EP1173330A2 - Film a orientation biaxiale destine a la production de condensateurs ceramique - Google Patents

Film a orientation biaxiale destine a la production de condensateurs ceramique

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Publication number
EP1173330A2
EP1173330A2 EP00917027A EP00917027A EP1173330A2 EP 1173330 A2 EP1173330 A2 EP 1173330A2 EP 00917027 A EP00917027 A EP 00917027A EP 00917027 A EP00917027 A EP 00917027A EP 1173330 A2 EP1173330 A2 EP 1173330A2
Authority
EP
European Patent Office
Prior art keywords
film
cover layer
layer
ceramic
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00917027A
Other languages
German (de)
English (en)
Inventor
Karl-Heinz Kochem
Kerstin MÜLLER-NAGEL
Robert Schmidt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Trespaphan GmbH and Co KG
Original Assignee
Trespaphan GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Trespaphan GmbH and Co KG filed Critical Trespaphan GmbH and Co KG
Publication of EP1173330A2 publication Critical patent/EP1173330A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • H01G4/308—Stacked capacitors made by transfer techniques
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2323/00—Polyalkenes
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/16—Capacitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/10—Peculiar tacticity
    • C08L2207/12—Syndiotactic polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to a biaxially oriented multilayer film made of polyolefin, which is used as a carrier film for ceramic layers.
  • the invention further relates to a method for producing ceramic capacitors.
  • Ceramic capacitors are capacitors in which the dielectric consists of ceramic layers.
  • a ceramic starting material generally a ceramic powder
  • suitable solvents and binders to give a highly viscous mass.
  • This mass is further processed into thin layers in subsequent process steps, which are then provided with a metal layer (capacitor electrodes).
  • the ceramic layers thus coated are formatted, stacked, pressed and finally fired at elevated temperatures in order to sinter the ceramic.
  • the usable capacitor is produced from these blanks by subsequent electrical contacting of the electrodes and enclosing them in a synthetic resin coating (Spectrum of Science September 1988, page 88 ff).
  • the ceramic layers can consist of different materials. Suitable ceramic materials are known in the art, such as metal oxides and / or titanates, e.g. Barium titanate, magnesium silicate, titanium dioxide, bismuth oxide and mixtures thereof. These ceramics are characterized by high dielectric constants.
  • the highly viscous, ceramic coating composition is first applied to a suitable flexible substrate and dried. This substrate must be removed again in later processing steps, and the ceramic layer or film thus obtained must not be damaged when detached. in the It is known in the prior art to use paper, polyester film or polypropylene film for this purpose.
  • JP 06305041 A describes an oriented, multilayer film with a polypropylene base layer and ethylene-propylene copolymer top layers, the surface roughness of which is said to be in the range from 0.08 to 0.5 ⁇ m.
  • the roughness of the two surfaces should not differ by more than 0.1 ⁇ m.
  • the ceramic layers produced on this film can only be dried at low temperatures, since otherwise the adhesion of the ceramic layer to the film becomes too great and defects are created in the ceramic film when the carrier film is detached.
  • JP 01196111 A describes a single-layer oriented polypropylene film which contains polydimethylsiloxane as a release agent from the ceramic layer.
  • the polydimethylsiloxane can be partially transferred to the surface of the ceramic layer and there deteriorates the adhesion of the metal coatings on this surface.
  • JP 60206620 H describes a film made from a mixture which contains polypropylene, polymethylpentene and HDPE.
  • the film should have good separation properties and surface roughness due to the HDPE.
  • the object of the present invention was to provide a film which should be suitable as a carrier film for ceramic layers.
  • a film which should be suitable as a carrier film for ceramic layers.
  • there should be sufficient adhesion between the film and the ceramic layer so that the ceramic material can be applied well and the coated film can be wound.
  • the ceramic layer must be able to be detached from the film without causing damage to the ceramic layer, in particular its surface.
  • the ceramic layer it is required that it must have as smooth a surface as possible after it has been detached from the film.
