• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A polyvinyl butyral composition useful as an interlayer in architectural glazing units is plasticized by a blend of a di(C5 to C9 alkyl) adipate and a C3 to C6 alkyl benzyl phthalate.
    公开号:SU841594A3
    申请号:SU792720158
    申请日:1979-01-29
    公开日:1981-06-23
    发明作者:Айрвинг Кристенсен Дональд；Арсур Снельгроув Джэмс
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to polymeric compositions, in particular to polyvinyl butyrhypea composition, and can be used in the chemical industry, and composition for intermediate layers of laminated glass of architectural glazing elements.
    The main property that a plasticized polyvinyl butyral liner must have is acceptable for the production of laminated materials used for architectural purposes, edge stability, i.e. their ability to resist flaking near the edges of the laminate, especially after many years of exposure to a humid environment. Layered materials used for architectural purposes must have an exceptionally high standard of edge stability,. those. meet the requirements that are not applicable to gasketing materials used in automotive windshields with a life expectancy shorter than the service life of architectural pads.
    Edge stability is closely related to compatibility in the sense that in this case, if the plasticizer is incompatible with the polymer, this can lead to its rapid loss near the sheet of the layered material, for example, due to migration to the surface (sweat) or leaching with water. Thus, if the plasticizer does not have exceptionally high compatibility, the layered material, in which polyvinyl butyral plasticized with such plasticizer is used as a gasket, does not have a sufficiently high degree of edge stability that would allow it to be used for architectural purposes. Another characteristic that is extremely desirable for an architectural vitrified laminate, is an appropriate impact strength. It is known that some Some plasticizers have a degrading effect on impact strength, especially at low temperatures, of multi-layer materials, which include an intermediate layer plasticized with such plasticizers. However, combinations of plasticizers of known compositions can be used to produce multi-layer materials, which also meet the requirements of the impact criteria necessary for their use as architectural glass. The known polyvinyl butyral position for the intermediate layers of laminated glass is an architectural glazing consisting of polyvinyl butyral and an ester plasticizer digexylapipate flj. The disadvantage of the composition is the insufficient resistance of the edges of the elements to exfoliation and the low-temperature impact strength of the glasses when used for very long periods of time. The purpose of the invention is to increase the stability of the edges of the elements to delaminate the Nr and increase the low-temperature impact strength of the glasses. This goal is achieved by the fact that the polyvinyl butyral composition for the intermediate layers of laminated glass elements of architectural glazing, consisting of polyvinyl butyral and ester plasticizer, contains as a last mix of dihexyl adipate with 20-80% by butyl benzylphthalate with the following ratio of components, parts: Polyvinyl butyral 100 Plasticizer35-47 Polyvinyl butyral composition, plasticized with an effective amount of a mixture of plasticizers, includes 20-80% vol. Of dihexylamine and accordingly Eighty-20% by volume butylbenzyl phthalate, the effectiveness of this combination is unexpected, because when the phthalate component is used individually, layered materials are obtained that have an exceptionally high edge stability, but the low-temperature impact strength of such smooth materials is noticeably lower. . On the other hand, in the case when laminated materials comprising one adipate plasticizer are subjected to tests under severe conditions for long periods of time, which is necessary to confirm the possibility of their use as architectural laminated glass, Exfoliation of the edge is observed to a certain extent, which may cause the inapplicability of the mentioned materials in some areas. The choice of the optimal composition for the combination of plasticizers depends on the stability of the edge and low-temperature impact strength. If the edge stability is more characteristic, then this combination contains phthalate as the main component, the impact strength of which is the main quality of the material, and the dominant component is adipate. In architectural glass, edge stability is the dominant effect, as a result of which the proposed composition contains 30-70% by volume of dipate and accordingly 70-30% by volume of talate. Polyvinyl butyral is obtained by reaction of butyraldehyde with hydrolyzed polyvinyl ether, in particular with polyvinyl acetate, therefore it contains residual alcohol and ether groups. Acceptable polyvinyl butyrals contain up to about 4% by weight of ester groups (defined as polyvinyl ether) and 10-30% by weight of hydroxyl groups (defined as polyvinyl alcohol), while the rest is polyvinyl butyral. Polymer molecules include 15-25 wt.