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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
  • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
• • 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
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
  • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
  • B32B37/203—One or more of the layers being plastic
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • 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
  • B32B2327/00—Polyvinylhalogenides
  • B32B2327/12—Polyvinylhalogenides containing fluorine
• • 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
  • B32B2331/00—Polyvinylesters
  • B32B2331/04—Polymers of vinyl acetate, e.g. PVA
• • 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
  • B32B2369/00—Polycarbonates
• • 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
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
  • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state

Definitions

• the present invention relates to a method for producing multilayer plastic composites.
• Fluoropolymers have a number of advantageous properties. They are resistant to most chemicals. They are resistant to environmental influences such as Weather and UV radiation. Fluoropolymers are therefore used for numerous purposes, especially as a protective layer against the effects of chemicals or as
• fluoropolymers have the disadvantage of being very expensive.
• their mechanical properties are sufficient, e.g. Impact strength does not meet the requirements of all applications. This is why fluoropolymers are sometimes used as a layer in multilayer plastic composites.
• the other layers contribute further advantageous properties, such as, for example, good mechanical properties or low costs, or functional properties such as, for example, ease of melting, as a result of which the plastic composite can be processed further into laminates.
• US-A 4 659 625 discloses three layer plastic composites, the first of which
• Coextrusion is a particularly advantageous method for producing multilayer plastic composites.
• the layers of the composite are brought together as melt layers in a coextrusion block and then extruded together through a die.
• a slot die is used in the extrusion.
• plastic composites from several layers one layer consisting of an ethylene-vinyl acetate copolymer and one layer consisting of polycarbonate, is not possible by coextrusion, since sufficiently low-viscosity polycarbonate melts have such a high temperature, typically 280 to 320 ° C. that the properties of the ethylene-vinyl acetate copolymers, for example be impaired by networking. There are deteriorations in the optical properties such. B. discoloration and deterioration of the mechanical properties such. B. the strength and elasticity. Such impairments are related to the use of plastic composites, especially e.g. in use in
• Plastic composites from three layers the first layer made of a fluoropolymer (in particular polyvinyl fluoride, hereinafter referred to as PVF), the second, middle layer made of polycarbonate (hereinafter referred to as PC) and the third
• EVA ethylene-vinyl acetate copolymer
• the present invention is therefore based on the object of providing a process for producing plastic composites from three layers, the first layer consisting of a fluoropolymer, the second, middle layer consisting of polycarbonate and the third layer consisting of ethylene-vinyl acetate copolymer, that does not have the disadvantages of the prior art.
• the object according to the invention is achieved by a method for producing plastic composites from three layers, the first layer consisting of a fluoropolymer, the second, middle layer consisting of polycarbonate and the third layer consisting of ethylene-vinyl acetate copolymer, characterized by the following in succession Steps to take:
• the method according to the invention has numerous advantages.
• the required plastic composites of three layers, the first layer consisting of a fluoropolymer, the second, middle layer made of polycarbonate and the third layer consisting of ethylene-vinyl acetate copolymer, can be produced in a simple and inexpensive manner by the process according to the invention without ethylene
• Vinyl acetate copolymer is thermally damaged, for example by crosslinking.
• the process is solvent-free and therefore economically and ecologically advantageous.
• the method according to the invention enables the continuous production of endless plastic composites and saves, for example in the later production of photovoltaic modules, the separate insertion and smoothing of the respective individual layers (foils or plates).
• the plastic composites according to the invention have good mechanical properties, e.g. high strength, high toughness and high elasticity. They have good optical properties such as high transparency and high gloss as well as low production-related discoloration. They have a high resistance to
• the fluoropolymer layer (optionally also the PC layer) is preferably provided with a sufficient amount of an adequate UV absorber.
• the PC layer is furthermore preferably protected by coextrusion, painting or lamination with a material containing UV absorber (for example 2-20% by weight of UV absorber), regardless of whether the PVF layer contains UV absorber or not , The layers of the plastic composite adhere well to one another.
• Method steps a) and b) of the method according to the invention can be carried out immediately one after the other or at a time and / or spacing from one another in order to, for. B. temporarily store the plastic composite from two layers. It is preferred to carry out the procedure one after the other. In this case, the plastic composite can be heated or cooled from two layers between process steps a) and b).
