TWI626999B - Method of manufacturing pattern forming body - Google Patents
Method of manufacturing pattern forming body Download PDFInfo
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- TWI626999B TWI626999B TW104131203A TW104131203A TWI626999B TW I626999 B TWI626999 B TW I626999B TW 104131203 A TW104131203 A TW 104131203A TW 104131203 A TW104131203 A TW 104131203A TW I626999 B TWI626999 B TW I626999B
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- Prior art keywords
- composition
- pattern
- acrylate
- meth
- film
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 226
- 238000000034 method Methods 0.000 claims abstract description 76
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims description 72
- 230000007547 defect Effects 0.000 abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 114
- 239000010408 film Substances 0.000 description 68
- -1 pillars Substances 0.000 description 51
- 239000000758 substrate Substances 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 26
- 229910052731 fluorine Inorganic materials 0.000 description 24
- 239000010410 layer Substances 0.000 description 23
- 238000001035 drying Methods 0.000 description 16
- 125000001153 fluoro group Chemical group F* 0.000 description 16
- 125000003827 glycol group Chemical group 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- 229920001515 polyalkylene glycol Polymers 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000007261 regionalization Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MXFQRSUWYYSPOC-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical class C=CC(=O)OCC(C)(C)COC(=O)C=C MXFQRSUWYYSPOC-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 2
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000007754 air knife coating Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 238000007601 warm air drying Methods 0.000 description 2
- PCORJEZCUPLHGW-UHFFFAOYSA-N (2-ethyl-1-hydroxy-2-methylhexyl) prop-2-enoate Chemical compound CCCCC(C)(CC)C(O)OC(=O)C=C PCORJEZCUPLHGW-UHFFFAOYSA-N 0.000 description 1
- DKZFIPFKXAGEBP-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) benzoate Chemical compound OCC(C)(C)COC(=O)C1=CC=CC=C1 DKZFIPFKXAGEBP-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- ZKJNETINGMOHJG-GGWOSOGESA-N (e)-1-[(e)-prop-1-enoxy]prop-1-ene Chemical compound C\C=C\O\C=C\C ZKJNETINGMOHJG-GGWOSOGESA-N 0.000 description 1
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- WGYZMNBUZFHYRX-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-ol Chemical compound COCC(C)OCC(C)O WGYZMNBUZFHYRX-UHFFFAOYSA-N 0.000 description 1
- XUIXZBXRQFZHIT-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]-3-methoxypropan-2-ol Chemical compound COCC(O)COC(C)COC(C)CO XUIXZBXRQFZHIT-UHFFFAOYSA-N 0.000 description 1
- VCEMVMJQVAYNAY-UHFFFAOYSA-N 1-[4-(2-phenylpropan-2-yl)phenoxy]ethane-1,2-diol Chemical compound C=1C=C(OC(O)CO)C=CC=1C(C)(C)C1=CC=CC=C1 VCEMVMJQVAYNAY-UHFFFAOYSA-N 0.000 description 1
- PHPRWKJDGHSJMI-UHFFFAOYSA-N 1-adamantyl prop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C=C)C3 PHPRWKJDGHSJMI-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YIXYZTDKMQGRRN-UHFFFAOYSA-N 2-(2-prop-1-enoxyethoxycarbonyl)benzoic acid Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)OCCOC=CC YIXYZTDKMQGRRN-UHFFFAOYSA-N 0.000 description 1
- FIOCEWASVZHBTK-UHFFFAOYSA-N 2-[2-(2-oxo-2-phenylacetyl)oxyethoxy]ethyl 2-oxo-2-phenylacetate Chemical compound C=1C=CC=CC=1C(=O)C(=O)OCCOCCOC(=O)C(=O)C1=CC=CC=C1 FIOCEWASVZHBTK-UHFFFAOYSA-N 0.000 description 1
- OBFOSROPNNOGQF-UHFFFAOYSA-N 2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]-1-phenoxyethanol Chemical compound OCCOCCOCCOCCOCCOCC(O)OC1=CC=CC=C1 OBFOSROPNNOGQF-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 125000004924 2-naphthylethyl group Chemical group C1=C(C=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
本發明提供一種可抑制圖案缺陷的產生並同時製造在凹凸圖案的表面形成有膜的圖案形成體的圖案形成體的製造方法。本發明的圖案形成體的製造方法包括：在凹凸圖案的表面應用包含溶劑與膜形成成分的第1組成物的步驟；在凹凸圖案的表面自應用的第1組成物露出之前，將表面張力比第1組成物低的第2組成物應用於凹凸圖案上的應用了第1組成物的區域上的步驟；對凹凸圖案上所應用的第1組成物及第2組成物進行乾燥，在凹凸圖案的表面形成膜的步驟。The present invention provides a method of producing a pattern forming body capable of suppressing generation of pattern defects and simultaneously producing a pattern forming body in which a film is formed on a surface of a concavo-convex pattern. The method for producing a pattern forming body according to the present invention includes the step of applying a first composition containing a solvent and a film forming component to the surface of the concave-convex pattern, and the surface tension ratio before the surface of the concave-convex pattern is exposed from the applied first composition. The second composition having a low first composition is applied to the region on which the first composition is applied to the concave-convex pattern; and the first composition and the second composition applied to the concave-convex pattern are dried, and the concave-convex pattern is applied. The step of forming a film on the surface.
Description
本發明是有關於一種圖案形成體的製造方法。更詳細而言是有關於一種在半導體積體電路、平面螢幕、微電機械系統、感測器元件、光碟、高密度記憶體磁碟等磁記錄媒體，繞射光柵或凹凸全像片等光學零件，奈米元件、光學元件、用以平面顯示器製作的光學膜或偏光元件、液晶顯示器的薄膜電晶體、有機電晶體、彩色濾光片、保護層(overcoat layer)、柱材、液晶配向用肋材、微透鏡陣列、免疫分析晶片、DNA分離晶片、微反應器、奈米生物元件、光波導管、光學濾光片、光子液晶(photonic liquid crystal)、壓印用模具、永久膜等的製作中所使用的圖案形成體的製造方法。 The present invention relates to a method of producing a pattern forming body. More specifically, it relates to an optical recording medium such as a semiconductor integrated circuit, a planar screen, a microelectromechanical system, a sensor element, a compact disk, a high-density memory disk, or the like, a diffraction grating or a concave-convex photographic film. Parts, nano components, optical components, optical films or polarizing elements for flat panel displays, thin film transistors for liquid crystal displays, organic transistors, color filters, overcoat layers, pillars, liquid crystal alignment Fabrication of ribs, microlens arrays, immunoassay wafers, DNA separation wafers, microreactors, nano-biocomponents, optical waveguides, optical filters, photonic liquid crystals, imprint dies, permanent films, etc. A method of producing a pattern forming body used in the present invention.