% Hydroxyl groups (defined as polyvinyl alcohol). The compatibility of the plasticizer with polyvinyl butyral is measured by its cloud point or the absorption of the plasticizer by polyvinyl butyral. The cloud point is determined by preparing a solution of 0.5 g of polyvinylbutyral in 10 ml (at room temperature) of a plasticizer at the temperature at which a clear solution is formed, and then the temperature is gradually lowered (the measurement is carried out using a thermometer immersed in the solution) to such a level in which the solution becomes turbid due to the separation of the polymer from the solution. The temperature at which the readings of the thermometer scale behind the test tube become indistinguishable is the cloud point. Tests using a series of plasticizers under identical conditions to determine their cloud point make it possible to achieve very precise indications of their relative ability to combine with the polymer. The lower the cloud point, the higher the compatibility of both components. Absorption is determined by immersing a thin sheet of polyvinyl butyral in a plasticizer for a certain period of time, after which it is removed, the suitcase is weighed. This process is repeated until the weight gain of the sheet stops. If such a test is carried out with the use of various plasticizer compositions, all other things being equal, the relative absorption data of plasticizers by polyvinyl butyral indicates the relative compatibility of various plasticizers with polyvinyl butyral. These two tests are conducted to obtain preliminary data indicating the possibility of using
    blends as effective plasticizers for polyvinyl butyral for use in the manufacture of laminated glass that can withstand prolonged exposure to sunlight and atmospheric factors without degrading properties. Samples of materials that have passed through such tests have been exposed in Florida and Arizona for 2 years. outdoors, . after which they were subjected to tests to evaluate the appearance and stability of the film.
    Compatibility of various mixtures of plasticizers with polyvinyl butyral is determined by performing tests of the two types described, and mixtures with the best compatibility properties were tested to determine their properties after aging in the most severe conditions.
    Example 1. The cloud point of various combinations of butyl benzyl phthalate (BBP) with dihexyl adipate (DHA) is determined.
    In the same total volume of plasticizer, the same amount of polyvinyl butyral is dissolved, the hydroxyl content of which, measured as polyvinyl alcohol, is 20.8 wt.%. Note the temperature at which turbidity begins to occur, and the temperature at which the thermometer scale becomes indistinguishable.
    . The results obtained with changes in the relative content of BBF and DHA in the xc position of plasticizers are summarized in Table 1.
    Table 1
    Thus, sometimes the cloud point is lower than the minimum fixed temperature.
    It follows from the above that DGA is characterized by a minimum level of compatibility with the polyvinyl butyral used. However, partial replacement of DHA with a BBF component increases the degree of compatibility up to the moment
    0 when the ratio between BBF and DGA reaches approximately 70:80, after which the compatibility begins to fall again. Thus, in a certain range, ranging from 5 to approximately 95: 5-40: 60 for, respectively, ICF and DHA (in terms of volume ratio), the cloud point of the combination of the components is below the cloud point for any of the components separately. This indicates the possibility of using an intermediate layer, the material of which includes, as a plasticizer, a composition with a ratio of components within the specified limits, for
    5 for the manufacture of a layered material, the stability of which is nrs, which exceeds the stability of the edges of the material with intermediate wood plasticized with any of the plasticizers used separately.
    Example 2: Effect on the absorption of a mixture of plasticizers, including BBP and DHA, and the change in the ratios between these components. At the same time use the described technology. The results obtained are summarized in table 2.
    2
    Table
    40
    98
    122
    100
    110
    138
    20
    110 138
    40
    96
    119
    60
    40
    From the data of Table 2, it follows that the experiment is repeated using DHA, which is of minimal compatibility. In the case when the DHA plasticizer is mixed with more than 45 vol.% BBF, the compatibility of the mixture of plasticizers exceeds the compatibility of any of its components, taken separately, and with a volume ratio between BBB and DHA in the range from 40:60 to 80:20 mixture is maximized.
    EXAMPLE 3 Results of layering materials that include one intermediate layer of polyvinylbutyrs plasticized with a mixture of BBF and DHA in a volume ratio of 60:40 vol.%, Throughout the year in Florida. For comparison, two other intermediate layers are tested. The same plasticizer is used in one such layer, with the exception that BBF is used instead of dibutyl phthalate (DBP). In the composition of the other layer, a technical plasticizer, triethylene glycol di-2gethylhexylbutyral, is used, which is widely used for plasticizing polyvinyl butyral, instead of the proposed mixture.
