JP2014046598A - Thermoplastic resin laminate - Google Patents
Thermoplastic resin laminate Download PDFInfo
- Publication number
- JP2014046598A JP2014046598A JP2012192207A JP2012192207A JP2014046598A JP 2014046598 A JP2014046598 A JP 2014046598A JP 2012192207 A JP2012192207 A JP 2012192207A JP 2012192207 A JP2012192207 A JP 2012192207A JP 2014046598 A JP2014046598 A JP 2014046598A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- layer
- resin
- resin laminate
- polyester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 111
- 229920001225 polyester resin Polymers 0.000 claims abstract description 58
- 239000004645 polyester resin Substances 0.000 claims abstract description 58
- 239000011342 resin composition Substances 0.000 claims abstract description 38
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 29
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 29
- 150000002009 diols Chemical class 0.000 claims abstract description 27
- 239000004925 Acrylic resin Substances 0.000 claims description 36
- 229920000178 Acrylic resin Polymers 0.000 claims description 36
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 230000003373 anti-fouling effect Effects 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- 229920006026 co-polymeric resin Polymers 0.000 claims 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 208000035874 Excoriation Diseases 0.000 abstract 2
- 230000035939 shock Effects 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 72
- 238000011156 evaluation Methods 0.000 description 57
- 238000000034 method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- -1 Aliphatic diols Chemical class 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000000470 constituent Substances 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000004420 Iupilon Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012792 core layer Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- QLMQETZMAZOZRM-UHFFFAOYSA-N (4-hydroxy-2,3-diphenylphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 QLMQETZMAZOZRM-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RYRZSXJVEILFRR-UHFFFAOYSA-N 2,3-dimethylterephthalic acid Chemical compound CC1=C(C)C(C(O)=O)=CC=C1C(O)=O RYRZSXJVEILFRR-UHFFFAOYSA-N 0.000 description 1
- HYCOKAJECXFYRA-UHFFFAOYSA-N 2-(1-carboxy-2-methylpropan-2-yl)-5-ethyl-1,3-dioxane-5-carboxylic acid Chemical compound CCC1(C(O)=O)COC(C(C)(C)CC(O)=O)OC1 HYCOKAJECXFYRA-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- HXEWWQYSYQOUSD-UHFFFAOYSA-N 2-[5-ethyl-5-(hydroxymethyl)-1,3-dioxan-2-yl]-2-methylpropan-1-ol Chemical compound CCC1(CO)COC(C(C)(C)CO)OC1 HXEWWQYSYQOUSD-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- VPMIEDAGSULEBW-UHFFFAOYSA-N 3-[3-(1-carboxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-3-methylbutanoic acid Chemical compound C1OC(C(C)(CC(O)=O)C)OCC21COC(C(C)(C)CC(O)=O)OC2 VPMIEDAGSULEBW-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KKQNEOAHDGRPDJ-UHFFFAOYSA-N CO.CO.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1 Chemical compound CO.CO.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1 KKQNEOAHDGRPDJ-UHFFFAOYSA-N 0.000 description 1
- HDICIMRANLAWOM-UHFFFAOYSA-N CO.CO.C1CCc2ccccc2C1 Chemical compound CO.CO.C1CCc2ccccc2C1 HDICIMRANLAWOM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000551547 Dione <red algae> Species 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- XUGISPSHIFXEHZ-GPJXBBLFSA-N [(3r,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C=C2C[C@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XUGISPSHIFXEHZ-GPJXBBLFSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- KYQRDNYMKKJUTH-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-dicarboxylic acid Chemical compound C1CC2(C(O)=O)C(C(=O)O)CC1C2 KYQRDNYMKKJUTH-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-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
- 230000003287 optical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000010409 thin film Substances 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は、透明性、耐熱性、耐擦傷性、耐衝撃性、高温高湿環境での寸法安定性に優れた熱可塑性樹脂積層体に関するものである。 The present invention relates to a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high temperature and high humidity environment.
樹脂製透明板は、屋外看板、カーポートのエクステリア用途や、ＯＡ機器、携帯電子機器の表示部前面板の光学用途等、多岐に応用される。近年、携帯電話端末や携帯電子遊具、携帯情報端末といった携帯型ディスプレイデバイスの前面パネルには、透明性や視認性、耐擦傷性に加え、厳しい環境で使用する際のより高い寸法安定性が求められている。この前面パネルに用いられる透明樹脂として、透明性、耐候性、耐擦傷性に優れるアクリル樹脂が広く用いられている。しかしながら、アクリル樹脂は耐衝撃性に乏しく、タッチパネルディスプレイ等の衝撃が加わりやすい用途では前面パネルに割れが発生しやすいという問題があった。 Resin-made transparent plates are used in a wide variety of applications, such as exterior signs for outdoor signage and carports, and optical uses for display unit front plates of OA devices and portable electronic devices. In recent years, front panels of portable display devices such as mobile phone terminals, portable electronic playground equipment, and portable information terminals are required to have higher dimensional stability when used in harsh environments in addition to transparency, visibility, and scratch resistance. It has been. As a transparent resin used for the front panel, an acrylic resin excellent in transparency, weather resistance, and scratch resistance is widely used. However, acrylic resins have poor impact resistance, and there is a problem that cracks are likely to occur in the front panel in applications where impacts such as touch panel displays are likely to be applied.
特許文献１では、一般式（１）：
しかしながら、当該公報に開示されている多層シートは低湿環境での耐熱性に優れているものの、温度８５℃、湿度８５％のような高温高湿環境での寸法安定性は十分ではなかった。 However, although the multilayer sheet disclosed in the publication is excellent in heat resistance in a low humidity environment, the dimensional stability in a high temperature and high humidity environment such as a temperature of 85 ° C. and a humidity of 85% is not sufficient.
本発明の目的は、前記のような状況に鑑み、透明性、耐熱性、耐擦傷性、耐衝撃性、高温高湿環境での寸法安定性に優れた熱可塑性樹脂積層体を提供することにある。 An object of the present invention is to provide a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high temperature and high humidity environment in view of the above situation. is there.
本発明者らは、鋭意検討を重ねた結果、ジオール成分とジカルボン酸成分の少なくとも一方が環状アセタール骨格を有する化合物を含む原料モノマーを重合して得られたポリエステル樹脂（ａ）とポリカーボネート樹脂（ｂ）を含む熱可塑性樹脂組成物からなる層と、ポリエステル樹脂（ａ）以外のポリエステル樹脂、アクリル樹脂、およびメチルメタクリレート−スチレン共重合体から成る群から選ばれた少なくとも１種を含むことを特徴とする熱可塑性樹脂からなる層とを有する熱可塑性樹脂積層体が、透明性、耐熱性、耐擦傷性、且つ高温高湿環境での寸法安定性に優れることを見出し、本発明に到達した。 As a result of intensive studies, the present inventors have determined that a polyester resin (a) and a polycarbonate resin (b) obtained by polymerizing a raw material monomer containing a compound in which at least one of a diol component and a dicarboxylic acid component has a cyclic acetal skeleton. And a layer made of a thermoplastic resin composition containing at least one polyester resin (a) and at least one selected from the group consisting of a polyester resin other than the polyester resin (a), an acrylic resin, and a methyl methacrylate-styrene copolymer. The present inventors have found that a thermoplastic resin laminate having a layer made of a thermoplastic resin that is excellent in transparency, heat resistance, scratch resistance, and dimensional stability in a high-temperature and high-humidity environment has reached the present invention.
