TWI492993B - Ink compositions and decorative sheets using them - Google Patents
Ink compositions and decorative sheets using them Download PDFInfo
- Publication number
- TWI492993B TWI492993B TW100129734A TW100129734A TWI492993B TW I492993 B TWI492993 B TW I492993B TW 100129734 A TW100129734 A TW 100129734A TW 100129734 A TW100129734 A TW 100129734A TW I492993 B TWI492993 B TW I492993B
- Authority
- TW
- Taiwan
- Prior art keywords
- layer
- group
- resin
- decorative sheet
- ink composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 46
- 239000010410 layer Substances 0.000 claims description 166
- 229920005989 resin Polymers 0.000 claims description 73
- 239000011347 resin Substances 0.000 claims description 73
- -1 acryl fluorenyl group Chemical group 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 38
- 239000010954 inorganic particle Substances 0.000 claims description 32
- 230000005865 ionizing radiation Effects 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 25
- 125000000524 functional group Chemical group 0.000 claims description 21
- 239000012948 isocyanate Substances 0.000 claims description 16
- 238000001746 injection moulding Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 238000005510 radiation hardening Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000012546 transfer Methods 0.000 description 15
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 14
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 10
- 239000004640 Melamine resin Substances 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000002087 whitening effect Effects 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- 238000007646 gravure printing Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 238000005034 decoration Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000007756 gravure coating Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920000265 Polyparaphenylene Polymers 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 239000012461 cellulose resin Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- CWZQYRJRRHYJOI-UHFFFAOYSA-N 1,1,1-trimethoxydecane Chemical compound CCCCCCCCCC(OC)(OC)OC CWZQYRJRRHYJOI-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 125000005442 diisocyanate group Chemical group 0.000 description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- 230000000873 masking effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
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- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
