EP2102004A1 - Composant transparent - Google Patents

Composant transparent

Info

Publication number
EP2102004A1
EP2102004A1 EP07847765A EP07847765A EP2102004A1 EP 2102004 A1 EP2102004 A1 EP 2102004A1 EP 07847765 A EP07847765 A EP 07847765A EP 07847765 A EP07847765 A EP 07847765A EP 2102004 A1 EP2102004 A1 EP 2102004A1
Authority
EP
European Patent Office
Prior art keywords
mol
polyamide
weight
layer
xylylenediamine
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Withdrawn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
EP07847765A
Other languages
German (de)
English (en)
Inventor
Roland Wursche
Karl Kuhmann
Beatrice Küting
Patrick Kreidler
Kirsten LÜTZELER
Klaus Hülsmann
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2102004A1 publication Critical patent/EP2102004A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • 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]
    • Y10T428/31721—Of polyimide
    • 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]
    • Y10T428/31725—Of polyamide
    • 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]
    • Y10T428/31725—Of polyamide
    • Y10T428/31736—Next to polyester
    • 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]
    • Y10T428/31725—Of polyamide
    • Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
    • Y10T428/31757—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to a transparent member containing an outer layer of a polyamide molding compound derived from xylylenediamine and a higher dicarboxylic acid.
  • Transparent components such as lenses, displays, glazings, sight glasses, etc. are often made of amorphous materials such as polycarbonate, PMMA or transparent polyamides. These have a good transparency, but show a poor chemical resistance and low scratch resistance. For applications in which contact of such materials with chemicals or solvents may occur, the low chemical resistance is disadvantageous, since it can cause phenomena such as turbidity or cracking. Poor scratch resistance shortens the life of the transparent objects as scratching also leads to undesirable clouding.
  • a cover layer of a partially crystalline polyamide can be used to achieve improved resistance of transparent objects to chemicals.
  • EP 0 696 501 A2 describes that this deficiency can be remedied by a well-adhering coating of polyalkyl (meth) acrylate molded parts with polyamide, in which case an adhesion promoter must be used.
  • the application of this concept to polyarylate molded parts is described in DE 197 02 088 A1. Further state of the art can be found in WO 2005/123384, WO 2006/072496, WO 2006/087250, WO 2006/008357 and WO 2006/008358;
  • the object of the invention is to provide a transparent component whose surface is characterized by high scratch resistance, abrasion resistance and high chemical resistance. This object has been achieved by a transparent component which contains the following components:
  • a cover layer of a polyamide molding composition which contains the following constituents: a) 50-100 parts by weight, preferably 60-98 parts by weight, more preferably 70-95 parts by weight
  • Parts and in particular preferably 75-90 parts by weight of polyamide which can be prepared from the following monomers: ⁇ ) 70-100 mol%, preferably 75-99 mol%, particularly preferably 80-98 mol% and particularly preferably 85- 97 mol% m- and / or p-xylylenediamine and ß) 0 - 30 mol%, preferably 1 - 25 mol%, particularly preferably 2 - 20 mol% and particularly preferably 3-15 mol% of other diamines with 6 to 14 carbon atoms, wherein the mol% data here refers to the sum of diamine, and ⁇ ) 70-100 mol%, preferably 75-99 mol%, particularly preferably 80-98 mol% and particularly preferably 85-97 mol% of aliphatic dicarboxylic acids having 10 to 18 C atoms and ⁇ ) 0-30 mol%, preferably 1-25 mol%, particularly preferably 2-20 mol% and particularly preferably 3-15 mol -% of other di
  • any existing adhesion promoter layer and any other layers contain no particulate additives that reduce the transparency recognizable and b) the substrate at a layer thickness of 1 mm within of the visible spectrum from 380 to 800 mm in the transmission curve a maximum of at least 30% and preferably at least 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% and 80% wherein the transparency is determined according to ASTM D 1003 on injection-molded plates.
  • Particulate additives are here in particular pigments and metal particles, which are frequently used for coloring a color layer, but impair or destroy the transparency. According to the invention, however, nanoparticles which have essentially no effect on the transmission can be contained in the abovementioned layers.
  • Such nanoparticles have a number-average effective particle diameter dso in the molding composition of less than 150 nm, preferably less than 120 nm, more preferably less than 90 nm, more preferably less than 70 nm and most preferably less than 50 nm or less than 40 nm.
