Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0041—Optical brightening agents, organic pigments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
  • C09K2323/06—Substrate layer characterised by chemical composition
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
  • H01H2219/00—Legends
  • H01H2219/054—Optical elements
  • H01H2219/06—Reflector
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Definitions

• the present invention relates to a thermoplastic resin composition and a molded article using the same, and more particularly, to a thermoplastic resin composition having a high light-shielding property while ensuring reflectance, and a thermosetting resin composition having the same.
• the present invention relates to a molded article obtained by molding a plastic resin composition.
• Polycarbonate resin has excellent mechanical strength (particularly impact resistance), electrical properties, transparency, etc., and is used as an engineering plastic in the fields of OA equipment, electrical equipment, electronic equipment, automobiles, etc. Is widely used in various fields.
• LCDs liquid crystal displays
• the use of liquid crystal displays (LCDs) has expanded to notebook computers, monitors, and televisions. At the same time, higher image quality has progressed, and higher brightness is required for backlights, which are LCD lighting devices.
• the light-shielding property is remarkably reduced as the thickness of the molded article is reduced, and light is easily transmitted.
• the thickness of recent notebook PC frames has been reduced to a minimum of 0.5 mm, so that black light-shielding tape may be attached to necessary places to prevent light from passing through, and in other cases, white Special measures, such as the use of a combination of a molded product and a black molded product, are required separately, which has led to complicated processes, increased costs, and an obstacle to free design.
• Patent Document 2 a technique of coextruding a layer having a light-shielding property to produce a laminated film
• Patent Document 3 a technique of laminating a black film on the back surface of a white reflective film
• Patent Document 4 a spacer for an electro-optical panel containing a manganese oxide-based black pigment for the purpose of light absorption has been proposed (Patent Document 4). In this case, even if a black pigment is used, light absorption is not eliminated. A lighting device that uses the reflected light to reduce the intensity of the molded product using the light has a disadvantage in that the brightness decreases.
• Patent Document 1 Japanese Patent Application Laid-Open No. 9 330048
• Patent Document 2 Japanese Patent Application Laid-Open No. 2003-305811
• Patent Document 3 JP 2004-053759 A
• Patent Document 4 Japanese Patent Application Laid-Open No. 2004-046205
• the present invention has been made in view of the above circumstances, and a thermoplastic resin composition having high light-shielding properties (ie, low total light transmittance) while ensuring good reflectivity, and It is an object to provide a molded article used.
• the present inventors have conducted intensive studies to achieve this object. As a result, in a resin composition containing a thermoplastic resin and a white pigment such as titanium oxide, a black coloring material and a blue coloring material were further added. It has been found that it is effective to incorporate them in combination, and the present invention has been completed. That is, the present invention includes the following components.
• thermoplastic resin composition containing (A) a thermoplastic resin and (B) a white pigment in a mass ratio of 50: 50-90: 10, and (C) a black coloring material and a blue coloring material.
• a thermoplastic resin composition characterized by containing.
• thermoplastic resin according to the above 1 or 2 wherein the white pigment of the component (B) is titanium oxide powder. Composition.
• thermoplastic resin composition according to any one of the above items 1 to 3, wherein the black coloring material in the component (C) is carbon black, and the blue coloring material is phthalocyanine blue.
• thermoplastic resin according to any one of the above items 1 to 4, wherein the content of the component (C) is 0.1 to 50 mass ppm based on the total mass of the component (A) and the component (B). Composition.
• thermoplastic resin composition according to any one of the above items 1 to 4, wherein the content of the component (C) is 1 to 50 mass ppm based on the total mass of the component (A) and the component (B). .
• thermoplastic resin composition according to any one of 1 to 6, wherein the mass ratio of the black color material to the blue color material is in the range of 30:70 to 70:30.
• thermoplastic resin composition 8.
• the optical characteristics of the thermoplastic resin composition are such that the molded product obtained when molded into a molded product having a thickness of 0.5 mm has a total light transmittance of 0.2 or less and a reflectance (Y value).
