![]() Laminated glass
专利摘要:
1. A laminated pane comprising a glass sheet, a transparent intermediate layer based on polyurethane having energy-absorbing properties, and a transparent coating layer of self-healing plastics material, notably based on a thermosetting polyurethane, characterised in that the intermediate layer based on polyurethane having energy-absorbing properties is formed essentially of a polyurethane obtained by reactive casting on a flat horizontal support of a reaction mixture of an isocyanate component of viscosity less than 5 Pas at 40 degrees C and a polyol component, the isocyanate component comprising at least one aliphatic or cycloaliphatic di-isocyanate or an isocyanate prepolymer, the isocyanate component containing urea functions, the content of urea being up to 10% of the total weight of isocyanate component, the content of urea preferably being from 5 to 7%, the polyol component comprising at least one long difunctional polyol of molecular weight from 500 to 4000 and at least one short diol as a chain lengthening agent, the ratio of isocyanate group equivalents to hydroxyl group equivalents is about 1, the proportions of the different polyols are selected such that the number of hydroxyl group equivalents due to the short polyol represents from 20 to 70% of the total hydroxyl groups, and this layer having at a thickness of about 0.5 mm, a flow stress sigma y at -20 degrees C not exceeding 3 daN/mm**2 , a rupture stress sigma R at 40 degrees C of at least 2 daN/mm**2 , a lengthening at rupture vepsiln R at + 20 degrees C from 250 to 500%, and a tear resistance Ra at + 20 degrees C of at least 9 daN/mm. 公开号:SU1517756A3 申请号:SU843791616 申请日:1984-07-10 公开日:1989-10-23 发明作者:Браве Жан-Луи;Кольмон Даниель;Дод Жерар;Моншо Мишель-Жан 申请人:Сэн-Гобэн Витраж (Фирма); IPC主号:
专利说明:
The invention relates to laminated glass, in particular to car windshields, including a rigid transparent base made of silicate glass, a transparent layer of plastic material having energy absorbent properties and a layer of transparent: scratch-resistant and abrasion-resistant coating, called self-repairing layer or another layer of internal protection, since it is oriented inside the cabin (in the case of a windshield - ll). s The purpose of the invention is to improve the optical-mechanical properties of glass. Example 1. A movable layer of silicate glass coated with a separation agent, which is a 0.5% by weight aqueous solution of dodecyl polyglycol ether of disodium sulfosuccinate, is continuously poured into a homogeneous mixture of 1000 g of polyether mol mol.m.50 obtained by condensation of 1,2-propylene oxide with 2,2-bis- (hydroxymethyl) -1-butanol and having a content of free hydroxyl groups of 10.5%, containing 1 wt.% bis- (2.2 , 6,6-tetramethyl-4-piperidyl) sebacinate as a stabilizer, 0.05% by weight of dibutyl tin dilaurate as catalysis ora, and 0.1 wt.% silicone resin as a rheology improving agent and 1020 g of 1,6-geksandiizotsianatbiureta having a content of free isocyanate groups GOVERNMENTAL 23.2%. A uniform layer is formed which, after polymerization at 120 ° C for 15 minutes, has a thickness of 0.19 mm. A layer of 0.53 mm thick consisting of 75.60 May of a mixture of polytetramethylene glycol mol.m. is poured on this layer (layer A). 1000 and butanediol-1, And at a ratio of hydroxyl equivalents of 0.37: 0.63, containing 0.5% by weight of bis- (2.2, 6.6-tetramethyl-A-piperidyl) -sebaccate as a stabilizer , 0.5 wt.% Silicone resin brand VP 303 as improving the rheological properties of the agent and 0.02 wt.% Dilaurate dibutyl tin as a catalyst, and 23.83 wt.% Dilaurate dibutyl tin as a catalyst, and 23.83 wt.