CN114381081A - Resin composition, resin laminate, and molded article - Google Patents
Resin composition, resin laminate, and molded article Download PDFInfo
- Publication number
- CN114381081A CN114381081A CN202111153594.6A CN202111153594A CN114381081A CN 114381081 A CN114381081 A CN 114381081A CN 202111153594 A CN202111153594 A CN 202111153594A CN 114381081 A CN114381081 A CN 114381081A
- Authority
- CN
- China
- Prior art keywords
- resin
- resin composition
- ultraviolet absorber
- benzotriazole
- mass
- 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.)
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- 229920005989 resin Polymers 0.000 title claims abstract description 162
- 239000011347 resin Substances 0.000 title claims abstract description 162
- 239000011342 resin composition Substances 0.000 title claims abstract description 99
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 78
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 36
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 36
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012964 benzotriazole Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000113 methacrylic resin Substances 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 46
- 230000001681 protective effect Effects 0.000 claims description 28
- -1 2H-benzotriazol-2-yl Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 17
- 239000004417 polycarbonate Substances 0.000 description 14
- 239000011241 protective layer Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 229920000515 polycarbonate Polymers 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 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 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 229920005497 Acrypet® Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- UXUFTKZYJYGMGO-CMCWBKRRSA-N (2s,3s,4r,5r)-5-[6-amino-2-[2-[4-[3-(2-aminoethylamino)-3-oxopropyl]phenyl]ethylamino]purin-9-yl]-n-ethyl-3,4-dihydroxyoxolane-2-carboxamide Chemical class O[C@@H]1[C@H](O)[C@@H](C(=O)NCC)O[C@H]1N1C2=NC(NCCC=3C=CC(CCC(=O)NCCN)=CC=3)=NC(N)=C2N=C1 UXUFTKZYJYGMGO-CMCWBKRRSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004419 Panlite Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- FXPHJTKVWZVEGA-UHFFFAOYSA-N ethenyl hydrogen carbonate Chemical class OC(=O)OC=C FXPHJTKVWZVEGA-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention addresses the problem of providing a resin composition suitable as a coating material that, when provided with a cured film obtained by curing an ultraviolet-curable resin composition on a resin substrate made of a polycarbonate resin or the like, can satisfactorily maintain the appearance of the product and can impart weather resistance, a resin laminate comprising the resin composition, and a molded article comprising the resin laminate. The resin composition comprises a methacrylic resin (A) and a benzotriazole-based ultraviolet absorber (B1), wherein the benzotriazole-based ultraviolet absorber (B1) has a molecular weight of 500 or more.
Description
Technical Field
The present invention relates to a resin composition, a resin laminate, and a molded article.
Background
Polycarbonate resins are used as housings and exterior parts of mobile phones, electric and electronic devices, and the like. However, the polycarbonate-based resin has a problem of insufficient scratch resistance because of low surface hardness. Further, the polycarbonate-based resin has a problem of insufficient weather resistance because it discolors when exposed to ultraviolet rays such as sunlight.
As a method for improving the scratch resistance of a polycarbonate resin, patent document 1 proposes a resin laminate in which a cured coating film made of an ultraviolet-curable resin is formed on the surface of a polycarbonate resin layer.
As a method for improving the weather resistance of a polycarbonate resin, patent documents 2 to 6 propose a resin laminate in which an acrylic resin layer containing an ultraviolet absorber is laminated on the surface of a polycarbonate resin layer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2014-124786
Patent document 2: japanese patent laid-open publication No. 2013-202815
Patent document 3: japanese laid-open patent publication No. 11-58626
Patent document 4: japanese patent laid-open publication No. 2010-221648
Patent document 5: japanese patent laid-open No. 2010-234640
Patent document 6: international publication No. 2014/157149
Disclosure of Invention
Problems to be solved by the invention
However, in the resin laminate disclosed in patent document 1, the polycarbonate resin layer is colored by ultraviolet irradiation when a cured film is formed. In the resin laminates disclosed in patent documents 2 to 6, at least one of the acrylic resin layer and the polycarbonate resin layer is cracked by irradiation with ultraviolet rays for a long time.
An object of the present invention is to provide a resin laminate in which the above problems are solved, and a molded article including the resin laminate.
Means for solving the problems
As a result of extensive studies to solve the above problems, the present inventors have found that the above problems can be solved by providing a protective film on a resin base material made of a polycarbonate resin and then forming a cured film thereon before forming the cured film thereon, and have completed the present invention.
Namely, the present invention is as follows.
[1] A resin composition comprising: a methacrylic resin (A), a benzotriazole-based ultraviolet absorber (B1) having a molecular weight of 500 or more, and a benzotriazole-based ultraviolet absorber (B2) having a molecular weight of 400 or less.
[2] The resin composition according to [1], wherein the molecular weight of the benzotriazole-based ultraviolet absorber (B1) is 600 or more.
[3] The resin composition according to [1] or [2], wherein the benzotriazole-based ultraviolet absorber (B2) has a molecular weight of 270 or less.
[4] The resin composition according to any one of [1] to [3], wherein the benzotriazole-based ultraviolet absorber (B1) is a compound represented by the following general formula (I),
[ solution 1]
(in the formula (I), R1And R2Each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms. )
[5] The resin composition according to any one of [1] to [4], wherein the benzotriazole-based ultraviolet absorber (B1) is 2, 2-methylenebis [4- (1,1,3, 3-tetramethylenebutyl) -6- (2H-benzotriazol-2-yl) phenol ].
[6] The resin composition according to any one of [1] to [5], wherein the benzotriazole-based ultraviolet absorber (B2) is a compound represented by the following general formula (II),
[ solution 2]
(in the formula (II), R is a C1-6 straight-chain or branched alkyl group.)
[7] The resin composition according to any one of [1] to [6], wherein the benzotriazole-based ultraviolet absorber (B2) is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
[8] The resin composition according to any one of [1] to [7], wherein the content of the benzotriazole-based ultraviolet absorber (B1) is 1.3 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the methacrylic resin (A).
