• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    1504198 Impact-resistant polycarbonate laminates GENERAL ELECTRIC CO 16 April 1975 [26 April 1974] 15707/75 Heading B5N In an impact-resistant adhesively-bonded laminate for use as a window or windscreen, the innermost layer is a polycarbonate layer of thickness at least 30 and less than 220 mils, e.g. 60-150 mils. having a relatively more brittle scratch-resistant coating of thickness up to 2 mils. on at least its exposed face. The layers may be bonded by a block polysiloxane-polycarbonate copolymer adhesive as defined below. Glass sheets may be strengthened or unstrengthened. Lamination may be carried out in an autoclave using a vacuum bag or ring; an adhesion primer may be used. Suitable scratch - resistant coatings are listed. In examples the following laminates are prepared from glass sheets (G) and polycarbonate layers having scratch-resistant coatings on the exposed faces only (A) or on both faces (B), or not coated (C) (figures represent thickness in mils.); (i) G125-C500-A125, (ii) A500-C500-B60, (iii) A250-C500-C500-B93, (iv) A250- C500-C500-A93, (v) A125-C375-C375- A125, (vi) G125-C250-A375 and (vii) A250- C500-A250; (v) may be used with either face inwards and (vi) and (vii) are comparison examples not within the invention. The adhesive may be 15-60 mils. thick and is prepared by reacting (A) a halogen chainstopped polydiorgarosiloxane composed of 5-200 siloxy units connected by Si-O-Si linkages and (B) a dihydric phenol where Z is H, halogen or lower alkyl and R is H, hydrocarbon or halohydrocarbon and phosgenating the reaction product.
    公开号:SU1056895A3
    申请号:SU752131504
    申请日:1975-04-25
    公开日:1983-11-23
    发明作者:Эдгар Молари Ричард (Младший)
    申请人:Дженерал Электрик Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to multilayer products with increased resistance to impact, such as windshields in vehicles. A multi-layered product is known that includes polycarbonate glass layers with a protective coating applied to the latter, and layers of a silisoxan block copolymer interposed between them. The thickness of the protective layer is 0.005-0.05 mm 1J. The disadvantages of such a product are the delamination of the product during an impact and, as a result, the low strength. The purpose of the invention is to reduce the delamination of the product upon impact. The goal is achieved by the fact that in a multilayer product, including polycarbonate layers, interconnected by adhesive, layers, and a protective coating applied at least to the outer surface of the polycarbonate, the adhesive layers are made of polysiloxane-polycarbonate block copolymer, obtained by the interaction A-on lordorganosiloxane with terminal halide-containing groups containing 5-200 diorganosiloxane groups linked by silicon-silicon-silicon bonds, in which each silicon atom has two radicals la, and b-dihydric phenol of the formula (h R where Z is hydrogen atoms, lower alkyls or halogen atoms, as well as various combinations of these groups, followed by processing the resulting product phosgeneram, and the thickness of the polycarbonate layer to which a protective coating is applied, 0.75 -5.5 mm. In this case, the product can be provided with a layer of glass located on the side of the impact impact. The notch sensitivity of the rear polycarbonate layer with a relatively brittle coating that is part of the impact resistant laminate means no reduced if this layer has a thickness in the range 0.755 and 5 mm, it is recommended to use thick layers. 1.5-3.75 mm. Using layers with a thickness of 0.75 mm from a practical point of view is impractical. Any commonly used polycarbonate resins can be used as components of the laminated materials. For the manufacture of protective laminates based on glass, any conventional types of glasses can be used, including both glass with a surface coating or uncoated glass, both hardened or toughened. chemical processing of glass, as well as ordinary unbaked glass. In order to improve the adhesion, the surface can be pretreated, if necessary, using appropriate means (vinylalkoxysilanes, aminoalkylalkoxysilanes, / alkoxysilanes, silyl peroxides and amino-alkoxysilanes). The structure of the polysiloxane-polycarbonate block copolymers can be described by the formula
    (I)
    de hs: l (preferably, h And was an integer from 1 to 1000;
    a 1-200, .50
    B 5-200 (average value from 12 to 90), and the ratio a / b may vary from about 0.05 to 3 (if b has an average value from 15 to 55 | 90, it is recommended that the ratio o / b be from about 0.067 to 0.45);
    dtl
    Y- group of formula60
    R (ZU
    R
    hydrogen atom or a group of the formula
    -6s.
    a hydrogen atom, a monovalent hydrocarbon radical, or a halogenated monovalent hydrocarbon radical; monovalent hydrocarbon radical, halogenated monovalent hydrocarbon 1) adical or cyanoalkyl, monovalent hydrocarbon, radical or halogenated radical;
    Z is a hydrogen atom, a lower alkyl halogen atom, or some combination of these groups.