すなわち、本発明は、
熱可塑性樹脂組成物からなる層（Ａ）と、前記層（Ａ）の少なくとも一方の面に設けられた熱可塑性樹脂からなる層（Ｂ）を含む熱可塑性樹脂積層体であって、前記層（Ａ）が、ポリエステル樹脂（ａ）とポリカーボネート樹脂（ｂ）からなり、前記ポリエステル樹脂（ａ）はジオール構成単位、ジカルボン酸構成単位の少なくとも一方に、環状アセタール骨格を有する構成単位を含むことを特徴とする熱可塑性樹脂積層体である。
ポリエステル樹脂（ａ）は、より好ましくはジカルボン酸構成単位とジオール構成単位からなる下記（I）または（II）に記載のポリエステル樹脂である。
（I）全ジオール構成単位中の１０〜６０モル％が下記式（１）：
（II）全ジカルボン酸構成単位中の１０〜６０モル％が下記式（３）：
とポリカーボネート樹脂（ｂ）から成ることを特徴とする熱可塑性樹脂積層体。
（式（１）〜（４）において、Ｒ1 、Ｒ2 、およびＲ3はそれぞれ独立して、炭素数が１〜１０の脂肪族基、炭素数が３〜１０の脂環式基、及び炭素数が６〜１０の芳香族基からなる群から選ばれる有機基を表す。）
That is, the present invention
A thermoplastic resin laminate comprising a layer (A) comprising a thermoplastic resin composition and a layer (B) comprising a thermoplastic resin provided on at least one surface of the layer (A), wherein the layer ( A) comprises a polyester resin (a) and a polycarbonate resin (b), and the polyester resin (a) includes a structural unit having a cyclic acetal skeleton in at least one of a diol structural unit and a dicarboxylic acid structural unit. And a thermoplastic resin laminate.
The polyester resin (a) is more preferably a polyester resin described in the following (I) or (II) comprising a dicarboxylic acid structural unit and a diol structural unit.
(I) 10-60 mol% in all diol structural units is represented by the following formula (1):
(II) 10 to 60 mol% in all dicarboxylic acid structural units is represented by the following formula (3):
(In the formulas (1) to (4), R 1 , R 2 , and R 3 are each independently an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and This represents an organic group selected from the group consisting of aromatic groups having 6 to 10 carbon atoms.)
本発明によれば、透明性、耐熱性、耐擦傷性、耐衝撃性、高温高湿環境での寸法安定性に優れた熱可塑性樹脂積層体が提供され、該熱可塑性樹脂積層体は、透明性基板材料、透明性保護材料として用いられ、特にディスプレイデバイスの前面パネルに好適に使用される。 According to the present invention, a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance, and dimensional stability in a high-temperature and high-humidity environment is provided, and the thermoplastic resin laminate is transparent. It is used as a conductive substrate material and a transparent protective material, and particularly suitably used for a front panel of a display device.
以下で本発明について詳細に説明する。本発明の熱可塑性樹脂積層体は、熱可塑性樹脂組成物からなる層（Ａ）および熱可塑性樹脂からなる層（Ｂ）から成り、前記層（Ａ）の少なくとも一方の面に前記層（Ｂ）を有する熱可塑性樹脂積層体であり、前記層（Ａ）が、ポリエステル樹脂（ａ）とポリカーボネート樹脂（ｂ）からなり、前記ポリエステル樹脂（ａ）はジオール構成単位、ジカルボン酸構成単位の少なくとも一方に、環状アセタール骨格を有する構成単位を含むことを特徴とする。 The present invention is described in detail below. The thermoplastic resin laminate of the present invention comprises a layer (A) made of a thermoplastic resin composition and a layer (B) made of a thermoplastic resin, and the layer (B) is formed on at least one surface of the layer (A). The layer (A) is composed of a polyester resin (a) and a polycarbonate resin (b), and the polyester resin (a) is at least one of a diol constituent unit and a dicarboxylic acid constituent unit. And a structural unit having a cyclic acetal skeleton.
本発明に用いるポリエステル樹脂（ａ）は、ジオール構成単位とジカルボン酸構成単位からなり、ジオール構成単位、ジカルボン酸構成単位の少なくとも一方に、環状アセタール骨格を有する。ポリエステル樹脂（ａ）はより好ましくは、下記（I）または（II）に記載されたポリエステル樹脂である。
（I）全ジオール構成単位中の１０〜６０モル％が式（１）または式（２）で表される環状アセタール骨格を有するジオールに由来する構成単位であるポリエステル樹脂、（II）全ジカルボン酸構成単位中の１０〜６０モル％が式（３）または式（４）で表される環状アセタール骨格を有するジカルボン酸に由来する構成単位であるポリエステル樹脂。
(I) Polyester resin in which 10 to 60 mol% of all diol constituent units is a constituent unit derived from a diol having a cyclic acetal skeleton represented by formula (1) or formula (2), (II) all dicarboxylic acids The polyester resin which is a structural unit derived from dicarboxylic acid which has 10-60 mol% in a structural unit and has a cyclic acetal skeleton represented by Formula (3) or Formula (4).
前記式（１）または式（２）で表される環状アセタール骨格を有するジオールにおいて、Ｒ1 、Ｒ2は好ましくは、メチレン基、エチレン基、プロピレン基、ブチレン基又はこれらの構造異性体、例えば、イソプロピレン基、イソブチレン基である。Ｒ3 は好ましくは、メチル基、エチル基、プロピル基、ブチル基、又はこれらの構造異性体、例えば、イソプロピル基、イソブチル基を表す。中でも前記環状アセタール骨格を有するジオールとしては、３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、５−メチロール−５−エチル−２−（１，１−ジメチル−２−ヒドロキシエチル）−１，３−ジオキサン等が特に好ましい。 In the diol having a cyclic acetal skeleton represented by the formula (1) or the formula (2), R 1 and R 2 are preferably methylene group, ethylene group, propylene group, butylene group or structural isomers thereof, for example, , Isopropylene group and isobutylene group. R 3 preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, or a structural isomer thereof such as an isopropyl group or an isobutyl group. Among them, as the diol having the cyclic acetal skeleton, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 5-methylol -5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane and the like are particularly preferable.
本発明に用いるポリエステル樹脂（ａ）における、環状アセタール骨格を有するジオール以外のジオールとしては、特に制限はされないが、エチレングリコール、トリメチレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、プロピレングリコール、ネオペンチルグリコール等の脂肪族ジオール類；ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等のポリエーテル化合物類；１，３−シクロヘキサンジメタノール、１，４−シクロヘキサンジメタノール、１，２−デカヒドロナフタレンジメタノール、１，３−デカヒドロナフタレンジメタノール、１，４−デカヒドロナフタレンジメタノール、１，５−デカヒドロナフタレンジメタノール、１，６−デカヒドロナフタレンジメタノール、２，７−デカヒドロナフタレンジメタノール、テトラリンジメタノール、ノルボルネンジメタノール、トリシクロデカンジメタノール、ペンタシクロドデカンジメタノール等の脂環式ジオール類；４，４’−（１−メチルエチリデン）ビスフェノール、メチレンビスフェノール（ビスフェノールＦ）、４，４’−シクロヘキシリデンビスフェノール（ビスフェノールＺ）、４，４’−スルホニルビスフェノール（ビスフェノールＳ）等のビスフェノール類；前記ビスフェノール類のアルキレンオキシド付加物；ヒドロキノン、レゾルシン、４，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルベンゾフェノン等の芳香族ジヒドロキシ化合物；及び前記芳香族ジヒドロキシ化合物のアルキレンオキシド付加物等が例示出来る。 The diol other than the diol having a cyclic acetal skeleton in the polyester resin (a) used in the present invention is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, Aliphatic diols such as 1,6-hexanediol, diethylene glycol, propylene glycol, neopentyl glycol; polyether compounds such as polyethylene glycol, polypropylene glycol, polybutylene glycol; 1,3-cyclohexanedimethanol, 1,4- Cyclohexanedimethanol, 1,2-decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-decahydronaphthalene dimethano , Cycloaliphatic diols such as 1,6-decahydronaphthalene diethanol, 2,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornene dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol; 4 Bisphenols such as 4,4 ′-(1-methylethylidene) bisphenol, methylene bisphenol (bisphenol F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), 4,4′-sulfonylbisphenol (bisphenol S); Alkylene oxide adducts of bisphenols; aromatic diones such as hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone Dorokishi compound; and alkylene oxide adducts of the aromatic dihydroxy compound can be exemplified.
