WO2006077813A1 - Composition de resine de polycarbonate aromatique et article diffusant la lumiere - Google Patents

Composition de resine de polycarbonate aromatique et article diffusant la lumiere Download PDF

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Publication number
WO2006077813A1
WO2006077813A1 PCT/JP2006/300495 JP2006300495W WO2006077813A1 WO 2006077813 A1 WO2006077813 A1 WO 2006077813A1 JP 2006300495 W JP2006300495 W JP 2006300495W WO 2006077813 A1 WO2006077813 A1 WO 2006077813A1
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Prior art keywords
aromatic polycarbonate
polycarbonate resin
mass
resin composition
light
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PCT/JP2006/300495
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English (en)
Japanese (ja)
Inventor
Yasuhiko Nabeshima
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Mitsubishi Rayon Co., Ltd.
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Priority to JP2006553887A priority Critical patent/JP5285220B2/ja
Publication of WO2006077813A1 publication Critical patent/WO2006077813A1/fr

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Definitions

  • the present invention relates to an aromatic polycarbonate resin composition and a light diffusing molded article.
  • Molded products made of aromatic polycarbonate resins are excellent in transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc. It is used in a wide range of fields such as ⁇ equipment, optical parts, precision machinery, automobiles, security and medical care, building materials, and miscellaneous goods.
  • a light diffusible molded article made of a resin composition in which an aromatic polycarbonate resin is mixed with a light diffusing agent such as inorganic fine particles or polymer fine particles is more resistant to heat and heat than a light diffusible molded article made of acrylic resin.
  • light covers for electric lamp covers, meters, signboards (especially internal lighting), resin window glass, image reading devices or image display devices (for example, in backlight modules such as liquid crystal display devices).
  • Light diffusion plates used for projection display screens such as projector televisions
  • light diffusion films for example, high transmission light diffusion films used for improving the brightness of liquid crystal display devices, etc.
  • an aromatic polycarbonate resin composition used as a material of a light diffusive molded article a resin composition obtained by adding a light diffusing agent such as calcium carbonate, barium sulfate, silicon oxide, titanium oxide to an aromatic polycarbonate resin.
  • Patent Document 1 resin composition in which partially crosslinked polymer particles are added to an aromatic polycarbonate resin
  • Patent Document 2 resin composition in which partially crosslinked polymer particles are added to an aromatic polycarbonate resin
  • Patent Documents 3 and 4 A resin composition (Patent Documents 3 and 4) added to a group polycarbonate resin has been proposed.
  • the light diffusing molded products in particular, light diffusion plates used in image display devices and There is an increasing demand for light diffusing films that are larger, thinner (lighter), more complicated in shape, higher in performance, etc., and have an aromatic polycarbonate resin composition with excellent moldability (melt flowability). Is required ing.
  • the light diffusive molded article may be subjected to surface treatment such as mattness imparting by printing or the like, and improvement in chemical resistance is required.
  • the aromatic polycarbonate resin is usually amorphous, it has a problem that the molding process temperature is high, the melt fluidity is poor, and the chemical resistance is also poor.
  • Patent Document 8 For the purpose of further improving the melt fluidity of the aromatic polycarbonate resin composition, (4) a method of adding a polyester oligomer (for example, Patent Document 8), (5) a method of adding an oligomer of a polycarbonate (Patent Document 9). ), (6) A method of adding a low molecular weight styrene copolymer (for example, Patent Documents 10 to 12) has been proposed.
  • the melt fluidity is greatly improved, a decrease in molecular weight more than necessary impairs the heat resistance, chemical resistance, and impact resistance of a molded product made of an aromatic polycarbonate resin. Therefore, there is a limit to improving the melt fluidity of the aromatic polycarbonate resin composition by reducing the molecular weight of the aromatic polycarbonate resin while maintaining the excellent characteristics of the molded product.
  • the balance between the peel resistance of the molded article and the melt fluidity of the aromatic polycarbonate resin composition is still insufficient.
  • the method (2) is excellent in the melt flowability of the aromatic polycarbonate resin composition, but the compatibility is still inadequate, so that the surface of the molded product is peeled off and the appearance and mechanical properties are immediately observed. Greatly decreases.
  • the method (3) is excellent in the compatibility of the aromatic polycarbonate resin composition and the transparency of the molded article is good, but the effect of improving the melt fluidity of the aromatic polycarbonate resin composition is small.
  • the method (6) it is possible to improve the melt flowability of the aromatic polycarbonate resin composition while maintaining the heat resistance of the molded product to some extent by adding a small amount of low molecular weight styrene copolymer.
  • the compatibility is still insufficient.
  • the surface layer peels off immediately after the molded product, and this is accompanied by the problem that the impact strength, the weld appearance that is practically important, and the surface impact are not sufficient.
  • any of the conventional methods can improve the melt fluidity and chemical resistance of an aromatic polycarbonate resin-based composition that does not impair the excellent characteristics of a molded article made of the aromatic polycarbonate resin-based composition. It is still inadequate in terms of improvement.
  • Patent Document 1 Japanese Patent Publication No.57-24186
  • Patent Document 2 Japanese Patent Laid-Open No. 3-143950
  • Patent Document 3 Japanese Patent Laid-Open No. 10-17761
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-298710
  • Patent Document 5 Japanese Patent Publication No.59-42024
  • Patent Document 6 Japanese Patent Laid-Open No. 62-138514
  • Patent Document 7 Japanese Patent No. 2622152
  • Patent Document 8 Japanese Patent Publication No. 54_37977
  • Patent Document 9 Japanese Patent Laid-Open No. 3-24501
  • Patent Document 10 Japanese Patent Publication No. 52-784
  • Patent Document 11 JP-A-11-181197
  • Patent Document 12 Japanese Unexamined Patent Publication No. 2000-239477
  • the object of the present invention is to provide melt flowability (moldability) and resistance to the excellent properties (light diffusibility, heat resistance, impact resistance, dimensional stability, etc.) of the obtained light diffusible molded article.
