JP7442490B2 - Method for producing a plateable polylactic acid resin base material and method for producing a polylactic acid resin molded article having a plating film using the same - Google Patents
Method for producing a plateable polylactic acid resin base material and method for producing a polylactic acid resin molded article having a plating film using the same Download PDFInfo
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- JP7442490B2 JP7442490B2 JP2021197007A JP2021197007A JP7442490B2 JP 7442490 B2 JP7442490 B2 JP 7442490B2 JP 2021197007 A JP2021197007 A JP 2021197007A JP 2021197007 A JP2021197007 A JP 2021197007A JP 7442490 B2 JP7442490 B2 JP 7442490B2
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- polylactic acid
- acid resin
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- resin base
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 160
- 239000004626 polylactic acid Substances 0.000 title claims description 159
- 229920005989 resin Polymers 0.000 title claims description 109
- 239000011347 resin Substances 0.000 title claims description 109
- 239000000463 material Substances 0.000 title claims description 65
- 238000007747 plating Methods 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002585 base Substances 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 30
- 230000008025 crystallization Effects 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- 238000005530 etching Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 23
- 238000007772 electroless plating Methods 0.000 claims description 22
- 230000003750 conditioning effect Effects 0.000 claims description 18
- 230000001737 promoting effect Effects 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 238000009713 electroplating Methods 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- -1 steam Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 238000011282 treatment Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 229920006167 biodegradable resin Polymers 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229920001432 poly(L-lactide) Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は、めっき可能なポリ乳酸樹脂基材の製造方法およびそれを用いためっき皮膜を有するポリ乳酸樹脂成形体の製造方法に関する。 The present invention relates to a method for producing a plateable polylactic acid resin base material and a method for producing a polylactic acid resin molded article having a plating film using the same.
近年、地球環境に優しい樹脂として種々の生分解性樹脂が注目されている。そのうち、ポリ乳酸は、当該生分解性樹脂の代表的なものであり、その応用範囲の拡大が所望されている。 In recent years, various biodegradable resins have attracted attention as resins that are friendly to the global environment. Among these, polylactic acid is a typical biodegradable resin, and it is desired to expand its application range.
一方、自動車に代表される数々の工業製品では、装飾性の向上等の観点から、銅、ニッケル、クロム、金等のめっき皮膜の形成を求められることがある。しかし、ポリ乳酸樹脂からなる成形体へのめっき皮膜の形成は必ずしも容易ではない。 On the other hand, in many industrial products such as automobiles, it is sometimes required to form plating films of copper, nickel, chromium, gold, etc. from the viewpoint of improving decorativeness. However, it is not always easy to form a plating film on a molded article made of polylactic acid resin.
例えば、特許文献１によれば、ポリ乳酸樹脂成形体を被めっき物としてめっき処理を行う場合には、エッチング液として従来知られているクロム酸－硫酸混合液を用いると、エッチング効果が十分ではなく、満足のいくめっき密着性を得ることができないことが指摘されている。しかも、クロム酸－硫酸混合液は、有毒な６価クロムを含有するため作業環境が悪く、排水処理のために６価クロムを３価に還元する必要があり、現場での作業時の安全性や排水処理にかかる負担は大きいと言わざるを得ない。 For example, according to Patent Document 1, when plating is performed using a polylactic acid resin molded object as the object to be plated, if a conventionally known chromic acid-sulfuric acid mixed solution is used as an etching solution, the etching effect may not be sufficient. It has been pointed out that it is not possible to obtain satisfactory plating adhesion. Moreover, the chromic acid-sulfuric acid mixture contains toxic hexavalent chromium, which creates a poor working environment, and it is necessary to reduce hexavalent chromium to trivalent for wastewater treatment, making it difficult to work safely on site. It must be said that the burden of water and wastewater treatment is significant.
特許文献１は、この問題を解決するために、ポリ乳酸樹脂成形体に対して無電解めっき用の触媒付与のために所定の前処理を行うことを提案している。しかし、この前処理のためにはポリ乳酸樹脂成形体の結晶性を高めるために、当該ポリ乳酸樹脂成形体を高温でかつ長時間のアニール処理が必要とされるため、当該アニール処理の段階でポリ乳酸樹脂成形体がその形状を保持できず、結果として、所望のめっき皮膜を有するポリ乳酸樹脂成形体を得ることが困難である点が指摘されている。 In order to solve this problem, Patent Document 1 proposes performing a predetermined pretreatment on a polylactic acid resin molded article in order to impart a catalyst for electroless plating. However, for this pretreatment, in order to increase the crystallinity of the polylactic acid resin molded product, it is necessary to anneal the polylactic acid resin molded product at high temperature and for a long time. It has been pointed out that a polylactic acid resin molded article cannot maintain its shape, and as a result, it is difficult to obtain a polylactic acid resin molded article having a desired plating film.
本発明は、上記課題の解決を課題とするものであり、その目的とするところは、高温かつ長時間のアニール処理を用いることなく適切な結晶性を付与できる、めっき可能なポリ乳酸樹脂基材の製造方法およびそれを用いためっき皮膜を有するポリ乳酸樹脂成形体の製造方法を提供することにある。 The present invention aims to solve the above problems, and its purpose is to provide a plateable polylactic acid resin base material that can be imparted with appropriate crystallinity without the need for high-temperature and long-term annealing treatment. An object of the present invention is to provide a method for producing a polylactic acid resin molded article having a plating film using the same.
本発明は、めっき可能なポリ乳酸樹脂基材の製造方法であって、
（ａ１）金型内に溶融したポリ乳酸を充填する工程、
（ｂ１）該金型を、該金型内の該ポリ乳酸の温度が該ポリ乳酸の結晶化促進温度に到達するまで５℃／秒から２０℃／秒の平均冷却速度で冷却する工程、および
（ｃ１）該（ｂ１）工程の後、該金型内の該ポリ乳酸の温度を該ポリ乳酸の該結晶化促進温度で３０秒間から５分間保持する工程、
を包含する、方法である。
The present invention is a method for producing a plating-enabled polylactic acid resin base material, comprising:
(a1) Filling the mold with molten polylactic acid,
(b1) cooling the mold at an average cooling rate of 5°C/sec to 20°C/sec until the temperature of the polylactic acid in the mold reaches the crystallization promoting temperature of the polylactic acid; (c1) After the step (b1), maintaining the temperature of the polylactic acid in the mold at the crystallization promoting temperature of the polylactic acid for 30 seconds to 5 minutes;
It is a method that includes.
１つの実施形態では、上記（ｂ１）工程における上記金型の上記平均冷却速度は５℃／秒から１２℃／秒である。 In one embodiment, the average cooling rate of the mold in the step (b1) is from 5°C/second to 12°C/second.
１つの実施形態では、上記ポリ乳酸の上記結晶化促進温度は８５℃から１５０℃である。 In one embodiment, the crystallization promoting temperature of the polylactic acid is 85°C to 150°C.
１つの実施形態では、上記ポリ乳酸の上記結晶化促進温度は９０℃から１０５℃である。 In one embodiment, the crystallization promoting temperature of the polylactic acid is from 90°C to 105°C.