所謂「壓印法」是藉由施壓形成有圖案的模具(一般稱為「模具」、「壓模」)而於材料上轉印微細圖案的技術。藉由使用壓印法而可簡易地製作精密的微細圖案，因此近年來期待於各種領域中的應用。特別是形成奈米級水準的微細圖案的奈米壓印技術得到關注。 The "imprint method" is a technique in which a fine pattern is transferred onto a material by pressing a mold (generally referred to as a "mold" or a "die"). Since a precise fine pattern can be easily produced by using an imprint method, it has been expected to be applied to various fields in recent years. In particular, a nanoimprint technique that forms a fine pattern of nanometer level has attracted attention.
作為壓印法，根據其轉印方法提出了被稱為「熱壓印法」、「光壓印法」的方法。熱壓印法是在加熱至玻璃轉移溫度以上的熱塑性樹脂上壓上模具後，將熱塑性樹脂冷卻至玻璃轉移溫 度以下後對模具進行脫模，藉此在基板上的樹脂上轉印微細構造的方法。 As the imprint method, a method called "hot stamping method" or "photoimprint method" has been proposed in accordance with the transfer method. The hot stamping method is to pressurize the thermoplastic resin to the glass transfer temperature after pressing the mold on the thermoplastic resin heated to the glass transition temperature or higher. After the mold is demolded below, the method of transferring the fine structure on the resin on the substrate is performed.
另一方面，光壓印法是通過透光性模具或透光性基板進行光照射而使硬化性組成物光硬化後，將模具剝離，藉此而將微細圖案轉印於光硬化物上的方法。該方法是對未硬化物的壓印，因此無需高壓、高溫加熱，可容易地製作微細的圖案。另外，變得可在室溫下壓印，因此可應用於半導體積體電路的製作等超微細圖案的精密加工領域中。 On the other hand, in the photoimprint method, the curable composition is light-cured by a light-transmitting mold or a light-transmitting substrate, and then the mold is peeled off, whereby the fine pattern is transferred onto the photocured material. method. This method is an imprint of an uncured material, so that it is easy to produce a fine pattern without high-pressure, high-temperature heating. In addition, since it can be imprinted at room temperature, it can be applied to the field of precision processing of ultrafine patterns such as fabrication of a semiconductor integrated circuit.
而且，近年來正研究使用藉由壓印法而所得的凹凸圖案作為永久膜。在將凹凸圖案用作永久膜時，亦研究將包含溶劑與膜形成成分的組成物(膜形成用組成物)塗佈於凹凸圖案的表面而形成膜，賦予功能性的嘗試。 Moreover, in recent years, a concavo-convex pattern obtained by an imprint method has been studied as a permanent film. When a concave-convex pattern is used as a permanent film, a composition (a film-forming composition) containing a solvent and a film-forming component is applied to the surface of the uneven pattern to form a film, and an attempt is made to impart functionality.
在專利文獻1中記載了在利用溶膠-凝膠法(sol-gel method)而製造的壓印圖案上塗佈矽烷材料，形成撥水層。 Patent Document 1 describes that a decane material is applied onto an embossed pattern produced by a sol-gel method to form a water-repellent layer.
而且，在專利文獻2中提出了在壓印光微影步驟中利用多層膜的方法，且記載了圖案形成層使用不含矽的聚合性組成物，使用包含矽的聚合性組成物作為積層結構物。 Further, Patent Document 2 proposes a method of using a multilayer film in the step of imprinting photolithography, and describes that a polymerizable composition containing no antimony is used for the pattern forming layer, and a polymerizable composition containing antimony is used as a laminated structure. Things.
[專利文獻1]日本專利特開2011-183554號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-183554
[專利文獻2]日本專利特表2010-541193號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-541193
然而，在凹凸圖案的表面形成膜時，如圖2所示，在膜形成用組成物的乾燥時，圖案凸部1彎曲、崩塌，產生圖案缺陷。而且，自膜形成成分的溶解性、或塗佈性等觀點考慮，膜形成用組成物使用包含表面張力大的溶劑的組成物，但在使用表面張力大的膜形成用組成物的情況下，特別容易產生所述問題。 However, when a film is formed on the surface of the concavo-convex pattern, as shown in FIG. 2, when the film-forming composition is dried, the pattern convex portion 1 is bent and collapsed to cause pattern defects. In addition, a composition containing a solvent having a large surface tension is used for the film-forming composition from the viewpoint of the solubility of the film-forming component, the coating property, and the like. However, when a film-forming composition having a large surface tension is used, This problem is particularly prone to occur.
因此，本發明的目的在於提供可抑制圖案缺陷的產生並同時製造在凹凸圖案的表面形成有膜的圖案形成體的圖案形成體的製造方法。 Accordingly, an object of the present invention is to provide a method for producing a pattern forming body which can suppress the generation of pattern defects and simultaneously produce a pattern forming body in which a film is formed on the surface of the uneven pattern.
本發明者進行了銳意研究，結果認為應用於凹凸圖案的表面的膜形成用組成物進行乾燥，若液面成為圖案凸部以下，則由於對圖案凸部施加膜形成用組成物的毛細管力，從而產生圖案崩塌等圖案缺陷。並且認為，若能使施加於圖案凸部的所述毛細管力更小，則可抑制圖案缺陷的產生，從而完成本發明。本發明提供以下。 As a result of intensive studies, the inventors of the present invention have found that the film forming composition applied to the surface of the uneven pattern is dried. When the liquid surface is equal to or less than the pattern convex portion, the capillary force of the film forming composition is applied to the pattern convex portion. This causes pattern defects such as pattern collapse. Further, it is considered that if the capillary force applied to the pattern convex portion can be made smaller, generation of pattern defects can be suppressed, and the present invention can be completed. The present invention provides the following.