  • Aromatic polycarbonate resin composition with improved chemical properties, and excellent light diffusion, heat resistance, impact resistance, dimensional stability, chemical resistance, etc., larger size, thinner (lighter), and more complicated shape Therefore, the object is to provide a light diffusive molded product capable of high performance.
  • the aromatic polycarbonate resin composition of the present invention is an aromatic polycarbonate resin.
  • R is a hydrogen atom or a methyl group, and R is a phenyl group which may have a substituent.
  • the light diffusing molded article of the present invention is formed by molding the aromatic polycarbonate resin composition of the present invention.
  • the aromatic polycarbonate resin composition of the present invention is a conventional composition that does not impair the excellent properties (light diffusibility, heat resistance, impact resistance, dimensional stability, etc.) of the obtained light diffusible molded article. Excellent melt flowability (formability) and chemical resistance compared to the above.
  • the light diffusive molded product of the present invention is excellent in light diffusibility, heat resistance, impact resistance, dimensional stability, chemical resistance, etc., and is large in size, thin (light weight), complicated in shape, high Performance is possible Is
  • the aromatic polycarbonate resin (A) is an aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic hydroxy compound with a carbonic acid diester such as diphenyl carbonate or phosgene.
  • the aromatic polycarbonate resin (A) may be branched. In the case of the branched aromatic polycarbonate resin (A), an aromatic dihydroxy compound and an aromatic polyhydroxy compound are used in combination as the aromatic hydroxy compound.
  • aromatic polyhydroxy compound for example, fluorodalcine, 4,6-dimethyl_2,4,6_tri (4-hydroxyphenyl) heptene_2,4,6_dimethinole 1,4,6 _Tri (4-hydroxyphenyl) heptane, 2, 6-dimethyl _ 2, 4, 6 _Tri (4-hydroxyphenylheptene_3, 1, 3, 5_tri (4-hydroxyphenyl) benzene, 1, 1, 1_tri (4-hydroxyphenyl) ethane, etc.
  • the amount of the aromatic polyhydroxy compound used to obtain the branched aromatic polycarbonate resin (A) is the aromatic dihydroxy compound. against (100 mole 0/0), preferably from 0.01 to 10 mol 0/0, more preferably from 0.1 to 2 mol 0/0.
  • a monovalent aromatic hydroxy compound or a monovalent aromatic hydroxy compound derivative such as its chromate formate is used for the purpose of adjusting the molecular weight of the aromatic polycarbonate resin (A), adjusting the end group, etc. May be.
  • Monovalent aromatic hydroxy compounds and their derivatives include: phenol, m cresol, p crezo monore, p propyl phenol, p-tert Examples thereof include alkylphenols such as butylphenol and p long-chain alkyl-substituted phenols, and derivatives thereof.
  • the amount of the monovalent aromatic hydroxy compounds and / or derivatives thereof, aromatic dihydroxy compound (100 mol%) is usually 0.:! ⁇ 10 mole 0/0, preferably:! ⁇ 8 mol 0/0.
  • the aromatic polycarbonate-based resin (A) has a dicarboxylic acid for the purpose of copolymerizing a polymer or oligomer having a siloxane structure for the purpose of enhancing flame retardancy or for improving the melt fluidity during molding.
  • a derivative such as dicarboxylic acid chloride may be copolymerized.
  • the molecular weight of the aromatic polycarbonate resin (A) is a viscosity average calculated from the solution viscosity measured at 25 ° C. using methylene chloride as a solvent.
  • an aromatic polycarbonate polymer alloy obtained by combining the aromatic polycarbonate resin (A) and another resin or elastomer described later may be used.
  • the aromatic polycarbonate resin composition does not impair the excellent transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc. inherent to the aromatic polycarbonate resin (A).
  • other resin or elastomer may be blended in the range of 50 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
  • Examples of other resins include polystyrene (PSt), styrene random copolymers (eg, talylonitrile styrene resin (AS resin)), alternating copolymers of styrene and maleic anhydride, and Daraff copolymers ( Acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile, ethylene propylene rubber, styrene resin (AES resin), acrylonitrile, acrylate, styrene resin (AAS resin, high impact polystyrene (HIPS), etc.) Resins: Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyesters of these copolymers, etc.
  • PSt polystyrene
  • AS resin talylonitrile styrene resin
  • AES resin acrylonitrile-butadiene-styrene resin
  • AES resin acryl
  • Polymethyl methacrylate (PMMA), methyl methacrylate Acrylic resin such as a copolymer having a monomer unit; Olefin resin such as polypropylene (PP), polyethylene (p E), ethylene- (meth) acrylic acid copolymer; Polyurethane; Silicone resin; Syndiotac Tick PS: Polyamides such as 6-nylon and 6, 6-nylon; Polyarylate; Polyphenylene sulfide; Polyetherketone; Polysulfone; Polyethersulfon polyamideimide; Polyacetal and various general-purpose resins or engineering plastics S.
  • Olefin resin such as polypropylene (PP), polyethylene (p E), ethylene- (meth) acrylic acid copolymer
  • Polyurethane Silicone resin
  • Syndiotac Tick PS Polyamides such as 6-nylon and 6, 6-nylon; Polyarylate; Polyphenylene sulfide; Polyetherketone; Polysulfone; Polyethersulfon
  • Elastomers include: isobutylene-isoprene rubber; polyester-based elastomer; styrene-butadiene rubber, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-one Styrene elastomers such as polyisoprene-polystyrene (SIS) and polystyrene-poly (ethylene-propylene) -polystyrene (SEPS); polyolefin-based elastomers such as ethylene-propylene rubber; polyamide-based elastomers; acrylic elastomers; Core shells typified by methyl methacrylate-butadiene styrene resin (MBS resin) and methyl methacrylate-acrylonitrile styrene resin (MAS
  • the fluidity improver (B) is an aromatic vinyl monomer (bl) 0.5 to 99.5 mass%, a monomer (b2) represented by the following formula (I) 0.5 to 99.5 % By weight and other monomers 3) 0 to 40% by weight of the monomer mixture [wherein the total of the monomers (bl) to (b3) is 100% by weight. ] Is a polymer obtained by polymerizing.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a phenyl group which may have a substituent.
