 carbon atoms
  • D is either an unsubstituted or substituted by fluorine, chlorine, C ] _Cg-alkyl or C ] _-C5-alkyl ester alkylene radical with 1 to 800 carbon atoms, where not each other adjacent methylene units by groups -O-, -COO-, -OCO-
  • Y n is a number from 1 to 4000, a is a number of at least 1, b is a number from 0 to 40, c is a number from 0 to 30 and d is a number greater than 0.
  • the laminate glass according to the invention has good optical as well as excellent vibration and sound damping properties over a wide temperature range and can be used for both vehicle, aircraft and architectural glazings.
  • architectural glazing is understood to be glazing used in the manufacture of buildings and their furnishings, such as windows, doors, translucent partition walls, glass structures and glazings with an optical or artistic purpose.
  • the laminate glasses according to the invention exhibit a transparency of at least 89 for the wavelength range from 350 to 800 nm.
  • the refractive index of the intermediate layers in the laminate glasses according to the invention is at least 1.38 in the wavelength range from 350 to 800 nm and avoids or reduces so any unwanted reflections.
  • the refractive index is 1.38 to 1.70 in this range.
  • the laminate glass according to the invention preferably contains at least two layers (A) of inorganic or organic glass.
  • inorganic or organic glass (A) for the purposes of this invention are hardened and uncured mineral glasses and organic glasses such as polycarbonate, Plexiglas, polyester, polystyrene, polyacrylate, polymethyl methacrylate, PVC, polypropylene and polyethylene and copolymers of these polymers.
  • R is a monovalent, hydrocarbon radical having 1 to 6 carbon atoms, in particular unsubstituted.
  • Particularly preferred radicals R are methyl, ethyl, vinyl and phenyl.
  • X is an alkylene radical having 1 to 10
  • the alkylene radical X is not interrupted.
  • X is preferably a methylene or propylene radical.
  • A is an NH group.
  • Z represents an oxygen atom or an NH group.
  • Y is a hydrocarbon radical having 3 to 13
  • Carbon atoms which is preferably unsubstituted.
  • Y is an aralkylene, linear or cyclic alkylene radical.
  • D is an alkylene radical having at least 2, in particular at least 4 carbon atoms and at most 12 carbon atoms.
  • D is a polyoxyalkylene radical, in particular polyoxyethylene radical or
  • Polyoxypropylene radical having at least 20, in particular at least 100 carbon atoms and at most 800, in particular at most 200 carbon atoms.
  • the radical D is not substituted.
  • n is preferably a number of at least 3, in particular at least 25 and preferably at most 800, in particular at most 400, particularly preferred at most 250.
  • a is a number of at most 50.
  • b is preferably a number of at most 50, especially at most 25.
  • c is preferably a number of at most 10, in particular at most 5.
  • d is preferably a number from 10 to 200, preferably from 30 to 100.
  • end groups of the organopolysiloxane / polyurea / polyurethane block copolymers conventional end groups can occur according to the prior art, which are standard in the synthesis of such polymers, such as amino or isocyanate end groups. These can be reacted during the synthesis or subsequently with other groups, such as amino or isocyanato-silanes.
  • the organopolysiloxane / polyurea / polyurethane block copolymers therefore preferably contain as end groups B a functional or non-functional organic or organosilicon radical.
  • end groups B are described, for example, in the abovementioned DE 10313936 A and DE 10326575 A.
  • the copolymer of the general formula (1) based on the sum of the urethane and urea groups, at least 50 mol%, in particular at least 75 mol% of urea groups.
  • a diisocyanate of the general formula (3) is preferably used.
  • diisocyanates of the general formula (3) to be used are aliphatic compounds, such as
  • chain extenders such as diamino compounds, dihydroxy compounds or water in addition to the urea groups
  • a significant improvement in the mechanical properties of the block copolymers can be achieved.
  • b is at least 1, in the second step up to 95 percent by weight, based on all components used, of chain extenders selected from the group of diamines, isocyanate-blocked hydroxy compounds, dihydroxy compounds and mixtures thereof can be used.
  • the chain extenders have the general formula (4)
  • D and Z have the above meanings. If Z has the meaning O (oxygen), the chain extender (4) can be reacted with diisocyanate (3) even before the reaction of polydiorganosiloxane diamine (2) with diisocyanate (3).
  • the OC, ⁇ -OH-terminated alkylenes of the general formula (4) are preferably polyalkylenes or polyoxyalkylenes. These are preferably substantially free of contaminants from mono-, tri or higher polyoxyalkylenes.
  • polyether polyols polytetramethylene diols, polyester polyols, polycaprolactone diols, but also CC, ⁇ -OH-terminated polyalkylenes based on polyvinyl acetate, polyvinyl acetate-ethylene copolymers, polyvinyl chloride copolymer, polyisobutlydiols.
  • Such compounds are commercially available as base materials, inter alia, for polyurethane flexible foams and for coating applications with molecular masses M n to over 10,000.
  • base materials such as polyurethane flexible foams and for coating applications with molecular masses M n to over 10,000.
  • examples of these are the BAYCOLL® polyether polyols and polyester polyols from Bayer AG, Germany or the Acclaim® polyether polyols from Lyondell Inc., Housten, USA. It is also possible to use monomeric OC, ⁇ -alkylene diols, such as ethylene glycol, propanediol, butanediol or hexanediol.
  • dihydroxy compounds in the sense of The invention also Bishydroxyalkylsilicone to understand how they are for example sold by the company Goldschmidt GmbH, Essen, Germany under the name Tegomer H-Si 2111, 2311 and 2711.
  • the water content of the copolymers of formula (1) prepared according to the present invention is preferably less than 0.5% by weight and most preferably less than 0.1% by weight.
  • the preparation of the above-described copolymers of the general formula (1) can be carried out both in solution and in solid substance, continuously or discontinuously. It is essential that for the selected polymer mixture under the reaction conditions, an optimal and homogeneous mixing of the components takes place and a
  • Phase incompatibility is optionally prevented by solubilizers. Preference is given to a synthesis without solvent,
  • the homogenization of the mixture is of crucial importance in the reaction.
  • the polymerization can also be controlled by the choice of the reaction sequence in a step synthesis.
  • the preparation is preferably carried out for better reproducibility generally with the exclusion of moisture and under protective gas, usually nitrogen or argon.
  • the reaction can be carried out both with addition and without addition of a catalyst.
  • Suitable catalysts for the preparation are dialkyltin compounds, such as
  • metal carboxylates such as bismuth, tin or zinc carboxylates or tertiary amines such as N, N-dimethylcyclohexanamine, 2-dimethylaminoethanol, 4-dimethylaminopyridine.
  • the laminates of the invention show good optical quality, due to the good adhesion of (B) to (A), as well as by the hydrophobic properties of (B).
  • the laminate glass according to the invention may additionally contain further layers (C) selected from the group comprising polyvinyl butyral, polyurethanes, polyureas,
  • a polyester suitable as layer (C) is, for example, polyterephthalate.
  • Suitable silicones are, for example, UV- or hot-curing silicones, cold-curing 2-component silicones and moisture-crosslinking silicones.
  • the additional layers (C) may also contain plasticizers.
  • adhesion-promoting silanes to the block copolymer (B), for example silanes with hydrolyzable groups and SiC-bonded vinyl, acryloyloxy, methacryloxy, isocyanato, epoxy, acid anhydride, acid, ester or ether groups as well as their partial and mixed hydrolysates.
  • adhesion promoters are 3-
  • Silanes with vinyl groups and silanes with epoxy groups which contain ethoxy or acetoxy groups as hydrolyzable groups are preferred.
  • Glycidoxypropyltriethoxysilane, vinyltriethoxysilane and vinyltriacetoxysilane, and their partial and mixed hydrolysates are particularly preferred.
  • the adhesion promoters are added in amounts of 0.01% to 5%, preferably 0.1% to 2%, particularly preferably between 0.4% and 0.7%, in each case based on the total mass of block copolymer (B).
  • adhesion-promoting silanes or their solutions and hydrolysis condensation products, can also be applied to the surface of the films produced from the block copolymers (B).
  • adhesion-promoting silanes are prepared after production on the sheet of organopolysiloxane / polyurea / polyurethane block copolymer (B), on the inorganic or organic glass (A), on the second layer (C) or on all 3 components (A), (B ) and (C) applied.
  • the adhesion-promoting silanes are applied according to the prior art, prior to the preparation of the composite, to the block copolymer (B), the inorganic or organic glass (A) and / or the further layer (C).
  • a solution of adhesion promoters in a suitable solvent can be used.
  • the term primer has become common.
  • the block copolymer (B) may be added further additives selected from the group consisting of dyes, pigments, fillers, catalysts, heat stabilizers, plasticizers, crosslinkers, flame retardants and light stabilizers or mixtures thereof.
  • additives are known to those skilled in the polyurethane and silicone chemistry.
  • the preparation of the composite between the layer (A) or the layers (A) and the block copolymer (B) is carried out according to the prior art.
  • the laminate glass is sandwiched and consists of at least one layer (A) and a layer of block copolymer (B) located thereon, but usually at least two layers (A) and an intermediate layer (B), the layers (A) together combines.
  • the layers (A) may consist of either inorganic glasses, such as float glass and / or organic glasses, such as polycarbonate (PC) or polymethyl methacrylate (PMMA) glass.
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • the anorg. or org. Glass layers (A) can also be laminated with several polymer layers, but of which at least one must consist of the block copolymer (B) according to the invention.
  • the layer of block copolymer (B) can thus consist of a uniform material, or itself be multilayer composed of different layers of block copolymer (B) or be a laminate of various polymers, of which at least one of block copolymer (B) must exist.
  • the linear organopolysiloxane / polyurea / polyurethane block copolymer (B) is prepared and then applied to at least one layer (A).
  • One possibility for producing the laminate glass is to apply liquefied block copolymer (B) to one of the layers (A) by, for example, doctoring, rolling or screen printing.
  • the laminated glass is then finally obtained by placing the second layer (A) on the layer of block copolymer (B) and passing through
  • a second possibility is that the two optionally in turn treated with adhesion promoter layers (A) are assembled by suitable spacers so that a gap of defined width is obtained.
  • Liquefied block copolymer (B) is then introduced from a suitable heated storage vessel through a metering device into this gap, wherein the edges of the glass plates are closed in such a way that the polymer melt does not escape at undesired points and only the air located between the glass plates can escape.
  • Another embodiment of this method uses 1-component or 2-component molding compounds, which cure either at room temperature, thermally or optically in the intermediate layer.
  • the preferred way of producing the laminate glass is to produce the layer of block copolymer (B) as a film.
  • an embossed film with a defined surface roughness is used to minimize air pockets during lamination.
  • the composite is then obtained by placing the film of (B) between the two layers (A) and permanently bonded under pressure and temperature. This treatment is preferably carried out by heating the superimposed layers in a hot Vorverbundofen and then pressing for several hours in a pressure autoclave at about 100 to 150 0 C.
  • a hot Vorverbundofen and then pressing for several hours in a pressure autoclave at about 100 to 150 0 C.
  • the preferred method for producing the laminated glass according to the invention is characterized in that a) the layer (B) is produced as a film, b) at least one film (B) is subsequently placed between two layers (A) and c) permanently under pressure and temperature is connected.
  • At least one layer (C) is introduced into the laminate glass.
  • (C) is also a film.
  • the layers (A), (B) and (C) may each independently have different thicknesses.
  • the layer (A) shows layer thicknesses of more than 0.5 mm. Layer thicknesses of 1 to 20 mm are preferred.
  • the block copolymer (B) shows layer thicknesses of more than 0.01 mm. Where a layer thickness of 0.1 to 3 mm is preferred.
  • the layer thickness is particularly preferably 0.3 to 1.5 mm.
  • the layer (C) shows layer thicknesses of more than 0.01 mm. Where a layer thickness of 0.1 to 3 mm is preferred. The layer thickness is particularly preferably 0.3 to 1.5 mm.
  • the layers (B) and (C) are a co-extrusion film.
  • the three-layer coextrusion film may consist of an inner layer (B) and two outer layers (C) or vice versa.
  • Coextrusion films with more than 3 layers can also be used.
  • the films of (B), (C) and the coextrusion films are preferably subjected to roughness embossing.
  • PVB is preferably used as the polymer (C).
  • the laminate glass according to the invention may contain a layer of a mixture of (B) and (C).
  • Example 1 (Inventive): Production of the TPSE Films Without Embossing
  • Geniomer® 80, Geniomer® 140, Geniomer® 140 with increased siloxane content such that the SiO chain length was extended from about 36 to about 80
  • Wacker-Chemie GmbH, Kunststoff , Germany melted in granular form at an extrusion processing temperature of 150-180 0 C and extruded in each case to 0.76 mm thick films.
  • Each gave a film having a transparency of 91.85% and a refractive index of 1.425.
  • Example 2 (according to the invention): Production of the TPSE foils with embossing
  • Example 3 to 5 Production of TPSE laminated glass panes for testing in accordance with DIN EN 20140-3 (autoclave step, 0.76 mm thick film without embossing)
  • Example 1 For the production of panes for testing in accordance with DIN EN 20140-3, the unembossed films from Example 1 were placed between two glass panes (float glass) of thickness 4 mm and the structure was run slowly through a 400 ° C. pre-composite oven. This procedure was repeated several times. This included a laminated glass pane, which still contained some small air bubbles.