  • the effective particle diameter should not be confused with the diameter of the primary particles. For the transparency, not the latter is crucial, but what matters is the size of the aggregates or agglomerates that are actually present in the molding composition. In the case of very good dispersion, however, the effective particle diameter may, in the limiting case, fall to the diameter of the primary particles.
  • the determination of effective particle diameters of nanoscale particles or their aggregates or agglomerates in molding compositions and the associated distribution function is carried out by preparing a thin section of the molding composition.
  • a thin section of the molding composition For polyamides a low-temperature thin-section at -100 0 C is made advantageously.
  • a number of TEM images are taken to allow a statistical evaluation of a sufficiently large number of particles. Depending on the case, this number of particles is at least two hundred, but better still a thousand particles. With the aid of an evaluation program, the particles are measured in terms of their diameter. The obtained data is converted into a distribution function.
  • the transparency of the molding composition when measured according to ASTM D 1003 on a film with a thickness of 200 microns and at a light wavelength of 589 nm may be deteriorated by at most 2%.
  • the cover layer Preferably, the cover layer, a possibly present adhesion promoter layer as well as any further layers present at most 1% by weight of nanoparticles. This amount is perfectly adequate for the purpose of nucleation or laser marking.
  • the polyamide molding compound according to I. may contain not more than 20% by weight, not more than 16% by weight, not more than 12% by weight, not more than 8% by weight or not more than 4% by weight of auxiliaries or additives Wt .-% - refer to the total polyamide composition.
  • the other diamine optionally used under a) .beta. Can be, for example, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1.9-nonamethylenediamine, 1.10-decamethylenediamine, 1,12-dodecamethylenediamine, 1,1,4-tetradecamethylenediamine, 1,4-cyclohexanediamine, 1,3- or 1,4-bis (aminomethyl) hexane , 4,4'-diaminodicyclohexylmethane and / or isophoronediamine.
  • the dicarboxylic acid of component a) ⁇ ) is preferably linear.
  • 1.10-decanedioic acid, 1.11-undecanedioic acid, 1.12-dodecanedioic acid, 1.13-tridecanedioic acid, 1.14-tetradecanedioic acid, 1.16-hexadecanoic acid and 1.18-octadecanoic acid are suitable, with 1.12-dodecanedioic acid and 1.14-tetradecanedioic acid being preferred.
  • Mixtures can also be used.
  • the other dicarboxylic acid optionally used under a) ⁇ ) is, for example
  • the polyamide according to a) contains substantially no monomer units which originate from a component a) .beta.).
  • the polyamide according to a) contains substantially no monomer units which originate from a component a) ⁇ ).
  • the monomer units derived from component a) ⁇ ) are derived from a single dicarboxylic acid, since mixtures of dicarboxylic acids indeed give a higher transparency of the polyamide; but this leads to losses in the resistance to chemicals.
  • the component a) ⁇ ) is composed of
  • the component a) ⁇ ) is composed of
  • the component a) may consist of a mixture of two or more different polyamides, which in themselves have the composition described under a).
  • polyamide according to b) may be, for example, PA6 or PA66, however, higher polyamides having an average of at least 8 carbon atoms in the monomer units such.
  • PA88, PA610, PA612, PA614, PA810, PA812, PA814, PAlOlO, PA1012, PA1014, PA1212, PAI l or PA 12 are preferred.
  • the polyamide according to b) is derived from a diamine which is sterically similar to xylylenediamine, i. H. that the educated
  • Monomer units have a similar length, which is the case with hexamethylenediamine for example. Moreover, it is advantageous if the polyamide according to b) derives from the same or a similar dicarboxylic acid as the polyamide a). In these cases, the most easily transparent blends can be obtained.
  • the polyamide composition may additionally contain other components, for example: a) nucleating agents selected from nanoscale fillers and basic metal salts, metal oxides or metal hydroxides; the latter are added to ensure the desired transparency, at most in such an amount as they can be dissolved in the melt in reaction with the carboxyl end groups of the polyamides; b) customary auxiliaries or additives in the amounts customary for polyamide molding compositions, for example stabilizers, UV absorbers or lubricants, c) colorants which do not significantly affect the transparency and d) nucleating agents based on organic compounds, which do not essentially influence the transparency ,
  • nucleating agents selected from nanoscale fillers and basic metal salts, metal oxides or metal hydroxides
  • Polycondensates based on xylylenediamines are known from the literature. This also includes the use of dodecanedioic acid as diacid (for example US 3,803,102 and US 4,433,136).