前記式（３）または式（４）で表される環状アセタール骨格を有するジカルボン酸において、Ｒ1 、Ｒ2は好ましくは、メチレン基、エチレン基、プロピレン基、ブチレン基又はこれらの構造異性体、例えば、イソプロピレン基、イソブチレン基である。Ｒ3 は好ましくは、メチル基、エチル基、プロピル基、ブチル基、又はこれらの構造異性体、例えば、イソプロピル基、イソブチル基を表す。
中でも前記環状アセタール骨格を有するジカルボン酸としては、３，９−ビス（１，１−ジメチル−２−カルボキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、５−カルボキシ−５−エチル−２−（１，１−ジメチル−２−カルボキシエチル）−１，３−ジオキサン等が特に好ましい。
In the dicarboxylic acid having a cyclic acetal skeleton represented by the formula (3) or the formula (4), R 1 and R 2 are preferably a methylene group, an ethylene group, a propylene group, a butylene group or structural isomers thereof, For example, an isopropylene group or an isobutylene group. R 3 preferably represents a methyl group, an ethyl group, a propyl group, a butyl group, or a structural isomer thereof such as an isopropyl group or an isobutyl group.
Among them, examples of the dicarboxylic acid having a cyclic acetal skeleton include 3,9-bis (1,1-dimethyl-2-carboxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 5- Carboxy-5-ethyl-2- (1,1-dimethyl-2-carboxyethyl) -1,3-dioxane and the like are particularly preferable.
本発明に用いるポリエステル樹脂（ａ）の環状アセタール骨格を有するジカルボン酸以外のジカルボン酸としては、特に制限はされないが、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸、シクロヘキサンジカルボン酸、デカンジカルボン酸、ノルボルナンジカルボン酸、トリシクロデカンジカルボン酸、ペンタシクロドデカンジカルボン酸等の脂肪族ジカルボン酸及びこれらのエステル形成性誘導体；テレフタル酸、イソフタル酸、フタル酸、２−メチルテレフタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸、テトラリンジカルボン酸等の芳香族ジカルボン酸及びこれらのエステル形成性誘導体が例示出来る。 The dicarboxylic acid other than the dicarboxylic acid having a cyclic acetal skeleton of the polyester resin (a) used in the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , Dodecane dicarboxylic acid, cyclohexane dicarboxylic acid, decane dicarboxylic acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecane dicarboxylic acid and other aliphatic dicarboxylic acids and ester-forming derivatives thereof; terephthalic acid, isophthalic acid, phthalic acid And aromatic dicarboxylic acids such as 2-methylterephthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid, and ester-forming derivatives thereof.
本発明に用いるポリエステル樹脂（ａ）における、全ジオール構成単位中の環状アセタール骨格を有するジオールに由来する構成単位の割合、または全ジカルボン酸構成単位中の環状アセタール骨格を有するジカルボン酸に由来する構成単位の割合は、１０〜６０モル％が好ましく、より好ましくは１５〜５０モル％である。前記割合が１０モル％より小さい場合には、ポリエステル樹脂（ａ）が十分な耐熱性を示さない場合があり好ましくない。また６０モル％より大きい場合には耐衝撃性が低下する場合があり、好ましくない。 In the polyester resin (a) used in the present invention, the proportion of structural units derived from diols having a cyclic acetal skeleton in all diol structural units, or a structure derived from dicarboxylic acids having a cyclic acetal skeleton in all dicarboxylic acid structural units The proportion of units is preferably 10 to 60 mol%, more preferably 15 to 50 mol%. When the ratio is less than 10 mol%, the polyester resin (a) may not exhibit sufficient heat resistance, which is not preferable. On the other hand, if it is more than 60 mol%, the impact resistance may decrease, which is not preferable.
ポリエステル樹脂（ａ）としては、全ジオール構成単位中の３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンに由来する構成単位の割合が１０〜６０モル％であり、エチレングリコールに由来する構成単位が４０〜９０モル％であるジオール構成単位と、全ジカルボン酸構成単位中のテレフタル酸に由来する構成単位の割合が７０モル％以上であるジカルボン酸構成単位からなるポリエステル樹脂が最も好ましい。上記ジオール構成単位とジカルボン酸構成単位を有することにより、本発明のシートは耐熱性、機械的性能、経済性に優れたものとなる。 As the polyester resin (a), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane in all diol constituent units is used. The proportion of the structural unit derived from 10 to 60 mol%, the structural unit derived from ethylene glycol being 40 to 90 mol%, and the structural unit derived from terephthalic acid in all dicarboxylic acid structural units Most preferred is a polyester resin composed of dicarboxylic acid structural units in a proportion of 70 mol% or more. By having the said diol structural unit and dicarboxylic acid structural unit, the sheet | seat of this invention becomes the thing excellent in heat resistance, mechanical performance, and economical efficiency.
本発明に用いるポリエステル樹脂（ａ）を製造する方法は特に制限はなく、従来公知の方法を適用することができる。例えば、エステル交換法、直接エステル化法等の溶融重合法、又は溶液重合法等が挙げられる。ポリエステル樹脂（ａ）には、一般に用いられる各種の添加剤を添加しても良く、添加剤としては、エステル交換触媒、エステル化触媒、エーテル化防止剤、熱安定剤、光安定剤等の各種安定剤、重合調整剤等が挙げられる。 The method for producing the polyester resin (a) used in the present invention is not particularly limited, and conventionally known methods can be applied. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method. Various kinds of commonly used additives may be added to the polyester resin (a). Examples of the additives include transesterification catalysts, esterification catalysts, etherification inhibitors, heat stabilizers, light stabilizers, and the like. Stabilizers, polymerization regulators and the like can be mentioned.
本発明に用いるポリカーボネート樹脂（ｂ）は、芳香族ジヒドロキシ化合物又はこれと少量のポリヒドロキシ化合物とホスゲンとを界面重合法により得られるか、または、上記の芳香族ジヒドロキシ化合物と炭酸のジエステルとのエステル交換反応により作られる分岐していてもよい熱可塑性ポリカーボネート重合体であり、例えばビスフェノールＡを主原料とする炭酸エステル重合物が使用される。用いるポリカーボネート樹脂（ｂ）の分子量は、通常の押出成形によりシートを製造出来ることが好ましく、ポリスチレン換算の重量平均分子量４ ５ ， ０ ０ ０〜 ７ ０ ， ０ ０ ０ であることが好ましい。該重量平均分子量の範囲内において、ポリカーボネート樹脂基材の線膨張率は６ × １ ０ − ５ ／ ℃ 〜 ８ × １ ０ − ５ ／ ℃ 範囲にある。ポリカーボネート樹脂（ｂ）には、一般に用いられる各種の添加剤を添加しても良く、添加剤としては、例えば、酸化防止剤、着色防止剤、紫外線吸収剤、光拡散剤、難燃剤、離型剤、滑剤、帯電防止剤、染顔料等が挙げられる。 The polycarbonate resin (b) used in the present invention is obtained by an interfacial polymerization method of an aromatic dihydroxy compound or a small amount thereof and a polyhydroxy compound and phosgene, or an ester of the above aromatic dihydroxy compound and a diester of carbonic acid. A thermoplastic polycarbonate polymer which may be branched by an exchange reaction, for example, a carbonate polymer containing bisphenol A as a main raw material is used. The molecular weight of the polycarbonate resin (b) to be used is preferably such that a sheet can be produced by ordinary extrusion molding, and the weight average molecular weight in terms of polystyrene is preferably 4 5, 0 0 0 to 7 0, 0 0 0. Within the scope of the weight average molecular weight, linear expansion coefficient of the polycarbonate resin substrate is 6 × 1 0 - in 5 / ° C. range - 5 / ℃ ~ 8 × 1 0. Various kinds of commonly used additives may be added to the polycarbonate resin (b). Examples of the additives include an antioxidant, an anti-coloring agent, an ultraviolet absorber, a light diffusing agent, a flame retardant, and a release agent. Agents, lubricants, antistatic agents, dyes and pigments, and the like.
