WO2009123271A1 - 芳香族ポリカーボネート樹脂組成物およびその成形品 - Google Patents
芳香族ポリカーボネート樹脂組成物およびその成形品 Download PDFInfo
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- WO2009123271A1 WO2009123271A1 PCT/JP2009/056833 JP2009056833W WO2009123271A1 WO 2009123271 A1 WO2009123271 A1 WO 2009123271A1 JP 2009056833 W JP2009056833 W JP 2009056833W WO 2009123271 A1 WO2009123271 A1 WO 2009123271A1
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- IRWKRXQJWZXOFC-UHFFFAOYSA-H lanthanum(3+) hexafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[La+3].[La+3] IRWKRXQJWZXOFC-UHFFFAOYSA-H 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- SMIZARYCGYRDGF-UHFFFAOYSA-N phenyl dipropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC1=CC=CC=C1 SMIZARYCGYRDGF-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- FDGZUBKNYGBWHI-UHFFFAOYSA-N trioctadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC FDGZUBKNYGBWHI-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
-
- 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]
Definitions
- the present invention relates to a resin composition containing an aromatic polycarbonate resin and having heat ray shielding properties, and a molded product thereof. Specifically, the present invention relates to a resin composition that effectively shields heat rays from sunlight and gives a molded article having excellent transparency, and the molded article.
- Aromatic polycarbonate resins have excellent transparency, heat resistance and mechanical strength, and are widely used in electrical, mechanical, automotive and medical applications. For example, it is used for optical information recording media, optical lenses, and building glazing materials. So-called window materials such as glazing materials for buildings and vehicles are required to shield the heat rays from sunlight in order to suppress temperature rise in the room and in the car. In response to such a demand, a resin composition in which hexaboride particles are contained in an aromatic polycarbonate resin has been proposed.
- Patent Document 1 proposes a heat ray shielding sheet in which hexaboride fine particles are dispersed in an aromatic polycarbonate resin or acryl resin.
- Patent Document 2 proposes a resin sheet in which lanthanum boride fine particles having an average particle size of 10 Onm or less are dispersed in an aromatic polycarbonate resin.
- Patent Document 3 discloses a resin composition containing a boric fine particle and a low molecular compound having at least one functional group selected from a hydroxyl group and a carboxyl group in an aromatic polycarbonate resin, and a molded product thereof. Proposed.
- Patent Document 4 proposes a resin composition in which boride fine particles are combined with an aromatic polycarbonate resin having a terminal hydroxyl group concentration in the range of 100 to 1,800 ppm, and a molded product thereof.
- a melt extrusion method is generally used. Specifically, a master batch containing hexaboride particles and various additives was prepared. Then, the resin composition is prepared by melt-kneading the master batch and the aromatic polycarbonate resin. In general, mass batches are made by repeating the process of mixing hexaboride particles and various additives with an aromatic polycarbonate resin multiple times. However, depending on the production method of the masterbatch, there is a problem that the haze of the resin composition increases.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2003-327717
- Patent Document 2 JP 2005-47179 A
- Patent Document 3 (Patent Document 3) Special Table 2007-519804
- Patent Document 4 Japanese Unexamined Patent Publication No. 2006-307172
- An object of the present invention is to provide a resin composition that contains an aromatic polycarbonate resin, effectively shields heat rays from sunlight, and gives a molded product having excellent transparency, and a molded product thereof.
- Another object of the present invention is to provide a method for producing a resin composition in which hexaboride particles are uniformly dispersed.
- the present inventors dispersed hexaboride particles in a resin that is a dispersant, and then mixed with an aromatic polycarbonate resin to obtain a master batch having a predetermined concentration, and then mixed with an aromatic polycarbonate resin.
- a resin composition hexaboride particles (particles (1)) and particles composed of a dispersant and hexaboride particles (particles (2)) are formed, and these are adjusted to a predetermined particle diameter.
- the inventors have found that a resin composition that gives a molded article excellent in heat ray shielding and transparency can be obtained, and completed the present invention.
- the present invention includes the following inventions.
- Aromatic polycarbonate resin (component A), Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, and Ca Containing hexaboride particles (B-1 component) of at least one element selected from the group, and resins other than component A (B-2 component),
- the total content of B-1 component and B-2 component is 0.001-1 parts by weight with respect to 100 parts by weight of component A. It contains particles composed of B—1 component (1), and particles composed of B—1 component and B—2 component (2). Both particle (1) and particle (2) have a number average of 2 A resin composition having a secondary particle size of 50 m or less and a maximum secondary particle size of 300 m or less.
- B-1 component and B-2 component are mixed to prepare B component, and then obtained by mixing 100 parts by weight of A component and 0.001 to 1 part by weight of B component. Resin composition.
- the coating layer of hexaboride particles (B—one component) is mainly composed of a pre-coating film with a surface modifier formed on the surface of the hexaboride particles and an Si oxide formed thereon. 4.
- nitride particles are nitride particles of at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb and Ta. 1 1.
- a molded article comprising the resin composition as described in 1 above.
- FIG. 1 is a front schematic view [1 1 A] and a side view [1 1 B] of a molded article produced in the example.
- FIG. 2 is an EF-TEM photograph of the test piece obtained in Example 1. Explanation of symbols
- the aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting divalent phenol with a carbonate precursor.
- reaction method examples thereof include an interfacial polymerization method, a melt transesterification method, a solid phase ester exchange method of a carbonate precursor, and a ring-opening polymerization method of a cyclic carbonate compound.