[9] A resin laminate comprising a resin base material and a protective film provided on at least a part of the resin base material, wherein the protective film comprises the resin composition according to any one of [1] to [8 ].
[10] The resin laminate according to [9], wherein the resin base material comprises a polycarbonate resin composition.
[11] The resin laminate according to [9] or [10], which has a cured film on at least a part of the protective film.
[12] A molded article comprising the resin laminate according to any one of the above [9] to [11 ].
Effects of the invention
According to the present invention, a resin composition, a resin laminate, and a molded article having excellent product appearance in which a polycarbonate resin layer is not colored or cracked and improved weather resistance can be provided.
Detailed Description
The present invention will be described in detail below.
In the present specification, "(meth) acrylic acid" means at least 1 selected from "acrylic acid" and "methacrylic acid".
In the present specification, "monomer" means an unpolymerized compound, and "repeating unit" and "structural unit" mean a unit derived from a monomer formed by polymerizing the monomer. The repeating unit and the structural unit may be units directly formed by a polymerization reaction, or may be units obtained by treating a polymer to convert a part of the units into other structures.
In the present specification, the term "obtained resin laminate" refers to a resin laminate obtained by forming a protective film comprising the resin composition of the present invention on at least one surface of a resin base material composed of a polycarbonate resin composition.
In the present specification, "mass%" means a content ratio of a specific component contained in the total amount of 100 mass%.
In the present specification, unless otherwise specified, a numerical range represented by the term "to" means a range including the numerical values described before and after the term "to" as a lower limit value and an upper limit value, and "a to B" means a value not less than a and not more than B.
In the present invention, "transparency" means that the total light transmittance measured according to JIS K7361-1 is 75% or more.
< resin composition >
The resin composition of the present invention is a resin composition containing a methacrylic resin (a), a benzotriazole-based ultraviolet absorber (B1), and a benzotriazole-based ultraviolet absorber (B2).
In particular, the resin composition of the present invention is characterized by comprising: a benzotriazole-based ultraviolet absorber (B1) and an ultraviolet absorber (B2) having a lower molecular weight than the benzotriazole-based ultraviolet absorber (B1).
Since the resin composition of the present invention contains the methacrylic resin (a), a resin laminate (hereinafter referred to as "obtained resin laminate") having a protective layer containing the resin composition on the surface of a resin base material made of a polycarbonate resin composition has excellent transparency.
The resin composition of the present invention contains both the benzotriazole-based ultraviolet absorber (B1) and the benzotriazole-based ultraviolet absorber (B2), and therefore the resulting resin laminate is excellent in weather resistance and product appearance.
The resin composition of the present invention may contain, if necessary, known additives such as an impact strength modifier, a mold release agent, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, and a flame retardant, in a range not to impair the effects of the present invention.
< methacrylic resin (A) >
The methacrylic resin (a) is one of the constituent components constituting the resin composition of the present invention.
The methacrylic resin (a) in the present invention preferably contains 70% by weight or more of repeating units derived from methyl methacrylate (hereinafter referred to as "methyl methacrylate units") based on the total mass of the methacrylic resin (a).
One embodiment of the methacrylic resin (a) in the present invention includes a homopolymer of methyl methacrylate, or a methyl methacrylate copolymer (hereinafter, also referred to as "polymer (a 1)") in which the content ratio of methyl methacrylate units in the methacrylic resin (a) is 70 mass% or more and less than 100 mass%.
< Polymer (A1) >
The polymer (a1) is a homopolymer of methyl methacrylate, or a methyl methacrylate copolymer containing 70 mass% or more and less than 100 mass% of methyl methacrylate units and more than 0 mass% and 30 mass% or less of repeating units derived from another monomer copolymerizable with methyl methacrylate (hereinafter referred to as "other monomer units").
Among these polymers (a1), a copolymer or a homopolymer of methyl methacrylate in which the content of methyl methacrylate units in the polymer (a1) is 90% by mass or more with respect to methyl methacrylate units is preferable, and a copolymer or a homopolymer of methyl methacrylate in which the content of methyl methacrylate units in the polymer (a1) is 95% by mass or more is more preferable.
The other monomer is not particularly limited as long as it is a monomer copolymerizable with methyl methacrylate, and examples thereof include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methyl methacrylate, and the like, (meth) acrylate compounds other than methyl methacrylate such as 2-hydroxypropyl (meth) acrylate; (meth) acrylic acid; (meth) acrylonitrile; (meth) acrylamide compounds such as (meth) acrylamide and N-dimethyl (meth) acrylamide; aromatic vinyl compounds such as styrene and α -methylstyrene; vinyl ether compounds such as vinyl methyl ether, vinyl ethyl ether and 2-hydroxyethyl vinyl ether; vinyl carbonate compounds such as vinyl acetate and vinyl butyrate; olefin compounds such as ethylene, propylene, butene and isobutylene. These other monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Among these other monomers, (meth) acrylate compounds other than methyl methacrylate are preferred from the viewpoint of not impairing the original performance of the acrylic resin, and methyl acrylate, ethyl acrylate and n-butyl acrylate are more preferred, and methyl acrylate and ethyl acrylate are still more preferred, from the viewpoint of excellent thermal decomposition resistance of the resulting resin molded article.
When the polymer (a1) contains another monomer unit, the content of the other monomer unit is preferably 20 mass% or less, more preferably 10 mass% or less, and still more preferably 5 mass% or less, based on 100 mass% of the polymer (a 1).
Examples of the method for producing the polymer (a1) include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among these polymerization methods, the bulk polymerization method and the suspension polymerization method are preferable, and the bulk polymerization is more preferable, from the viewpoint of excellent productivity.