• a preferred embodiment of the method according to the invention is that in which the plastic composite consisting of two layers, which in method step a) is produced, an adhesion promoter layer is applied to the polycarbonate layer before application of the third layer in process step b).
• Suitable adhesion promoters are, for example, those based on acrylate.
• Another preferred embodiment of the process according to the invention is that at which the plastic composite of two layers in process step b) has a temperature at which the ethylene-vinyl acetate copolymer is not subjected to thermal damage, and at which the layer of ethylene-vinyl acetate copolymer is considered Film is applied to the plastic composite from two layers.
• the plastic composite of two layers in process step b) preferably has a temperature of 20 ° C. to 120 ° C., particularly preferably a temperature of 50 to 90 ° C.
• the EVA film is preferably fed in at a temperature of 10 to 60 ° C., particularly preferably 20 to 40 ° C.
• a further preferred embodiment of the process according to the invention is that at which the plastic composite consisting of two layers in process step b) has a temperature at which the ethylene-vinyl acetate copolymer has no thermal damage, e.g. experienced through crosslinking, and in which the layer of ethylene
• Vinyl acetate copolymer is applied as a melt to the plastic composite from two layers.
• the plastic composite consisting of two layers in process step b) preferably has a temperature of 20 to 120 ° C., particularly preferably 50 to 90 ° C.
• the melt preferably has a temperature of 80 to 150 ° C., particularly preferably 90 to 130 ° C., and is preferably applied to the plastic composite consisting of two layers after extrusion through a slot die.
• Another preferred embodiment of the method according to the invention is that in which the plastic composite of two layers in method step a) is applied by extrusion of a polycarbonate melt onto the polycarbonate layer of a plastic composite made of polycarbonate and fluoropolymer.
• the originally existing layer of polycarbonate and the additionally applied layer of polycarbonate combine to form a single polycarbonate layer, so that a plastic composite of two layers, a fluoropolymer layer and a polycarbonate layer, is obtained.
• the plastic composite made of polycarbonate and fluoropolymer to which the polycarbonate melt is applied can contain an adhesion promoter layer between the fluoropolymer layer and the polycarbonate layer. Suitable adhesion promoters are, for example, acrylate polymers.
• a further preferred embodiment of the method according to the invention is that in which the plastic composite consisting of two layers in method step a) is applied to a solid fluoropolymer layer by extrusion of a polycarbonate melt.
• An adhesion promoter layer can be used between the layer of polycarbonate and the layer of fluoropolymer.
• Another preferred embodiment of the method according to the invention is that in which the plastic composite is produced from two layers in method step a) by gluing a layer of polycarbonate and a layer of fluoropolymer.
• a particularly preferred embodiment of the process according to the invention is that at which the plastic composite from step a) in process step b) has a temperature at which the ethylene-vinyl acetate copolymer does not experience any significant thermal damage, and at which the layer of ethylene-vinyl acetate Copolymer is applied as a melt to the plastic composite from two layers.
• Process steps a) and b) are preferably carried out immediately one after the other, the temperature control of the plastic composite being carried out from two layers by cooling on a transport route.
• Ethylene-vinyl acetate copolymers for the purposes of the present invention are copolymers of vinyl acetate and ethylene, which preferably contain a vinyl acetate content of at least 30% by weight.
• ethylene-vinyl acetate copolymers are known and are sold as commercial products.
• ethylene vinyl acetate film type Elvax 485 from BP Chemicals, D-89165 Dietenheim, Germany. They can be produced by known methods.
• polycarbonates are those based on the diphenols of the formula (II)
• A is a single bond C j -C 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -S- or -SO2-,
• R 7 and R 8 independently of one another, in each case hydrogen, halogen, preferably chlorine or bromine, Cj-Cg-alkyl, C 5 -C 6 cycloalkyl, C 6 -C 10 aryl, preferably phenyl, and C 7 -C j2 - Aralkyl, preferred especially benzyl,
• n is an integer of 4, 5, 6 or 7, preferably 4 or 5,
• R 9 and R 10 can be selected individually for each Z, independently of one another hydrogen or C r C 6 alkyl
• Carbon means with the proviso that at least one atom ZR 9 and R 10 simultaneously mean alkyl.