  • the disc was then placed in a gum bag and deaerated in an autoclave for 20 minutes at 20 torr vacuum. Subsequently, it was laminated at a pressure of 12 kg / cm 2 and at a temperature of 140 ° C. This gave bubble-free laminated glass, which was then subjected to a sound insulation test according to DIN EN 20140-3.
  • Examples 3 to 5 according to the invention show an improved sound insulation property. Even compared to Comparative Example 1, which corresponds to the prior art in this application, a significant improvement of Examples 3 to 5 according to the invention is present. It can also be seen from Examples 4 and 5 according to the invention that the extension of the siloxane chain of the copolymer (B) leads to an improvement in the sound insulation properties.
  • Examples 6 to 8 (according to the invention): Production of TPSE laminated glass panes (without autoclave step, foil without embossing) To produce disks, the films with defined surface roughness from Example 2 were placed between two 4 mm thick glass panes and the structure was slowly run through a 400 ° C. pre-composite furnace. This procedure was repeated several times, containing a laminated glass pane containing fine air bubbles.
  • the films with defined surface roughness from Example 2 were placed between two 4 mm thick glass panes and the structure was slowly run through a 400 ° C. pre-composite furnace. This procedure was repeated several times, containing a bubble-free laminated glass.
  • Example 12 Production of glass PVB Geniomer® PVB glass laminates with a three-layer polymer film
  • PVB film 0.76 mm PVB film (Trosifol standard from HT Troplast GmbH, Troisdorf, Germany);
  • the individual layers were placed on each other and hot-laminated in a hot press at 150 0 C for 20 minutes. A laminate with good adhesion between the layers was obtained. At the interfaces PVB glass were still a few small air bubbles.
  • the disc was then placed in a rubber bag and laminated in an autoclave at a pressure of 12 kg / cm 2 and at a temperature of 140 ° C. It was completely free of bubbles laminated glass.
  • the individual layers were placed on each other and hot-laminated in a hot press at 150 0 C for 20 minutes. This gave a bubble-free laminate with good interlayer adhesion and excellent transparency.
  • a glass laminate with two polymeric intermediate layers was produced with the following layer structure (outer dimensions 20 ⁇ 20 cm):
  • PVB film 0.76 mm PVB film (Trosifol standard from HT Troplast GmbH, Troisdorf, Germany); 4 mm float glass;
  • the individual sheets were placed on each other and heat-laminated in a hot press at 150 0 C for 20 minutes. This gave a bubble-free laminate with good interlayer adhesion and excellent transparency. At the interface PVB glass were still a few small air bubbles.
  • the disc was then placed in a rubber bag and placed in an autoclave at a pressure of 12 kg / cm 2 and a Temperature of 140 0 C laminated. It was completely free of bubbles laminated glass.
  • Examples 12 to 14 show the production according to the invention of laminated glass with 2 or more intermediate polymeric layers.

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Abstract

The invention provides a laminated glass which comprises (A) at least one layer selected from the group containing organic or inorganic glass and (B) at least one layer of a linear organopolysiloxane/ polyurea/polyurethane block copolymer of the general formula (1), where R is a monovalent hydrocarbon radical having 1 to 20 carbon atoms which is optionally substituted by fluorine or chlorine, X is an alkylene radical having 1 to 20 carbon atoms, in which methylene units not adjacent to one another may have been replaced by -O- groups, A is an oxygen atom or an amino group -NR`-, Z is an oxygen atom or an amino group -NR`-, R` is hydrogen or an alkyl radical having 1 to 10 carbon atoms, Y is a divalent, unsubstituted or fluorine- or chlorine-substituted hydrocarbon radical having 1 to 20 carbon atoms, D is an alkylene radical having 1 to 800 carbon atoms which is unsubstituted or substituted by fluorine, chlorine, C1-C6 alkyl or C1-C6 alkyl ester and in which methylene units not adjacent to one another may have been replaced by -O-, -COO-, -OCO-, or -OCOO- groups, n is a number from 1 to 4000, a is a number which is at least 1, b is a number from 0 to 40, c is a number from 0 to 30 and d is a number greater than 0.

Description

Glaslaminate mit thermoplastischen Polysiloxan-Harnstoff- Glass laminates with thermoplastic polysiloxane-urea
Copolymerencopolymers
Gegenstand der Erfindung sind Glaslaminate, bei denen mindestens eine Schicht aus thermoplastischen Polysiloxan-Harnstoff-The invention relates to glass laminates in which at least one layer of thermoplastic polysiloxane-urea
Copolymeren besteht, ein Verfahren zu deren Herstellung und Ihre Verwendung .There is a copolymer, a process for their preparation and their use.
Glaslaminate sind seit langer Zeit bekannt und haben einen weiten Einsatzbereich als Verbundgläser im Automobil-, Fahrzeug- und Flugzeugbau sowie in der Bauindustrie.Glass laminates have been known for a long time and have a wide range of uses as laminated glasses in the automotive, vehicle and aircraft construction as well as in the construction industry.
Verbundglas ist sandwichartig aufgebaut und besteht aus mindestens einer Glastafel und einer darauf befindlichen polymeren Schicht. Am häufigsten wird als polymereLaminated glass is sandwiched and consists of at least one glass sheet and a polymeric layer thereon. Most commonly used as polymeric
Zwischenschicht weichgemachtes Polyvinylbutyral (PVB) in Folienform verwendet. Diese Technologie wird seit über 70 Jahren erfolgreich eingesetzt und wurde ständig weiterentwickelt und verfeinert, sowohl hinsichtlich der Polymerfolien als auch hinsichtlich der Verarbeitungstechnologien. Des Weiteren kann die Zwischenschicht auch aus Polyurethan oder Polyacrylat bestehen oder aus einer Kombination mehrerer verschiedener Werkstoffe .Interlayer plasticized polyvinyl butyral (PVB) used in film form. This technology has been used successfully for over 70 years and has been constantly refined and refined, both in terms of polymer films and processing technologies. Furthermore, the intermediate layer can also consist of polyurethane or polyacrylate or of a combination of several different materials.
Das Laminatglas hat gegenüber normalem Glas verschiedeneThe laminated glass is different from ordinary glass
Vorteile. Bei einem Bruch durch Gewalteinwirkung bindet die polymere Schicht die Splitter, so dass die Verletzungsgefahr wesentlich geringer ist als bei normalem Glas. Der Vorteil gegenüber Einscheibensicherheitsglas liegt darin, dass die Laminatglasscheibe nach einem Bruch auch weiterhin durchsichtig ist. Laminatglas erschwert auch das Durchdringen der Scheibenkonstruktion durch Gewalteinwirkung, wie Einbruch mit Werkzeugen, Projektile, oder bei Wirbelstürmen umherfliegende Gegenstande, wie beispielsweise größere Holzsplitter.Advantages. In the event of breakage by force, the polymeric layer binds the splinters, so that the risk of injury is considerably lower than with normal glass. The advantage over toughened safety glass is that the laminate glass pane continues to be transparent after a breakage. Laminate glass also complicates the penetration of the disc structure by violence, such as burglary with Tools, projectiles, or hurricanes flying objects, such as larger pieces of wood.
Durch den schichtweisen Aufbau und mit Hilfe von geeigneten polymeren Zwischenschichten kann Verbundglas neben den optischen und Sicherheitsaspekten auch gute zusatzliche Schall- und Wärmedämmung erreichen. Besonders guteDue to the layered structure and with the help of suitable polymeric interlayers, laminated glass can achieve good sound and heat insulation in addition to the optical and safety aspects. Especially good
Schalldammungseigenschaften erzielt man mit polymeren Zwischenschichten, die gute Vibrationsdampfung und einen hohen Verlustfaktor aufweisen. Durch die vibrationsdampfendenSoundproofing properties are achieved with polymeric interlayers that have good vibration damping and high loss factor. By the vibration steaming
Schichten wird die Übertragung der Schallwellen von der äußeren auf die innere Glas-Schicht gedampft und im Idealfall sogar unterbunden .Layers, the transmission of sound waves from the outer to the inner glass layer is evaporated and ideally even prevented.
Die Patentschrift WO 2004/039581 Al beschreibt ein schalldampfendes Verbundglas für Fahrzeuge, welches aus zwei Glasscheiben und einer einzigen dazwischenliegenden PVB-Lage besteht. Die PVB-Lage vereint dabei sowohl Schallabsorption als auch Durchdringfestigkeit und Haftung. Naturgemäß verlaufen gute Durchdringfestigkeiten und Schalldampfung kontrar, weshalb dem Material Grenzen bezuglich Schalldampfung gesetzt sind, wenn der Sicherheitsaspekt zusatzlich erfüllt sein soll.The document WO 2004/039581 Al describes a sound-damping laminated glass for vehicles, which consists of two glass panes and a single intermediate PVB layer. The PVB layer combines both sound absorption and penetration resistance and adhesion. Naturally, good penetration resistance and soundproofing run counter to each other, which is why the material has limits for soundproofing if the safety aspect is to be additionally fulfilled.
Ein sehr gravierender Nachteil der Laminatglaser aus PVB-Folien resultiert aus der relativ hohen Glasubergangstemperatur Tg des weichgemachten PVB, die im Falle der weichmacherhaltigen Typen normalerweise auf etwa 16°C eingestellt wird. Bei Temperaturen deutlich unterhalb oder deutlich oberhalb derA very serious disadvantage of the laminate glass of PVB films results from the relatively high glass transition temperature Tg of the plasticized PVB, which is usually set to about 16 ° C in the case of plasticized types. At temperatures well below or well above the
Glasubergangstemperatur verschlechtern sich viele der positiven Eigenschaften des Laminatglas-Verbunds wie beispielsweise die guten Sicherheitseigenschaften oder die schall- und vibrationsabsorbierende Wirkung. Besonders bei Temperaturen unter dem Gefrierpunkt wird das PVB so hart und spröde, dass die Sicherheitseigenschaften und besonders die schalldämmenden Eigenschaften des Verbundsicherheitsglases stark nachlassen.Glass transition temperature worsen many of the positive properties of the laminated glass composite such as the good safety properties or the sound and vibration absorbing effect. Especially at temperatures below freezing, the PVB becomes so hard and brittle that the Safety properties and especially the sound-insulating properties of the laminated safety glass greatly diminish.
Alternative Materialien für die polymere Zwischenschicht sind Polyurethane, Polyharnstoffe, Polyvinylchlorid, Epoxide,Alternative materials for the polymeric intermediate layer are polyurethanes, polyureas, polyvinyl chloride, epoxides,
Polyester wie beispielsweise Polyterephthalat, (Meth) -Acrylate, Silicone wie beispielsweise UV- oder heissvernetzende Silicone, kaltvernetzende 2-K-Silicone, feuchtigkeitsvernetzende Silicone, Siliconharzpolymere, modifizierte Silicon-Polymere, Heißschmelz- Klebstoffe, Beschichtungen und Dichtungsmassen, Piastisole, Polyethylen, Polypropylen, PVC, Polystyrol, Polycarbonat und Polyvinylacetat . Diese Materialien können zusätzlich Weichmacher enthalten. Laminate aus solchen Materialien sind beispielsweise in der Patentschrift WO 99/62707 beschrieben.Polyesters such as polyterephthalate, (meth) acrylates, silicones such as UV or hot-curing silicones, cold-curing 2-component silicones, moisture-crosslinking silicones, silicone resin polymers, modified silicone polymers, hot-melt adhesives, coatings and sealants, plastisols, polyethylene, polypropylene , PVC, polystyrene, polycarbonate and polyvinyl acetate. These materials may additionally contain plasticizers. Laminates of such materials are described, for example, in WO 99/62707.
Auch Polymerblends aus Thermoplastischen Silikonelastomeren, TPSE, und den oben erwähnten Materialien können als polymere Zwischenschicht eingesetzt werden.Also, polymer blends of thermoplastic silicone elastomers, TPSE, and the above-mentioned materials can be used as a polymeric interlayer.
