CN100365441C - Light reflector made of terephthialic acid butanediol ester, and its mfg. method - Google Patents
Light reflector made of terephthialic acid butanediol ester, and its mfg. method Download PDFInfo
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- CN100365441C CN100365441C CNB2004100078271A CN200410007827A CN100365441C CN 100365441 C CN100365441 C CN 100365441C CN B2004100078271 A CNB2004100078271 A CN B2004100078271A CN 200410007827 A CN200410007827 A CN 200410007827A CN 100365441 C CN100365441 C CN 100365441C
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- optical system
- reflective optical
- polybutylene terephthalate
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- reflective
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- -1 butanediol ester Chemical class 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002253 acid Substances 0.000 title description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 21
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 21
- 239000011256 inorganic filler Substances 0.000 claims abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000011164 primary particle Substances 0.000 claims abstract description 9
- 230000003287 optical effect Effects 0.000 claims description 55
- 239000000835 fiber Substances 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- 235000012222 talc Nutrition 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 6
- 239000011342 resin composition Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 241001597008 Nomeidae Species 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000008301 phosphite esters Chemical class 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229940075507 glyceryl monostearate Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 229960005082 etohexadiol Drugs 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XDILCINHTMZTGG-UHFFFAOYSA-N 3-(3-dodecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical class CCCCCCCCCCCCOC(=O)CCSCCC(O)=O XDILCINHTMZTGG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011157 data evaluation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Abstract
Provided is a method for manufacturing a light reflector made of polybutylene terephthalate resin which has extremely high surface gloss of a molded product and little production of gas so that a light reflecting metal layer can be directly formed on the molded product without applying a primer coat such as undercoat onto the molded product and which has not only high mirror surface property/high luminance appearance but excellent adhesiveness with the metal layer/heat resistance. The reflector is obtained by molding a resin composition containing: (A) 100 pts. wt. of polybutylene terephthalate resin; (B) 5 to 80 pts. wt. of polyethylene terephthalate resin; (C) 0.05 to 2.0 pts. wt. of polyglycerin stearate; (D) 2 to 50 pts. wt. of non-fibrous inorganic filler having <=5 [mu]m average primary particle size; and (E) 0.1 to 3.0 pts. wt. of an antioxidant. Then a light reflecting metal layer is formed on at least a part of the molded product.
Description
Technical field
The present invention relates to the manufacture method of the reflective optical system that polybutylene terephthalate makes, and the reflective optical system that obtains with this method.More specifically, the present invention relates to the manufacture method of the reflective optical system that polybutylene terephthalate makes, the surface gloss of the mechanograph of making according to this method is very high, and suppressing gas produces, thereby in continuously moulding, obtain outward appearance excellence, goods that turbidity is little, thereby can directly form reflective metal layer in molded article surface, and do not need any undercoat; The invention still further relates to the reflective optical system that polybutylene terephthalate is made, this reverberator not only guarantees high gloss, also guarantee to keep excellent appearance (thermotolerance) when at high temperature using, and excellent and cohesive metal level.
Resin-based reflective optical system of the present invention is preferably used for the parts around the lamp in auto industry, building measurement instrument industry and the various industrial circle.Particularly, this reverberator is preferably used for requiring reverberator, extension around the auto lamp of high surface gloss, high surface flatness and the high optical reflection degree parts that grade.
Background technology
Up to now, to being used for the reverberator that the auto lamp extension grades, aspect high gloss, high smooth degree, uniform reflectance and high-fire resistance, adopted the crystallization thermoplastic vibrin, especially independent polybutylene terephthalate, or the material that obtains of the blending of the potpourri by various reinforcing agents and polybutylene terephthalate and polyethylene terephthalate; After mechanograph carried out pre-service (primary coat),, form reflective metal layer, thereby obtain the reflective optical system of target in molded article surface by technology such as the vacuum vapor deposition technology.
Yet,, therefore require to obtain even without any the high gloss reflective optical system of undercoat because primary coat sharply increases cost.In order to make the reverberator that forms the reflective metal layer of no undercoat at least one surface of mechanograph have high gloss and uniform reflectance, resin formed article itself must have excellent surface smoothness and high gloss.In addition, the thermotolerance of resin sees it also is a major issue from its applicable cases.
