• 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:
    For use as a heat sealable, high temperature, insulative wrapping, a laminar structure of a polyimide inner layer and two fluoropolymer outer layers wherein the outer layers are pigmented for a combination of color, increased heat aged bond retention, and reduced heat seal energy requirements.
    公开号:SU1436894A3
    申请号:SU823480215
    申请日:1982-08-06
    公开日:1988-11-07
    发明作者:Катц Мортон
    申请人:Е.И.Дюпон Де Немур Энд Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to electrical engineering, in particular, to laminated film materials in which the main substrate layer of polyimide is coated on both sides with a heat-sealable fluoropolymer, and can be used as an insulating material for electrical wires intended for operation at high temperatures. .
    The purpose of the invention is to increase the bond strength between the layers during thermal aging while reducing
    To increase the adhesion between the polyimide inner layer and the outer layers of fluorocarbon polymer, a small amount of cleavage of the specific silane substance can be added between these layers. Alpha-chloromethylphenyltrialkoxysilane containing chemical groups that are attracted to polyimide and fluoropolymer causing adhesion of the layers is used as the strong compound. Silane is present as an adhesion promoter, but does not form an independent
    energy consumption for heat treatment of ma- 15 layer, which can be installed in
    teriala.
    A film with a layered structure forms an inner layer of polyimide and two outer layers of fluoropolymer, which contains 1-10 wt.% Of finely divided pigment substance. The pigment substance is evenly distributed in the material of the outer layers and performs several functions. Preferably, the pigments are carbon black.
    The film is intended for insulation and electrical wires and cables. A film in the form of tapes is wound onto a wire and then, when heated, is sealed to obtain a continuous coating. With this use, the inner polyimide layer forms an electrical insulation with high temperature stability, and the fluoropolymer outer layers form a cosiness additional electrical insulation and, more importantly, heat sealing with a coating. Pigmentation in both outer layers forms a permanent dyeing, increased heat sealing strength — with heat aging and a selective infrared absorber for heat sealing with reduced energy consumption.
    The polyimide of the inner layer is yt-. eg ethylene acceptable for is50
    with polypirmethylimides bis- (alpha-aminophenyl) ether.
    The inner layer must be thick enough to provide adequate electrical properties of the insulation, as well as the mechanical strength and integrity of the film and, at the same time, have a thickness that does not reduce the flexibility of the film and its ability to wrap around the surface of the insulated wires, B In most cases of use, the polyimide layer should be 10-150 µm thick.
    use subject to j that the melt point of the fluoropolymer is not more than 300 ° C
    Fluoropolymer outer layers provide, in particular, heat sealing (insulation) by sintering. layers when heated to the melt temperature of the material layers. Thermal hermeticization is most effective with when the thickness of the outer layers is from 2 to 50 µm. ) and the thinner thickness of the layer decreases the bonding forces between the layers and at the same time increases the duration of the sealing process.
    0 5
    0 d
    five
    layered film structure. The silane is present in a concentration of 0.1-0.3 wt.% By weight of the film and 0.5-1.0 wt.% By weight of the outer layers.
    The fluoropolymer of the outer layers is preferably a copolymer of hexafluoropropylene and tetrafluoroethylene, in which 5-50% by weight of hexafluoropropipene and 95-50% by weight of tetrafluoroethylene. Copolymers with different proportions may be used, but the sum of properties provided by this range is most desirable.
    Essential when choosing a fluorocarbon polymer for the outer layers is the melting point of the copolymer. If the melting point of the polymer is more than 300 ° C, the temperature destruction of the individual components of the wire, in particular the destruction of protective coatings, becomes possible during the heat sealing of the insulation. Therefore, fluorocarbon polymers, in particular tetrafluoroethylene homopolymers, having a high melt temperature, are not suitable for realization. Tetrafluoroethylene with perfluoroalkyl vinyl ether copolymers, such as per- / fluoropropyl vinyl ether or with olefins.
    0
    subject to condition j, that the melt point of the fluoropolymer is not more than 300 ° C,
    Fluoropolymer outer layers provide, in particular, heat sealing (insulation) by sintering. layers when heated to the temperature of the melt material layers. Heat sealing is most effective when the thickness of the outer layers is from 2 to 50 µm. ) and the thinner thickness of the layer decreases the bonding forces between the layers and at the same time increases the duration of the sealing process.