熱可塑性樹脂組成物からなる層（Ａ）におけるポリエステル樹脂（ａ）とポリカーボネート樹脂（ｂ）の割合としては、ポリエステル樹脂（ａ）とポリカーボネート樹脂（ｂ）の合計に対するポリカーボネート樹脂（ｂ）の割合が１０〜９０重量％であることが好ましい。ポリカーボネート樹脂（ｂ）が１０重量％未満であると、高温高湿環境での寸法安定性が乏しくなり、９０重量％を超えると、押出成形によるシート製造が困難になる。より好ましくはポリエステル樹脂（ａ）とポリカーボネート樹脂（ｂ）の合計に対するポリカーボネート樹脂（ｂ）の割合が２０〜５０重量％の範囲である。上記組成とすることにより、本発明の熱可塑性樹脂積層体は耐衝撃性、高温高湿環境での寸法安定性に優れるという特長が得られる。 As a ratio of the polyester resin (a) and the polycarbonate resin (b) in the layer (A) made of the thermoplastic resin composition, the ratio of the polycarbonate resin (b) to the total of the polyester resin (a) and the polycarbonate resin (b) is It is preferably 10 to 90% by weight. When the polycarbonate resin (b) is less than 10% by weight, the dimensional stability in a high-temperature and high-humidity environment is poor, and when it exceeds 90% by weight, it is difficult to produce a sheet by extrusion. More preferably, the ratio of the polycarbonate resin (b) to the total of the polyester resin (a) and the polycarbonate resin (b) is in the range of 20 to 50% by weight. By setting it as the said composition, the thermoplastic resin laminated body of this invention has the characteristics that it is excellent in impact resistance and the dimensional stability in a high temperature, high humidity environment.
本発明の熱可塑性樹脂からなる層（Ｂ）中に主成分として含まれる樹脂としては、ポリエステル樹脂（ａ）以外のポリエステル樹脂；ポリスチレン樹脂；アクリル樹脂；ポリカーボネート樹脂；メチルメタクリレート−スチレン共重合体；アクリロニトリル−ブタジエン−スチレン共重合体；塩化ビニル樹脂；脂環式ポリオレフィン樹脂が挙げられ、上記の樹脂を単独で用いてもよく、２種以上を組み合わせて用いてもよい。技術的に容易に多層化できる観点から、層（Ｂ）の主成分としてポリエステル樹脂（ａ）以外のポリエステル樹脂、アクリル樹脂、メチルメタクリレート−スチレン共重合体が好ましく用いられ、より好ましくはアクリル樹脂を用いることができる。熱可塑性樹脂からなる層（Ｂ）にアクリル樹脂を用いることにより、本発明の熱可塑性樹脂積層体は耐擦傷性に優れるという特長が得られる。上記、ポリエステル樹脂（ａ）以外のポリエステル樹脂としては、具体的に、ポリエチレンテレフタレート、ポリエチレンナフタレート、イソフタル酸変性ポリエチレンテレフタレート、１，４−シクロヘキサンジメタノール変性ポリエチレンテレフタレート、ポリアリレートが挙げられる。 As a resin contained as a main component in the layer (B) made of the thermoplastic resin of the present invention, a polyester resin other than the polyester resin (a); a polystyrene resin; an acrylic resin; a polycarbonate resin; a methyl methacrylate-styrene copolymer; Examples include acrylonitrile-butadiene-styrene copolymer; vinyl chloride resin; alicyclic polyolefin resin, and the above resins may be used alone or in combination of two or more. From the viewpoint of easy technical multilayering, polyester resin other than polyester resin (a), acrylic resin, and methyl methacrylate-styrene copolymer are preferably used as the main component of layer (B), more preferably acrylic resin. Can be used. By using an acrylic resin for the layer (B) made of the thermoplastic resin, the thermoplastic resin laminate of the present invention has the advantage of being excellent in scratch resistance. Specific examples of the polyester resin other than the polyester resin (a) include polyethylene terephthalate, polyethylene naphthalate, isophthalic acid-modified polyethylene terephthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, and polyarylate.
本発明における熱可塑性樹脂組成物からなる層（Ａ）および熱可塑性樹脂からなる層（Ｂ）には各種添加剤を混合して使用しても良く、添加剤としては、例えば抗酸化剤、紫外線吸収剤、抗着色剤、抗帯電剤、離型剤、滑剤、染料、顔料、無機フィラー、樹脂フィラー等が挙げられる。混合の方法は特に限定されず、全量コンパウンドする方法、マスターバッチをドライブレンドする方法、全量ドライブレンドする方法等を用いることが出来る。 Various additives may be mixed and used in the layer (A) made of the thermoplastic resin composition and the layer (B) made of the thermoplastic resin in the present invention. Examples of the additives include antioxidants and ultraviolet rays. Absorbers, anticolorants, antistatic agents, mold release agents, lubricants, dyes, pigments, inorganic fillers, resin fillers, and the like can be given. The method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.
本発明の熱可塑性樹脂積層体は、熱可塑性樹脂組成物からなる層（Ａ）と、前記層（Ａ）の少なくとも一方の面に設けられた、熱可塑性樹脂からなる層（Ｂ）を含んで成る。 The thermoplastic resin laminate of the present invention includes a layer (A) made of a thermoplastic resin composition and a layer (B) made of a thermoplastic resin provided on at least one surface of the layer (A). Become.
本発明の熱可塑性樹脂積層体の製造方法としては共押出法、共押出ラミネート法、押出ラミネート法、ドライラミネート法等の公知の積層化技術を用いることが出来る。また、これらの積層化のために樹脂間に適した接着剤、あるいは接着性樹脂を用いても良い。 As a method for producing the thermoplastic resin laminate of the present invention, a known laminating technique such as a coextrusion method, a coextrusion laminating method, an extrusion laminating method, or a dry laminating method can be used. Moreover, you may use the adhesive agent suitable between resin for these lamination | stacking, or adhesive resin.
