WO2006072352A1 - Substratmaterialien für transparente spritzgussteile - Google Patents
Substratmaterialien für transparente spritzgussteile Download PDFInfo
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- WO2006072352A1 WO2006072352A1 PCT/EP2005/013222 EP2005013222W WO2006072352A1 WO 2006072352 A1 WO2006072352 A1 WO 2006072352A1 EP 2005013222 W EP2005013222 W EP 2005013222W WO 2006072352 A1 WO2006072352 A1 WO 2006072352A1
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- Prior art keywords
- potential
- substrate
- substrate material
- hydroxyphenyl
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Classifications
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
- G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
- G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
- G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
- G11B7/248—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes porphines; azaporphines, e.g. phthalocyanines
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/258—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers
- G11B7/259—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers based on silver
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/258—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers
- G11B7/2595—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers based on gold
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- 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
- Y10T428/21—Circular sheet or circular blank
Definitions
- the invention relates to polycarbonates as substrate material for the production of transparent injection-molded parts, in particular for the production of injection-molded parts to be coated, as well as molded parts obtainable from the polycarbonates according to the invention.
- Molded parts can e.g. transparent plates, lenses, optical storage media or articles in the field of automotive glazings such. Be scattered light discs.
- the invention relates in particular to optical storage media or carriers for optical storage media, such as, for example, optical media. recordable optical data memories which have good coatability and wettability, and which are described in, for example, US Pat. suitable for the application of dyes a ⁇ s solution, especially from non-polar media.
- the optical injection molded parts of the polycarbonates according to the invention have a lower tendency to fouling.
- Transparent injection-molded parts are particularly important in the field of glazing and storage media.
- Optical data recording materials are increasingly used as a variable recording and / or archiving medium for large amounts of data.
- Examples of this kind of optical data storage are CD, Super Audio CD, CD-R, CD-RW, DVD, DVD-R, DVD + R, DVD-RW, DVD + RW and BD.
- Transparent thermoplastics such as polycarbonate, polymethylmethacrylate and chemical modifications thereof are typically used for optical storage media.
- Polycarbonate as a substrate material is particularly suitable for write-once and multi-readable as well as multi-writable optical discs and for the production of moldings from the field of automotive glazings, such. of scattered light disks.
- This thermoplastic material has excellent mechanical stability, is less susceptible to dimensional changes and is characterized by high transparency and impact strength.
- Polycarbonate prepared by the interfacial process can be used for the fabrication of optical data memories of the formats described above, e.g. for Compact Discs (CD) or
- DVD Digital Versatile Disks
- These discs often have the property to build a high electric field during their injection molding production. This high field starch on the substrate leads during the production of the optical data storage, for example, to attract dust from the environment, or for bonding the injection molded articles such as the discs among themselves, which reduces the quality of the finished injection molded article and complicates the injection molding process.
- nonpolar media such as e.g. a non-polar dye or a dye-applied solvent, e.g. Dibutyl ether, ethyl cyclohexane, tetrafluoropropanol, cyclohexane, methylcyclohexane or octafluoropropanol leads.
- a high electric field on the surface of the substrate during dye application to recordable data storage media causes an irregular dye coating, resulting in defects in the information layer.
- the degree of electrostatic charging of a substrate material may be e.g. be quantified by measuring the electric field at a certain distance to the substrate surface.
- antistatic agents are added as additives to the substrate material.
- Antistatic polycarbonate compositions are described, for example, in JP 62 207 358-A.
- phosphoric acid derivatives are added as antistatic agents to the polycarbonate.
- EP 0922 728 describes various antistatics such as polyalkylene glycol derivatives, ethoxylated sorbitan monolaurate, polysiloxane derivatives, phosphine oxides and distearylhydroxyamine, which are used individually or as mixtures.
- Japanese application JP 62 207 358 describes esters of phosphorous acid as additives.
- US Pat. No. 5,668,202 describes sulfonic acid derivatives.
- the described additives may also adversely affect the properties of the substrate material as they tend to leak out of the material. While this is a desirable effect for the antistatic properties, it can lead to deposit formation or poor impression taking. Furthermore, the content of oligomers in the polycarbonate can lead to a poorer mechanical property level and to a lowering of the glass transition temperature. Furthermore, these additives can cause side reactions. The subsequent "end-capping" of polycarbonate, which was obtained from the transesterification process, is laborious and the results achieved are not optimal.Adding new end groups into the material is associated with high costs.