本発明はまた、めっき皮膜を有するポリ乳酸樹脂成形体の製造方法であって、
（ａ２）上記方法で得られたポリ乳酸樹脂基材を、アルカリ金属水酸化物を含有するエッチング処理液に接触させる工程、
（ｂ２）該（ａ２）の工程後、該ポリ乳酸樹脂基材を無電解めっきする工程、
（ｃ２）該無電解めっきした該ポリ乳酸樹脂基材を電気めっきする工程
を包含する、方法である。
The present invention also provides a method for producing a polylactic acid resin molded article having a plating film, comprising:
(a2) a step of bringing the polylactic acid resin base material obtained by the above method into contact with an etching solution containing an alkali metal hydroxide;
(b2) After the step (a2), electroless plating the polylactic acid resin base material,
(c2) A method including the step of electroplating the electrolessly plated polylactic acid resin base material.
１つの実施形態では、上記（ａ２）工程の後、かつ上記（ｂ２）工程の前に、上記ポリ乳酸樹脂基材を、界面活性剤を含むコンディショニング液に接触させることを含む。 One embodiment includes contacting the polylactic acid resin base material with a conditioning liquid containing a surfactant after the step (a2) and before the step (b2).
本発明によれば、煩雑な操作を必要とすることなく、めっき皮膜を有するポリ乳酸樹脂成形体を簡便に得ることができる。本発明は、様々な形態を有するポリ乳酸樹脂基材に対してめっき皮膜が形成可能であり、工業製品におけるポリ乳酸が利用範囲を一層拡張することができる。 According to the present invention, a polylactic acid resin molded article having a plating film can be easily obtained without requiring complicated operations. According to the present invention, plating films can be formed on polylactic acid resin base materials having various forms, and the range of use of polylactic acid in industrial products can be further expanded.
（めっき可能なポリ乳酸樹脂基材の製造方法）
本発明の方法では、まず（ａ１）工程として、金型内に溶融したポリ乳酸が充填される。
(Method for manufacturing a plating-capable polylactic acid resin base material)
In the method of the present invention, first, in step (a1), a mold is filled with molten polylactic acid.
ポリ乳酸は、生分解性を有する樹脂として知られている。ポリ乳酸の構成単位である乳酸は１つの不斉炭素を有し、Ｌ体とＤ体との２種類が存在する。ここで、Ｌ体のみを重合させたものはポリ－Ｌ－乳酸（ＰＬＬＡ）、Ｄ体のみを重合させたものはポリ－Ｄ－乳酸（ＰＤＬＡ）とも呼ばれ、これらはその立体配置により、互いに逆回りのらせん構造をとることが知られている。 Polylactic acid is known as a biodegradable resin. Lactic acid, which is a constituent unit of polylactic acid, has one asymmetric carbon and exists in two types: L-form and D-form. Here, polymerized only L-isomer is called poly-L-lactic acid (PLLA), and polymerized only D-isomer is also called poly-D-lactic acid (PDLA), and these are mutually exclusive due to their steric configuration. It is known to have a reverse helical structure.
本発明において使用されるポリ乳酸は、ポリ－Ｌ－乳酸、ポリ－Ｄ－乳酸、およびこれらの組み合わせ（例えばステレオコンプレックス型ポリ乳酸（ＳＣ－ＰＬＡ））のいずれであってもよい。 The polylactic acid used in the present invention may be poly-L-lactic acid, poly-D-lactic acid, or a combination thereof (eg, stereocomplex polylactic acid (SC-PLA)).
なお、これらのポリ乳酸は、直鎖または任意の分岐鎖を有するものであってもよく、例えば、５０，０００～４００，０００、好ましくは１００，０００～２５０，０００の重量平均分子量を有する。 Note that these polylactic acids may have a straight chain or any branched chain, and have a weight average molecular weight of, for example, 50,000 to 400,000, preferably 100,000 to 250,000.
このようなポリ乳酸は、例えば、乳酸の脱水縮合により得られたもの、およびラクチドの開環重合により得られたもの、ならびにそれらの組み合わせのいずれであってもよく、例えば、トウモロコシ、サツマイモ、ジャガイモ、およびサトウキビ、ならびにそれらの組み合わせでなどの植物性材料から構成されバイオマスを由来とするものであってもよい。 Such polylactic acid may be, for example, one obtained by dehydration condensation of lactic acid, one obtained by ring-opening polymerization of lactide, or a combination thereof, such as corn, sweet potato, potato, etc. , sugarcane, and combinations thereof, and may be derived from biomass.
本発明においてポリ乳酸は、酸化防止剤、劣化防止剤、フィラー、加工助剤、架橋剤（例えば、硫黄系架橋剤、過酸化物架橋剤）、および着色剤、ならびにこれらの組み合わせなどの他の添加剤が含有されたものであってもよく、ペレット状、タブレット上、顆粒等の任意の形態を有する樹脂組成物の形態で提供されるものであってもよい。本明細書において、このようなポリ乳酸樹脂組成物についても「ポリ乳酸」との用語で呼ぶことがある。 In the present invention, the polylactic acid may contain other additives such as antioxidants, deterioration inhibitors, fillers, processing aids, crosslinkers (e.g., sulfur-based crosslinkers, peroxide crosslinkers), and colorants, and combinations thereof. The resin composition may contain additives or may be provided in the form of a resin composition having any form such as pellets, tablets, or granules. In this specification, such a polylactic acid resin composition may also be referred to as "polylactic acid."
本発明に用いられるポリ乳酸は、好ましくは８５℃～１５０℃、より好ましくは９０℃～１０５℃の結晶化促進温度を有する。ここで、本明細書中に用いられる用語「結晶化促進温度」とは、樹脂の結晶化を高めるために設定され得る温度であり、結晶性樹脂（例えばポリ乳酸分子それ自体）が結晶化し始める結晶化温度（Ｔｃ）およびその付近（±１０℃、好ましくは±５℃）を包含する。結晶化促進温度は、使用するポリ乳酸のみによって決定されるものではなく、例えば、金型に充填されたポリ乳酸とその他の添加剤との全体の関係において当該ポリ乳酸の結晶化がより効果的に開始する温度を指していう。使用されるポリ乳酸の結晶化促進温度が９０℃を下回ると、結晶化が十分に進まない状態で固化するため、良好な成形体を得ることが困難となることがある。使用されるポリ乳酸の結晶化促進温度が１５０℃を上回ると、同様に、結晶化が十分に進まない状態で固化も不十分なため、良好な成形体を得ることが困難となることがある。 The polylactic acid used in the present invention preferably has a crystallization promoting temperature of 85°C to 150°C, more preferably 90°C to 105°C. Here, the term "crystallization promoting temperature" as used herein is a temperature that can be set to enhance crystallization of the resin, at which the crystalline resin (for example, polylactic acid molecules themselves) begin to crystallize. It includes the crystallization temperature (Tc) and its vicinity (±10°C, preferably ±5°C). The crystallization promotion temperature is not determined only by the polylactic acid used; for example, the crystallization of the polylactic acid is more effective depending on the overall relationship between the polylactic acid filled in the mold and other additives. It refers to the temperature at which the temperature starts. If the crystallization promotion temperature of the polylactic acid used is lower than 90° C., the polylactic acid will solidify without sufficiently proceeding with crystallization, which may make it difficult to obtain a good molded product. If the crystallization promotion temperature of the polylactic acid used exceeds 150°C, crystallization will not progress sufficiently and solidification will also be insufficient, making it difficult to obtain a good molded product. .