The mass average molecular weight of the polymer (A1) is preferably 20,000 to 200,000, more preferably 50,000 to 150,000. When the mass average molecular weight of the polymer (A1) is 20,000 or more, the resulting resin molded article is excellent in mechanical properties. Further, if the mass average molecular weight of the polymer (a1) is 200,000 or less, the fluidity at the time of melt molding is excellent.
In the present specification, the mass average molecular weight is a value measured by gel permeation chromatography using standard polystyrene as a standard sample.
The lower limit of the content of the methacrylic resin (a) in the total mass (100 mass%) of the resin composition of the present invention is preferably 55 mass% or more in view of transparency, heat resistance, weather resistance and the like of the obtained resin molded product. More preferably 70% by mass or more, and still more preferably 90% by mass or more. The upper limit of the content of the methacrylic resin (a) is preferably 99 mass% or less in view of excellent scratch resistance of the resulting resin molded product. More preferably 98% by mass or less, and still more preferably 97% by mass or less.
The above-mentioned preferable upper limit and preferable lower limit may be arbitrarily combined. For example, the content of the methacrylic resin (a) in the total mass (100 mass%) of the resin composition of the present invention is 55 mass% or more, preferably 99 mass% or less, more preferably 70 mass% or more and 98 mass% or less, and further preferably 90 mass% or more and 97 mass% or less.
Commercially available methacrylic resins include ACRYPET (registered trademark) VH, MD, MF, IRK304, VRL40 (both trade names, manufactured by mitsubishi chemical corporation), and the like.
< benzotriazole-based ultraviolet absorber (B1) >
The benzotriazole-based ultraviolet absorber (B1) (hereinafter referred to as "ultraviolet absorber (B1)") is one of the constituent components constituting the resin composition of the present invention.
By including the ultraviolet absorber (B1) in the resin composition of the present invention, a resin laminate having excellent weather resistance and excellent product appearance can be provided.
The lower limit of the wavelength at which the ultraviolet absorber (B1) exhibits an absorbance maximum is 340nm or more, more preferably 343nm or more, and still more preferably 345nm or more. When the wavelength is such a wavelength, coloring due to ultraviolet irradiation can be suppressed when a cured film is formed on the surface of the resin base material.
On the other hand, the upper limit of the wavelength at which the maximum value of absorbance is expressed is 400nm or less, more preferably 385nm or less, and still more preferably 370nm or less. If the wavelength is such, ultraviolet rays irradiated when a cured film is formed on the surface of the resin substrate can be efficiently absorbed, and coloring of the resin substrate can be prevented.
The above-mentioned preferable upper limit and preferable lower limit may be arbitrarily combined. For example, the wavelength at which the ultraviolet absorber (B1) exhibits an absorbance maximum is 340nm to 400 nm. More preferably 343nm to 385nm, still more preferably 345nm to 370 nm.
The lower limit of the molecular weight of the ultraviolet absorber (B1) is 500 or more, from the viewpoint of particularly excellent weather resistance of the resulting resin laminate. More preferably 550 or more, and still more preferably 600 or more. On the other hand, the upper limit of the molecular weight is not particularly limited, but is 1300 or less from the viewpoint of excellent solubility in the resin composition. More preferably 1000 or less, and still more preferably 750 or less.
Presume that: when the lower limit of the molecular weight of the ultraviolet absorber (B1) is 500 or more, the ultraviolet absorber does not bleed out onto the surface of the protective layer or is locally present in the vicinity of the surface, and the ultraviolet absorber is also present inside the protective layer, and therefore the resulting resin laminate has excellent weather resistance.
The above-mentioned preferable upper limit and preferable lower limit may be arbitrarily combined. For example, the molecular weight of the ultraviolet absorber (B1) in the present invention may be 500 or more and 1300 or less. More preferably 550 to 1000, and still more preferably 600 to 750.
Examples of the ultraviolet absorber (B1) include 2, 2-methylenebis [4- (1,1,3, 3-tetramethylenebutyl) -6- (2H-benzotriazol-2-yl) phenol ], poly (ethylene glycol) 300- β - [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl ] -propionic acid, poly (ethylene glycol) 300-bis { β - [3- (2H-benzotriazol-2-yl) -4-hydroxy-5-t-butylphenyl ] -propionic acid }, and the like. Specifically, commercially available products such as ADK STAB (registered trademark) LA-31G, LA-31RG (product name, manufactured by ADEKA corporation) and Tinuvin (registered trademark) 1130 (product name, manufactured by BASF corporation) can be used. These ultraviolet absorbers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The structure of the ultraviolet absorber (B1) is not particularly limited, and a compound represented by the following general formula (I) is preferable from the viewpoint of excellent weather resistance of the obtained resin molded product and excellent product appearance.
[ solution 1]
(in the formula (I), R1And R2Independently of each other, a straight-chain or branched alkyl group having 1 to 16 carbon atoms. )
Specific examples of the compound represented by the general formula (I) include commercially available compounds such as ADK STAB (registered trademark) LA-31G, LA-31RG (product name, compound name: 2, 2-methylenebis [4- (1,1,3, 3-tetramethylenebutyl) -6- (2H-benzotriazol-2-yl) phenol ], ADEKA company).
The lower limit of the content of the ultraviolet absorber (B1) in the resin composition is not particularly limited, but is preferably 0.01 part by mass or more based on 100 parts by mass of the methacrylic resin (a) from the viewpoint of excellent weather resistance of the resulting resin molded article and excellent product appearance. More preferably 0.1 part by mass or more, still more preferably 0.3 part by mass or more, and particularly preferably 1.3 parts by mass or more. On the other hand, the lower limit of the content of the ultraviolet absorber (B1) is not particularly limited, but is preferably 10 parts by mass or less based on 100 parts by mass of the methacrylic resin (a) from the viewpoint of suppressing coloring of the obtained resin laminate by the ultraviolet absorber (B1) itself and maintaining the product appearance satisfactorily. More preferably 7.0 parts by mass or less, still more preferably 5.0 parts by mass or less, and particularly preferably 3.0 parts by mass or less.