<1>一種圖案形成體的製造方法，其包括：在凹凸圖案的表面應用包含溶劑與膜形成成分的第1組成物的步驟；在凹凸圖案的表面自應用的第1組成物露出之前，將表面張力比第1組成物低的第2組成物應用於凹凸圖案上的應用了第1組成物的區域上的步驟；對凹凸圖案上所應用的第1組成物及第2組成物進行乾燥，在凹凸圖案的表面形成膜的步驟。 <1> A method for producing a pattern forming body, comprising: applying a first composition including a solvent and a film forming component to a surface of the concave-convex pattern; and before the surface of the concave-convex pattern is exposed from the applied first composition, The second composition having a lower surface tension than the first composition is applied to the region of the concave-convex pattern to which the first composition is applied, and the first composition and the second composition applied to the concave-convex pattern are dried. A step of forming a film on the surface of the concavo-convex pattern.
<2>如<1>所述的圖案形成體的製造方法，其中，第1組成物的25℃的表面張力與第2組成物的25℃的表面張力的差為2mN/m以上。 The method of producing a pattern forming body according to the above aspect, wherein a difference between a surface tension of 25 ° C of the first composition and a surface tension of 25 ° C of the second composition is 2 mN/m or more.
<3>如<1>或<2>所述的圖案形成體的製造方法，其中，第1組成物的25℃的表面張力超過23mN/m。 <3> The method for producing a pattern forming body according to the above aspect, wherein the surface tension of the first composition at 25 ° C exceeds 23 mN/m.
<4>如<1>或<2>所述的圖案形成體的製造方法，其中，第2組成物的25℃的表面張力為23mN/m以下。 The method for producing a pattern forming body according to the above aspect, wherein the second composition has a surface tension at 25 ° C of 23 mN/m or less.
<5>如<1>~<4>中任一項所述的圖案形成體的製造方法，其中，將第1組成物應用於凹凸圖案上之後，在10秒以內將第2組成物應用於凹凸圖案上的應用了第1組成物的區域。 The method for producing a pattern forming body according to any one of the aspects of the present invention, wherein, after applying the first composition to the uneven pattern, the second composition is applied within 10 seconds. A region on the concave-convex pattern to which the first composition is applied.
<6>如<1>~<5>中任一項所述的圖案形成體的製造方法，其中，凹凸圖案是使用光硬化性組成物而形成的凹凸圖案。 The method for producing a pattern forming body according to any one of the above aspects, wherein the uneven pattern is a concave-convex pattern formed using a photocurable composition.
<7>如<6>所述的圖案形成體的製造方法，其中，光硬化性組成物是包含具有一個聚合性基的聚合性化合物。 The method for producing a pattern forming body according to the above aspect, wherein the photocurable composition is a polymerizable compound containing one polymerizable group.
<8>如<6>所述的圖案形成體的製造方法，其中，光硬化性組成物以相對於光硬化性組成物中所含的聚合性化合物總量而言為0質量%~60質量%的比例含有具有一個聚合性基的聚合性化合物。 The method of producing a pattern forming body according to the above aspect, wherein the photocurable composition is 0% by mass to 60% by mass based on the total amount of the polymerizable compound contained in the photocurable composition. The proportion of % contains a polymerizable compound having one polymerizable group.
<9>如<1>~<8>中任一項所述的圖案形成體的製造方法，其中，凹凸圖案是藉由壓印法而形成的凹凸圖案。 The method for producing a pattern forming body according to any one of the aspects of the present invention, wherein the uneven pattern is a concave-convex pattern formed by an imprint method.
<10>如<1>~<9>中任一項所述的圖案形成體的製造方法，其中，凹凸圖案是包含寬300nm以下的圖案。 The method for producing a pattern forming body according to any one of the above aspects, wherein the uneven pattern includes a pattern having a width of 300 nm or less.
根據本發明，可抑制圖案缺陷的產生並同時製造在凹凸圖案的表面形成有膜的圖案形成體。 According to the present invention, it is possible to suppress the generation of pattern defects and simultaneously produce a pattern forming body in which a film is formed on the surface of the concavo-convex pattern.
1‧‧‧圖案凸部 1‧‧‧ pattern convex
11‧‧‧凹凸圖案 11‧‧‧ concave pattern
12‧‧‧膜 12‧‧‧ film
圖1是藉由本發明的方法而所得的圖案形成體的一例的概念圖。 Fig. 1 is a conceptual diagram showing an example of a pattern formation body obtained by the method of the present invention.
圖2是表示圖案缺陷的產生機制的概念圖。 Fig. 2 is a conceptual diagram showing a mechanism of generating a pattern defect.
於以下中，關於本發明的內容而加以詳細說明。 Hereinafter, the contents of the present invention will be described in detail.
於本說明書中，「~」以包含其前後所記載的數值作為下限值及上限值的含義而使用。 In the present specification, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.
於本說明書中，「(甲基)丙烯酸酯」表示丙烯酸酯及甲基丙烯酸酯，「(甲基)丙烯酸基」表示丙烯酸基及甲基丙烯酸基，「(甲基)丙烯醯基」表示丙烯醯基及甲基丙烯醯基。 In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic group" means acrylic group and methacryl group, and "(meth)acryloyl group" means propylene. Mercapto and methacrylonitrile.
於本說明書中，「壓印」較佳為指1nm~10mm的尺寸的圖案轉印，更佳為指約10nm~100μm的尺寸(奈米壓印)的圖案轉印。 In the present specification, "imprint" preferably means a pattern transfer of a size of from 1 nm to 10 mm, and more preferably a pattern transfer of a size (nano embossing) of about 10 nm to 100 μm.
在本說明書中的基(原子團)的表述中，並未記載取代及未經取代的表述不僅包含不具有取代基的基(原子團)，並且亦包含具有取代基的基(原子團)。例如「烷基」不僅包含不具有取代基的烷基(未經取代的烷基)，亦包含具有取代基的烷基(經取代的 烷基)。 In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes not only a group having no substituent (atomic group) but also a group having a substituent (atomic group). For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl).