- the object is to provide a composition or a substrate material which meets the requirements of the lowest possible potential (amount) in conjunction with low potential differences at the substrate surface (measured at a certain distance from the substrate surface) and avoids the disadvantages described above ,
- the antistatics described in EP-A 922 728 such as polyoxyethyl sensor bitane monolaurate, polyoxyethylene monolaurate and polyoxyethylene monostearate in the added amounts of 50-200 ppm, are effective in antistatic properties, they may be detrimental to the overall performance of the injection molded body as described above.
- additives may be included in the material, e.g. Flame retardants, mold release agents, UV stabilizers, heat stabilizers, as they are known for aromatic see polycarbonates.
- the amount of additives used should be kept as low as possible.
- examples of such additives are mold release agents based on stearic acid and / or stearic alcohol, particularly preferably pentaerythritol stearate, trimethylolpropane tristearate, pentaerythritol distearate, stearyl stearate, and glycerol monostearate, and also heat stabilizers based on phosphanes, phosphites and phosphoric acid.
- the present invention provides a substrate material which is particularly useful for rewritable optical media with good coating and wettability and low tendency to fouling available.
- the inventive substrate material leads to a low rejection rate in the production process.
- such substrate materials are suitable for the production of transparent moldings to be coated, which after processing into the injection molded part have a certain potential distribution on the surface of the injection-molded part. This potential distribution can be visualized by certain imaging techniques, eg with the aid of a so-called Monroe probe with coupled evaluation. It was found that especially those injection molded parts are advantageous, which have a low amount of potential in connection with a very homogeneous potential distribution on the surface.
- disks which have a low amount of potential in combination with the most homogeneous possible distribution of potential on the surface are of particular advantage for rewritable optical data memories.
- the invention therefore relates to a substrate material, preferably polycarbonate, for the production of transparent injection-molded parts to be coated, wherein up to 95-100% of the surface of the molded part obtained after an injection molding process, potential ranges between -1.5 and +1.5 kV, to 0 to 5 % of the surface have charge ranges between -1.5 and -2.5 or between +1.5 and +2.5 kV and up to 1% have ranges ⁇ -2.5 or> 2.5 kV.
- a substrate material preferably polycarbonate
- Materials with these properties can be e.g. especially good with non-polar media, e.g. coated with dyes dissolved in organic solvents.
- the injection-molded part to be coated is preferably a scattered-light disk or carrier material for an optically recordable data memory.
- the standard deviation of the potential resulting from the electrical charge can serve.
- the standard deviation of the potential resulting from the electrical charge in the surface segments should not exceed 0.6 kV.
- only the surface of the injection-molded body is relevant, ie in the case of a CD or DVD, for example, only the area up to the stacking ring and not the inner-hole area.
- the electrical potential caused by surface charges on the respective substrate is largely dependent on the geometry and dimensions of the injection molded article and the nature of the injection molding process. Therefore, it is important to measure the coating on the injection molded body itself, such as a disc for an optical disc to perform.
- ionizers are often used, which conduct an ionized air flow over the discs.
- the abovementioned measured values for substrate materials according to the invention were achieved without the use of ionizers.
- ionizers can also be used.
- the invention likewise relates to the molded parts produced from the substrate materials according to the invention, such as e.g. Discs for recordable optical data storage or materials from the field of automotive glazings such. Diffusers.
- Thermoplastics such as polycarbonate based on bisphenol A (BPA-PC), polycarbonate based on trimethylcyclohexyl-bisphenol polycarbonate (TMC-PC), fluorenyl polycarbonate, polymethyl methacrylate, cyclic polyolefin copolymer, hydrogenated polystyrenes (HPS) as well as amorphous polyols and polyesters.
- BPA-PC bisphenol A
- TMC-PC trimethylcyclohexyl-bisphenol polycarbonate
- HPS hydrogenated polystyrenes
- the substrate materials according to the invention and injection molded articles obtainable therefrom, in particular disks, can be produced by selecting suitable process parameters.
- the charge distribution on an injection molded body obtained after processing the substrate material may be influenced by several factors. For example, the purity of the reactants and auxiliaries is important. Furthermore, process parameters such as the molar ratio of bisphenol used and phosgene, temperatures during the reaction, reaction and Residence times prevail. For a person skilled in the art, the task is to control the process such that a substrate material is provided which generates the desired charge distribution on the injection-molded body.