  • the fluidity improver (B) is compatible with the aromatic polycarbonate resin (A) during melt molding.
  • compatibility affinity
  • aromatic polycarbonate resin (A) which exhibits a release behavior and in the operating temperature range of the light diffusive molded product, it has a good level of peel resistance.
  • the fluidity improver (B) includes the mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization, and the content of each monomer constituent unit in the polymer after polymerization. It is preferable that (mass%) matches.
  • the polymerization rate of the monomer mixture is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 97% by mass or more. Further preferred. If the polymerization rate is 90% by mass or more, the mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization and the content of each monomer constituent unit in the polymer after polymerization (Mass%) is almost the same. When the polymerization rate is less than 90% by mass, the mixing ratio (% by mass) of each monomer in the monomer mixture and the content (% by mass) of monomer constituent units contained in the polymer after polymerization. %) May be different.
  • aromatic butyl monomer (bl) examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-t butylstyrene, ⁇ -methoxystyrene, o-methoxystyrene, and 2,4 dimethylstyrene. Chlorostyrene, bromostyrene, butanolene, vinylnaphthalene, vinylanthracene and the like. These may be used alone or in combination of two or more. Of these, styrene, ⁇ -methylstyrene, and p t butylstyrene are preferable.
  • the content of the aromatic bul monomer (bl) is 0.5 to 99.5 mass% in the monomer mixture (100 mass%). If the content of the aromatic bur monomer (bl) is within this range, the fluidity improver (B) exhibits an excellent effect of improving melt fluidity and chemical resistance.
  • the compatibility with the aromatic polycarbonate resin (A) becomes insufficient, and as a result, the light diffusive molded product is delaminated. May damage the appearance and mechanical properties. If the content of the aromatic vinyl monomer (bl) is less than 0.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes too good, so that the phase separation behavior is fully exhibited during melting. It is not possible to improve the melt flowability, and the chemical resistance improvement effect tends to decrease.
  • the content of the aromatic bur monomer (bl) is preferably 98% by mass or less, and preferably 96% by mass or less. More preferred is 93% by mass or less, and further preferred is 90% by mass or less. Further, the content of aromatic bulle monomer (bl) is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more. preferable.
  • the monomer (b2) represented by the formula (I) includes (meth) acrylic acid phenyl, (meth) acrylic acid 4_t-butylphenyl, (meth) acrylic acid bromophenyl, (meth) acrylic acid dibromophenyl. And (meth) acrylic acid 2,4,6_tribromophenyl, (meth) monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. Of these, phenyl (meth) acrylate is particularly preferred.
  • “(meth) acrylic acid” means acrylic acid and Z or methacrylic acid.
  • the content of the monomer (b2) is 0.5 to 99.5 mass% in the monomer mixture (100 mass%).
  • the fluidity improver (B) exhibits an excellent effect of improving compatibility (peeling resistance).
  • the compatibility with the aromatic polycarbonate resin (A) becomes insufficient, and as a result, the light diffusion molded product causes delamination and the appearance. And may damage the mechanical properties. If the content of the monomer (b2) exceeds 99.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes too good, so that the phase separation behavior can be sufficiently exhibited during melting. However, the improvement effect of the chemical resistance tends to decrease while the improvement effect of the melt fluidity decreases.
  • the content of monomer (b2) is preferably 90% by mass or less, more preferably 80% by mass or less. 50% by mass or less is more preferred and 30% by mass or less is particularly preferred.
  • the content of the monomer (b2) is preferably 2% by mass or more, more preferably 4% by mass or more, more preferably 7% by mass or more, and further preferably 10% by mass or more.
  • the polymer constituting the fluidity improver (B) is copolymerized with the aromatic vinyl monomer (bl) and the monomer (b2) as necessary within the range not impairing the above-mentioned characteristics. Possible other simple Containing 0-40% by mass of (b3).
  • the other monomer (b3) is an ⁇ , unsaturated monomer.
  • Such monomers include (meth) methyl acrylate, (meth) acrylate ethyl, butyl (meth) acrylate, 2-ethylhexyl acrylate, lauryl (meth) acrylate, (meth) acrylic Such as stearyl acid, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, etc.
  • (Meth) acrylic acid alkyl ester (meth) acrylic acid, (meth) acrylic acid 2-hydroxyethyl, (meth) glycidyl acrylate, phthalic acid 2-methacryloyloxychetyl, (meth) acrylic alcohol, 1, (3)-(Meth) acrylic acid ester having reactive functional group such as petitylene dimethallylate; Maleic anhydride, N-phenylmaleimide, cyclohexylmaleimide, dibutenebenzene and the like. These may be used alone or in combination of two or more.
  • the content of the other monomer (b3) is 0 to 40% by mass in the monomer mixture (100% by mass). When the content of the monomer (b3) exceeds 40% by mass, the effect of improving the melt fluidity and chemical resistance of the aromatic polycarbonate resin composition tends to decrease.
  • the content of the other monomer (b3) is preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • the fluidity improver (B) Since the fluidity improver (B) is excellent in compatibility with the aromatic polycarbonate resin (A), the light diffusible molded article comprising the aromatic polycarbonate resin composition containing the flow improver (B) transmits all light. The rate is high.
  • the polymer constituting the fluidity improver (B) is a two-component system consisting of an aromatic vinyl monomer (bl) and a monomer (b2) represented by the formula (I). By making it within the specific range, the total light transmittance can be further increased.
  • Polymers that further increase the total light transmittance of the molded product include aromatic vinyl monomer (bl) 0.5 to 40% by mass, monomer (b2) 60 to 99.5% by mass, force, However, the total of (bl) and (b2) is 100% by mass.
  • the mass average molecular weight of the polymer constituting the fluidity improver (B) is preferably 5000 to 200,000.