- dihydric phenols used here include hydroquinone, resorcinol, 4, 4, monobiphenol, 1, 1-bis (4-hydroxyphenol) ethane, 2, 2-bis (4 —Hydroxyphenyl) Propane (commonly referred to as bisphenol A (hereinafter sometimes abbreviated as “BPA”)), 2, 2_bis (4-Hydroxymethyl-3-methylphenyl) propane, 2, 2-bis ( 4-hydroxyphenyl) butane, 1, 1 bis (4-hydroxyphenyl) — 1 monophenyl, 1, 1 bis (4-hydroxyphenyl) cyclohexane, 1, 1 bis (4 hydroxy Enyl) 1, 3, 3, 5-trimethylcyclohexane, 2, 2_bis (4-hydroxyphenyl) pentane, 4, 4 '-(p-phenylene diisopropylidene) diphenol, 4, 4, 1 ( m— Dienediol isopropylidene) diphenol, 1, 1 bis (4-hydroxyphenyl) -4
- the bisphenol A-based polycarbonate which is a general-purpose aromatic polycarbonate-bonbon
- BPM 4, 4 'one (m-phenol di-diisopropylidene) diphenol
- B is—TMC 1,1 bis (4- Hydroxyphenyl) cyclohexane
- TMC 1,1-bis (4-Hydroxyphenyl) —3,3,5-Trimethylcyclohexane
- BCF Aromatic polycarbonate using bis (4-hydroxy-1-methylphenol) fluorene
- divalent phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire divalent phenol component constituting the polycarbonate.
- the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
- BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the divalent phenol component constituting the aromatic polycarbonate
- BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
- 88 is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%).
- a BCF of 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
- 8 1 ⁇ is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%).
- These special aromatic polycarbonates may be used singly or as a mixture of two or more. These can also be used by mixing with the widely used bisphenol A type polycarbonate.
- an aromatic polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.113% and Tg of 120 to 180, or
- Tg is 160 to 25 Ot: preferably 170 to 230 X: and the water absorption rate is 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0. Aromatic polycarbonate that is 14-0.27%.
- the water absorption rate of the aromatic polycarbonate is the water content after being immersed in water at 23 according to IS ⁇ 62-1980 using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. It is a value obtained by measuring the rate.
- Tg glass transition temperature
- DSC differential scanning calorimetry
- carbonate precursor carbonyl halide, carbonic acid diester, haloformate or the like is used, and specifically, phosgene, diphenyl carbonate or dihaloformate of divalent phenol can be mentioned.
- Aromatic polycarbonate resin is a branched polycarbonate resin obtained by copolymerization of a polyfunctional compound having three or more functional groups, or a polyester carbonate obtained by copolymerization of an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Resins, copolymer polycarbonate resins copolymerized with bifunctional alcohols (including !! ring), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and bifunctional alcohols. Further, it may be a mixture in which two or more of the obtained aromatic polycarbonate resins are mixed.
- the branched polycarbonate resin is preferably used since it can further synergistically improve the drip prevention ability of the resin composition of the present invention.
- Trifunctional or higher polyfunctional aromatic compounds used in such branched polystrengthen ponate resins include fluorodalcine, fluorodalside, or 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl). Heptene 2, 2, 4, 6-trimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1, 3, 5-tris (4-hydroxyphenyl) benzene, 1, 1, 1 tris (4-hydroxy Phenyl) ethane, 1,1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-1-5-methylbenzyl) 1-4-methylphenol, 4- ⁇ 4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene ⁇ -, trisphenol such as ⁇ -dimethylbenzylphenol.
- Tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4 monobis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic Examples include acids, benzophenone tetracarboxylic acids, and acid chlorides thereof. Of these, 1,1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are particularly preferable, and 1,1,1-tris ( 4-Hydroxyphenyl) ethane is preferred.
- the ratio of the polyfunctional compound in the branched polycarbonate resin is from 0.001 to 1 mol%, preferably from 0.05 to 0.9 mol%, more preferably from 0.01 to 0.1 mol%, based on the total amount of the polycarbonate resin. It is ⁇ 0.8 mol%, particularly preferably 0.05 to 0.4 mol%.
- a branched structure may occur as a side reaction.
- the amount of the branched structure is also preferably within the above-mentioned range in the total amount of the polycarbonate resin. Such a branched structure amount can be calculated by 1 ⁇ ⁇ ⁇ - ⁇ R measurement.
- the aliphatic bifunctional carboxylic acid is preferably ⁇ , ⁇ -dicarboxylic acid.
- aliphatic bifunctional carboxylic acids include linear saturated fats such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid.
- Preferred are aliphatic dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
- an alicyclic diol is more preferable, and examples thereof include cyclohexane dimethanol, cyclohexane diol, and tricyclodecane dimethanol. Furthermore, it is possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units.
- Reaction formats such as interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, which are methods for producing aromatic polycarbonate resin, are various literatures and patents. This is a well-known method in gazettes. Details of other reaction formats are well known in various documents and patent publications.
- the viscosity-average molecular weight of aromatic polycarbonate resin (M) is preferably 1 X 1 0 4 ⁇ 5 X 1 0 4, more preferably 1. a 4 X 10 4 ⁇ 3 X 10 4 , preferably La Is between 1.4 X 1 0 4 and 2.4 X 1 0 4 .
- Aromatic polycarbonate resins with a viscosity average molecular weight of less than 1 X 10 4 may not provide the impact resistance expected in practical use, etc. Inferior.
- a resin composition obtained from an aromatic polyester-poneed resin having a viscosity average molecular weight exceeding 5 ⁇ 10 4 is inferior in versatility in that it has poor fluidity during injection molding.
- the viscosity average molecular weight is obtained from a solution in which a specific viscosity (r? SP ) calculated by the following formula is 20 and 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride using a host viscometer,
- the shape of the aromatic polycarbonate resin is not particularly limited, but the aromatic polycarbonate resin powder is preferable in terms of improving the dispersibility of the hexaboride particles and nitride particles with respect to the aromatic polycarbonate resin.