• Y value a reflectance
• thermoplastic resin composition according to any one of 1 to 8 above is molded into a molded body having a thickness of 0.5 mm, the molded article has a total light transmittance of 0.2 or less, A molded article having a reflectance (Y value) of 79 or more.
• the molded article obtained by molding the thermoplastic resin composition according to any one of the above 1 to 8 into a molded article having a wall thickness of 1.Omm has a total light transmittance of 0.2 or less. And a reflectance (Y value) of 90 or more.
• the thermoplastic resin used as the component (A) includes a polycarbonate resin, a polycarbonate polyorganosiloxane copolymer (hereinafter sometimes abbreviated as a PC-PDMS copolymer), Examples include acrylic resin, polystyrene resin (transparent type), and polymethylpentene 1.
• a polycarbonate resin a polycarbonate polyorganosiloxane copolymer
• acrylic resin polystyrene resin (transparent type)
• polymethylpentene 1 polymethylpentene 1.
• Each of these thermoplastic resins may be used alone, or two or more of them may be used in combination. In particular, the viewpoint of improving the average brightness when white pigments such as titanium oxide are blended. High transparency is preferred.
• Polycarbonate resin, a mixture of polycarbonate resin and PC-PDMS copolymer A mixture of an acrylic resin such as rimethymethacrylate or a polycarbonate resin and an acrylic resin such as polymethyl methacrylate is preferred.
• Polycarbonate resins can be easily produced by reacting a divalent phenol with phosgene or a carbonate ester in the presence of an acid acceptor or a terminal terminator. There is no.
• divalent phenols examples include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) -Le) oxide, bis (4-hydroxyphenyl) snolefide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 9,9-bis (4-hydroxyphenyl) fluorene
• bishalogen A that is, 2,2-bis (4-hydroxyphenyl) propane is suitable.
• Examples of the carbonate compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as getyl carbonate and dimethyl carbonate.
• the terminal terminating agent may be of any structure as long as it is a monovalent phenol, and is not particularly limited.
• Specific examples of the terminal stopper include p-tert-butylphenol, p-tert-octylphenol, p-tamylphenol, phenol, p-tert-amylphenol, p-norphenol, p-cresol, tri- Bromophenol, p-bromophenol, 4-hydroxybenzophenone and the like can be mentioned.
• One type of terminal terminator may be used alone, or two or more types may be used in combination.
• a polycarbonate resin having a branched structure may be used as the polycarbonate resin.
• the branching agent used to obtain the polycarbonate resin having the branched structure includes 1, 1, 1 tris (4 —Hydroxyphenyl) ethane, ⁇ , ⁇ ′, ⁇ ”—Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1— ( ⁇ -methyl-1-a- (4" —hydroxy Feel) Ethyl) -4- ( ⁇ ', ⁇ '-bis (4 "-hydroxyphenyl) ethyl) benzenephloroglucin, trimellitic acid, isatin bis ( ⁇ -cresol), etc. ing.
• the viscosity average molecular weight of the polycarbonate resin is preferably 10,000 to 40,000.
• the viscosity average molecular weight of the polycarbonate resin is more preferably 12,000 to 350,000, and still more preferably 15,000 to 30,000.
• the PC-PDMS copolymer is a block copolymer capable of cooperating with a polyorganosiloxane moiety, and has a viscosity average molecular weight of preferably 10,000 to 40,000, more preferably 12,000 to 35,000. is there.
• Such a PC-PDMS copolymer includes, for example, a polycarbonate oligomer (hereinafter abbreviated as “PC oligomer”) constituting a polycarbonate portion prepared in advance and a polyorganosiloxane portion having a reactive group at a terminal constituting a polyorganosiloxane portion.
• organosiloxane for example, polydimethylsiloxane (PDMS), polydialkylsiloxane such as polyethylsiloxane, or polymethylphenol.
• organosiloxane for example, polydimethylsiloxane (PDMS), polydialkylsiloxane such as polyethylsiloxane, or polymethylphenol.
• the acrylic resin is a generic name for a polymer of acrylic acid and its derivatives, and includes polymers and copolymers of acrylic acid and its esters, acrylamide, acrylonitrile, methacrylic acid and its esters, and the like. I do.