  • this object is achieved by using a polyolefinic, oriented multilayer film as a carrier film in the production of a ceramic capacitor, the multilayer film consisting of a base layer and at least one cover layer A, the cover layer A containing a propylene polymer and at least one incompatible polyolefin, and that incompatible polyolefin is an LDPE, HDPE, MDPE, or ethylene-propylene copolymer or and • the surface of the top layer A has a greater roughness than the other
  • the base layer of the multilayer film according to the invention essentially consists of a polyolefin, preferably of a propylene polymer and optionally added additives in effective amounts in each case.
  • the base layer generally contains at least 90% by weight, preferably 95 to ⁇ 100% by weight, of the polyolefin.
  • the polypropylene polymer contains predominantly (at least 90%) propylene and has a melting point of 140 ° C or higher, preferably 150 to 170 ° C.
  • Isotactic polypropylene with an n-heptane soluble content of 6% by weight or less, copolymers of ethylene and propylene with an ethylene content of 5% by weight or less, copolymers of propylene with C 4 -C8- ⁇ -olefins with an ⁇ -olefin content of 5% by weight or less are preferred propylene polymers for the base layer, with isotactic polypropylene being particularly preferred.
  • the propylene polymer of the base layer generally has a melt flow index of 0.5 g / 10 min to 15 g / 10 min, preferably 3 g / 10 min to 8 g / 10 min, at 230 ° C. and a force of 21.6 N ( DIN 53 735).
  • the percentages by weight refer to the respective copolymer.
  • the cover layer A arranged on the surface of the base layer contains a propylene polymer and at least one incompatible polyolefin.
  • the incompatible polyolefin is generally present in the top layer in an amount of 0.5 to 30% by weight, preferably 1 to 25% by weight, in particular 3 to 15% by weight.
  • the propylene polymer is contained in an amount of 70 to 99.5% by weight, preferably 75 to 99% by weight, in particular 85 to 97% by weight. If necessary, the cover layer can additionally contain additives in effective amounts in each case.
  • the propylene polymer of the outer layer A contains for the most part (at least 90%) propylene and has a melting point of 120 ° C. or higher, preferably 140 to 170 ° C.
  • Isotactic polypropylene with an n-heptane soluble content of 6% by weight or less, copolymers of ethylene and propylene with an ethylene content of 10% by weight or less, copolymers of propylene with C 4 -C ⁇ - ⁇ -olefins with an ⁇ - Olefin content of 5% by weight or less are preferred propylene polymers for cover layer A, with isotactic propylene homopolymer being particularly preferred.
  • the propylene polymer of the cover layer generally has a melt flow index of 0.5 g / 10 min to 15 g / 10 min, preferably 3 g / 10 min to 10 g / 10 min, at 230 ° C. and a force of 21.6 N (DIN 53 735).
  • the percentages by weight refer to the respective copolymer.
  • the MFI of the top layer polymer should be at least as large, generally higher (approx. 25 to 100%) than the MFI of the base layer.
  • Incompatible polyolefins are those which are not completely miscible with the polypropylene of the outer layer A and which form a separate phase. This incompatibility causes some surface roughness which is desirable for the present invention.
  • Suitable incompatible polyolefins are HDPE, MDPE, LDPE or syndiotactic polypropylenes or Cycloolefin polymers.
  • High-density polyethylene is preferred for the invention, which has a melt flow index MFI, measured according to ISO 1133 at 21.6 N / 190 ° C., in the range from 0.1 to 2.0 g / 10 min, preferably from 0, 5 to 1.5 g / 10 min and a density, measured at 23 ° C. according to DIN 53 479, method A, or ISO 1183, in the range from 0.935 to 0.97 g / cm 3 , preferably 0.94 to 0, 96 g / cm 3 and a melting point, measured with DSC (maximum of the melting curve, heating rate 20 ° C./min), between 120 and 150 ° C., preferably between 125 and 135 ° C.
  • MFI melt flow index measured according to ISO 1133 at 21.6 N / 190 ° C.
  • MDPE Medium density polyethylene
  • MFI melt flow index measured according to ISO 1133 at 21.6N / 190 ° C., in the range from 0.1 to 3.0 g / 10 min, preferably from 0.6 to 1 , 5 g / 10 min and a density, measured at 23 ° C. according to DIN 53 479, method A, or ISO 1183, in the range from 0.925 to 0.94 g / cm 3 , preferably 0.925 to 0.935 g / cm 3 and one Melting point, measured with DSC (maximum of the melting curve, heating rate 20 ° C./min), between 115 and 145 ° C., preferably between 115 and 130 ° C.
  • MFI melt flow index measured according to ISO 1133 at 21.6N / 190 ° C.