• Suitable diphenols of formula (II) are e.g. Hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane (ie bisphenol A), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxy-phenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) - propane.
• Preferred diphenols of the formula (II) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis (4th -hydroxypheny l) -cyclo-hexane.
• Preferred diphenols of the formula (III) are l, l-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1, 1-bis (4-hydroxyphenyl) -2,4,4-trimethyl-cyclopentane.
• Polycarbonates suitable according to the invention are both homopolycarbonates and
• Copolycarbonates A mixture of the thermoplastic polycarbonates defined above is also suitable.
• Polycarbonates can be made in a known manner from diphenols with phosgene according to the interfacial process or with phosgene according to the process in a homogeneous manner
• Suitable chain terminators are e.g. Phenol, cumylphenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (l, l, 3,3-tetramethylbutyl) phenol or monoalkylphenol or dialkylphenol a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethyl-heptyl) phenol and 4- (3rd , 5-dimethyl-heptyl) phenol.
• alkylphenols such as 4- (l, l, 3,3-tetramethylbutyl) phenol or monoalkylphenol or dialkylphenol a total of 8 to 20 carbon atoms in the
• the amount of chain terminators is generally between 0.5 and 10 mol%, based on the sum of the diphenols of the formulas (II) and / or (III) used in each case.
• the polycarbonates suitable according to the invention have average molecular weights (M w weight average), measured for example by ultracentrifugation or scattered light measurement) from 10,000 to 200,000 g / mol, preferably 18,000 to 80,000 g / mol, particularly preferably 19,000 to 38,000 g / mol.
• Preferred here is l, l, l-tris (4-hydroxyphenyl) ethane and bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
• the polycarbonates suitable according to the invention can be branched in a known manner, preferably by incorporating 0.05 to 2 mol%, based on the sum of the diphenols used, of three or more than three-functional compounds, e.g. those with three or more than three phenolic groups.
• preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of 2,2-bis (3,5-dibromo-4- hydroxyphenyl) propane and the copolycarbonates of bisphenol A with up to 60 mol%, based on the molar sum of diphenols, l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
• polycarbonates can be replaced by aromatic polyester carbonates.
• aromatic polycarbonates can also polysiloxane
• the fluoropolymers used are polymers in which the hydrogen atoms in the carbon chain of polyethylene are replaced in whole or in part by fluorine atoms, and chlorine or fluorine-chlorine derivatives and copolymers derived therefrom.
• the fluoropolymers used are preferably polyvinyl fluoride or polyvinylidene fluoride. Polyvinyl fluoride is particularly preferred.
• a plastic composite in the sense of the present invention is, in particular, a plastic plate or a plastic film.
• the thickness of the plate or film is preferably 300 ⁇ m to 12 mm, particularly preferably 500 ⁇ m to 5 mm.
• the thickness of the fluoropolymer layer is preferably 10 ⁇ m to 500 ⁇ m, particularly preferably 20 ⁇ m to 200 ⁇ m.
• the thickness of the polycarbonate layer is preferred
• the thickness of the ethylene-vinyl acetate copolymer layer is preferably 100 ⁇ m to 1 mm, particularly preferably 300 ⁇ m to 800 ⁇ m.
• the plastic composites according to the invention can be used, for example, for the production of photovoltaic modules.
• solar cells based on silicon can be embedded between two plastic composites with the three-layer structure of fluoropolymer-polycarbonate-ethylene-vinyl acetate copolymer in such a way that the layer sequence of fluoropolymer-polycarbonate-ethylene-vinyl acetate acetate copolymer-solar cells-ethylene-vinyl acetate copolymer Polycarbonate fluoropolymer is present.
• this arrangement is heated so strongly that the EVA softens, so that the two EVA layers bond, including the solar cells.
• the plastic composites according to the invention can be used for numerous other purposes. For example, they can be used as a material in the chemical industry, the food industry or the pharmaceutical industry due to the high chemical resistance of the fluoropolymer layer and due to their high weather resistance and UV resistance, if necessary after lamination to carrier materials by means of the ethylene-vinyl acetate copolymer layer.