- the particle size distribution of the aromatic polycarbonate resin powder is not particularly limited, but the content of powder with a particle size of 7 10; m or more with respect to the whole powder is 50% by weight or less, more preferably 40% by weight. %, And the content of powder with a particle diameter of less than 180 jm with respect to the whole powder is preferably 0 to 40% by weight, more preferably 10 to 30% by weight.
- the aromatic polycarbonate resin powder and hexaboride particles or nitride particles are produced in the process of producing the resin composition of the present invention.
- classification and the like easily occur between the hexaboride particles and nitride particles in the resin composition, and secondary aggregation easily occurs.
- high transparency and heat ray absorption performance depending on the blending amount of hexaboride particles and nitride particles may not be obtained.
- the particle size distribution of the aromatic polystrength resin resin powder referred to in the present invention is as follows. First, 200 g of the aromatic polycarbonate resin powder is placed in a stainless steel JIS standard sieve (22 mesh, mesh size 7 10 m). Cover the top and make 100 round trips (1 round trip distance is 40 cm, 1 round trip time is 1 second), then measure the mass of powder remaining on the standard sieve, Calculate the percentage of the mass of the powder and use it as the content of powder with a particle size of 7 10 m or more.
- 2 2 mesh standard Put the powder dropped from the sieve into a JIS standard sieve (83 mesh, mesh opening 180 m), cover the top and reciprocate 100 times, and then measure the mass of the powder remaining on the standard sieve.
- the B-1 component of the present invention includes Y (yttrium), La (lanthanum), Ce (cerium), Pr (prasedium), Nd (neodymium), Sm (samarium), Eu (plutonium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), Lu (lutetium), Sr (strontium) and Ca It is a hexaboride particle of at least one element selected from the group consisting of (calcium).
- the resin composition of the present invention contains particles (1) composed of B-1 component.
- the number average secondary particle diameter of the particles (1) is 50 zm or less, preferably 20 Aim or less, more preferably 5 / im or less, and most preferably 1 / ⁇ m or less.
- the maximum secondary particle size of the particles (1) is 300 / m or less, preferably 100 // m or less, more preferably 50 zm or less, and most preferably 20 // m or less. If the number average secondary particle size is larger than 50 m, or if the maximum secondary particle size is larger than 300 // m, not only will the haze increase, the transparency will decrease, but for example a vehicle window. When viewed as a product, it is recognized as a foreign object and may not be a product.
- the number average secondary particle size and the maximum secondary particle size are measured by the following method. In other words, after binarizing the image observed with a laser microscope or video microscope, the number average secondary particle size and the maximum secondary particle size are measured using particle size distribution analysis software. The number of measurements shall be 1,000.
- hexaboride particles La, Ce, Nd, and Gd are preferable, La and Ce are more preferable, and La is particularly preferable.
- the hexaboride particles have a particle size of 2 n m to l 0 nm is preferable, and 5 to 90 nm is particularly preferable.
- KHD S-06 manufactured by Sumitomo Metal Mining Co., Ltd. is commercially available and easily available. It is desirable that the hexaboride particles (B-1 component) have a coating layer on the surface.
- the coating layer is preferably composed mainly of a metal oxide.
- the coating layer is mainly composed of an oxide of at least one metal selected from the group consisting of Si, Ti, A1, and Zr.
- a coating layer mainly containing an Si oxide is most preferable.
- the ratio of Si to oxide hexaboride is more preferably in the range of 0.001 to 100 parts by weight per 1 part by weight of hexaboride fine particles in terms of Si contained in the key oxide. Is in the range of 0.1 to 10 parts by weight. This is because if the ratio of the key oxide compound is less than 0.01 part by weight, it is difficult to form a secondary coating film, whereas if it exceeds 100 parts by weight, aggregation between particles occurs.
- the thickness of the coating film is preferably 1 to 100 nm, more preferably 5 to 90 nm, and still more preferably 10 to 80 nm.
- the coating layer is formed by dispersing the hexaboride particles in a solvent, adding a surface treatment agent containing a metal oxide to the solvent, mixing it, and allowing it to react by chemical reaction or by physical coating. can do.
- a coating layer containing Si as a main component has a silazane-based treatment agent, a chlorosilane-based treatment agent, an inorganic-type treatment agent having an alkoxy group in the molecular structure, and an amino group-containing alkoxysilane that can be expected to improve water repellency. It is formed by a surface treatment agent containing a key, such as an organic treatment agent having a terminal or side chain and an organic treatment agent having an alkoxy group at the molecular end or side chain.
- the solvent used include organic solvents such as water and alcohol, or a mixture of water and an organic solvent.
- the coating layer consists of a pre-coating film with a surface modifier formed on the surface of hexaboride particles (B-1 component), and a coating mainly composed of an Si oxide formed thereon. More preferably, it consists of a film. That is, it is preferable to form a preliminary coating film on the surface of the hexaboride particles in advance with a surface modifier such as a silane coupling agent, and then form a coating film mainly composed of an Si oxide. .
- B-1 component content is preferably 100 parts by weight of resin (B-2 component) Is 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, still more preferably 7 to 20 parts by weight.
- the B-2 component is a resin other than the aromatic polycarbonate resin (component A).
- the B 1-2 component is preferably a resin having a polar functional group and a main chain having an affinity for the aromatic polycarbonate resin (A component).
- the functional group include an amino group, a strong lpoxyl group, a sulfonyl group, and a salt thereof.
- the functional group is not particularly limited as long as the functional group has an affinity for the coated hexaboride particles.