熱可塑性樹脂組成物からなる層（Ａ）と多層化する熱可塑性樹脂からなる層（Ｂ）の種類および層構成（積層順、層の数）は用途により選択すれば良い。例えば、表面硬度と高温高湿環境での寸法安定性を同時に必要とする用途では、アクリル樹脂をスキン層に、熱可塑性樹脂組成物からなる層（Ａ）をコア層に用いた２種２層の層構成（アクリル樹脂層／熱可塑性樹脂組成物からなる層（Ａ））および２種３層の層構成（アクリル樹脂層／熱可塑性樹脂組成物からなる層（Ａ）／アクリル樹脂層）とすることで、透明性、耐熱性、耐擦傷性、耐衝撃性および高温高湿環境での寸法安定性に優れた熱可塑性樹脂積層体が得られる。また、ＰＥＴのシートにさらに耐熱性を付与し、且つ高温高湿環境での寸法安定性を維持するために、ＰＥＴをスキン層、熱可塑性樹脂組成物からなる層（Ａ）をコア層に用いた２種２層の層構成（ＰＥＴ樹脂層／熱可塑性樹脂組成物からなる層（Ａ））２種３層の層構成（ＰＥＴ樹脂層／熱可塑性樹脂組成物からなる層（Ａ）／ＰＥＴ樹脂層）とすることで、透明性、耐熱性、耐衝撃性、高温高湿環境での寸法安定性に優れた熱可塑性樹脂積層体が得られる。 What is necessary is just to select the kind and layer structure (lamination order, number of layers) of the layer (A) which consists of a thermoplastic resin composition, and the layer (B) which consists of a thermoplastic resin to make a multilayer according to a use. For example, in applications that require both surface hardness and dimensional stability in a high-temperature and high-humidity environment, two types and two layers using an acrylic resin as a skin layer and a layer (A) made of a thermoplastic resin composition as a core layer Layer structure (acrylic resin layer / layer (A) composed of thermoplastic resin composition) and two-layer / three-layer structure (acrylic resin layer / layer composed of thermoplastic resin composition (A) / acrylic resin layer) By doing so, a thermoplastic resin laminate excellent in transparency, heat resistance, scratch resistance, impact resistance and dimensional stability in a high temperature and high humidity environment can be obtained. Further, in order to further impart heat resistance to the PET sheet and maintain dimensional stability in a high-temperature and high-humidity environment, PET is used as the skin layer, and the layer (A) made of the thermoplastic resin composition is used as the core layer. 2 types and 2 layers (PET resin layer / layer made of thermoplastic resin composition (A)) 2 types and 3 layers (PET resin layer / layer made of thermoplastic resin composition (A) / PET By using the resin layer, a thermoplastic resin laminate excellent in transparency, heat resistance, impact resistance, and dimensional stability in a high temperature and high humidity environment can be obtained.
本発明における熱可塑性樹脂積層体の厚みは０．１〜１０．０ｍｍの範囲であることが好ましい。０．１ｍｍ未満の範囲であるとバンク抜けによる転写不良や厚み精度不良が発生する場合がある。また１０．０ｍｍを超える範囲であると成形後の冷却ムラなどによる厚み精度不良や外観不良が発生する場合がある。より好ましくは０．３〜５．０ｍｍの範囲であり、さらに好ましくは０．３〜３．０ｍｍの範囲である。 The thickness of the thermoplastic resin laminate in the present invention is preferably in the range of 0.1 to 10.0 mm. If the thickness is less than 0.1 mm, transfer failure or thickness accuracy failure may occur due to bank omission. In addition, when the thickness exceeds 10.0 mm, a thickness accuracy defect or an appearance defect due to uneven cooling after molding may occur. More preferably, it is the range of 0.3-5.0 mm, More preferably, it is the range of 0.3-3.0 mm.
本発明における熱可塑性樹脂積層体の熱可塑性樹脂からなる層（Ｂ）の厚み（片側）は熱可塑性樹脂積層体全体の厚みの２５％以下であることが好ましく、１０〜５００μｍの範囲であることが好ましい。層（Ｂ）の厚み（片側）が熱可塑性樹脂積層体全体の厚みの２５％を超えると、高温高湿環境で反りが発生する場合がある。また、１０μｍ未満の範囲であると耐擦傷性や耐候性が不足する場合があり、５００μｍを超える範囲であると高温高湿環境で反りが発生する場合がある。より好ましくは３０〜１５０μｍの範囲である。 The thickness (one side) of the layer (B) made of the thermoplastic resin of the thermoplastic resin laminate in the present invention is preferably 25% or less of the total thickness of the thermoplastic resin laminate, and is in the range of 10 to 500 μm. Is preferred. When the thickness (one side) of the layer (B) exceeds 25% of the total thickness of the thermoplastic resin laminate, warping may occur in a high temperature and high humidity environment. If the thickness is less than 10 μm, the scratch resistance and weather resistance may be insufficient, and if it exceeds 500 μm, warping may occur in a high-temperature and high-humidity environment. More preferably, it is the range of 30-150 micrometers.
本発明の熱可塑性樹脂積層体の片面または両面にはハードコート処理を施すことができる。例えば、光エネルギーを用いて硬化させる感光性ハードコート塗料を用いることによりハードコート層を形成する。光エネルギーを用いて硬化させる感光性ハードコート塗料としては、１官能および／または多官能であるアクリレートモノマーおよび／またはオリゴマーからなる樹脂組成物に光重合開始剤が加えられた光硬化性樹脂組成物等が挙げられる。例えば、トリス（アクロキシエチル）イソシアヌレート（ｃ１）４０〜８０重量％と、（ｃ１）と共重合可能な２官能および／または３官能のメタクリレート化合物（ｃ２）２０〜４０重量％とからなる樹脂組成物１００重量部に光重合開始剤（ｃ３）が１〜１０重量部添加された光硬化性樹脂組成物等が挙げられる。 One side or both sides of the thermoplastic resin laminate of the present invention can be subjected to a hard coat treatment. For example, the hard coat layer is formed by using a photosensitive hard coat paint that is cured using light energy. As a photosensitive hard coat paint to be cured using light energy, a photocurable resin composition in which a photopolymerization initiator is added to a resin composition composed of monofunctional and / or polyfunctional acrylate monomers and / or oligomers. Etc. For example, a resin comprising 40 to 80% by weight of tris (acryloxyethyl) isocyanurate (c1) and 20 to 40% by weight of a bifunctional and / or trifunctional methacrylate compound (c2) copolymerizable with (c1) Examples thereof include a photocurable resin composition in which 1 to 10 parts by weight of the photopolymerization initiator (c3) is added to 100 parts by weight of the composition.
本発明におけるハードコート塗料を塗布する方法は特に限定されず、公知の方法を用いることができる。例えば、刷毛、グラビアロール、ディッピング、流し塗り、スプレー、インクジェット等が挙げられる。 The method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. For example, a brush, a gravure roll, dipping, a flow coating, a spray, an inkjet, etc. are mentioned.
本発明の熱可塑性樹脂積層体にはその片面または両面に反射防止処理、防汚処理、帯電防止処理、耐候性処理および防眩処理のいずれか一つ以上を施すことができる。反射防止処理、防汚処理、帯電防止処理、耐候性処理および防眩処理の方法は特に限定されず、公知の方法を用いることができる。例えば反射低減塗料を塗布する方法、誘電体薄膜を蒸着する方法、帯電防止塗料を塗布する方法等が挙げられる。 The thermoplastic resin laminate of the present invention can be subjected to one or more of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one side or both sides. The methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing coating, a method of depositing a dielectric thin film, a method of applying an antistatic coating, and the like can be mentioned.
本発明の熱可塑性樹脂積層体の全光線透過率は、厚さ１．０ｍｍで８５％以上であることが好ましく、より好ましくは８８％以上、さらに好ましくは９０％以上である。 The total light transmittance of the thermoplastic resin laminate of the present invention is preferably 85% or more at a thickness of 1.0 mm, more preferably 88% or more, and still more preferably 90% or more.
本発明の熱可塑性樹脂積層体は、透明性に優れており、各種の基板材料あるいは保護材料として利用される。具体的にはディスプレイデバイスの前面パネル等に好適に使用される。 The thermoplastic resin laminate of the present invention is excellent in transparency and is used as various substrate materials or protective materials. Specifically, it is suitably used for a front panel of a display device.
以下、実施例により本発明を具体的に説明する。ただし、本発明はこれらの実施例によりその範囲を限定されるものではない。
実施例および比較例で得られた熱可塑性樹脂積層体の評価は以下のように行った。
Hereinafter, the present invention will be described specifically by way of examples. However, the scope of the present invention is not limited by these examples.
The thermoplastic resin laminates obtained in the examples and comparative examples were evaluated as follows.