Das US-Patent US 6,156,417 beschreibt Polyurethane, die auch durch Siloxane modifiziert sein können. Neben einer bloßen Zumischung von Siloxanen wird beschrieben, dass die Produkte durch Umsetzung von Siloxanolen mit Isocyanaten erhalten werden können, wodurch Silylurethane entstehen, die ebenfalls nicht hydrolysestabil sind. Darüber hinaus sind die mechanischen Festigkeiten, die sich mit siloxanhaltigen Polyurethanen erreichen lassen, für den Einsatzzweck im Laminatglas nicht ausreichend. Daran ändert sich auch nichts, wenn man hydrolysestabile hydroxyalkylfunktionelle Siloxane als Bausteine einsetzt. In der deutschen Patentschrift DE 1 596 960 sind Sicherheitsverbundglasgegenstände beschrieben, bei denen die Zwischenschicht aus einem siliciumhaltigen Polyurethan besteht. Diese siliciumhaltigen Polyurethane enthalten Umsetzungsprodukte aus Polyolen mit Siliconverbindungen, die Silanol- oder Alkoxysilangruppen enthalten. Dabei bilden sich polymere Verbindungen, die Si-O-C-Verknüpfungen enthalten, welche bekanntermaßen nicht hydrolysestabil sind. Im Laufe des Gebrauchs würden deshalb Laminatgläser mit solchen Polymeren von den Rändern her ihre Eigenschaften einbüßen, da eine allmähliche Zerstörung der Polymere eintritt. Die Funktion des Laminatglases ist damit in diesen Zonen nicht mehr gegeben. Die Polyurethane von DE 1 596 960 können auch siliciumhaltige Verbindungen mit Si-CH2-OH-Gruppen enthalten. Solche Verbindungen sind allerdings nur sehr schwer zugänglich und somit teuer in der Herstellung. Des Weiteren wird ausgeführt, dass Aminogruppen über Aminoalkohole eingeführt werden können, welche allerdings zu Produkten führen, die ebenfalls nicht hydrolysestabil sind und außerdem noch zum Verfärben neigen.US Pat. No. 6,156,417 describes polyurethanes which may also be modified by siloxanes. In addition to a mere addition of siloxanes is described that the products can be obtained by reacting siloxanols with isocyanates, whereby silylurethanes are formed, which are also not resistant to hydrolysis. In addition, the mechanical strengths that can be achieved with siloxane-containing polyurethanes are not sufficient for use in laminated glass. This is not changed by using hydrolysis-stable hydroxyalkyl-functional siloxanes as building blocks. German Patent DE 1 596 960 describes laminated safety glass articles in which the intermediate layer consists of a silicon-containing polyurethane. These silicon-containing polyurethanes contain reaction products of polyols with silicone compounds containing silanol or alkoxysilane groups. This forms polymeric compounds containing Si-OC linkages, which are known to be not resistant to hydrolysis. In the course of use, therefore, laminate glasses with such polymers would lose their properties from the edges, as a gradual destruction of the polymers occurs. The function of the laminate glass is thus no longer given in these zones. The polyurethanes of DE 1 596 960 may also contain silicon-containing compounds having Si-CH 2 -OH groups. However, such compounds are very difficult to access and therefore expensive to manufacture. Furthermore, it is stated that amino groups can be introduced via amino alcohols, which, however, lead to products which are likewise not resistant to hydrolysis and, moreover, tend to become discolored.
Die Anforderungen an die polymeren Schichten oder Zwischenschichten sind sehr groß und sollten idealerweise neben hoher Durchdringfestigkeit und sehr guter schalldämpfender Eigenschaft auch weitere Eigenschaften aufweisen wie zum Beispiel geringe oder keine Trübung, hohe Festigkeit, sehr gute UV-Stabilität, sehr gute Haftung auf Glas und geringe Feuchtigkeitsaufnahme bei sehr guter Feuchtigkeitsbeständigkeit.The requirements for the polymeric layers or intermediate layers are very large and should ideally in addition to high penetration resistance and very good sound-damping properties also have other properties such as little or no haze, high strength, very good UV stability, very good adhesion to glass and low Moisture absorption with very good moisture resistance.
Da ein Material kaum alle Eigenschaften gleichzeitig aufweist, wird in einer Reihe von Erfindungen auch eine Kombination von verschiedenen Polymerlagen aus teils unterschiedlichen Materialien beschrieben, von denen mindestens eine Schicht eine sehr gute Glashaftung und/oder Durchdringfestigkeit einerseits, eine weitere auf gute Schalldämpfung andererseits optimiert ist.Since a material hardly has all the properties at the same time, a number of inventions also describe a combination of different polymer layers of partly different materials, of which at least one layer is a very good glass adhesion and / or penetration resistance on the one hand, another optimized for good soundproofing on the other hand.
Die Patentschrift EP 0 457 190 Bl beschreibt ein schalldämpfendes Verbundglas, welches aus zwei Glasscheiben und mindestens zwei dazwischenliegenden PVB-Lagen besteht. Eine PVB- Lage dient dabei in erster Linie der Schallabsorption, während die andere für den Sicherheitsaspekt verantwortlich ist. Das hier beschriebene Laminat hat bei Raumtemperatur gute Schallabsorption und Sicherheitseigenschaften. Bei tieferThe patent EP 0 457 190 Bl describes a sound-absorbing laminated glass, which consists of two glass sheets and at least two intermediate PVB layers. One PVB layer primarily serves to absorb sound, while the other is responsible for the safety aspect. The laminate described here has good sound absorption and safety properties at room temperature. At lower
Temperatur verschlechtern sich durch das Einfrieren der PVB- Schichten diese Eigenschaften zwar nicht so drastisch wie bei Laminatscheiben mit einlagigen PVB-Folien, aber trotzdem deutlich.Although these properties are not so drastically impaired by the freezing of the PVB layers as in the case of laminate panes with single-layer PVB films, they nevertheless clearly deteriorate.
Die Patentschrift WO 98/26927 beschreibt ebenfalls schalldämpfende Glaslaminate, die ähnlich aufgebaut sind wie in der Patentschrift EP 0 457 190 Bl. Zwischen zwei Glasplatten befinden sich mindestens zwei Polymerlagen, von denen die eine flexibel ist und zu Sicherheitszwecken dient und beispielsweise aus weichgemachtem PVB besteht, während die zweite Lage schalldämpfende Eigenschaften trägt und beispielsweise aus Acrylatpolymeren besteht. Die hier beschriebenen Laminate haben bei Raumtemperatur gute Schallabsorption und Sicherheitseigenschaften, bei tiefer Temperatur nehmen diese Eigenschaften durch das Einfrieren der Acrylatschicht aber naturgemäß schnell ab. Außerdem ist die vibrationsdämpfende Acrylatschicht besonders empfindlich gegen Weichmacher oder Chemikalien, die aus den benachbarten PVB-Lagen oder besonders aus dem Randbereich eindiffundieren. Um Weichmacherwanderung zwischen den einzelnen Polymerschichten zu verhindern, werden auch Laminate beschrieben, die zwischen den einzelnen Polymerschichten Sperrschichten aus dünnen transparenten Polymeren aufweisen, die Weichmacherresistent sind. Nachteil ist hier der höhere Aufwand bei der Produktion und damit in den Hersteilkosten .The patent specification WO 98/26927 likewise describes sound-damping glass laminates of similar construction as in the patent EP 0 457 190 B1. Between two glass plates there are at least two polymer layers, one of which is flexible and serves for security purposes and consists for example of plasticized PVB while the second layer carries sound-absorbing properties and consists for example of acrylate polymers. The laminates described here have good sound absorption and safety properties at room temperature, but at low temperatures these properties naturally decrease rapidly as a result of the freezing of the acrylate layer. In addition, the vibration-damping acrylate layer is particularly sensitive to plasticizers or chemicals that diffuse from the adjacent PVB layers or especially from the edge area. In order to prevent plasticizer migration between the individual polymer layers, laminates are also described which have barrier layers of thin transparent layers between the individual polymer layers Have polymers that are plasticizer resistant. Disadvantage here is the higher cost of production and thus in the Hersteilkosten.
Die Patentschrift WO 2004/089616 Al beschreibt Laminatglas, welches als flexible und gleichzeitig schalldämpfende Schicht ein verzweigtes Polysiloxan-Harnstoff-Urethan-Copolymer enthält, welches ein Verhältnis von Harnstoff- zu Urethangruppen von mindestens 4:1 aufweist. Durch den Einbau der verzweigten Strukturen wird zwar die Festigkeit der polymerenThe patent document WO 2004/089616 A1 describes laminated glass which contains as a flexible and at the same time sound-damping layer a branched polysiloxane-urea-urethane copolymer which has a ratio of urea to urethane groups of at least 4: 1. By incorporating the branched structures, although the strength of the polymeric
Zwischenschicht erhöht, die schalldämpfenden Eigenschaften unterscheiden sich jedoch nicht von denen gewöhnlicher PVB- Folie. Eine weitere Verbesserung der schalldämpfenden Eigenschaften ist auch hier wünschenswert.Intermediate layer increased, but the sound-damping properties do not differ from those of ordinary PVB film. A further improvement of the sound-damping properties is also desirable here.
Aufgabe dieser Erfindung war es daher, ein Laminatglas zur Verfügung zu stellen, welches verbesserte schalldämmende Eigenschaften zeigt bei gleichzeitig guter Haftung, Stabilität und guten optischen Eigenschaften.It was therefore an object of this invention to provide a laminated glass which exhibits improved sound-insulating properties while at the same time having good adhesion, stability and good optical properties.
Diese Aufgabe konnte dadurch gelöst werden, dass als schalldämmende Schicht ein lineares Blockcopolymer verwendet wird, welches zu einer wesentlichen Verbesserung der schalldämmenden Eigenschaften des Glaslaminates führte.This object could be achieved by using a linear block copolymer as the sound-absorbing layer, which led to a substantial improvement in the sound-insulating properties of the glass laminate.
Gegenstand der Erfindung ist daher ein Laminatglas, welches umfasstThe invention therefore relates to a laminated glass comprising
(A) mindestens eine Schicht ausgewählt aus der Gruppe enthaltend anorganisches oder organisches Glas und (B) mindestens eine Schicht aus einem linearen(A) at least one layer selected from the group consisting of inorganic or organic glass and (B) at least one layer of a linear one
Organopolysiloxan/Polyharnstoff/Polyurethan-Blockcopolymer der allgemeinen Formel (1)Organopolysiloxane / polyurea / polyurethane block copolymer of the general formula (1)
RR
II
A-X — Si- O Si -X- A-C-N- Y- N-C- Z-D-Z C-N-Y- N-CA-X-Si-O-Si-X-A-C-N-Y-N-C-Z-D-Z C-N-Y-N-C
Il H H Il M H H M R O O O O nIl H H Il M H H M R O O O n n
:D: D
R IR I
-A-X — Si- O Si -X-A- -C-N- Y-N-C- N- Y-N-C--A-X - Si-O-Si -X-A-C-N-Y-N-C-N-Y-N-C-
Il H H M H H MIl H H M H H M
R o o oR o o o
wobeiin which
R einen einwertigen, gegebenenfalls durch Fluor oder Chlor substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen,R is a monovalent, optionally substituted by fluorine or chlorine hydrocarbon radical having 1 to 20 carbon atoms,
X einen Alkylen-Rest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen - 0- ersetzt sein können,X is an alkylene radical having 1 to 20 carbon atoms, in which non-adjacent methylene units may be replaced by groups - 0 -,
A ein Sauerstoffatom oder eine Aminogruppe -NRΛ-, Z ein Sauerstoffatom oder eine Aminogruppe -NRΛ-, RΛ Wasserstoff oder einen Alkylrest mit 1 bis 10 Kohlenstoffatomen,A is an oxygen atom or an amino group -NR Λ -, Z represents an oxygen atom or an amino group -NR Λ - Λ R is hydrogen or an alkyl radical having 1 to 10 carbon atoms,
Y einen zweiwertigen, unsubstituierten oder durch Fluor, Chlor oder Sauerstoff substituierten oder unterbrochenen Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen, D entweder einen unsubstituierten oder durch Fluor, Chlor, C]_- Cg-Alkyl- oder C]_-C5-Alkylester substituierten Alkylenrest mit 1 bis 800 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -0-, -COO-, -OCO-Y is a divalent, unsubstituted or fluorine, chlorine or oxygen-substituted or interrupted hydrocarbon radical having 1 to 20 carbon atoms, D is either an unsubstituted or substituted by fluorine, chlorine, C ] _Cg-alkyl or C ] _-C5-alkyl ester alkylene radical with 1 to 800 carbon atoms, where not each other adjacent methylene units by groups -O-, -COO-, -OCO-
, oder -OCOO-, ersetzt sein können, oder Y n eine Zahl von 1 bis 4000, a eine Zahl von mindestens 1, b eine Zahl von 0 bis 40, c eine Zahl von 0 bis 30 und d eine Zahl größer 0 bedeuten., or -OCOO-, may be replaced, or Y n is a number from 1 to 4000, a is a number of at least 1, b is a number from 0 to 40, c is a number from 0 to 30 and d is a number greater than 0.
Das erfindungsgemäße Laminatglas besitzt neben guten optischen auch hervorragende vibrations- und schalldämpfende Eigenschaften über einen weiten Temperaturbereich und kann sowohl für Fahrzeug-, Flugzeug- und Architekturverglasungen eingesetzt werden. Unter Architekturverglasung im Sinne dieser Erfindung versteht man Verglasungen, die bei der Herstellung von Gebäuden und Ihrer Einrichtung zum Einsatz kommen, wie beispielsweise Fenster, Türen, lichtdurchlässige Trennwände, Glasbauten und Verglasungen mit optischem oder künstlerischem Zweck.The laminate glass according to the invention has good optical as well as excellent vibration and sound damping properties over a wide temperature range and can be used for both vehicle, aircraft and architectural glazings. For the purposes of this invention, architectural glazing is understood to be glazing used in the manufacture of buildings and their furnishings, such as windows, doors, translucent partition walls, glass structures and glazings with an optical or artistic purpose.