The above-mentioned preferable upper limit and preferable lower limit may be arbitrarily combined. That is, the content of the ultraviolet absorber (B1) in the resin composition is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8.5 parts by mass, still more preferably 0.3 to 7.0 parts by mass, and particularly preferably 1.3 to 5.0 parts by mass, based on 100 parts by mass of the methacrylic resin (a).
< benzotriazole-based ultraviolet absorber (B2) >
The benzotriazole-based ultraviolet absorber (B2) (hereinafter referred to as "ultraviolet absorber (B2)") is one of the constituent components constituting the resin composition of the present invention.
The resin composition of the present invention can further contain an ultraviolet absorber (B2) in addition to the ultraviolet absorber (B1), and can provide a resin laminate having excellent weather resistance and product appearance.
The upper limit of the molecular weight of the ultraviolet absorber (B2) is less than 500 from the viewpoint of more excellent weather resistance of the resulting resin laminate. More preferably 400 or less, and still more preferably 270 or less. On the other hand, the lower limit of the molecular weight is not particularly limited, and is preferably 150 or more from the viewpoint of heat resistance and blocking resistance (surface adhesion) of the resin laminate. More preferably 180 or more, and still more preferably 200 or more.
By using the ultraviolet absorber (B2) in combination with the ultraviolet absorber (B1), the ultraviolet absorber (B1) is present inside the protective layer of the resin laminate obtained as described above, while the ultraviolet absorber (B2) having a small molecular weight bleeds out to the surface of the protective layer made of the resin composition or is locally present in the vicinity of the surface. It is presumed that the ultraviolet absorbers are present on the surface, near the surface, and inside of the protective layer, and therefore the obtained resin laminate is more excellent in weather resistance.
The above-mentioned preferable upper limit and preferable lower limit may be arbitrarily combined. For example, the molecular weight of the ultraviolet absorber (B2) in the present invention may be 150 or more and less than 500. More preferably 180 to 400, and still more preferably 200 to 270.
The lower limit of the wavelength at which the ultraviolet absorber (B2) exhibits the maximum absorbance is not particularly limited. From the viewpoint of complementing the ultraviolet absorbing action of the ultraviolet absorber (B1), it is 320nm or more, more preferably 330nm or more, and still more preferably 335nm or more.
On the other hand, the upper limit of the wavelength showing the maximum value of absorbance is 360nm or less, more preferably 355nm or less, and still more preferably 350nm or less.
The above-mentioned preferable upper limit and preferable lower limit may be arbitrarily combined. For example, the wavelength at which the ultraviolet absorber (B1) in the present invention exhibits the maximum absorbance is 320nm to 360 nm. More preferably 330nm to 355nm, still more preferably 335nm to 350 nm.
Examples of the ultraviolet absorber (B2) include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2 ' -methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol ], 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [ 5-chloro- (2H) -benzotriazol-2-yl ] -4-methyl-6- (tert-butyl) phenol, and mixtures thereof, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and the like. Specifically, commercially available products such as ADK STAB (registered trademark) LA-24, LA-29, LA-32, LA-36 (product name, manufactured by ADEKA Co., Ltd.), Tinuvin (registered trademark) P, PS, 99-2, 326, 384-2, 900, 929 (product name, manufactured by BASF Co., Ltd.) and the like can be used.
The structure of the ultraviolet absorber (B2) is not particularly limited, and a compound represented by the following general formula (II) is preferable from the viewpoint of excellent weather resistance of the obtained resin molded product and excellent product appearance.
[ solution 2]
(in the formula (II), R represents a C1-6 straight-chain or branched alkyl group.)
< method for producing resin composition >
The resin composition of the present invention is produced by mixing a mixture containing the methacrylic resin (a), the ultraviolet absorber (B1) and the ultraviolet absorber (B2).
The method of mixing is not particularly limited, and for example, a known melt kneading method, a known solvent kneading method, a known dry blending method, or the like is used, and the melt kneading method is preferably used in view of productivity. As the apparatus used for mixing, a usual mixer, a kneader or the like can be used, and specific examples thereof include a single-shaft kneading extruder, a twin-shaft kneading extruder, a ribbon mixer, a henschel mixer, a banbury mixer, a tumble mixer and the like.
In the resin composition of the present invention, the use of a biaxial kneading extruder enables the ultraviolet absorber (B1) and the ultraviolet absorber (B2) (hereinafter referred to as "ultraviolet absorbers (B1, B2)") to be uniformly dispersed in the resin composition without aggregation, and therefore the resulting resin laminate is excellent in weather resistance and product appearance.
Specifically, a mixture containing the methacrylic resin (a) and the ultraviolet absorbers (B1, B2) is melted and mixed in a temperature range of the melting point of the methacrylic resin (a) to the melting point +100 ℃ using a biaxial kneading extruder, and the mixture is obtained as a pellet-shaped resin composition.
By setting the temperature at which the mixture containing the methacrylic resin (a) and the ultraviolet absorbers (B1, B2) is melted and mixed using a biaxial kneading extruder to a temperature range of not less than the melting point of the methacrylic resin (a) but not more than the melting point +100 ℃, the deterioration and coloring due to heating of the mixture can be suppressed, and the resulting resin laminate is excellent in transparency.
The resin composition of the present invention may contain, as required, various additives, for example, known additives such as an antioxidant, a stabilizer, an ultraviolet absorber, a lubricant, a processing aid, an antistatic agent, a colorant, an impact resistance aid, a foaming agent, a filler, and a matting agent, within a range not impairing the effects of the present invention.
The resin composition of the present invention can be suitably used as a coating material for imparting weather resistance to a resin substrate made of a polycarbonate resin composition without impairing the appearance of the product.
Therefore, the resin composition of the present invention is suitably used as a protective layer for coating a resin base material made of a polycarbonate resin composition in applications to a mobile phone case, a mobile phone front panel, or an electric and electronic device case.