- the described charge distribution measurement is a suitable instrument for the skilled person to control the process.
- a suitable selection of process parameters to obtain the desired substrate material may be as follows:
- One possibility for producing the substrate material according to the invention is the selection of specific process parameters during the production of the substrate material in a continuous phase interface process. While the excess of phosgene used, based on the sum of the bisphenols used, is between 3 and 100 mol%, preferably between 5 and 50 mol%, in the conventional continuous polycarbonate synthesis, the substrate material according to the invention is obtained at phosgene excesses of from 5 to 20 mol%. %, preferably 8 to 17 mol% produced.
- the pH of the aqueous phase during and after the phosgene dosage in the alkaline range, preferably maintained between 8.5 and 12, while it is adjusted to 10 to 14 after the addition of catalyst via one or more replenishment of sodium hydroxide solution or appropriate addition of bisphenolate ,
- the temperature during the phosgenation is 0 0 C to 40 0 C, preferably 5 ° C to 36 ° C.
- the polycarbonates according to the invention are prepared by the interfacial process. This process for polycarbonate synthesis has been widely described in the literature; For example, see H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, p. 33 et seq., Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1964, Chapter VHI, p. 325, to Dres. U. Grigo, K. Kircher and P.
- a disodium salt of a bisphenol (or a mixture of different bisphenols) in aqueous alkaline solution (or suspension) is carried out in the presence of an inert organic solvent or solvent mixture which forms a second phase.
- oligocarbonates are condensed with the aid of suitable catalysts to high molecular weight, dissolved in the organic phase, polycarbonates.
- the organic phase is finally separated and the polycarbonate isolated from it by various work-up steps.
- suitable dihydroxyaryl compounds are those of the formula (2)
- Z is an aromatic radical having 6 to 30 carbon atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members.
- Z in formula (2) preferably represents a radical of the formula (3)
- R 6 and R 7 independently represent H, C r Ci 8 alkyl, Ci-C] 8 -alkoxy, halogen, such as Cl or Br, or respectively optionally substituted aryl or aralkyl, preferably H or C r C 2 - Alkyl, particularly preferably H or C 1 -C 8 -alkyl and very particularly preferably H or methyl, and
- X is a single bond, -SO 2 -, -CO-, -O-, -S-, C 1 - to C 6 -alkylene, C 2 - to C 5 -alkylidene or C 5 - to C 6 -cycloalkylidene, which with C 1 - to C 6 -alkyl, preferably methyl or ethyl, and furthermore C 6 - to C 2 -arylene, which may optionally be condensed with further heteroatom-containing aromatic rings is.
- X is preferably a single bond, C 1 to C 3 -alkylene, C 2 to C 5 -alkylidene, C 5 to C 6 -cycloalkylidene, -O-, -SO-, -CO-, -S-, - SO 2 -,
- R 8 and R 9 for each X 1 individually selectable, independently of one another are hydrogen or C 1 to C 6 alkyl, preferably hydrogen, methyl or ethyl, and
- n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1 , R 8 and R 9 are simultaneously alkyl.
- dihydroxyaryl compounds are: dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) -aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones , Bis (hydroxyphenyl) sulfites, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, 1,1 'bis (hydroxyphenyl) diisopropylbenzenes, and their nuclear alkylated and nuclear halogenated compounds.
- Diphenols suitable for the preparation of the polycarbonates to be used according to the invention are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfites, bis (hydroxyphenyl) ethers , Bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes, and their alkylated, nuclear alkylated and nuclear halogenated compounds.
- Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -l-phenyl-propane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxy-phenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methyl-butane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl ) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2 - (3,5-dimethyl-4-
- diphenols are 4,4'-dihydroxydiphenyl, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3,5 -dimethyl-4-hydroxyphenyl) -propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
- the monofunctional chain terminators needed to control the molecular weight such as phenol or alkylphenols, in particular phenol, p-tert. Butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators, either with the bisphenolate or the bisphenolates of the reaction or added at any time during the synthesis, as long as phosgene in the reaction mixture or Chlorkohlenquipreend phenomenon are present or in the case of acid chlorides and chloroformate as a chain terminator as long as enough phenolic end groups of the forming polymer are available.