  • Low density polyethylene is preferred for the invention, which has a melt flow index MFI, measured according to ISO 1133 at 21.6 N / 190 ° C., in the range from 0.1 to 3.5 g / 10 min, preferably from 0, 5 to 2.0 g / 10 min and a density, measured at 23 ° C. according to DIN 53 479, method A, or ISO 1183, in the range from 0.91 to 0.925 g / cm 3 , preferably 0.915 to 0.925 g / cm 3 and a melting point, measured with DSC (maximum of the melting curve, heating rate 20 ° C./min), between 110 and 135 ° C., preferably between 110 and 125 ° C.
  • MFI melt flow index measured according to ISO 1133 at 21.6 N / 190 ° C.
  • Cycloolefin polymers are homopolymers which are made up of only one type of cycloolefins, or copolymers which are made of cyclo- olefins and comonomers are built up (COC), the comonomer fraction being at most 50% by weight, based on the weight of the cycloolefin polymer.
  • Cycloolefins are mono- or polyunsaturated polycyclic ring systems such as cycloalkenes, bicycloalkenes, tricycloalkenes or tetracycloalkenes. The ring systems can be substituted one or more times.
  • cycloolefins which are composed of monoalkylated or unsubstituted cycloolefins.
  • Particularly preferred cycloolefin homopolymers are polynorbornene, polydimethyl-octahydronaphthalene, polycyclopentene and poly (5-methyl) norbornene.
  • the cycloolefin polymers can also be branched. Products of this type can have comb or star structures.
  • the cycloolefins described above can also be copolymerized with comonomers.
  • These cycloolefin copolymers (COC) contain up to 50% by weight, preferably 1-35% by weight, in particular 5 to 25% by weight, based on the weight of the COC, comonomer.
  • Preferred comonomers are olefins having 2 to 6 carbon atoms, in particular ethylene and butylene.
  • the cycloolefin polymers can be prepared with the aid of transition metal catalysts. Manufacturing processes are described, for example, in DD-A-109 225, EP-A-0 407 870 and EP-A-0 485 893, to which reference is hereby expressly made.
  • Syndiotactic polypropylenes are homo- or copolymers with a propylene content of at least 70% by weight, preferably more than 80% by weight, in particular in the range from 95 to 100% by weight, based on the total weight of the polymer.
  • the propylene content of the polymer has an isotaxy of ⁇ 15%, in particular ⁇ 6%.
  • the mean sequence length of the syndiotactic sequences are> 20%, preferably> 25%.
  • olefins having 2 to 8 carbon atoms are suitable, of which ethylene and / or butylene are preferred.
  • the polypropylene and the incompatible polyolefin are used as a mixture or as a blend.
  • Mixtures for the purposes of the present invention are understood to mean mechanical mixtures which are produced from the individual components. In general, the individual components are pressed as small size molded articles, for. B. lenticular or spherical granules, poured together and mechanically mixed with a suitable vibrator.
  • a blend in the sense of the present invention is an alloy-like composite of the individual components, which can no longer be broken down into the original components.
  • a blend has properties like a homogeneous substance and can be characterized accordingly by suitable parameters.
  • the surface of the cover layer A is rougher than the opposite film surface. It has been found that a rougher surface is essential for the processing behavior of the film when used according to the invention. Due to the smooth opposite surface C, the film tends to block. In addition, the winding behavior with a smooth surface is extremely problematic. According to the prior art, antiblocking agents are incorporated into one of the cover layers to remedy such problems. It has been found that the incorporation of antiblocking agents into the top layer A is disadvantageous for the use according to the invention. It has been found that embodiments with antiblocking agents in the cover layer A lead to damaged ceramic layers, since the antiblocking agents in the cover layer A leave impressions in the ceramic layer or can be transferred to the latter when the coated film is wound up. Such damaged ceramic layers can no longer be used for Manufacture of capacitors can be used.
  • a surface roughness of the cover layer A is produced using a mixture of polypropylene and incompatible polyolefins.
  • the surface structure produced in this way is sufficiently rough to process the film well, despite the smooth opposite surface.
  • the film can be wound up and unwound without any problem, without the incompatible polyolefin incorporated in the cover layer matrix being mechanically released.
  • the structure of the rough surface of the film according to the invention (in particular due to the low hardness of the incompatible polymer) does not lead to any damage or surface deformation of the ceramic layer during winding and unwinding.