< resin laminate >
The resin laminate of the present invention is a resin laminate having a protective film on at least one surface of a resin base material.
In the resin laminate of the present invention, the resin base material is composed of a polycarbonate resin composition.
The resin laminate obtained by forming the resin base material from the polycarbonate resin composition has excellent transparency.
The resin laminate of the present invention may be: a cured film described later is further formed on the surface of the protective film, and the pencil hardness of the surface of the cured film in the resin laminate is 4H or more.
(polycarbonate resin composition)
The polycarbonate resin composition of the present invention is a material for forming the resin base of the resin laminate of the present invention, and is a resin composition containing a polycarbonate resin described later.
The polycarbonate resin composition contains a polycarbonate resin, and the resin laminate of the present invention has excellent transparency.
The polycarbonate-based resin composition may be composed of 100 mass% of a polycarbonate-based resin. Alternatively, or in addition, the polycarbonate-based resin composition may contain 80 mass% or more of the polycarbonate-based resin relative to 100 mass% of the total mass of the polycarbonate-based resin composition. When the content of the polycarbonate-based resin is 80% by mass or more, the transparency of the resulting resin laminate can be improved.
The polycarbonate resin composition may contain, as necessary, known additives such as an impact strength modifier, a mold release agent, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, a flame retardant, a lubricant, a plasticizer, an antistatic agent, a weather resistance stabilizer, a light resistance stabilizer, a heat stabilizer, a filler, a pigment, a dye, and a fluorescent agent, as long as the effects of the present invention are not impaired.
(polycarbonate-series resin)
Examples of the polycarbonate-based resin that can be used as the transparent resin in the present invention include resins obtained by reacting a known dihydric phenol with a known carbonylating agent by an interfacial polycondensation method, a melt transesterification method, or the like; a resin obtained by polymerizing a known carbonate prepolymer by a solid-phase transesterification method or the like; and resins obtained by polymerizing known cyclic carbonate compounds by ring-opening polymerization.
Commercially available polycarbonate resins include Panlite series (trade name, manufactured by Dimitsubishi chemical Co., Ltd.), Upilon series (trade name, manufactured by Mitsubishi engineering plastics Co., Ltd.), SD PolyCA series (trade name, manufactured by Sumitomo Dow Co., Ltd.), CALIBER series (trade name, manufactured by Dow chemical Co., Ltd.), CZ series, PCZ series (trade name, manufactured by Mitsubishi gas chemical Co., Ltd.), and APEC series (trade name, manufactured by Bayer).
In the resin laminate of the present invention, the protective film comprises the resin composition of the present invention.
The protective film is formed by using the resin composition of the present invention, and the obtained resin laminate is excellent in weather resistance and molded appearance for the above reasons.
The lower limit of the overall thickness of the resin laminate of the present invention is not particularly limited, and may be set to 100 μm or more from the viewpoint of ensuring sufficient mechanical strength. On the other hand, the upper limit of the thickness is not particularly limited, and may be 3000 μm or less from the viewpoint of moldability of the resin laminate.
In the resin laminate of the present invention, the thickness of the protective film is not particularly limited, and may be 1 to 50% of the total thickness from the viewpoint of improving the weather resistance of the resin laminate and the appearance of the product.
In the resin laminate of the present invention, the lower limit of the thickness of the resin base material is not particularly limited, and may be 100 μm or more from the viewpoint of ensuring sufficient mechanical strength. On the other hand, the upper limit of the thickness is not particularly limited, and may be 3000 μm or less from the viewpoint of moldability of the resin laminate.
< method for producing resin laminate >
The method for producing the resin laminate of the present invention is not particularly limited, and examples thereof include the following methods.
Coextrusion molding method: the polycarbonate resin composition is melt-coextruded at a temperature preferably higher by 100 to 200 ℃ than the glass transition temperature (hereinafter referred to as Tg) of the polycarbonate resin composition, and the resin composition of the present invention is melt-coextruded at a temperature higher by 100 to 200 ℃ than the Tg of the resin composition, and then cooled by a cooling roll of 80 to 160 ℃.
Injection molding: the polycarbonate resin composition is molded separately at a temperature 100 to 200 ℃ higher than the Tg of the polycarbonate resin composition, and the resin composition of the present invention is molded separately at a temperature 100 to 200 ℃ higher than the Tg of the transparent resin composition. Alternatively, a molded piece of one of the polycarbonate resin composition and the transparent resin composition of the present invention, which is molded in advance by extrusion molding, injection molding, or the like, is placed in a mold, and the other is then injection molded to be integrated.
Hot pressing and connecting: the molded polycarbonate resin composition sheet molded in advance by extrusion molding, injection molding, or the like is thermocompression bonded to the molded resin composition sheet of the present invention by a laminator or a press. Alternatively, the polycarbonate-based resin composition immediately after extrusion and the resin composition of the present invention are thermally press-bonded to one sheet of the other sheet which has been molded in advance. In this case, the temperature for thermocompression bonding is preferably set to a temperature 100 to 200 ℃ higher than the Tg of the polycarbonate resin composition or the resin composition of the present invention, which is higher than the Tg.
The resin laminate of the present invention may be produced by bonding a molded piece of a polycarbonate resin composition molded in advance to a molded piece of a transparent resin composition of the present invention with an adhesive or the like.
< cured coating film >
The resin laminate of the present invention may further have a cured film formed by curing an ultraviolet-curable resin composition on the surface of the protective film.
By forming a cured coating film on the surface of the protective film, the resulting resin laminate is more excellent in scratch resistance. Specifically, the cured film is preferably formed so that the pencil hardness of the surface of the cured film in the resin laminate becomes 4H or more.
The pencil hardness can be controlled by appropriately selecting the composition of the resin composition used as the protective film, the composition of the ultraviolet-curable composition used as a raw material for the cured film, and the thickness of the cured film.