- the chain terminator (s) are added after phosgenation at one point or at a time when phosgene is no longer present but the catalyst has not yet been metered, or before the catalyst, with the catalyst together or in parallel.
- any branching or branching mixtures to be used are added to the synthesis, but usually before the chain terminators.
- trisphenols, quarterphenols or acid chlorides of tri- or tetracarboxylic acids are used, or mixtures of polyphenols or acid chlorides.
- trinifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
- Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri (4-hydroxyphenyl) -ethane.
- the catalysts used in the phase interface synthesis are tert. Amines, in particular triethylamine, tributylamine, trioctylamine, N-ethylpiperidine, N-methylpiperidine, Ni / n-propylpiperidine; quaternary ammonium salts such as tetrabutylammonium / tributylbenzylammonium / tetraethylammonium hydroxide / chloride / bromide / hydrogensulfate / tetrafluoroborate; and the phosphonium compounds corresponding to the ammonium compounds. These compounds are described as typical phase interface catalysts in the literature, are commercially available and familiar to those skilled in the art.
- the catalysts may be added individually, in admixture or else side by side and sequentially to the synthesis, if appropriate also prior to phosgenation, but preference is given to doses after phosgene introduction, unless an onium compound or mixtures of onium compounds is used as catalysts, then an addition before the phosgene dosage is preferred.
- the metered addition of the catalyst or of the catalysts can be carried out in bulk, in an inert solvent, preferably that of the polycarbonate synthesis, or else as an aqueous solution, in the case of tert. Amines then as their ammonium salts with acids, preferably mineral acids, in particular hydrochloric acid, take place.
- the total amount of catalysts used is between 0.001 to 10 mol% based on moles of bisphenols, preferably 0.01 to 8 mol%, particularly preferably 0.05 to 5 mol%.
- the polycarbonates according to the invention may also be added to the usual additives for polycarbonates in the usual amounts.
- the addition of additives serves to extend the useful life or the color (stabilizers), to simplify the processing (eg, remover, flow aids, antistatics) or to adapt the polymer properties to specific loads (impact modifiers, such as rubbers, flame retardants, colorants, glass fibers). ,
- additives can be added individually or in any desired mixtures or several different mixtures of the polymer melt, namely directly in the isolation of the polymer or after melting of granules in a so-called compounding step.
- the additives or mixtures thereof as a solid, i. be added as a powder or as a melt of the polymer melt.
- Another type of dosing is the use of masterbatches or mixtures of masterbatches of the additives or additive mixtures.
- Suitable additives are described, for example, in “Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999", in the “Plastics Additives Handbook, Hans Zweifel, Hanser, Kunststoff 2001”
- Preferred thermal stabilizers are, for example, organic phosphites, phosphonates and phosphanes, usually those in which the organic radicals consist entirely or partially of optionally substituted aromatic radicals.
- UV straighteners e.g. substituted benzotriazoles used.
- stabilizers may be used singly or in combinations and added to the polymer in the above-mentioned forms.
- processing aids such as mold release agents, usually derivatives of long-chain fatty acids, can be added.
- processing aids such as mold release agents, usually derivatives of long-chain fatty acids, can be added.
- Preferred are e.g. Pentaerythritol tetrastearate and glycerol monostea- rat. They are used alone or in a mixture, preferably in an amount of 0.02 to 1% by weight, based on the mass of the composition.
- Suitable flame retardant additives are phosphate esters, i. Triphenyl phosphate, resorcinol diphosphoric acid esters, bromine-containing compounds such as brominated phosphoric acid esters, brominated oligocarbonates and polycarbonates, and preferably salts of fluorinated organic sulfonic acids.
- Suitable impact modifiers are, for example, graft polymers comprising one or more grafting bases selected from at least one polybutadiene rubber, acrylate rubber (preferably ethyl or butyl acrylate rubber), ethylene-propylene rubbers and grafting monomers selected from at least one monomer from the group of styrene, acrylonitrile, alkyl rubber.
- graft polymers comprising one or more grafting bases selected from at least one polybutadiene rubber, acrylate rubber (preferably ethyl or butyl acrylate rubber), ethylene-propylene rubbers and grafting monomers selected from at least one monomer from the group of styrene, acrylonitrile, alkyl rubber.