% 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl diisocyanate containing urea groups and isocyanate groups in the amount of 31.5%. In this composition, the equivalent ratio of isocyanate and hydroxyl groups is 1. The resulting layer (hereinafter layer B) is subjected to polymerization at 120 ° C for 25 minutes. The ratio of the thicknesses of the layers A and B is 0.358: 1. After polymerization, the resulting bilayer film is removed from the substrate and used to make laminated glass. The mechanical properties of laminated glass manufactured using the two-layer film of Example 1 are determined as follows. A two-layer film with a side formed by layer B is placed on a layer of glass 2.6 mm thick. The connection of the layers is carried out in two stages, during the first of which the preliminary connection is made by passing the compound between the two rollers. During the second stage, the obtained laminated glass is placed in an autoclave, where it is held for about 1 hour under a pressure of about 10 bar and at a temperature of about 135 C. The optical permeability of the obtained double-layer glass is 90.1%. The adhesion between the glass layer and the two-layer polyurethane film is defined as follows. A 5 cm wide strip is cut out of laminated glass. One end of this strip is fixed and pulled in a direction perpendicular to the glass surface at a speed of 5 cm / min. The test is carried out at 20 ° C. Record the amount of average tractive effort required to strip the strip. This value is 10 daN / 5 cm. Tests are also carried out. impact strength at different temperatures. The first impact strength test is carried out with a steel ball weighing 2.260 kg (a test with a heavy ball), which falls on the central part of the sample, which has the shape of a square with a side of 30.5 cm and installed in a rigid frame. The height of the drop is measured approximately at which 90% of the samples are not pierced through the ball. For laminated glass obtained in the manner described, this height is 8 m. A second impact strength test is conducted with a steel ball weighing 0.227 kg and a diameter of 38 mm (a test with a light ball). One test was carried out at -20 ° C, and the second at +40 ° C. The results obtained are respectively 11 and. EXAMPLE 2 Example 1 is repeated with the difference that a mixture of polytetramethylene glycol mol.m. is used as the polyol component of layer B. 1000, 1, 4-butanediol and polycaprolactontriol with a ratio one hydroxyl equivalents of 0.35: 0.55: 0.10; At the same time, layers A and B are thick with a thickness of 0.16 and 0.66 mm, respectively. The ratio of the thickness is 0.242: 1. The mechanical properties of laminated glass manufactured using the two-layer film of Example 2 are as follows: 9 m for a test with a heavy ball, 13 and 13 m, respectively for a test with a light ball at -20 and +40 C, respectively. Optical transmittance 90.2% EXAMPLE 1 Example 1 is repeated, with the difference that a mixture of polytetramethylene glycol mol.Mo1000, 1,4-butanediol and polycaprolactontriol is used as the polyol component of layer B at a ratio of hydroxyl equivalents of 0.35: : O, 45: O, 20; In this case, layers A and B are 0.31 and 0.48 mm thick, respectively. The ratio of the thickness of 90%, the mechanical properties of laminated glass manufactured using the two-layer film of example 3, the following: 5 m; a test with heavy LuapHKOM, 10 and 12 m with a test with a light ball at -20 and C, respectively, and Optical pro) density of 90%, Examples 4-6. Example 1 is repeated, with the difference that the film is placed on a layer of silicate glass with a thickness of 2.4 and 5 