- Examples of B-2 components include acrylic resins, polyurethane resins, polyether resins, and polyester resins. Among these, acrylic resin power is particularly preferable.
- the acrylic resin include those obtained by polymerizing methyl methacrylate, methyl butyl methacrylate, cyclohexyl methacrylate, and the like by a known polymerization method, force prolacton-modified carboxyl (meth) acrylate, (Meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, jetylaminopropyl ( Examples thereof include those obtained by polymerizing monomers such as (meth) acrylate, 2-hydroxydimethylaminopropyl (meth) acrylate, aminoethyl (meth) acrylate and the like by a known polymer
- Polyether dispersants such as DIS PARLO NDA325, as well as trade names manufactured by Avecia, So 1 sperse 22000, Sol sperse 24000SC, So ls pe rse 24000 GR, So ls pe rse 26000, So ls pe rse 27000 So ls pe rse 28000, So ls pe rse 3 6000, So ls pe rse 36600, Solsperse 38500, and Enomoto Kasei's trade names DIS PARLONDA70350, DI SPARL ONDA705, DIS PARLONDA725, DIS PARLONDA86 0, DIS PARLONDA873 N Examples thereof include polyester dispersants, and among them, polyacrylate dispersants are preferable.
- the resin composition of the present invention contains particles (2) composed of B-1 component and B-2 component.
- the number average secondary particle size of the particles (2) is 50 m or less, preferably 20; um or less, more preferably 5 m or less, and most preferably 1 / m or less.
- the maximum secondary particle diameter of the particles (2) is 300 zm or less, preferably 100 m or less, more preferably 50 m or less, and most preferably 20 / zm or less.
- the number average secondary particle size of particles (2) is greater than 50 zm, or if the maximum secondary particle size is greater than 300 / im, not only will the haze increase and transparency will decrease, but for example vehicles When viewed as a product such as a window, it may not be a product because it is recognized as a foreign object.
- the number average secondary particle size and the maximum secondary particle size are measured by the same method as for particles (1).
- the ratio of particles (1) to particles (2) in the resin composition of the present invention is such that the ratio of particles (1) / particles (2) is preferably 3/7 to 7Z3, more preferably 4-6. ⁇ 6 4.
- the B-1 component is separated from the B component, so that particles (1) and particles (2) are contained in the resin composition of the present invention. Will be.
- the resin composition of the present invention preferably contains 0.1 to 50 parts by weight of nitride particles with respect to 100 parts by weight of the resin (B-2 component).
- the nitride particles are preferably nitride particles of at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, and Ta.
- the total content of the B-1 component and the B-2 component is 0.001 to: 100 parts by weight of the aromatic polycarbonate resin (component A)! Parts by weight, more preferably from 0.01 to 0.5 parts by weight, still more preferably from 0.05 to 0.3 parts by weight.
- the resin composition of the present invention is prepared by mixing B-1 component and B-2 component to prepare B component, and then adding 100 parts by weight of A component and 0.001 to 1 part by weight of B component. It is preferable that the resin composition is obtained by mixing.
- the resin composition of the present invention may contain a heat stabilizer (C component).
- a heat stabilizer is preferably a hindered phenol stabilizer.
- the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
- the phosphite compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphate, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphate, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di) — Tert _Butyl-4 monomethylphenyl) Pen Yueri!
- Rudiphosphite 2,2-methylenebis (4,6 di-tert-butylphenyl) octylphosphite, bis (nonylphenyl) Pen Yueri! ⁇ One Ruj Phosphite, Bis (2,4-ji tert-butylphenyl) Pen Yueri 1 Rudiphosphite and distearyl pen erythritol diphosphite.
- phosphate compound examples include tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmonoxoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, and disopropyl phosphate.
- Phosphonite compounds include tetrakis (2,4-di-iso-propylphenyl) 1,4,4'-biphenyl di-range phosphonai ⁇ , terakis (2,4-di-n-butylphenyl) —4, 4 '—bihue Dirange Phosphonite, Tetrakis (2, 4-ji tert-butyl phenyl) 1, 4, 4 'Bibi Dirange Phosphonite, Tetrakis (2, 4-di- tert-butyl phenyl) —4, 3' — Biphenyl Dirange Phospho Knight, Tetrakis (2,4-di-tert-butylphenyl) V) 1,3'-biphenyl diphosphonate, Tetrakis (2,6-di-iso-propyl phenyl) 1,4,4-biphenyl Phosphonite, Tetrakis (2, 6-di-n-butylpheny
- Examples of the phosphonate compound include dimethyl benzenephosphonate, jetyl benzenephosphonate, and dipropyl benzenephosphonate.
- the content of the heat stabilizer (component C) is preferably 0.005 to 5 parts by weight, more preferably 0.008 to 2 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin (component A). More preferably, the content is 0.01 to 0.5 parts by weight.
- the resin composition of the present invention may contain a release agent (component D).
- a release agent component D
- Known release agents can be used.
- the D component has the properties of a plasticizer, and the addition of the D component to the resin composition of the present invention has the effect of improving the dispersibility of the B component.
- the content of the release agent (D component) is preferably 0.005 to 5 parts by weight, more preferably 0.008 to 2 parts by weight, more preferably 100 parts by weight of the aromatic polycarbonate resin (component A).
- the amount is preferably 0.01 to 0.5 parts by weight, most preferably 0.08 to 0.5 parts by weight.
- the resin composition of the present invention may contain an ultraviolet absorber (E component).
- ultraviolet absorbers include benzophenone compounds, benzotriazol compounds, hydroxyphenyl triazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers.