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- 239000004431 polycarbonate resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- 150000003077 polyols Chemical class 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
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- 238000010023 transfer printing Methods 0.000 description 2
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- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
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- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- ZXQQMIAWFZOPGJ-UHFFFAOYSA-N 1-imino-3-(methylamino)thiourea Chemical compound CNNC(=S)N=N ZXQQMIAWFZOPGJ-UHFFFAOYSA-N 0.000 description 1
- JPEWDCTZJFUITH-UHFFFAOYSA-N 1-methoxydecane Chemical compound CCCCCCCCCCOC JPEWDCTZJFUITH-UHFFFAOYSA-N 0.000 description 1
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- PQJUJGAVDBINPI-UHFFFAOYSA-N 9H-thioxanthene Chemical compound C1=CC=C2CC3=CC=CC=C3SC2=C1 PQJUJGAVDBINPI-UHFFFAOYSA-N 0.000 description 1
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- DBJFSFSBHGPDPG-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC Chemical compound C(C(=C)C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC DBJFSFSBHGPDPG-UHFFFAOYSA-N 0.000 description 1
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- CUPAYLZQQKODHW-UHFFFAOYSA-N C(C=C)(=O)OCCCC(C(OCC)(OCC)C)CCCCCCCC Chemical compound C(C=C)(=O)OCCCC(C(OCC)(OCC)C)CCCCCCCC CUPAYLZQQKODHW-UHFFFAOYSA-N 0.000 description 1
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- XRNDMACZMJPCRX-UHFFFAOYSA-N C(CC)C(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(CC)C(C(OCC)(OCC)OCC)CCCCCCCC XRNDMACZMJPCRX-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
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Description
本發明係關於一種油墨組成物,更詳而言之,係關於一種形成加飾薄片用之油墨組成物,其可賦予加飾成形品優異之高硬度性、能賦予可製得複雜形狀之成形性、並且具有耐黏連性。
以往,於具有三維曲面等複雜表面形狀之樹脂成形體之加飾,係使用射出成形同時加飾方法。所謂係使用射出成形同時加飾方法,係指於射出成形之際,使插入於模具內之加飾薄片、與射出注入於模穴內之熔融之射出樹脂一體化,而於樹脂成形體表面實施加飾之方法。於該方法,根據與樹脂成形體一體化之加飾薄片之構成的不同,一般而言,係大致分為射出成形同時層合加飾法與射出成形同時轉印加飾法。
於射出成形同時轉印加飾法中,使加飾薄片密合於模具內面而合模後,將熔融於模穴內之射出樹脂射出使該加飾薄片與射出樹脂一體化,接著,將加飾成形品冷卻由模具取出後,將基材薄膜剝離,藉此製得轉印有轉印層之加飾成形品。
如此所得之加飾成形品,除以往所使用之家庭用電化製品、汽車內裝品等領域外,近年來,例如伴隨電腦市場的擴大,包含日常可攜帶之行動個人電腦之筆記型電腦之領域的使用、或汽車外裝、行動電話領域之使用亦受到注目。於該等領域中,對於加飾薄片,要求可賦予加飾成型品優異之高硬度性等表面特性的同時、亦具有可得形狀更複雜之成形品之成形性。
為了滿足如此之要求,提出一種具有使用含有低分子量之聚合物與多官能異氰酸酯之活性能量線硬化性樹脂組成物之保護層的轉印材料(例如,專利文獻1)。然而,使用有該樹脂組成物之保護層難以作成無黏性,為了作成無黏性,需要以150℃之高溫之烘烤或長時間之加熱處理。又,於上述之保護層,亦具有無法因應高硬度性等表面特性中之更嚴苛之要求的問題。
於可得高硬度性等表面物性的目的下,提出一種具有含低分子量之聚合物、硬化劑與凝膠二氧化矽粒子之保護層的轉印材料(例如,專利文獻2)。然而,該保護層,對於鉛筆硬度之H以上之更嚴苛要求不足,且於將加飾薄片捲繞成滾筒狀時會有黏連(內移)的情形,再者,對於形狀更複雜之成形品,會有保護層白化而產生塗裝破裂的問題。高硬度性等表面特性與耐黏連及成形性為相對的性能,能以高等級實現該等相對性能之加飾薄片目前並不存在。