＜透明性評価＞
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、全光線透過率はＪＩＳ Ｋ ７１０５、ＡＳＴＭ Ｄ１００３に準じて、色差計（日本電色工業（株）製：ＣＯＨ―４００）にて測定した。全光線透過率９０％以上のものを合格とした。
<Transparency evaluation>
For the thermoplastic resin laminates obtained in the following examples and comparative examples, the total light transmittance is a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd .: COH-400) in accordance with JIS K 7105 and ASTM D1003. Measured with Those having a total light transmittance of 90% or more were accepted.
＜耐熱性評価＞
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、１．０ｍｍ厚の熱可塑性樹脂積層体から、押出方向を縦、幅方向を横として、縦９０ｍｍ、横６０ｍｍの長方形試験片を切り出し、水平面との角度が６０°となるよう試験片短手の下部１０ｍｍを固定し、オーブン内で４８時間加熱した。試験後の試験片を上に凸として水平面に静置し、試験片の各４辺の中央部と水平面との隙間長さの変形量を測定し、その変形量の合算値が１．０ｍｍを超えないものを合格とした。
<Heat resistance evaluation>
About the thermoplastic resin laminates obtained in the following Examples and Comparative Examples, from a 1.0 mm thick thermoplastic resin laminate, a rectangular test of 90 mm in length and 60 mm in width with the extrusion direction as the length and the width direction as the width. A piece was cut out, the lower 10 mm of the short test piece was fixed so that the angle with the horizontal plane was 60 °, and heated in an oven for 48 hours. The test piece after the test is convex on the horizontal plane, and the amount of deformation of the gap length between the center of each of the four sides of the test piece and the horizontal plane is measured, and the total value of the deformation amount is 1.0 mm. Those that did not exceed were considered acceptable.
＜耐擦傷性評価＞
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、鉛筆硬度はＪＩＳ Ｋ ５６００−５−４に準じて、各種硬度の鉛筆（三菱鉛筆（株）製 ユニ）を用いて熱可塑性樹脂（Ｂ）層の鉛筆硬度を測定した。鉛筆硬度３Ｈ以上のものを合格とした。
<Abrasion resistance evaluation>
For the thermoplastic resin laminates obtained in the following Examples and Comparative Examples, the pencil hardness is in accordance with JIS K 5600-5-4, using a pencil of various hardness (Uni, manufactured by Mitsubishi Pencil Co., Ltd.). The pencil hardness of the plastic resin (B) layer was measured. Those having a pencil hardness of 3H or more were accepted.
＜耐衝撃性試験＞
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、耐衝撃性は熱可塑性樹脂（Ｂ）層を上側、熱可塑性樹脂組成物（Ａ）層を下側として、落球試験にて評価した。落球試験は、φ５０のフランジの間にサンプルを固定し、φ２５、６３．７ｇの金属球を落とし、底部に装着した試験片が破断したときの高さを１０ｃｍ間隔で計測する方法で行い、その破断時点の高さが最高１５０ｃｍまでの値を測定した。破断時点での高さが１００ｃｍ以上のものを合格とした。
<Impact resistance test>
For the thermoplastic resin laminates obtained in the following examples and comparative examples, the impact resistance was measured in the falling ball test with the thermoplastic resin (B) layer on the upper side and the thermoplastic resin composition (A) layer on the lower side. And evaluated. The falling ball test is performed by fixing the sample between φ50 flanges, dropping a φ25, 63.7 g metal ball, and measuring the height when the test piece mounted on the bottom breaks at 10 cm intervals. The value up to a maximum height of 150 cm at the time of breaking was measured. The thing with the height at the time of a fracture | rupture of 100 cm or more was set as the pass.
＜高温高湿環境での寸法安定性評価＞
以下の実施例、比較例にて得られた熱可塑性樹脂積層体について、１．０ｍｍ厚の熱可塑性樹脂積層体から、押出方向を縦、幅方向を横として、縦９０ｍｍ、横６０ｍｍの長方形試験片を切り出し、水平面との角度が６０°となるよう試験片短手の下部１０ｍｍを固定し、温度８５℃、湿度８５％に設定した恒温恒湿機内で４８時間加熱した。試験後の試験片を上に凸として水平面に静置し、試験片の各４辺の中央部と水平面との隙間長さの変形量を測定し、その変形量の合算値が５．０ｍｍを超えないものを合格とした。
<Dimensional stability evaluation in high temperature and high humidity environment>
About the thermoplastic resin laminates obtained in the following Examples and Comparative Examples, from a 1.0 mm thick thermoplastic resin laminate, a rectangular test of 90 mm in length and 60 mm in width with the extrusion direction as the length and the width direction as the width. A piece was cut out, the lower 10 mm of the short side of the test piece was fixed so that the angle with the horizontal plane was 60 °, and heated in a thermo-hygrostat set at a temperature of 85 ° C. and a humidity of 85% for 48 hours. The test piece after the test is convex on the horizontal surface, and is placed on the horizontal plane. The deformation amount of the gap length between the center of each of the four sides of the test piece and the horizontal plane is measured, and the total value of the deformation amount is 5.0 mm. Those that did not exceed were considered acceptable.
合成例１（ポリエステル樹脂（ａ））
ジカルボン酸成分としてジメチルテレフタル酸、ジオール成分として３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンとエチレングリコールをそれぞれ４５モル％、５５モル％とした原料モノマーを、ジカルボン酸成分１００モルに対し酢酸マンガン四水和物０．０３モルの存在下、窒素雰囲気下で２００℃まで昇温してエステル交換反応を行った。メタノールの留出量が理論量に対して９０％以上に達した後、ジカルボン酸成分１００モルに対し、酸化アンチモン（III）０．０１モルとトリフェニルホスフェート０．０６モルを加え、昇温と減圧を徐々に行い、最終的に２８０℃、０．１ＭＰａ以下で重合を行った。適度な溶融粘度になった時点で反応を終了し、ポリエステル樹脂（ａ）を得た。
Synthesis example 1 (polyester resin (a))
Dimethylterephthalic acid as the dicarboxylic acid component, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane and ethylene glycol as the diol component In the presence of 0.03 mol of manganese acetate tetrahydrate with respect to 100 mol of the dicarboxylic acid component, the raw material monomers of 45 mol% and 55 mol%, respectively, were heated to 200 ° C. in a nitrogen atmosphere to conduct a transesterification reaction. went. After the amount of distilled methanol reached 90% or more of the theoretical amount, 0.01 mol of antimony (III) oxide and 0.06 mol of triphenyl phosphate were added to 100 mol of the dicarboxylic acid component, The pressure was gradually reduced, and polymerization was finally performed at 280 ° C. and 0.1 MPa or less. The reaction was terminated when an appropriate melt viscosity was reached, and a polyester resin (a) was obtained.
製造例１（熱可塑性樹脂組成物（Ａ１〜Ａ４）の製造）
表１に示した割合でポリエステル樹脂（ａ）、ポリカーボネート樹脂〔三菱ガス化学（株）製、商品名：ユーピロン Ｓ３０００〕（ｂ）をタンブラーで乾式混合し、軸径３７ｍｍの二軸押出機（東芝機械株式会社製ＴＥＭ３７ＢＳ）により、シリンダ温度２１０〜２８０℃、ダイ温度２４０〜２７５℃、スクリュー回転数１００ｒｐｍの条件で溶融混練を行い、それぞれペレット状の熱可塑性樹脂組成物（Ａ１〜Ａ４）を得た。
Production Example 1 (Production of thermoplastic resin composition (A1 to A4))
Polyester resin (a) and polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S3000] (b) were dry-mixed with a tumbler at the ratio shown in Table 1, and a twin screw extruder (Toshiba) By TEM37BS manufactured by Kikai Co., Ltd., melt kneading is performed under conditions of a cylinder temperature of 210 to 280 ° C., a die temperature of 240 to 275 ° C., and a screw rotation speed of 100 rpm to obtain pellet-shaped thermoplastic resin compositions (A1 to A4). It was.