As the cured film, for example, a resin cured product obtained by curing a known ultraviolet-curable resin composition can be used from the viewpoint of excellent productivity and workability.
The type of the ultraviolet-curable resin composition is not particularly limited, and examples thereof include at least 1 curable resin composition selected from the group consisting of an acrylic curable resin composition, a polyurethane curable resin composition, a urethane acrylate curable resin composition, a silicone resin curable resin composition, a polyether curable resin composition, a polyester curable resin composition, a phenol curable resin composition, a melamine curable resin composition, and an epoxy curable resin composition. A resin cured product obtained by curing these curable resin compositions is excellent not only in scratch resistance and transparency but also in adhesion to the protective layer.
Among the ultraviolet curable resin compositions, particularly, the acrylic curable resin composition is advantageous because it has excellent adhesion to the protective layer.
Examples of the acrylic curable resin composition include a curable composition containing a polyfunctional acrylate compound as a main component (hereinafter referred to as "polyfunctional acrylate curable composition").
The multifunctional acrylate curable composition is a curable composition containing a compound (c1) having at least 2 or more (meth) acryloyl groups in the molecule and a polymerization initiator (c 2). Specific examples thereof include the compositions disclosed in paragraphs [0006] and [0007] of Japanese patent application laid-open No. 2005-248070. Further, as for details of the acrylic cured film, the paragraphs [0014] to [0033] of the publication can be referred to.
In the resin laminate of the present invention, a method for forming a cured coating film on the surface of the protective film is not particularly limited, and for example, an ultraviolet curable composition may be first applied to the surface of the protective layer of the resin laminate by a known application method such as roll coating, bar coating, or slit die coating.
Next, the ultraviolet curable composition applied to the surface of the protective layer is irradiated with ultraviolet rays, and the ultraviolet curable composition is cured to obtain a resin cured product. As a method of irradiating ultraviolet rays, an ultraviolet lamp may be used.
Examples of the ultraviolet lamp include a high-pressure mercury lamp, a metal halide lamp, and a fluorescent ultraviolet lamp. The curing by ultraviolet irradiation may be performed in 1 stage, or may be performed in 2 stages such as performing the curing in the first stage, further performing the curing in the second stage by further ultraviolet irradiation, and the like. A resin laminate having a cured coating film formed on the surface of the protective layer can be obtained.
The light to be irradiated in the curing treatment is, for example, an electron beam or ultraviolet ray, and the kind of light to be irradiated and the irradiation conditions are appropriately selected depending on the kind of the component of the curable composition to be used. Usually, the irradiation light quantity is 500 to 2000mJ/cm2The ultraviolet ray is irradiated to a high degree, and a high-strength cured coating film which contributes to the improvement of the scratch resistance of the resin laminate can be formed.
In the resin laminate of the present invention, the thickness of the cured film is not particularly limited, and is usually 0.5 to 50 μm in terms of satisfying both the improvement of durability and the optical properties of the resin laminate. The thickness may be 5 to 40 μm, or 10 to 30 μm.
< molded article >
The resin laminate of the present invention is excellent in weather resistance and product appearance. Therefore, a molded article comprising the resin laminate of the present invention can be suitably used for a mobile phone case, a mobile phone front panel, or an electric and electronic device case.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
< evaluation method >
The evaluations in the examples and comparative examples were carried out by the following methods.
(1) Surface hardness
As an index of scratch resistance, the scratch resistance was measured in accordance with ISO 2409: 1992 the pencil hardness of the surface of the protective film of the resin laminate obtained in examples and comparative examples was measured to evaluate the surface hardness.
In comparative examples in which the resin laminate was composed of only the resin base material without the protective film, the surface of the resin base material was evaluated.
In the case of the resin laminate having the cured film on the surface of the protective film, the surface of the cured film of the resin laminate was evaluated.
(2) Appearance of the article
As an index of product appearance, the resin laminate obtained in examples and comparative examples was visually observed from a direction parallel to the principal plane of the resin laminate (resin substrate) while being irradiated with light from a desk lamp (fluorescent lamp 27W), and the degree of increase in coloring of the resin substrate with respect to reference example 1 was observed, and the following criteria were used for determination. The results are shown in Table 2.
(criteria for determination)
O: almost no increase in coloration in the resin base material was observed.
And (delta): a slight increase in coloration in the resin substrate was observed.
X: a significant increase in coloration in the resin substrate was observed.
(3) Weather resistance
As an index of weather resistance, a Super accelerated weather resistance Tester ("EYE Super UV Tester SUV-W161" manufactured by yazaki electric corporation) was used for the resin laminate obtained in examples and comparative examples and the resin substrate of production example 1, and a accelerated weather resistance test was performed with the following 3 steps as 1 cycle.
(1) UV irradiation step (irradiation intensity: 150 mW/cm)2And temperature: 63 ℃ and humidity: 50%) for 6 hours
(2) The condensation step (temperature: 60 ℃ C., humidity: 90%) was carried out for 4 hours
(3) Rest procedure 2 hours
Next, a test piece having a size of 300mm in length and 300mm in width was cut from the resin laminate (reference example 1 was a resin substrate) after the test time of 300 hours, and the periphery of the crack (fissure) visually observed was inspected with an oil pen while irradiating the resin laminate with light from a desk lamp (fluorescent lamp 27W manufactured by panasonic corporation) in a dark room. The above observation was performed on both surfaces of the resin laminate (reference example 1 is a resin base), and the total number of cracks in the protective film and the resin base was measured and determined by the following criteria. The total number of cracks observed in the laminate composed of the protective film and the resin base material was measured by this method. The results are shown in Table 2.
(criteria for determination)
O: no cracks were observed.
And (delta): the number of cracks is 1-9.
X: the number of cracks was 10 or more.
(raw materials)
In addition, the compounds used in examples and comparative examples are abbreviated as follows.