    Radicals R R formula (T) can be aryls and halogenated aryls including phenyl, - chlorophenyl, xylyl and tolyl, arilkily in particular phenylethyl and benzyl, aliphatic, galoidalifaticheskie and tsikloalifatiches Kie radicals, in particular alkyl, alkenyl, cycloalkyl and haloalkyl , including methyl, ethyl, propyl, butyl, chlorobutyl and cyclohexyl. The radicals R could have all been the same, or at least two or more of them should be listed as radicals, and it is recommended that the radicals R be methyl radicals As the radicals R could T radicals present, nye listed for R, except hydrogen atom, and the radicals R can be all the same or have the same although two or more of them should belong to a given list of radicals. It is recommended that R be a methyl radical.
    In addition, the radicals R can be cyanoalkyls, for example cyanoethyls or cyanobutyls. As Z radicals, hydrogen atoms, methyls, ethyls, cuts, chlorine, bromine or iodine atoms or some combination of these radicals can be present in the compounds of formula (I). In a preferred embodiment, the radical Z is hydrogen.
    The structure used of copolymers resistant to hydrolysis can be presented as a chain consisting of a series of alternating copolymer blocks. The copolymer consists of polydiorganosiloxane groups linked by a substituted aryloxy group, silicon, with polyester groups derived from dihydric phenol and a carbonic derivative. Each of the links of the polymer chain named. the copolymer contains on average about 10-75% by weight of polydiorganosiloxane groups, and it is recommended that the content of these groups be about 40-70% by weight.
    The essential feature of the copolymers used is the presence in them of the recurring units of the polymer chain containing polydiorganosiloxane groups, which are linked by substituted ivui arcoxy-silicon bonds with polyester groups, derived from carbonic acid and dihydric phenol.
    To obtain a material with specified characteristics, these substances can be used either in pure form or in combination with known modifiers.
    A copolymer of the LR-3320 brand was used as a block copolymer. This copolymer has a weight of 1.12, a tensile strength of 182-224 kg / cm, an elongation of 300–3.0 times, a tensile strength of 0.178 kg / cm, a brittleness temperature below - 59s and the temperature of the deflection deformation when heated to 7lc. This temperature corresponds to a deflection of 0.254 mm with a load of 4.62 kg / cm2.
    Example (by a known method). The tracks were connected to each other in the autoclave using a vacuum chamber at 121 ° C, pressure .17.5 exposure time, autoclave 45 Inn. The composition of the layered material consisted of a 3.1 mm thick glass layer with a pretreated surface connected using a block polysiloxane block layer with a polycarbonate brand LR-5630 1.5 mm thick and a polycarbonate layer 6.3 mm thick. The polycarbonate layer is in turn connected using a layer of a block copolymer of polysiloxane with polycarbonate brand LR-3320 0.75 m thick with a thick layer of polycarbonate 9.5 mm thick, and on the back side of this polycarbonate layer a relatively brittle coating 6 is applied scratching. When, when tested in the surface of a glass layer with an arrow of a medium-power bullet at 13c, the rear surface of a polycarbonate layer with a thickness of 9.5 mm is protected | sounded brittle fracture and, although the pool did not break through all the layers, yet the cardboard indicators placed behind the test specimen of laminated glass at a distance of about 46.6 cm from the sample were damaged. This example illustrates the so-called notch sensitivity of a relatively thick polycarbonate layer upon impact of this layer.