  • Polyamides having the basic structure MXD6 or MXD12 are used for the production of films in the packaging sector (for example EP-A-I 172 202, US Pat. No. 5,955,180, EP-A-0 941 837, WO 00/23508). These films can also be multilayered.
  • the use of the claimed polyamide compositions for the production of transparent components is not yet described in the literature. German Patent Application No. 10 2005 05 1126.0 discloses the use of the claimed polyamide composition for the production of composite parts, about the transparency of which no statements are made.
  • the largely amorphous polymer which forms the basis for the molding material of the substrate is not limited in type. In principle, it is possible to use any known, largely amorphous polymer. Examples of these are polyamides, polyalkyl (meth) acrylates, polycarbonate, polyester carbonate, polyesters, polyimides, polyetherimides, polymethacrylimides, polysulfone, styrene polymers, polyolefms with cyclic building blocks, olefin-maleimide copolymers or polymers based on vinylcyclohexane.
  • the substantially amorphous polymer preferably has a melting enthalpy of less than 12 J / g, preferably less than 8 J / g, more preferably less than 6 J / g, more preferably less than 4 J / g and most preferably less as 3 J / g, measured by the DSC method according to ISO 11357 for the 2nd heating and integration of the possible melting peak.
  • Examples of largely amorphous polyamides which can be used according to the invention are: the polyamide of terephthalic acid and / or isophthalic acid and the isomer mixture of 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the polyamide of isophthalic acid and 1,6-hexamethylenediamine, the copolyamide of a mixture of terephthalic acid / Isophthalic acid and 1,6-hexamethylenediamine, optionally in admixture with 4,4'-diaminodicyclohexylmethane, - the copolyamide of terephthalic acid and / or isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and laurolactam or caprolactam, the (co) polyamide from 1,12-dodecanedioic acid or sebacic acid , 3.3'-dimethyl-4,4'-d
  • Dicarboxylic acid such.
  • these examples can be obtained by adding further components (eg caprolactam, Laurolactam or diamine / dicarboxylic acid combinations) or by partial or total replacement of starting components by other components as much as possible.
  • polyalkyl (meth) acrylates having 1 to 6 C atoms in the carbon chain of the alkyl radical, the methyl group being preferred as the alkyl group.
  • the polyalkyl (meth) acrylates usually have a MeIt flow rate of 0.5 to 30 g / 10 min, preferably 0.8 to 15 g / 10 min, measured according to ISO 1133 at 230 0 C with a load of 3 , 8 kg.
  • Examples include polymethylmethacrylate and polybutylmethacrylate mentioned.
  • copolymers of the polyalkyl (meth) acrylates it is also possible to use copolymers of the polyalkyl (meth) acrylates.
  • the molding composition can be adjusted to impact strength, for example by adding a core / shell rubber customary for such molding compositions.
  • thermoplastics such as SAN (styrene / acrylonitrile Copolymer) and / or polycarbonate.
  • the substrate may be composed of a molding compound containing a polycarbonate as a main component.
  • Polycarbonates suitable according to the invention contain units which
  • Carbonic acid diesters of diphenols are.
  • diphenols may be, for example, the following: hydroquinone, resorcinol, dihydroxybiphenyls, bis (hydroxyphenyl) alkanes, bis- (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfites, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, CC, ⁇ ' - Bis (hydroxyphenyl) diisopropylbenzenes and their ring-alkylated or ring-halogenated derivatives or ⁇ , C0-bis (hydroxyphenyl) polysiloxanes.
  • Preferred diphenols are, for example, 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (3-chloro-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl )
  • the diphenols can be used both alone and in admixture with each other.
  • the diphenols are known from the literature or can be prepared by methods known from the literature (see, for example, H. J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p.
  • the polycarbonates used according to the invention are prepared by known processes, for example by the phase boundary process or by the melt transesterification process. They have weight average molecular weights M w (determined by gel permeation chromatography and polystyrene standard calibration) of between 5,000 and 200,000, preferably between 10,000 and 80,000 and more preferably between 15,000 and 40,000.
  • the polycarbonate molding composition can, for example, to less than 50 wt .-%, preferably less than 40 wt .-%, more preferably less than 30 wt .-% and particularly preferably less than 20 wt .-%, based on the total Polymer base, other polymers such as polyethylene terephthalate, polybutylene terephthalate, polyesters of cyclohexanedimethanol, ethylene glycol and terephthalic acid, polyesters of cyclohexanedimethanol and cyclohexanedicarboxylic acid, polyalkyl (meth) acrylates, SAN, styrene (Meth) acrylate copolymers, polystyrene (amorphous or syndiotactic), polyetherimides, polyimides, polysulfones, polyarylates (eg based on bisphenol A and isophthalic acid / terephthalic acid).