- the benzotriazole compounds include 2- (2H-benzotriazole-2yl) —p-cresol, 2- (2H-benzotriazole-2-yl) 1-4 1 (1, 1, 3, 3-tetramethylbutyl) phenol, 2- (2H-benzotriazole-2-yl) —4, 6-bis (1 methyl _ 1 monophenyl) phenol, 2— [5— Black mouth (2H) —Benzotriazole— 2—yl] —4 monomethyl-6— tert-butylphenol, and 2,2′-methylenebis [6-(2 H—benzotriazol roux 2 _il) —4— ( (1, 1, 3, 3-tetramethylbutyl) phenol] and the like are preferable examples.
- hydroxyphenyltriazine compound 2- (4,6-diphenyl-1,3,5-triazine1-2-yl) 15-[(hexyl) oxy] phenol is preferably exemplified.
- Preferred examples of the cyclic imino ester compound include 2,2′-p-phenylenebis (3,1 benzoxazine 4-1one).
- cyanoacrylate compounds examples include 1,3-bis [(2-cyanol-3,3-diphenylacryloyl) oxy] -1,2-bis [[(2-cyanol-3,3-diphenylacryloyl) oxy [Methyl] propane is a preferred example.
- the UV absorber should have the structure of a monomer compound capable of radical polymerization.
- a polymer type ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and a monomer such as alkyl (meth) acrylate may be used.
- Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. .
- a more preferable ultraviolet absorber includes a cyclic imino ester compound.
- a relatively high molecular weight results in better heat resistance.
- 2— (4, 6-diphenyl-1,2,5, triazine, 1-2 yl), 1-5 — [(hexyl) oxy] phenol
- 1 3-bis [(2-Cyanol-3,3-diphenylacryloyl) oxy] -1,2-bis [[(2-Cyanol-3,3-diphenylacryloyl) oxy] methyl] propane
- UV absorber (component E) is aromatic polycarbonate resin (component A).
- Preferably it is 0.005-5 parts by weight, more preferably 0.
- the amount is from 1 to 3 parts by weight, more preferably from 0.5 to 0.5 parts by weight.
- the resin composition of the present invention can contain various conventionally known additives as required.
- additives include antioxidants, light stabilizers, colorants, sliding agents, light diffusing agents, fluorescent whitening agents, antistatic agents, flame retardants, flame retardant aids, plasticizers, and reinforcing fillers.
- impact modifiers include impact modifiers, photocatalytic antifouling agents, and photochromic agents.
- a hindered phenol compound is preferably exemplified.
- the content of these antioxidants is preferably 0.005 to 5 parts by weight, more preferably 0.01 to I parts by weight per 100 parts by weight of the aromatic polycarbonate resin (component A).
- the content of these light stabilizers is preferably from 0.01 to 5 parts by weight, more preferably from 0.05 to 1 part by weight, per 100 parts by weight of the aromatic polycarbonate resin (component A).
- the resin composition of the present invention can be blended with a colorant as required, but is not particularly limited as long as it can be colored.
- the pigments include carbon black, titanium oxide, copper phthalocyanine, barium sulfate, and bisbenzoxazolyl stilbene.
- Optical brighteners such as conductors, bisbenzoxazolyl-naphthalene derivatives, bisbenzoxazolyl-thiophene derivatives, and coumarin derivatives can be used.
- the content of these dyes and fluorescent brighteners is aromatic polycarbonate resin 1
- Per 00 parts by weight From 0.000 to 1 part: I parts by weight are preferred, and from 000 to 0.5 parts by weight are more preferred.
- the resin composition of this invention can be manufactured by each process of a process (i), a process (ii), and a process (iiii).
- Step (i) is a step of preparing B component by mixing hexaboride particles (B-1 component) and resin other than A component (B-2 component).
- the B-1 component is preferably used in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, and even more preferably 7 to 20 parts by weight with respect to 100 parts by weight of the B-2 component.
- the B component is preferably prepared by mixing and dispersing the B-1 and B-2 components in a solvent and then drying to evaporate the solvent.
- Step (i i) is a step in which an aromatic polycarbonate resin (component A) and a component B are mixed to prepare a mass batch.
- the amount of component B is preferably 0.1 to 20 parts by weight, more preferably 1 to 12 parts by weight, and still more preferably 3 to 12 parts by weight with respect to 100 parts by weight of component A.
- the dispersibility of the particles (1) and the particles (2) is improved in the step (iii) by setting the amount of the B component in the mass batch to the above range.
- the particles The number average secondary particle size of (1) and particles (2) can be 50 / im or less, and the maximum secondary particle size can be 300 m or less.
- Mixing is performed by premixing with a V-type blender, Henschel mixer, mechanochemical equipment, extrusion blender, etc., then melt-kneaded with an extruder represented by a Ben-type twin screw ruder, and pelletized by a pelletizer or other equipment. Is preferable. After the premixing, it may be granulated by an extrusion granulator or a pre-ketting machine. , ⁇
- one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used.
- a vacuum pump is preferably installed to efficiently discharge generated moisture and volatile gas to the outside of the extruder.
- a screen for removing foreign substances mixed in the extrusion raw material in the zone in front of the extruder die and remove the foreign substances from the resin composition. Examples of such screens include wire meshes, screen changers, and sintered metal plates (such as disk fills).
- the extruder in addition to a twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, a multi-screw extruder having three or more axes, and the like can be used.
- the resin extruded as described above is directly cut into pellets, or after forming a strand, the strand is cut with a pelletizer and pelletized.
- the shape of the obtained pellet can be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder.
- the diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm.
- the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.
- the obtained master batch may be further mixed with component A to prepare a secondary mass batch.
- the amount of component A is preferably 1 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to the master batch.