金型内に充填されるポリ乳酸は、溶融した状態、例えば１７０℃～２５０℃、好ましくは１９０℃～２１０℃に加熱された状態で金型内に充填される。充填される金型は８０℃～１５０℃に設定されていることが好ましい。 The polylactic acid to be filled into the mold is heated to a temperature of 170° C. to 250° C., preferably 190° C. to 210° C., in a molten state. The temperature of the mold to be filled is preferably set at 80°C to 150°C.
金型は、射出成形法、ガスアシスト成形法、射出圧縮成形法、押出成形法、ブロー成形法、プレス成形法、真空圧空成形法など、当該分野において公知の成形方法に使用され得る金型であり、冷却を行うため、種々の冷却手段や温度センサを備えるものが使用され得る。 The mold is a mold that can be used for molding methods known in the art, such as injection molding, gas-assisted molding, injection compression molding, extrusion molding, blow molding, press molding, and vacuum-pressure molding. In order to perform cooling, devices equipped with various cooling means and temperature sensors can be used.
金型の冷却は、例えば金型内の冷却手段に所定の媒体を通すことにより行われる。媒体の種類としては、必ずしも限定されないが、例えば冷却水、スチーム、空気、窒素ガス等の不活性期待等の流体が挙げられる。あるいは、こうした媒体に代えて、ヒーターで温度調節することにより金型の冷却を行ってもよい。 Cooling of the mold is performed, for example, by passing a predetermined medium through cooling means within the mold. The type of medium is not necessarily limited, but includes, for example, cooling water, steam, air, inert fluids such as nitrogen gas, and the like. Alternatively, instead of using such a medium, the mold may be cooled by controlling the temperature with a heater.
本発明においては、金型に充填されたポリ乳酸の結晶化を効果的に行うために、金型の冷却速度（特に平均冷却速度）を適切に制御することが重要である。具体的には、溶融したポリ乳酸を充填した後、金型内のポリ乳酸の温度がポリ乳酸の結晶化促進温度に到達するまで所定の平均冷却速度で金型の冷却が行われる。 In the present invention, in order to effectively crystallize the polylactic acid filled in the mold, it is important to appropriately control the cooling rate (especially the average cooling rate) of the mold. Specifically, after filling the mold with molten polylactic acid, the mold is cooled at a predetermined average cooling rate until the temperature of the polylactic acid in the mold reaches the crystallization promoting temperature of polylactic acid.
このような平均冷却速度は５℃／秒～２０℃／秒（すなわち１秒当たり平均で５℃～２０℃の割合での金型内のポリ乳酸の温度の低下）、好ましくは５℃／秒～１２℃／秒（すなわち１秒あたり平均で５℃～１２℃の割合での金型内のポリ乳酸の温度の低下）が採用され得る。採用する平均冷却速度が５℃／秒を下回ると、ポリ乳酸の結晶化促進温度に到達するまでにより多くの時間が必要となり、得られるポリ乳酸樹脂基材の生産性を著しく低下されるおそれがある。採用する平均冷却速度が２０℃／秒を上回ると、より急速な冷却を可能とする複雑かつ高額な設備投入が必要となり、得られるポリ乳酸樹脂基材の汎用性を低下されるおそれがある。 Such an average cooling rate is between 5°C/sec and 20°C/sec (i.e. a decrease in the temperature of the polylactic acid in the mold at an average rate of between 5°C and 20°C per second), preferably 5°C/sec. ˜12° C./sec (ie, decreasing the temperature of the polylactic acid in the mold at an average rate of 5° C. to 12° C. per second) may be employed. If the average cooling rate employed is less than 5°C/sec, it will take more time to reach the crystallization promoting temperature of polylactic acid, which may significantly reduce the productivity of the resulting polylactic acid resin base material. be. If the average cooling rate employed exceeds 20° C./sec, it will be necessary to invest in complicated and expensive equipment to enable more rapid cooling, which may reduce the versatility of the resulting polylactic acid resin base material.
言い換えれば、本発明において採用される上記平均冷却速度は、金型内のポリ乳酸の結晶化を効率良く促しかつ生産性を著しく損わない点での両立を図ることができる。 In other words, the average cooling rate employed in the present invention can promote the crystallization of polylactic acid in the mold efficiently while not significantly impairing productivity.
なお、金型における上記平均冷却速度は冷却期間中、略一定に制御されてもよく、あるいは可変的に制御されてもよい。 Note that the average cooling rate in the mold may be controlled to be substantially constant during the cooling period, or may be controlled variably.
金型をポリ乳酸の結晶化促進温度まで冷却した後、金型内のポリ乳酸の温度はポリ乳酸の結晶化促進温度で所定時間をかけて保持される。保持される時間は、３０秒間から５分間、好ましくは５０秒間～７０秒間である。ポリ乳酸の結晶化促進温度で保持される時間が３０秒間を下回ると、金型内のポリ乳酸の結晶化が不十分であり、得られるポリ乳酸樹脂基材上にめっき皮膜が適切に形成されないことがある。ポリ乳酸の結晶化促進温度で保持される時間が５分間を上回ると、１つの金型から得られるポリ乳酸樹脂基材の生産性が低下して、結果としてめっき皮膜を有するポリ乳酸樹脂成形体自体の生産性を著しく低下させることがある。本発明では、上記のような保持時間によって、金型内のポリ乳酸について、後述するめっき皮膜の形成に十分な結晶化が行われる。 After the mold is cooled to a temperature that promotes crystallization of polylactic acid, the temperature of the polylactic acid in the mold is maintained at the temperature that promotes crystallization of polylactic acid over a predetermined period of time. The holding time is from 30 seconds to 5 minutes, preferably from 50 seconds to 70 seconds. If the time held at the polylactic acid crystallization promoting temperature is less than 30 seconds, the crystallization of the polylactic acid in the mold will be insufficient, and a plating film will not be properly formed on the resulting polylactic acid resin base material. Sometimes. If the time maintained at the crystallization promoting temperature of polylactic acid exceeds 5 minutes, the productivity of the polylactic acid resin base material obtained from one mold will decrease, resulting in a polylactic acid resin molded product having a plating film. may significantly reduce its own productivity. In the present invention, sufficient crystallization of the polylactic acid in the mold is performed by the holding time as described above to form a plating film, which will be described later.
このようにして、少なくとも表面が適切に結晶化しためっき可能なポリ乳酸樹脂基材を得ることができる。 In this way, it is possible to obtain a polylactic acid resin base material that is suitably crystallized at least on the surface and can be plated.
上記保持時間の経過後、得られたポリ乳酸樹脂基材は金型から取り出され、次のめっき工程に使用することができる。なお、得られたポリ乳酸樹脂基材は、めっき皮膜の形成をより効果的に行うために所定の手段を用いてその表面の脱脂が行われてもよい。 After the above holding time has elapsed, the obtained polylactic acid resin base material is taken out from the mold and can be used for the next plating step. Note that the surface of the obtained polylactic acid resin base material may be degreased using a predetermined method in order to more effectively form a plating film.
（めっき皮膜を有するポリ乳酸樹脂成形体の製造方法）
本発明においては、まず上記により得られたポリ乳酸樹脂基材がエッチング処理液に接触させられる。
(Method for manufacturing a polylactic acid resin molded body having a plating film)
In the present invention, first, the polylactic acid resin base material obtained as described above is brought into contact with an etching treatment liquid.
エッチング処理液は、有効成分としてアルカリ金属酸化物を含有する。アルカリ金属水酸化物の例としては、水酸化ナトリウム、水酸化カリウム、および水酸化リチウム、ならびにそれらの組み合わせが挙げられる。汎用性に富むとの理由から、水酸化ナトリウムを用いることが好ましい。 The etching solution contains an alkali metal oxide as an active ingredient. Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide, and combinations thereof. It is preferable to use sodium hydroxide because of its versatility.