專利文獻1:日本專利第3233595號公報
專利文獻2:日本特開2009-137219號公報
因此,本發明之目的在於提供一種形成加飾薄片用之油墨組成物,其於賦予加飾成型品優異之高硬度性的同時,亦賦予可得形狀更複雜之成形品之成形性,且可視需要僅以熱乾燥將硬塗層形成層作成無黏性。
又,本發明之另一目的在於,提供使用上述油墨組成物之加飾成形品之製造方法。
再者,本發明之又一目的在於,提供以上述製造方法所製得之加飾成形品。
本發明之油墨組成物,係含有下列而成:具有選自乙烯基、(甲基)丙烯醯基及烯丙基所構成群中之至少一種之電離輻射線硬化性官能基A之重量平均分子量為50000以上的多官能性自由基聚合性預聚物;於表面具有電離輻射線硬化性官能基B之反應性無機粒子;與多官能異氰酸酯化合物。
又,本發明之另一樣態之加飾薄片,係於基材薄膜之單面,至少依序具備脫模層與硬塗層形成層之加飾薄片,其中,該硬塗層形成層係使用上述之油墨組成物所形成者。
再者,本發明之另一樣態之加飾成形品之製造方法,其係使用上述加飾薄片之加飾成形品之製造方法,其含有:於射出成形模具內配置該加飾薄片之步驟;將熔融樹脂射出至該射出成形模具之模穴內,進行冷卻、固化,而使樹脂成形體與加飾薄片層合一體化之射出步驟;將該樹脂成形體與該加飾薄片層合一體化後之成形體,由該射出成形模具取出之步驟;將加飾薄片之基材薄膜由該成形體剝離之步驟;及使用電離輻射線使設置於該成形體上之硬塗層形成層硬化之硬塗層形成步驟。
本發明,係提供以上述之製造方法所製得之加飾成形品。
藉由本發明,可實現於賦予加飾成型品優異之高硬度性的同時,亦賦予可得形狀更複雜之成形品之成形性,且可視需要僅以熱乾燥將硬塗層形成層作成無黏性之可賦予加飾薄片優異之製造效率之油墨組成物。
本發明之油墨組成物,作為必須成分含有:具有選自乙烯基、(甲基)丙烯醯基及烯丙基所構成群中之至少一種之電離輻射線硬化性官能基A之重量平均分子量為50000以上的多官能性自由基聚合性預聚物;於表面具有電離輻射線硬化性官能基B之反應性無機粒子;與多官能異氰酸酯化合物。以下,說明構成本發明之油墨組成物之各成分。
本發明中,所謂「電離輻射線硬化性」,係指具有於電磁波或荷電粒子線之中可使分子交聯、聚合之能量量子者,亦即,藉由紫外線或電子線等之照射而激發、產生聚合反應,藉此交聯、硬化之性能。又,所謂「電離輻射線硬化性官能基」,係指可發揮電離輻射線硬化性之官能基之意,係指具有乙烯基(甲基)丙烯醯基及烯丙基之乙烯性不飽和鍵之官能基之意。
多官能性自由基聚合性預聚物,只要具有電離輻射線硬化性官能基A之預聚物即可,並無特別限制,較佳可舉例如,(甲基)丙烯酸丙烯酸酯系預聚物、胺基甲酸酯(甲基)丙烯酸酯系預聚物、聚酯(甲基)丙烯酸酯系預聚物、環氧(甲基)丙烯酸酯系預聚物、及聚醚(甲基)丙烯酸酯系預聚物等預聚物,其中,較佳為(甲基)丙烯酸丙烯酸酯系預聚物。本發明中,可將該等預聚物單獨或組合複數使用。
此處,(甲基)丙烯酸丙烯酸酯系預聚物,係(甲基)丙烯酸烷基酯、與可與其共聚合之(甲基)丙烯酸環氧丙酯、(甲基)丙烯醯胺、(甲基)丙烯酸羥基烷基酯等含有官能基之(甲基)丙烯酸系化合物、或與(甲基)丙烯酸、馬來酸、富馬酸、衣康酸等羧酸共聚合而成之預聚物。
胺基甲酸酯(甲基)丙烯酸酯系預聚物,例如,可藉由將聚醚聚醇或聚酯聚醇之反應所得之聚胺基甲酸酯預聚物,以(甲基)丙烯酸酯化而得。
聚酯(甲基)丙烯酸酯系預聚物,例如,可藉由將多元羧酸與多元醇之縮合所得之於兩末端具有羥基聚酯預聚物之羥基,以(甲基)丙烯酸酯化,或者,將於多元羧酸加成環氧烷所得之預聚物之末端之羥基,以(甲基)丙烯酸酯化而得。
環氧(甲基)丙烯酸酯系預聚物,例如,可藉由將分子量較低之雙酚型環氧樹脂或酚醛清漆型環氧樹脂之環氧乙烷環,以(甲基)丙烯酸酯化而得。又,亦可使用將該環氧(甲基)丙烯酸酯系預聚物以二元性羧酸酐局部變性之羧基變性型之環氧(甲基)丙烯酸酯系預聚物。
聚醚(甲基)丙烯酸酯系預聚物,可藉由將聚醚聚醇之羥基以(甲基)丙烯酸酯化而得。
上述之多官能性自由基聚合型預聚物之重量平均分子量,需要50000以上、較佳為50000~145000、更佳為53000~115000。重量平均分子量若為上述範圍內,則可得油墨組成物之觸變性故容易塗佈,且可得良好之成形性。又,重量平均分子量,係以凝膠滲透層析(GPC)所測定之值,係以於標準樣品使用聚苯乙烯之條件所測定之值。
又,由可得優異之表面特性的觀點考量,上述之預聚物之為100~800、較佳為150~500、更佳為150~300。又,雙鍵當量,係電離輻射線硬化性官能基每1mol之分子量之意。
本發明之油墨組成物,含有於表面具有電離輻射線硬化性官能基B之反應性無機粒子。電離輻射線硬化性官能基B,較佳可舉例如乙烯基、(甲基)丙烯醯基、及烯丙基之乙烯性不飽和鍵、或環氧基、矽烷醇基等,由高硬度性及提升耐刮痕性的觀點考量,以乙烯基、(甲基)丙烯醯基、及烯丙基較佳。
無機粒子,較佳可舉例如二氧化矽粒子(凝膠二氧化矽、煙燻二氧化矽、沉降性二氧化矽等)、氧化鋁粒子、氧化鋯粒子、氧化鈦粒子、氧化鋅粒子等金屬氧化物粒子等。由高硬度性的觀點考量,較佳為氧化矽粒子及氧化鋁粒子,特佳為二氧化矽粒子。
無機粒子之形狀,可舉例如球、橢圓體、多面體、鱗片形等,而該等形狀以均勻、整粒為佳。又,無機粒子之平均粒徑,可視油墨組成物所形成之層之厚度來加以適當選擇,而通常為0.005~0.5μm、較佳為0.01~0.1μm。又,所謂平均粒徑,係以動態光散射法測定溶液中之粒子,以累積分布表示粒徑分布時之50%粒徑(d50:中位直徑),可使用Microtrac粒度分析計(日機裝股份有限公司製)測定。