As the resin material that is used for this purpose, the applicant has proposed a kind of composition that comprises the polybutylene terephthalate of polyethylene terephthalate and non-fibrous inorganic filler in JP-A 2000-35509.In this resin material, some effective measures shows on the surface smoothness and glossiness as above-mentioned purpose.Yet according to research subsequently, therefore some deficiency of image sharpness when high temperature is used down requires further to improve.In lamp part, except that above-mentioned performance, also require at camera lens or the optical haze that do not produce on glass.
Therefore, need a kind of reflective optical system of exploitation, even this reflective optical system no any undercoat ground directly during the vapour deposition reflective metal layer on resin formed article, also have excellent glossiness, high reflectance and excellent metal adhesion, even and at high temperature use and also can have the thermotolerance that keeps these performances.
Summary of the invention
In order to address the above problem, the inventor furthers investigate, and can directly form the method for reflective metal layer to small part polybutylene terephthalate mechanograph to provide a kind of, and the reflective optical system with high gloss is provided.The inventor finds as a result, when adopting when comprising the mechanograph that the resin combination of polybutylene terephthalate, polyethylene terephthalate, specific inorganic filler and polyglycereol stearate obtains, can form and obtain to have excellent fusible metal level by mold pressing.The present invention finishes based on this discovery.
More specifically, the present invention is the manufacture method of the reflective optical system made of polybutylene terephthalate, comprise and to comprise the non-fiber inorganic filler that (A) 100 weight portion polybutylene terephthalates, (B) 5-80 weight portion polyethylene terephthalate, (C) 0.05-2.0 weight portion polyglycereol stearate, (D) 2-50 weight portion primary particle size are no more than 5 μ m, (E) resin combination of 0.1-3.0 weight portion antioxidant is molded in the mechanograph, and is directly forming reflective metal layer to the small part mechanograph.
Embodiment
Below detailed description is used for the constituent of resin combination of the present invention.
At first, as the polybutylene terephthalate (A) of the base resin of the resin combination of the present invention polybutylene terephthalate that to be the derivant that can form ester by for example terephthalic acid (TPA) or its obtain with the polycondensation reaction of the aklylene glycol with 4 carbon atoms or its derivant that can form ester.In addition, polybutylene terephthalate can be the multipolymer that contains 70% (weight) or more polybutylene terephthalate itself.
For copolymerisable monomer, other dicarboxylic acid components except that terephthalic acid (TPA) and its low-carbon-ester can comprise that aliphatic polyprotonic acid, aromatics polyprotonic acid or its can form the derivant of ester, for example isophthalic acid, naphthalene dicarboxylic acids, hexane diacid, decanedioic acid, 1,2,4-benzenetricarboxylic acid and succinic acid.In addition, remove 1, other outer glycol component of 4-butylene glycol can comprise such as ethylene glycol, diglycol, propylene glycol, trimethylene glycol, 1 aklylene glycol commonly used of 6-hexanediol, neopentyl glycol and cyclohexanedimethanol; Such as 1, the low-grade alkylidene glycol of 3-ethohexadiol; Such as bisphenol-A and 4, the aromatic alcohol of 4 '-dihydroxybiphenyl; Such as the epoxyalkane of epoxypropane (3mol) adduct of oxirane (2mo1) adduct of bisphenol-A and bisphenol-A and the adduct of alcohol; With can form the derivant of ester such as the polyol of glycerine and pentaerythrite or its.In the present invention, by all can be used as composition of the present invention (A) as any polybutylene terephthalate of the polycondensation reaction manufacturing of monomer component with above-claimed cpd.Although they can use separately or use with its two or more potpourri, preferably adopt polybutylene terephthalate.In addition, also can adopt the branched polymer that belongs to multipolymer.Term used herein " polybutylene terephthalate branched polymer " refers to mainly be made of polybutylene terephthalate or mutual-phenenyl two acid bromide two alcohol ester's monomer, and by adding the so-called polyester that polyfunctional compound's branching forms.The adoptable polyfunctional compound of this paper comprises 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, their alcohol ester, glycerine, trimethylolethane, trimethylolpropane and pentaerythrite.
Be used for polybutylene terephthalate of the present invention and have the 40meq/kg of being not more than, the terminal carboxyl group content of preferred 30meq/kg, the powdery sample of this content by the polybutylene terephthalate that will make with above-mentioned monomer polycondensation reaction be dissolving 10 minutes in benzylalcohol under 215 ℃, measures with the method for this solution of 0.01N sodium hydrate aqueous solution titration then.