    The pigment introduced into the material of the outer layers must be chemically inert with respect to the fluoropolymer and be stable at temperatures up to 700 ° C. Pigments such as carbon black, graphite, titanium dioxide, red cadmium, zinc chromate and the like can be used. Most preferred are pigments with increased infrared absorption, such as graphite and carbon black. Gas soot and titanium dioxide give increased sintering strength after heat aging,
    Dp of intensive coloring pigments should be used in an amount of 0.5-10 wt.% From the mass of the film. , For most pigments, DNP is sufficient for staining purposes with 1 to 5% by weight of pigment.
    The introduction of the pigment reduces the energy consumption during heat treatment compared with the energy consumption during heat treatment of non-pigmented film. Films in the form of tapes back. wound radially.: on a wire or cable with a positive overlap, and then heated by radiation. When irradiated, the energy in the infrared part of the spectrum is intensively absorbed by the material of the outer layers, which are heated to a given temperature. The pigment in the outer layers for selective absorption in the infrared part of the spectrum not only reduces the energy consumption when heated, but also allows for sintering at a lower wire temperature than the sintering temperature of the wire insulation from non-pigmented tapes. Thus, the use of a pigmented film with a layered structure allows insulating the wire with less risk of thermal aging of the components of the insulated wire.
    Since the absorption of energy in the infrared part of the spectrum depends on the pigment concentration, the larger the pigment, the easier the outer layers melt and sinter together. The smallest amount of pigment is 1 wt.% By weight of the outer layers. A pigment concentration of more than 10 wt.% Can reduce the strength and thermal stability of the fluoropolymer material and
    0
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    interferes with adhesion between fluoropolymer and polyimide.
    In addition, when a tape with a structure according to the invention is wound onto a wire with a positive overlap, the outer layer on one side of the tape is installed opposite the outer layer on the other side of the tape. In this case, irradiation with radiation energy leads to the melting of both outer layers simultaneously with the same speed. For these reasons, the distribution of pigment in the material of the outer layers should be uniform and there should be an equal amount of pigment in each layer.
    The presence of pigment in the outer layers also leads to increased preservation of the bond strength of thermal sintering after heat aging. Thermal sintering of two pigmented films retains, as a rule, not less than 60% of the initial strength after thermal 5 starings for 21 days at 200 ° C, whereas thermal sintering of non-pigmented films retains no more than 50% of the initial strength of sintering after heat aging.
    The preferred concentration of pigment in the fluoropolymer to maintain the strength of sintering during thermal aging is 2-7% by weight of the weight of the outer fluoropolymer layers. At a concentration of more than 8% by weight, no increase in strength after aging is observed.
    It has been established that the shape of the film structure is more important than the method of its manufacture. The manufacture of the proposed film is made by coating with dispersions on a test film of polyimide. A film with a layered structure can also be obtained by 5 joint extrusion of the inner and outer layers or by coagulating together the obtained films.
    Several pieces of polyimide film 25 µm thick are coated with various aqueous dispersions of fluoropolymer pigmented according to the present invention and non-pigmented to form a control film.
    The outer layers of fluorocarbon polymer are applied to the inner layer by coating with fluoropolymer aqueous dispersions followed by
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    drying the coating and coalescing the fluoropolymer particles to form a continuous (continuous) coating.
    Aqueous dispersions are prepared in the following manner.
    Dispersion A is the initial dispersion for all subsequent coating options. Dispersion A is 20% by weight of a copolymer dispersion, 7-27% by weight of hexafluoro-propylene and 93- 73% by weight of tetrafluoroethylene in distilled water.
    Dispersion B is a dispersion containing additional substances for increased adhesion and equal coating of the dispersion layer. The solution is prepared from 0.8 g of a surfactant, in particular polyvinylcarboxylic acid, in 27 g of distilled P1G water, which regulate pH at 9 with g / ammonium oxide. C This solution is mixed with 214 g of dispersion A. Other surfactants can be used which allow a more homogeneous product to be obtained, however it is not necessary to implement this invention.