上述之無機粒子之中,由高硬度性的觀點考量,以異形無機粒子較佳。異形無機粒子,係平均連結數2~40個之無機粒子連結凝集之無機粒子群所構成者,於本發明包含於無機粒子中。連結凝集,可為規則、亦可為不規則。形成無機粒子群之無機粒子,較佳可舉例如由二氧化矽(凝膠二氧化矽、煙燻二氧化矽、沉降性二氧化矽等)、氧化鋁、氧化鋯、氧化鈦、氧化鋅等金屬氧化物所構成之無機粒子,由高硬度性的觀點考量,較佳為二氧化矽或氧化鋁所構成之異形無機粒子。亦即,異形無機粒子,較佳為,平均連結數2~40個之二氧化矽粒子或氧化鋁粒子連結凝集之二氧化矽粒子群或氧化鋁粒子群所構成者,特佳為,平均連結數2~40個之二氧化矽粒子連結凝集之二氧化矽粒子群所構成之異形二氧化矽粒子。
形成無機粒子群之無機粒子之形狀,較佳可舉例如球、橢圓體、多面體、鱗片形等,該等形狀以均勻、整粒為佳。形成無機粒子群之無機粒子的平均粒徑,較佳為0.005~0.5μm、更佳為0.01~0.1μm。又,異形無機粒子之平均粒徑,可視油墨組成物所形成之層之厚度來加以適當選擇,而通常以0.005~0.5μm為佳、更佳為0.01~0.1μm。又,此處之平均粒徑,係與上述之無機粒子之平均粒徑以相同方法測定。
反應性無機粒子,較佳為,上述之於二氧化矽粒子或異形二氧化矽粒子之表面具有電離輻射線硬化性官能基B之反應性二氧化矽粒子或反應性異形二氧化矽粒子,而以經矽烷耦合劑表面裝飾者為佳。
矽烷耦合劑,較佳可舉例如具有乙烯基、環氧基、(甲基)丙烯醯基、烯丙基等之周知之矽烷耦合劑,更具體而言,可舉例如γ-甲基丙烯氧基丙基甲基二甲氧矽烷、γ-甲基丙烯氧基丙基二甲基甲氧矽烷、γ-甲基丙烯氧基丙基三乙氧矽烷、γ-甲基丙烯氧基丙基二甲基乙氧矽烷、γ-丙烯氧基丙基三甲氧矽烷、γ-丙烯氧基丙基甲基二甲氧矽烷、γ-丙烯氧基丙基二甲基甲氧矽烷、γ-丙烯氧基丙基三乙氧矽烷、γ-丙烯氧基丙基甲基二乙氧矽烷、γ-丙烯氧基丙基二甲基乙氧矽烷、乙烯基三乙氧矽烷、γ-環氧丙氧基丙基三甲氧矽烷等。該等之中,較佳為,γ-甲基丙烯氧基丙基三甲氧矽烷、γ-甲基丙烯氧基丙基甲基二甲氧矽烷、γ-甲基丙烯氧基丙基二甲基甲氧矽烷。
將無機粒子以矽烷耦合劑表面裝飾之方法,並無特別限制,可採用周知之方法。可舉例如,將矽烷耦合劑噴霧之乾式之方法、或使無機粒子分散於溶劑後加入矽烷耦合劑使其反應之濕式之方法等。
本發明之油墨組成物,含有具2個以上異氰酸酯基之多官能異氰酸酯化合物。多官能異氰酸酯,可舉例如,2,4-甲苯二異氰酸酯(TDI)、二甲苯二異氰酸酯(XDI)、萘二異氰酸酯、4,4-二苯基甲烷二異氰酸酯等芳香族異氰酸酯,或者,1,6-六亞甲基二異氰酸酯(HMDI)、異佛酮二異氰酸酯(IPDI)、亞甲基二異氰酸酯(MDI)、加氫二異氰酸酯、加氫二苯基甲烷二異氰酸酯等脂肪族(至脂環式)二異氰酸酯等聚異氰酸酯。又,亦可為該等各種異氰酸酯之加成體或聚合物,例如,甲苯二異氰酸酯之加成體、甲苯二異氰酸酯之三聚物(trimer)等、或封端化之異氰酸酯化合物等。
又,本發明中,多官能異氰酸酯化合物之中,由高硬度性的觀點考量,特佳為,具有選自乙烯基、(甲基)丙烯醯基、烯丙基及環氧基所構成群中之至少一種電離輻射線硬化性官能基C者。具體而言,較佳為,如「Laromer LR9000(商品名)」(BASF製)之具有至少1個乙烯性不飽和鍵之官能基、與2個以上之異氰酸酯基之多官能異氰酸酯化合物。
本發明之油墨組成物,除上述成分以外,於調整黏度的目的下,亦可含有溶劑。溶劑,較佳可舉例如,甲苯、二甲苯等烴類;甲醇、乙醇、異丙醇、丁醇、異丁醇、甲甘醇、甲甘醇乙酸酯、甲基賽路蘇、乙基賽路蘇、丁基賽路蘇等醇類;丙酮、甲乙酮、甲基異丁基酮、環己酮、二丙酮醇等酮類;甲酸甲酯、乙酸甲酯、乙酸乙酯、乳酸乙酯、乙酸丁酯等酯類;硝基甲烷、N-甲基吡咯烷酮、N,N-二甲基甲醯胺等含氮化合物;丙二醇單甲醚、二異丙醚、四氫呋喃、二噁烷、二氧戊環等醚類;二氯甲烷、氯仿、三氯乙烷、四氯乙烷等鹵素化烴;二甲亞碸、碳酸丙烯等其他者;或該等之混合物。更佳之溶劑,可舉例如甲乙酮、甲基異丁基酮等。
油墨組成物之溶劑之量,可視組成物之黏度加以適當選擇,而符合該預聚物之固體成分、反應性無機粒子及其他後述之光聚合起始劑等之固體成分之含量,通常為成為10~70質量%左右、較佳為20~50質量%之量。
本發明之油墨組成物,亦可含有光聚合起始劑。光聚合起始劑,可舉例如苯乙酮系、酮系、二苯基酮系、安息香系、縮酮系、蒽醌系、二硫化物系、硫雜蔥酮系、甲硫碳醯胺(thiuram)系、氟化胺(fluoro amine)系等之光聚合起始劑。其中,較佳可舉例如苯乙酮系、酮系、二苯基酮系。該等之光聚合起始劑,可分別單獨、或組合複數使用。
光聚合起始劑之含量,相對於該預聚物之固體成分100質量份,較佳為0.5~10質量份左右、更佳為1~8質量份、再更佳為3~8質量份。
本發明之油墨組成物,視所得之所欲物性,亦可含有各種添加劑。添加劑,可舉例如,紫外線吸收劑、紅外線吸收劑、光安定劑、聚合禁止劑、交聯劑、抗靜電劑、抗氧化劑、整平劑、觸變性賦予劑、耦合劑、可塑劑、消泡劑、充填劑、熱自由基產生劑、鋁螯合劑等。
又,本發明之油墨組成物,於不阻害其效果的範圍內,亦可含有丙烯酸系樹脂、纖維素系樹脂、胺基甲酸酯系樹脂、聚酯樹脂、環氧系樹脂等聚合物、或具有選自乙烯基、(甲基)丙烯醯基、烯丙基及環氧基所構成群中之至少一種電離輻射線硬化性官能基之單體,例如胺基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及聚醚(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯等反應性單體。
油墨組成物中之預聚物之固體成分之含量,相對於預聚物之固形分與反應性無機粒子之合計,以95質量%以下為佳、更佳為85質量%以下、特佳為70質量%以下。又,預聚物之固體成分之含量之下限的範圍,以30質量%以上為佳、更佳為40質量%以上、特佳為50質量%以上。聚合物之含量若為上述範圍內,則於使用油墨組成物形成硬塗層形成層之際,塗佈油墨組成物於脫模層上所形成之硬塗層形成層,視需要可僅以熱乾燥作成無黏性。其之結果,於不進行藉電離輻射線之照射或高溫之烘烤等之半硬化處理之下,即使將薄片捲繞成滾筒狀亦不會黏連(內移)。又,由於不需要上述之半硬化處理,故於成形之際,即使成形前後之加飾薄片之面積比為130%以上之深拉(deep drawing),於最大延伸部亦無產生塗膜破裂或白化,能形成可良好地追尋模具形狀之硬塗層形成層。再者,藉由於成型轉印後使用電離輻射線將硬塗層形成層硬化,可得優異之高硬度性。