Acrylic resin (A-1): ACRYPET (registered trademark) VH (trade name, manufactured by Mitsubishi chemical corporation), an acrylic resin containing 95 mass% or more of repeating units derived from methyl methacrylate and having a mass average molecular weight of 8 ten thousand)
PC resin (1): polycarbonate resin (product name: Upilon S-2000, manufactured by Mitsubishi engineering plastics Co., Ltd.)
Benzotriazole-based ultraviolet absorber (B1-1): 2, 2-methylenebis [4- (1,1,3, 3-tetramethylenebutyl) -6- (2H-benzotriazol-2-yl) phenol ], a molecular weight of 659, and a wavelength of 350m (trade name: ADK STAB (registered trade Mark) LA-31RG, manufactured by ADEKA Co., Ltd.) showing an absorbance maximum
Benzotriazole-based ultraviolet absorber (B2-1): 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, molecular weight 225, and wavelength 341nm showing maximum absorbance (trade name: Tinuvin P, manufactured by BASF)
Examples of the resin composition and the resin laminate of the present invention are disclosed below in examples.
Production example 1
100 parts by mass of an acrylic resin (A-1), 1.5 parts by mass of a benzotriazole-based ultraviolet absorber (B1-1) as an ultraviolet absorber (B1), and 0.1 part by mass of a benzotriazole-based ultraviolet absorber (B2-1) as an ultraviolet absorber (B2) were supplied to a biaxial extruder (model name "PCM 30", manufactured by Chiba, Ltd.), and kneaded at 250 ℃ to obtain a granular methacrylic resin composition, which was used as the resin composition (X-1).
Production examples 2 to 8
Granular methacrylic resin compositions were obtained in the same manner as in example 1 except for the compounding ratios shown in Table 1, and these were used as resin compositions (X-2) to (X-8).
[ Table 1]
Production example 9
An ultraviolet-curable composition (1) as a material for a cured film was produced according to the following procedure. 31.5 parts of a urethane compound obtained by reacting 3 moles of 3-acryloyloxy-2-hydroxypropyl methacrylate with 1 mole of triisocyanate composed of a 3-mer of hexamethylene diisocyanate, 6 parts of pentaerythritol triacrylate, 4 parts of pentaerythritol tetraacrylate, 58.5 parts of 1, 6-hexanediol diacrylate, and 1.5 parts of benzoin ethyl ether as a photopolymerization initiator were mixed and dissolved to prepare an ultraviolet-curable composition (1).
[ example 1]
PC resin (1) was melted by a single-screw extruder (manufactured by Toshiba machine Co., Ltd.) having a screw diameter of 60mm, the resin composition (X-1) obtained in production example 1 was melted by a single-screw extruder (manufactured by Toshiba machine Co., Ltd.) having a screw diameter of 40mm, and the melted resin composition was laminated and integrated into 2 layers by a feed block method (フィードブロック method), and the 2 layers were extruded through a T-die having a set temperature of 280 ℃ to obtain a sheet, and the obtained sheet was cooled by a smooth-surfaced metal roll, thereby producing a resin laminate having a 2-layer structure in a sheet form having a thickness of 300mm and a protective layer of 50 μm formed from a transparent resin composition (X-1) formed on the surface of a resin base having a thickness of 1000 μm.
Next, the ultraviolet-curable composition (1) produced in production example 8 was applied to the surface of the protective layer of the obtained 2-layer resin laminate using a bar coater so that the film thickness became 27 μm, and a layer of the pre-cured film (1-1) was provided.
Next, the resin laminate was passed through a high-pressure mercury lamp (output: 30W/cm) at a speed of 10 m/min so that the layer of the pre-cured coating film (1-1) was on the upper side2) And irradiating the pre-cured coating film (1-1) with ultraviolet light from a high-pressure mercury lamp at a position 20cm below the substrate, thereby curing the pre-cured coating film (1-1) to obtain a cured coating film. That is, a sheet-like 3-layer structure resin laminate having a thickness of 1075 μm was obtained in which a cured film having a thickness of 25 μm was further laminated on the surface of the resin laminate.
The evaluation results of the obtained resin laminate having a 3-layer structure are shown in table 2.
Examples 2 to 3 and comparative examples 1 to 5
A sheet-like resin laminate having a 3-layer structure was obtained in the same manner as in example 1, except that the types of the resin compositions used for the protective film were as shown in table 1. The evaluation results of the obtained resin laminate having a 3-layer structure are shown in table 2.
[ reference example 1]
The PC resin (1) was melted by a single-screw extruder (manufactured by Toshiba machine Co., Ltd.) having a screw diameter of 60mm, extruded through a T-die having a set temperature of 280 ℃ and the obtained sheet-like material was cooled by a smooth-surfaced metal roll to produce a sheet-like resin substrate made of the PC resin (1) and having a thickness of 1000 μm and a width of 300 mm.
The evaluation results of the obtained sheet-like resin substrate are shown in table 2. The pencil hardness was measured on the surface of the resin substrate. The resin base material was evaluated for weather resistance.
Comparative example 6
On the surface of the resin substrate obtained in reference example 1, a sheet-like laminate having a 2-layer structure with a thickness of 1025 μm was obtained in the same manner as in example 1, in which a cured film having a thickness of 25 μm obtained by curing the ultraviolet-curable composition (1) produced in production example 8 was laminated. The evaluation results of the obtained 2-layer laminate are shown in table 2.
[ Table 2]
The resin laminates obtained in examples 1 and 2 were excellent in weather resistance and product appearance.
In the resin laminate obtained in comparative example 1, the protective film does not contain the ultraviolet absorber (B1) and the ultraviolet absorber (B2), and therefore the appearance and weather resistance of the product are poor.
In the resin laminate obtained in comparative example 2, the protective film contained no ultraviolet absorber (B1), and therefore the appearance and weather resistance of the product were insufficient.