  • the weight average molecular weight is less than 5,000, relatively low molecular weight substances are increased, which may reduce various properties such as heat resistance and rigidity. In addition, there is a possibility that problems such as smoke, mist, mechanical contamination, appearance defects of molded products such as fish eyes and syno levers during melt molding may increase. If a light diffusible molded article with good total light transmittance at high temperatures (light diffusible molded article with low haze temperature dependence) is required, the polymer should have a higher mass average molecular weight. Therefore, the mass average molecular weight of the polymer is preferably 10 000 or more, more preferably 15000 or more, more preferably 30000 or more, and more preferably 400000 or more.
  • the mass average molecular weight of the polymer exceeds 200,000, the melt viscosity of the aromatic polycarbonate resin composition becomes high, and there is a possibility that a sufficient effect of improving melt fluidity cannot be obtained. If you only want to improve chemical resistance, there is no particular problem even if the weight average molecular weight of the polymer exceeds 200,000. If a significant improvement in melt fluidity is required, the polymer should have a lower mass average molecular weight. Therefore, the weight average molecular weight of the polymer is preferably 170,000 or less, more preferably 150,000 or less, more preferably 120,000 or less, and even more preferably 100,000 or less.
  • the molecular weight distribution of the polymer constituting the fluidity improver (B), that is, the mass average molecular weight (Mw) / number average molecular weight (Mn) is preferably smaller.
  • the molecular weight distribution is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. If the molecular weight distribution exceeds 4.0, the melt viscosity of the aromatic polycarbonate resin composition also becomes high, and there is a possibility that sufficient effect of improving melt flowability cannot be obtained.
  • Examples of the method for producing the polymer constituting the fluidity improver (B) include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method and the like.
  • the suspension polymerization method and the emulsion polymerization method are preferable because the recovery method is easy.
  • residual salt in the polymer may cause thermal decomposition of the aromatic polycarbonate resin. Therefore, during emulsion polymerization, use a carboxylate emulsifier, etc., recover the polymer by acid precipitation coagulation, etc., or use a nonionic anionic emulsifier such as phosphate ester, etc.
  • the body is preferably recovered by salting out coagulation using a calcium acetate salt or the like.
  • the blending amount of the fluidity improver (B) may be appropriately determined according to the desired physical properties.
  • a fluidity improver ( The blending amount of B) is preferably 0.:! To 30 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A), other resin, and Z or elastomer. If the blending amount of the fluidity improver (B) is less than 0.1 parts by mass, sufficient melt fluidity and chemical resistance may not be improved.
  • Fluidity improver (B) is added in an amount of 2 parts by mass, preferably 1 part by mass or more with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resins and / or elastomers. More preferred is 3 parts by mass or more.
  • the blending amount of the fluidity improver (B) is preferably 25 parts by mass or less with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resins and / or elastomers. More preferred is 10 parts by mass or less.
  • the light diffusing agent (C) is fine particles having a light diffusing ability.
  • fine particles include inorganic fine particles and polymer fine particles.
  • Examples of the inorganic fine particles include glass filler, calcium carbonate, barium sulfate, silica, talc, my strength, wollastonite, titanium oxide and the like. Of these, calcium carbonate is preferred.
  • the shape of the inorganic fine particles is preferably granular (including irregular shapes) or plate-like, rather than fibrous.
  • a glass filler glass beads, glass balloons, glass milled fibers, glass flakes, ultrathin glass flakes (manufactured by the Zonole-gel method), amorphous glass and the like can be mentioned.
  • other inorganic fine particles having various shapes can be employed.
  • the inorganic fine particles may be surface-treated with various silicone compounds such as silane coupling agents and polyorganohydrogensiloxane compounds, fatty acid ester compounds, and olefin compounds. Surface-treated inorganic fine particles are effective in improving thermal stability and hydrolysis resistance.
  • the refractive index of the inorganic fine particles is preferably 1.4 to 1.8. If the refractive index of the inorganic fine particles is within this range, both the light diffusibility and the total light transmittance are good.
  • the refractive index of inorganic fine particles is known from various documents, and can be easily measured by a liquid immersion method or the like.
  • the polymer fine particles are more preferable as they have a shape close to a true spherical shape, which is preferable.
  • organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer; silicone-based crosslinked particles; amorphous heat-resistant polymer particles such as polyethersulfone particles; epoxy resin particles, urethane resin Examples thereof include particles, melamine resin particles, benzoguanamine resin particles, and phenol resin particles.
  • amorphous heat-resistant polymer particles the shape of the particles is not impaired when kneaded with the aromatic polycarbonate resin (A) while heating, and therefore a crosslinkable monomer is not necessarily required.
  • organic crosslinked particles are particularly preferred.
  • non-crosslinkable monomer used in the organic crosslinked particles examples include non-crosslinkable vinyl monomers such as acrylic monomers, styrene monomers, and acrylonitrile monomers; olefin monomers.
  • Acrylic monomers include methyl acrylate, ethyl acrylate, propylene acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid 2 — Ethylhexenoyl, phenyl methacrylate and the like. Of these, methyl methacrylate is particularly preferred.
  • styrenic monomer examples include alkylstyrene such as styrene, ⁇ -methylol styrene, methino styrene (vinyl styrene), ethyl styrene, and halogenated styrene such as brominated styrene. Of these, styrene is particularly preferred.
  • acrylonitrile monomers include acrylonitrile and methacrylonitrile.
  • olefin monomers include ethylene and various norbornene compounds.
  • organic crosslinked particles can also have units such as N-methyldaltalimide.
  • These monomers may be used alone or as a mixture of two or more.
  • crosslinkable monomer used in the organic crosslinked particles examples include dibutenebenzene, methacrylic acid allylic acid, triaryl cyanurate, triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meta).
  • Atalylate Propyleneglycolole (Meth) Atalylate, 1,6-Hexanediol Di (meth) Atalylate, Trimethylolpropane (Meth) Atalylate, Pentaerythritol Tetra (meth) Atalylate, Bisphenol A Di (Meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl di (meth) acrylate, N-methylol (meth) acrylamide and the like.
  • Examples of the method for producing organic crosslinked particles include emulsion polymerization, suspension polymerization, soap-free polymerization using an initiator such as potassium persulfate, seed polymerization, and two-stage swelling polymerization.