又,油墨組成物中之多官能異氰酸酯化合物之固體成分之含量,相對於預聚物之固體成分100質量份,以1~30質量份為佳、更佳為1~20質量份、再更佳為3~15質量份。多官能異氰酸酯化合物之固體成分之含量若為上述範圍內,則可於維持優異之高硬度性與成形性之下,得到成形時之耐熱性。
本發明之加飾薄片,係於基材薄膜之單面至少依序具備脫模層與硬塗層形成層者,硬塗層形成層係使用上述之油墨組成物所形成者。以下,參照圖1及圖2說明本發明之加飾薄片。圖1,係本發明之加飾薄片之一較佳樣態之截面模式圖。圖2,係本發明之加飾成形品之一較佳樣態之截面模式圖。
本發明之加飾薄片10,如圖1所示,係於聚酯薄膜所構成之基材薄膜11之一表面,依序層合脫模層12、硬塗層形成層13、固定層(anchor layer)14、圖案層15及接著層16,而於基材薄膜11之另一面(設置脫模層12之相反側之面)層合有抗靜電層19者。
又,本發明之加飾成形品20,如圖2所示,係於樹脂成形體21之表面,依序層合有接著層16、圖案層15、固定層14及硬塗層形成層13硬化所成之硬塗層22者。以下,說明構成加飾薄片及加飾成形品之各構件。
基材薄膜,可利用聚乙烯、聚丙烯等聚烯烴系樹脂;聚氯乙烯、聚偏二氯乙烯、聚乙烯醇、乙烯‧乙酸乙烯酯共聚物、乙烯‧乙烯醇共聚物等乙烯系樹脂;聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯系樹脂;聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸乙酯等丙烯酸系樹脂;聚苯乙烯等苯乙烯系樹脂、丙烯腈‧丁二烯‧苯乙烯共聚物、三乙酸纖維素、賽璐玢、聚碳酸酯、聚胺基甲酸酯系等彈性體系樹脂所得者。該等之中,由成形性及剝離性良好的觀點考量,較佳為聚酯樹脂、特佳為聚對苯二甲酸乙二酯(以下稱為「PET」)。
基材薄膜之厚度,由成形性及形狀追尋性、操作容易的觀點考量,以25~150μm之範圍為佳、以25~75μm之範圍為更佳。
脫模層12,係用以使依序層合硬塗層形成層13、固定層14、圖案層15及接著層16所成之轉印層17容易由基材薄膜11剝離所設之層。藉由具備脫模層12,可將轉印層17確實、且容易地由本發明之加飾薄片轉印至被轉印體,並可將基材薄膜11、脫模層12、及視需要所設置之抗靜電層19所構成之剝離層18確實地剝離。
脫模層12,較佳可使用三聚氰胺樹脂系脫模劑、聚矽氧樹脂系脫模劑、氟樹脂系脫模劑、纖維素樹脂系脫模劑、尿素樹脂系脫模劑、聚烯烴樹脂系脫模劑、石蠟系脫模劑、丙烯酸樹脂系脫模劑及該等之複合型脫模劑等脫模劑。該等之中,由可使脫模層與硬塗層形成層之剝離強度為既定範圍內、而確實地剝離剝離層18的觀點,較佳為,三聚氰胺樹脂系脫模劑及丙烯酸樹脂系脫模劑、或丙烯酸-三聚氰胺系等之將該等複合者。
當使用三聚氰胺樹脂系脫模劑時,為了促進脫模劑之硬化,以使用酸觸媒為佳。上述酸觸媒並無特別限定,較佳可舉例如對甲苯磺酸、十二苯磺酸、二壬基萘磺酸、二壬基萘二磺酸等。酸觸媒之使用量,相對於三聚氰胺樹脂系脫模劑所含之三聚氰胺樹脂之固體成分,以0.05~3%左右為佳、更佳為0.05~1%。又,為了促進脫模劑之硬化,較佳為,以130~170℃進行加熱處理30秒~2分鐘左右。
脫模層12之形成,可將於上述脫模劑添加必須之添加劑所成者溶解或分散於適當之溶劑所調製成之油墨,於基材薄膜11以周知之手段進行塗佈、乾燥。脫模層12之厚度,以0.1~5μm左右為佳。
硬塗層形成層,係使用上述之油墨組成物所形成之層,藉由硬化而成為加飾成形品20中之硬塗層22。硬塗層22,係加飾成形品之最外層,係用以由磨耗或藥品等保護成形品或圖案層之層。因此,硬塗層形成層13,必須為藉由硬化而具有優異之高硬度性與耐刮痕性、且具有耐藥品性及耐污染性等表面物性優異之性能之層。
硬塗層形成層,可藉由將上述之油墨組成物,以凹版塗佈法、輥塗法、刮刀式塗佈、模具塗佈法等塗佈法、凹版印刷法、網版印刷法等進行塗佈,來形成。
硬塗層形成層之厚度,較佳為0.5~30μm之範圍、更佳為3~15μm之範圍。厚度若為上述範圍,則當然優異之高硬度性與耐刮痕性,並可得耐藥品性及耐污染性等表面物性,同時可得優異之成形性及形狀追尋性。又,於材料費的觀點上亦有利。
固定層14,係用體提升硬塗層形成層13與接著層16、或具圖案層15時之與圖案層15之密合性,視需要所設置之層。固定層14,可由2液性硬化胺基甲酸酯樹脂、熱硬化性胺基甲酸酯樹脂、三聚氰胺系樹脂、纖維素酯系樹脂、含氯之橡膠樹脂、含氯之乙烯系樹脂、丙烯酸系樹脂、環氧系樹脂、乙烯系共聚合樹脂等所形成。例如,可藉由將該等之樹脂,於上述之硬塗層形成層13之上,以凹版塗佈法、輥塗法、刮刀式塗佈等塗佈法、凹版印刷法、網版印刷法等塗佈來形成。固定層14之厚度,通常為0.1~5μm左右、較佳為1~5μm左右。
圖案層15,係用以賦予加飾成形品所欲之設計性之層,視需要所設置之層。圖案層15之圖案為任意,可舉例如木紋、石紋、大理石紋、灰紋、幾何學花紋、文字等所構成之圖案。又,圖案層15,可將表現上述圖案之圖案層及整面內層單獨或組合來設置,整面內層,通常係作為掩蔽層、著色層、著色掩蔽層等使用。
圖案層15,通常係於如上述所形成之硬塗層形成層13上、或固定層14之上,將含有以聚乙烯系樹脂、聚酯系樹脂、丙烯酸系樹脂、聚乙烯縮醛系樹脂、纖維素系樹脂等樹脂作為黏結劑、以適當顏色之顏料或染料作為著色劑之印刷油墨,藉由印刷來形成。印刷方法,可舉例如凹版印刷、平版印刷、絲網印刷、來自轉印薄片之轉印印刷、昇華轉印印刷、噴墨印刷等周知之印刷法。圖案層15之厚度,由設計性之觀點考量以5~40μm為佳、5~30μm為更佳。
