Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • 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
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • 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
  • B32B2305/00—Condition, form or state of the layers or laminate
  • B32B2305/72—Cured, e.g. vulcanised, cross-linked
• • 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
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • 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
  • B32B2307/558—Impact strength, toughness
• • 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
  • B32B2307/584—Scratch resistance
• • 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
  • B32B2307/70—Other properties
  • B32B2307/712—Weather resistant
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the present invention relates to a composite system composed of a polycarbonate layer which has a coating of polyacrylate on at least one of its surfaces, which is coated on its outer surface with a fluoropolymer which is crosslinked with methylmelamine and / or polysilicic acid, in the case of crosslinking with polysilicic acid the Si0 2 content is a maximum of 60% by weight, based on the total weight of crosslinking agent and crosslinked fluoropolymer.
• Molded parts made of polycarbonate have a combination of excellent properties: high light transmission, high impact resistance and high heat resistance.
• a disadvantage of molded parts made of polycarbonate - like molded parts made from all other thermoplastics - is their relatively low scratch resistance. Due to the low scratch resistance, there are many fine scratch marks in the surface during practical use, which cause optical opacity and reduce transparency.
• Such a coating of molded parts made of polycarbonate makes the system weatherproof, especially when the polyacrylate film applied to polycarbonate contains a UV absorber; these coatings practically do not change the scratch resistance.
• molded parts made of polycarbonate can be coated with a scratch-resistant coating based on methylmelamine-crosslinked, hydroxylated fluoropolymers.
• this polymer can have up to 60% by weight of silicon dioxide, based on the combined weight of silicon dioxide and crosslinked polymer. This is described in DT-OS 1.963.278.
• a disadvantage of these polycarbonate moldings coated in this way is the poor weather stability of these coatings. After a short period of weathering, the scratch resistance and the adhesive strength of the coating decrease.
• the silicon dioxide-modified coatings are somewhat more weatherproof than the silicon dioxide-free coatings. Nevertheless, the weather stability must also be described as poor.
• molded parts made of polyacrylate can be coated with a scratch-resistant coating made of a methylmelamine-crosslinked hydroxylated fluoropolymer. This is described in DT-OS 1.963.278. These coatings on molded parts made of polyacrylate are scratch-resistant and weather-resistant.
• the disadvantage of this composite system is its low impact strength.
• the present invention now relates to a clear-transparent, high-impact, scratch and weatherproof composite system made of polycarbonate as a substrate, which has a film of polyacrylate on at least one of its surfaces, which has a coating based on methylmelamine-crosslinked and / or polysilicic acid-crosslinked hydroethylated Fluoropolymers.
• Uncoated molded parts made of polycarbonate have high impact strength. According to DIN 53 453, the test specimens remain "unbroken". In contrast, molded parts made of polyacrylate have a significantly lower impact resistance. When testing the impact strength, values of 14-26 kJ / m 2 are obtained. Moldings made of polycarbonate coated with polyacrylate have an impact resistance that is significantly lower than that of the uncoated polycarbonate moldings.
• the polyacrylate film can have a thickness of 0.010 to 1.25 mm.
• the coating of methyl melamine crosslinked hydroxylated fluoropolymer can have a thickness of 0.005 to 0.5 mm.
• This invention further relates to a method for producing a scratch-resistant composite system, in which a coating of polyacrylate is applied either continuously or discontinuously to the molded parts made of polycarbonate, and then a coating of methylmeiamin-crosslinked hydroxylated fluoropolymer on this acrylate layer.
• a coating of polyacrylate is applied either continuously or discontinuously to the molded parts made of polycarbonate, and then a coating of methylmeiamin-crosslinked hydroxylated fluoropolymer on this acrylate layer.
• This can be done by first coating the polycarbonate moldings with a polyacrylate varnish and treating them with a fluoropolymer coating solution after curing.
• the polycarbonate substrate can also be connected on one or both sides with polyacrylate films and the polyacrylate layer can then be coated with fluoropolymer.
• the composite system according to the invention is produced by connecting a film of polyacrylate coated with fluoropolymer on one side to the polycarbonate substrate in
• the bond between polyacrylate film and polycarbonate substrate can be achieved in a press under heat and pressure.