於本說明書中，「光」不僅僅包含紫外、近紫外、遠紫外、可見、紅外等區域的波長的光、或電磁波，亦包含放射線。放射線例如包含微波、電子束、極紫外線(extreme ultraviolet，EUV)、X射線。而且，亦可使用248nm準分子雷射、193nm準分子雷射、172nm準分子雷射等雷射光。該些光可使用通過光學濾光片的單色光(單一波長光)，亦可為多種波長不同的光(複合光)。 In the present specification, "light" includes not only light of a wavelength in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared, or the like, but also electromagnetic waves, and also includes radiation. The radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser may be used. The light may be monochromatic light (single-wavelength light) passing through the optical filter, or light of a plurality of different wavelengths (composite light).
本發明中的質量平均分子量及數量平均分子量若無特別敍述，則是指藉由凝膠滲透層析法(Gel Penetration Chromatography，GPC)而測定者。GPC是關於所得的聚合物，可藉由將溶媒除去而進行分離，藉由四氫呋喃將所得的固體成分稀釋至0.1質量%，藉由HLC-8020GPC(東曹股份有限公司製造)，將串列連結有3根TSKgel Super Multipore HZ-H(東曹股份有限公司製造、4.6mm ID×15cm)而成者作為管柱而進行測定。作為條件，可將試樣濃度設為0.35質量%，將流速設為0.35mL/min，將樣品注入量設為10μL，將測定溫度設為40℃，使用折射率(refractive index，RI)檢測器而進行。 The mass average molecular weight and the number average molecular weight in the present invention are those measured by gel permeation chromatography (GPC) unless otherwise specified. GPC is a polymer obtained, which can be separated by removing the solvent, and the obtained solid component is diluted to 0.1% by mass with tetrahydrofuran, and is linked in series by HLC-8020GPC (manufactured by Tosoh Corporation). Three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) were used as the column. As a condition, the sample concentration can be set to 0.35% by mass, the flow rate can be set to 0.35 mL/min, the sample injection amount can be set to 10 μL, and the measurement temperature can be set to 40 ° C, and a refractive index (RI) detector can be used. And proceed.
於本說明書中，所謂「所有固體成分」是指自組成物的所有組成中除去溶劑的成分的總質量。 In the present specification, "all solid components" means the total mass of components from which solvent is removed from all compositions of the composition.
本說明書中的固體成分是25℃的固體成分。 The solid content in the present specification is a solid component at 25 °C.
於本說明書中，表面張力是使用協和界面科學股份有限公司製造的表面張力計SURFACE TENS-IOMETER CBVP-A3，使用鉑 板而在25±0.2℃下進行測定，將板下端浸漬於測定樣品中之後提拉時的值。鉑板在測定前藉由酒精燈進行加熱而實施表面的清洗。 In this specification, the surface tension is SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd., using platinum. The plate was measured at 25 ± 0.2 ° C, and the lower end of the plate was immersed in the measurement sample and then pulled up. The platinum plate was subjected to surface cleaning by heating with an alcohol lamp before the measurement.
於本說明書中，黏度是使用東機產業股份有限公司製造的RE-80L型旋轉黏度計，在25±0.2℃下在0.5mPa．s以上、不足5mPa．s時將測定時的旋轉速度設定為100rpm，在5mPa．s以上、不足10mPa．s時將測定時的旋轉速度設定為50rpm，在10mPa．s以上、不足30mPa．s時將測定時的旋轉速度設定為20rpm，在30mPa．s以上、不足60mPa．s時將測定時的旋轉速度設定為10rpm而測定的值。 In this specification, the viscosity is a RE-80L rotary viscometer manufactured by Toki Sangyo Co., Ltd. at 0.5 ± 0.2 °C at 25 ± 0.2 °C. Above s, less than 5mPa. When s, the rotation speed at the time of measurement is set to 100 rpm at 5 mPa. Above s, less than 10mPa. When s, the rotation speed at the time of measurement is set to 50 rpm at 10 mPa. Above s, less than 30mPa. When s, the rotation speed at the time of measurement is set to 20 rpm at 30 mPa. Above s, less than 60mPa. In the case of s, the rotational speed at the time of measurement was set to a value measured at 10 rpm.
本發明的圖案形成體的製造方法包括：在凹凸圖案的表面應用包含溶劑與膜形成成分的第1組成物的步驟；在凹凸圖案的表面自應用的第1組成物露出之前，將表面張力比第1組成物低的第2組成物應用於凹凸圖案上的應用了第1組成物的區域上的步驟；對凹凸圖案上所應用的第1組成物及第2組成物進行乾燥，在凹凸圖案的表面形成膜的步驟。 The method for producing a pattern forming body according to the present invention includes the step of applying a first composition containing a solvent and a film forming component to the surface of the concave-convex pattern, and the surface tension ratio before the surface of the concave-convex pattern is exposed from the applied first composition. The second composition having a low first composition is applied to the region on which the first composition is applied to the concave-convex pattern; and the first composition and the second composition applied to the concave-convex pattern are dried, and the concave-convex pattern is applied. The step of forming a film on the surface.
根據本發明，在凹凸圖案的表面應用第1組成物之後，凹凸圖案的表面自第1組成物露出之前，將表面張力比第1組成物低的第2組成物應用於凹凸圖案上的應用了第1組成物的區域上，因此凹凸圖案的表面所應用的組成物進行乾燥而使液面成為凸部以下，亦可使對圖案凸部施加的毛細管力比僅僅應用第1組成物的情況更小。因此，可抑制組成物的乾燥所伴隨的圖案崩塌等圖案缺陷的產生，於凹凸圖案的表面形成膜。特別是在使用表面張 力高的組成物作為第1組成物的情況下，根據本發明的方法亦可使對圖案凸部所施加的毛細管力更小。 According to the invention, after the first composition is applied to the surface of the concavo-convex pattern, the surface of the concavo-convex pattern is applied to the concavo-convex pattern before the first composition is exposed, and the second composition having a lower surface tension than the first composition is applied to the concavo-convex pattern. In the region of the first composition, the composition applied to the surface of the uneven pattern is dried to make the liquid surface equal to or lower than the convex portion, and the capillary force applied to the pattern convex portion can be made more than the case where only the first composition is applied. small. Therefore, it is possible to suppress the occurrence of pattern defects such as pattern collapse accompanying drying of the composition, and to form a film on the surface of the uneven pattern. Especially when using surface sheets In the case where the composition having a high force is the first composition, the capillary force applied to the convex portion of the pattern can be made smaller according to the method of the present invention.