- the obtained secondary master batch may be further mixed with component A to prepare a tertiary master batch.
- the amount of component A is preferably 1 to 100 parts by weight, more preferably 10 to 5 parts by weight with respect to the master batch.
- Step (i i i) is a step of obtaining a resin composition by mixing the master batch obtained in step (i i) and component A. Mixing can be performed in the same manner as in step (i ⁇ .
- the molded article of the present invention can be obtained by injection molding a pellet made of the resin composition of the present invention.
- injection molding not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including supercritical fluid injection method), insert molding, in-mold coating molding, heat insulation gold Examples include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, laminate molding, and ultra-high speed injection molding.
- a cold runner method or a hot runner method can be selected for molding.
- the resin composition can be extruded and formed into various shaped extruded products, sheets, films and the like.
- the inflation method, the calendar method, and the casting method can also be used.
- it can be formed as a heat-shrinkable tube by applying a specific stretching operation.
- the resin composition of the present invention can be formed into a molded body by rotational molding or single mouth molding. These molding processes are described in detail in, for example, Japanese Patent Application Laid-Open No. 2 0 205-1 795 5 4.
- the molded product of the present invention has a thickness of 2 to 50 mm, preferably 4 to 30 mm, and a maximum projected area of 400 to 23, 000 cm 2 , preferably 60 to 0 to 1. It is preferably 8, 0 0 0 cm 2 .
- the molded product can be used as a living space or a vehicle window.
- the molded article of the present invention can be provided with various functional layers including a hard coat layer on the surface thereof. Among these, it is preferable to provide a hard coat layer from the viewpoint of improving the scratch resistance and weather resistance of the surface of the molded product.
- Other functional layers include: design layer, conductive layer (heat generation layer, electromagnetic wave absorption layer, antistatic layer), water / oil repellent layer, hydrophilic layer, ultraviolet absorption layer, infrared absorption layer, crack prevention layer, and metal layer (Metalizing layer) and the like are exemplified.
- These functional layers are the surface of the hard coat layer, the surface of the molded product opposite to the hard coat layer, between the molded product layer and the molded product layer when there are multiple molded product layers, the primer layer and the molded product surface. And a part between the primer layer and the top layer of the hard coat.
- the pattern layer is usually formed by printing.
- conventionally known printing methods such as gravure printing, flat plate printing, flexographic printing, dry offset printing, pad printing, and screen printing can be used according to the product shape and printing application.
- the formation method and characteristics of the hard coat layer are described in detail in, for example, Japanese Patent Application Laid-Open No. 2 0 0 5-1 795 5 4, Japanese Patent Application Laid-Open No. 2 0 0 6-2 5 5 9 28, and the like It has been.
- the composition of the printing ink used in printing can be resin-based and oil-based as the main component.
- resin-based natural resins such as rosin, gilsonite, shellac, copal, and phenolic and their Derivatives, Amino resins, Pyrylated urea, Melamine resins, Polyester alkyd resins, Styrene resins, Acrylic resins, Phenolic resins, Epoxy resins, Polyamide resins, Aromatic polycarbonate resins, Saturated polyester resins, Amorphous poly resins
- Use synthetic resins such as arylate resin, amorphous polyolefin resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, petital resin, methyl cellulose resin, ethyl cellulose resin, urethane resin, etc.
- a printing ink having an aromatic polycarbonate resin and an amorphous polyarylate resin as a binder is preferably exemplified. Moreover, it can be adjusted to a desired color by using a pigment or a dye on the printing ink.
- the obtained molded body was evaluated by the following method.
- HA ZE (%) of a test piece having a thickness of 18 mm, a length of 55 mm, and a width of 55 mm was measured with HR-1100 manufactured by Murakami Color Research Laboratory.
- test piece having a thickness of 18 mm, a length of 55 mm and a width of 55 mm was observed with a laser microscope (VK9700, manufactured by Kiens Corporation), and the number average secondary particle size and the maximum secondary particle size were measured. The number of measurements was 1,000.
- test piece having a thickness of 18 mm, a length of 55 mm and a width of 55 mm was visually observed and evaluated according to the following criteria.
- Pellets were produced according to the following steps U) to (i i i).
- Lanthanum hexaboride particles with an average particle size of 8 Onm (manufactured by Sumitomo Metal Mining Co., Ltd .: KHD S-06) 8 parts by weight of aminopropyltrie, a silane coupling agent Toxisilane was mixed with 0.5 parts by weight and 392 parts by weight of water, and surface modification was performed by adsorbing aminoaminopropyltriethoxysilane on the surface of the lanthanum hexaboride particles.
- titanium nitride particles with an average particle size of 80 nm manufactured by Sumitomo Metal Mining Co., Ltd.
- 75 parts by weight of toluene, acrylic resin dispersant (B-2, 2 components, EFKA) 5% by weight was added to the dispersion, and a dispersion of titanium nitride particles was obtained (liquid (ii)).
- (i) liquid and (i ⁇ liquid were mixed with a weight ratio of lanthanum hexaboride and titanium nitride particles in the coated lanthanum hexaboride particles of 8: 2 (coated lanthanum hexaboride particles and titanium nitride). The mixture was mixed so that the weight ratio of the particles became 95: 5), after which the toluene was removed with a centrifuge and dried to obtain a particle-containing resin (component B).
- the obtained 5 parts by weight of the secondary masterbatch and 95 parts by weight of PC (component A) were supplied to the extruder.
- the extruder used was a vent type twin-screw extruder with a screw diameter of 77 ⁇ (manufactured by Nippon Steel Works: TEX77CHT (completely meshed, rotating in the same direction, double thread screw)).
