WO2007057342A1 - Stratifie de verre qui presente des copolymeres thermoplastiques de siloxane et d'uree - Google Patents

Stratifie de verre qui presente des copolymeres thermoplastiques de siloxane et d'uree 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)
English (en)
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/fr

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    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un verre stratifié qui comprend (A) au moins une couche sélectionnée dans l'ensemble constitué des verres minéraux et des verres organiques et (B) au moins une couche constituée d'un copolymère linéaire séquencé d'organosiloxane, d'urée et d'uréthane de formule générale (1) dans laquelle R représente un groupe hydrocarbure qui compte de 1 à 20 atomes de carbone, monovalent et éventuellement substitué avec du fluor ou du chlore, X un groupe alkylène qui compte de 1 à 20 atomes de carbone dans lequel des unités méthylène non voisines l'une de l'autre peuvent être remplacées par des groupes -O-, A un atome d'oxygène ou un groupe amino-NR'-, Z un atome d'oxygène ou un groupe amino-NR'-, dans lesquels R' représente l'hydrogène ou un groupe alkyle qui compte de 1 à 10 atomes de carbone, Y représente un groupe hydrocarbure qui compte de 1 à 20 atomes de carbone, bivalent, non substitué ou substitué avec du fluor ou du chlore, D un groupe alkylène qui compte de 1 à 800 atomes de carbone, non substitué ou substitué avec un atome de fluor, un atome de chlore, un groupe alkyle en C<SUB>1</SUB> à C<SUB>6</SUB> ou un groupe alkylester en C<SUB>1</SUB> à C<SUB>6</SUB> et dans lequel des unités méthylène non voisines l'une de l'autre peuvent être remplacées par les groupes -O-, -COO-, -OCO- ou -OCOO-, n représentant un nombre compris entre 1 et 4 000, A un nombre supérieur ou égal à 1, B un nombre compris entre 0 et 40, C un nombre compris entre 0 et 30 et D un nombre supérieur à 0.
PCT/EP2006/068285 2005-11-15 2006-11-09 Stratifie de verre qui presente des copolymeres thermoplastiques de siloxane et d'uree WO2007057342A1 (fr)

Applications Claiming Priority (2)

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DE102005054413.4 2005-11-15
DE200510054413 DE102005054413A1 (de) 2005-11-15 2005-11-15 Glaslaminate mit thermoplastischen Polysiloxan-Harnstoff-Copolymeren

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US20100233489A1 (en) * 2007-10-22 2010-09-16 Wacker Chemie Ag Fluoropolymer-silicon compounds and method for production
CN110093099A (zh) * 2019-03-25 2019-08-06 江苏铁锚玻璃股份有限公司 一种飞机有机玻璃用聚氨酯涂层及其制备方法

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JPH07126342A (ja) * 1993-10-21 1995-05-16 Saint Gobain Vitrage ポリウレタンの製造方法
DE19705586C1 (de) * 1997-02-14 1998-04-16 Sekurit Saint Gobain Deutsch Schalldämpfendes Verbundglas
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JPH07126342A (ja) * 1993-10-21 1995-05-16 Saint Gobain Vitrage ポリウレタンの製造方法
DE19705586C1 (de) * 1997-02-14 1998-04-16 Sekurit Saint Gobain Deutsch Schalldämpfendes Verbundglas
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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 (zh) * 2019-03-25 2019-08-06 江苏铁锚玻璃股份有限公司 一种飞机有机玻璃用聚氨酯涂层及其制备方法
CN110093099B (zh) * 2019-03-25 2022-01-04 江苏铁锚玻璃股份有限公司 一种飞机有机玻璃用聚氨酯涂层及其制备方法

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