mm, respectively. The mechanical properties of the tests of the two-layer product are summarized in the table, Examples 7-8, Example 2 is repeated with the difference that the film is placed on a layer of silicate glass with a thickness of 2 and 5 mm, respectively. The test results of the two-layer product are summarized in the table. PRI me R 9 (comparative), Example 1 is repeated with the difference that adipic and sebacic acid polyetherdiol, caprolactone, 2,2-dimethyl-1,3-propanediol and 1 are used as the polyol component of layer B , 4-butanediol, The mechanical properties of the two-layer laminated glass produced in Example 9 are as follows: 8 daN / 5 cm bond, 4 m heavy ball test, 8.5 and 9 m light ball test. The optical permeability is 89.8%. 77566 Example 10 (cf. YelpyG)), Example 1 is repeated, with the difference that layer B contains the product of the intercalibration of pollcaprolactoptriol, ethylene glycol, N-methyldiethanolamine and trimethylolpropane as the polyol component. MexaHi-gic properties manufactured using The 10 bilayer films of Example 10 laminated glass are skinny: a test with a 6 m heavy ball, a test with a light U ball and 10 m. The optical permeability is 89.8%. 15 PRI me R 11 (comparative), Example 1 is repeated, with the difference that a composition is poured onto layer A, which instead of a mixture of polytetramethylene glycol mol.m., 1000 and butanedio-g 20 la-1,4, contains only polytetramethylene glycol, 1000. The mechanical properties are made by i-roro using a two-layer film of this comparative at 25 The measure of laminated glass is as follows: 8 daN / 5 cm clutch, 3.5 m heavy ball test, 8 and 8 m light ball test. Optical permeability. 90.1%. Comparison of the results of example 11 with the results of example 1 shows that when using polytetramethyphenol instead of its mixture with butanethiol-1.4, the purpose of the invention cannot to be achieved. At the same time, the glass of example 11 does not even satisfy the requirements of the European industrial standard P 43, according to which with a sample consisting of a layer of glass 2.6 mm thick with a 0.72 mm thick polymer layer applied on it, the minimum height should be 4; eight; 5 and 9 m respectively. FormU-Gla invention Laminated glass containing a layer of silicate glass and coated on Q with a coating of chemically bonded at the interface of the phases a layer of thermoplastic polyurethane and a layer of heat-curable polyurethane based on propylene oxide polyester and 2,2- (hydroxymethyl) -1-butanol mol. m., 450 and the content of free hydroxyl groups of 10.5% and 1,6-hexane-isocyanatobiuret with a content of free isocyanate groups of 23.2%, differing in the fact that, in order to study the optical-mechanical parameters of laminated glass, silicate glass layer te rmoplastic polyurethane based on u-groups containing 3-isocyanatomethyl-3, 5,5-trimethyl cyclohexyl isocyanate containing 31.5% isocyanate groups and a polyol component consisting of a mixture of polytetramethylene glycol MOL..M, 1000 with butanediol-1, A when the ratio of hydroxyl equivalent Com. 0.37: 0.63 or polytetramethylene glycol mixtures mol.m. 1000, butanediol-1, A and polycaprolactontriol with a ratio of hydroxyl equivalents of 0.35: 0.45-0.55: 0.10-0.20, respectively, and the thermoplastic polyurethane layer (A) is made with a thickness of 0.48 -0.66 mm, and the layer of thermosetting polyurethane (B) is made 0.16-0.31 mm thick with the thickness ratio B: A equal to (0.242-0.646): while the silicate glass layer is 2-5 mM thick Compiled by G, .Russian Editor NoRogulich Tehred A. Kravchuk Proofreader V. Kabatsiy Order 6404/58 Circulation 415 VNIIPI State Committee for Inventions and Discoveries at the State Committee on Science and Technology of the USSR 113035, Moscow, Zh-35, Raushsk nab. 4/5 Production and publishing plant Patent, Uzhgorod, st. Gagarin, 101 Subscription