• the polyacrylate film can optionally be applied to polycarbonate sheets by pressing the acrylic sheet and the polycarbonate sheet through the nip of a pair of rolls, the rolls of which are heated.
• the temperature used should be at least 160 ° C and the pressure at least 1.4 kg / cm 2 . The higher the temperature, the shorter the time required and the lower the pressure required.
• Suitable polycarbonates for the purposes of the invention are polycondensates obtainable by reacting diphenols, in particular dihydroxydiarylalkanes, with phosgene or diesters of carbonic acid, of which unsubstituted dihydroxydiarylalkanes are also suitable whose aryl radicals in the o- and / or m-position to the hydroxyl group Wear methyl groups or halogen atoms.
• Branched polycarbonates are also suitable.
• Polycarbonates have average weight average molecular weights Mw between 10,000 and 100,000, preferably between 20,000 and 40,000, determined by measurements of the rel. Viscosity in CH 2 Cl 2 at 25 ° C and a concentration of 0.5% by weight. _
• Suitable diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (hydroxyphenyl) alkanes such as C, -C s alkylene or C 2 -C 8 -Alkylidenbisphenole, bis (hydroxyphenyl) cycloalkanes such as C 5 ⁇ C 15 cycloalkylene or C 5 ⁇ C 15 cycloalkylidene bisphenols, bis (hydroxyphenyl) sulfides, ethers, ketones, sulfoxides or sulfones; also a, a'-bis (hydroxyphenyl) diisopropylbenzene and the corresponding ring-alkylated or ring-halogenated compounds.
• Polycarbonates based on bis (4-hydroxyphenyl) propane-2,2 (bisphenol A), bis-4-hydroxy-3,5-dichlorophenyl) propane-2,2 (tetrachlorobisphenol A), bis - are preferred.
• the polyacrylate film used according to the invention or the lacquer based on polyacrylate used according to the invention can consist of any polyacrylate or polymethacrylate.
• Polyacrylates and polymethacrylates are homo- and copolymers of the acrylic acid ester and methacrylic acid ester with molecular weights of 10 3 to 10 7 and with 4 to 18 carbon atoms in the monomer unit, such as, for example, polyacrylic acid isobutyl ester, polymethacrylic acid methyl ester, polymethacrylic acid ethyl hexyl ester, polyacrylic acid and ethyl copolymers / or methacrylic acid esters such as, for example, methyl methacrylate - cyclohexyl acrylate - copolymers, further copolymers of acrylic acid esters and / or methacrylic acid esters with crosslinking agents such as, for example, 1,4-butanediol dimethacrylate, glycol dim
• the methyl-melamine-crosslinked coating mass of hydroxylated fluoropolymer according to the invention is a crosslinked polymer which has fluorine-containing polymer chains which carry a multiplicity of oxygen / methylmelamine bonds, the oxygen being bonded to a carbon atom in the skeleton of the fluorine-containing polymer chain or to a side chain and the carbon atom has at least one hydrogen atom, the chains containing at least 20% by weight of fluorine and crosslinked by the oxygen-methylmelamine bonds, characterized in that fluorine is arranged in the skeleton of the polymer chain, each polymer chain having a unit weight of not more than 700 per oxygen atom in the crosslinked 0 - methyl melamine bond and the methyl melamine of the oxygen melamine bond has the following formula: wherein at least two of the CH 2 groups are attached to the oxygen atom in the crosslinked oxygen / methylmelamine bond.
• the hydroxylated fluoropolymers can be crosslinked with polysilicic acid instead of methylmelamine. Both networking options can also be used side by side.
• the fluoropolymers crosslinked with polysilicic acid should contain a maximum of 60% by weight of silicon dioxide, based on the total weight of crosslinking agent and crosslinked polymer.
• the polymer chain of the methylmelamine cross-linked polymer results from fluorine-containing monomer units. preferably tetrafluoroethylene or chlorotrifluoroethylene and optionally from copolymerized fluorine-free, ethylenically unsaturated monomer units, the units having oxygen bonded to methylmelamine.
• fluorine-free, ethylenically unsaturated monomer unit is derived from a hydroxyalkyl viryl ether, e.g. Hydroxybutyl vinyl 3-ether, 2-hydroxypropyl vinyl ether or 6-hydroxy hexyl vinyl ether or vinyl acetate.