- the extruder has a kneading zone composed of a combination of a needing disk for feeding and a needing disk for reverse feeding in the order of LZD about 8 to 11 as viewed from the screw root, and thereafter an LZD force S of about 16 It had a kneading zone consisting of a feeding kneading disk in the portion ⁇ 17. Furthermore, the extruder had a reverse-fed full flight zone with an LZD of 0.5 length immediately after the latter kneading zone. One vent port was provided in the LZD section of 18.5-20.
- the extrusion conditions were a discharge rate of 320 kgZh, a screw rotation speed of 160 rpm, and a vent vacuum of 3 kPa.
- the extrusion temperature was a temperature configuration in which the temperature gradually increased from the first supply port 230 to the die portion 280.
- the strand extruded from the die was cooled in a hot water bath, cut and pelletized by a pelletizer.
- the pellets immediately after being cut passed through the vibrating screen for about 10 seconds, and long pellets and cut waste that were insufficiently cut were removed.
- Molding is cylinder temperature 275, hot runner set temperature 275, mold temperature is fixed side 115, movable side 120t :, press stroke: 0.5mm, mold moving speed from intermediate mold clamping state to final mold clamping state 0.02 mm // sec, and pressurization holding time: 600 sec.
- the pressure at the time of compression was 25 MPa, and the pressure was maintained for the holding time of pressurization.
- the injection speed was 5 mm, second in the area until filling the gate, and 16 mm / second in the subsequent areas.
- the movable mold parting surface was not in contact with the fixed mold parting surface in the final forward position.
- the runner was a valve gate type hot runner manufactured by HOT SYS (diameter 8mm (.
- the mold compression was started immediately before filling was completed, and the overlap was 0.5 seconds.
- the valve gate was turned on.
- the tan 0 representing the amount of tilt and the amount of twist is maintained at about 0.00000025 or less by this four-axis parallel control mechanism. It was.
- the obtained molded product was taken out and allowed to cool for 60 minutes.
- the molded product was green with high transparency.
- the center part of the molded product indicated by the oblique lines in FIG. 1 was cut out to be 55 mm long ⁇ 55 mm wide to obtain a test piece.
- Table 1 shows the results of evaluating the test pieces obtained by the method (I I) above.
- Figure 2 shows an EF-TEM photograph of the test piece (electron transmission type transmission electron microscope, magnification: 25,000 times).
- the white part is the resin (B-2 component)
- the black dots are the covered lanthanum hexaboride particles (B-1 component)
- the particles (1) consisting only of the B-1 component
- B-1 the particles (1) consisting only of the B-1 component
- step (ii) 0.09 part by weight of PC (component A) and particle-containing resin (component B) 0.01 part by weight are uniformly mixed in Superflow evening, and 0.1 part by weight of master batch. was prepared.
- step (ii-1) 0.1 parts by weight of mass batch, 4.45 parts by weight of PC (component A), 0.02 parts by weight of 3100-8, 0.03 parts by weight of PEP Q, 0.10 parts by weight of VPG and 0.30 parts by weight of UV 1577 were uniformly mixed in a tumbler to obtain 5 parts by weight of a secondary masterbatch for feeding to the extruder. Except for the above steps, pellets were produced in the same manner as in Example 1. Thereafter, the same molding as in Example 1 was performed to prepare a test piece. Table 1 shows the results of evaluating the test pieces obtained. Comparative Example 1
- step (ii) 0.04 parts by weight of PC (component A) and particle-containing resin (component B) 0.01 parts by weight are uniformly mixed in a super flow to prepare a mass ratio. did.
- step (ii-1) 0.05 parts by weight of the mass batch and 0.23 parts by weight of PC (component A) were uniformly mixed in a V-type renderer, and 0.28 parts by weight of the secondary A mass evening batch was prepared.
- Example 2 0.28 parts by weight of the secondary masterbatch, 4.27 parts by weight of O, 0.02 parts by weight of S 100A, 0.03 parts by weight of PEPQ, 0.10 parts by weight of VPG and 0.30 parts by weight of A pellet was produced in the same manner as in Example 1 except that UV1577 was uniformly mixed with a tumbler to obtain 5 parts by weight of a tertiary masterbatch for feeding to the extruder. Thereafter, the same molding as in Example 1 was performed to prepare a test piece. The results of evaluating the test pieces obtained are shown in Table 1. Comparative Example 2
- step (ii) only 0.28 parts by weight of PC (component A) was uniformly mixed in a super flow overnight to prepare 0.29 parts by weight of a master batch.
- Example 3 A pellet raw material was produced in the same manner as in Example 1 except for the above steps. Then the example The same molding as 1 was performed to create a test piece of resin plate. The results of evaluating the test pieces obtained are shown in Table 1. Comparative Example 3
- step (ii) 41 parts by weight of PC and particle-containing resin (component B) 1.5 parts by weight were uniformly mixed in a super flow to prepare 42.5 parts by weight of a master batch.
- Example 1 Pellets were produced in the same manner as in Example 1 except for the above steps. Thereafter, the same molding as in Example 1 was performed to prepare a test piece. The results of evaluating the test pieces obtained are shown in Table 1.
- PC Aromatic polycarbonate resin powder with viscosity average molecular weight of 23,700 produced from bisphenol A and phosgene by interfacial polycondensation method (manufactured by Teijin Chemicals Ltd .: Panlite L 1 1250WP (trade name))
- VPG Full ester of pen erythritol and aliphatic carboxylic acid (based on stearic acid and palmitic acid) (manufactured by Cognis Japan KK: Roxyol V P G 861)
- PEPQ Phosphonite-based heat stabilizer (Sando z: Sands evening P—EP Q)
- the hexaboride particles are uniformly dispersed in the resin composition of the present invention, the heat rays from sunlight are effectively shielded and excellent in transparency.