  • a suspension polymerization method a water phase and a monomer phase are maintained separately, and both are accurately supplied to a continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser;
  • a method in which the monomer phase is supplied by passing it through a small diameter orifice of several to several tens of ⁇ m or a porous filter in an aqueous liquid having dispersibility, and the particle size can be controlled.
  • the silicone-based crosslinked particles have a siloxane bond as a main skeleton and an organic substituent on a silicon atom, and those having a high degree of crosslinking typified by polymethylsilsesquioxane, and methylsilicone rubber particles Some of them have a low degree of crosslinking.
  • those having a high degree of crosslinking represented by polymethyl cinresesquioxane are preferred.
  • Examples of the organic substituent bonded to the silicon atom of the silicone-based crosslinked particles include alkyl groups such as a methyl group, an ethynole group, a propyl group, and a butyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; Group, carbonyl group, ester group, ether group and the like.
  • Examples of the method for producing silicone-based crosslinked particles include a method of forming three-dimensionally crosslinked particles while growing siloxane bonds by hydrolysis and condensation reaction of trifunctional alkoxysilanes in water.
  • the particle diameter of the silicone-based crosslinked particles can be controlled by the amount of alkali as a catalyst, stirring conditions, and the like.
  • polymer fine particle production methods include spray-drying, submerged curing (coagulation), phase separation (coacervation), solvent evaporation, and reprecipitation. Further, a nozzle vibration method or the like may be combined with these methods.
  • Examples of the structure of the polymer fine particle include a single-phase structure, a core-shell structure, and an IPN structure in which two or more components are intertwined with each other. Further, it may be a composite particle having an inorganic fine particle as a core and a component of an organic crosslinked particle as a shell, or a composite particle having an organic crosslinked particle as a core and an epoxy resin, urethane resin or the like as a shell.
  • the refractive index of the polymer fine particles is usually about 1.33 to: 1.7. When the refractive index of the polymer fine particles is within this range, a sufficient light diffusing function is exhibited in a state of being blended in the resin composition.
  • polymer fine particles are preferable to inorganic fine particles.
  • the polymer fine particles are generally less effective in improving the rigidity and dimensional stability of the molded product than the inorganic fine particles, but the aromatic polycarbonate resin composition of the present invention is combined with other components. As a result, the rigidity and dimensional stability of the molded product are improved, so that the polymer fine particles can be used without any problem.
  • the average particle size of the light diffusing agent (C) is preferably from 0.01 to 50 ⁇ m, more preferably from 0.1 to 10 ⁇ m, and more preferably from 0 to 8 ⁇ m. .
  • the average particle size is expressed as 50% (D50) of the cumulative distribution of particle sizes obtained by the laser light scattering method.
  • the light diffusing agent (C) is more preferably one having a distribution in which the particle size distribution is narrow and the fine particles in the range of the average particle size of ⁇ 2 xm that are preferred are 70% by mass or more of the total. .
  • the absolute value of the difference between the refractive index of the light diffusing agent (C) and the refractive index of the aromatic polycarbonate resin (A) is preferably 0.02 to 0.2. When the difference in refractive index is within this range, it is possible to achieve both light diffusibility and total light transmittance at a high level.
  • the refractive index of the light diffusing agent (C) is more preferably lower than the refractive index of the aromatic polycarbonate resin (A).
  • the blending amount of the light diffusing agent (C) is 0 with respect to a total of 100 parts by mass of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). :!
  • 0.3 to 20 parts by weight are more preferred 0.4 to 15 parts by weight are more preferred 0.5 to 10 parts by weight are particularly preferred. If the amount of the light diffusing agent (C) is within this range, a high light diffusing function is exhibited.
  • a flame retardant for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, etc.
  • a flame retardant for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, etc.
  • Brominated polyacrylates monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, organic sulfonic acid alkali metal salts, organic sulfonic acid alkaline earths Metal salts, silicone flame retardants, etc.), flame retardant aids (eg, sodium antimonate, antimony trioxide, etc.), anti-dripping agents (eg, polytetrafluoroethylene having fibril-forming ability), antioxidants (eg, hindered) Phenolic compounds, io antioxidants, etc.), UV absorbers, light stability , Mold release agent, lubricant, dye, antistatic agent, organic or organic antibacterial agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorber, photochromic simultaneous J, fluorescent whitening agent, etc. May be blended.
  • flame retardant aids eg, sodium antimonate, antimony
  • the aromatic polycarbonate resin composition of the present invention preferably contains a phosphorus-containing heat stabilizer.
  • Phosphorus esters such as trimethyl phosphate; triphenyl phosphite, trisnonyl phenyl phosphite, distearyl pentaerythritol norresiphosphite, bis (2,6 di-tert-butyl 4- Methylphenol) pentaerythritol diphosphite, tris (2,4-di-tert_butylphenol) phosphite, 2,2 methylenebis (4,6-di_tert_butylphenyl) octylphosphite, bis (2, 4-di-tert-butylphenol) Phenol erythritol diphosphite and other phosphite esters; Tetrakis (2,4_di-tert-butylphenyl) -1,4,4
  • the content of the phosphorus-containing heat stabilizer in the aromatic polycarbonate resin composition (100% by mass) is preferably from 0.00:! To 1% by mass, more preferably from 0.01 to 0.5% by mass. More preferably, 0.01 to 0.2% by mass is more preferable.
  • Phosphorus-containing thermal stability By blending the agent, the thermal stability of the aromatic polycarbonate resin composition is further improved, and good molding characteristics can be obtained.
  • Examples of the method for preparing the aromatic polycarbonate resin composition of the present invention include aromatic polycarbonate resin (A), fluidity improver (B), and light diffusing agent (C). Examples include a method of premixing the components, then melt-kneading and pelletizing
  • Examples of the apparatus used for the preliminary mixing include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer.
  • granulation may be performed by an extrusion granulator, a pre-ketting machine or the like.
  • melt kneading examples include melt kneaders such as a vent type twin screw extruder, a Banbury mixer, a kneading roll, and a constant-temperature stirring vessel. Of these, a multi-screw extruder such as a vented twin-screw extruder is preferred.