When the terminal carboxyl group content of this polybutylene terephthalate surpassed 40meq/kg, the gained mechanograph had tangible optical haze, and therefore this content is not preferred.
In the present composition, add polyethylene terephthalate (B) then.
This polyethylene terephthalate (B) is by adding in the polybutylene terephthalate (A), with the basis of the surface flatness that improves gained mechanograph and reflective metal layer, glossiness etc.Polyethylene terephthalate has the crystallization rate lower than polybutylene terephthalate.Therefore, when adding this polyethylene terephthalate, it plays the effect of the Model Transfer performance of improving resin combination.It also has inhibition that reflective optical system is placed owing to light or the hot high temperature surface smoothness of following time that produces or the effect of glossiness variation, distortion etc.From above-mentioned 2, polyethylene terephthalate is the basis that is used to obtain excellent light reflection appearance product among the present invention.
The polyethylene terephthalate that is used for this purpose polymkeric substance that to be the derivant that can form ester by terephthalic acid (TPA) or its obtain with the polycondensation reaction of the aklylene glycol with 2 carbon atoms or its derivant that can form ester maybe can be to contain 70% (weight) or the multipolymer of poly ethylene glycol terephthalate itself more.
For copolymerisable monomer, other dicarboxylic acid components except that terephthalic acid (TPA) and low-carbon-ester thereof can comprise that aliphatic polyprotonic acid, aromatics polyprotonic acid or its can form the derivant of ester, for example isophthalic acid, naphthalene dicarboxylic acids, hexane diacid, decanedioic acid, 1,2,4-benzenetricarboxylic acid and succinic acid.In addition, other glycol component except that ethylene glycol can comprise such as diglycol, propylene glycol, trimethylene glycol, 1, the aklylene glycol commonly used of 6-hexanediol, neopentyl glycol and cyclohexanedimethanol; Such as 1, the low-grade alkylidene glycol of 3-ethohexadiol; Such as the epoxyalkane of epoxypropane (3mol) adduct of oxirane (2mol) adduct of bisphenol-A and bisphenol-A and the adduct of alcohol; With can form the derivant of ester such as the polyol of glycerine and pentaerythrite or its.
As being used for polyethylene terephthalate of the present invention, preferably adopt unmodified polyethylene terephthalate.Yet,, also can obtain to have the excellent surface flatness and the reflective optical system of high gloss even adopt the pet copolymer of isophthalic acid modification.It is desirable to adopt the pet copolymer of preferred 5-40mol% isophthalic acid modification this moment.
In addition, from flowability or appearance, be used for the limiting viscosity [η] that polyethylene terephthalate of the present invention preferably has 0.5-1.0.
In addition, the addition of polyethylene terephthalate (B) is counted the 5-80 weight portion with 100 weight portion compositions (A), preferably the 20-50 weight portion.
When addition too hour, can not obtain preferred Model Transfer performance, thereby can not obtain reflective optical system with high gloss and excellent surface smoothness as the object of the invention.When addition is too big, not only can produce such as prolonging molding cycle or problem during the molding of demolding performace variation, also, cause undesirably variation of glossiness and surface smoothness aspect because the gas of generation brings open defect.
Add the polyglycereol stearate then in the present invention, polyglycereol stearic acid partial ester preferably is as composition (C).This composition and all is very important obtaining to have on the mechanograph of good appearance continuously not only on the demolding performace that improves between shaping period.That is to say, when adding this composition, it extrude and shaping period between play the effect of internal lubricant when carrying out the fusion kneading, suppressing the decomposition of resin between melting stage, thereby might obtain to reduce the mechanograph of the outward appearance excellence of the optical haze that causes owing to gas bonding etc. continuously.
In addition, from flowability or appearance, be used for polyglycereol stearate of the present invention and preferably have the number-average molecular weight of 400-1600.This is especially effective for the optics generator being placed high temperature following time suppress to ooze out to wait, thereby even at high temperature use for a long time, also can prevent on the reflective optical system generation optical haze etc.
The addition of polyglycereol stearate (C) is counted the 0.05-0.2 weight portion with 100 weight portion compositions (A).When addition too hour, extrude with processing and forming during can improve the shearing force of resin, can cause resin decomposition etc., therefore be difficult to obtain continuously the product of outward appearance excellence.When addition is too big, depend on working temperature, disagreeable optical haze or ooze out and to become serious.