- methacrylate preferably methyl methacrylate
- colorants such as organic dyes or pigments or inorganic pigments, IR absorbers, individually, in admixture or also in combination with stabilizers, glass fibers, glass (hollow) spheres, inorganic fillers may be added.
- the present application furthermore relates to the extrudates and moldings obtainable from the substrate materials according to the invention, in particular those for use in the transparent region, more particularly in the field of optical applications, such as e.g. Plates, web plates, glazing, lenses, lamp covers, or optical data storage, such as audio CD, CD-R (W), DVD, DVD-R (W), mini discs in their various read only or rewritable, possibly also repeatedly described embodiments.
- optical applications such as e.g. Plates, web plates, glazing, lenses, lamp covers, or optical data storage, such as audio CD, CD-R (W), DVD, DVD-R (W), mini discs in their various read only or rewritable, possibly also repeatedly described embodiments.
- the present invention furthermore relates to the use of the polycarbonates according to the invention for the production of extrudates and molded parts.
- the erf ⁇ ndungswashe substrate material preferably polycarbonate
- a disk thus prepared may e.g. an audio CD, a super audio CD, CD-R, CD-RW, DVD, DVD-R, DVD + R, DVD-RW, DVD + RW or BR.
- the CD-R (write once, read many) consists of a substrate with concentrically shaped guide recesses (Pregroove), which are transferred in the injection molding process by a nickel matrix. Via a matrix which contains depressions on a submicrometer scale, these are transferred in the injection molding process exactly on the surface of the substrate.
- the CD-R consists of the above-mentioned substrate, a dye-recording layer, a reflection layer, and a protective layer which are laminated on the substrate in this order.
- DVD-R Another example of a write once and multiple read-back optical disk is the DVD-R, which consists of the substrate, a dye recording layer, a reflective layer, and optionally a protective layer, and also in this order on the substrate described above are applied and glued to a second disk ("Dummy Disk").
- the application of the dye layer takes place via a "spin-coating" process
- the respective dye dissolved in an organic solvent
- the dye layer is dried.
- the dye to be used for the application described above has an absorption range which is in the range of the laser used (300-850 nm).
- dye types are, for example, cyanines, phthalocyanines, squarylium dyes, polymethines, pyrilium and thiopyrilium dyes, indoanilines, naphthoquinones, anthraquinones, various metal chelate complexes such as azo coordination compounds, cyanines or phthalocyanines.
- cyanines for example, cyanines, phthalocyanines, squarylium dyes, polymethines, pyrilium and thiopyrilium dyes, indoanilines, naphthoquinones, anthraquinones, various metal chelate complexes such as azo coordination compounds, cyanines or phthalocyanines.
- These dyes have good signal sensitivity as well as good solubility in organic solvents and light fastness and are thus preferred dyes for applications described above.
- solvents examples include esters such as butyl acetate, ketones such as methyl ethyl ketone, cyclohexanone, methyliosbutyl ketone and 2,4-dimethyl-4-heptanone (DMH), chlorinated hydrocarbons such as 1,2-dichloroethane, and chloroform, amides such as dimethylformamide, hydrocarbons such as cyclohexane , Methylcyclohexane or ethylcyclohexane, ethers such as THF and dioxane, alcohols such as ethanol, propanol, isoprpanol, n-butanol, and diacetone alcohol, fluorinated solvents such as 2,2,3,3-tetrafluoropropanol, and glycol ethers such as ethylene glycol monomethyl ether, and propylene glycol monomethyl ether. These can be used individually or as mixtures. Preferred solvents are fluorin
- a reflective layer e.g. be applied consisting of gold or silver.
- a protective layer may be applied to the reflective layer.
- the disk substrate according to the invention and the optical disk according to the invention show markedly improved antistatic properties and improved coatability.
- the injection molded part is obtained by conventional injection molding.
- the injection-molded part is produced as follows:
- an optical disk is selected;
- the following injection molding parameters and conditions are set:
- Mold temperature on die side 60 0 C
- a new audio stamper is inserted into the machine.
- the entire injection molding system must be cleaned of previous material so that the measured values are not falsified.
- the method for measuring the surface potential is carried out using a Monroe probe from MONROE ELECTRONICS, INC., Lyndonville, NY 14098, USA, which is suitable for measuring electrical potentials.
- the measurement takes place at a distance of 3.5 mm from the substrate surface.