  • melt kneading As a method of melt kneading, (i) a method in which an aromatic polycarbonate resin (A), a fluidity improver (B) and a light diffusing agent (C) are simultaneously melt kneaded; (ii) an aromatic polycarbonate system A master batch in which a light diffusing agent (C) is added to a part of the resin (A) is prepared in advance, and this is supplied to the extruder together with the remaining aromatic polycarbonate resin (A) and the fluidity improver (B). And melt-kneading.
  • the method (ii) is carried out for the purpose of ensuring the measurement accuracy because the amount of the light diffusing agent (C) is small. Of these, the method (i) is preferred.
  • the aromatic polycarbonate resin composition of the present invention can be used for molding by injection molding, extrusion molding or the like. As a result, the fluidity during molding can be improved, and a molded product having high heat resistance, chemical resistance, transparency, and light diffusibility can be obtained.
  • the utility of applying the polycarbonate resin composition of the present invention is useful. Is big.
  • the light diffusing aromatic polycarbonate resin composition of the present invention is often used in molded products that require high optical properties, it can reduce the presence of foreign substances that impair optical properties. preferable.
  • raw materials with a small amount of foreign matter are used, and manufacturing equipment such as an extruder and pelletizer is installed in a clean air atmosphere, and cooling water for the cooling bath is also used with little foreign matter.
  • the raw material supply hopper, supply flow path, pellet storage tank, and the like are filled with clean air. For example, it is appropriate to adopt a method similar to the method proposed in Japanese Patent Laid-Open No. 11-21357.
  • the light diffusable molded article of the present invention can be obtained by melt-molding the aromatic polycarbonate resin composition of the present invention by a known melt molding method.
  • injection molding methods include injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including supercritical fluid injection), insert molding, and in-mold coating molding that can be performed only by ordinary injection molding methods. Insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, ultra-high speed injection molding, and the like. The advantages of these molding methods are already widely known.
  • the formation may be either a cold runner method or a hot runner method.
  • an extrusion molding method as the melt molding method, various modified extrusion molded articles, sheets, films and the like having a light diffusion function can be produced.
  • an inflation method, a calendar method, a casting method, and the like can be employed.
  • a heat-shrinkable tube can be produced by subjecting a sheet or film to a specific stretching treatment.
  • a hollow molded product can be manufactured by rotational molding, blow molding, or the like.
  • Examples of the light diffusing molded article of the present invention include a light diffusing plate, a light diffusing film, an electronic device, an OA device part, a vehicle part, a machine part, an agricultural material, a fishery material, a transport container, a packaging container, Goods are listed.
  • a light diffusing plate for an image display device a light diffusing plate used for a backlight module such as a liquid crystal display device, a light diffusing plate used for a screen of a projection display device such as a projector television
  • an image reading device Light diffusing plate, electric lamp cover, meter, signboard (especially internally lit), resin window glass, vehicle roofing material, ship roofing material, housing Residential roofing materials, solar cell covers and the like.
  • Various light sources can be used as backlight modules for liquid crystal display devices.
  • the aromatic polycarbonate resin composition of the present invention is particularly suitable for the production of a large and thin light diffusion plate (particularly a light diffusion plate for an image display device).
  • a light diffusing plate having a surface area of 500 to 50000 cm 2 is obtained.
  • the surface area of the light diffusion plate is preferably 1000 to 25000 cm 2 , and the preferred thickness is 0.3 to 3 mm.
  • the light diffusing plate may be a single-layer plate having a surface shape such as a Fresnel lens shape or a cylindrical lens shape, or another material having a surface shape such as a Fresnel lens shape or a cylindrical lens shape may be used as the light diffusing plate.
  • stacked on may be sufficient.
  • a single-layer plate having a surface shape such as a Fresnel lens shape or a cylindrical lens shape is formed by molding the aromatic polycarbonate resin composition of the present invention into a desired shape by an injection molding method, a compression molding method, an extrusion molding method, or the like. Can be manufactured.
  • a method for forming a Fresnel lens shape (uneven shape) on the surface, (i) a method of providing unevenness corresponding to the Fresnel lens shape on the mold cavity surface or transfer roll surface, and transferring the unevenness to the surface of the molded product; ) Insert another material with irregularities corresponding to the shape of the Fresnel lens into the mold cavity, or laminate it during extrusion to integrate the different material and the molded product, and then add the different material.
  • the method of removing and transferring unevenness on the surface of the molded product and the like.
  • a concavo-convex shape such as a Fresnel lens shape may be omitted by laminating a layer containing a bright pigment on the light diffusion plate.
  • the light diffusing plate for an image display device has various light reflection preventing films formed on its light source side surface (surface opposite to the observer) to prevent reflection of light from the light source. Also good.
  • the light diffusible molded article of the present invention is excellent in chemical resistance, it can be subjected to surface modification and, as a result, can be provided with other functions.
  • Surface modification means that the surface of a light diffusive molded product is newly applied by vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electric plating, electroless plating, melting plating, etc.), painting, coating, printing, etc. This means to provide a proper layer.
  • Examples of surface modification methods for providing a metal layer or metal oxide layer on the surface of a light diffusive molded article include vapor deposition methods (physical vapor deposition methods and chemical vapor deposition methods), thermal spraying methods, and plating methods.
  • Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating.
  • Examples of chemical vapor deposition (CVD) methods include thermal CVD, plasma CVD, and photo-CVD.
  • Examples of the thermal spraying method include an atmospheric pressure plasma spraying method and a low pressure plasma spraying method.
  • Examples of the plating method include an electroless plating method, a melting plating method, and an electrical plating method.
  • An example of the electric plating method is a laser plating method.
  • a metal oxide layer is provided on the surface of the light diffusible molded article, which is preferably an evaporation method or a plating method. Is preferably an evaporation method. Vapor deposition and plating may be used in combination. For example, it is possible to employ a method of performing electrical plating using a metal layer formed by vapor deposition.
  • part and % mean “part by mass” and “% by mass” unless otherwise specified.