     Dispersion C is a dispersion obtained by introducing into the dispersion B a specific silane adhesion promoter. Get a solution containing 0.04 g of alpha-chloromethylphenyltrimethoxysilane, BND acetic acid, 1.78 g of water and 1.78 g of isopropyl alcohol. This solution is mixed with dispersion B.
    After trying the outer layers, graphite is introduced. To obtain a graphite dispersion, 8.8 g of granite and 400 g of dispersion B are placed in a pebble mill. Graphite has an average particle size of 0.56-0.62 microns and a purity of 99.6%. In a pebble mill, the mixture is treated for 16 hours. To obtain the composition of the outer layers, 60 g of the mixture of dispersion B with graphite is mixed with 83 g of dispersion B.
    The graphite-fluoropolymer composition of the coating is applied in the form of a wet layer with a thickness of 25 µm to the polyimide sheets. The coated film is suspended in a vertical position before drying, after which the coating is coalesced in an oven with air circulation at 400 ° C for 4 minutes. Since only one side of the test strips was used for thermal tests; aging bonding strength, sintering,.
    This test required coating only on one side of the film. When using films with a layered structure as insulation for wires or cables, it is necessary and important that both sides of the polyimide sheet are coated with a fluoropolymer.
    From polyimide sheets coated with fluoropolymer, tapes are cut, 2.5 cm wide. Tapes are placed close to covered sides and exposed to a temperature of 350 ° C at. 138 kPa for 20 s. Thermal aging of the baked films is carried out in an oven with air circulation at 200 ° C. After thermal aging, the ribbons are split with a measure of the splitting force. Heat aging is carried out at several values of the aging duration in order to determine the dependence of the bond strength on the aging time.
    Example 2. The outer layers contain lamp soot in the same concentration as graphite in Example 1. The main dispersion of lamp soot is obtained by grinding in a pebble mill for 1 h of a mixture of 300 g of dispersion B with 6.6 g of lamp soot. Lamp soot has an average particle size of 0.1-0.4 μm and a purity of 97.9%. The coating composition is prepared by mixing 60 g of the indicated carbon black basic dispersion with 80 g of the dispersion.
    The coating of polyimide sheets with fluoropolymer, cutting into ribbons, sintering and testing is carried out according to example I.
    Example 3 As a pigment, titanium dioxide with an average particle size of 0.2 μm with a purity of 94% is used. The main dispersion of titanium dioxide is obtained by grinding in a healing mill 300 g of dispersion B,. 30 g of titanium dioxide and 0.045 g of polyphosphate. potassium as a surfactant for 16 hours. The composition of the coating is obtained by mixing 10 g of the resulting basic dispersion of dioxide with 94 g of dispersion B.
    Sheeting, strip cutting, sintering and testing are carried out as in Example 1,
    Example4. Graphite is used as a pigment in the same concentration as in Example 1. However, dispersion C is used as a fluoropolymer dispersion. Grinding in a pebble mill, mixing, coating sheets, cutting into ribbons, sintering and testing are carried out as in Example 1.
    PRI me R 4a (comparative). The polyd sheet sheets are coated with dispersion B without pigment. The modes of coating, drying, coalescing and all subsequent operations are carried out as in Example 1. The test results are given in Table. one
    II p and me 4 p (comparative). Polyimide sheets are coated with dispersion C without pigment. Modes of coating and subsequent operations are performed in Example 1.
    The results are shown in table 1.
    From a comparison of the results in examples 1-3 with those of example 4a, it follows that aging in the presence of pigment occurs slowly as compared to the coating without pigment: bond strength after 21 days of aging at 16-24% Bbmie. Comparison of the test results in Example 46 with Example 6 shows that when using the silane adhesion promoter, the strength of sinter bond in the presence of pigment is preserved during heat aging to a greater extent, although the absolute values of bond strength remain somewhat higher in the absence of pigment.
    II p and measure 5. Polymer polyamide sheets are made in the same modes.
    and from the same materials as in aluminum 35, above aluminum measure 1, but with different concentration of wire braiding and winding: - a concentration of glass fiber pigment. Spois (graphite) tapes with 4.6 wt.% Of the amount of fluoride-based poly-polyide polymer; B - pigment concentration according to winding spirally over 7 wt.% With a particle size of I micron; 40 windings of glass filaments; c - pigment concentration of 7 wt.% With a particle size of 1 micron; d is the pigment concentration of 7% by weight with a particle size of 0.25-3.0 µm; e is the pigment concentration of 3.5% by weight with a particle size of 0.25-3.0 µm.