• the viscosity average molecular weight of the acrylic resin is preferably 100,000 to 600,000, more preferably 150,000 to 500,000.
• inorganic filler powders such as titanium oxide, zinc oxide, calcium carbonate, barium sulfate, and talc are selected in accordance with the requirements of the preferred product. can do.
• thermoplastic resins may be used alone or in combination of two or more.
• titanium oxide powder is preferred from the viewpoint of imparting the reflective functionality.
• the above-mentioned oxidized titanium powder may be a rutile type or an anatase type, which may be shifted! 1S
• the rutile type is also preferred because of its excellent thermal stability and weather resistance.
• the titanium oxide powder be treated with various surface treating agents to coat the surface thereof.
• surface treatment agents hydrated aluminum, silica, zinc and the like are usually used.
• the shape of the titanium oxide powder is not particularly limited, and can be appropriately selected from scaly, spherical, amorphous, and the like. Further, the size (particle size) is preferably about 0.2 to 5 m. In order to improve the dispersibility of the titanium oxide powder in the resin, a silicone oil-polyol or the like may be used.
• the content ratio of the thermoplastic resin (A) and the white pigment (B) is selected in a mass ratio of 50:50 to 90:10. It is. If the amount of the white pigment is less than the above range, the total light transmittance at a wall thickness of 0.5 mm is high, and it is difficult to obtain a molded article having a light shielding property of 0.2% or less. Further, when the amount of the white pigment is larger than the above range, it is expected that both extremely high reflectance and light-shielding property can be ensured. However, when the titanium oxide powder is added, the deterioration of the resin becomes large. When the fat composition is formed into a desired shape, generation of silver (silver stripes) becomes remarkable.
• the content ratio of the thermoplastic resin (A) to the white pigment of the component (B) is 65:35 by mass.
• the range of ⁇ 90: 10 is preferred. Further, the range of 80: 20 ⁇ 90: 10 is particularly preferred considering the balance of reflectivity, light-shielding properties and moldability! /.
• the thermoplastic resin (A) and the white pigment (B) and the composition which is also strong further contain a combination of a black coloring material and a blue coloring material as the component (C). It is necessary to make it happen.
• a decrease in the reflectance (Y value) is suppressed and higher light-shielding properties as compared with a case where the black color material is simply added.
• N neutral range
• V ⁇ 0.5 as V / C
• the black color material carbon black, lamp black, horn black, graphite, iron black, arlin black, cyanine black, or a mixture of dyes or pigments in the above-specified black range Colors such as colorants can also be selected and used, especially carbon black.
• Blue colorants include phthalocyanine dyes or pigments such as phthalocyanine blue, anthraquinone dyes or pigments, complex oxide pigments, ultramarine, navy blue, cobalt blue, dioxazine pigments, and sullen pigments. Although it can be used, phthalocyanine blue is preferred.
• the black color material and the blue color material as the component (C) are contained in an amount of 0.1 to 50 ppm by mass based on the total mass of the components (A) and (B). .
• the amount is more preferably 1 to 50 ppm by mass.
• the component (C) be contained in an amount of 3 to 30 ppm by mass. Within this range, it can be set freely according to the requirements of the reflectance and the light shielding property.
• the content ratio of the black color material to the blue color material is preferably 30:70 to 70:30 by mass ratio! / ,.
• the ratio of the black color material is preferably 30:70 to 70:30 by mass ratio! / ,.
• thermoplastic resin composition according to the present invention has a total light transmittance of 0.2 or less and a reflectance (Y value) of 79 or more. It is preferable that When the total light transmittance exceeds 0.2, the light from the cold cathode tube and the like placed on the back side of the molded product is transparent enough to be visually confirmed in an atmosphere where the surroundings are kept relatively dark. If the Y value is less than S79, the molded article is not visually apparently white, but is recognized as gray or dark. From the same viewpoint, it is more preferable that the molded article having a thickness of 1.
• Omm has a total light transmittance of 0.2 or less and a reflectance (Y value) of 90 or more.