- the molded article of the present invention is excellent in heat ray shielding and transparency. According to the method for producing a resin composition of the present invention, it is possible to produce a resin composition in which hexaboride particles are uniformly dispersed and excellent in shielding properties and transparency.
- the molded article of the present invention can be used as a living space or a vehicle window.
Abstract
Description
Claims
Priority Applications (5)
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EP09727251.2A EP2261287B1 (en) | 2008-03-31 | 2009-03-26 | Aromatic polycarbonate resin composition and molded article thereof |
BRPI0909396-6A BRPI0909396B1 (pt) | 2008-03-31 | 2009-03-26 | Composição de resina, artigo moldado, e, método para produzir a composição de resina |
JP2010505979A JP5371957B2 (ja) | 2008-03-31 | 2009-03-26 | 芳香族ポリカーボネート樹脂組成物およびその成形品 |
CN2009801072409A CN101959958B (zh) | 2008-03-31 | 2009-03-26 | 芳香族聚碳酸酯树脂组合物及其成型品 |
US12/935,422 US8415410B2 (en) | 2008-03-31 | 2009-03-26 | Aromatic polycarbonate resin composition and a molded article thereof |
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JP (1) | JP5371957B2 (ja) |
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CN (1) | CN101959958B (ja) |
BR (1) | BRPI0909396B1 (ja) |
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WO2011102494A1 (ja) * | 2010-02-16 | 2011-08-25 | 帝人化成株式会社 | ポリカーボネート樹脂組成物およびそれからなる成形品 |
CN112375363A (zh) * | 2020-11-06 | 2021-02-19 | 金发科技股份有限公司 | 一种玻纤增强的聚碳酸酯组合物及其制备方法和应用 |
CN112375362A (zh) * | 2020-11-06 | 2021-02-19 | 金发科技股份有限公司 | 一种pcabs组合物及其制备方法和应用 |
CN112457645A (zh) * | 2020-11-06 | 2021-03-09 | 金发科技股份有限公司 | 一种聚碳酸酯合金组合物及其制备方法和应用 |
CN112480625A (zh) * | 2020-11-06 | 2021-03-12 | 金发科技股份有限公司 | 一种聚酯合金组合物及其制备方法和应用 |
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KR101532071B1 (ko) * | 2013-09-24 | 2015-06-26 | 롯데케미칼 주식회사 | 광 차단이 개선된 폴리카보네이트 수지 조성물 및 수지 성형품 |
JP6727483B2 (ja) | 2014-10-08 | 2020-07-22 | コンシューマー ライティング (ユー.エス.),エルエルシー | 照明装置のカラーフィルター用材料および光学部品 |
BR112017013679A2 (pt) | 2015-01-06 | 2018-03-13 | GE Lighting Solutions, LLC | guia de luz, componente óptico e unidade de iluminação |
EP3541621B1 (de) * | 2016-11-17 | 2020-10-07 | Covestro Intellectual Property GmbH & Co. KG | Transparenter mehrschichtkörper zum wärmemanagement |
CN110621725A (zh) * | 2017-05-24 | 2019-12-27 | 三菱瓦斯化学株式会社 | 由碳纤维强化热塑性树脂构成的片材和该片材的制造方法 |
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Cited By (9)
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WO2011102494A1 (ja) * | 2010-02-16 | 2011-08-25 | 帝人化成株式会社 | ポリカーボネート樹脂組成物およびそれからなる成形品 |
JP2011168636A (ja) * | 2010-02-16 | 2011-09-01 | Teijin Chem Ltd | ポリカーボネート樹脂組成物及びそれからなる成形品 |
CN102762662A (zh) * | 2010-02-16 | 2012-10-31 | 帝人化成株式会社 | 聚碳酸酯树脂组合物以及由其构成的成型品 |
EP2537898A4 (en) * | 2010-02-16 | 2015-10-21 | Teijin Chemicals Ltd | POLYCARBONATE RESIN COMPOSITION AND MOLDED ARTICLE COMPRISING THE SAME |
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CN112375362A (zh) * | 2020-11-06 | 2021-02-19 | 金发科技股份有限公司 | 一种pcabs组合物及其制备方法和应用 |
CN112457645A (zh) * | 2020-11-06 | 2021-03-09 | 金发科技股份有限公司 | 一种聚碳酸酯合金组合物及其制备方法和应用 |
CN112480625A (zh) * | 2020-11-06 | 2021-03-12 | 金发科技股份有限公司 | 一种聚酯合金组合物及其制备方法和应用 |
CN112375362B (zh) * | 2020-11-06 | 2022-03-22 | 金发科技股份有限公司 | 一种pc/abs组合物及其制备方法和应用 |
Also Published As
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BRPI0909396A2 (pt) | 2015-12-22 |
EP2261287A4 (en) | 2015-09-16 |
TW200948893A (en) | 2009-12-01 |
JP5371957B2 (ja) | 2013-12-18 |
EP2261287A1 (en) | 2010-12-15 |
CN101959958B (zh) | 2013-05-08 |
EP2261287B1 (en) | 2021-01-27 |
KR20100125241A (ko) | 2010-11-30 |
JPWO2009123271A1 (ja) | 2011-07-28 |
CN101959958A (zh) | 2011-01-26 |
BRPI0909396B1 (pt) | 2019-07-09 |
TWI452087B (zh) | 2014-09-11 |
RU2467038C2 (ru) | 2012-11-20 |
US20110028601A1 (en) | 2011-02-03 |
KR101600105B1 (ko) | 2016-03-04 |
RU2010144538A (ru) | 2012-05-10 |
US8415410B2 (en) | 2013-04-09 |
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