权利要求:
Claims (1) [1] Claim Laminated glass containing a layer of silicate glass and a coating deposited on it from a layer of thermoplastic polyurethane chemically bonded at the interface and a layer of thermosetting polyurethane based on polyester made of propylene oxide and 2,2- (oxymethyl) -1-butanol with mol.m. 450 and the content of free hydroxyl groups of 10.5% and 1,6-hexanediisocyanatobiuret with the content of free isocyanate groups of 23.2%, which is characterized by the fact that, in order to increase the optical-mechanical properties of laminated glass, a layer of thermoplastic polyurethane bonded to silicate glass made on the basis of urea groups containing 3-isocyanateomethyl-3, 5,5-trimethylcyclohexyl isocyanate with an isocyanate group content of 31.5% and a polyol component consisting of a mixture of polytetramethylene glycol mol.m. 1000 with butanediol-1.4 with a ratio of hydroxyl equivalents of 0.37: 0.63 or a mixture of polytetramethylene glycol mol.m. 1000, butanediol-1.4 and polycaprolactontriol with a ratio of hydroxyl equivalents of 0.35: 0.45-0.55: 0.10-0.20, respectively, with a layer of thermoplastic polyurethane (A) made of a thickness of 0.48-0.66 mm, and the layer of thermosetting polyurethane (B) is made with a thickness of 0.16-0.31 mm with a ratio of thicknesses B: A equal to (0.242-0.646): 1, and the layer of silicate glass is made with a thickness of 2-5 mm. Example Adhesion daN / 5 cm Impact Strength, m The optical permeability,% Heavy ball Easy-20 ° C ball| + 40 ° C 4 9 9.0 13.5 13.5 90.1 5 9 9.0 1 1,0 12.0 90.1 6 9 7.0 10.5 10.0 90, 1 7 10 9.0 13.5 13.5 90.2 89 10 9.5 12.0 12.0 90.2 (famous) 810 4.0 8.5 9.0 89.8 (comp.)eleven 6 6.0 9.0 10.0 89.8 8 3,5 8.0 8.0 90, 1
类似技术:
公开号 | 公开日 | 专利标题 SU1517756A3|1989-10-23|Laminated glass US4584229A|1986-04-22|Glazing article US4671838A|1987-06-09|Preparation of bilayer laminate and preformed sheet for use therein US4997901A|1991-03-05|Reaction curable composition comprising a polyisocyanate component and a polyol component US4925734A|1990-05-15|Glazing laminates USRE32224E|1986-08-12|Polyurethane coated safety glass KR920005548B1|1992-07-06|Process and device for producing a plastic layer of high optical quality US4824926A|1989-04-25|Bilayer windshield with an abrasion and solvent resistant polyurethane protective coating US5277944A|1994-01-11|Process for the manufacture of a sheet or film made of polycarbonate with a soft scratch-resistant coating SU1491326A3|1989-06-30|Laminated glass SU1611212A3|1990-11-30|Composition for producing polyurethane sheet for laminated glass US4923757A|1990-05-08|Bilayer windshield with an abrasion and solvent resistant polyurethane protective coating KR100191877B1|1999-06-15|Polyurethane layer having energy absorbing properties and its use in laminated safety glass US4732725A|1988-03-22|Process and device for the production of a safety pane USRE34538E|1994-02-08|Glazing laminates
同族专利:
公开号 | 公开日 EP0132198A1|1985-01-23| FI842765A|1985-01-12| DK337084D0|1984-07-09| JPH0567418B2|1993-09-24| EP0132198B1|1988-01-13| PT78882B|1986-06-05| KR850001514A|1985-03-30| AU572168B2|1988-05-05| ES534171A0|1985-09-01| FI77601C|1989-04-10| MX168250B|1993-05-13| NO161968C|1989-10-18| DK337084A|1985-01-12| NO842805L|1985-01-14| DK162976B|1992-01-06| DE3468648D1|1988-02-18| JPS6071252A|1985-04-23| DK162976C|1992-06-09| NO161968B|1989-07-10| FI77601B|1988-12-30| AT31897T|1988-01-15| IL72359D0|1984-11-30| HU194789B|1988-03-28| HUT40384A|1986-12-28| YU120784A|1986-10-31| IL72359A|1994-01-25| NZ208856A|1987-10-30| AU3045484A|1985-01-17| YU43578B|1989-08-31| FI842765A0|1984-07-10| BR8403425A|1985-06-25| FR2549036A1|1985-01-18| MA20174A1|1985-04-01| PT78882A|1984-08-01| IN161465B|1987-12-12| CA1253425A|1989-05-02| ES8507435A1|1985-09-01| KR920005473B1|1992-07-04| ZA845290B|1986-10-29| FR2549036B1|1985-10-18|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US4024113A|1976-04-28|1977-05-17|Ppg Industries, Inc.|Polycarbonate polyurethanes based on particular aliphatic/cycloaliphatic polycarbonates| DE2629779C3|1976-07-02|1985-04-04|Saint Gobain|Process for the production of a two-layer film with self-healing properties using polyurethanes as a shatterproof layer on safety glass| FR2385751B1|1977-03-28|1980-12-26|Ppg Industries Inc| FR2442128B1|1978-11-23|1981-06-26|Saint Gobain| FR2470682B1|1979-12-06|1983-08-12|Saint Gobain| CA1174577A|1980-04-30|1984-09-18|Vernon G. Ammons|Polyurethane composition for safety glass interlayer| FR2496089B1|1980-12-11|1984-08-24|Saint Gobain Vitrage| JPS6261428B2|1981-06-03|1987-12-21|Asahi Glass Co Ltd| DE3135672A1|1981-09-09|1983-03-24|Bayer Ag, 5090 Leverkusen|Use of low-viscosity self-curing mixtures for polyurethane interlayers in laminated panes|FR2549037B1|1983-07-11|1985-10-18|Saint Gobain Vitrage|SAFETY SHEET GLAZING| JPH0737122B2|1985-06-25|1995-04-26|旭硝子株式会社|Bent safety glass| DE3678132D1|1985-12-19|1991-04-18|Ppg Industries Inc|PLANE WIND PROTECTION.| US4824926A|1987-12-16|1989-04-25|Ppg Industries, Inc.|Bilayer windshield with an abrasion and solvent resistant polyurethane protective coating| FR2646667B1|1989-05-03|1991-08-23|Saint Gobain Vitrage|GLAZING WITH FILTERING STRIP AND MANUFACTURING METHOD| DE4010485A1|1990-03-31|1991-10-02|Ver Glaswerke Gmbh|METHOD FOR PRODUCING A PLATE OR FILM FROM POLYCARBONATE WITH A SOFT SCRATCH-PROOF COATING| DE4021113A1|1990-07-03|1992-01-09|Bayer Ag|Adhesives based on polyols and polyisocyanates| GB9108672D0|1991-04-23|1991-06-12|Triplex Aircraft And Special P|Lightweight glazings| ES2156881T3|1993-07-28|2001-08-01|Asahi Glass Co Ltd|PREPARATION PROCEDURE FOR A LAMINATED GLASS.| FR2717795B1|1994-03-22|1996-05-24|Saint Gobain Vitrage|Vehicle glazing and plastic sheet used in this glazing.| FR2720328B1|1994-05-27|1996-07-05|Saint Gobain Vitrage|Laminated glazing and manufacturing process.| FR2721252B1|1994-06-17|1996-08-09|Saint Gobain Vitrage|Laminated glazing with low energy transmission for transport vehicle.| FR2725399B1|1994-10-06|1996-11-08|Saint Gobain Vitrage|SAFETY GLASS| FR2827855B1|2001-07-25|2004-07-02|Saint Gobain|GLAZING PROVIDED WITH A STACK OF THIN FILMS REFLECTING INFRARED AND / OR SOLAR RADIATION| WO2007048141A2|2005-10-21|2007-04-26|Entrotech Composites, Llc|Composite articles comprising protective sheets and related methods| WO2009041964A1|2007-09-25|2009-04-02|Entrotech, Inc.|Paint replacement films, composites therefrom, and related methods| US10981371B2|2008-01-19|2021-04-20|Entrotech, Inc.|Protected graphics and related methods| FR3013043B1|2013-11-08|2015-11-20|Saint Gobain|SUBSTRATE COATED WITH A FUNCTIONAL LAYER STACK HAVING IMPROVED MECHANICAL PROPERTIES| FR3015973B1|2013-12-31|2016-01-01|Saint Gobain|LUMINOUS GLAZING WITH OPTICAL ISOLATOR AND ITS MANUFACTURE| FR3015926B1|2013-12-31|2017-03-24|Saint-Gobain Glass France|LUMINOUS GLAZING WITH OPTICAL ISOLATOR| FR3017332B1|2014-02-10|2016-02-19|Saint Gobain|LUMINOUS GLAZING WITH OPTICAL ISOLATOR.|
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申请号 | 申请日 | 专利标题 FR8311506A|FR2549036B1|1983-07-11|1983-07-11|SAFETY SHEET GLAZING| 相关专利
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