    A square-shaped laminate is heated in an oil-filled autoclave, before, after removal, it is cleaned, cut into squares, and held in the open air and sun for a year in Florida.
    At the end of the year, square samples are subjected to edge stability testing. Edges in which there are more than three sections (along an edge 15 cm long) where the intermediate layer does not completely coincide with the edge of the glass are considered unsatisfactory. The obtained results of edge stability are summarized in Table III.
    Table 3
    Example 4. Characteristics of layered materials made using intermediate layers plasticized in accordance with the invention.
    Sheets of plivin1 1, butyral, plasticized with various combinations of plasticizer, are used as spacers between the sheets of glass, and the materials thus prepared are kept in weather conditions in the state of Florida for 18 months. After a period of one year and -Then again after 18 months, the laminates are tested to detect defects.
    In this case, material defects are considered to be points at which the intermediate layer shrinks relative to the edge of laminated glass, revealing the peeling of the edge.
    The results are summarized in table 4.
    Table 4
    10/0 10/4 10/7 10/0 10/0 10/7 10/10
    Intermediate layer A is polyvinyl butyral containing 20% hydroxyl groups (defined as polyvinyl alcohol) plasticized 40 hours / 100 hours plasticizer.
    Intermediate layer B is polyvinyl butyral, the molecules of which contain 18.3% hydroxyl groups (defined as polyvinyl alcohol), plasticized ... 35.5 parts / 100 hours plasticizer.
    Intermediate layer C is polyvinyl butyral, the molecules of which contain 18.6% hydroxyl groups (defined as polyvinyl alcohol), plasticized with 34 parts / 10 O. of plasticizer.
    In each case, the detected defects are areas along the edges of the laminated materials where the shrinkage of the intermediate layer causes the intermediate layer to separate from the edge of the glass to a depth of less than 1 mm. For most laminates plasticized in accordance with the invention, no even a minor type of spots was found along the edges.
    Example 5. This example illustrates the change in low-temperature impact strength depending on 41.5 / 10013.3 (0.75) 17.5 (0.79) 41.0 / 10013.8 (0.76) 18.7 (0, 79) 40.5 / 10015.3 (0.75) 23.3 (0.79) 39.5 / 10019.5 (0.75) 26.4 (0.79) 38.5 / 10019.5 ( 0.75) 30.4 (0.79)
    The results of the velocity measurement of the penetration are divided into two parts, A and B. In part A, raw data are given which can only be compared approximately. In Part B, a computer mosel is used to adjust this raw data and place it on a strictly comparable basis using intermediate layer thickness and adhesion values.
    on the relative content of the plasticizer components.
    In polyvinyl butyral, the molecules of which contain 21.5% of the HYDOOXYL Groups (determined as polyvinyl alcohol), various mixtures of plasticizers are listed in Table 5.
    Using various plasticized specimens, sheets of approximately 0.76 mm thick are molded, which are then combined as
    o intermediate layers under identical conditions with glass sheets to obtain a laminate with a thickness of approximately 2.5 mm. Adhesive - The ability of the intermediate layer to 5 glass regulate the addition of a metal salt.
    The average penetration rate is determined by the drop of a cast-iron ball 0 weighing 2.27 kg into square samples of laminate with a side length of 30.5 cm until the ball either penetrates the specimen or forms a crack longer than one side of the specimen. Speed
    The 5 movements of the ball upon impact are calculated from the height from which the ball falls.
    The dependence of impact strength on the composition of the plasticizer is given in table.5.
    Table5
    The data table. 5 show that the higher the relative content of butyl benzyl phthalate, the lower the low-temperature impact strength measured by the average penetration rate. From the evaluation of the given values it is obvious that. at low temperatures, the higher the relative content of DHA, the higher the impact strength, which is unexpected in this part of the compositional change interval 31.7 (0.77) 1416.931.1 34.1 (0.77) 1418.434, 0 39.9 (0.76) 15.322.439.4 40.1 (0.76) 20.125.040.6 41.2 (0.77) 19.829.640.4
    Compositions in which the compatibility increases with increasing DHA content.
    As follows from the examples, the proposed composition can significantly improve the resistance to delamination and low-temperature impact strength of glasses.
    权利要求:
    Claims (1)
    [1]
    1. US patent No. 3884805, CL.210-65, published. 1965.
    类似技术:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/873,346|US4144217A|1978-01-30|1978-01-30|Plasticizer blends for polyvinyl butyral interlayers|
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