  • other polymers such as poly
  • Polyestercarbonates are composed of at least one diphenol, of at least one aromatic dicarboxylic acid and of carbonic acid.
  • diphenols the same as for polycarbonate are suitable.
  • the amount derived from aromatic dicarboxylic acids, based on the sum of the parts derived from aromatic dicarboxylic acids and from carbonic acid, is at most 99.9 mol%, at most 95 mol%, at most 90 mol%, at most 85 mol%, at most 80 Mol% or at most 75 mol%, while their minimum proportion is 0.1 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol% or 25 mol%.
  • aromatic dicarboxylic acids examples include orthophthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 2,2-bis ( 4-carboxyphenyl) propane and trimethyl 3-phenylindane-4,5-dicarboxylic acid.
  • terephthalic acid and / or isophthalic acid are preferably used.
  • Suitable thermoplastic polyesters are preferably either fully aromatic or mixed aliphatic / aromatic.
  • the first case is polyarylates; These are derived from diphenols and aromatic dicarboxylic acids. As diphenols, the same as for polycarbonate are suitable, while as dicarboxylic acid are the same as suitable for polyester carbonates.
  • the polyesters are derived from one or more aromatic dicarboxylic acids and one or more diols; for example, it is polyethylene terephthalate or copolyesters of terephthalic acid, 1,4-cyclohexanedimethanol and ethylene glycol.
  • Suitable polysulfones are generally prepared by polycondensation of a bisphenol / Dihalogendiarylsulfon mixture in an aprotic solvent in the presence of a base such.
  • B sodium carbonate.
  • bisphenol for example those can be used which are also suitable for the production of polycarbonates, but in particular bisphenol A, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenyl and hydroquinone, although mixtures of different bisphenols can be used.
  • the Dihalogen compound is in most cases 4,4'-dichlorodiphenylsulfone; however, it is also possible to use any other dihalogen compound in which the halogen is activated by a para-containing sulfone group.
  • fluorine is also suitable in addition to chlorine.
  • polysulfone also includes those polymers commonly referred to as “polyethersulfone” or “polyphenylene sulfone.” Suitable types are commercially available.
  • Polyimides are prepared in a known manner from tetracarboxylic acids or their anhydrides and diamines. When the tetracarboxylic acid and / or the diamine contains an ether group, a polyetherimide results.
  • a particularly suitable ether-containing tetracarboxylic acid is the compound I; from it are obtained together with aromatic diamines amorphous polyetherimides, which are commercially available.
  • polyacrylimides are polymethacrylimides, sometimes referred to as polyacrylimides or polyglutarimides. These are products starting from polyalkyl acrylates or polyalkyl methacrylates, in which two adjacent carboxylate groups have been converted to a cyclic acid imide. The imide formation is preferably with ammonia or primary amines, such as. As methylamine performed.
  • the products and their preparation are known (Hans R. Kricheldorf, Handbook of Polymer Synthesis, Part A, Publisher Marcel Dekker Inc. New York-Basel-Hong Kong, p 223 f., HG Elias, macromolecules, Wegig and Wepf Verlag Basel- Heidelberg-New York; US 2,146,209 A; US 4,246,374).
  • Suitable styrene polymers are, for example, homopolystyrene or copolymers of styrene with up to 50 mol%, based on the monomer mixture, of other monomers such. For example, methyl methacrylate, maleic anhydride, acrylonitrile or maleimides. Styrene-maleimide copolymers are also accessible, for example, by reacting styrene-maleic anhydride copolymers with ammonia or primary amines such as methylamine or aniline.
  • Polyolefins with cyclic building blocks can be prepared by copolymerization of at least one cyclic or polycyclic olefin, for example norbornene or tetracyclododecene, with at least one acyclic olefin, for example ethene (WO 00/20496, US Pat. No. 5,635,573, EP-A-0 729 983, EP -AO 719 803).
  • This substance class is called COC.
  • COP Suitable class of compounds, commonly referred to as COP, are optionally hydrogenated products of the ring-opening metathetic polymerization of polycyclic olefins, for example norbornene, dicyclopentadiene, substituted derivatives or Diels-Alder adducts thereof (EP-A-0 784 066, WO 01/14446, EP-A-0 313 838, US 3 676 390, WO 96/20235).