• the methylmelamine in the sense of the invention is preferably derived from hexa- (methoxymethyl) -melamine or hexa- (cyclohexyloxymethyl) -melamine.
• the composite system according to the invention can either contain transparent, colorless, transparent, translucent or opaque colored individual components or can be constructed from appropriate layers.
• a hydrolyzed ethyl silicate solution was prepared by treating 100 g of tetraethyl orthosilicate with 69.5 g of anhydrous ethanol and 22.5 g of 0.1 N hydrochloric acid. After aging for 24 hours, a 120 g portion of this solution was mixed with 102 g of methyl isoamyl ketone and heated at 32 ° under reduced pressure until the weight of the residue was 120 g.
• a (tetrafluoroethylene / 4-hydroxybutyl vinyl ether) / silica coating composition (ratio 60: 401 was prepared by mixing 200 g of the above polysilicic acid solution with 164 g of tetrahydrofuran and 136 g of a 33% solution of the hydroxylated fluoropolymer (a) in methanol.
• the coating After hardening, the coating had a thickness of approx. 8 ⁇ .
• Polycarbonate sheets coated according to Example 3 were immersed in the coating solution according to Example A for 2 minutes, removed from the solution at a rate of 40 cm / min and cured at 135 ° C. for 1 hour.
• the coating obtained was hard, colorless, transparent and of high gloss.
• the laminate made of polymethyl methacrylate / polycarbonate / polymethacrylate was produced during the extrusion of polycarbonate based on bisphenol A ( ⁇ rel. 1.31) at a melting temperature of 280 ° C. using a slot die. Films made of polymethyl methacrylate with a layer thickness of 0.025 mm were applied to the surfaces of the extruded polycarbonate sheet with the aid of rollers in such a way that continuous production was possible. This was achieved in that the 4.0 mm thick PC plate and the two films made of polymethyl methacrylate were passed through the nip of a pair of rolls in such a way that the films covered the two outer surfaces of the polycarbonate plate.
• the temperature of the rollers was set at 60 ° C; the temperature of the extruded polycarbonate sheet at the confluence was 160 ° C. and the pressure of the two rollers against each other was 1.4 kg / cm.
• Laminates as described above were immersed in the coating solution according to Example A for 2 minutes, removed from the solution at a rate of 15 cm / min and cured at 135 ° C. for 1 hour.
• the extruded polycarbonate sheet was 4.0 mm thick; the polymethyl methacrylate film had a thickness of 0.05 mm.
• the plate and film were passed through the same nip.
• Plates thus prepared were coated on the polymethyl methacrylate side with the coating solution of Example A using a film applicator.
• the peeling speed was 40 cm / min.
• the coating was then cured at 135 ° C. for 1 hour.
• a film of polymethyl methacrylate of 1.0 mm thickness was coated with the coating solution of Example A using a film applicator.
• the peeling speed was 15 cm per min.
• the coating was then cured at 135 ° C. for 1 hour.
• the films coated in this way were cut into 15 ⁇ 20 cm pieces.
• Polycarbonate sheets with a thickness of 4.0 mm and the same area dimensions were connected on one side to the acrylate films in a heat sealing press in such a way that the coating was facing outwards.
• the bond was achieved under the following conditions: temperature: 160 ° C; Pressure: 35 kg / cm 2; Duration: 5 min.
• test specimens each were measured and the values determined. With test specimens coated on one side, the coating lay in the tensile zone during the test.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Applications Claiming Priority (2)

Publications (2)

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Family Applications (1)

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• 1977
  • 1977-06-04 DE DE19772725317 patent/DE2725317A1/de not_active Withdrawn
• 1978
  • 1978-06-01 DE DE7878100034T patent/DE2860159D1/de not_active Expired
  • 1978-06-01 EP EP78100034A patent/EP0000022B1/de not_active Expired
  • 1978-06-02 US US05/911,740 patent/US4301212A/en not_active Expired - Lifetime
  • 1978-06-02 IT IT49667/78A patent/IT1104702B/it active
  • 1978-06-02 AU AU36823/78A patent/AU518059B2/en not_active Expired
  • 1978-06-02 JP JP6588778A patent/JPS5416585A/ja active Granted
  • 1978-06-02 CA CA000304666A patent/CA1120845A/en not_active Expired

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