エッチング処理液は、アルカリ金属水酸化物の溶解性を高めるために水が溶媒として使用され得る。水は、例えば、純水、蒸留水、イオン交換水、ＲＯ水、および水道水のいずれが使用されてもよい。 In the etching solution, water may be used as a solvent to increase the solubility of the alkali metal hydroxide. As water, for example, pure water, distilled water, ion exchange water, RO water, or tap water may be used.
エッチング処理液中のアルカリ金属水酸化物の濃度は、好ましくは５０ｇ／Ｌ～８００ｇ／Ｌであり、より好ましくは１００ｇ／Ｌ～７５０ｇ／Ｌである。エッチング処理液に含まれるアルカリ金属酸化物の濃度がこのような範囲内にあることにより、上記ポリ乳酸樹脂基材の表面に対してめっき皮膜の形成に有効なエッチングを効果的に行うことができるとともに、当該エッチングによって当該ポリ乳酸樹脂基材の表面を必要以上に侵食しないようにすることができる。 The concentration of alkali metal hydroxide in the etching solution is preferably 50 g/L to 800 g/L, more preferably 100 g/L to 750 g/L. When the concentration of the alkali metal oxide contained in the etching treatment solution is within this range, etching that is effective for forming a plating film can be effectively performed on the surface of the polylactic acid resin base material. At the same time, it is possible to prevent the etching from corroding the surface of the polylactic acid resin base material more than necessary.
ポリ乳酸樹脂基材へのエッチング処理液の接触は、特に限定はなく、ポリ乳酸樹脂基材（被めっき物）の表面をエッチング処理液に十分に接触させることができる方法が採用され得る。例えば、エッチング処理液を含む浴中に当該ポリ乳酸樹脂基材を浸漬させる方法、ポリ乳酸樹脂基材に当該エッチング処理液を塗布または噴霧してそのまま放置する方法等が採用される。エッチングをより効果的に行うことができるとの理由から、本発明においては、エッチング処理液を含む浴中に当該ポリ乳酸樹脂基材を浸漬させる方法を採用することが好ましい。 There are no particular limitations on the contact of the etching solution to the polylactic acid resin base material, and any method that can bring the surface of the polylactic acid resin base material (object to be plated) into sufficient contact with the etching solution may be adopted. For example, a method in which the polylactic acid resin base material is immersed in a bath containing an etching treatment liquid, a method in which the polylactic acid resin base material is coated or sprayed with the etching treatment liquid and left as it is, etc. are employed. In the present invention, it is preferable to adopt a method in which the polylactic acid resin base material is immersed in a bath containing an etching treatment liquid because etching can be performed more effectively.
エッチングに要する条件は特に限定されず、例えば、上記エッチング処理液への浸浸による方法が採用される場合には、エッチング処理液の浴温は、好ましくは２０℃～９０℃、より好ましくは５０℃～８０℃に設定される。さらに、浸漬時間についても特に限定されず、好ましくは３分間～４０分間、より好ましくは１０分間～３０分間が採用され得る。 The conditions required for etching are not particularly limited. For example, when the method of immersion in the etching treatment liquid is adopted, the bath temperature of the etching treatment liquid is preferably 20°C to 90°C, more preferably 50°C. The temperature is set between ℃ and 80℃. Further, the immersion time is not particularly limited either, and preferably 3 minutes to 40 minutes, more preferably 10 minutes to 30 minutes.
なお、上記エッチング処理液との接触後のポリ乳酸樹脂基材については、基材表面に付着している不要なエッチング処理液を除去するために中和処理が行うことが好ましい。中和処理は、例えば無機酸を含む水溶液を用いてポリ乳酸樹脂基材の表面の洗浄を通じて行われる。中和処理に使用され得る無機酸としては、例えば、塩酸が挙げられる。中和処理に採用され得る条件は特に限定されず、ポリ乳酸樹脂基材の表面に付着したエッチング処理液を十分に除去できる条件が当業者によって適宜選択され得る。例えば、３５％の塩酸を用いて中和処理を行う場合には、例えばそれを水で３０ｇ／Ｌ～１００ｇ／Ｌの濃度になるまでに希釈した（塩酸）水溶液が調整され、例えば２０℃～４０℃の温度で１分間～３分間浸漬させる条件が採用され得る。 Note that the polylactic acid resin base material after contact with the etching treatment liquid is preferably subjected to a neutralization treatment in order to remove unnecessary etching treatment liquid adhering to the surface of the substrate. The neutralization treatment is performed, for example, by washing the surface of the polylactic acid resin base material using an aqueous solution containing an inorganic acid. Examples of inorganic acids that can be used for neutralization include hydrochloric acid. The conditions that can be adopted for the neutralization treatment are not particularly limited, and those skilled in the art can appropriately select conditions that can sufficiently remove the etching solution adhering to the surface of the polylactic acid resin base material. For example, when performing neutralization treatment using 35% hydrochloric acid, an aqueous (hydrochloric acid) solution is prepared by diluting it with water to a concentration of 30 g/L to 100 g/L, for example, at 20°C to 100g/L. A condition of immersion at a temperature of 40° C. for 1 minute to 3 minutes may be adopted.
本発明においては、上記エッチング処理液によるエッチングの後、必要に応じて上記ポリ乳酸樹脂基材がコンディショニング液に接触させ得られてもよい。 In the present invention, after etching with the etching solution, the polylactic acid resin base material may be brought into contact with a conditioning solution, if necessary.
コンディショニング液は有効成分として界面活性剤を含有する。コンディショニング液との接触によって、ポリ乳酸樹脂基材はこの後の触媒付与処理において、当該ポリ乳酸樹脂基材の表面に一層均一な触媒膜を付着させることが可能となり、無電解めっきの析出性や外観を向上させることができる。 The conditioning liquid contains a surfactant as an active ingredient. Contact with the conditioning liquid makes it possible for the polylactic acid resin base material to adhere a more uniform catalyst film to the surface of the polylactic acid resin base material in the subsequent catalyst application treatment, which improves the deposition properties of electroless plating. Appearance can be improved.
コンディショニング液で使用する界面活性剤としては、カチオン性界面活性剤、アニオン性界面活性剤、ノニオン性界面活性剤、および両性界面活性剤、ならびにそれらの組み合わせが挙げられる。 Surfactants used in conditioning liquids include cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants, and combinations thereof.
カチオン性界面活性剤の例としては、脂肪族アミン塩、脂肪族４級アンモニウム塩、芳香族４級アンモニウム塩、および複素環４級アンモニウム塩、ならびにそれらの組み合わせが挙げられる。 Examples of cationic surfactants include aliphatic amine salts, aliphatic quaternary ammonium salts, aromatic quaternary ammonium salts, and heterocyclic quaternary ammonium salts, and combinations thereof.