  • polycyclic olefins for example norbornene, dicyclopentadiene, substituted derivatives or Diels-Alder adducts thereof (EP-A-0 784 066, WO 01/14446, EP-A-0 313 838, US 3 676 390, WO 96/20235).
  • Olefin-maleimide copolymers are known, for example, from US Pat. No. 7,018,697.
  • Vinylcyclohexane-based polymers can be prepared either by polymerization or copolymerization of vinylcyclohexane or by catalytic hydrogenation of
  • the molding compound of the substrate can also be further conventional auxiliary or
  • Additives contain such. As stabilizers, processing aids, flame retardants, plasticizers, antistatic agents, isorefractive fillers or reinforcing agents, isorefractive impact modifiers, dyes that do not significantly affect the transparency, flow agents, mold release agents or other polymers that do not significantly affect the transparency.
  • the amount of all auxiliaries and additives is a total of at most 50 wt .-%, preferably at most 40 wt .-%, more preferably at most 30 wt .-% and particularly preferably at most 20 wt .-%.
  • the bonding of the cover layer to the substrate can be done in any known manner, for example by multi-component injection molding, coextrusion, injection molding of a film, extrusion laminating, laminating, pressing or gluing.
  • the multi-component injection molding is used to produce moldings with layers or areas of different plastics or colorations.
  • Various process variants are possible, which are known to the person skilled in the art.
  • two or more injection molding units are used, which operate sequentially in a tool. After the first unit has filled a tool cavity, the mold nest for the
  • Injection molding of the second unit for example, by traversing movements of the tool halves, turning tool halves or parts or Kernzugambaen for releasing additional Kavticians Kunststoffe increased. It is also possible to work sequentially with several tools on standard one-component machines by inserting molded parts into the next tool and spraying the following component on. In addition, it is also possible to work in such a way that a partial filling of the tool is carried out with the first unit and the melt of the second unit displaces the melt of the first from the core area to the surface of the molded part, wherein the finished component has a skin-core structure ( Sandwich structure).
  • Sandwich structure Sandwich structure
  • Another variant is the monosandwich process, in which the melts are conveyed via two separate plasticizing units into a common injection space and spatially stacked one behind the other. During injection, one component displaces the other component to the surface.
  • Multilayer structures can be produced for example by coextrusion.
  • coextrusion several melt streams of the same or different types of plastics are combined.
  • the process variants are known to the person skilled in the art.
  • the union of melts before, in or behind a tool can be done.
  • Merging the melts behind (eg during blow molding) or in the mold offers the advantage that the melts can be tempered at different temperatures.
  • adapter tools the melts are brought together before they enter the forming tool.
  • the multilayer structures eg multilayer boards
  • the coextrusion process can be supplemented by a subsequent blow molding process.
  • the composite material can also be produced by further processes, for example by extrusion laminating.
  • a prefabricated substrate is continuously combined with a prefabricated cover layer, wherein the compound is brought about by a plastic melt, which is fed to the contact point of the former components.
  • a plastic melt which is fed to the contact point of the former components.
  • a variant consists in extruding the substrate material onto the prefabricated cover layer or the cover layer on a prefabricated substrate.
  • Another possibility is provided by continuous lamination processes, the connection being realized by the introduction of adhesives (solvent-based, hotmelt, etc.).
  • composites may also be made by compression molding, the bond between the prefabricated joining partners being affected by the action of pressure and temperature, e.g. in a press, is evoked.
  • adhesives, etc. may be additionally used.
  • the surface can be structured, for example, by embossing. A structuring of the surface is also possible upstream in the context of film extrusion, for example by specially designed rollers.
  • the resulting composite part can then be further formed.
  • connection between cover layer and substrate can be done by positive locking, for example by means of undercuts.
  • a cohesive compound is preferred.
  • the materials must adhere to each other, which is effected for example by chemical attachment or by entanglement of the macromolecules.
  • a welding process eg laser welding is also possible for joining the cover layer and substrate or semifinished product and substrate.
  • an adhesion promoter may be used, for example in the form of a multilayer film containing a substrate-side primer layer.
  • the nature of the bonding agent is not critical; however, it should preferably be sufficiently transparent at the selected layer thickness.
  • the primer contains a blend of a polymer that is identical or similar to the polymer of the topcoat, and a polymer that is identical or similar to the amorphous polymer of the substrate.