• FIG. 1 represents only a preferred embodiment.
• a two-layer film 1 made of a polycarbonate layer 2 and a polyvinyl fluoride layer 3 is passed over a three-roll calender 4. Between the first and the second roller of the calender, a melt film made of polycarbonate is fed through the slot die 5, which is fed with a polycarbonate melt by an extruder. This connects to the polycarbonate layer 2, so that a thicker, still hot polycarbonate layer and thus, in turn, a two-layer film 6 is formed. This is cooled by transport on a roller conveyor 7 to the required temperature at which the film made of ethylene-vinyl acetate copolymer 9 is no longer thermally damaged, but is softened sufficiently to bring about good adhesion. Then a film of ethylene-vinyl acetate copolymer 9 is applied to the polycarbonate layer. The resulting plastic composite of three layers 10 is drawn off via two further rollers 11 and 12 and can then optionally be wound up after cooling or otherwise processed.
• an EVA film was applied to the top of the plate and a PVF-PC film to the underside of the plate during PC plate extrusion.
• the PC plate was produced by extrusion through a slot die with a width of 800 mm and a die lip gap of 5 mm.
• the PC plate had a thickness of 3 mm and a width of 780 mm.
• Makrolon® 3103 from Bayer AG, Leverkusen, Germany was used as the polycarbonate. This is a homopolycarbonate based on bisphenol A.
• Ethylene-vinyl acetate copolymer Elvax ® 485.00, BP Chemicals, D-89165 Teodone Fa, Germany.
• Film thickness 500 ⁇ m film width: 660 mm
• the EVA film was not pre-dried, the Makrofol EPC film was pre-dried at 80 ° C in a circulating air dryer.
• the PVF-PC film was fed from below through the 1st roller to the 1st roller nip.
• the PC side of the film (smooth film side) was in contact with the PC melt.
• the bead remained on roller 2 (contrary to the experience with fabric lamination).
• the film was fed through the cross-beam, the film being held under a little tension. The unwinding speed resulted from the plate take-off speed.
• the EVA film was fed from above over a chrome roller (1 1), the
• Plate was carried out under the roll (film feed from above, pressure applied by roll). The plate temperature at this point was 76 ° C. The film melted slightly at this position and could not be removed by hand. The unwinding speed resulted from the plate pull-off speed.
• a protective film made of PE was fed between the EVA film and the chrome roller, which also served as a protective film for the composite.
• the PE film was later easily removed from the laminated board.

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• 1999
  • 1999-08-30 DE DE19941214A patent/DE19941214A1/de not_active Withdrawn
• 2000
  • 2000-08-18 MX MXPA02002148A patent/MXPA02002148A/es unknown
  • 2000-08-18 EP EP00960483A patent/EP1214192A1/de not_active Withdrawn
  • 2000-08-18 BR BR0013702-2A patent/BR0013702A/pt not_active Application Discontinuation
  • 2000-08-18 KR KR1020027002545A patent/KR20020020973A/ko not_active Application Discontinuation
  • 2000-08-18 RU RU2002108176/04A patent/RU2245793C2/ru not_active IP Right Cessation
  • 2000-08-18 JP JP2001520288A patent/JP2003515463A/ja active Pending
  • 2000-08-18 IL IL14790600A patent/IL147906A0/xx not_active IP Right Cessation
  • 2000-08-18 WO PCT/EP2000/008070 patent/WO2001015895A1/de not_active Application Discontinuation
  • 2000-08-18 AU AU72773/00A patent/AU766880B2/en not_active Ceased
  • 2000-08-18 CA CA002382700A patent/CA2382700A1/en not_active Abandoned
  • 2000-08-18 US US10/088,147 patent/US6780473B1/en not_active Expired - Fee Related
  • 2000-08-18 CN CNB008123047A patent/CN1198718C/zh not_active Expired - Fee Related
• 2002
  • 2002-01-29 ZA ZA200200777A patent/ZA200200777B/en unknown
• 2003
  • 2003-03-20 HK HK03102050.0A patent/HK1049979A1/zh unknown

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