接著層16,係用以將轉印層17接著性佳地轉印至樹脂成形體所形成之層。該接著層16,係適當使用適合樹脂成形體之原料之感熱性或感壓性的樹脂。例如,當樹脂成形體之材質為丙烯酸系樹脂時,較佳為使用丙烯酸系樹脂。又,當樹脂成形體之材質為聚苯醚‧聚苯乙烯系樹脂、聚碳酸酯系樹脂、苯乙烯系樹脂時,較佳為使用與該等樹脂具親合性之丙烯酸系樹脂、聚苯乙烯系樹脂、聚醯胺系樹脂等。再者,當樹脂成形體之材質為聚丙烯樹脂時,較佳為使用氯化聚烯烴樹脂、氯化乙烯-乙酸乙烯酯共聚物樹脂、環化橡膠、苯並呋喃-茚樹脂。
接著層16之形成方法,可舉例如凹版塗佈法、輥塗法等塗佈法、凹版印刷法、網版印刷法等印刷法。又,當圖案層15對樹脂成形體具有充分之接著性時,亦可不設置接著層16。接著層16之厚度,通常以0.1~5μm左右為佳。
本發明之加飾薄片,亦可具備抗靜電層。抗靜電層19,係用以防止異物附著於加飾薄片所設置者,係設置於基材薄膜11之設置脫模層之面的相反面。
抗靜電層所使用之抗靜電劑,較佳可舉例如羧酸系、磺酸系、磷酸系等陰離子界面活性劑;四級銨系等陽離子界面活性劑;烷基甜菜鹼系、烷基咪唑啉系、烷基丙胺酸系等兩性界面活性劑;環氧烷聚合物、環氧烷共聚物、脂肪族醇-環氧烷加成物等非離子系界面活性劑;碳、或金、鉑、銀、銅、鋁、鎳、鈦、鉬等各種金屬粉末等無機導電性物質;聚乙炔、聚吡咯、聚對苯撐、聚苯胺、聚噻吩、聚對苯撐伸乙烯、聚乙烯咔唑、或胺基羧酸、二羧酸及聚乙二醇所構成之聚醚酯醯胺樹脂等導電性高分子等。
抗靜電層,係藉由將上述之抗靜電劑及有機溶劑等所構成之塗料,以凹版印塗佈法、輥塗法等塗佈法、或凹版印刷法、網版印刷法等印刷法塗佈來形成。如此所形成之抗靜電層之厚度,通常以0.1~5μm為佳。抗靜電層之厚度若為上述範圍內,可有效率地得到優異之抗靜電性能。
本發明之加飾薄片,硬塗層形成層可視需要僅藉熱乾燥作成無黏性,故耐黏連性優異,同時亦可賦予耐熱性,故製造效率優異。又,由於不需要進行用以作成無黏性之電離輻射線之照射或高溫之烘烤等之半硬化處理,故成為具有優異之成形性及形狀追尋性者。再者,藉由於成型轉印後使用電離輻射線使硬塗層形成層硬化,可得優異之高硬度性及耐刮痕性。因此,可使用於家庭用電化製品、汽車內裝品等領域、或個人電腦之領域、特別是個人電腦之框體等廣泛之領域中。
<加飾成形品之製造方法>
本發明之加飾成型品之製造方法,含有:於射出成形模具內配置該加飾薄片之步驟(第1步驟);將熔融樹脂射出至該射出成形模具之模穴內,進行冷卻、固化,而使樹脂成形體與加飾薄片層合一體化之射出步驟(第2步驟);將該樹脂成形體與該加飾薄片層合一體化後之成形體,由該射出成形模具取出之步驟(第3步驟);將加飾薄片之基材薄膜由該成形體剝離之步驟(第4步驟);及使用電離輻射線使設置於該成形體上之硬塗層形成層硬化之
硬塗層形成步驟(第5步驟)。以下,說明各步驟。
<第1步驟>
第1步驟,係將上述加飾薄片配置於成形模具內夾持之步驟。具體而言,係將加飾薄片,於可動模具與固定模具所構成之成形用模具,以使內使轉印層17為內側、亦即使基材薄膜11為固定模具側的方式,送入加飾薄片。此時,可一片一片送入數片之加飾薄片,亦可間歇地送入長條之加飾薄片的必要部分。
於將加飾薄片配置於成形模具內之際,可進行下述來配置:(i)僅加熱模具,以對該模具真空抽吸以使其密合的方式配置;或(ii)使用熱盤由轉印層17側加熱使其軟化,使加飾薄片以沿著模具內之形狀的方式預備成型,使其密合於模具內面合模。(ii)時之加熱溫度,較佳為,基材薄膜11之玻璃轉移溫度附近以上、且未滿熔融溫度(或熔點)之範圍,通常係以玻璃轉移溫度附近進行。又,上述所謂玻璃轉移溫度附近,係玻璃轉移溫度±5℃左右之範圍,一般係70~130℃左右。又,於(ii)的情況下,為了使加飾薄片更密合於成形模具表面,於以熱盤加熱加飾薄片使其軟化時,亦可進行真空抽吸。
<第2步驟>
第2步驟,係將熔融樹脂射出至模穴內,進行冷卻、固化,而使樹脂成形體與加飾薄片層合一體化之射出步驟。當射出樹脂為熱可塑性樹脂時,可藉加熱熔融作成流動狀態,而當射出樹脂為熱硬化性樹脂時,可適當加熱未硬化之液狀組成物而以流動狀態射出,並進行冷卻使其固化。藉此,加飾薄片與樹脂成形體一體化而貼附,成為加飾成形品。射出樹脂之加熱溫度,雖係視射出樹脂,而一般為180~280℃左右。
加飾成形品所使用之射出樹脂,只要為能射出成形之熱可塑性樹脂、或熱硬化性樹脂(含2液熱硬化性樹脂)即可,可使用各種樹脂。如此之熱可塑性樹脂材料,可舉例如聚苯乙烯系樹脂、聚烯烴系樹脂、ABS樹脂(含耐熱ABS樹脂)、AS樹脂、AN樹脂、聚苯醚系樹脂、聚碳酸酯系樹脂、聚縮醛系樹脂、丙烯酸系樹脂、聚對苯二甲酸乙二酯系樹脂、聚對苯二甲酸丁二酯系樹脂、聚碸系樹脂、聚苯硫系樹脂等。又,熱硬化性樹脂,可舉例如2液反應硬化型之聚胺基甲酸酯系樹脂、環氧系樹脂等。該等樹脂可單獨使用、亦可混合二種以上使用。
第3步驟,係將加飾薄片與樹脂成形體一體化後之成形體由模具取出之步驟,第4步驟,係由成形體將加飾薄片之基材薄膜剝離之步驟。基材薄膜11,由於具有脫模層12,故於該脫模層12與硬塗層形成層13之境界面,可容易地將含基材薄膜11與脫模層12、及視需要所設置之抗靜電層19之剝離層18由加飾成形品20剝離。如此,可得於樹脂成形體21之表面依序層合有接著層16、圖案層15、固定層14及硬塗層形成層13之成形品。
第5步驟,係使用電離輻射線使上述第4步驟所得之成形品中之硬塗層形成層13硬化,而形成硬塗層之步驟。第5步驟之硬化,可於氧濃度2%以下之環境氣氛下照射電離輻射線來進行。如此藉由進行硬化,可得更優異之高硬度性及耐刮痕性。
可於氧濃度2%以下之環境氣氛,例如,可藉由使用氮、氬、氫等、較佳為使用氮,或進行真空抽吸使氧濃度為2%以下左右等之方法來得到。
硬塗層形成層13之硬化,可照射電子線及紫外線等電離輻射線來進行。當使用電子線作為電離輻射線時,關於其之加速電壓,可視所使用之預聚物或單體的種類、或硬塗層形成層13之厚度來加以適當選定,而通常加速電壓以70~300kV左右為佳。照射線量,通常係以5~300kGy(0.5~30Mrad)、較佳為10~50kGy(1~5Mrad)之範圍選定。又,電子線源,並無特別限制,例如,可使用柯克勞夫-沃耳吞型、凡德格拉夫型、共振變壓器型、絕緣核變壓器型、或直線型、高頻高壓型、高頻型等各種電子線加速器。