    Example 2. The method of Example 1 was used. The surface to which the shot was fired was the surface of a layer of impact-resistant toughened glass 3.1 mm thick. This glass layer is connected with a thick layer of polycarbonate with a thickness of 12.7 mm using a layer of block copolymer of the brand LR-5630 with a thickness of 1.5 mm. This polycarbonate layer is in turn connected by means of a block copolymer layer of the brand LR-3320 0.75 mm thick with a back or inner polycarbonate layer 3.1 mm thick, on the back side of which a coating made of melamine resin is applied. A medium-power automatic weapon made a shot into the surface of a layer of glass, at room temperature and at 13 and 35 ° C. The pool did not penetrate the test specimen and the destruction of the back or inner polycarbonate layer did not take place. Froze A scratch-resistant coating made of melamine resin was applied to the front surface of the 12.7 mm thick polycarbonate layer. The face layer is connected to the inner layer of polycarbonate with the help of a layer of a block copolymer of the brand LR-3350 with a thickness of 0.37 mm. 12.7 lei, and the inner layer, in turn, is connected with a back layer of polycarbonate with a thickness of 1.5 mm, using a LR-3320 block copolymer with a thickness of 0.37 mm, with a scratch resistant coating on both sides of the back layer. from melamine resin. When this specimen was tested in the first two shots by a medium-power bullet, neither brittle fracture nor the formation of a protrusion was observed from the back side of the specimen as the bullet penetrated into the thickness of the specimen. As a result of the third shot, plastic deformation was observed, although this did not prevent brittle fracture; Thus, the thickness of the polycarbonate layer to which the protective coating is applied, more than 5.5 mm does not eliminate delamination. EXAMPLE 4 The sample was made in an atmosphere of air in an autoclave with a peripheral vacuum chamber or ring at 125 ° C, a pressure of 13.3-14.7 kg / cm and a sample retention time in an autoclave is 15 minutes. During the entire period from the initial stage of production to the final stage of cooling and decomposition, a constant vacuum was maintained. The impact layer of the specimen was a 6.3 mm thick polycarbonate layer. On the front surface of this layer is coated with melamine resin. This layer of polycarbonate is combined with a layer of a block copolymer of the brand LR-3320, 0.37 mm thick, and connected to a layer of polycarbonate 12.7 mm thick, and this layer, in turn, is connected with a layer of block copolymer LR-3320 measurer with a back layer of polycarbonate with a thickness of 2.36 mm, on both sides of which a scratch resistant coating is applied. When testing this sample using ammunition. increased power was not observed penetration of the bullet either in the inner or in the back layer of polycarbonate, and also there was no destruction of the back or inner layers. Thus, the proposed multilayer products (laminates) have increased resistance to impact, the sensitivity of polycarbonate layers to the formation of scratches and cracks in them is overcome by applying a layer of relatively fragile material to the polycarbonate layer on the side opposite to the side that is subjected to impact. The invention makes it possible to produce layered materials suitable for practical applications, which not only have enhanced impact resistance, but are also resistant to the formation of scratches, cracks and other defects that can make the material less bright or reduce its transparency when using such laminates. for the manufacture of vehicle windshields, WINDOW glass, sight windows, as well as for glazing and other purposes.
    权利要求:
    Claims (2)
    [1]
    1. MULTI-LAYERED PRODUCT, including polycarbonate layers interconnected by adhesive layers, and a protective coating applied at least on the outer surface of the polycarbonate, a join is the fact that, in order to reduce the delamination of the product upon impact, adhesive the layers are made of a polysiloxane-polycarbonate block copolymer obtained by the interaction of A-polydiorganosiloxane with final halogen-containing groups containing 5-200 diorganosiloxane groups joined by silicon-oxygen-silicon bonds in which each silicon atom has two radicals, and a B-diatomic phenol where Z is hydrogen atoms, lower alkyls or halogen atoms, as well as various combinations of these groups with subsequent g treatment of the obtained product with phosphogen, and the thickness of the polycarbonate layer deposited protective coating, 0.75-5.5 mm.
    [2]
    2. The product according to claim 1, with a join order in that it is equipped with a glass body located on the side of the impact.
    1056895 A
    1Q56895
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    USRE32406E|1987-04-21|Impact resistant soft coated laminates and process for making the same
    US4647493A|1987-03-03|Puncture resistant laminate
    US5126208A|1992-06-30|Optical laminates
    同族专利:
    公开号 | 公开日
    FR2268639A1|1975-11-21|
    AR203140A1|1975-08-14|
    DD118851A5|1976-03-20|
    NL7504891A|1975-10-28|
    IT1037625B|1979-11-20|
    BE828347A|1975-08-18|
    BR7502562A|1976-03-09|
    DE2513684A1|1975-11-13|
    JPS5926472B2|1984-06-27|
    JPS50146687A|1975-11-25|
    GB1504198A|1978-03-15|
    AU7968375A|1976-10-07|
    FR2268639B1|1978-10-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2503544C2|2009-02-23|2014-01-10|Гардиан Индастриз Корп.|Method of protective anti-scratch coat application and articles with said coat|
    US4322476A|1979-12-12|1982-03-30|General Electric Company|Impact resistant laminate|
    US4312903A|1980-03-05|1982-01-26|General Electric Company|Impact resistant double glazed structure|
    DE3119872A1|1981-05-19|1982-12-09|General Electric Co., Schenectady, N.Y.|Improved impact-resistant double-glass structure|
    FR2507238B1|1981-06-04|1985-05-10|Gen Electric|
    GB2119704B|1982-04-30|1985-09-11|Glaverbel|Process of forming multi-ply laminates|
    GB2157618B|1984-04-04|1987-11-04|Pilkington Brothers Plc|Impact-resistant laminate|
    CA1248822A|1984-04-04|1989-01-17|Christopher W.G. Hall|Impact resistant laminate|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US46460374A| true| 1974-04-26|1974-04-26|
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