As mentioned above, in the present invention, when adding polyethylene terephthalate (B) in polybutylene terephthalate (A), and when further adding polyglycereol stearate (C), the polybutylene terephthalate composition molded articles that is obtained has excellent outward appearance.Therefore, even directly form reflective metal layer on molded article surface, mechanograph also has high gloss and excellent light reflective surface.
In addition, in the present invention, add the non-fiber inorganic filler (D) that primary particle size is no more than 5 μ m, so that further give uniform glossiness and thermotolerance.Non-fiber inorganic filler used herein is specifically restriction not, as long as it has and is no more than 5 μ m, the primary particle size of preferred 0.04-5 μ m gets final product.Preferably be selected from one or more of talcum, mica, clay, porcelain earth, wollastonite, glass microballoon, glass flake and zinc sulphide.Especially preferred be selected from talcum, clay and kaolinic one or more.
The addition of non-fiber inorganic filler is counted the 2-50 weight portion with 100 weight portion polybutylene terephthalates (A), preferred 5-25 weight portion.When the addition of non-fiber inorganic filler during less than 2 weight portions, thermotolerance is just not enough, because rigidity not enough surface tension just takes place easily, ripples etc., therefore this addition is not preferred.When addition surpassed 50 weight portions, just very difficult such as the operation of extruding, the outward appearance of inorganic filler became outstanding on the gained molded article surface.Therefore, be difficult to obtain uniform light reflective surface.
Then, in the present invention, further add antioxidant as composition (E), to improve the thermal stability of resin combination between shaping period that constitutes reflective optical system, and suppress because from the resin combination deposits yields outward appearance and the glossiness variation that cause of the gas that under continuously shaped situation, produces, low molecular weight compositions, the influence of oozing out etc. particularly.Specifically, the antioxidant that preferably comprises one or both or the multiple combination that are selected from hindered phenol, thioether and organic phosphite.The adding of these compositions helps improving the melt thermal stability during the extruding or in block press, therefore not only reduce because of surperficial optical haze by the bonding generation of gas, can be used for obtaining continuously the mechanograph of outward appearance and surface smoothness excellence, and because place hot conditions following time when reflective optical system, be suppressed by the decomposition product of resin generation or the generation of gas, be particularly useful for the outward appearance and the surface smoothness that keep excellent.
The instantiation of antioxidant used herein comprises that { methylene-3-(3 such as four, 5-di-t-butyl 4-hydroxy phenyl) propionic ester } methane, triethylene glycol two { 3-(the 3-tert-butyl group-5-methyl 4-hydroxy phenyl) propionic ester }, with 1, the hindered phenol of 6-hexanediol-two { 3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester }; Thioether such as four { methylene-3-(dodecyl sulfo-) propionic ester } methane, myristyl thiodipropionate and two dodecyl thiodipropionates; And such as two (2,6-two-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4-two-tert-butyl-phenyl) pentaerythritol diphosphites, four (2,4-two-tert-butyl-phenyl)-4, the organophosphite of 4 '-xenyl phosphite ester and three (2,4-two-tert-butyl-phenyl) phosphite ester.Special the combining of hindered phenol and thioether, the hindered phenol of effectively adopting combines with organophosphite, and the combination of these three kinds of antioxidants.What in addition, can preferably replace organophosphite series antioxidant is metal phosphate.Its instantiation comprises the monohydrate of V 90 and monobasic sodium phosphate.
The addition of used antioxidant (E) is counted the 0.1-3.0 weight portion with 100 weight portion polybutylene terephthalates (A).When addition too hour, the raising of gained resin thermal stability is just not enough, in the time of at high temperature, will produce open defect between shaping period, and because generation gas causes surperficial optical haze, and surface smoothness and glossiness variation.When addition is too big, can produces gas in the antioxidant (especially end group) of reflective optical system when high temperature uses down, thereby cause producing disagreeable optical haze.
In the present invention, the preferable methods of making reflective optical system is to form metal film or the metal level with bright luster by being used for plating method (PVD method) on the resin formed article surface, thereby forms the method for reflective metal layer.In addition, do the plating method and preferably include the vacuum vapor deposition technology, wherein particularly preferably be and be evacuated down to 1 * 10
-2Pa or lower, preferred 2 * 10
-3After Pa or the lower initial vacuum, with the evaporation rate vapor deposited metal of 0.5-5nm/s.
In addition, as metal film or metal level, preferably aluminium.