當使用紫外線作為電離輻射線時,係照射含波長190~380nm之紫外線者,其之照射線量為500~1500mJ左右。紫外線源並無特別限制,例如可使用高壓水銀燈、低壓水銀燈、金屬鹵素燈、碳弧燈等。
如此所得之本發明之加飾成形品,係具有優異之高硬度性、耐藥品性或耐污染性等表面物性亦優異者。又,藉由使用可得能因應形狀更複雜之成形品之成形性的本發明之加飾薄片,可得成品外觀更優異之加飾成形品。
本發明之加飾成形品,活用該等優異之特性,可使用於家庭用電化製品、汽車內裝品等領域、或個人電腦之領域、特別是個人電腦之框體等廣泛之領域中。
接著,藉由實施例更詳細地說明本發明,但本發明並不因該等實施例而產生任何限定。又,實施例之評價方法,係如以下方式進行。
於基材薄膜(「F99(商品編號)」,厚度:50μm,東雷股份有限公司製)上,以塗佈量2g/m2
凹版印刷三聚氰胺樹脂系脫模劑(添加三聚氰胺樹脂之固體含量比0.5%之酸觸媒(對甲苯磺酸)),於150℃之烘箱內加熱處理60秒鐘而形成脫模層之上,以棒塗器塗佈各實施例及比較例所使用之油墨組成物,以100℃之烘箱內乾燥60秒鐘,製得試驗樣品。此處,油墨組成物之塗佈量係使乾燥後之油墨塗佈層之厚度成為6g/m2
之量。
於試驗樣品之油墨塗佈層面,疊合試驗樣品之製作所使用之PET薄膜,使用油墨黏連試驗機(「DG-BT(型號)」,大和印刷股份有限公司製),於施加1kg/cm2
之荷重之下,放置於40℃之烘箱內12小時。之後,取出試驗樣品,將疊合之PET薄膜剝離。以下述基準評價剝離之PET薄膜之油墨塗佈層之沾附(內移)。
A:完全無內移
B:雖有些許之內移,但於實用上無問題
C:內移顯著
將試驗樣品以各實施例及比較例中之硬化方法硬化後,根據JIS K5600-5-4,使用鉛筆刮搔塗膜硬度試驗機(「D-NP(型號),東洋精機製作所股份公司製)、及鉛筆刮搔值試驗用鉛筆(三菱鉛筆股份有限公司製)測定鉛筆硬度。以各硬度之鉛筆對油墨塗佈層進行刮搔試驗5次,將未產生痕跡3次以上之鉛筆硬度,作為試驗樣品之鉛筆硬度。
於附冷卻器、滴入漏斗及溫度計之2L四口燒瓶,裝填甲基異丁基酮(MIBK)120g、甲乙酮(MEK)210g,於該四口燒瓶,以2小時由滴入漏斗滴下甲基丙烯酸環氧丙酯(GMA)80g、甲基丙烯酸甲酯(MMA)20g及偶氮系之起始劑(偶氮雙異丁腈,AIBN-1)0.75g所構成之混合液,於100~110℃之溫度下反應4小時後,再加入偶氮系之起始劑(偶氮雙異丁腈,AIBN-2)0.6g,保溫3小時後,冷卻至室溫。於其加入丙烯酸(AA)40.6g、三苯膦2g、及甲氧苯酚0.5g所構成之混合液,進行加成反應。以氫氧化鉀溶液之中和滴定,確認反應性生物之酸價的消失,使反應結束。
所得之反應生成物(預聚物1)之重量平均分子量為80000,雙鍵當量為250g/mol(計算值),固體成分為30%。又,重量平均分子量,係以凝膠滲透層析(GPC)所測定之值,係於標準樣品使用聚苯乙烯之條件所測定之值。
於合成例1(預聚物1之合成)中,除將所使用之劑量改成表1所示之量以外,於合成例1同樣地,合成預聚物2。將所得之預聚物2之重量平均分子量、雙鍵當量及樹脂固體成分示於表1。又,表中之配合組成欄之數值,皆為公克。
於基材薄膜(「F99(商品編號)」,厚度:50μm,東雷股份有限公司製)上,以塗佈量2g/m2
凹版印刷以三聚氰胺系樹脂為主成分之塗佈液(「美蘭265」(商品編號),日立化成工業股份有限公司製,異丁醇變性三聚氰胺樹脂)以形成脫模層,以塗佈量6g/m2
凹版印刷下述所示組成之油墨組成物而形成硬塗層形成層。
預聚物1:20.0質量份(固體成分6質量份)、丙烯酸丙烯酸酯系預聚物(合成例1所合成之預聚物1、分子量:80000、雙鍵當量:250g/mol)
反應性異型二氧化矽粒子:10質量份(固體成分4質量份)、(「ELCOMV-8803(商品編號)」,日揮觸媒化成股份有限公司製,反應性異型二氧化矽粒子,平均連結數:規則地2~10個,異形無機粒子之平均粒徑:25nm)
反應性多官能異氰酸酯:1質量份(固體成分1質量份)、(「Laromer LR9000(商品編號)」,BASF製)光聚合起始劑:0.4質量份(「IRGACURE 184(商品編號)」,汽巴‧日本股份有限公司製,1-羥基環己基苯酮)
溶劑:6.7質量份,甲乙酮與甲基異丁基酮之混合溶劑(配合比70:30)
接著,以塗佈量4g/m2
凹版印刷以丙烯酸系樹脂為主成分之塗料形成固定層,接著,將丙烯酸系印刷油墨以塗佈量8g/m2
,凹版印刷木紋模樣形成圖案層,以厚度4μm塗佈丙烯酸系塗佈液形成接著層。再者,於基材薄膜之設置脫模層之面的相反面,以塗佈量1g/m2
凹版印刷以陽離子系界面活性劑為主成分之塗佈液(陽離子系界面活性劑:四級銨鹽),形成抗靜電層,製得實施例1之加飾薄片。又,使用實施例1所使用之油墨組成物,根據上述1.試驗樣品之製作製作試驗樣品,進行耐黏連性(薄片捲繞適性)之評價、高硬度性之評價。評價結果係如下述表2所示。
將上述所得之加飾薄片,抽吸至加熱為70℃之模具,使其密合於模具內面。模具,係使用80mm邊長之大小,高度10mm、角部為3維盤狀之深拉度高的形狀。
另一方面,使用ABS樹脂(「Clastic MTH-2(商品編號)」,日本A&L股份有限公司製)作為射出樹脂,將其以230℃作成溶融狀態後,射出至模穴內。冷卻、從模具取出後,將基材薄膜剝離,製得於樹脂成形品之表面依序具有接著層、印刷層、固定層及硬塗層形成層的成形品。再者,於大氣環境氣氛下,使用可變輸出型UV燈系統(「DRS-10/12QN(商品編號)」,Fusion UV系統‧日本股份有限公司製),以照射線量:1000mJ,對該成形品照射紫外線,使硬塗層形成層硬化,作成硬塗層形成層,製得實施例1之樹脂成形品。
對所得之樹脂成形品,以下述之基準評價其之外觀(成形性)。
A:於硬塗層(及其之形成層)完全無確認到塗裝破裂或白化,可良好地追尋模具之形狀