• total light transmittance is measured based on the method described in JIS K 7105. Means.
• the “Y value” is defined as the stimulus value, when the tristimulus values X, ⁇ , and ⁇ ⁇ ⁇ ⁇ for the color of the sample (molded body) are determined by spectral colorimetry according to the method described in JIS ⁇ 7105. Meaning, this ⁇ value corresponds to the luminance factor or the luminous reflectance.
• the ⁇ value can be measured using, for example, MS2020 Plus manufactured by Mcbeth.
• a stabilizing agent is optionally added to the thermoplastic composition.
• the type of the stabilizer is not particularly limited, and is a phosphorus compound, an organosiloxane containing an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group), an organohydrogensiloxane, an alkoxysilane compound, or an epoxysilane compound.
• a kissy dagger can be used.
• Specific examples of the above-mentioned phosphorus compounds include (2,4-di-tert-butylphenyl) biphenyl-diphosphonite, trimethyl phosphate, benzyl phosphonate, organic phosphonate, and organic phosphonate. And dialkyl alkyl phosphonates.
• Specific examples of the organosiloxane containing an alkoxy group include an organopolysiloxane containing an organooxysilyl group bonded to a silicon atom via a divalent hydrocarbon group.
• organohydrogensiloxane examples include polyorganohydrosiloxane, end-blocked polyorganohydrosiloxane, and the like.
• specific examples of the above-mentioned alkoxysilane compounds include methyltrimethoxysilane, alkylaminosilane and the like.
• Specific examples of the epoxy conjugate include epoxy resin, epoxidized soybean oil, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and the like.
• an alkoxy group is preferred from the viewpoint that even when the concentration of titanium oxide in the polycarbonate resin composition is increased, the generation of silver during molding can be suppressed relatively low.
• Organosiloxanes are particularly preferred.
• One type of stabilizer may be used alone, or two or more types may be used in combination.
• the addition amount of the polycarbonate resin stabilizing agent is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (B).
• a light diffusing agent may be added, if desired, in order to lower the total light transmittance without substantially lowering the Y value of the molded article having the polycarbonate resin composition power.
• the light diffusing agent examples include acrylic beads, silica beads, silicone resin beads and glass beads, and hollow beads, amorphous powders, and plate-like powders of the same material.
• the addition amount of the light diffusing agent is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the total amount of the component ( ⁇ ) and the component ( ⁇ ).
• thermoplastic resin composition of the present invention a fluorine resin may be added, if desired, for imparting higher flame retardancy.
• a fluorine resin polytetrafluoroethylene having an average molecular weight of 500,000 or more and having a fibril-forming ability is preferable.
• Polytetrafluoroethylene having the ability to form fibrils functions as an anti-dropping agent (an anti-dripping agent for ignition resin).
• the fibril-forming ability refers to the ability to fibrillate (fiberize) when subjected to shearing stress of plasticity in kneading or injection molding, and is effective in obtaining high flame retardancy.
• Polytetrafluoroethylene (PTFE) having a fibril-forming ability as described above can be prepared, for example, by adding tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, or ammonium dimethyldisulphide. It can be obtained by polymerization at a pressure of about 100 psi and a temperature of about 0 to 200 ° C, preferably 20 to 100 ° C.
• thermoplastic resin composition As described above, the composition of the thermoplastic resin composition according to the present invention has been described. However, in addition to the above-mentioned components, various fillers, additives, and other synthetic resins may be used in the thermoplastic resin composition. ⁇ Fats, elastomers, etc. can be included as needed. Specific examples of the above fillers include fibrous fillers such as glass fiber, carbon fiber, potassium titanate whiskers, mineral fibers, and wollastonite, and plate-like fillers such as talc, myriki, glass flakes and clay. Fillers and the like.
• antioxidants such as hindered phenols, phosphites and phosphates
• ultraviolet absorbers such as benzotriazoles and benzophenones
• light absorbers such as hindered amines.