  • the use according to the invention thus enables the production of thin ceramic layers which have a desirable smooth surface and have no defects or other damage.
  • the thickness of the cover layer A is greater than 0.3 ⁇ m and is preferably in the range from 0.4 to 3 ⁇ m, preferably 0.6 to 1.5 ⁇ m.
  • the opposite surface of the film is smoother than the surface of the cover layer A.
  • This smooth surface can be the surface of the base layer.
  • the film has a second cover layer C, through which the smoother surface is formed.
  • the cover layer C consists essentially of a polyolefin, preferably a propylene polymer and optionally added additives, in each case in effective amounts.
  • the cover layer C generally contains at least 90 % By weight, preferably 95 to ⁇ 100% by weight of the polyolefin.
  • olefinic polymers examples include propylene homopolymer or a copolymer of
  • Suitable propylene homopolymers contain for the most part (at least 90%) propylene and have a melting point of 140 ° C. or higher, preferably 150 to 170 ° C., isotactic homopolypropylene with an n-heptane-soluble fraction of 6% by weight or less, based on isotactic homopolypropylene is preferred.
  • the homopolymer has generally a melt flow index of 0.5 g / 10 min to 15 g / 10 min, preferably 1.5 g / 10 min to 10 g / 10 min, at 230 ° C. and a force of 21.6 N (DIN 53 735) .
  • the copolymers and / or terpolymers described above used in the top layer C generally have a melt flow index of 1.5 to 30 g / 10 min, preferably 3 to 15 g / 10 min.
  • the melting point is in the range from 120 to 140 ° C. All melt flow indices given above are measured at 230 ° C and a force of 21.6 N (DIN 53 735).
  • the smoother surface of the cover layer C is provided with a ceramic coating. It has been found that the polyolefinic surface has sufficient adhesion to apply a thin layer of ceramic material thereon. At the same time, however, the adhesion between the surface of the film and the ceramic layer is low enough to separate the carrier film from the ceramic layer after appropriate drying and / or processing steps, without damaging the ceramic layer produced in this way.
  • Embodiments with a homopolymer top layer have proven to be particularly advantageous, since they have a higher temperature resistance than co- or terpolymer layers and thereby enable higher drying and / or processing temperatures in the production of the ceramic layer. In addition, it was found that the ceramic layer can be separated from the carrier film with a homopolymer cover layer more easily.
  • the cover layer C can contain conventional neutralizing agents, stabilizers, optionally antistatic agents and lubricants. It is essential for the use according to the invention that the top layer C contains no antiblocking agents which increase the surface roughness. The increased surface roughness would be transferred to the surface of the ceramic layer during coating.
  • the ceramic layers are intended for use as a dielectric have a surface that is as smooth as possible to avoid imperfections and air pockets.
  • the antiblocking agent particles get stuck in the ceramic layer when the carrier film is removed! This is extremely undesirable because the antiblock particles in the ceramic layer lead to electrical defects and air pockets.
  • the thickness of the cover layer C is greater than 0.3 ⁇ m and is preferably in the range from 0.4 to 3 ⁇ m, preferably 0.6 to 1.5 ⁇ m.
  • the total thickness of the polyolefin multilayer film according to the invention can vary within wide limits and depends on the intended use. It is 6 to 70 ⁇ m, preferably 10 to 50 ⁇ m, the base layer making up approximately 50 to 98% of the total film thickness.
  • both the base layer and the cover layer (s) can contain further additives in a respectively effective amount, preferably antistatic agents and / or lubricants and / or stabilizers and / or neutralizing agents. All quantities in the following version in percent by weight (% by weight) relate to the layer or layers to which the additive can be added.
  • Preferred antistatic agents are alkali alkane sulfonates, polyether-modified, ie ethoxylated and / or propoxylated, polydiorganosiloxanes (polydialkylsiloxanes, polyalkylphenylsiloxanes and the like) and / or the essentially straight-chain and saturated aliphatic, tertiary amines with an aliphatic radical, the ones with 10 to 20 carbon atoms ⁇ -Hydroxy- (-C-C 4 ) alkyl groups are substituted, N, N-bis (2-hydroxyethyl) alkylamines having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, being particularly suitable in the alkyl radical.
  • the effective amount of antistatic is in the range of 0.05 to 0.3% by weight.
  • Lubricants are higher aliphatic acid amides, higher aliphatic acid esters, waxes and metal soaps as well as polydimethylsiloxanes.