Dabei ist die Beibehaltung einer hohen Transparenz inThe maintenance of high transparency is in
Wellenlängenbereich zwischen 400 - 800 nm von mindestens 89 % durch das erfindungsgemäße Laminatglas gewährleistet um die optische Qualität des Verbundglases nicht zu beeinflussen. Um eventuelle unerwünschte Reflexionen zu vermeiden oder zumindest zu minimieren ist ein Brechungsindex der polymerenWavelength range between 400 - 800 nm of at least 89% guaranteed by the laminate glass according to the invention in order not to influence the optical quality of the laminated glass. In order to avoid or at least minimize any undesired reflections, a refractive index of the polymeric
Zwischenschicht von 1,35 bis 1,80 im Bereich zwischen 400 und 800 nm erforderlich und auch durch das erfindungsgemäße Material gewährleistet. Die erfindungsgemäßen Laminatgläser zeigen eine Transparenz von mindestens 89 für den Wellenlängebereich von 350 bis 800 nm. Der Brechungsindex der Zwischenschichten in den erfindungsgemäßen Laminatgläsern beträgt im Wellenlängenbereich von 350 bis 800 nm mindestens 1,38 und vermeidet oder vermindert so eventuelle unerwünschte Reflexionen. Bevorzugt liegt der Brechungsindex bei 1,38 bis 1,70 in diesem Bereich.Intermediate layer of 1.35 to 1.80 required in the range between 400 and 800 nm and also ensured by the material according to the invention. The laminate glasses according to the invention exhibit a transparency of at least 89 for the wavelength range from 350 to 800 nm. The refractive index of the intermediate layers in the laminate glasses according to the invention is at least 1.38 in the wavelength range from 350 to 800 nm and avoids or reduces so any unwanted reflections. Preferably, the refractive index is 1.38 to 1.70 in this range.
Je längerkettiger die Siloxanketten im Copolymer sind, desto besser ist die Schalldämpfung des damit hergestellten Laminats. Im Unterschied zum weichgemachten PVB bleiben die vibrationsdämpfenden und sicherheitsrelevanten Eigenschaften des erfindungsgemäßen Laminatglases besonders bei tiefen Temperaturen konstant, was gegenüber dem Stand der Technik einen großen Vorteil darstellt. Die hervorragenden optischenThe longer-chain the siloxane chains in the copolymer, the better the soundproofing of the laminate produced therewith. In contrast to the plasticized PVB, the vibration-damping and safety-relevant properties of the laminate glass according to the invention remain constant, especially at low temperatures, which represents a great advantage over the prior art. The excellent optical
Eigenschaften und die Substrathaftung des Blockcopolymers im erfindungsgemäßen Laminatglas werden nicht durch eindiffundierende Weichmacher oder sonstige Chemikalien beispielsweise aus Dichtstoffen des Randverbundes von Isolierglas-Fenstern verschlechtert.Properties and the substrate adhesion of the block copolymer in the laminated glass according to the invention are not impaired by diffusing plasticizers or other chemicals, for example from sealants of the edge bond of insulating glass windows.
Bevorzugt enthält das erfindungsgemäße Laminatglas mindestens zwei Schichten (A) aus anorganischem oder organischem Glas.The laminate glass according to the invention preferably contains at least two layers (A) of inorganic or organic glass.
Als anorganisches oder organisches Glas (A) im Sinne dieser Erfindung sind gehärtete und ungehärtete Mineralgläser sowie organische Gläser wie Polycarbonat, Plexiglas, Polyester, Polystyrol, Polyacrylat, Polymethylmethacrylat, PVC, Polypropylen und Polyethylen sowie Copolymere aus diesen Polymeren.As inorganic or organic glass (A) for the purposes of this invention are hardened and uncured mineral glasses and organic glasses such as polycarbonate, Plexiglas, polyester, polystyrene, polyacrylate, polymethyl methacrylate, PVC, polypropylene and polyethylene and copolymers of these polymers.
Organopolysiloxan/Polyharnstoff/Polyurethan-Blockcopolymere (B) und Verfahren zu ihrer Herstellung sind beispielsweise in den Patentschriften DE 10137855 A, DE 10313936 A, DE 10313938 A und DE 10326575 A beschrieben, deren diesbezügliche Offenbarung auch Gegenstand dieser Anmeldung sein soll. Vorzugsweise bedeutet R einen einwertigen, Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen, insbesondere nicht substituiert. Besonders bevorzugte Reste R sind Methyl, Ethyl, Vinyl und Phenyl . Vorzugsweise bedeutet X einen Alkylen-Rest mit 1 bis 10Organopolysiloxane / polyurea / polyurethane block copolymers (B) and processes for their preparation are described, for example, in the patents DE 10137855 A, DE 10313936 A, DE 10313938 A and DE 10326575 A, the disclosure of which is also intended to be the subject of this application. Preferably, R is a monovalent, hydrocarbon radical having 1 to 6 carbon atoms, in particular unsubstituted. Particularly preferred radicals R are methyl, ethyl, vinyl and phenyl. Preferably, X is an alkylene radical having 1 to 10
Kohlenstoffatomen . Vorzugsweise ist der Alkylen-Rest X nicht unterbrochen. Bevorzugt ist X ein Methylen- oder Propylenrest .Carbon atoms. Preferably, the alkylene radical X is not interrupted. X is preferably a methylene or propylene radical.
Vorzugsweise bedeutet A eine NH-Gruppe.Preferably, A is an NH group.
Vorzugsweise bedeutet Z ein Sauerstoffatom oder eine NH-Gruppe.Preferably, Z represents an oxygen atom or an NH group.
Vorzugsweise bedeutet Y einen Kohlenwasserstoffrest mit 3 bis 13Preferably, Y is a hydrocarbon radical having 3 to 13
Kohlenstoffatomen, der vorzugsweise nicht substituiert ist.Carbon atoms, which is preferably unsubstituted.
Vorzugsweise bedeutet Y einen Aralkylen-, linearen oder cyclischen Alkylen-Rest.Preferably, Y is an aralkylene, linear or cyclic alkylene radical.
Vorzugsweise bedeutet D einen Alkylenrest mit mindestens 2, insbesondere mindestens 4 Kohlenstoffatomen und höchstens 12 Kohlenstoffatomen . Ebenfalls vorzugsweise bedeutet D einen Polyoxyalkylenrest, insbesondere Polyoxyethylenrest oderPreferably, D is an alkylene radical having at least 2, in particular at least 4 carbon atoms and at most 12 carbon atoms. Also preferably, D is a polyoxyalkylene radical, in particular polyoxyethylene radical or
Polyoxypropylenrest mit mindestens 20, insbesondere mindestens 100 Kohlenstoffatomen und höchstens 800, insbesondere höchstens 200 Kohlenstoffatomen . Vorzugsweise ist der Rest D nicht substituiert .Polyoxypropylene radical having at least 20, in particular at least 100 carbon atoms and at most 800, in particular at most 200 carbon atoms. Preferably, the radical D is not substituted.
n bedeutet vorzugsweise eine Zahl von mindestens 3, insbesondere mindestens 25 und vorzugsweise höchstens 800, insbesondere höchstens 400, besonders bevorzugt höchstens 250.n is preferably a number of at least 3, in particular at least 25 and preferably at most 800, in particular at most 400, particularly preferred at most 250.
Vorzugsweise bedeutet a eine Zahl von höchstens 50.Preferably, a is a number of at most 50.
Wenn b ungleich 0, bedeutet b vorzugsweise eine Zahl von höchstens 50, insbesondere höchstens 25. c bedeutet vorzugsweise eine Zahl von höchstens 10, insbesondere höchstens 5.When b is not 0, b is preferably a number of at most 50, especially at most 25. c is preferably a number of at most 10, in particular at most 5.
d bedeutet vorzugsweise eine Zahl von 10 bis 200, bevorzugt von 30 bis 100.d is preferably a number from 10 to 200, preferably from 30 to 100.
Als Endgruppen der Organopolysiloxan/Polyharnstoff/Polyurethan- Blockcopolymere können übliche Endgruppen nach dem Stand der Technik vorkommen, die bei der Synthese solcher Polymere standardmäßig entstehen, wie beispielsweise Amino- oder Isocyanat-Endgruppen . Diese können während der Synthese oder nachträglich noch mit weiteren Gruppen umgesetzt werden, wie beispielsweise Amino- oder Isocyanato-Silanen . Die Organopolysiloxan/Polyharnstoff/Polyurethan-Blockcopolymere enthalten daher vorzugsweise als Endgruppen B einen funktionellen oder nicht-funktionellen organischen oder siliciumorganischen Rest. Solche Endgruppen B sind beispielsweise in der oben erwähnten DE 10313936 A und DE 10326575 A beschrieben.As end groups of the organopolysiloxane / polyurea / polyurethane block copolymers conventional end groups can occur according to the prior art, which are standard in the synthesis of such polymers, such as amino or isocyanate end groups. These can be reacted during the synthesis or subsequently with other groups, such as amino or isocyanato-silanes. The organopolysiloxane / polyurea / polyurethane block copolymers therefore preferably contain as end groups B a functional or non-functional organic or organosilicon radical. Such end groups B are described, for example, in the abovementioned DE 10313936 A and DE 10326575 A.
Als Polydiorganosiloxandiamin wird bevorzugt solches der allgemeinen Formel (2)As polydiorganosiloxanediamine, preference is given to those of the general formula (2)
H2N-X- [ S iR2 O ] nS iR2 -X-NH2 ( 2 )H 2 NX- [S iR 2 O] n S iR 2 -X-NH 2 ( 2 )
wobei R, X und n die oben dafür angegebene Bedeutung haben, eingesetzt .wherein R, X and n have the meaning given above, used.
Vorzugsweise sind im Copolymer der allgemeinen Formel (1), bezogen auf die Summe der Urethan- und Harnstoffgruppen, mindestens 50 Mol-%, insbesondere mindestens 75 Mol-% Harnstoffgruppen enthalten. Als Polyisocyanat wird bevorzugt ein Diisocyanat der allgemeinen Formel (3)Preferably, in the copolymer of the general formula (1), based on the sum of the urethane and urea groups, at least 50 mol%, in particular at least 75 mol% of urea groups. As the polyisocyanate, a diisocyanate of the general formula (3) is preferably used.
OCN-Y-NCO (3)OCN-Y-NCO (3)
wobei Y die oben dafür angegebene Bedeutung hat, eingesetzt .where Y has the meaning given above, used.
Beispiele für die zu verwendenden Diisocyanate der allgemeinen Formel (3) sind aliphatische Verbindungen wieExamples of the diisocyanates of the general formula (3) to be used are aliphatic compounds, such as
Isophorondiiscyanat, Hexamethylen-1, 6-diisocyanat, 2,2,4-und 2,4, 4-Trimethylhexamethylendiisocyanat, Cyclohexylendiisocyanat, Tetramethylen-1 , 4-diisocyanat und Methylendicyclohexy-4, 4 Λ- diisocyanat oder aromatische Verbindungen wie Methylendiphenyl- 4, 4 Λ-diisocyanat, 2, 4-Toluoldiisocyanat, 2, 5-Toluoldiisocyanat, 2, 6-Toluoldiisocyanat, m-Phenylendiisocyanat, p-Phenylen- diisocyanat, m-Xyloldiisocyanat, Tetramethyl-m-xylol- diisocyanat, Mischungen dieser Isocyanate oder geblockte Typen. Ein Beispiel für kommerziell erhältliche derartige Verbindungen sind die Diisocyanate der DESMODUR®-Reihe (H, I, M, T, W) der Bayer AG, Leverkusen, Deutschland oder die Vestanat-Reihe der Degussa AG, Düsseldorf, Deutschland. Bevorzugt sind aliphatische Diisocyanate, bei denen Y ein Alkylenrest ist, da diese Copolymere mit verbesserter UV-Stabilität ergeben, was bei einer Außenanwendung der Polymere von Vorteil ist.Isophorone diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, cyclohexylene diisocyanate, tetramethylene-1,4-diisocyanate and methylenedicyclohexy- 4,4 -diisocyanate or aromatic compounds, such as methylenediphenyl-4 , 4 Λ diisocyanate, 2, 4-toluene diisocyanate, 2, 5-toluene diisocyanate, 2, 6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, m-xylene diisocyanate, tetramethyl-m-xylene diisocyanate, mixtures of these isocyanates or blocked types. An example of commercially available such compounds are the diisocyanates of the DESMODUR® series (H, I, M, T, W) of Bayer AG, Leverkusen, Germany or the Vestanat series of Degussa AG, Dusseldorf, Germany. Preference is given to aliphatic diisocyanates in which Y is an alkylene radical since these give copolymers having improved UV stability, which is advantageous in the case of external application of the polymers.
Vor allem durch den Einsatz von Kettenverlängerern wie Diaminoverbindungen, Dihydroxyverbindungen oder Wasser zusätzlich zu den Harnstoffgruppen kann eine deutliche Verbesserung der mechanischen Eigenschaften der Blockcopolymere erreicht werden. So können Materialien erhalten werden, die in den mechanischen Eigenschaften mit herkömmlichen Siliconkautschuken durchaus vergleichbar sind, jedoch eine erhöhte Transparenz aufweisen und in die kein zusätzlicher aktiver Füllstoff eingearbeitet werden muss. Falls b mindestens 1 ist, können im zweiten Schritt bis zu 95 Gewichtsprozent, bezogen auf alle eingesetzten Komponenten, Kettenverlängerer ausgewählt aus der Gruppe von Diaminen, Isocyanat-geblockten Hydroxy-Verbindungen, Dihydroxy- Verbindungen und Mischungen davon, eingesetzt werden.Especially through the use of chain extenders such as diamino compounds, dihydroxy compounds or water in addition to the urea groups, a significant improvement in the mechanical properties of the block copolymers can be achieved. Thus, it is possible to obtain materials which are comparable in their mechanical properties to conventional silicone rubbers, but have increased transparency and in which no additional active filler has to be incorporated. If b is at least 1, in the second step up to 95 percent by weight, based on all components used, of chain extenders selected from the group of diamines, isocyanate-blocked hydroxy compounds, dihydroxy compounds and mixtures thereof can be used.