- the scanning range is 12 cm each in the X and Y directions.
- the surface potential is measured in increments of 2 mm in the X and Y directions.
- the potential values are converted to an equivalent voltage value at the analog output of the measuring amplifier of the Monroe probe.
- These voltage values are first stored in a PC from the analogue input of a BurrBrown PC interface card by means of proprietary software (TurboPascal) using TurboPascal routines from BurrBrown, and after the scan has been completed the entire data is stored as a text file on a floppy disk. For a better visual representation of the measured values, the values are converted into a false color image by means of the software Origin.
- the potency range from -3500 V to +3500 V is divided into 32 color areas. The colors go from blue to green and yellow to red. For example, the color dark blue is assigned to the most negative potential range -3500 V to -3281 V and the color dark red to the most positive potential range +3281 V to +3500 V.
- the measured values are converted into Cartesian coordinates in a value range of -30 to +30. These values are then converted to even polar coordinates. To capture only the relevant area, all values with r ⁇ 12 mm (inner hole area) or r> 29 mm are eliminated. The resulting values are sorted into the corresponding charge areas and counted.
- the discs are measured for potential distribution within the first 24 hours after production.
- the disc must not come into contact with metal, otherwise the potential measurement will be impaired. Furthermore, any existing ionizers must be switched off.
- the humidity during the measurement is 30 to 60%, preferably 35 to 50% and the room temperature is 25 to 28 ° C.
- the dye application can be carried out as described above by "spin coating.”
- the dyestuff used is preferably a phthalocyanine and preferably dibutyl ether as solvent
- the speed of rotation when the dyestuff is applied is 200 rpm
- the velocity is spread over the entire disk to dissolve the solution Increased 5000 rpm.
- Dye-coatability can be measured, for example, by visual inspection, by camera scanner or by light microscopic examination of the interior of the dye-coated disk. If a deviation from the color band of 0.5 mm or higher is determined at one point of the outer edge of the dye, the wetting behavior of this disc is considered insufficient.
- Another indirect way to measure coatability is to check the e.g. Dye-coated disc with a camera or laser system.
- the recorded information is evaluated via image processing software and any wetting errors that occur are detected ("in-line" detection). Defective discs are automatically sorted out.
- Figs. 1 and 2 show the charge distribution of a disk (black and white copy of the false color representation).
- the preparation of the polycarbonate is carried out by the known interfacial process. It is worked according to a Konti procedure.
- the bisphenolate solution bisphenol A, alkali content 2.12 mol NaOH / mol BPA
- the solvent diichloromethane / chlorobenzene 1: 1
- the temperature in the reactor is 35 ° C.
- sodium hydroxide solution 32 wt .-%) with 9.97 kg / h is also added.
- the resulting granules are then processed into discs using a Netstal Discjet injection molding machine (see above) at 4.4 second cycle time under the parameters given above.
- the template is an audio stamper.
- the disks are coated as described above with a phthalocyanine dissolved in dibutyl ether in the spin coat process.
- the rotational speed when applying the dye is 200 U / min. To spread the solution over the entire disk, the speed is increased to 5000 rpm. The visual inspection gives no defects of the dye layer.
- the preparation of the polycarbonate is carried out as described in Example 1. However, the bisphenolate solution (bisphenol A) at 750 kg / h (14.93% by weight), the solvent (dichloromethane / chlorobenzene 1: 1) at 646 kg / h and the phosgene at 58.25 kg / h fed. Furthermore, sodium hydroxide solution (32% by weight) is also metered in at 12.34 kg / h. The second amount of sodium hydroxide is 36.20 kg / h; the amount of chain terminator 34.18 kg / h at the concentrations given in Example 5. The amount of catalyst is 33 kg / h. The work-up is carried out as indicated in Example 1.
- the resulting granules are then processed into discs using a Netstal Discjet injection molding machine (see above) at 4.4 second cycle time under the parameters given above.
- the template is an audio stamper.
- Dye coated discs show significant defects in the dye layer.