  • anionic emulsifier (Latem Nore ASK", manufactured by Kao Corporation) (solid content 28./.) 1.0 part (solid content), 295 parts distilled water And heated to 80 ° C in a water bath under a nitrogen atmosphere.
  • a solution of 0.0001 part ferrous sulfate, 0.0003 part disodium ethylenediammine tetraacetate, and 0.3 part Rongalite in 5 parts distilled water was placed in a separable flask equipped with a condenser and a stirrer.
  • a polymer (flowability improver (B-2)) was obtained in the same manner as in Production Example 1 except that the amount of n-octyl mercaptan was changed from 0.5 part to 0.2 part (polymerization). The rate is 98%).
  • the mass average molecular weight (Mw) was 97000, and the molecular weight distribution (Mw / Mn) was 2.0.
  • a polymer (flowability improver (B 1) was prepared in the same manner as in Production Example 1, except that 20 parts of styrene, 80 parts of phenyl methacrylate, and the amount of n-octyl mercaptan were changed from 0.5 parts to 2 parts. 3)) was obtained (polymerization rate 99%).
  • the weight average molecular weight (Mw) was 27000, and the molecular weight distribution (Mw / Mn) was 1 ⁇ 9.
  • a separable flask equipped with a condenser and a stirrer was charged with 0.4 parts of calcium phosphate and 150 parts of distilled water, and then a mixture of 96 parts of styrene, 4 parts of ⁇ -butyl methacrylate and 1.2 parts of benzoyl peroxide was dissolved. After stirring and stirring for a while, nitrogen publishing was performed for 30 minutes. The mixture was stirred at 80 ° C for 4 hours under a nitrogen atmosphere, and further stirred at 90 ° C for 1 hour. The precipitate was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (flowability improver ( ⁇ ′4)) (polymerization rate was 97%).
  • the weight average molecular weight (Mw) was 150,000, and the molecular weight distribution (Mw / Mn) was 3.3.
  • Table 1 shows the charged amount (parts) of each component, polymerization mode, polymerization rate, mass average molecular weight (Mw), and molecular weight distribution (MwZMn) of the obtained polymer.
  • St is styrene
  • PhMA is phenyl methacrylate
  • BA is n-butyl acrylate
  • BPO is benzoyl peroxide.
  • the polymerization rate was calculated based on the mass conversion of the obtained polymer solid.
  • the mass average molecular weight (Mw) and the number average molecular weight (Mn) were measured by the GPC method (eluent: black mouth form).
  • PC1 Aromatic polycarbonate resin, I "Panlite L1225WSj, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 210,000.
  • PC2 Aromatic polycarbonate resin, “Panlite L1225ZLJ, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 18,000.
  • the fluidity improver and the aromatic polycarbonate resin were mixed in the formulation shown in Table 2 (100 parts in total), and the light diffusing agent (bead-shaped crosslinked silicone particles “Tospearl 120J, average particle diameter: 2 / xm, manufactured by GI Toshiba Silicone Co., Ltd.
  • the spiral flow length (SFL) of the aromatic polycarbonate resin composition was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
  • the molding temperature was 280 ° C
  • the mold temperature was 80 ° C
  • the injection pressure was 98 MPa.
  • the thickness of the molded product was 2 mm and the width was 15 mm.
  • the protruding pin trace of the light diffusive molded product obtained in (2) was cut with a cutter, and the peeled state was visually observed.
  • the evaluation criteria are as follows.
  • a light diffusive molded article with a thickness of 1Z4 inches was molded by an injection molding machine (“IS_100”, manufactured by Toshiba Machine Co., Ltd.).
  • the deflection temperature under load of the light diffusing molded article was measured in accordance with ASTM D648.
  • the annealing process was performed at 120 ° C for 1 hour, and the load was 1.82 MPa.
  • a backlight unit having a cold cathode tube force was placed on the lower side of the light diffusive molded product obtained in (5), and the light diffusible molded product was observed from the upper side to evaluate the light uniformity. Those with good uniformity were marked with ⁇ , and those with poor uniformity were marked with X.
  • the light diffusing aromatic polycarbonate resin composition obtained in Comparative Examples 2 and 3 did not contain a fluidity improver, and a sufficient balance between fluidity and chemical resistance could not be obtained.
  • PC3 Aromatic polycarbonate resin, “Panlite L1225LL”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 150,000.
  • C-1 Beaded cross-linked silicone particle "Tospearl 120", average particle size: 2 x m, manufactured by GI Toshiba Silicone Co., Ltd.
  • C1-2 Beaded crosslinked acrylic particle “MB30X-5”, average particle size: 5 x m, manufactured by Sekisui Plastics Co., Ltd.
  • Aromatic polycarbonate resin, fluidity improver, and light diffusing agent were mixed in the formulation shown in Table 3 (100 parts in total of aromatic polycarbonate resin and fluidity improver), and an ultraviolet absorber (" Tinuvin 329, manufactured by Ciba 'Specialty' Chemicals Co., Ltd.
  • antioxidant (“Ilganox 1076”, manufactured by Ciba 'Specialty' Chemicals Co., Ltd.) 0 ⁇ 1 part, heat stabilizer (Adeka Stub 2112, manufactured by Asahi Denka Kogyo Co., Ltd.) 0.1 part is added and supplied to a twin-screw extruder (model name “ ⁇ -35”, manufactured by Toshiba Machine Co., Ltd.) and melted at 280 ° C. The mixture was kneaded to obtain an aromatic polycarbonate resin composition.
  • the spiral flow length (SFL) of the aromatic polycarbonate resin composition was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
  • the molding temperature was 280 ° C
  • the mold temperature was 80 ° C
  • the injection pressure was 98 MPa.
  • the thickness of the molded product was 2 mm and the width was 15 mm.
  • the diffusivity of the light diffusing molded product obtained in (2) was measured at 23 ° C. according to DIN 5036.
  • the aromatic polycarbonate resin composition of the present invention has a melt flow that does not impair the excellent properties (light diffusibility, heat resistance, impact resistance, dimensional stability, etc.) of the resulting light diffusive molded article. (Formability) and chemical resistance are improved.