アニオン性界面活性剤の例としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸の炭素数１２～１８のカルボン酸の塩（例えば、ナトリウム塩、カリウム塩）、炭素数１２～１８のＮ－アシルアミノ酸、Ｎ－アシルアミノ酸塩、ポリオキシエチレンアルキルエーテルカルボン酸塩、炭素数１２～１８のアシル化ペプチド等のカルボン酸塩；アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ナフタレンスルホン酸塩ホルマリン重縮合物、スルホコハク酸塩、α－オレフィンスルホン酸塩、Ｎ－アシルスルホン酸塩等のスルホン酸塩；硫酸化油、アルキル硫酸塩、アルキルエーテル硫酸塩、ポリオキシエチレン硫酸塩、ポリオキシエチレンアルキルアリルエーテル硫酸塩、アルキルアミド硫酸塩等の硫酸エステル塩；ポリオキシエチレンアルキルエーテルリン酸塩、ポリオキシエチレンアルキルフェニルエーテルリン酸塩、アルキルリン酸塩等のリン酸エステル塩；ならびにそれらの組み合わせが挙げられる。 Examples of anionic surfactants include salts of carboxylic acids having 12 to 18 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid (e.g., sodium salts and potassium salts); N-acylamino acids, N-acylamino acid salts, polyoxyethylene alkyl ether carboxylates, carboxylic acid salts of acylated peptides having 12 to 18 carbon atoms; alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonic acids Salts, naphthalene sulfonates, formalin polycondensates, sulfosuccinates, α-olefin sulfonates, N-acylsulfonates, and other sulfonates; sulfated oils, alkyl sulfates, alkyl ether sulfates, polyoxyethylene Sulfate ester salts such as sulfates, polyoxyethylene alkyl allyl ether sulfates, and alkyl amide sulfates; Phosphate esters such as polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, and alkyl phosphates salts; as well as combinations thereof.
ノニオン性界面活性剤の例としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、アルキルアリルホルムアルデヒド縮合ポリオキシエチレンエーテル、ポリオキシエチレンポリオキシプロピレンブロックコポリマー、ポリオキシエチレンポリオキシプロピルアルキルエーテル等のエーテル型界面活性剤；ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、ポリオキシエチレン脂肪酸アルカノールアミド硫酸塩等のエーテルエステル型界面活性剤；ポリエチレングリコール脂肪酸エステル、エチレングリコール脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ショ糖脂肪酸エステル等のエステル型界面活性剤；脂肪酸アルカノールアミド、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンアルキルアミン等の含窒素型界面活性剤；ならびにそれらの組み合わせが挙げられる。 Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, alkylaryl formaldehyde condensation polyoxyethylene ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropyl alkyl ether, etc. Ether type surfactants such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate; polyethylene glycol fatty acid ester, Ester type surfactants such as ethylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester; fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkyl amine and other nitrogen-containing surfactants; and combinations thereof.
両性界面活性剤の例としては、カルボキシベタイン型界面活性剤、アミノカルボン酸塩、イミダゾリウムベタイン、レシチン、ならびにそれらの組み合わせが挙げられる。 Examples of amphoteric surfactants include carboxybetaine type surfactants, aminocarboxylic acid salts, imidazolium betaine, lecithin, and combinations thereof.
上記界面活性剤のうち、特に、脂肪族アミン塩、脂肪族４級アンモニウム塩、芳香族４級アンモニウム塩等のカチオン性界面活性剤；カルボキシベタイン、アミノカルボン酸塩等の両性界面活性剤等が好ましく、特に、脂肪族アミン塩、アミノカルボン酸塩などが好ましい。 Among the above surfactants, cationic surfactants such as aliphatic amine salts, aliphatic quaternary ammonium salts, and aromatic quaternary ammonium salts; amphoteric surfactants such as carboxybetaine and aminocarboxylic acid salts are particularly preferred. Preferred are aliphatic amine salts, aminocarboxylic acid salts, and the like.
コンディショニング液には水が媒体として使用され得る。水は、例えば、純水、蒸留水、イオン交換水、ＲＯ水、および水道水のいずれが使用されてもよい。 Water may be used as a medium for conditioning liquids. As water, for example, pure water, distilled water, ion exchange water, RO water, or tap water may be used.
コンディショニング液に含まれる上記界面活性剤の濃度は、好ましくは０．０５ｇ／Ｌ～５０ｇ／Ｌ、より好ましくは０．１ｇ／Ｌ～１０ｇ／Ｌである。 The concentration of the surfactant contained in the conditioning liquid is preferably 0.05 g/L to 50 g/L, more preferably 0.1 g/L to 10 g/L.
ポリ乳酸樹脂基材へのコンディショニング液の接触は、特に限定はなく、ポリ乳酸樹脂基材（被めっき物）の表面をコンディショニング液に十分に接触させることができる方法が採用され得る。例えば、コンディショニング液を含む浴中に当該ポリ乳酸樹脂基材を浸漬させる方法、ポリ乳酸樹脂基材に当該コンディショニング液を塗布または噴霧してそのまま放置する方法等が採用される。コンディショニング液との接触をより確実に行うことができるとの理由から、本発明においては、コンディショニング液を含む浴中に当該ポリ乳酸樹脂基材を浸漬させる方法を採用することが好ましい。 The method of contacting the conditioning liquid to the polylactic acid resin base material is not particularly limited, and any method that can bring the surface of the polylactic acid resin base material (object to be plated) into sufficient contact with the conditioning liquid may be adopted. For example, a method of immersing the polylactic acid resin base material in a bath containing a conditioning liquid, a method of applying or spraying the conditioning liquid onto the polylactic acid resin base material and leaving it as it is, etc. are employed. In the present invention, it is preferable to adopt a method in which the polylactic acid resin base material is immersed in a bath containing a conditioning liquid, since this enables more reliable contact with the conditioning liquid.
コンディショニング液との接触に要する条件については特に限定されず、当業者によって適切な条件が設定され得る。例えば、上記ポリ乳酸樹脂基材をコンディショニング液に浸漬させる方法が採用される場合は、コンディショニング液を含む浴は、好ましくは１０℃～５０℃、より好ましくは２０℃～４５℃の温度に設定され、当該ポリ乳酸樹脂基材を好ましくは１分間～１０分間、より好ましくは１分間～５分程度浸漬させられる。 The conditions required for contact with the conditioning liquid are not particularly limited, and appropriate conditions can be set by those skilled in the art. For example, when the method of immersing the polylactic acid resin base material in a conditioning liquid is adopted, the bath containing the conditioning liquid is preferably set at a temperature of 10°C to 50°C, more preferably 20°C to 45°C. The polylactic acid resin base material is preferably immersed for about 1 minute to 10 minutes, more preferably about 1 minute to 5 minutes.
次いで、本発明においては、ポリ乳酸樹脂基材の無電解めっきが行われる。 Next, in the present invention, electroless plating of the polylactic acid resin base material is performed.
この無電解めっきにあたり、具体体にはポリ乳酸樹脂基材には無電解めっき用の触媒が付与される。 For this electroless plating, a catalyst for electroless plating is applied to the polylactic acid resin base material.
無電解めっき用の触媒は、特に限定されず、例えばパラジウム、銀、金、白金、ルテニウムなどの他の樹脂に採用され得る無電解めっき用触媒である。例えば、ポリ乳酸樹脂基材にパラジウム触媒が付与される場合、いわゆる、センシタイザー－アクチベーター法、キャタリスト－アクセレーター法などの方法が採用され得る。 The catalyst for electroless plating is not particularly limited, and may be a catalyst for electroless plating that can be used for other resins such as palladium, silver, gold, platinum, and ruthenium. For example, when a palladium catalyst is applied to a polylactic acid resin base material, methods such as the so-called sensitizer-activator method and catalyst-accelerator method may be employed.