- Standard deviation is the variance of the individual charge segments.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Manufacturing Optical Record Carriers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP05823764A EP1834194B1 (de) | 2004-12-22 | 2005-12-09 | Substratmaterialien für transparente spritzgussteile |
| BRPI0519204-8A BRPI0519204A2 (pt) | 2004-12-22 | 2005-12-09 | materiais de substrato para peÇas moldadas por injeÇço transparentes |
| AU2005324117A AU2005324117A1 (en) | 2004-12-22 | 2005-12-09 | Substrate materials for transparent injection moulded pieces |
| JP2007547248A JP2008524775A (ja) | 2004-12-22 | 2005-12-09 | 透明射出成形部品用基板材料 |
| CN2005800485425A CN101124493B (zh) | 2004-12-22 | 2005-12-09 | 透明注塑件的基底材料 |
| CA002592023A CA2592023A1 (en) | 2004-12-22 | 2005-12-09 | Substrate materials for transparent injection moulded pieces |
| MX2007007492A MX2007007492A (es) | 2004-12-22 | 2005-12-09 | Materiales sustrato para piezas de moldeo por inyeccion transparentes. |
| ES05823764T ES2389845T3 (es) | 2004-12-22 | 2005-12-09 | Materiales de sustrato para piezas de moldeo por inyección transparentes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004061753A DE102004061753A1 (de) | 2004-12-22 | 2004-12-22 | Substratmaterialien für transparente Spritzgussteile |
| DE102004061753.8 | 2004-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006072352A1 true WO2006072352A1 (de) | 2006-07-13 |
Family
ID=35989600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2005/013222 Ceased WO2006072352A1 (de) | 2004-12-22 | 2005-12-09 | Substratmaterialien für transparente spritzgussteile |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US20060134366A1 (enExample) |
| EP (1) | EP1834194B1 (enExample) |
| JP (2) | JP2008524775A (enExample) |
| KR (1) | KR20070086484A (enExample) |
| CN (1) | CN101124493B (enExample) |
| AU (1) | AU2005324117A1 (enExample) |
| BR (1) | BRPI0519204A2 (enExample) |
| CA (1) | CA2592023A1 (enExample) |
| DE (1) | DE102004061753A1 (enExample) |
| ES (1) | ES2389845T3 (enExample) |
| MX (1) | MX2007007492A (enExample) |
| RU (1) | RU2421763C2 (enExample) |
| TW (1) | TW200640989A (enExample) |
| WO (1) | WO2006072352A1 (enExample) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6974260B2 (en) * | 2003-07-30 | 2005-12-13 | Emcore Corporation | Flexible substrate for routing fibers in an optical transceiver |
| DE102007022130B4 (de) | 2007-05-11 | 2015-02-19 | Bayer Intellectual Property Gmbh | Verfahren zur Herstellung von Polycarbonat nach dem Schmelzeumesterungsverfahren |
| DE102007052968A1 (de) * | 2007-11-07 | 2009-05-14 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polycarbonat nach dem Schmelzeumesterungsverfahren |
| US9290618B2 (en) * | 2011-08-05 | 2016-03-22 | Sabic Global Technologies B.V. | Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions |
| US8691915B2 (en) | 2012-04-23 | 2014-04-08 | Sabic Innovative Plastics Ip B.V. | Copolymers and polymer blends having improved refractive indices |
| US9821523B2 (en) | 2012-10-25 | 2017-11-21 | Sabic Global Technologies B.V. | Light emitting diode devices, method of manufacture, uses thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0922728A2 (en) * | 1997-12-12 | 1999-06-16 | General Electric Company | Static resistant polycarbonate compositions |
| US6140457A (en) * | 1999-02-26 | 2000-10-31 | General Electric Company | Static-resistant polycarbonates having DI-t-alkylphenyl end groups |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3674740A (en) * | 1969-04-22 | 1972-07-04 | Bayer Ag | Process of producing polycarbonate |
| CH554908A (de) * | 1971-01-15 | 1974-10-15 | Basf Ag | Verfahren zur kontinuierlichen herstellung hochmolekularer, linearer polycarbonate. |