B:於硬塗層(及其之形成層)確認到些微之塗裝破裂或輕微的白化
C:於硬塗層(及其之形成層)雖確認到部分之塗裝破裂或輕微的白化,但於實用上無問題
D:於硬塗層(及其之形成層)確認到顯著之塗裝破裂或白化
評價結果係如下述表2所示。
又,對所得之樹脂成形品,以下述之基準評價澆口部(樹脂射出部)周圍的外觀(耐熱性)。
A:於硬塗層(及其之形成層)完全無確認到流動所至之變形或白化
B:於硬塗層(及其之形成層)確認到些微之流動所至之變形或輕微的白化
C:於硬塗層(及其之形成層)雖確認到部分之流動所至之變形或輕微的白化,但於實用上無問題
D:於硬塗層(及其之形成層)確認到顯著之流動所至之變形或白化
評價結果係如下述表2所示。
實施例1中,除將油墨組成物作成表2所示以外,與實施例1同樣地,製得實施例2、3及比較例1~7之加飾薄片及加飾成形品。對所使用油墨組成物,進行上述之耐黏連性(薄片捲繞適性)之評價、高硬度性之評價,對所得之加飾成形品,進行上述之外觀評價。評價結果係如下述表2所示。
10‧‧‧加飾薄片
11‧‧‧基材薄膜
12‧‧‧脫模層
13‧‧‧硬塗層形成層
14‧‧‧固定層
15‧‧‧圖案層
16‧‧‧接著層
17‧‧‧轉印層
18‧‧‧剝離層
19‧‧‧抗靜電層
20‧‧‧加飾成形體
21‧‧‧樹脂成形體
22‧‧‧硬塗層
圖1,本發明之加飾薄片之一實施型態之截面模式圖。
圖2,本發明之加飾成形品之一實施型態之截面模式圖。
10...加飾薄片
11...基材薄膜
12...脫模層
13...硬塗層形成層
14...固定層
15...圖案層
16...接著層
17...轉印層
18...剝離層
19...抗靜電層
Claims (9)
- 一種油墨組成物,其特徵係在於含有下列而成:具有選自乙烯基、(甲基)丙烯醯基及烯丙基所構成群中之至少一種之電離輻射線硬化性官能基A之重量平均分子量為50000以上的多官能性自由基聚合型預聚物;於表面具有電離輻射線硬化性官能基B之反應性無機粒子;與多官能異氰酸酯化合物,該電離輻射線硬化性官能基B係選自乙烯基、(甲基)丙烯醯基、烯丙基、環氧基及矽烷醇基中之至少一種。
- 如申請專利範圍第1項之油墨組成物,其中,該反應性無機粒子,係反應氧化矽粒子。
- 如申請專利範圍第2項之油墨組成物,其中,該反應氧化矽粒子,係反應性異形氧化矽粒子。
- 如申請專利範圍第1或2項之油墨組成物,其中,該多官能性自由基聚合型預聚物,係(甲基)丙烯酸丙烯酸酯系預聚物。
- 如申請專利範圍第1或2項之油墨組成物,其中,該多官能異氰酸酯化合物,係具有選自乙烯基、(甲基)丙烯醯基、烯丙基及環氧基所構成群中之至少一種之電離輻射線硬化性官能基C。
- 一種加飾薄片,其係於基材薄膜之單面,至少依序具備脫模層與硬塗層形成層之加飾薄片,其特徵係:該硬塗層形成層係使用如申請專利範圍第1至5項中任一項之油墨組成物所形成。
- 如申請專利範圍第6項之加飾薄片,其中,於該基材薄膜之設置有該脫模層之面的相反面,具備抗靜電層。
- 一種方法,其係使用如申請專利範圍第6項之加飾薄片之加飾成形品之製造方法,其特徵係含有第1~第5步驟而成:第1步驟:於射出成形模具內配置該加飾薄片之步驟;第2步驟:將熔融樹脂射出至該射出成形模具之模穴內,進行冷卻、固化,而使樹脂成形體與加飾薄片層合一體化之射出步驟;第3步驟:將該樹脂成形體與該加飾薄片層合一體化後之成形體,由該射出成形模具取出之步驟;第4步驟:將加飾薄片之基材薄膜由該成形體剝離之步驟;及第5步驟:使用電離輻射線使設置於該成形體上之硬塗層形成層硬化之硬塗層形成步驟。
- 一種加飾成形品,其係由如申請專利範圍第8項之製造方法所得。
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US11624000B2 (en) | 2017-05-23 | 2023-04-11 | Alpha Assembly Solutions Inc. | Graphene enhanced and engineered materials for membrane touch switch and other flexible electronic structures |
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JP2021079646A (ja) * | 2019-11-20 | 2021-05-27 | スリーエム イノベイティブ プロパティズ カンパニー | 低光沢な外観を呈する無機ナノ粒子含有表面層を含む積層体及び無機ナノ粒子含有放射線硬化型インク |
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TW200907401A (en) * | 2007-06-26 | 2009-02-16 | Konica Minolta Opto Inc | Clear hard coat film, and antireflection film, polarizing plates and displays, made by using the same |
JP2009137219A (ja) * | 2007-12-10 | 2009-06-25 | Nissha Printing Co Ltd | 耐箔バリ性に優れた転写材の製造方法と転写材 |
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JP2012041479A (ja) | 2012-03-01 |
JP5732778B2 (ja) | 2015-06-10 |
TW201221586A (en) | 2012-06-01 |
WO2012023543A1 (ja) | 2012-02-23 |
CN103052693B (zh) | 2014-06-18 |
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