  • the light diffusive molded article comprising the aromatic polycarbonate resin composition of the present invention is excellent in light diffusibility, chemical resistance, etc., and is large-sized, thin (light weight), complicated in shape, high Light diffusion plates for image display devices that can be improved in performance and are particularly required to be large and thin (for example, light diffusion plates used in backlight modules such as liquid crystal display devices, projection televisions) Projection-type display devices such as light diffusing plates used for screens), high-performance light diffusing films surface-treated by printing, etc. (for example, high-transmission light used to improve the brightness of liquid crystal display devices, etc.) Suitable as a diffusion film).

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention décrit une composition de résine de polycarbonate aromatique ayant une meilleure fluidité à chaud (aptitude au moulage) et une meilleure résistance aux produits chimiques, sans détérioration des propriétés de diffusion de la lumière, résistance à la chaleur, résistance au choc, stabilité dimensionnelle et similaires d'un article moulé obtenu à partir de ladite composition. Un article diffusant la lumière est également décrit. L'invention décrit spécifiquement une composition de résine de polycarbonate aromatique contenant une résine de polycarbonate aromatique (A), un fluidifiant (B) [lequel est un polymère obtenu par polymérisation d'un mélange de monomères composé de 0,5 à 99,5 % en masse d'un monomère vinylique aromatique (b1), de 0,5 à 99,5 % en masse d'un monomère (b2) de formule (I) ci-dessous et de 0 à 40 % en masse d'un autre monomère (b3)] et un agent diffusant la lumière (C). L'invention décrit également un article diffusant de la lumière obtenu par moulage de ladite composition de résine de polycarbonate aromatique. Formule chimique 1 (I) (Dans la formule, R1 représente un atome d'hydrogène ou un groupe méthyle et R2 représente un groupe phényle éventuellement substitué.)
PCT/JP2006/300495 2005-01-19 2006-01-17 Composition de resine de polycarbonate aromatique et article diffusant la lumiere WO2006077813A1 (fr)

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US8202943B2 (en) * 2006-12-25 2012-06-19 Mitsubishi Rayon Co., Ltd. Fluidity-improving agent, aromatic polycarbonate resin composition, and shaped article thereof
JP2013091794A (ja) * 2008-03-21 2013-05-16 Cheil Industries Inc 相溶性が向上した熱可塑性樹脂組成物
US8642699B2 (en) 2008-03-11 2014-02-04 Mitsubishi Rayon Co., Ltd. Fluidity improver for aromatic polycarbonate resin, process for producing the fluidity improver for aromatic polycarbonate resin, aromatic polycarbonate resin composition, and molded product
WO2014024949A1 (fr) * 2012-08-06 2014-02-13 住友化学株式会社 Composition de résine, et procédé de fabrication ainsi que corps moulé de celle-ci
US8729205B2 (en) 2003-09-30 2014-05-20 Mitsubishi Rayon Co., Ltd. Flowability improver for engineering plastics, thermoplastic resin compositions containing the same and molded articles of the compositions
WO2018186002A1 (fr) * 2017-04-07 2018-10-11 ソニー株式会社 Composition de résine, son utilisation et son procédé de production
JP2021073363A (ja) * 2015-04-10 2021-05-13 中国石油化工股▲ふん▼有限公司 改善されたヘイズ度及び透光率を有する樹脂組成物及びその調製方法
CN114621531A (zh) * 2022-03-04 2022-06-14 成都金发科技新材料有限公司 一种具有泡孔结构的光学扩散板及其制备方法和应用

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US9272113B2 (en) 2012-03-30 2016-03-01 Carefusion 207, Inc. Transporting liquid in a respiratory component
CN111732823A (zh) * 2020-07-07 2020-10-02 佛山市德联邦盛光电科技股份有限公司 一种sebs增韧的扩散板
CN113352536B (zh) * 2021-06-16 2022-08-16 宁波浙铁大风化工有限公司 发泡光扩散材料及其制备方法

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US8729205B2 (en) 2003-09-30 2014-05-20 Mitsubishi Rayon Co., Ltd. Flowability improver for engineering plastics, thermoplastic resin compositions containing the same and molded articles of the compositions
US8202943B2 (en) * 2006-12-25 2012-06-19 Mitsubishi Rayon Co., Ltd. Fluidity-improving agent, aromatic polycarbonate resin composition, and shaped article thereof
JP5269585B2 (ja) * 2006-12-25 2013-08-21 三菱レイヨン株式会社 流動性向上剤、芳香族ポリカーボネート系樹脂組成物、及びその成形品
US8642699B2 (en) 2008-03-11 2014-02-04 Mitsubishi Rayon Co., Ltd. Fluidity improver for aromatic polycarbonate resin, process for producing the fluidity improver for aromatic polycarbonate resin, aromatic polycarbonate resin composition, and molded product
JP2013091794A (ja) * 2008-03-21 2013-05-16 Cheil Industries Inc 相溶性が向上した熱可塑性樹脂組成物
WO2014024949A1 (fr) * 2012-08-06 2014-02-13 住友化学株式会社 Composition de résine, et procédé de fabrication ainsi que corps moulé de celle-ci
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JP2021073363A (ja) * 2015-04-10 2021-05-13 中国石油化工股▲ふん▼有限公司 改善されたヘイズ度及び透光率を有する樹脂組成物及びその調製方法
WO2018186002A1 (fr) * 2017-04-07 2018-10-11 ソニー株式会社 Composition de résine, son utilisation et son procédé de production
JPWO2018186002A1 (ja) * 2017-04-07 2020-02-13 ソニー株式会社 樹脂組成物、及び樹脂組成物の製造方法
JP7060013B2 (ja) 2017-04-07 2022-04-26 ソニーグループ株式会社 樹脂組成物、及び樹脂組成物の製造方法
CN114621531A (zh) * 2022-03-04 2022-06-14 成都金发科技新材料有限公司 一种具有泡孔结构的光学扩散板及其制备方法和应用

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