    The test results are shown in table 2.
    II pmeper 6. A polyimide film (from example 1) is coated with one hundred to five degrees by immersing it in a dispersion (from example 5e), which additionally contains 1% by weight of the silane adhesion promoter, as in example 4. After drying and koapestsirovany film with a size of 55 liters reduction consumed power to tape 0.63 cm wide. The properties can only be explained by the outer layers have a thickness of 2.5 microns. more intense absorption of the ray. The tapes are spirally wound on copper energy of the pigmented material, wire with a diameter of 0.81 mm with a 50% scrap of the coating. At the same time good kag
    The same cable was used as a control sample, but with a winding over a glass winding of non-pigmented tapes with a layered structure. 45 Cable samples are placed in a radiant heat oven. The kiln consumed power required for sintering the wound belts is measured. Pigmented tape sheaths are sintered at 4 kilowatts of furnace power, while non-pigmented shells are sintered when they are set to 7 kW. Since the introduction of the pigment does not change the distribution point
    five
    0 5
    overlapping edges. A second winding of the same film, but with the opposite direction of winding, is applied to the first winding. As a control sample, a spiral winding is used, which is applied to a wire of tapes with the same structure, but without pigment.
    Both wires are treated in an oven in air at 495 C for 24 s.
    The insulant formed from pre-foiled films has a brilliant black color. Since the polyimide film has a dark color that is close to the color of copper, it is difficult to visually distinguish the insulation of gshenok with pigment from that of films without pigment.
    Samples subjected to heat aging for 26 days at 230 ° C. After aging, the insulation removed in the form of a tube from a wire is stretched to break.
    The test results are shown in table 3.
    Example 7. The tapes were prepared according to Example 6, but 1.25 cm wide, using dp spiral winding on the cable. A coaxial cable is used as a cable. The cable has a single-conductor conductor, on top of which polyethylene insulation is placed, then aluminum winding, wire braid and fiberglass winding on top of the aluminum winding. Tapes with a polyinide-based structure are coiled according to a spiral over a winding of glass filaments,
    The reduction in power consumption can only be explained by the more intense absorption of radiant energy by the pigmented coating material. At the same time good kag
    The same cable was used as a control sample, but with a winding over a glass winding of non-pigmented tapes with a layered structure. Samples of cables are placed in an oven with radiation heating. The kiln consumed power required for sintering the wound belts is measured. Pigmented tape sheaths are sintered at 4 kilowatts of furnace power, while non-pigmented shells are sintered when they are set to 7 kW. Since the introduction of pigment does not change the sintering point, it can be obtained only with the introduction of pigment in both outer layers in an equal amount, since there is a uniform heat release in both contacting layers and their simultaneous melting and sintering at the same minimum radiator power .
    权利要求:
    Claims (1)
    [1]
    1. Film material with a layered structure, containing an inner layer of polyimide and two outer layers of fluoropolymer, different from. I
    in order to increase
    Titanium dioxide 4.4
    386
    It contains I, 0 wt.% To the mass of fluoropolymer alpha-chlorophenylmethyl-trimethoxy silane as an adhesion promoter.
    strength of the bond between the layers during heat aging while reducing the energy consumption for heat treatment of the material; an inorganic pigment is introduced into each of the outer layers, which has an increased absorption in the infrared part of the spectrum in an amount of 1-10 wt.%.
    2, The material in accordance with claim 1, 1, and O.L.H. is also due to the fact that alpha-chloromethylphenyltrialkoxysysilane is introduced along the layer boundaries.
    3, The material according to PP, 1 and 2, about tl and is due to the fact that graphite or titanium dioxide is used as a pigment.
    Table 1
    366
    272
    252
    65
    Control sample
    568
    Control sample
    181
    204
    157
    28
    ol i
    Table 3
    200,158
    103 85
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US29087081A| true| 1981-08-07|1981-08-07|
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