首先，對凹凸圖案加以說明。 First, the concave and convex pattern will be described.
凹凸圖案的材質並無特別限定。可列舉光硬化性組成物、熱硬化性組成物、矽、碳化矽、金屬等，較佳為光硬化性組成物。藉由光硬化性組成物而形成的凹凸圖案多數情況下強度低，因此在凹凸圖案的表面形成膜時，存在若為現有的方法則容易產生圖案崩塌的傾向，若根據本發明的方法，則即使對於強度低的凹凸圖案，亦可抑制圖案崩塌等圖案缺陷的產生，且於表面形成膜。 The material of the concave-convex pattern is not particularly limited. The photocurable composition, the thermosetting composition, ruthenium, tantalum carbide, metal, etc. are mentioned, and a photocurable composition is preferable. The uneven pattern formed by the photocurable composition is often low in strength. Therefore, when a film is formed on the surface of the uneven pattern, the pattern tends to collapse due to the conventional method, and according to the method of the present invention, Even in the uneven pattern having low strength, generation of pattern defects such as pattern collapse can be suppressed, and a film can be formed on the surface.
凹凸圖案較佳為包含寬300nm以下的圖案，更佳為包含寬100nm以下的圖案。 The uneven pattern preferably includes a pattern having a width of 300 nm or less, and more preferably a pattern having a width of 100 nm or less.
亦可將藉由壓印法而形成的圖案作為遮罩，藉由蝕刻等方法對基材進行加工而形成凹凸圖案。 The pattern formed by the imprint method may be used as a mask, and the substrate may be processed by etching or the like to form a concavo-convex pattern.
而且，亦可藉由圖案反轉法而形成凹凸圖案。所謂「圖案反轉法」，具體而言是在碳膜(SOC)等基材上形成抗蝕劑圖案。其次，藉由含Si膜(SOG)等包覆抗蝕劑圖案後，對含Si膜的上部進行回蝕而使抗蝕劑圖案露出，藉由氧電漿等將所露出的抗蝕劑圖案除去，由此可形成含Si膜的反轉圖案。進一步將含Si膜的反轉圖案作為蝕刻遮罩，對處於其下層的基材進行蝕刻，藉此而於基材上轉印反轉圖案。最後，將轉印了反轉圖案的基材作為蝕刻遮罩，對基材進行蝕刻加工的方法。此種方法的例子可參考日本專利特開平5-267253號公報、日本專利特開2002-110510號公報、 日本專利特表2006-521702號公報的段落0016~段落0030，其內容可併入至本說明書中。 Further, the concavo-convex pattern may be formed by a pattern inversion method. The "pattern inversion method" specifically forms a resist pattern on a substrate such as a carbon film (SOC). Next, after the resist pattern is coated by a Si-containing film (SOG) or the like, the upper portion of the Si-containing film is etched back to expose the resist pattern, and the exposed resist pattern is exposed by oxygen plasma or the like. Removal, whereby an inverted pattern of the Si-containing film can be formed. Further, the reverse pattern of the Si-containing film is used as an etching mask, and the underlying substrate is etched, whereby the reverse pattern is transferred onto the substrate. Finally, a method of etching the substrate by using a substrate on which the reverse pattern is transferred is used as an etching mask. An example of such a method can be referred to Japanese Patent Laid-Open No. Hei 5-267253, No. 2002-110510, Japanese Patent Laid-Open Publication No. 2006-521702, paragraph 0016 to paragraph 0030, the contents of which are incorporated herein by reference.
於本發明中，自可低成本且高精度地形成微細的圖案的理由考慮，凹凸圖案的形成方法更佳為壓印法，進一步更佳為光壓印法。 In the present invention, the method of forming the uneven pattern is more preferably an imprint method, and more preferably a photo imprint method, for the reason that a fine pattern can be formed at low cost and with high precision.
<利用壓印法的凹凸圖案的形成方法> <Method of Forming Concavo-Concave Pattern by Imprint Method>
利用壓印法的凹凸圖案的形成方法包括：將光硬化性組成物應用於基材上或具有圖案的模具上而形成圖案形成層的步驟；藉由基材與模具夾持圖案形成層而進行壓接的步驟；對圖案形成層照射光的步驟；自圖案形成層的表面使模具脫模的步驟。以下加以說明。 The method for forming a concavo-convex pattern by an imprint method includes the steps of: applying a photocurable composition to a substrate or a patterned mold to form a pattern forming layer; and performing the pattern forming layer by sandwiching the substrate and the mold a step of crimping; a step of irradiating the pattern forming layer with light; and a step of demolding the mold from the surface of the pattern forming layer. This will be explained below.
將光硬化性組成物應用於基材上或具有圖案的模具上而形成圖案形成層。 The photocurable composition is applied to a substrate or a patterned mold to form a pattern forming layer.
關於光硬化性組成物，如後所述。 The photocurable composition will be described later.
基材並無特別限定，可根據各種用途而選擇。例如可列舉石英、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等的金屬基板、紙、旋塗碳(Spin On Carbon，SOC)、旋塗玻璃(Spin On Glass，SOG)、聚酯膜、聚碳酸酯膜、聚醯亞胺膜等聚合物基板、薄膜電晶體(thin film transistor，TFT)陣列基板、電漿顯示面板(plasma display panel，PDP)的電極板、氧化銦錫(Indium-Tin Oxide，ITO)或金屬等的導電性基板、絕緣性基板、矽、氮化矽、多晶矽、氧化矽、非晶矽等半導體製作基 板等。 The substrate is not particularly limited and can be selected according to various uses. Examples thereof include quartz, glass, optical film, ceramic material, vapor deposited film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, and Fe, paper, spin on carbon (SOC), and spin-on glass. (Spin On Glass, SOG), polyester film, polycarbonate film, polymer substrate such as polyimide film, thin film transistor (TFT) array substrate, plasma display panel (PDP) Electrode plate, conductive substrate such as Indium-Tin Oxide (ITO) or metal, insulating substrate, germanium, tantalum nitride, polycrystalline germanium, germanium oxide, amorphous germanium, etc. Board and so on.