In addition, preferably obtain excellent light reflective surface by such method, wherein pass through direct current or high frequency waves argon gas formation plasma earlier, the resin formed article surface is exposed to carries out surface active under the argon plasma, form reflective metal layer then from the teeth outwards 2.5-3.5Pa; Preferred by such method acquisition, wherein behind surface active, the resin formed article surface is exposed under oxygen, nitrogen or its mixed gas, introduce functional group from the teeth outwards, or the resin formed article surface is exposed under the reactive monomer, introduce the molecular layer or the hydrophilic polymer layer of activation from the teeth outwards, form reflective metal layer then on the surface.According to these methods, can obtain excellent high gloss light reflective surface.
In addition, composition of the present invention can mix the known material that usually adds in the thermoplastic resin etc., to give the performance that requires according to purposes.For example, can mix any antistatic agent, release agent except that mentioned component (C), such as the colorant of dyestuff or pigment.
Composition of the present invention is easy to by the extensively means and the method manufacturing of employing of conventional resin combination manufacture method.For example, (1) comprises that the composition that predetermined quantity is constituted the present composition collects mixedly, with single shaft or biaxial extruder fusion kneading potpourri, obtains having the method for the section of objective composition; Or (2) comprise with single shaft or biaxial extruder with two or more starting material charging apertures, add resin, stabilizing agent, pigment composition etc. from first charging aperture, fusion kneading potpourri, add inorganic filler from the second starting material charging aperture then, and fusion kneading potpourri, obtain having the method for the section of objective composition.
The forming method that charges into resin in mold has injection moulding, injection compression molding method etc.What extensively adopt is injection moulding.
Embodiment
Hereinafter with the present invention of reference example more detailed description, but the present invention is not limited to this.The measuring method that is used for assessment item shown in following examples is as follows.
(1) outward appearance of light reflective surface
In order to counterdie goods (flat board), under condition shown in embodiment and the comparative example, carry out the aluminium vapour deposition.Estimate the apparent condition of the light reflective surface of this reflective optical system with image transparency measurement mechanism.Honeycomb width with 1mm passes through the data evaluation image definition.The higher better image definition of image sharpness C (%) value representation.
In addition, above-mentioned reflective optical system is placed 180 ℃ heated 72 hours down.Estimate the apparent condition of light reflective surface then similarly with the image definition measurement mechanism.
(condition of molding)
The flat board (62mm * 52mm * 2mm thick) of reflective optical system by being used in following condition compacted under carries out vapour deposition and obtains under following vapor deposition conditions.
Make-up machine: EC40-1A (Toshiba Corporation)
Condition of molding:
Nozzle C1 C2 C3
Barrel temperature (℃) 260 260 240 220
Injection speed 2.0m/min
Compacting pressure 400kg/cm
2
95 ℃ of mold temperatures
Vapor deposition conditions: the pressure in the vapor phase growing apparatus drops to 1.0 * 10
-2Pa, with the speed of 1.0nm/s with the aluminium vapour deposition to the 100nm thickness.
(2) optical haze test
Cut above-mentioned flat board and be enclosed in the testing tube.With glass plate coverage test pipe and immersed in 180 ℃ of oil baths 8 hours.Detect by an unaided eye then attached to the optical haze state on the testing tube, and according to following standard evaluation.
A: do not produce any optical haze;
B: the place produces slight optical haze at the testing tube upper opening;
C: on testing tube top about 1/2, produce optical haze;
D: on testing tube top about 3/4, produce dense optical haze.
Embodiment 1
With 100 weight portion limiting viscosities (η) be 0.75, terminal carboxyl group content (CEG content) for the polybutylene terephthalate of 30meq/kg (A) and 45 weight portion limiting viscosities (η) is 0.63 polyethylene terephthalate (B) (BELPET EFG10, Kanebo Gohsen, Ltd. manufacturing), 0.5 weight portion is as polyglycereol stearic acid partial ester (C-1) (the RIKEMARL AF-70 of lubricant, Riken VitaminCo., Ltd. makes; 760), 38 weight portion primary particle sizes are that (TRANSLINK 445 for the porcelain earth (D-1) of 1.4 μ m number-average molecular weight:, Hayashi Kasei Co., Ltd. manufacturing), { methylene-3-(3 for 0.9 weight portion four, 5-two-tert-butyl-hydroxy phenyl) propionic ester } methane (E-1), with 0.4 weight portion four (2,4-two-tert-butyl-phenyl)-4,4 '-xenyl phosphite ester (E-2) is mixed.Resin combination with such acquisition obtains above-mentioned mechanograph.On this mechanograph, make reflective optical system with the said method vapor deposition of aluminum.Estimate reflective optical system then.