  • Similar means that the polymers concerned can be melt-blended into phase-stable blends, or that layers of both polymers have sufficient adhesion to each other after coextrusion or back-injection, that is, the polymers are compatible with one another
  • the blend is usually prepared by melt blending and suitable weight percent mixing ratios are 20-80: 80-20, preferably 30-70: 70-30, and more preferably 40-60: 60-40 a compatibilizer may also be included, for example a branched polymer such as a polyamine-polyamide graft copolymer (EP-A-065 048), a polymer having reactive groups capable of undergoing a chemical reaction with at least one of the blend partners block copolymer.
  • EP-A-065 048 polyamine-polyamide graft copolymer
  • the adhesion promoter contains 2 to 100 wt .-%, preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-%, particularly preferably 15 to 60 wt .-% and most preferably 20 to 40 %
  • a copolymer containing the following monomer units From 70 to 99.9% by weight of monomer units derived from vinylic compounds selected from acrylic acid derivatives, methacrylic acid derivatives, ⁇ -olefins and vinylaromatics, and from 0.1 to 30% by weight of monomer units which are functional Contain a group selected from a carboxylic acid anhydride group, an epoxy group and an oxazoline group.
  • the copolymer preferably contains the following monomer units: 1. from about 70 to about 99.9% by weight, preferably from 80 to 99.4% by weight and more preferably from 85 to 99% by weight of monomer units selected from units of the following formulas:
  • R 1 as above.
  • the limitation of the chain length in the substituents R 1 to R 5 and R 7 is due to the fact that longer alkyl radicals lead to a lowered glass transition temperature and thus to a reduced heat resistance. This may be accepted in individual cases.
  • the units of the formula (I) are derived, for example, from acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate or isobutyl methacrylate.
  • the units of the formula (II) are derived, for example, from acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide or N, N-dimethylacrylamide.
  • the units of the formula (III) are derived from acrylonitrile or methacrylonitrile.
  • the units of the formula (IV) are derived from ethene, propene, styrene or ⁇ -methylstyrene; the latter can be replaced in whole or in part by other polymerizable aromatics such as p-methylstyrene or indene, which have the same effect.
  • the units of the formula (V) are derived from optionally substituted maleimides, such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide or N-methylaconitic imide.
  • maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide or N-methylaconitic imide.
  • the units of the formula (VI) are derived from optionally substituted maleic anhydrides, such as maleic anhydride or aconitic anhydride. The latter may be wholly or partly by other unsaturated acid anhydrides such. B. itaconic anhydride are replaced, which have the same effect.
  • the units of formula (VII) are derived from glycidyl acrylate or glycidyl methacrylate and the units of formula (VIII) of vinyloxazoline or isopropenyloxazoline.
  • copolymer various embodiments are preferred which contain the following units:
  • polyacrylimides or polymethacrylimides In the presence of units of formula (V), such copolymers are referred to as polyacrylimides or polymethacrylimides or sometimes also as polyglutarimides.
  • These are products starting from polyalkyl acrylates or polyalkyl methacrylates, in which two adjacent carboxylate groups have been converted to a cyclic acid imide.
  • the imide formation is preferably with ammonia or primary amines, such as.
  • the products and their preparation are known (Hans R. Kricheldorf, Handbook of Polymer Synthesis, Part A, Publisher Marcel Dekker Inc.
  • Such copolymers are prepared in a known manner by free-radically initiated copolymerization of z.
  • Such copolymers are accessible in a known manner by free-radically initiated copolymerization of acrylic acid, methacrylic acid and / or their esters, optionally aliphatically unsaturated aromatics or olefins and unsaturated carboxylic anhydrides.
  • Copolymers of this kind are obtainable in a known manner by free-radically initiated copolymerization of acrylic acid, methacrylic acid and / or their esters, acrylonitrile or methacrylonitrile and unsaturated carboxylic acid anhydrides.
  • the copolymer may additionally comprise further monomer units, for example those derived from maleic diesters, fumaric diesters, itaconic esters or vinyl acetate, as long as the desired adhesion-promoting effect is not appreciably impaired thereby.
  • the adhesion promoter may consist entirely of the copolymer; in a variant thereof, the copolymer contains an impact modifier, e.g. an acrylate rubber.
  • the adhesion promoter contains 2 to 99.9 wt .-%, preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-%, particularly preferably 15 to 60 wt .-% and most preferably 20 to 40 wt .-% of the copolymer and 0.1 to 98 Wt .-%, preferably 10 to 95 wt .-%, particularly preferably 20 to 90 wt .-%, particularly preferably 40 to 85 wt .-% and very particularly preferably 60 to 80 wt .-% of a polymer which is selected from the group polyamide of the top layer, polymer of the substrate, polyamide similar to the polyamide of the top layer, polymer similar to the polymer of the substrate, or mixtures thereof.