基材的形狀亦無特別限定，可為板狀，亦可為卷狀。而且，可根據與模具的組合等而選擇透光性、或非透光性的基材。 The shape of the substrate is not particularly limited, and may be a plate shape or a roll shape. Further, a light-transmitting or non-translucent substrate can be selected in accordance with a combination with a mold or the like.
基材為了提高與光硬化性組成物的密接性，亦可使用在基材表面應用下層膜形成用組成物，形成有下層膜的基材。下層膜形成用樹脂組成物例如可使用包含聚合性化合物與溶劑的組成物。下層膜形成用樹脂組成物例如可使用日本專利特開2014-24322號公報的段落編號0017~段落編號0068、日本專利特開2013-93552號公報的段落編號0016~段落編號0044中所記載者，其內容可併入至本申請案說明書中。下層膜形成用樹脂組成物的應用方法較佳為塗佈法。塗佈法例如可列舉所述方法。 In order to improve the adhesion to the photocurable composition, a substrate having a lower film formed by applying a composition for forming an underlayer film on the surface of the substrate may be used. As the resin composition for forming the underlayer film, for example, a composition containing a polymerizable compound and a solvent can be used. For the resin composition for forming an underlayer film, for example, those described in paragraph number 0017 to paragraph number 0068 of JP-A-2014-24322, and paragraph number 0016 to paragraph number 0044 of JP-A-2013-93552, The content thereof can be incorporated into the specification of the present application. The application method of the resin composition for forming an underlayer film is preferably a coating method. The coating method is, for example, the above method.
在模具上形成有所需轉印的圖案。模具上的圖案例如可藉由光微影或電子束描繪法等，根據所期望的加工精度而形成圖案。例如，在模具中較佳為形成寬300nm以下的圖案，更佳為形成寬100nm以下的圖案。而且，圖案的縱橫比較佳為0.1~10，更佳為1~5。 A pattern to be transferred is formed on the mold. The pattern on the mold can be patterned by, for example, photolithography or electron beam drawing or the like according to a desired processing precision. For example, it is preferable to form a pattern having a width of 300 nm or less in the mold, and it is more preferable to form a pattern having a width of 100 nm or less. Moreover, the aspect ratio of the pattern is preferably from 0.1 to 10, more preferably from 1 to 5.
模具的材質並無特別限定，若為具有規定的強度、耐久性者即可。具體而言可例示玻璃、石英、丙烯酸樹脂、聚碳酸酯樹脂等光透明性樹脂、透明金屬蒸鍍膜、聚二甲基矽氧烷等柔軟膜、光硬化膜、金屬膜等。而且，在使用透光性的基材的情況下，亦可使用非透光型的模具。非透光型的模具的材質並無特別限定，若具有規定的強度即可。具體而言可例示陶瓷材料、蒸鍍膜、磁 性膜、反射膜、Ni、Cu、Cr、Fe等的金屬基板、SiC、矽、氮化矽、多晶矽、氧化矽、非晶矽等，並無特別制約。而且，模具的形狀亦無特別制約，可為板狀模具、卷狀模具的任意者。特別是在需要轉印的連續生產性的情況下應用卷狀模具。 The material of the mold is not particularly limited, and may have a predetermined strength and durability. Specifically, a light-transparent resin such as glass, quartz, acrylic resin, or polycarbonate resin, a transparent metal vapor-deposited film, a soft film such as polydimethyl siloxane or a photocured film, a metal film, or the like can be exemplified. Further, in the case of using a light-transmitting substrate, a non-light-transmitting mold can also be used. The material of the non-transmissive mold is not particularly limited, and may have a predetermined strength. Specifically, ceramic materials, vapor deposited films, and magnetic materials can be exemplified A metal film such as a film, a reflective film, or Ni, Cu, Cr, or Fe, SiC, tantalum, tantalum nitride, polycrystalline germanium, cerium oxide, or amorphous germanium is not particularly limited. Further, the shape of the mold is not particularly limited, and may be any of a plate mold and a roll mold. In particular, a roll mold is applied in the case of continuous productivity requiring transfer.
為了提高光硬化性組成物與模具表面的剝離性，模具亦可使用進行了脫模處理者。此種模具亦可適宜使用進行了矽系或氟系等矽烷偶合劑的處理者，例如大金工業股份有限公司製造的的奧普次(OPTOOL)DSX、或住友3M股份有限公司製造的的諾維克(Novec)EGC-1720等市售的脫模劑。 In order to improve the peelability of the photocurable composition from the surface of the mold, the mold may be used for demolding. Such a mold can also be suitably used for a treatment of a decane coupling agent such as a lanthanide or a fluorine-based oxime coupling agent, such as OPTOOL DSX manufactured by Daikin Industries Co., Ltd., or a product manufactured by Sumitomo 3M Co., Ltd. A commercially available release agent such as Novec EGC-1720.
光硬化性組成物的應用方法較佳為塗佈法。塗佈法例如可列舉浸塗法、氣刀塗佈法(air knife coat)、簾塗法(curtain coating)、線棒塗佈法(Wire Bar Coating Method)、凹版塗佈法(gravure coating method)、擠出塗佈法(extrusion coat method)、旋塗方法、狹縫掃描法(slit scanning)、噴墨法等。 The application method of the photocurable composition is preferably a coating method. Examples of the coating method include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, and a gravure coating method. , an extrusion coating method, a spin coating method, a slit scanning method, an inkjet method, or the like.