Embodiment 2
Estimate with the mode identical with embodiment 1, different is with primary particle size is that the talcum (D-2) (Ltd. makes for UPN HST0.5, Hayashi Kasei Co.) of 2.7 μ m replaces (D-1) among the embodiment 1.
Comparative example 1
Estimate with the mode identical with embodiment 1, different is with primary particle size is that the talcum (D '-1) (Ltd. makes for PKNN, Hayashi Kasei Co.) of 8-10 μ m replaces (D-1) among the embodiment 1.
Comparative example 2
Estimate with the mode identical with embodiment 1, different is with glyceryl monostearate (C '-1) (number-average molecular weight: 358) replace (C-1) among the embodiment 1.
Comparative example 3
Estimate with the mode identical with embodiment 2, different is with glyceryl monostearate (C '-1) (number-average molecular weight: 358) replace (C-1) among the embodiment 2.
The results are shown in table 1.
Table 1
| Embodiment | Comparative example | ||||||
| 1 | 2 | 1 | 2 | 3 | |||
| (A) polybutylene terephthalate | Weight portion | 100 | 100 | 100 | 100 | 100 | |
| (B) polyethylene terephthalate | Weight portion | 45 | 45 | 45 | 45 | 45 | |
| (C) lubricant (C-1) polyglycereol stearic acid partial ester (C '-1) glyceryl monostearate | Weight portion | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| (D) (D-2) talcum (2.7 μ m) (D '-1) talcum (8-10 μ m) of non-fiber inorganic filler (D-1) porcelain earth (1.4 μ m) | Weight portion | 38 | 38 | 38 | 38 | 38 | |
| (E) antioxidant (E-1) (E-2) | Weight portion | 0.9 0.4 | 0.9 0.4 | 0.9 0.4 | 0.9 0.4 | 0.9 0.4 | |
| Reflective optical system appearance images acutance (%) | Instant after the vapour deposition | 97.5 | 96.7 | 87.3 | 96.8 | 95.6 | |
| After 180 ℃/72 hours | 95.2 | 92.6 | 85.3 | 77.4 | 74.7 | ||
| The optical haze test | A | A | A | D | D | ||
As mentioned above, when with polybutylene terephthalate and polyethylene terephthalate, polyglycereol stearate and primary particle size are no more than the mixed mechanograph that obtains of non-fiber inorganic filler of 5 μ m, and on the described mechanograph of at least a portion, directly form reflective metal layer, thereby during the reflective optical system that the polybutylene terephthalate that manufacturing obtains according to the present invention is made, this reverberator has not only obtained very high glossiness, even and they are continuously shaped and exposure at high temperature also seldom reduces owing to optical haze causes glossiness, and have excellent metal adhesion and thermotolerance.
This reflective optical system especially is preferably used for requiring the vehicle lamp reflector and the extension of high reflectance.
Claims (10)
1. the manufacture method of the reflective optical system made of a polybutylene terephthalate, this method comprises and will comprise
(A) 100 weight portion polybutylene terephthalates,
(B) 5-80 weight portion polyethylene terephthalate,
(C) 0.05-2.0 weight portion polyglycereol stearate,
(D) 2-50 weight portion primary particle size be no more than 5 μ m non-fiber inorganic filler and
(E) resin combination of 0.1-3.0 weight portion antioxidant is molded into mechanograph, and directly forms reflective metal layer at least a portion of these goods.
2. the manufacture method of the reflective optical system made of the described polybutylene terephthalate of claim 1, wherein polybutylene terephthalate (A) has the terminal carboxyl group content that is no more than 40meq/kg.
3. the manufacture method of the reflective optical system made of claim 1 or 2 described polybutylene terephthalates, wherein polyethylene terephthalate (B) has the limiting viscosity [η] of 0.5-1.0.
4. the manufacture method of the reflective optical system made of claim 1 or 2 described polybutylene terephthalates, wherein polyglycereol stearate (C) has the number-average molecular weight of 400-1600.
5. the manufacture method of the reflective optical system made of claim 1 or 2 described polybutylene terephthalates, wherein non-fiber inorganic filler (D) comprises one or more and is selected from talcum, clay and kaolinic filler.