無電解めっき用触媒を付与した後、ポリ乳酸樹脂基材には無電解めっき液が付与される。このような無電解めっき液には、公知の自己触媒型無電解めっき液が使用され得る。無電解めっき液の例としては、無電解ニッケルめっき液、無電解銅めっき液、無電解金めっき液、無電解コバルトめっき液などが挙げられる。 After applying the electroless plating catalyst, an electroless plating solution is applied to the polylactic acid resin base material. A known autocatalytic electroless plating solution may be used as such an electroless plating solution. Examples of electroless plating solutions include electroless nickel plating solutions, electroless copper plating solutions, electroless gold plating solutions, and electroless cobalt plating solutions.
無電解めっきに採用され得る条件は特に限定されず、当業者によって適切な条件が採用され得る。また、必要に応じて少なくとも２回の無電解めっきを行うことにより、ポリ乳酸樹脂基材の表面に少なくとも２相の無電解めっき層を設けてもよい。無電解めっきによって形成される無電解めっき皮膜の膜厚は特に限定されず、当業者によって適宜選択され得る。 Conditions that can be adopted for electroless plating are not particularly limited, and appropriate conditions can be adopted by those skilled in the art. Furthermore, at least two-phase electroless plating layer may be provided on the surface of the polylactic acid resin base material by performing electroless plating at least twice as necessary. The thickness of the electroless plated film formed by electroless plating is not particularly limited, and can be appropriately selected by those skilled in the art.
その後、本発明においては、上記無電解めっきしたポリ乳酸樹脂基材に電気めっきが行われる。 Thereafter, in the present invention, electroplating is performed on the electrolessly plated polylactic acid resin base material.
本発明においては上記のようにポリ乳酸樹脂基材の表面に一旦無電解めっきの被膜が形成されており、当該無電解めっきの被膜は、均一性かつ密着性に優れた導電性皮膜である。このため、このような無電解めっきの被膜上に電気めっき皮膜を形成することによって、密着性に優れた良好な外観の電気めっき皮膜を形成することができる。 In the present invention, as described above, an electroless plating film is once formed on the surface of the polylactic acid resin base material, and the electroless plating film is a conductive film with excellent uniformity and adhesion. Therefore, by forming an electroplated film on such an electroless plated film, it is possible to form an electroplated film with excellent adhesion and a good appearance.
電気めっきに使用され得る電気めっき液の種類は、特に限定されず、公知の任意の電気めっき液が使用可能である。また、電気めっきの条件もまた公知のものが採用され得る。 The type of electroplating solution that can be used for electroplating is not particularly limited, and any known electroplating solution can be used. Further, known conditions for electroplating may also be employed.
本発明において使用され得る電気めっき処理の例としては、銅めっき、ニッケルめっき、クロムめっき、金メッキ、および銀めっき、ならびにそれらの組み合わせが挙げられる。 Examples of electroplating processes that may be used in the present invention include copper plating, nickel plating, chrome plating, gold plating, and silver plating, and combinations thereof.
銅めっきが行われる場合、めっき液として公知の硫酸銅めっき液が用いられる。硫酸銅めっき液は、例えば、１００ｇ／Ｌ～２５０ｇ／Ｌの硫酸銅、２０ｇ／Ｌ～１２０ｇ／Ｌの硫酸、および２０ｐｐｍ～７０ｐｐｍの塩素イオンを含有する水溶液であり、公知の光沢剤を含有していてもよい。硫酸銅めっきの条件には、例えば約２５℃の液温にて３Ａ／ｄｍ２程度の電流密度が採用され得る。 When copper plating is performed, a known copper sulfate plating solution is used as the plating solution. The copper sulfate plating solution is, for example, an aqueous solution containing 100 g/L to 250 g/L copper sulfate, 20 g/L to 120 g/L sulfuric acid, and 20 ppm to 70 ppm chlorine ions, and does not contain a known brightening agent. You can leave it there. As the conditions for copper sulfate plating, for example, a liquid temperature of about 25° C. and a current density of about 3 A/dm 2 may be adopted.
ニッケルめっきが行われる場合、めっき液は、通常のワット浴であり、例えば、２００ｇ／Ｌ～３５０ｇ／Ｌの硫酸銅めっき液、３０ｇ／Ｌ～８０ｇ／Ｌの塩化ニッケル、および２０ｇ／Ｌ～６０ｇ／Ｌのホウ酸を含有する水溶液である。市販のニッケルめっき浴用光沢剤が含有されていてもよい。ニッケルめっきの条件には、例えば、５５℃～６０℃の液温にて、３Ａ／ｄｍ２程度の電流密度が採用され得る。 When nickel plating is performed, the plating solution is a normal Watts bath, for example, 200 g/L to 350 g/L copper sulfate plating solution, 30 g/L to 80 g/L nickel chloride, and 20 g/L to 60 g /L of boric acid. A commercially available brightener for nickel plating baths may be included. As the conditions for nickel plating, for example, a liquid temperature of 55° C. to 60° C. and a current density of about 3 A/dm 2 may be adopted.
クロムめっきが行われる場合、めっき液は、通常のサージェント浴であり、例えば２００ｇ／Ｌ～３００ｇ／Ｌの無水クロム酸、および２ｇ／Ｌ～５ｇ／Ｌの硫酸を含有する水溶液である。クロムめっきの条件には、例えば、約４５℃の液温にて２０Ａ／ｄｍ２程度の電流密度が採用され得る。 When chromium plating is performed, the plating solution is a normal Sargent bath, for example an aqueous solution containing 200 g/L to 300 g/L of chromic anhydride and 2 g/L to 5 g/L of sulfuric acid. As the conditions for chromium plating, for example, a liquid temperature of about 45° C. and a current density of about 20 A/dm 2 may be employed.
このようにして、めっき皮膜を有するポリ乳酸樹脂成形体を製造することができる。 In this way, a polylactic acid resin molded article having a plating film can be manufactured.
本発明により得られたポリ乳酸樹脂成形体は、審美性に優れかつ良好なめっき皮膜を有する。これにより、様々な用途のめっき皮膜を有する樹脂成形体について、生分解性を活かしたポリ乳酸への置き換えが可能となる。 The polylactic acid resin molded article obtained by the present invention has excellent aesthetics and a good plating film. This makes it possible to replace resin molded bodies with plating films for various uses with polylactic acid that takes advantage of its biodegradability.
応用可能な、めっき皮膜を有する樹脂成形体の例としては、スプーン、フォーク、ナイフなどの食器；バンパー、ラジエーターグリル、ホイールキャップ、エンブレム等の自動車部品；ノートパソコン、スマートフォン、タブレット端末などの筐体その他の部品；などが挙げられる。 Examples of resin molded bodies with plating films that can be applied include tableware such as spoons, forks, and knives; automobile parts such as bumpers, radiator grills, hubcaps, and emblems; housings for notebook computers, smartphones, and tablet devices. Other parts; etc.
以下、実施例により本発明を詳述する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be explained in detail with reference to Examples. However, the present invention is not limited to these.