実施例１（熱可塑性樹脂組成物（Ａ１）層／アクリル樹脂（Ｂ）層）
軸径３２ｍｍの単軸押出機と、軸径６５ｍｍの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたＴダイとを有する多層押出装置を用いて熱可塑性樹脂積層板を成形した。軸径３２ｍｍの単軸押出機にアクリル樹脂〔旭化成ケミカルズ（株）製、商品名：デルペット ８０Ｎ〕（Ｂ）を連続的に導入し、シリンダ温度２５０℃、吐出速度３．４ｋｇ／ｈの条件で押し出した。また、軸径６５ｍｍの単軸押出機にはポリエステル樹脂（ａ）とポリカーボネート樹脂〔三菱ガス化学（株）製、商品名：ユーピロン Ｓ３０００〕（ｂ）をそれぞれ重量比９０：１０とした熱可塑性樹脂組成物（Ａ１）を連続的に導入し、シリンダ温度２６０℃、吐出速度６７ｋｇ／ｈで押し出した。全押出機に連結されたフィードブロックは２種２層の分配ピンを備え、温度２６０℃として熱可塑性樹脂組成物（Ａ１）層の片面にアクリル樹脂（Ｂ）層を導入し積層した。その先に連結された温度２６０℃のＴダイでシート状に押し出し、３本の鏡面仕上げロールで鏡面を転写しながら冷却し、熱可塑性樹脂組成物（Ａ１）の片面にアクリル樹脂（Ｂ）が積層した熱可塑性樹脂積層体を得た。このときロールの設定温度は上流側から順に８５℃、８５℃、１０７℃とした。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍ、アクリル樹脂（Ｂ）層の厚みは中央付近で５０μｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であり、総合判定は合格であった。
Example 1 (thermoplastic resin composition (A1) layer / acrylic resin (B) layer)
Thermoplastic using a multilayer extruder having a single screw extruder with a shaft diameter of 32 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to the full extruder, and a T-die connected to the feed block. A resin laminate was molded. Acrylic resin [manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Delpet 80N] (B) was continuously introduced into a single-screw extruder having a shaft diameter of 32 mm, and the cylinder temperature was 250 ° C. and the discharge speed was 3.4 kg / h. Extruded with In addition, a single-screw extruder having a shaft diameter of 65 mm has a thermoplastic resin in which a polyester resin (a) and a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S3000) (b) are in a weight ratio of 90:10, respectively. The composition (A1) was continuously introduced and extruded at a cylinder temperature of 260 ° C. and a discharge rate of 67 kg / h. The feed block connected to the entire extruder was provided with two types and two layers of distribution pins, and the acrylic resin (B) layer was introduced and laminated on one side of the thermoplastic resin composition (A1) layer at a temperature of 260 ° C. Extruded into a sheet with a T-die with a temperature of 260 ° C. connected to the tip and cooled while transferring the mirror surface with three mirror finish rolls, the acrylic resin (B) was placed on one side of the thermoplastic resin composition (A1). A laminated thermoplastic resin laminate was obtained. At this time, the set temperature of the roll was set to 85 ° C., 85 ° C., and 107 ° C. in order from the upstream side. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin (B) layer was 50 μm near the center.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, and dimensional stability evaluation in a high-temperature and high-humidity environment were satisfactory, and the overall judgment was acceptable.
実施例２（熱可塑性樹脂組成物（Ａ２）層／アクリル樹脂（Ｂ）層）
実施例１で使用した熱可塑性樹脂組成物（Ａ１）の代わりにポリエステル樹脂（ａ）とポリカーボネート樹脂〔三菱ガス化学（株）製、商品名：ユーピロン Ｓ３０００〕（ｂ）をそれぞれ重量比７５：２５とした熱可塑性樹脂組成物（Ａ２）を使用した以外は実施例１と同様にして熱可塑性樹脂組成物（Ａ２）の片面にアクリル樹脂（Ｂ）が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍ、アクリル樹脂（Ｂ）層の厚みは中央付近で５０μｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であり、総合判定は合格であった。
Example 2 (thermoplastic resin composition (A2) layer / acrylic resin (B) layer)
Instead of the thermoplastic resin composition (A1) used in Example 1, polyester resin (a) and polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S3000] (b) were respectively used in a weight ratio of 75:25. A thermoplastic resin laminate in which the acrylic resin (B) was laminated on one side of the thermoplastic resin composition (A2) was obtained in the same manner as in Example 1 except that the thermoplastic resin composition (A2) was used. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin (B) layer was 50 μm near the center.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, and dimensional stability evaluation in a high-temperature and high-humidity environment were satisfactory, and the overall judgment was acceptable.
実施例３（熱可塑性樹脂（Ａ３）層／アクリル樹脂（Ｂ）層）
実施例１で使用した熱可塑性樹脂組成物（Ａ１）の代わりにポリエステル樹脂（ａ）とポリカーボネート樹脂〔三菱ガス化学（株）製、商品名：ユーピロン Ｓ３０００〕（ｂ）をそれぞれ重量比５０：５０とした熱可塑性樹脂組成物（Ａ３）を使用した以外は実施例１と同様にして熱可塑性樹脂組成物（Ａ３）の片面にアクリル樹脂（Ｂ）が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍ、アクリル樹脂（Ｂ）層の厚みは中央付近で５０μｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であり、総合判定は合格であった。
Example 3 (thermoplastic resin (A3) layer / acrylic resin (B) layer)
In place of the thermoplastic resin composition (A1) used in Example 1, a polyester resin (a) and a polycarbonate resin [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S3000] (b) were respectively used in a weight ratio of 50:50. A thermoplastic resin laminate in which the acrylic resin (B) was laminated on one side of the thermoplastic resin composition (A3) was obtained in the same manner as in Example 1 except that the thermoplastic resin composition (A3) was used. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin (B) layer was 50 μm near the center.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, and dimensional stability evaluation in a high-temperature and high-humidity environment were satisfactory, and the overall judgment was acceptable.
実施例４（熱可塑性樹脂組成物（Ａ４）層／アクリル樹脂（Ｂ）層）
実施例１で使用した熱可塑性樹脂組成物（Ａ１）の代わりにポリエステル樹脂（ａ）とポリカーボネート樹脂〔三菱ガス化学（株）製、商品名：ユーピロン Ｓ３０００〕（ｂ）をそれぞれ重量比３０：７０とした熱可塑性樹脂組成物（Ａ４）を使用した以外は実施例１と同様にして熱可塑性樹脂組成物（Ａ４）の片面にアクリル樹脂（Ｂ）が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍ、アクリル樹脂（Ｂ）層の厚みは中央付近で５０μｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であり、総合判定は合格であった。
Example 4 (thermoplastic resin composition (A4) layer / acrylic resin (B) layer)
Instead of the thermoplastic resin composition (A1) used in Example 1, a polyester resin (a) and a polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S3000] (b) were respectively used in a weight ratio of 30:70. A thermoplastic resin laminate in which the acrylic resin (B) was laminated on one side of the thermoplastic resin composition (A4) was obtained in the same manner as in Example 1 except that the thermoplastic resin composition (A4) was used. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin (B) layer was 50 μm near the center.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, impact resistance evaluation, and dimensional stability evaluation in a high-temperature and high-humidity environment were satisfactory, and the overall judgment was acceptable.