Vorzugsweise weisen die Kettenverlängerer die allgemeine Formel (4)Preferably, the chain extenders have the general formula (4)
HZ-D-ZH (4)HZ-D-ZH (4)
auf, wobei D und Z die vorstehenden Bedeutungen aufweisen. Falls Z die Bedeutung O (Sauerstoff) hat, kann der Kettenverlängerer (4) mit Diisocyanat (3) umgesetzt werden auch vor der Umsetzung des Polydiorganosiloxandiamins (2) mit Diisocyanat (3).wherein D and Z have the above meanings. If Z has the meaning O (oxygen), the chain extender (4) can be reacted with diisocyanate (3) even before the reaction of polydiorganosiloxane diamine (2) with diisocyanate (3).
Die OC, ω-OH-terminierten Alkylene der allgemeinen Formel (4) sind bevorzugt Polyalkylene oder Polyoxyalkylene . Diese sind vorzugsweise weitgehend frei von Kontaminationen aus mono-, trioder höherfunktionellen Polyoxyalkylenen . Hierbei können Polyetherpolyole, Polytetramethylendiole, Polyesterpolyole, Polycaprolactondiole, aber auch CC, ω-OH-terminierte Polyalkylene auf Basis von Polyvinylacetat, Polyvinylacetatethylencopolymere, Polyvinylchloridcopolymer, Polyisobutlydiole eingesetzt werden. Bevorzugt werden dabei Polyoxyalkyle verwendet, besonders bevorzugt Polypropylenglykole . Derartige Verbindungen sind als Basismaterialien unter anderem für Polyurethan-Weichschäume und für Beschichtungsanwendungen kommerziell mit Molekularmassen Mn bis über 10 000 erhältlich. Beispiele hierfür sind die BAYCOLL® Polyetherpolyole und Polyesterpolyole der Bayer AG, Deutschland oder die Acclaim® Polyetherpolyole der Firma Lyondell Inc., Housten, USA. Es können auch monomere OC, ω-Alkylendiole, wie Ethylenglykol, Propandiol, Butandiol oder Hexandiol eingesetzt werden. Weiterhin sind als Dihydroxyverbindungen im Sinne der Erfindung auch Bishydroxyalkylsilicone zu verstehen, wie sie beispielsweise von der Firma Goldschmidt GmbH, Essen, Deutschland unter dem Namen Tegomer H-Si 2111, 2311 und 2711 vertrieben werden.The OC, ω-OH-terminated alkylenes of the general formula (4) are preferably polyalkylenes or polyoxyalkylenes. These are preferably substantially free of contaminants from mono-, tri or higher polyoxyalkylenes. In this case, it is possible to use polyether polyols, polytetramethylene diols, polyester polyols, polycaprolactone diols, but also CC, ω-OH-terminated polyalkylenes based on polyvinyl acetate, polyvinyl acetate-ethylene copolymers, polyvinyl chloride copolymer, polyisobutlydiols. Preference is given here polyoxyalkyls are used, more preferably polypropylene glycols. Such compounds are commercially available as base materials, inter alia, for polyurethane flexible foams and for coating applications with molecular masses M n to over 10,000. Examples of these are the BAYCOLL® polyether polyols and polyester polyols from Bayer AG, Germany or the Acclaim® polyether polyols from Lyondell Inc., Housten, USA. It is also possible to use monomeric OC, ω-alkylene diols, such as ethylene glycol, propanediol, butanediol or hexanediol. Furthermore, as dihydroxy compounds in the sense of The invention also Bishydroxyalkylsilicone to understand how they are for example sold by the company Goldschmidt GmbH, Essen, Germany under the name Tegomer H-Si 2111, 2311 and 2711.
Der Wassergehalt der gemäß der vorliegenden Erfindung hergestellten Copolymere von Formel (1) liegt bevorzugt unter 0,5 Gew.-% und ganz besonders bevorzugt unter 0.1 Gew.-%.The water content of the copolymers of formula (1) prepared according to the present invention is preferably less than 0.5% by weight and most preferably less than 0.1% by weight.
Die Herstellung der oben beschriebenen Copolymere der allgemeinen Formel (1) kann sowohl in Lösung als auch in Festsubstanz, kontinuierlich oder diskontinuierlich erfolgen. Wesentlich dabei ist, dass für die gewählte Polymermischung unter den Reaktionsbedingungen eine optimale und homogene Durchmischung der Bestandteile erfolgt und eineThe preparation of the above-described copolymers of the general formula (1) can be carried out both in solution and in solid substance, continuously or discontinuously. It is essential that for the selected polymer mixture under the reaction conditions, an optimal and homogeneous mixing of the components takes place and a
Phasenunverträglichkeit gegebenenfalls durch Lösungsvermittler verhindert wird. Bevorzugt ist eine Synthese ohne Lösungsmittel,Phase incompatibility is optionally prevented by solubilizers. Preference is given to a synthesis without solvent,
Für die Reaktion ohne Lösungsmittel ist die Homogenisierung der Mischung von entscheidender Bedeutung bei der Umsetzung. Ferner kann die Polymerisation auch durch die Wahl der Reaktionsfolge bei einer Stufensynthese gesteuert werden.For the reaction without solvent, the homogenization of the mixture is of crucial importance in the reaction. Furthermore, the polymerization can also be controlled by the choice of the reaction sequence in a step synthesis.
Die Herstellung erfolgt vorzugsweise für eine bessere Reproduzierbarkeit generell unter Ausschluss von Feuchtigkeit und unter Schutzgas, üblicherweise Stickstoff oder Argon.The preparation is preferably carried out for better reproducibility generally with the exclusion of moisture and under protective gas, usually nitrogen or argon.
Die Umsetzung kann sowohl unter Zugabe als auch ohne Zugabe eines Katalysators erfolgen. Geeignete Katalysatoren für die Herstellung sind Dialkylzinnverbindungen, wie beispielsweiseThe reaction can be carried out both with addition and without addition of a catalyst. Suitable catalysts for the preparation are dialkyltin compounds, such as
Dibutylzinndilaurat, Dibutylzinndiacetat, Metallcarboxylate wie Bismut-, Zinn- oder Zinkcarboxylate oder tertiäre Amine wie beispielsweise N, N-Dimethylcyclohexanamin, 2- Dimethylaminoethanol, 4-Dimethylaminopyridin . Die erfindungsgemäßen Laminate zeigen gute optische Qualität, bedingt durch die gute Haftung von (B) an (A) , als auch durch die hydrophoben Eigenschaften von (B) .Dibutyltin dilaurate, dibutyltin diacetate, metal carboxylates such as bismuth, tin or zinc carboxylates or tertiary amines such as N, N-dimethylcyclohexanamine, 2-dimethylaminoethanol, 4-dimethylaminopyridine. The laminates of the invention show good optical quality, due to the good adhesion of (B) to (A), as well as by the hydrophobic properties of (B).
Das erfindungsgemäße Laminatglas kann zusätzlich weitere Schichten (C) enthalten ausgewählt aus der Gruppe enthaltend Polyvinylbutyral, Polyurethane, Polyharnstoffe,The laminate glass according to the invention may additionally contain further layers (C) selected from the group comprising polyvinyl butyral, polyurethanes, polyureas,
Polyvinylchlorid, Epoxide, Polyester, (Meth) -Acrylate, Silicone, Siliconharzpolymere, modifizierte Silicon-Polymere, Heißschmelz- Klebstoffe, Beschichtungen und Dichtungsmassen, Piastisole, Polyethylen, Polyvinylacetat, Polypropylen, PVC, Polystyrol, Polycarbonat und deren Mischungen.Polyvinyl chloride, epoxies, polyesters, (meth) acrylates, silicones, silicone resin polymers, modified silicone polymers, hot melt adhesives, coatings and sealants, plastisols, polyethylene, polyvinyl acetate, polypropylene, PVC, polystyrene, polycarbonate, and mixtures thereof.
Ein als Schicht (C) geeigneter Polyester ist beispielsweise Polyterephthalat . Geeignete Silicone sind beispielsweise UV- oder heissvernetzende Silicone, kaltvernetzende 2-K-Silicone und feuchtigkeitsvernetzende Silicone .A polyester suitable as layer (C) is, for example, polyterephthalate. Suitable silicones are, for example, UV- or hot-curing silicones, cold-curing 2-component silicones and moisture-crosslinking silicones.
Die zusätzlichen Schichten (C) können ebenfalls auch Weichmacher enthalten .The additional layers (C) may also contain plasticizers.
Zur Verbesserung der Haftung können dem Blockcopolymer (B) haftvermittelnde Silane zugegeben werden, wie beispielsweise Silane mit hydrolysierbaren Gruppen und SiC-gebundenen Vinyl-, Acryloxy-, Methacryloxy-, Isocyanato-, Epoxy-, Säureanhydrid-, Säure-, Ester- oder Ethergruppen sowie deren Teil- und Mischhydrolysate .To improve the adhesion, it is possible to add adhesion-promoting silanes to the block copolymer (B), for example silanes with hydrolyzable groups and SiC-bonded vinyl, acryloyloxy, methacryloxy, isocyanato, epoxy, acid anhydride, acid, ester or ether groups as well as their partial and mixed hydrolysates.
Beispiele für Haftvermittler sind 3-Examples of adhesion promoters are 3-
Isocyanatopropyltrimethoxysilan, 3-Isocyanatopropyltriethoxy- silan, 3-Isocyanatopropyldimethoxymethylsilan, 3-Isocyanatopro- pyldiethoxymethylsilan, 3-Isocyanatopropylmethoxydimethylsilan, 3-Isocyanatopropylethoxydimethylsilan, Isocyanatomethyltrimeth- oxysilan, Isocyanatomethyltriethoxysilan, Isocyanatomethyldi- methoxymethylsilan, Isocyanatomethyldiethoxymethylsilan, Isocya- natomethylmethoxydimethylsilan und Isocyanatomethylethoxydi- methylsilan3-Aminopropyltrimethoxysilan, 3-Aminopropyltriethoxy- silan, 3- (2-Aminoethyl) aminopropyltrimethoxysilan, 3- (2-Ami- noethyl) aminopropyltriethoxysilan, 3-Aminopropylmethyldimethoxy- silan, 3- (2-Aminoethyl) aminopropylmethyldimethoxysilan, Cyclohe- xylaminomethyltriethoxysilan, Glycidoxypropyltrimethoxysilan, Glycidoxypropyltriethoxysilan .Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanato-propyldiethoxymethylsilane, 3-isocyanatopropylmethoxydimethylsilane, 3-isocyanatopropylethoxydimethylsilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane, isocyanatomethyldiethoxymethylsilane, isocyanatomethylmethoxydimethylsilane and isocyanatomethylethoxydimethylsilane-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, cyclohexylaminomethyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane.
Silane mit Vinylgruppen und Silane mit Epoxygruppen, die als hydrolysierbare Reste Ethoxy- oder Acetoxygruppen enthalten, sind bevorzugt. Glycidoxypropyltriethoxysilan, Vinyltriethoxysilan und Vinyltriacetoxysilan, bzw. deren Teil- und Mischhydrolysate sind besonders bevorzugt.Silanes with vinyl groups and silanes with epoxy groups which contain ethoxy or acetoxy groups as hydrolyzable groups are preferred. Glycidoxypropyltriethoxysilane, vinyltriethoxysilane and vinyltriacetoxysilane, and their partial and mixed hydrolysates are particularly preferred.
Die Haftvermittler werden in Mengen von 0,01% bis 5%, bevorzugt 0,1% bis 2%, besonders bevorzugt zwischen 0,4% und 0,7%, jeweils bezogen auf die Gesamtmasse an Blockcopolymer (B) zugegeben.The adhesion promoters are added in amounts of 0.01% to 5%, preferably 0.1% to 2%, particularly preferably between 0.4% and 0.7%, in each case based on the total mass of block copolymer (B).
Die haftvermittelnden Silane, beziehungsweise deren Lösungen und Hydrolyse-Kondensationsprodukte, können auch auf die Oberfläche der aus den Blockcopolymeren (B) hergestellten Folien aufgebracht werden.The adhesion-promoting silanes, or their solutions and hydrolysis condensation products, can also be applied to the surface of the films produced from the block copolymers (B).