（実施例１：ポリ乳酸樹脂成形体（スプーン）の作製）
重量平均分子量が１３５，０００であるポリ乳酸（Ｂｉｏｗｏｒｋｓ株式会社製ＢＫＣ００２）を１９５℃にまで加熱して溶融し、これをスプーン用の射出成形金型内に充填した。充填後、金型を温度調節器により１１℃／秒の平均冷却速度で、使用したポリ乳酸の結晶化促進温度（９０℃）まで冷却し、その後５０秒間金型内の温度を保持することによりスプーン状のポリ乳酸樹脂基材（Ｅ１－１）を得た。
(Example 1: Production of polylactic acid resin molded object (spoon))
Polylactic acid (BKC002 manufactured by Bioworks Co., Ltd.) having a weight average molecular weight of 135,000 was heated to 195° C. and melted, and this was filled into an injection mold for a spoon. After filling, the mold was cooled to the crystallization promoting temperature (90 °C) of the polylactic acid used at an average cooling rate of 11 °C/sec using a temperature controller, and then the temperature inside the mold was maintained for 50 seconds. A spoon-shaped polylactic acid resin base material (E1-1) was obtained.
このポリ乳酸樹脂基材（Ｅ１－１）について、上村工業株式会社製スルカップＡＣＬ－００９の水溶液（５．５ｍＬ／Ｌ）を用いて５０℃で５分間脱脂処理を行い、その後水洗した。 This polylactic acid resin base material (E1-1) was degreased using an aqueous solution (5.5 mL/L) of Surcap ACL-009 manufactured by Uemura Kogyo Co., Ltd. at 50° C. for 5 minutes, and then washed with water.
次いで、得られたポリ乳酸樹脂基材（Ｅ１－１）を２００ｇ／Ｌの水酸化ナトリウム水溶液中で５０℃にて１０分間浸漬してエッチング処理し、その後取り出して水洗した。さらに、これを、界面活性剤（上村工業株式会社製ＭＤＰ－２）を１０ｍＬ／Ｌの濃度で含有し、かつ６２．５％硫酸を２ｍＬ／Ｌの濃度で含有する水溶液（コンディショニング液）に２５℃で２分間浸漬し、その後取り出して水洗した。 Next, the obtained polylactic acid resin base material (E1-1) was etched by immersing it in a 200 g/L aqueous sodium hydroxide solution at 50° C. for 10 minutes, and then it was taken out and washed with water. Furthermore, this was added to an aqueous solution (conditioning solution) containing a surfactant (MDP-2 manufactured by Uemura Kogyo Co., Ltd.) at a concentration of 10 mL/L and 62.5% sulfuric acid at a concentration of 2 mL/L. It was immersed at ℃ for 2 minutes, then taken out and washed with water.
さらに、このポリ乳酸樹脂基材（Ｅ１－１）に対して触媒（上村工業株式会社製ＭＡＴ－ＳＰ）を５０ｍＬ／Ｌの濃度で含有し、かつ１Ｎの水酸化ナトリウム水溶液を４０ｍＬ／Ｌの濃度で含有する混合溶液と接触させて触媒の付与を行い、水洗した。その後、この触媒を付与したポリ乳酸樹脂基材（Ｅ１－１）を、上村工業株式会社製ＭＡＢ－４－Ａを１０ｍＬ／Ｌの濃度で含有し、上村工業株式会社製ＭＡＢ－４－Ｃを５０ｍＬ／Ｌの濃度で含有し、かつ上村工業株式会社製ＭＲＤ－２－Ｃを１０ｍＬ／Ｌの濃度で含有する混合水溶液に４０℃で３分間接触させ、水洗して活性化処理を行った。 Furthermore, a catalyst (MAT-SP manufactured by Uemura Kogyo Co., Ltd.) was added to the polylactic acid resin base material (E1-1) at a concentration of 50 mL/L, and a 1N aqueous sodium hydroxide solution was added at a concentration of 40 mL/L. A catalyst was applied by contacting the sample with a mixed solution containing water, and the sample was washed with water. Thereafter, the polylactic acid resin base material (E1-1) provided with this catalyst was treated with MAB-4-A manufactured by Uemura Industries Co., Ltd. at a concentration of 10 mL/L, and MAB-4-C manufactured by Uemura Industries Co., Ltd. An activation treatment was carried out by contacting a mixed aqueous solution containing 50 mL/L of MRD-2-C manufactured by Uemura Kogyo Co., Ltd. at 10 mL/L at 40° C. for 3 minutes, and washing with water.
その後、このポリ乳酸樹脂基材（Ｅ１－１）に対して無電解ニッケルめっき液（上村工業株式会社製ベルニッケル）に４０℃で３分間浸漬して無電解めっきを行った（膜厚約０．５μｍ）。また、無電解めっき後のポリ乳酸樹脂基材（Ｅ１－１）を、光沢電気ニッケルめっき液に浸漬し、５０℃の液温かつ３Ａ／ｄｍ２の電流密度で１５分間の電気めっきを行うことにより、膜厚が約１０μｍのニッケルめっき皮膜を有するポリ乳酸樹脂成形体（スプーン）（Ｅ１－２）を得た（図１の（ａ））。 Thereafter, electroless plating was performed on this polylactic acid resin base material (E1-1) by immersing it in an electroless nickel plating solution (Bell Nickel, manufactured by Uemura Industries Co., Ltd.) at 40°C for 3 minutes (film thickness of approximately 0 .5 μm). Further, the polylactic acid resin base material (E1-1) after electroless plating is immersed in a bright electrolytic nickel plating solution, and electroplating is performed for 15 minutes at a solution temperature of 50° C. and a current density of 3 A/dm 2 . As a result, a polylactic acid resin molded article (spoon) (E1-2) having a nickel plating film with a thickness of about 10 μm was obtained ((a) in FIG. 1).
（実施例２：ポリ乳酸樹脂成形体（ボトル）の作製）
重量平均分子量が２４２，０００であるポリ乳酸（Ｂｉｏｗｏｒｋｓ株式会社製ＢＤＴＯ００１）を用いたこと以外は実施例１と同様にして溶融し、これをボトル用の射出成形金型内に充填した。その後、金型を１１℃／秒の平均冷却速度でポリ乳酸の結晶化促進温度（９０℃）まで冷却し、その後５０秒間金型内の温度を保持してボトル状のポリ乳酸樹脂基材（Ｅ２－１）を得た（図１の（ｂ））。
(Example 2: Production of polylactic acid resin molded body (bottle))
It was melted in the same manner as in Example 1 except that polylactic acid (BDTO001, manufactured by Bioworks Co., Ltd.) having a weight average molecular weight of 242,000 was used, and this was filled into an injection mold for a bottle. After that, the mold was cooled to the polylactic acid crystallization promotion temperature (90°C) at an average cooling rate of 11°C/sec, and the temperature inside the mold was then maintained for 50 seconds to form a bottle-shaped polylactic acid resin base ( E2-1) was obtained (FIG. 1(b)).
実施例１のスプーン状のポリ乳酸樹脂基材（Ｅ１－１）の代わりに、このボトル状のポリ乳酸樹脂基材（Ｅ２－１）を用いたこと以外は実施例１と同様にして、膜厚が約１０μｍのニッケルめっき皮膜を有するポリ乳酸樹脂成形体（ボトル）（Ｅ２－２）を得た。 A membrane was prepared in the same manner as in Example 1 except that this bottle-shaped polylactic acid resin base material (E2-1) was used instead of the spoon-shaped polylactic acid resin base material (E1-1) of Example 1. A polylactic acid resin molded body (bottle) (E2-2) having a nickel plating film with a thickness of about 10 μm was obtained.