比較例１（ポリエステル樹脂（ａ）層／アクリル樹脂（Ｂ）層）
実施例１で使用した熱可塑性樹脂組成物（Ａ１）の代わりにポリエステル樹脂（ａ）を使用した以外は実施例１と同様にしてポリエステル樹脂（ａ）の片面にアクリル樹脂（Ｂ）が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍ、アクリル樹脂（Ｂ）層の厚みは中央付近で５０μｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐擦傷性評価、耐衝撃性評価の結果はそれぞれ良好であったが、高温高湿環境での寸法安定性の結果は不良であり、総合判定では不合格であった。
Comparative Example 1 (polyester resin (a) layer / acrylic resin (B) layer)
The acrylic resin (B) was laminated on one side of the polyester resin (a) in the same manner as in Example 1 except that the polyester resin (a) was used instead of the thermoplastic resin composition (A1) used in Example 1. A thermoplastic resin laminate was obtained. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin (B) layer was 50 μm near the center.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, and impact resistance evaluation were good, respectively, but the results of dimensional stability in a high-temperature and high-humidity environment were poor. It was.
比較例２（ポリカーボネート樹脂（ｂ）層／アクリル樹脂（Ｂ）層）
実施例１で使用した熱可塑性樹脂組成物（Ａ１）の代わりにポリカーボネート樹脂〔三菱ガス化学（株）製、商品名：ユーピロン Ｓ３０００〕（ｂ）を使用した以外は実施例１と同様にしてポリカーボネート樹脂（ｂ）の片面にアクリル樹脂（Ｂ）が積層した熱可塑性樹脂積層体を得た。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍ、アクリル樹脂（Ｂ）層の厚みは中央付近で５０μｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であったが、耐擦傷性評価の結果は不良であり、総合判定は不合格であった。
Comparative Example 2 (polycarbonate resin (b) layer / acrylic resin (B) layer)
A polycarbonate resin was prepared in the same manner as in Example 1 except that the polycarbonate resin [Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S3000] (b) was used instead of the thermoplastic resin composition (A1) used in Example 1. A thermoplastic resin laminate in which an acrylic resin (B) was laminated on one side of the resin (b) was obtained. The thickness of the obtained thermoplastic resin laminate was 1.0 mm, and the thickness of the acrylic resin (B) layer was 50 μm near the center.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, impact resistance evaluation, and dimensional stability evaluation under high-temperature and high-humidity environment were good, respectively, but the result of scratch resistance evaluation was poor, and the comprehensive judgment was rejected. there were.
比較例３（ポリエステル樹脂（ａ）単層）
軸径６５ｍｍの単軸押出機とＴダイとを有する単層押出装置を用いて熱可塑性樹脂板を成形した。軸径６５ｍｍの単軸押出機にポリエステル樹脂（ａ）を連続的に導入し、シリンダ温度２５０℃、吐出速度６０ｋｇ／ｈで押し出した。その先に連結された温度２５０℃のＴダイでシート状に押し出し、３本の鏡面仕上げロールで鏡面を転写しながら冷却し、ポリエステル樹脂（ａ）の熱可塑性樹脂板を得た。得られた合成樹脂板の厚みは１．０ｍｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐衝撃性評価の結果はそれぞれ良好であったが、耐擦傷性評価、高温高湿環境での寸法安定性評価の結果は不良であり、総合判定は不合格であった。
Comparative Example 3 (Polyester resin (a) single layer)
A thermoplastic resin plate was formed using a single-layer extruder having a shaft diameter of 65 mm and a T-die. Polyester resin (a) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm and extruded at a cylinder temperature of 250 ° C. and a discharge speed of 60 kg / h. It was extruded in a sheet form with a T-die having a temperature of 250 ° C. connected to the tip, and cooled while transferring the mirror surface with three mirror finish rolls to obtain a thermoplastic resin plate of polyester resin (a). The thickness of the obtained synthetic resin plate was 1.0 mm.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, and impact resistance evaluation were good, respectively, but the results of scratch resistance evaluation and dimensional stability evaluation in a high temperature and high humidity environment were poor, and the overall judgment was rejected. there were.
比較例４（ポリカーボネート樹脂（ｂ）単層）
比較例３で使用したポリエステル樹脂（ａ）の代わりにポリカーボネート樹脂〔三菱ガス化学（株）製、商品名：ユーピロン Ｓ３０００〕（ｂ）を使用した以外は比較例３と同様にして、ポリカーボネート樹脂（ｂ）の熱可塑性樹脂板を得た。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐衝撃性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であったが、耐擦傷性評価の結果は不良であり、総合判定は不合格であった。
Comparative Example 4 (Polycarbonate resin (b) single layer)
Instead of the polyester resin (a) used in Comparative Example 3, a polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S3000) (b) was used in the same manner as in Comparative Example 3, except that the polycarbonate resin ( A thermoplastic resin plate b) was obtained. The thickness of the obtained thermoplastic resin laminate was 1.0 mm.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, impact resistance evaluation, and dimensional stability evaluation under high-temperature and high-humidity environment were good, respectively, but the result of scratch resistance evaluation was poor, and the comprehensive judgment was rejected. there were.
比較例５（アクリル樹脂（Ｂ）単層）
比較例３で使用したポリエステル樹脂（ａ）の代わりにアクリル樹脂〔旭化成ケミカルズ（株）製、商品名：デルペット ８０Ｎ〕（Ｂ）を使用した以外は比較例３と同様にして、アクリル樹脂（Ｂ）の熱可塑性樹脂板を得た。得られた熱可塑性樹脂積層体の厚みは１．０ｍｍであった。
評価結果を表１に示す。透明性評価、耐熱性評価、耐擦傷性評価、高温高湿環境での寸法安定性評価の結果はそれぞれ良好であったが、耐衝撃性評価の結果は不良であり、総合判定は不合格であった。
Comparative Example 5 (Acrylic resin (B) single layer)
In the same manner as in Comparative Example 3, except that an acrylic resin (manufactured by Asahi Kasei Chemicals Corporation, trade name: Delpet 80N) (B) was used instead of the polyester resin (a) used in Comparative Example 3, an acrylic resin ( A thermoplastic resin plate B) was obtained. The thickness of the obtained thermoplastic resin laminate was 1.0 mm.
The evaluation results are shown in Table 1. The results of transparency evaluation, heat resistance evaluation, scratch resistance evaluation, and dimensional stability evaluation in a high temperature and high humidity environment were satisfactory, but the impact resistance evaluation result was poor, and the overall judgment was rejected. there were.
本発明の熱可塑性樹脂積層体は透明性、耐熱性、耐擦傷性、高温高湿環境での寸法安定性に優れるという特徴を有し、該熱可塑性樹脂積層体は、透明性基板材料、透明性保護材料として用いられ、特にディスプレイデバイスの前面パネルに好適に用いられる。 The thermoplastic resin laminate of the present invention is characterized by being excellent in transparency, heat resistance, scratch resistance, and dimensional stability in a high-temperature and high-humidity environment. In particular, it is suitably used for a front panel of a display device.
Claims (7)
（I）全ジオール構成単位中の１０〜６０モル％が下記式（１）：
（II）全ジカルボン酸構成単位中の１０〜６０モル％が下記式（３）：
とポリカーボネート樹脂（ｂ）から成ることを特徴とする熱可塑性樹脂積層体。
（式（１）〜（４）において、Ｒ1 、Ｒ2 、およびＲ3はそれぞれ独立して、炭素数が１〜１０の脂肪族基、炭素数が３〜１０の脂環式基、及び炭素数が６〜１０の芳香族基からなる群から選ばれる有機基を表す。） A thermoplastic resin laminate comprising a layer (A) comprising a thermoplastic resin composition and a layer (B) comprising a thermoplastic resin provided on at least one surface of the layer (A), wherein the layer ( The polyester resin (a) according to (I) or (II) below, wherein A) is composed of a dicarboxylic acid structural unit and a diol structural unit:
(I) 10-60 mol% in all diol structural units is represented by the following formula (1):
(II) 10 to 60 mol% in all dicarboxylic acid structural units is represented by the following formula (3):
(In the formulas (1) to (4), R 1 , R 2 , and R 3 are each independently an aliphatic group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, and This represents an organic group selected from the group consisting of aromatic groups having 6 to 10 carbon atoms.)
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