Vorzugsweise werden haftvermittelnde Silane nach der Herstellung auf die Folie aus Organopolysiloxan/Polyharnstoff/Polyurethan- Blockcopolymer (B) , auf das anorganische oder organische Glas (A) , auf die zweite Schicht (C) oder auf alle 3 Komponenten (A), (B) und (C) aufgebracht. Das Aufbringen der haftvermittelnden Silane erfolgt nach dem Stand der Technik, vor der Herstellung des Verbundes, auf die Blockcopolymer (B) , das anorganische oder organische Glas (A) und/oder die weitere Schicht (C) . Es kann eine Lösung von Haftvermittlern in einem geeigneten Lösungsmittel eingesetzt werden. Für dieses Verfahren hat sich der Begriff Primern eingebürgert .Preferably, adhesion-promoting silanes are prepared after production on the sheet of organopolysiloxane / polyurea / polyurethane block copolymer (B), on the inorganic or organic glass (A), on the second layer (C) or on all 3 components (A), (B ) and (C) applied. The adhesion-promoting silanes are applied according to the prior art, prior to the preparation of the composite, to the block copolymer (B), the inorganic or organic glass (A) and / or the further layer (C). A solution of adhesion promoters in a suitable solvent can be used. For this method, the term primer has become common.
Dem Blockcopolymer (B) können weitere Additive zugegeben werden, ausgewählt aus der Gruppe enthaltend Farbstoffe, Pigmente, Füllstoffe, Katalysatoren, Hitzestabilisatoren, Weichmacher, Vernetzer, Flammschutzmittel und Lichtstabilisatoren oder deren Mischungen. Solche Additive sind dem Fachmann aus der Polyurethan- und Siliconchemie bekannt.The block copolymer (B) may be added further additives selected from the group consisting of dyes, pigments, fillers, catalysts, heat stabilizers, plasticizers, crosslinkers, flame retardants and light stabilizers or mixtures thereof. Such additives are known to those skilled in the polyurethane and silicone chemistry.
Ebenso können alle anderen Polymere (C) sowie die organischen Gläser der Schicht (A) , die zum Aufbau des Laminates verwendet werden, die oben genannten Additive enthalten. Alle diese Additive können materialspezifisch sein und sind dem Fachmann aus der Polymerchemie bekannt.Likewise, all other polymers (C) as well as the organic glasses of the layer (A), which are used for the construction of the laminate, containing the above-mentioned additives. All of these additives may be material-specific and are known to those skilled in polymer chemistry.
Die Herstellung des Verbundes zwischen der Schicht (A) beziehungsweise den Schichten (A) und dem Blockcopolymer (B) erfolgt gemäß dem Stand der Technik.The preparation of the composite between the layer (A) or the layers (A) and the block copolymer (B) is carried out according to the prior art.
Das Laminatglas ist sandwichartig aufgebaut und besteht aus mindestens einer Schicht (A) und einer darauf befindlichen Schicht aus Blockcopolymer (B) , in der Regel aber aus mindestens zwei Schichten (A) und einer Zwischenschicht (B) , die die Schichten (A) miteinander verbindet. Die Schichten (A) können entweder aus anorganischen Gläsern, wie zum Beispiel Floatglas und/oder aus organischen Gläsern, wie Polycarbonat- (PC) oder Polymethylmethacrylatglas (PMMA) bestehen. Die anorg. oder org. Glasschichten (A) können auch mit mehreren Polymerschichten laminiert werden, von der aber mindestens eine aus dem erfindungsgemäßen Blockcopolymer (B) bestehen muss. Die Schicht aus Blockcopolymer (B) kann also aus einem einheitlichen Material bestehen, oder auch selbst mehrschichtig aus verschiedenen Schichten aus Blockcopolymer (B) aufgebaut sein oder ein Laminat aus verschiedenartigen Polymeren sein, von der mindestens eine aus Blockcopolymer (B) bestehen muss.The laminate glass is sandwiched and consists of at least one layer (A) and a layer of block copolymer (B) located thereon, but usually at least two layers (A) and an intermediate layer (B), the layers (A) together combines. The layers (A) may consist of either inorganic glasses, such as float glass and / or organic glasses, such as polycarbonate (PC) or polymethyl methacrylate (PMMA) glass. The anorg. or org. Glass layers (A) can also be laminated with several polymer layers, but of which at least one must consist of the block copolymer (B) according to the invention. The layer of block copolymer (B) can thus consist of a uniform material, or itself be multilayer composed of different layers of block copolymer (B) or be a laminate of various polymers, of which at least one of block copolymer (B) must exist.
Für das Verfahren zur Herstellung des Laminatglases wird das lineare Organopolysiloxan/Polyharnstoff/ Polyurethan- Blockcopolymer (B) hergestellt und anschließend auf mindestens eine Schicht (A) aufgebracht.For the process for producing the laminate glass, the linear organopolysiloxane / polyurea / polyurethane block copolymer (B) is prepared and then applied to at least one layer (A).
Eine Möglichkeit zur Herstellung des Laminatglases besteht darin, dass auf eine der Schichten (A) verflüssigtes Blockcopolymer (B) durch beispielsweise Rakel, Walzen oder auch Siebdruck aufgebracht wird. Das Laminatglas wird dann schließlich erhalten, indem die zweite Schicht (A) auf die Schicht aus Blockcopolymer (B) gelegt wird und durchOne possibility for producing the laminate glass is to apply liquefied block copolymer (B) to one of the layers (A) by, for example, doctoring, rolling or screen printing. The laminated glass is then finally obtained by placing the second layer (A) on the layer of block copolymer (B) and passing through
Temperaturerhöhung, bis zum Erweichen des Blockcopolymeren (B) , und gleichzeitigem Pressen der Verbund erhalten wird.Temperature increase, until the softening of the block copolymer (B), and simultaneous pressing of the composite is obtained.
Eine zweite Möglichkeit besteht darin, dass die beiden gegebenenfalls wiederum mit Haftvermittler behandelten Schichten (A) durch geeignete Abstandshalter so zusammengesetzt werden, dass ein Spalt von definierter Breite erhalten wird. In diesen Spalt wird nun verflüssigtes Blockcopolymer (B) aus einem geeigneten beheizten Vorratsgefäß durch eine Dosiereinrichtung eingebracht, wobei die Kanten der Glastafeln so verschlossen sind, dass die Polymerschmelze nicht an unerwünschten Stellen austritt und nur die zwischen den Glastafeln befindliche Luft entweichen kann. Ein weitere Ausführungsform dieser Methode verwendet 1-Komponenten- oder 2-Komponenten-Gussmassen, die entweder bei Raumtemperatur, thermisch oder optisch in der Zwischenschicht aushärten.A second possibility is that the two optionally in turn treated with adhesion promoter layers (A) are assembled by suitable spacers so that a gap of defined width is obtained. Liquefied block copolymer (B) is then introduced from a suitable heated storage vessel through a metering device into this gap, wherein the edges of the glass plates are closed in such a way that the polymer melt does not escape at undesired points and only the air located between the glass plates can escape. Another embodiment of this method uses 1-component or 2-component molding compounds, which cure either at room temperature, thermally or optically in the intermediate layer.
Die bevorzugte Möglichkeit der Herstellung des Laminatglases besteht darin die Schicht aus Blockcopolymer (B) als Folie herzustellen. Bevorzugt wird eine geprägte Folie mit einer definierten Oberflächenrauhigkeit eingesetzt, um Lufteinschlüsse beim Laminieren zu minimieren. Der Verbund wird anschließend erhalten, indem die Folie aus (B) zwischen die beiden Schichten (A) gelegt wird und unter Druck und Temperatur dauerhaft verbunden wird. Diese Behandlung erfolgt bevorzugt durch Erhitzen der aufeinander liegenden Lagen in einem heißen Vorverbundofen und anschließendes mehrstündiges Verpressen im Druckautoklaven bei etwa 100 bis 1500C. Auch hier kann eineThe preferred way of producing the laminate glass is to produce the layer of block copolymer (B) as a film. Preferably, an embossed film with a defined surface roughness is used to minimize air pockets during lamination. The composite is then obtained by placing the film of (B) between the two layers (A) and permanently bonded under pressure and temperature. This treatment is preferably carried out by heating the superimposed layers in a hot Vorverbundofen and then pressing for several hours in a pressure autoclave at about 100 to 150 0 C. Again, a
Vorbehandlung der Schichten (A) und/oder (B) mit Haftvermittlern erfolgen .Pre-treatment of the layers (A) and / or (B) with adhesion promoters.
Das bevorzugte Verfahren zur Herstellung der erfindungsgemäßen Laminatgläsern ist dadurch gekennzeichnet, dass a) die Schicht (B) als Folie hergestellt wird, b) mindestens eine Folie (B) anschließend zwischen zwei Schichten (A) gelegt wird und c) unter Druck und Temperatur dauerhaft verbunden wird.The preferred method for producing the laminated glass according to the invention is characterized in that a) the layer (B) is produced as a film, b) at least one film (B) is subsequently placed between two layers (A) and c) permanently under pressure and temperature is connected.
In einer bevorzugten Ausführungsform wird zusätzlich mindestens eine Schicht (C) in das Laminatglas eingebracht. Bevorzugt ist (C) ebenfalls eine Folie.In a preferred embodiment, additionally at least one layer (C) is introduced into the laminate glass. Preferably, (C) is also a film.
Die Schichten (A), (B) und (C) können jeweils unabhängig voneinander unterschiedliche Dicken aufweisen. Die Schicht (A) zeigt Schichtdicken von mehr als 0,5 mm. Bevorzugt werden Schichtdicken von 1 bis 20 mm.The layers (A), (B) and (C) may each independently have different thicknesses. The layer (A) shows layer thicknesses of more than 0.5 mm. Layer thicknesses of 1 to 20 mm are preferred.
Das Blockcopolymer (B) zeigt Schichtdicken von mehr als 0,01 mm. Wobei eine Schichtdicke von 0,1 bis 3 mm bevorzugt ist.The block copolymer (B) shows layer thicknesses of more than 0.01 mm. Where a layer thickness of 0.1 to 3 mm is preferred.
Besonders bevorzugt beträgt die Schichtdicke 0,3 bis 1,5 mm.The layer thickness is particularly preferably 0.3 to 1.5 mm.
Die Schicht (C) zeigt Schichtdicken von mehr als 0,01 mm. Wobei eine Schichtdicke von 0,1 bis 3 mm bevorzugt ist. Besonders bevorzugt beträgt die Schichtdicke 0,3 bis 1,5 mm.The layer (C) shows layer thicknesses of more than 0.01 mm. Where a layer thickness of 0.1 to 3 mm is preferred. The layer thickness is particularly preferably 0.3 to 1.5 mm.
In einer weiteren Ausführungsform der erfindungsgemäßen Laminatgläser sind die Schichten (B) und (C) eine Coextrusionsfolie.In a further embodiment of the laminated glass according to the invention, the layers (B) and (C) are a co-extrusion film.
Bevorzugt werden Zweischicht- oder Dreischicht- Coextrusionsfolien aus Blockcopolymer (B) und Polymeren (C) . Wobei die Dreischicht-Coextrusionsfolie aus einer innenliegenden Schicht (B) und zwei äußeren Schichten (C) oder umgekehrt bestehen kann. Es können auch Coextrusionsfolien mit mehr als 3 Schichten verwendet werden. Die Folien aus (B), (C) und die Coextrusionsfolien werden bevorzugt einer Rauhigkeitsprägung unterzogen .Preference is given to two-layer or three-layer coextrusion films of block copolymer (B) and polymers (C). Wherein the three-layer coextrusion film may consist of an inner layer (B) and two outer layers (C) or vice versa. Coextrusion films with more than 3 layers can also be used. The films of (B), (C) and the coextrusion films are preferably subjected to roughness embossing.
Für die Zweischicht- und Dreischicht-Coextrusionsfolien wird als Polymer (C) bevorzugt PVB verwendet.For the two-layer and three-layer coextrusion films, PVB is preferably used as the polymer (C).
Wird für die Herstellung von Coextrusionsfolien PVB als PolymerUsed for the production of co-extrusion PVB as a polymer
(C) verwendet, so kann zwischen der PVB-Schicht und der Schicht aus Blockcopolymer (B) eine weitere Schicht aus Polymeren (C) liegen . Das erfindungsgemäße Laminatglas kann in einer weiteren Ausführungsform statt getrennter Schichten (B) und (C) eine Schicht aus einer Mischung aus (B) und (C) enthalten.(C) used, there may be another layer of polymers (C) between the PVB layer and the layer of block copolymer (B). In a further embodiment, instead of separate layers (B) and (C), the laminate glass according to the invention may contain a layer of a mixture of (B) and (C).
BeispieleExamples
Beispiel 1 (erfindungsgemäß) : Herstellung der TPSE-Folien ohne PrägungExample 1 (Inventive): Production of the TPSE Films Without Embossing
In einem Einschnecken-Extruder mit angeschlossener Breitschlitzdüse und Prägewalze wurde käufliches, Geniomer® 80, Geniomer® 140, Geniomer® 140 mit erhöhtem Siloxanteil, so dass die SiO-Kettenlänge von etwa 36 auf etwa 80 verlängert wurde, der Wacker-Chemie GmbH, München, Deutschland in Granulatform bei einer Extrusions-Verarbeitungstemperatur von 150-1800C aufgeschmolzen und jeweils zu 0,76 mm dicken Folien extrudiert. Man erhielt jeweils eine Folie mit einer Transparenz von 91,85 % und einem Brechungsindex von 1,425.In a single-screw extruder with attached slot die and embossing roll, commercially available, Geniomer® 80, Geniomer® 140, Geniomer® 140 with increased siloxane content, such that the SiO chain length was extended from about 36 to about 80, Wacker-Chemie GmbH, Munich , Germany melted in granular form at an extrusion processing temperature of 150-180 0 C and extruded in each case to 0.76 mm thick films. Each gave a film having a transparency of 91.85% and a refractive index of 1.425.