  • the effective amount of lubricant is in the range of 0.1 to 3% by weight.
  • the addition of higher aliphatic acid amides in the range from 0.15 to 0.25% by weight in the base layer and / or the top layers is particularly suitable.
  • a particularly suitable aliphatic acid amide is erucic acid amide.
  • polydimethylsiloxanes in the range from 0.3 to 2.0% by weight is preferred, in particular polydimethylsiloxanes with a viscosity of 10,000 to 1,000,000 mm / s.
  • the usual stabilizing compounds for ethylene, propylene and other ⁇ -olefin polymers can be used as stabilizers.
  • the amount added is between 0.05 and 2% by weight.
  • Phenotic stabilizers, alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates are particularly suitable.
  • Phenolic stabilizers are preferred in an amount of 0.1 to 0.6% by weight, in particular 0.15 to 0.3% by weight, and with a molar mass of more than 500 g / mol.
  • Pentaerythrityl tetrakis-3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiary-butyl-4- Hydroxy-benzyl) benzene are particularly advantageous.
  • alkaline earth stearates and carbonates are preferred in an amount of 0.01 to 0.05% by weight, in particular calcium stearate and / or calcium carbonate with an average particle size of less than 0.1 mm, preferably 0.03 to 0.07 mm. an absolute particle size of less than 5 ⁇ m and a specific surface area of at least 40 m 2 / g.
  • the film can also be used when using photoresists.
  • Photoresist layers are usually applied to a suitable film material and wound up with this carrier.
  • the adhesion between the carrier film and the applied photoresist layer is too high large, so that problems in unwinding and further processing can occur.
  • the film described above can advantageously be introduced into the winding as a release film in order to prevent sticking between the carrier film and the photoresist layer.
  • the procedure is such that the melts corresponding to the individual layers of the film are coextruded through a flat die, the film thus obtained is drawn off on one or more rollers for consolidation, and the film is then stretched biaxially (oriented), the biaxially stretched film is heat-set and wound up.
  • the biaxial stretching (orientation) can be carried out simultaneously or in succession, with the successive biaxial stretching, in which stretching first being longitudinal (in the machine direction) and then transversely (perpendicular to the machine direction) being preferred.
  • the polymer or the polymer mixture or the blend of the individual layers is compressed and liquefied in an extruder, it being possible for the additives which may have been added to be present in the polymer.
  • the melts are then simultaneously pressed through a flat die (slot die), and the pressed multilayer film is drawn off on one or more take-off rolls, as it cools and solidifies.
  • the film thus obtained is then stretched longitudinally and transversely to the direction of extrusion, which leads to an orientation of the molecular chains.
  • Stretching is preferably 4: 1 to 7: 1 in the longitudinal direction and preferably 8: 1 to 10: 1 in the transverse direction.
  • the longitudinal stretching is expediently carried out with the aid of two rollers running at different speeds in accordance with the desired stretching ratio, and the transverse stretching is carried out with the aid of a corresponding tenter frame. mens.
  • the biaxial stretching of the film is followed by its subject fixing (heat treatment), the film being held at a temperature of 150 to 160 ° C. for about 0.5 to 10 s.
  • the film is then wound up in a conventional manner using a winding device.
  • the biaxial stretching is advantageously carried out at an elevated temperature of the film, the longitudinal stretching preferably at 90 to 140 ° C. and the transverse stretching preferably at 150 to 190 ° C.
  • the invention further relates to a method for producing ceramic capacitors, in which the film described above is used according to the invention.
  • a ceramic starting material generally a ceramic powder
  • suitable ceramic materials are, for example, metal oxides and / or titanates, for example barium titanate, magnesium silicate, titanium dioxide, bismuth oxide and mixtures thereof. These ceramics are characterized by high dielectric constants.
  • the highly viscous, ceramic coating composition is applied to the smooth surface C of the film and dried. The film coated in this way is then wound up. If necessary, the ceramic surface can be metallized in a further processing step. Finally, the film is separated from the ceramic layer.
  • the ceramic layers produced in this way are then further processed to ceramic capacitors in a manner known per se.