（比較例１：ポリ乳酸樹脂成形体（カップ）の作製）
重量平均分子量が１１６，０００であるポリ乳酸（Ｂｉｏｗｏｒｋｓ株式会社製ＢＫＢ００６）を用いたこと以外は実施例１と同様にして溶融し、これをカップ用の射出成形金型内に充填した。その後、金型を１９℃／秒の平均冷却速度でポリ乳酸の結晶化促進温度（９０℃）を下回る３０℃まで冷却し、その後１０秒間金型内の温度を保持してカップ状のポリ乳酸樹脂基材（Ｃ１－１）を得た。
(Comparative Example 1: Production of polylactic acid resin molded body (cup))
It was melted in the same manner as in Example 1 except that polylactic acid (BKB006, manufactured by Bioworks Co., Ltd.) having a weight average molecular weight of 116,000 was used, and this was filled into an injection mold for a cup. After that, the mold was cooled at an average cooling rate of 19°C/sec to 30°C, which is lower than the crystallization promotion temperature (90°C) of polylactic acid, and then the temperature inside the mold was maintained for 10 seconds to form a cup-shaped polylactic acid. A resin base material (C1-1) was obtained.
得られたポリ乳酸樹脂基材（Ｃ１－１）はこの一連の操作によって変形した。このため、エッチング処理を含むそれ以降の処理を行うことができず、ポリ乳酸樹脂成形体の作製を断念した。 The obtained polylactic acid resin base material (C1-1) was deformed by this series of operations. For this reason, subsequent treatments including etching treatment could not be performed, and the production of a polylactic acid resin molded article was abandoned.
（比較例２：ポリ乳酸樹脂成形体（スプーン）の作製）
実施例１と同様にして、スプーン状のポリ乳酸樹脂基材（Ｅ１－１）を得た。このスプーン状のポリ乳酸樹脂基材（Ｅ１－１）についてエッチング処理を行わなかったこと以外は実施例１と同様にして、膜厚が約１０μｍのニッケルめっき皮膜を有するポリ乳酸樹脂成形体（スプーン）（Ｃ２－２）を得た（図１の（ｃ））。
(Comparative Example 2: Production of polylactic acid resin molded object (spoon))
In the same manner as in Example 1, a spoon-shaped polylactic acid resin base material (E1-1) was obtained. The spoon-shaped polylactic acid resin molded article (spoon ) (C2-2) was obtained ((c) in FIG. 1).
ただ、このポリ乳酸樹脂成形体（Ｃ２－２）のめっき皮膜は多数の箇所で皮膜が基材から剥離した状態が観察され、明らかに密着不良であることを確認した。 However, the plating film of this polylactic acid resin molded product (C2-2) was observed to be peeled off from the base material at many locations, and it was clearly confirmed that the adhesion was poor.
（密着性の評価）
実施例１で得られたポリ乳酸樹脂成形体（Ｅ１－２）、実施例２で得られたポリ乳酸樹脂成形体（Ｅ２－２）および比較例２で得られたポリ乳酸樹脂成形体（Ｃ２－２）の各めっき皮膜に十字マス状の切り込みを入れ、これらに粘着テープを十分に貼り付けた後、めっき面に対して垂直方向に引っ張り上げることにより、めっき面の剥離の有無を調べた。具体的には、粘着テープの貼着面の面積（ｃｍ２）に対して、当該粘着テープの引き上げにより剥離しためっき皮膜の面積（ｃｍ２）を測定し、以下の式にしたがってめっき皮膜の剥離率（％）を算出した。
(Evaluation of adhesion)
The polylactic acid resin molded article obtained in Example 1 (E1-2), the polylactic acid resin molded article obtained in Example 2 (E2-2), and the polylactic acid resin molded article obtained in Comparative Example 2 (C2). -2) Cross-shaped incisions were made in each plating film, adhesive tape was sufficiently attached to these, and the presence or absence of peeling of the plating surface was examined by pulling it up in a direction perpendicular to the plating surface. . Specifically, the area (cm 2 ) of the plating film peeled off by pulling up the adhesive tape is measured with respect to the area (cm 2 ) of the surface to which the adhesive tape is attached, and the peeling of the plating film is calculated according to the following formula. The percentage (%) was calculated.
結果を表１に示す。 The results are shown in Table 1.
表１に示すように実施例１および２で得られたポリ乳酸樹脂成形体（Ｅ１－１）および（Ｅ２－１）はいずれも、ニッケルめっき自体が困難であった比較例２のポリ乳酸樹脂成形体（Ｃ２－２）と比較してめっき皮膜の密着性が良好であり、ポリ乳酸樹脂基材に対してめっき皮膜が強固に密着して形成されていることがわかる。 As shown in Table 1, the polylactic acid resin molded bodies (E1-1) and (E2-1) obtained in Examples 1 and 2 are both polylactic acid resins of Comparative Example 2, in which nickel plating itself was difficult. It can be seen that the adhesion of the plating film is better than that of the molded article (C2-2), and the plating film is formed in strong adhesion to the polylactic acid resin base material.
本発明によれば、ポリ乳酸樹脂基材に対して強固なめっき皮膜を形成したポリ乳酸樹脂成形体を簡便にえることができる。本発明のポリ乳酸樹脂成形体は、平板に限らず様々な形状を有するポリ乳酸樹脂基材へのめっきが可能である。本発明は、例えば樹脂成形分野、自動車産業分野、電子・電気分野等において有用である。 According to the present invention, it is possible to easily obtain a polylactic acid resin molded article in which a strong plating film is formed on a polylactic acid resin base material. The polylactic acid resin molded article of the present invention can be plated on polylactic acid resin substrates having various shapes, not just flat plates. The present invention is useful, for example, in the resin molding field, the automobile industry, the electronic/electrical field, and the like.
Claims (6)
（ａ１）金型内に溶融したポリ乳酸を充填する工程、
（ｂ１）該金型を、該金型内の該ポリ乳酸の温度が該ポリ乳酸の結晶化促進温度に到達するまで５℃／秒から２０℃／秒の平均冷却速度で冷却する工程、および
（ｃ１）該（ｂ１）工程の後、該金型内の該ポリ乳酸の温度を該ポリ乳酸の該結晶化促進温度で３０秒間から５分間保持する工程、
を包含する、方法。 A method for producing a polylactic acid resin base material for plating, comprising:
(a1) Filling the mold with molten polylactic acid,
(b1) cooling the mold at an average cooling rate of 5°C/sec to 20°C/sec until the temperature of the polylactic acid in the mold reaches the crystallization promoting temperature of the polylactic acid; (c1) After the step (b1), maintaining the temperature of the polylactic acid in the mold at the crystallization promoting temperature of the polylactic acid for 30 seconds to 5 minutes;
A method that encompasses.
（ａ２）請求項１から４のいずれかに記載の方法で得られたポリ乳酸樹脂基材を、アルカリ金属水酸化物を含有するエッチング処理液に接触させる工程、
（ｂ２）該（ａ２）の工程後、該ポリ乳酸樹脂基材を無電解めっきする工程、
（ｃ２）該無電解めっきした該ポリ乳酸樹脂基材を電気めっきする工程
を包含する、方法。 A method for producing a polylactic acid resin molded article having a plating film, the method comprising:
(a2) a step of bringing the polylactic acid resin base material obtained by the method according to any one of claims 1 to 4 into contact with an etching solution containing an alkali metal hydroxide;
(b2) After the step (a2), electroless plating the polylactic acid resin base material,
(c2) A method comprising the step of electroplating the electrolessly plated polylactic acid resin base material.
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