In the resin laminates obtained in comparative examples 3 to 5, the protective films did not contain the ultraviolet absorber (B2), and therefore the appearance and weather resistance of the products were insufficient.
The resin substrate of reference example 1 had a poor pencil hardness because it did not have a cured coating. In addition, the weather resistance is poor.
The resin laminate obtained in comparative example 6 has no protective film, and therefore, the appearance and weather resistance of the product are poor.
Industrial applicability
The resin composition of the present invention is suitable as a coating material which can maintain the appearance of a product well and impart weather resistance when a cured film obtained by curing an ultraviolet-curable resin composition is provided on a resin substrate made of a polycarbonate resin composition.
The resin laminate of the present invention has a protective film comprising the resin composition of the present invention on the surface of a resin substrate made of a polycarbonate resin composition, and further has a cured coating film obtained by curing an ultraviolet-curable resin composition, and thus has excellent scratch resistance, as well as excellent product appearance and weather resistance.
The resin laminate of the present invention can be suitably used for a mobile phone case, a mobile phone front panel, or an electric and electronic device case.
Claims (12)
1. A resin composition comprising: a methacrylic resin (A), a benzotriazole-based ultraviolet absorber (B1) having a molecular weight of 500 or more, and a benzotriazole-based ultraviolet absorber (B2) having a molecular weight of 400 or less.
2. The resin composition according to claim 1, wherein the molecular weight of the benzotriazole-based ultraviolet absorber (B1) is 600 or more.
3. The resin composition according to claim 1 or 2, wherein the molecular weight of the benzotriazole-based ultraviolet absorber (B2) is 270 or less.
4. The resin composition according to any one of claims 1 to 3, wherein the benzotriazole-based ultraviolet absorber (B1) is a compound represented by the following general formula (I),
[ solution 1]
In the formula (I), R1And R2Each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms.
5. The resin composition according to any one of claims 1 to 4, wherein the benzotriazole-based ultraviolet absorber (B1) is 2, 2-methylenebis [4- (1,1,3, 3-tetramethylenebutyl) -6- (2H-benzotriazol-2-yl) phenol ].
6. The resin composition according to any one of claims 1 to 5, wherein the benzotriazole-based ultraviolet absorber (B2) is a compound represented by the following general formula (II),
[ solution 2]
In the formula (II), R represents a linear or branched alkyl group having 1 to 6 carbon atoms.
7. The resin composition according to any one of claims 1 to 6, wherein the benzotriazole-based ultraviolet absorber (B2) is 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole.
8. The resin composition according to any one of claims 1 to 7, wherein the content of the benzotriazole-based ultraviolet absorber (B1) is 1.3 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the methacrylic resin (A).
9. A resin laminate comprising a resin base material and a protective film provided on at least a part of the resin base material, wherein the protective film comprises the resin composition according to any one of claims 1 to 8.
10. The resin laminate according to claim 9, wherein the resin base material comprises a polycarbonate resin composition.
11. The resin laminate according to claim 9 or 10, wherein the protective film has a cured coating film on at least a part thereof.
12. A molded article comprising the resin laminate according to any one of claims 9 to 11.
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| JP2020169257 | 2020-10-06 | ||
| JP2020-169257 | 2020-10-06 |
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| CN114381081A true CN114381081A (en) | 2022-04-22 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000109652A (en) * | 1998-10-01 | 2000-04-18 | Arakawa Chem Ind Co Ltd | Ultraviolet-screening activation energy ray curable composition, curable coating material and molded product coated therewith |
| JP2008074916A (en) * | 2006-09-20 | 2008-04-03 | Sumitomo Chemical Co Ltd | Ultraviolet light-cutting film |
| CN101161454A (en) * | 2006-10-11 | 2008-04-16 | 住友化学株式会社 | Multilayer acrylic resin film |
| CN101844429A (en) * | 2009-03-25 | 2010-09-29 | 住友化学株式会社 | Scratch resistant resin board and use its display baffle and the display window protective panel of carrying type information terminal |
| CN107001762A (en) * | 2014-12-18 | 2017-08-01 | 株式会社艾迪科 | The layered product of acrylic acid resin composition and stacking said composition |
| CN107429032A (en) * | 2015-04-03 | 2017-12-01 | 株式会社可乐丽 | Resin combination and its manufacture method, formed body, film and article |
| CN109071953A (en) * | 2016-06-17 | 2018-12-21 | 东丽株式会社 | Resin combination, cured film, the manufacturing method of cured film and display device |
-
2021
- 2021-09-29 CN CN202111153594.6A patent/CN114381081A/en not_active Withdrawn
- 2021-10-06 JP JP2021164942A patent/JP2022061503A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000109652A (en) * | 1998-10-01 | 2000-04-18 | Arakawa Chem Ind Co Ltd | Ultraviolet-screening activation energy ray curable composition, curable coating material and molded product coated therewith |
| JP2008074916A (en) * | 2006-09-20 | 2008-04-03 | Sumitomo Chemical Co Ltd | Ultraviolet light-cutting film |
| CN101161454A (en) * | 2006-10-11 | 2008-04-16 | 住友化学株式会社 | Multilayer acrylic resin film |
| CN101844429A (en) * | 2009-03-25 | 2010-09-29 | 住友化学株式会社 | Scratch resistant resin board and use its display baffle and the display window protective panel of carrying type information terminal |
| CN107001762A (en) * | 2014-12-18 | 2017-08-01 | 株式会社艾迪科 | The layered product of acrylic acid resin composition and stacking said composition |
| CN107429032A (en) * | 2015-04-03 | 2017-12-01 | 株式会社可乐丽 | Resin combination and its manufacture method, formed body, film and article |
| CN109071953A (en) * | 2016-06-17 | 2018-12-21 | 东丽株式会社 | Resin combination, cured film, the manufacturing method of cured film and display device |
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| JP2022061503A (en) | 2022-04-18 |
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