  • a three-layer film with a layer structure ABC is extruded from a slot die at an extrusion temperature of 250 ° C.
  • the base layer consists essentially of a propylene homopolymer with an n-heptane-soluble fraction of 4.5% by weight and a melting point of 163 ° C.
  • the melt flow index of the propylene homopolymer is 3.3 g / 10 min at 230 ° C and 21.6 N load (DIN 53 735, ISO 1133).
  • the base layer contains 0.13% by weight of pentaerythrityl tetrakis 4- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( ⁇ Irganox 1010) and 0.06% by weight of calcium stearate as neutralizing agent.
  • the base layer also contains 0.14% by weight of N, N- bis (2-hydroxyethyl) - (C ⁇ o-C 2 o) -alkylamine ( ⁇ Armostat 300) as an antistatic and an erucic acid amide (Armoslip) in an amount of 0.2% by weight as a lubricant.
  • the cover layers A essentially consist of a mixture of 93% by weight of propylene homopolymer and 7% by weight of LDPE.
  • the propylene homopolymer had an n-heptane-soluble fraction of 5% by weight and a melting point of 164 ° C and a melt flow index of 8.0 g / 10 min at 230 ° C and 21.6 N load (DIN 53735, ISO 1133).
  • the propylene homopolymer contained 0.05% by weight of Irgafos 168 (Ths (2,4-ditert-butylphenyl phosphite) and 0.07% by weight of Irganox 1010 and 0.06% by weight of calcium stearate as neutralizing agent
  • the LDPE had a melting point of 113 ° C. (DSC) and a melt flow index of 0.85 g / 10 min at 190 ° C. and 21.6 N load (DIN 53 735, ISO 1133) and a density of 0.923 g / cm 3 .
  • the cover layer C consists essentially (i.e. about 100% by weight) of a propylene homopolymer.
  • the propylene homopolymer was n-heptane soluble
  • the propylene homopolymer contained 0.05% by weight of Irgafos 168 (tris (2,4-ditert-butylphenylphosphite) and 0.07% by weight of Irganox 1010 and 0.06% by weight of calcium stearate as neutralizing agent .
  • the extruded three-layer film is drawn off via a first take-off roll and a subsequent take-off roll and cooled, then preheated, stretched longitudinally, stretched, fixed and wound up over the corresponding process steps, the following individual conditions being selected:
  • the foil is about 45 microns thick, said base layer 43 microns and each cover layer 1, 0 ⁇ m thickness has.
  • Example 1 is repeated. Compared to Example 1, only the composition of the outer layer A was changed.
  • the cover layer A essentially consisted of the cover layer homopolymer described in Example 1.
  • the cover layer A essentially consisted of the cover layer homopolymer described in Example 1.
  • Cover layer 0.38 wt .-% of an antiblocking agent made of Si0 2 with a medium Particle diameter of 4.8 ⁇ m (Sylobloc 45). The process conditions were essentially not changed.
  • the film according to the example according to the invention is outstandingly suitable as a carrier film for the ceramic coating.
  • the film can be coated well.
  • the ceramic layer can be removed very easily after drying and has a smooth surface with no imperfections. Electron micrographs clearly show that the surface of the outer layer A has a uniform roughness, whereas the surface A of the film according to the comparative example shows individual particles (antiblocking agents) which protrude from the outer layer. The elevations undesirably push through to the opposite side into the surface of the ceramic coating. This creates disadvantageous defects in the ceramic layer.
  • the roughness was determined as the Rz and Rmax value based on DIN 4768 with a cut-off of 2.5 mm.
  • the sliding friction was determined based on DIN 53 375 at 23 ° C.
  • the modulus of elasticity is determined at the earliest 10 days after production in accordance with EN ISO 521-1 on a sample with a size of 15 * 100 mm 2 .
  • the longitudinal and transverse shrinkage values relate to the respective linear expansion of the film (along Lo and across Qo) before the shrinking process.
  • the longitudinal direction is the machine direction, the direction transverse to the machine run is defined accordingly as the transverse direction.
  • the test specimen of 10 * 10cm 2 is shrunk in a forced air oven at the respective temperature (from 100 to 140 ° C) over a period of 15 minutes.
  • the remaining length dimensions of the test specimen along and across are then determined again (Li and Qi).
  • the difference in the determined linear expansions in relation to the original length Lo and Qo times 100 is then given as the shrinkage in%.
  • This determination method for longitudinal and transverse shrinkage corresponds to DIN 40634.
  • the density is determined according to DIN 53479, method A.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