Beispiel 2 (erfindungsgemäß) : Herstellung der TPSE-Folien mit PrägungExample 2 (according to the invention): Production of the TPSE foils with embossing
In einem Extruder mit angeschlossener Breitschlitzdüse und Prägewalze wurde käufliches Geniomer® 60, Geniomer® 80 und Geniomer® 140 der Wacker-Chemie AG in Granulatform bei einer Extrusions-Verarbeitungstemperatur von 150-1800C aufgeschmolzen und jeweils zu 0,76 mm dicken Folien extrudiert und eine definierte Oberflächenrauhigkeit eingeprägt. Man erhielt jeweils eine Folie mit einer Transparenz von 91,85 % und einem Brechungsindex von 1,425.In an extruder with an attached sheet die and the embossing roller commercially available GENIOMER® 60, 80 and GENIOMER® GENIOMER® was melted 140 of Wacker-Chemie AG in the form of granules at an extrusion processing temperature of 150-180 0 C and each extruded into 0.76 mm thick sheets and a defined surface roughness embossed. Each gave a film having a transparency of 91.85% and a refractive index of 1.425.
Beispiel 3 bis 5 (erfindungsgemäß) : Herstellung von TPSE-Verbundglas-Scheiben für die Prüfung nach DIN EN 20140-3 (Autoklavenschritt enthalten, 0,76 mm dicke Folie ohne Prägung)Example 3 to 5 (according to the invention): Production of TPSE laminated glass panes for testing in accordance with DIN EN 20140-3 (autoclave step, 0.76 mm thick film without embossing)
Zur Herstellung von Scheiben für die Prüfung nach DIN EN 20140-3 wurden die ungeprägten Folien aus Beispiel 1 zwischen zwei Glasscheiben (Floatglas) der Dicke 4 mm gelegt und der Aufbau langsam durch einen 4000C heißen Vorverbundofen gefahren. Diese Prozedur wurde mehrmals wiederholt. Dabei wurde eine Verbundglasscheibe enthalten, die noch einige kleine Luftbläschen enthielt.For the production of panes for testing in accordance with DIN EN 20140-3, the unembossed films from Example 1 were placed between two glass panes (float glass) of thickness 4 mm and the structure was run slowly through a 400 ° C. pre-composite oven. This procedure was repeated several times. This included a laminated glass pane, which still contained some small air bubbles.
Vorverbund-Ofentemperaturen : Geschwindigkeit 0,8 m/min 1. Ofen 4000C 2. Ofen 600°CPre-composite oven temperatures: speed 0.8 m / min 1. oven 400 0 C 2. oven 600 ° C
Die Scheibe wurde anschließend in einen Gummisack gegeben und in einem Autoklaven 20 Minuten bei 20 Torr Vakuum entlüftet. Anschließend wurde bei einem Druck von 12 kg/cm2 und bei einer Temperatur von 1400C laminiert. Man erhielt blasenfreie Verbundglasscheiben, die anschließend einer Schalldämmprüfung nach DIN EN 20140-3 unterzogen wurden.The disc was then placed in a gum bag and deaerated in an autoclave for 20 minutes at 20 torr vacuum. Subsequently, it was laminated at a pressure of 12 kg / cm 2 and at a temperature of 140 ° C. This gave bubble-free laminated glass, which was then subjected to a sound insulation test according to DIN EN 20140-3.
Vergleichsbeispiel 1 und 2 (nicht erfindungsgemäß) :Comparative Example 1 and 2 (not according to the invention):
Herstellung von PVB-Verbundglas-Scheiben für die Prüfung nach DIN EN 20140-3Production of PVB laminated glass panes for testing in accordance with DIN EN 20140-3
Die Herstellung erfolgte analog zu den Beispielen 3 bis 5, wobei kommerziell erwerbliche Folien aus weichgemachtem PVB verwendet wurden. Für Vergleichsbeispiel 1 Trosifol Soundcontrol und für Vergleichbeispiel 2 Trosifol Standard der Firma HT Troplast GmbH, Troisdorf, Deutschland. Die verwendeten Folien für die Vebundglasherstellung und die Ergebnisse, in [dB] , der Schalldämmprüfung nach DIN EN 20140-3 sind in der Tabelle 1 wiedergegeben.The preparation was carried out analogously to Examples 3 to 5, wherein commercially commercially available films of plasticized PVB were used. For Comparative Example 1 Trosifol Soundcontrol and for Comparative Example 2 Trosifol Standard from HT Troplast GmbH, Troisdorf, Germany. The films used for the production of laminated glass and the results, in [dB], of the sound insulation test according to DIN EN 20140-3 are reproduced in Table 1.
Tabel le 1Table 1
Beispiel 3* Standard-Geniomer® 80 37 dBExample 3 * Standard Geniomer® 80 37 dB
Beispiel 4* Standard-Geniomer® 140 36 dBExample 4 * Standard Geniomer® 140 36 dB
Beispiel 5* Geniomer® 140 /höherer 37 dB SiloxananteilExample 5 * Geniomer® 140 / higher 37 dB siloxane content
Vergleichsbeispiel 1 Trosifol Soundcontrol 35 dBComparative Example 1 Trosifol Soundcontrol 35 dB
Vergleichsbeispiel 2 Trosifol Standard 34 dBComparative Example 2 Trosifol Standard 34 dB
*erfindungsgemäß* Invention
Die Messung der erfindungsgemäßen Beispiele 3 bis 5 wurden nach 1,5 Jahren Lagerdauer nochmals durchgeführt und konnten genau reproduziert werden. Es zeigt sich, dass die erfindungsgemäßen Beispiele 3 bis 5 eine verbesserte Schalldämmeigenschaft zeigen. Sogar gegenüber Vergleichsbeispiel 1, welches in dieser Applikation dem Stand der Technik entspricht, ist eine wesentliche Verbesserung der erfindungsgemäßen Beispiele 3 bis 5 vorhanden. Aus den erfindungsgemäßen Beispielen 4 und 5 ist zudem ersichtlich, dass die Verlängerung der Siloxankette des Copolymeren (B) zu einer Verbesserung der Schalldämmeigenschaften führt.The measurement of Examples 3 to 5 according to the invention were carried out again after 1.5 years of storage and could be reproduced exactly. It can be seen that Examples 3 to 5 according to the invention show an improved sound insulation property. Even compared to Comparative Example 1, which corresponds to the prior art in this application, a significant improvement of Examples 3 to 5 according to the invention is present. It can also be seen from Examples 4 and 5 according to the invention that the extension of the siloxane chain of the copolymer (B) leads to an improvement in the sound insulation properties.
Beispiel 6 bis 8 (erfindungsgemäß) : Herstellung von TPSE-Verbundglas-Scheiben (Ohne Autoklavenschritt, Folie ohne Prägung) Zur Herstellung von Scheiben wurden die Folien mit definierter Oberflächen-Rauhigkeit aus Beispiel 2 zwischen zwei Glasscheiben der Dicke 4 mm gelegt und der Aufbau langsam durch einen 4000C heißen Vorverbundofen gefahren. Diese Prozedur wurde mehrmals wiederholt, dabei wurde eine Verbundglasscheibe enthalten, die feine Luftbläschen enthielt.Examples 6 to 8 (according to the invention): Production of TPSE laminated glass panes (without autoclave step, foil without embossing) To produce disks, the films with defined surface roughness from Example 2 were placed between two 4 mm thick glass panes and the structure was slowly run through a 400 ° C. pre-composite furnace. This procedure was repeated several times, containing a laminated glass pane containing fine air bubbles.
Vorverbund-Ofentemperaturen : Geschwindigkeit 0,8 m/min 1. Ofen 4000C 2. Ofen 600°CPre-composite oven temperatures: speed 0.8 m / min 1. oven 400 0 C 2. oven 600 ° C
Beispiele 9 bis 11 (erfindungsgemäß) : Herstellung von TPSE-Verbundglas-Scheiben (Ohne Autoklavenschritt, Folie mit Prägung)Examples 9 to 11 (according to the invention): Production of TPSE laminated glass panes (without autoclave step, foil with embossing)
Zur Herstellung von Scheiben wurden die Folien mit definierter Oberflächen-Rauhigkeit aus Beispiel 2 zwischen zwei Glasscheiben der Dicke 4 mm gelegt und der Aufbau langsam durch einen 4000C heißen Vorverbundofen gefahren. Diese Prozedur wurde mehrmals wiederholt, dabei wurde eine blasenfreie Verbundglasscheibe enthalten .To produce disks, the films with defined surface roughness from Example 2 were placed between two 4 mm thick glass panes and the structure was slowly run through a 400 ° C. pre-composite furnace. This procedure was repeated several times, containing a bubble-free laminated glass.
Vorverbund-Ofentemperaturen : Geschwindigkeit 0,8 m/minPre-composite oven temperatures: speed 0.8 m / min
1. Ofen 400 °C1st oven 400 ° C
2. Ofen 600 °C2nd oven 600 ° C
Der Vergleich der Beispiele 6 bis 8 mit den Beispielen 9 bis 11 zeigt, dass die Verwendung von Folien in der bevorzugten Ausführungsform mit Prägung bereits im Vorverbund-Ofen zu blasenfreien Laminatgläsern führt.The comparison of Examples 6 to 8 with Examples 9 to 11 shows that the use of films in the preferred embossed embodiment already leads to bubble-free laminate glasses in the precombustion furnace.
Beispiel 12 (erfindungsgemäß) : Herstellung von Glas-PVB-Geniomer®-PVB-Glas-Laminaten mit einem dreischichtigen PolymerfilmExample 12 (according to the invention): Production of glass PVB Geniomer® PVB glass laminates with a three-layer polymer film
Es wurden Glas-Laminate mit mehreren polymeren Zwischenschichten hergestellt mit folgendem Schicht-Aufbau (Außenmasse 20 x 20 cm) :Glass laminates with several polymeric intermediate layers were produced with the following layer structure (outer dimensions 20 × 20 cm):
4 mm Floatglas;4 mm float glass;
0,76 mm PVB-Folie (Trosifol Standard der Firma HT Troplast GmbH, Troisdorf, Deutschland) ;0.76 mm PVB film (Trosifol standard from HT Troplast GmbH, Troisdorf, Germany);
0,76 mm Geniomer® 140 Standardfolie aus Beispiel 1 ;0.76 mm Geniomer® 140 standard film from example 1;
0,76 mm PVB-Folie (Trosifol Standard der Firma HT Troplast0.76 mm PVB film (Trosifol standard from HT Troplast
GmbH, Troisdorf, Deutschland) ;GmbH, Troisdorf, Germany);
4 mm Floatglas4 mm float glass
Dazu wurden die einzelnen Schichten aufeinander gelegt und in einer Heißpresse bei 1500C für 20 Minuten heißlaminiert. Man erhielt ein Laminat mit guter Haftung zwischen den Schichten. An der Grenzflächen PVB-Glas befanden sich noch wenige kleine Luftbläschen.For this purpose, the individual layers were placed on each other and hot-laminated in a hot press at 150 0 C for 20 minutes. A laminate with good adhesion between the layers was obtained. At the interfaces PVB glass were still a few small air bubbles.
Die Scheibe wurde anschließend in einen Gummisack gegeben und in einem Autoklaven bei einem Druck von 12 kg/cm2 und bei einer Temperatur von 1400C laminiert. Man erhielt völlig blasenfreie Verbundglasscheiben .The disc was then placed in a rubber bag and laminated in an autoclave at a pressure of 12 kg / cm 2 and at a temperature of 140 ° C. It was completely free of bubbles laminated glass.
Beispiel 13 (erfindungsgemäß) :Example 13 (according to the invention):
Herstellung von Glas-Geniomer®-PVB-Geniomer®-Glas-Laminaten (dreischichtiger Polymerfilm, inverser Folienaufbau)Production of glass Geniomer® PVB Geniomer® glass laminates (three-layer polymer film, inverse film structure)
Es wurden Glas-Laminate mit mehreren polymeren Zwischenschichten hergestellt mit folgendem Schicht-Aufbau (Außenmasse 20 x 20 cm) : 4 mm Floatglas;Glass laminates with several polymeric intermediate layers were produced with the following layer structure (outer dimensions 20 × 20 cm): 4 mm float glass;
0,76 mm Geniomer® 140 Standardfolie aus Beispiel 1 ; 0,76 mm PVB-Folie (Trosifol Standard der Firma HT Troplast GmbH, Troisdorf, Deutschland) ; 0,76 mm Geniomer® 140 Standardfolie aus Beispiel 1 ; 4 mm Floatglas0.76 mm Geniomer® 140 standard film from example 1; 0.76 mm PVB film (Trosifol standard from HT Troplast GmbH, Troisdorf, Germany); 0.76 mm Geniomer® 140 standard film from example 1; 4 mm float glass
Dazu wurden die einzelnen Schichten aufeinander gelegt und in einer Heißpresse bei 1500C für 20 Minuten heißlaminiert. Man erhielt ein blasenfreies Laminat mit guter Haftung zwischen den Schichten und hervorragender Transparenz.For this purpose, the individual layers were placed on each other and hot-laminated in a hot press at 150 0 C for 20 minutes. This gave a bubble-free laminate with good interlayer adhesion and excellent transparency.