• Stabilizers such as aliphatic carboxylic acid ester type, paraffin type, silicone oil, polyethylene wax and the like, or common flame retardants, flame retardant aids, mold release agents, antistatic agents, coloring agents, and the like.
• polyester polyethylene terephthalate, polybutylene terephthalate, etc.
• polyamide polyarylate, polyethylene, polypropylene, polymethyl methacrylate, polystyrene, ABS resin, and AS resin.
• elastomer examples include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, core-shell type elastomers such as MBS and MAS.
• the molded article of the present invention using the thermoplastic resin composition includes a ribbon blender, a Hensiel mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, and a multi-screw.
• a desired composition is obtained by a method using an extruder or the like, it can be obtained by molding the composition into a desired shape by a method such as injection molding, extrusion molding, or rotational molding.
• the molding temperature can be appropriately selected within a range of approximately 260 to 300 ° C.
• the mold temperature can be appropriately selected within the range of about 80 to 120 ° C.
• the shape of the molded article can be appropriately selected according to the intended use and the like.
• the shape of these components is not particularly limited as long as they can be integrally molded, and can be appropriately selected according to the use and the like.
• thermoplastic resin compositions used in Examples and Comparative Examples are as follows.
• ADK STAB PFR (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., flame retardant, Fehl's resorcinol polyphosphate]
• CD076 [trade name, manufactured by Asahi Glass Fluoropolymer Co., Ltd., polytetrafluoroethylene (PTF E)]
• BY16-161 (trade name, manufactured by Toray Dow Co. Ltd., an ethoxysilicone in which an ethoxy group is bonded to a silicon atom via a hydrocarbon group]
• thermoplastic resin polycarbonate resin (PC) or a mixture of PC and polycarbonate-polydimethyl copolymer is used, and titanium oxide powder, both blue and black color materials, and stabilizers are used. If necessary, PTFE and Z or an antioxidant were blended in the proportions shown in Tables 1 and 2, and after dry blending, a vented twin-screw extruder (TEM-35 manufactured by Toshiba Machine Co., Ltd.) was used. The mixture was kneaded at a cylinder temperature of 280 ° C. to obtain pellets having the same polycarbonate resin composition strength.
• the pellets obtained above were dried at 120 ° C for 5 hours and then subjected to injection molding at a molding temperature of 280 ° C and a mold temperature of 80 ° C by injection molding at 80 mm X 80 mm X O. 5 mm and 80 mm X 80 mm X 1.0.
• a test piece having a flat plate force of mm was obtained for each example.
• the mold used to obtain the test piece was a mold whose surface was mirror-polished with water paper (# 1000).
• Total light transmittance> The total light transmittance was measured using SZ Sigma 90 manufactured by Nippon Denshoku Industries Co., Ltd. ⁇ Yfg>
• the Y value was measured using MS 2020 Plus manufactured by Mcbeth. Light Transparency>
• the light can be transmitted through a cold cathode tube with a diameter of 4 mm (HMB manufactured by Harrison Electric Co., Ltd .; luminance: 2000 OcdZm 2 ) in close contact with the back side of the molded product (flat plate). , ⁇ (slightly transparent), X (very transparent).
• Polycarbonate resin is used as the thermoplastic resin, and the titanium oxide powder, the stabilizer, and none of the blue color material and the black color material are used, or only one of them is used.
• the tablets were blended at the ratios shown in the table, and pellets were prepared in the same manner as in Examples 1 to 18, and the same evaluation was performed. The results are shown in Tables 1 and 2.
• the composition of the present invention can maintain a Y value (reflectance) without increasing the amount of titanium oxide to obtain a molded article having higher light-shielding properties. Therefore, molding defects such as silver and foam can be reduced.
• complicated processes such as attaching black tape to the molded product or combining white and black molded products are required. Can be omitted.
• thermoplastic resin composition of the present invention can be used for components such as liquid crystal display backlights (reflectors, frames, lamp supports, etc.), components for general lighting devices (housings, reflectors, frames, etc.), LED reflection It can be effectively applied to products that require simultaneous reflection and blocking of light generated by a light source, such as operation panels for cases and automobiles.

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• 2005
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