  • the primer can the usual auxiliaries and additives such. As flame retardants, stabilizers, plasticizers, processing aids, dyes or the like. The amount of the said agents should be metered so that the desired properties are not seriously affected.
  • the film in addition to the layer of a polyamide molding composition according to the invention and optionally a bonding agent layer, the film, depending on the application, contain further layers, for example a substrate-side support layer of a molding composition, which preferably largely matches the substrate of the polymer composition, a color layer and / or a another polyamide layer, for example as a carrier layer.
  • a substrate-side support layer of a molding composition which preferably largely matches the substrate of the polymer composition
  • a color layer and / or a another polyamide layer for example as a carrier layer.
  • the color layer preferably consists of a colored thermoplastic layer.
  • the thermoplastic layer may be identical to the cover layer.
  • the color layer may adjoin the cover layer inwardly.
  • organic dyes are generally used as colorants.
  • a backing layer is a layer which provides greater strength to the film by its thickness.
  • a peelable protective film can be laminated onto the finished multilayer film, which acts as a transport or assembly protection and is removed after the production of the composite part.
  • the film has a thickness of 0.02 to 1.2 mm, particularly preferably 0.05 to 1 mm, very particularly preferably 0.08 to 0.8 mm and particularly preferably 0.15 to 0 , 6 mm.
  • the adhesion promoter layer has a thickness of from 0.01 to 0.5 mm, particularly preferably from 0.02 to 0.4 mm, very particularly preferably from 0.04 to 0.3 mm and in particular from 0, 05 to 0.2 mm.
  • the film is produced by known methods, for example by extrusion, or in the case of multilayer systems by coextrusion or lamination. It can then optionally be reshaped.
  • the cover layer When the component is produced by multi-component injection molding, the cover layer usually has a thickness of 0.1 to 10 mm, preferably 0.2 to 7 mm and particularly preferably 0.5 to 5 mm. Under special process conditions, layer thicknesses below 0.1 mm are possible. Low thicknesses generally lead to better transparency of the component.
  • the cover layer When produced by coextrusion, the cover layer generally has a thickness of 0.02 to 1.2 mm, preferably from 0.05 to 0.8 mm, particularly preferably from 0.08 to 0.6 mm and particularly preferably from 0, 12 to 0.5 mm.
  • the substrate can be of any thickness. In general, it has a thickness in the range of 0.5 to 100 mm, preferably in the range of 0.8 to 80 mm, more preferably in the range of 1 to 60 mm, particularly preferably in the range of 1, 2 to 40 mm and most preferably in the range of 1.4 to 30 mm. Other preferred upper limits of thickness are 25 mm, 20 mm, 15 mm, 10 mm, 6 mm, 5 mm and 4 mm. The thickness should be chosen so that the component has the required rigidity.
  • the component according to the invention is not a foil; In contrast, it is dimensionally stable.
  • the component according to the invention is used as an optical component.
  • optical component examples include lenses, headlight lenses, rear lights, lenses, prisms, lenses, displays, decorative display components, backlit switches, all kinds of glazing, and cell phone cases.
  • the starting materials were melted in a nitrogen atmosphere and heated with stirring in a closed autoclave to about 180 0 C, with an internal pressure of about 20 bar was established. This internal pressure was maintained for 2 hours; Thereafter, the melt was further heated to 280 0 C with continuous expansion to atmospheric pressure. Subsequently, nitrogen was passed over the melt for about 1 hour while maintaining the 280 ° C. until the desired torque was indicated. Thereafter, the melt was discharged by means of a gear pump and granulated as a strand. The granules were dried for 16 hours under water pump vacuum at 80 0 C.
  • a 100 l polycondensation reactor was filled with the following starting materials.
  • the copolymer a polymethacrylimide
  • PMMA polymethylmethacrylate
  • Methylamine solution for example in an extruder.