L'invention concerne l'utilisation d'un film multicouche comme film support lors de la production d'un condensateur céramique. Le film multicouche est composé d'une couche de base et au moins d'une couche de recouvrement A. La couche de recouvrement A contient un polymère propylénique et au moins une polyoléfine incompatible. La polyoléfine incompatible est un LDPE, HDPE, MDPE, copolymère éthylène/propylène ou un polymère cycloléfinique ou un polymère syndiotactique. La surface de la couche de revêtement A présente une rugosité supérieure à celle de la surface opposée du film et la surface plus lisse du film est dotée d'un revêtement céramique qui est séché puis retiré du film support.
EP00917027A 1999-04-20 2000-03-31 Film a orientation biaxiale destine a la production de condensateurs ceramique Withdrawn EP1173330A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19917790 1999-04-20
DE19917790A DE19917790A1 (de) 1999-04-20 1999-04-20 Biaxial orientierte Folie für die Herstellung von Keramikkondensatoren
PCT/EP2000/002875 WO2000063013A2 (fr) 1999-04-20 2000-03-31 Film a orientation biaxiale destine a la production de condensateurs ceramique

Publications (1)

Publication Number Publication Date
EP1173330A2 true EP1173330A2 (fr) 2002-01-23

Family

ID=7905185

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Application Number Title Priority Date Filing Date
EP00917027A Withdrawn EP1173330A2 (fr) 1999-04-20 2000-03-31 Film a orientation biaxiale destine a la production de condensateurs ceramique