6. the manufacture method of the reflective optical system made of the described polybutylene terephthalate of claim 1, wherein the formation of reflective metal layer is by forming metal film or layer with bright luster at product surface and carry out with doing the plating method.
7. the manufacture method of the reflective optical system of making according to the polybutylene terephthalate of claim 6 is wherein done the plating method and is comprised the vacuum vapor deposition technology.
8. the manufacture method of the reflective optical system of making according to the polybutylene terephthalate of claim 6 or 7, wherein metal is being evacuated down to 1 * 10
-2After Pa or the lower initial vacuum, carry out vapour deposition with the evaporation rate of 0.5-5nm/s.
9. the manufacture method of the reflective optical system of making according to the polybutylene terephthalate of claim 1 or 2, the metal that wherein constitutes reflective metal layer is an aluminium.
10. one kind has the reflective optical system of making by according to the polybutylene terephthalate of the method direct reflective metal layer that forms at least a portion of goods of any one in the claim 1 to 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30983/03 | 2003-02-07 | ||
| JP30983/2003 | 2003-02-07 | ||
| JP2003030983A JP2004240292A (en) | 2003-02-07 | 2003-02-07 | Light reflector made of polybutylene terephthalate resin and its manufacturing method |
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| Publication Number | Publication Date |
|---|---|
| CN1519591A CN1519591A (en) | 2004-08-11 |
| CN100365441C true CN100365441C (en) | 2008-01-30 |
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|---|---|---|---|
| CNB2004100078271A Expired - Fee Related CN100365441C (en) | 2003-02-07 | 2004-02-06 | Light reflector made of terephthialic acid butanediol ester, and its mfg. method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006016458A1 (en) * | 2004-08-11 | 2006-02-16 | Toray Industries, Inc. | Polyester resin composition for light-reflecting article |
| JP2006063199A (en) * | 2004-08-27 | 2006-03-09 | Mitsubishi Engineering Plastics Corp | Polybutylene terephthalate resin composition and molded article |
| JP2006117737A (en) * | 2004-10-19 | 2006-05-11 | Kaneka Corp | Polyester resin composition and molded form therefrom |
| JP5261876B2 (en) * | 2005-03-23 | 2013-08-14 | 東レ株式会社 | Polyester resin composition for light reflector |
| CN1955222B (en) * | 2005-10-28 | 2011-02-02 | 胜技高分子株式会社 | Flame-resistant polybutylene terephthalate resin composition for lead-free solder |
| CN101313098B (en) * | 2005-12-22 | 2010-12-29 | 东丽株式会社 | Light-reflecting sheet |
| MY157736A (en) * | 2006-11-03 | 2016-07-15 | Basf Se | Low-emission polyester molding materials |
| JP5236394B2 (en) * | 2007-11-12 | 2013-07-17 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition and thin-walled molded article |
| JP2009155367A (en) * | 2007-12-25 | 2009-07-16 | Wintech Polymer Ltd | Polybutylene terephthalate resin composition and thin molded article |
| JP5233769B2 (en) * | 2009-03-18 | 2013-07-10 | 東レ株式会社 | Polybutylene terephthalate resin composition |
| CN101838444B (en) * | 2010-04-13 | 2013-03-06 | 四川中物材料有限责任公司 | Primer-free polyester material for decorating pieces and method for preparing same |
| JP5805081B2 (en) * | 2010-06-09 | 2015-11-04 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition, metal composite part, and method for producing metal composite part |
| CN102002220B (en) * | 2010-12-10 | 2012-08-08 | 上海金发科技发展有限公司 | Polyester alloy composite material for decorative ring of vehicle lamp and preparation method thereof |
| JP5729169B2 (en) * | 2011-06-29 | 2015-06-03 | 東洋紡株式会社 | Thermoplastic polyester resin composition and light reflector using the same |
| US10501621B2 (en) | 2014-07-01 | 2019-12-10 | Mitsubishi Engineering-Plastics Corporation | Polyester resin composition, injection molded article, light-reflecting base body, and light-reflecting body |
| CN105295314B (en) * | 2015-10-20 | 2019-02-05 | 上海胜南复合材料有限公司 | A kind of high-performance exempts from primary coat PBT/PET alloy material and preparation method |
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| JPH06316641A (en) * | 1993-05-07 | 1994-11-15 | Asahi Chem Ind Co Ltd | Vinylidene chloride-based resin film |
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| JP2004240292A (en) | 2004-08-26 |
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