  • PMMA PLEXIGLAS ® 7N (Röhm GmbH)
  • PC Polycarbonate
  • LEXAN ® 101 R GE Plastics
  • PA type A TROGAMID CX9704 ®, a polyamide from 1,12-dodecanedioic acid and 4,4'-diaminodicyclohexylmethane (PA PACM12);
  • PA Type B GRILAMID TR90 ®, a polyamide from 1,12-dodecanedioic acid and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane;
  • PA Type C TROGAMID ® T5000, a polyamide of terephthalic acid and
  • the polyamides prepared and used in the comparative examples were, optionally together with the polyamides shown in the tables, with 0.75 wt .-% of a stabilizer mixture and 0.05 wt .-% of a nucleating agent (in each case based on the polyamide) on a twin-screw kneader of the type Werner + Pfleiderer ZSK 30 with a cylinder temperature of 240 0 C (PA MXD6: 280 0 C) at 150 rpm and a throughput of 20 kg / hour compounded.
  • a nucleating agent in each case based on the polyamide
  • the multilayer films were produced on a Collin plant at a take-off speed of 2.0 m / min. The extruded monolayers were combined and drove over a calender. The films had a width of 24 cm. 3. Injection
  • the back molding was done on a machine of the type Engel 650/200 with a mold temperature of 80 0 C and a melt temperature of 310 0 C and 260 0 C (PMMA).
  • the film was cut to a size of 100 mm x 150 mm and placed in a tool (plate 105 mm x 150 mm x 0.8 - 10 mm).
  • the thickness of the back-injected plate was 3 mm including the foil.
  • the transparency of the composite parts was not appreciably affected by the thin film.
  • Table 1 composites according to the invention (back-injected plates, total thickness 3 mm)
  • TROGAMID ⁇ CX7323 a partially crystalline PA PACM12 with a trans / trans diamine content of about 50 0 A.
  • the surface gloss was determined on back-sprayed multilayer films before and after a scratch test.
  • an abrasion tester according to Renault VI Specifications 31.03.406 / A, Issue 94-06 was used.
  • the gloss according to DIN 67530 was measured at different points on the test specimen to be tested. Then the specimen was installed horizontally in the holder provided for this purpose. The two punches on the underside of the lever arms were covered with a polyamide screen mesh (25 ⁇ m mesh), which was wetted with 0.1% Persil pollutants.
  • the lever arms with the Reibstkovn were then swung around so that the stamps rest on the specimen, and each provided with an additional weight of 3 kg.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne un composant transparent qui contient les éléments suivants : I) une couche externe en matière moulable polyamidique contenant les constituants suivants : a) de 50 à 100 parties en poids d'un polyamide qui peut être obtenu à partir des monomères suivants : a) de 70 à 100 % en moles d'une diamine choisie parmi la m-xylylène diamine, la p-xylylène diamine et des mélanges de celles-ci, ß) de 0 à 30 % en moles d'autres diamines ayant de 6 à 14 atomes de carbone, les pourcentages en moles indiqués ici se rapportant à la somme des diamines, ainsi que ?) de 70 à 100 % en moles d'acides dicarboxyliques aliphatiques ayant de 10 à 18 atomes de carbone et d) de 0 à 30 % en moles d'autres acides dicarboxyliques ayant de 6 à 9 atomes de carbone, les pourcentages en moles indiqués ici se rapportant à la somme des acides dicarboxyliques ; b) de 0 à 50 parties en poids d'un autre polyamide, la somme des parties en poids de a) et b) étant égale à 100 ; II) un substrat en matière moulable à base d'un polymère pratiquement amorphe. a) La couche externe, une couche adhésive éventuellement présente ainsi que d'autres couches éventuellement présentes ne contiennent aucun additif particulaire réduisant de manière perceptible la transparence et b) le substrat, à une épaisseur de couche de 1 mm, présente un maximum de sa courbe de transmission au moins égal à 30% dans le domaine du spectre visible de 380 à 800 nm, il est résistant aux rayures et aux produits chimiques et il est approprié pour des applications optiques.
EP07847765A 2006-12-13 2007-12-04 Composant transparent Withdrawn EP2102004A1 (fr)

Applications Claiming Priority (2)

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DE200610058681 DE102006058681A1 (de) 2006-12-13 2006-12-13 Transparentes Bauteil
PCT/EP2007/063261 WO2008071598A1 (fr) 2006-12-13 2007-12-04 Composant transparent

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EP2102004A1 true EP2102004A1 (fr) 2009-09-23

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EP (1) EP2102004A1 (fr)
JP (1) JP2010513054A (fr)
CN (1) CN101557935A (fr)
DE (1) DE102006058681A1 (fr)
WO (1) WO2008071598A1 (fr)

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WO2008071598A1 (fr) 2008-06-19
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US20100062272A1 (en) 2010-03-11
JP2010513054A (ja) 2010-04-30

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