Country Status (7)

Country Link
EP (1) EP1173330A2 (fr)
JP (1) JP2002542614A (fr)
KR (1) KR20010102451A (fr)
CN (1) CN1128061C (fr)
AU (1) AU3816700A (fr)
DE (1) DE19917790A1 (fr)
WO (1) WO2000063013A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013131624A1 (fr) 2012-03-05 2013-09-12 Treofan Germany Gmbh & Co. Kg Feuille séparatrice fortement poreuse avec revêtement partiel

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101882507B (zh) * 2009-05-08 2011-08-17 北京化工大学 一种多层结构的聚合物基电介质复合材料及其制备方法
EA022217B1 (ru) * 2010-05-12 2015-11-30 Бореалис Аг Полипропилен со специфическим содержанием стеарата кальция для специальных конденсаторов
WO2017022706A1 (fr) * 2015-08-03 2017-02-09 東レ株式会社 Film multicouche d'oléfine et condensateur à film
DE102017004111A1 (de) 2017-04-27 2018-10-31 Topas Advanced Polymers Gmbh Polyolefinfolie und deren Verwendung
DE102017118202A1 (de) * 2017-05-15 2018-11-15 Epcos Ag Folienkondensator
DE102021128332A1 (de) 2021-10-29 2023-05-04 Brückner Maschinenbau GmbH & Co. KG Biaxial-orientierte Folie enthaltend Cycloolefinpolymere und alpha-Olefinpolymere, Verfahren zu ihrer Herstellung, sowie ihre Verwendung im Kondensator

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GB1421805A (en) * 1972-11-13 1976-01-21 Ibm Method of forming a positive resist
DD109225A1 (fr) * 1973-07-19 1974-10-20
DE2851557C2 (de) * 1978-11-29 1982-04-01 Hoechst Ag, 6000 Frankfurt Biaxial gestreckte Polypropylenverbundfolie zur Verwendung als Elektroisolierfolie
DE3706528A1 (de) * 1987-02-28 1988-09-08 Du Pont Deutschland Schichtuebertragungsmaterial
JPH01196111A (ja) * 1988-02-01 1989-08-07 Honshu Paper Co Ltd セラミックコンデンサ製造用延伸ポリプロピレンフィルム
DE3922546A1 (de) * 1989-07-08 1991-01-17 Hoechst Ag Verfahren zur herstellung von cycloolefinpolymeren
JPH0468033A (ja) * 1990-07-10 1992-03-03 Toray Ind Inc 軟質ポリオレフィンフィルム
TW227005B (fr) * 1990-11-14 1994-07-21 Hoechst Ag
FR2684333B1 (fr) * 1991-12-03 1999-07-16 Bollore Technologies Film plastique bicouche bi-etire.
JP2932910B2 (ja) * 1993-11-18 1999-08-09 株式会社村田製作所 キャリヤーフイルムおよびこれを用いたセラミックグリーンシートの製造方法
DE19647954A1 (de) * 1996-11-20 1998-06-04 Hoechst Ag Biaxial orientierte Folie aus cycloolefinischen Polymeren, Verfahren zu deren Herstellung und deren Verwendung

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013131624A1 (fr) 2012-03-05 2013-09-12 Treofan Germany Gmbh & Co. Kg Feuille séparatrice fortement poreuse avec revêtement partiel
US10033070B2 (en) 2012-03-05 2018-07-24 Treofan Germany Gmbh & Co. Kg Highly porous separator film having partial coating

Also Published As

Publication number Publication date
WO2000063013A2 (fr) 2000-10-26
CN1128061C (zh) 2003-11-19
AU3816700A (en) 2000-11-02
CN1347367A (zh) 2002-05-01
JP2002542614A (ja) 2002-12-10
WO2000063013A3 (fr) 2001-05-10
KR20010102451A (ko) 2001-11-15
DE19917790A1 (de) 2000-11-02

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