Beispiel 14 (erfindungsgemäß) :Example 14 (according to the invention):
Herstellung von Glas-Geniomer®-PVB-Glas-Laminaten (zweischichtiger Polymerfilm)Production of glass Geniomer® PVB glass laminates (two-layer polymer film)
Es wurde ein Glas-Laminat mit zwei polymeren Zwischenschichten hergestellt mit folgendem Schicht-Aufbau (Außenmasse 20 x 20 cm) :A glass laminate with two polymeric intermediate layers was produced with the following layer structure (outer dimensions 20 × 20 cm):
4 mm Floatglas;4 mm float glass;
0,76 mm Geniomer® 140 Standardfolie;0.76 mm Geniomer® 140 standard film;
0,76 mm PVB-Folie (Trosifol Standard der Firma HT Troplast GmbH, Troisdorf, Deutschland) ; 4 mm Floatglas;0.76 mm PVB film (Trosifol standard from HT Troplast GmbH, Troisdorf, Germany); 4 mm float glass;
Dazu wurden die einzelnen Schichten aufeinander gelegt und in einer Heißpresse bei 1500C 20 min lang heißlaminiert. Man erhielt ein blasenfreies Laminat mit guter Haftung zwischen den Schichten und hervorragender Transparenz. An der Grenzfläche PVB-Glas befanden sich noch wenige kleine Luftbläschen. Die Scheibe wurde anschließend in einen Gummisack gegeben und in einem Autoklaven bei einem Druck von 12 kg/cm2 und bei einer Temperatur von 1400C laminiert. Man erhielt völlig blasenfreie Verbundglasscheiben .The individual sheets were placed on each other and heat-laminated in a hot press at 150 0 C for 20 minutes. This gave a bubble-free laminate with good interlayer adhesion and excellent transparency. At the interface PVB glass were still a few small air bubbles. The disc was then placed in a rubber bag and placed in an autoclave at a pressure of 12 kg / cm 2 and a Temperature of 140 0 C laminated. It was completely free of bubbles laminated glass.
Die Beispiele 12 bis 14 zeigen die erfindungsgemäße Herstellung von Laminatgläsern mit 2 und mehr polymeren Zwischenschichten. Examples 12 to 14 show the production according to the invention of laminated glass with 2 or more intermediate polymeric layers.

Claims

Patentansprüche claims
1. Laminatglas, welches umfasst1. Laminated glass comprising
(A) mindestens eine Schicht ausgewählt aus der Gruppe enthaltend anorganisches oder organisches Glas und(A) at least one layer selected from the group consisting of inorganic or organic glass and
(B) mindestens eine Schicht aus einem linearen Organopolysiloxan/Polyharnstoff/Polyurethan- Blockcopolymer der allgemeinen Formel (1)(B) at least one layer of a linear organopolysiloxane / polyurea / polyurethane block copolymer of the general formula (1)
RR
II
A-X — Si- O Si -X- A-C-N- Y- N-C- Z-D-Z- -C-N-Y- N-CA-X-Si-O-Si-X-A-C-N-Y-N-C-Z-D-Z-C-N-Y-N-C
Il H H Il M H H M R O O O O nIl H H Il M H H M R O O O n n
:D: D
RR
II
-A-X — Si- O Si -X-A C-N- Y-N-C- N- Y-N-C--A-X - Si-O-Si-X-A C-N-Y-N-C-N-Y-N-C-
Il H H M H H M R o o oIl H H M H H M R o o o
wobeiin which
R einen einwertigen, gegebenenfalls durch Fluor oderR is a monovalent, optionally fluorine or
Chlor substituierten Kohlenwasserstoffrest mit 1 bis 20Chloro-substituted hydrocarbon radical having 1 to 20
Kohlenstoffatomen, X einen Alkylen-Rest mit 1 bis 20 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durchCarbon atoms, X is an alkylene radical having 1 to 20 carbon atoms, in the non-adjacent methylene units
Gruppen -0- ersetzt sein können,Groups -0- can be replaced,
A ein Sauerstoffatom oder eine Aminogruppe -NRΛ-, Z ein Sauerstoffatom oder eine Aminogruppe -NRΛ-, RΛ Wasserstoff oder einen Alkylrest mit 1 bis 10A is an oxygen atom or an amino group -NR Λ -, Z represents an oxygen atom or an amino group -NR Λ - Λ R is hydrogen or an alkyl radical having 1 to 10
Kohlenstoffatomen, Y einen zweiwertigen, unsubstituierten oder durch Fluor oder Chlor substituierten Kohlenwasserstoffrest mit 1 bis 20 Kohlenstoffatomen,Carbon atoms, Y is a divalent, unsubstituted or fluorine- or chlorine-substituted hydrocarbon radical having 1 to 20 carbon atoms,
D einen unsubstituierten oder durch Fluor, Chlor, C1-C6- Alkyl- oder Cl-C6-Alkylester substituierten Alkylenrest mit 1 bis 800 Kohlenstoffatomen, in dem einander nicht benachbarte Methyleneinheiten durch Gruppen -0-, -COO-, -OCO-, oder -OCOO-, ersetzt sein können, n eine Zahl von 1 bis 4000, a eine Zahl von mindestens 1, b eine Zahl von 0 bis 40, c eine Zahl von 0 bis 30 und d eine Zahl größer 0 bedeuten.D is an unsubstituted or substituted by fluorine, chlorine, C 1 -C 6 -alkyl or C 1 -C 6 -alkyl ester alkylene radical having 1 to 800 carbon atoms, in which non-adjacent methylene units represented by groups -O-, -COO-, -OCO-, or N is a number from 1 to 4000, a is a number of at least 1, b is a number from 0 to 40, c is a number from 0 to 30 and d is a number greater than 0.
2. Laminatglas gemäß Anspruch 1, dadurch gekennzeichnet, dass es mindestens zwei Schichten (A) enthält.2. Laminated glass according to claim 1, characterized in that it contains at least two layers (A).
3. Laminatglas gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass es zusätzlich weitere Schichten (C) enthält ausgewählt aus der Gruppe enthaltend Polyvinylbutyral, Polyurethane, Polyharnstoffe, Polyvinylchlorid, Epoxide, Polyester, (Meth) -Acrylate, Silicone, Siliconharzpolymere, modifizierte Silicon-Polymere, Heißschmelz-Klebstoffe, Beschichtungen und Dichtungsmassen, Piastisole, Polyethylen, Polyvinylacetat, Polypropylen, PVC, Polystyrol, Polycarbonat und deren Mischungen ,3. Laminated glass according to claim 1 or 2, characterized in that it additionally contains further layers (C) selected from the group consisting of polyvinyl butyral, polyurethanes, polyureas, polyvinyl chloride, epoxies, polyesters, (meth) acrylates, silicones, silicone resin polymers, modified silicone Polymers, hot melt adhesives, coatings and sealants, plastisols, polyethylene, polyvinyl acetate, polypropylene, PVC, polystyrene, polycarbonate and mixtures thereof,
4. Laminatglas gemäß Anspruch 1 bis 3, dadurch gekennzeichnet, dass die Schichten (A) , (B) und (C) voneinander unabhängig unterschiedliche Dicken aufweisen können. 4. laminated glass according to claim 1 to 3, characterized in that the layers (A), (B) and (C) independently of one another may have different thicknesses.
5. Laminatglas gemäß Anspruch 1 bis 4, dadurch gekennzeichnet, dass es statt getrennter Schichten (B) und (C) eine Schicht aus einer Mischung aus (B) und (C) enthält.5. laminated glass according to claim 1 to 4, characterized in that instead of separate layers (B) and (C) comprises a layer of a mixture of (B) and (C).
6. Laminatglas gemäß Anspruch 1 bis 5, dadurch gekennzeichnet, dass die Schichten (B) und (C) eine Coextrusionsfolie sind.6. laminated glass according to claim 1 to 5, characterized in that the layers (B) and (C) are a coextrusion film.
7. Laminatglas gemäß Anspruch 1 bis 6, dadurch gekenzeichnet, dass sie eine eine Transparenz von mindestens 89 für den Wellenlängebereich von 350 bis 800 nm zeigen.7. Laminated glass according to claim 1 to 6, characterized in that they show a transparency of at least 89 for the wavelength range of 350 to 800 nm.
8. Laminatglas gemäß Anspruch 1 bis 7, dadurch gekenzeichnet, dass der Brechungsindex der Zwischenschichten im Wellenlängenbereich von 350 bis 800 nm mindestens 1,38 beträgt.8. Laminated glass according to claim 1 to 7, characterized thereby that the refractive index of the intermediate layers in the wavelength range from 350 to 800 nm is at least 1.38.
9. Verfahren zur Herstellung des Laminatglases gemäß Anspruch 1 bis 8, dadurch gekennzeichnet, dass das lineare Organopolysiloxan/Polyharnstoff/ Polyurethan-Blockcopolymer (B) hergestellt wird und anschließend auf mindestens eine Schicht (A) aufgebracht wird.9. A process for producing the laminated glass according to claim 1 to 8, characterized in that the linear organopolysiloxane / polyurea / polyurethane block copolymer (B) is prepared and then applied to at least one layer (A).
10. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, dass a) die Schicht (B) als Folie hergestellt wird, b) mindestens eine Folie (B) anschließend zwischen zwei10. The method according to claim 9, characterized in that a) the layer (B) is produced as a film, b) at least one film (B) then between two
Schichten (A) gelegt wird und c) unter Druck und Temperatur dauerhaft verbunden wird.Layers (A) is laid and c) permanently connected under pressure and temperature.
11. Verfahren gemäß Anspruch 9 oder 10, dadurch gekennzeichnet, dass zusätzlich mindestens eine Schicht (C) in das11. The method according to claim 9 or 10, characterized in that additionally at least one layer (C) in the
Laminatglas eingebracht wird.Laminated glass is introduced.
12. Verwendung des Laminatglases gemäß einem der Ansprüche 1 bis 8 für Fahrzeug-, Flugzeug- und Architekturverglasungen . 12. Use of the laminate glass according to one of claims 1 to 8 for vehicle, aircraft and architectural glazing.
PCT/EP2006/068285 2005-11-15 2006-11-09 Glass laminates with thermoplastic polysiloxane-urea copolymers WO2007057342A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100233489A1 (en) * 2007-10-22 2010-09-16 Wacker Chemie Ag Fluoropolymer-silicon compounds and method for production
CN110093099A (en) * 2019-03-25 2019-08-06 江苏铁锚玻璃股份有限公司 A kind of aircraft organic glass polyurethane coating and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142228A1 (en) * 1983-08-31 1985-05-22 Negami Chemical Industrial Co Ltd Polycarbonate-modified urethane acrylate adhesive
JPH07126342A (en) * 1993-10-21 1995-05-16 Saint Gobain Vitrage Production of polyurethane
DE19705586C1 (en) * 1997-02-14 1998-04-16 Sekurit Saint Gobain Deutsch Composite glass material with noise insulation properties
DE10316521B3 (en) * 2003-04-10 2004-08-05 Wacker-Chemie Gmbh Laminated glass, for use e.g. in automobiles or buildings, comprising layer(s) of (in)organic glass and layer(s) of polysiloxane-urea copolymer obtained from linear and branched polysiloxanes and polyisocyanate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0142228A1 (en) * 1983-08-31 1985-05-22 Negami Chemical Industrial Co Ltd Polycarbonate-modified urethane acrylate adhesive
JPH07126342A (en) * 1993-10-21 1995-05-16 Saint Gobain Vitrage Production of polyurethane
DE19705586C1 (en) * 1997-02-14 1998-04-16 Sekurit Saint Gobain Deutsch Composite glass material with noise insulation properties
DE10316521B3 (en) * 2003-04-10 2004-08-05 Wacker-Chemie Gmbh Laminated glass, for use e.g. in automobiles or buildings, comprising layer(s) of (in)organic glass and layer(s) of polysiloxane-urea copolymer obtained from linear and branched polysiloxanes and polyisocyanate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Geniomer 60", TECHNISCHES INFORMATIONSBLATT VON WACKER, XX, XX, 17 August 2004 (2004-08-17), pages 1 - 2, XP002405088 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100233489A1 (en) * 2007-10-22 2010-09-16 Wacker Chemie Ag Fluoropolymer-silicon compounds and method for production
US8343629B2 (en) * 2007-10-22 2013-01-01 Wacker Chemie Ag Fluoropolymer-silicon compounds and method for production
CN110093099A (en) * 2019-03-25 2019-08-06 江苏铁锚玻璃股份有限公司 A kind of aircraft organic glass polyurethane coating and preparation method thereof
CN110093099B (en) * 2019-03-25 2022-01-04 江苏铁锚玻璃股份有限公司 Polyurethane coating for organic glass of airplane and preparation method thereof

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