圖案形成層的膜厚因所使用的用途而異。例如較佳為乾燥後的膜厚為0.03μm~30μm左右。而且，亦可藉由多重塗佈而塗佈光硬化性組成物。於藉由噴墨法等而於基材上設置液滴的方法中，液滴的量較佳為1pl~20pl左右，較佳為隔開間隔而於基材上或模具上配置液滴。 The film thickness of the pattern forming layer varies depending on the use to be used. For example, it is preferred that the film thickness after drying is about 0.03 μm to 30 μm. Further, the photocurable composition may be applied by multiple coating. In the method of providing droplets on a substrate by an inkjet method or the like, the amount of droplets is preferably from about 1 pl to about 20 pl, and it is preferred to arrange droplets on the substrate or on the mold at intervals.
其次，為了將圖案轉印於圖案形成層上，將模具壓接於圖案形成層表面上。藉此可將模具的按壓表面上所預先形成的微細圖案轉印於圖案形成層上。 Next, in order to transfer the pattern onto the pattern forming layer, the mold is crimped onto the surface of the pattern forming layer. Thereby, the fine pattern previously formed on the pressing surface of the mold can be transferred onto the pattern forming layer.
而且，將模具按壓於圖案形成層表面上時，亦可將氦氣導入至模具與圖案形成層表面之間。藉由使用此種方法，可促進氣體透過模具，從而促進殘留氣泡的消失。而且，藉由使圖案形成層中的溶氧減低，可抑制曝光中的自由基聚合阻礙。而且，亦可於模具與圖案形成層之間導入凝縮性氣體而代替氦氣。藉由使用此種方法，利用所導入的凝縮性氣體凝縮而體積減少的現象，可進一步促進殘留氣泡的消滅。所謂「凝縮性氣體」是指因溫度或壓力而凝縮的氣體，例如可使用三氯氟甲烷、1,1,1,3,3-五氟丙烷等。關於凝縮性氣體，例如可參考日本專利特開2004-103817號公報的段落0023、日本專利特開2013-254783號公報的段落0003的記載，該些內容可併入至本說明書中。 Further, when the mold is pressed against the surface of the pattern forming layer, helium gas may be introduced between the mold and the surface of the pattern forming layer. By using this method, gas can be promoted to pass through the mold, thereby promoting the disappearance of residual bubbles. Further, by reducing the dissolved oxygen in the pattern forming layer, it is possible to suppress the radical polymerization inhibition during exposure. Further, a condensable gas may be introduced between the mold and the pattern forming layer instead of the helium gas. By using such a method, the phenomenon in which the introduced condensable gas is condensed and the volume is reduced can further promote the elimination of residual bubbles. The term "condensed gas" means a gas which is condensed by temperature or pressure. For example, trichlorofluoromethane or 1,1,1,3,3-pentafluoropropane or the like can be used. For the condensable gas, for example, the description of paragraph 0023 of Japanese Patent Laid-Open Publication No. 2004-103817, and paragraph 0003 of Japanese Patent Laid-Open Publication No. 2013-254783, the contents of which are incorporated herein by reference.
其次，在按壓模具的狀態下進行光照射而使光硬化性組成物硬化。光照射的照射量若比光硬化性組成物的硬化所需的照射量足夠大即可。硬化所需的照射量可通過調查光硬化性組成物的不飽和鍵的消耗量或硬化膜的黏性而適宜決定。 Next, light irradiation is performed in a state where the mold is pressed, and the photocurable composition is cured. The irradiation amount of the light irradiation may be sufficiently larger than the irradiation amount required for the curing of the photocurable composition. The amount of irradiation required for hardening can be appropriately determined by investigating the consumption of the unsaturated bond of the photocurable composition or the viscosity of the cured film.
光照射時的基板溫度通常在室溫下進行，為了提高反應性，亦可一面進行加熱一面進行光照射。作為光照射之前的階段，若預先設為真空狀態，則於防止氣泡混入、抑制因氧氣混入所造成的反應性降低、使模具與光硬化性組成物的接著性提高的方面具有效果，因此亦可於真空狀態下進行光照射。光照射時的較佳的真空度較佳為10-1Pa至常壓的範圍。 The substrate temperature at the time of light irradiation is usually performed at room temperature, and in order to improve the reactivity, light irradiation may be performed while heating. When it is set to a vacuum state in advance, it is effective in preventing the incorporation of air bubbles, suppressing the decrease in reactivity due to the incorporation of oxygen, and improving the adhesion between the mold and the photocurable composition. Light irradiation can be performed under vacuum. The preferred degree of vacuum at the time of light irradiation is preferably in the range of 10 -1 Pa to atmospheric pressure.
用以使光硬化性組成物硬化的光並無特別限定，例如可 列舉高能量電離放射線、近紫外、遠紫外、可見、紅外等區域的波長的光或放射線。高能量電離放射線源例如藉由柯克勞夫(Cockcroft)型加速器、凡德格拉夫(van de graaff)型加速器、直線加速器、貝他加速器、回旋加速器等加速器而進行了加速的電子束於工業上最便利且經濟地使用，另外亦可使用自放射性同位元素或核反應爐等所放射的γ射線、X射線、α射線、中子射線、陽子射線等放射線。紫外線源例如可列舉紫外線螢光燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、碳弧燈、太陽燈等。放射線例如包含微波、極紫外線(EUV)。而且，發光二極體(Light Emitting Diode，LED)、半導體雷射光、或248nm的KrF準分子雷射光或193nm的ArF準分子雷射光等在半導體的微細加工中所使用的雷射光亦可於本發明中適宜地使用。該些光可使用單色光，亦可使用多種波長不同的光(混合光)。 The light for hardening the photocurable composition is not particularly limited, and for example, Light or radiation of wavelengths in areas of high energy ionizing radiation, near ultraviolet, far ultraviolet, visible, infrared, etc. are listed. High-energy ionizing radiation sources, such as electron beams accelerated by an accelerator such as a Cockcroft type accelerator, a van de graaff type accelerator, a linear accelerator, a beta accelerator, a cyclotron, etc. It is most convenient and economical to use, and radiation such as gamma rays, X rays, alpha rays, neutron rays, and neutron rays emitted from a radioactive isotope or a nuclear reactor may be used. Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a sun lamp. The radiation includes, for example, microwaves and extreme ultraviolet rays (EUV). Further, a laser light used in microfabrication of a semiconductor such as a light emitting diode (LED), a semiconductor laser beam, or a 248 nm KrF excimer laser light or a 193 nm ArF excimer laser light can also be used. It is suitably used in the invention. The light can use monochromatic light, and a plurality of different wavelengths of light (mixed light) can also be used.