| DE2305144C2 (de) * | 1973-02-02 | 1982-05-06 | Basf Ag, 6700 Ludwigshafen | Verfahren zur kontinuierlichen Herstellung von Polycarbonaten |
| EP1221459A1 (en) * | 1993-08-26 | 2002-07-10 | Teijin Limited | A stabilized polycarbonate |
| WO1997004033A1 (en) * | 1995-07-21 | 1997-02-06 | Mitsubishi Rayon Co., Ltd. | Photopolymerizable composition and optical disc having hardened coating made from the composition |
| US5973102A (en) * | 1997-12-12 | 1999-10-26 | General Electric Company | Static resistant polycarbonate compositions |
| BR9916574A (pt) * | 1998-12-23 | 2001-10-02 | Bayer Ag | Policarbonatos com baixo ìndice de yellowness |
| US6022943A (en) * | 1999-04-07 | 2000-02-08 | General Electric Company | Optical quality polycarbonates with reduced static charge and method for making same |
| DE10118307A1 (de) * | 2001-04-12 | 2002-10-17 | Bayer Ag | Vefahren zur Herstellung von Polycarbonaten |
| EP1304358B1 (en) * | 2001-10-22 | 2005-06-22 | Mitsubishi Chemical Corporation | Polycarbonate composition, write once read many optical disc substrate and write once read many optical disc using the same and process for production of write once read many optical disc |
| JP2003137998A (ja) * | 2001-10-30 | 2003-05-14 | Mitsubishi Engineering Plastics Corp | 光ディスク |
| EP1775322A4 (en) * | 2004-06-25 | 2009-11-11 | Mitsubishi Eng Plastics Corp | AROMATIC POLYCARBONATE RESIN COMPOSITIONS AND SUPPORT FOR AN OPTICAL INFORMATION RECORDING MEDIUM USING THE SAME, TRANSPARENT OPTICAL PART, COVER FOR LIGHTING AND TRANSPARENT ELEMENTS FOR A VEHICLE |
-
2004
- 2004-12-22 DE DE102004061753A patent/DE102004061753A1/de not_active Withdrawn
-
2005
- 2005-12-09 ES ES05823764T patent/ES2389845T3/es not_active Expired - Lifetime
- 2005-12-09 KR KR1020077014044A patent/KR20070086484A/ko not_active Withdrawn
- 2005-12-09 RU RU2007127789/28A patent/RU2421763C2/ru not_active IP Right Cessation
- 2005-12-09 WO PCT/EP2005/013222 patent/WO2006072352A1/de not_active Ceased
- 2005-12-09 MX MX2007007492A patent/MX2007007492A/es active IP Right Grant
- 2005-12-09 BR BRPI0519204-8A patent/BRPI0519204A2/pt not_active IP Right Cessation
- 2005-12-09 JP JP2007547248A patent/JP2008524775A/ja not_active Withdrawn
- 2005-12-09 CA CA002592023A patent/CA2592023A1/en not_active Abandoned
- 2005-12-09 CN CN2005800485425A patent/CN101124493B/zh not_active Expired - Fee Related
- 2005-12-09 EP EP05823764A patent/EP1834194B1/de not_active Expired - Lifetime
- 2005-12-09 AU AU2005324117A patent/AU2005324117A1/en not_active Abandoned
- 2005-12-20 US US11/312,013 patent/US20060134366A1/en not_active Abandoned
- 2005-12-21 TW TW094145426A patent/TW200640989A/zh unknown
-
2010
- 2010-04-14 JP JP2010093360A patent/JP5289377B2/ja not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0922728A2 (en) * | 1997-12-12 | 1999-06-16 | General Electric Company | Static resistant polycarbonate compositions |
| US6140457A (en) * | 1999-02-26 | 2000-10-31 | General Electric Company | Static-resistant polycarbonates having DI-t-alkylphenyl end groups |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008524775A (ja) | 2008-07-10 |
| KR20070086484A (ko) | 2007-08-27 |
| EP1834194A1 (de) | 2007-09-19 |
| EP1834194B1 (de) | 2012-07-18 |
| RU2421763C2 (ru) | 2011-06-20 |
| ES2389845T3 (es) | 2012-11-02 |
| CN101124493A (zh) | 2008-02-13 |
| JP2010211916A (ja) | 2010-09-24 |
| CN101124493B (zh) | 2012-02-08 |
| JP5289377B2 (ja) | 2013-09-11 |
| RU2007127789A (ru) | 2009-01-27 |
| CA2592023A1 (en) | 2006-07-13 |
| DE102004061753A1 (de) | 2006-07-06 |
| TW200640989A (en) | 2006-12-01 |
| US20060134366A1 (en) | 2006-06-22 |
| BRPI0519204A2 (pt) | 2008-12-30 |
| MX2007007492A (es) | 2007-09-11 |
| AU2005324117A1 (en) | 2006-07-13 |
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