在曝光時，理想的是將曝光照度設為1mW/cm2~50mW/cm2的範圍。藉由設為1mW/cm2以上，可縮短曝光時間，因此生產性提高；藉由設為50mW/cm2以下，存在可抑制因產生副反應而造成的永久膜的特性劣化的傾向而較佳。曝光量理想的是5mJ/cm2~1000mJ/cm2的範圍。若為該範圍，則光硬化性組成物的硬化性良好。另外，在曝光時，為了防止因氧所造成的自由基聚合的阻礙，亦可流入氮或氬等惰性氣體，而將氧濃度控制為不足100mg/L。 At the time of exposure, it is desirable to set the exposure illuminance to a range of 1 mW/cm 2 to 50 mW/cm 2 . When the exposure time is 1 mW/cm 2 or more, the exposure time can be shortened, and the productivity is improved. When the thickness is 50 mW/cm 2 or less, it is preferable to suppress deterioration of characteristics of the permanent film due to side reactions. . Over exposure amount is 5mJ / cm range of 2 ~ 1000mJ / cm 2 in. When it is this range, the hardenability of the photocurable composition is favorable. Further, at the time of exposure, in order to prevent the inhibition of radical polymerization by oxygen, an inert gas such as nitrogen or argon may be introduced to control the oxygen concentration to less than 100 mg/L.
在藉由光照射而使圖案形成層(包含光硬化性組成物的 層)硬化之後，亦可視需要包含對所硬化的圖案進行加熱而進一步使其硬化的步驟。加熱溫度例如較佳為150℃~280℃，更佳為200℃~250℃。而且，加熱時間例如較佳為5分鐘~60分鐘，更佳為15分鐘~45分鐘。 Patterning layer (including photocurable composition) by light irradiation After the layer) is hardened, it may optionally include a step of heating the hardened pattern to further harden it. The heating temperature is, for example, preferably from 150 ° C to 280 ° C, more preferably from 200 ° C to 250 ° C. Further, the heating time is, for example, preferably from 5 minutes to 60 minutes, more preferably from 15 minutes to 45 minutes.
如上所述而使光硬化性組成物硬化後，自基材將模具剝離，藉此可於基材上形成沿著模具的形狀的圖案(凹凸圖案)。圖案尺寸因用途而異。例如，較佳為具有寬300nm以下的圖案，更佳為具有寬100nm以下的圖案。而且，圖案的縱橫比較佳為0.1~10，更佳為1~5。 After the photocurable composition is cured as described above, the mold is peeled off from the substrate, whereby a pattern (concavo-convex pattern) along the shape of the mold can be formed on the substrate. The pattern size varies depending on the application. For example, it is preferably a pattern having a width of 300 nm or less, and more preferably a pattern having a width of 100 nm or less. Moreover, the aspect ratio of the pattern is preferably from 0.1 to 10, more preferably from 1 to 5.
利用壓印法的圖案形成方法的詳細可參考日本專利特開2010-109092號公報(對應的US申請是US2011/199592)的段落編號0103~段落編號0115的記載，該些內容可併入至本申請案說明書中。 For the details of the pattern forming method using the imprint method, the description of Paragraph No. 0103 to Paragraph No. 0115 of Japanese Patent Laid-Open No. 2010-109092 (corresponding US Application No. US 2011/199592) can be incorporated into the present disclosure. In the application note.
<圖案形成體的製造方法> <Method of Manufacturing Pattern Forming Body>
其次，關於本發明的圖案形成體的製造方法而加以說明。 Next, a method of producing the pattern forming body of the present invention will be described.
本發明的圖案形成體的製造方法包括：在凹凸圖案的表面應用包含溶劑與膜形成成分的第1組成物的步驟(步驟1)；在凹凸圖案的表面自應用的第1組成物露出之前，將表面張力比第1組成物低的第2組成物應用於凹凸圖案上的應用了第1組成物的區域上的步驟(步驟2)；對凹凸圖案上所應用的第1組成物及第2組成物進行乾燥，在凹凸圖案的表面形成膜的步驟(步驟3)。 The method for producing a pattern forming body according to the present invention includes the step of applying a first composition containing a solvent and a film forming component to the surface of the uneven pattern (step 1); and before the surface of the concave-convex pattern is exposed from the applied first composition, The second composition having a lower surface tension than the first composition is applied to the region of the concave-convex pattern on the region where the first composition is applied (step 2); the first composition applied to the concave-convex pattern and the second composition The composition is dried to form a film on the surface of the concavo-convex pattern (step 3).
以下，關於各步驟而加以說明。 Hereinafter, each step will be described.
<<步驟1>> <<Step 1>>
在步驟1中，在凹凸圖案的表面應用包含溶劑與膜形成成分的第1組成物。 In the step 1, a first composition containing a solvent and a film forming component is applied to the surface of the uneven pattern.
膜形成成分是在乾燥後的膜中作為固形物而殘存的成分，因用途及目的而異。例如可列舉親水性塗佈劑、疏水性塗佈劑、硬塗劑、抗靜電劑、金屬墨水、紫外線吸收劑、熱射線截止劑、耐指紋性塗佈劑、折射率調整劑等。 The film-forming component is a component remaining as a solid in the dried film, and varies depending on the use and purpose. For example, a hydrophilic coating agent, a hydrophobic coating agent, a hard coating agent, an antistatic agent, a metallic ink, an ultraviolet absorber, a heat ray-cutting agent, a fingerprint-resistant coating agent, a refractive index adjusting agent, etc. are mentioned.
親水性塗佈劑可列舉大阪有機化學工業製造的藍比克(LAMBIC)系列等。 Examples of the hydrophilic coating agent include the LABIC series manufactured by Osaka Organic Chemical Industry.
疏水性塗佈劑可列舉矽烷化合物、氟樹脂等。矽烷化合物可列舉矽烷偶合劑、矽氧烷等。矽烷偶合劑的市售品可列舉大金工業股份有限公司製造的OPTOOL系列、信越矽利光股份有限公司製造的KBM系列、KBE系列等。矽氧烷可列舉信越矽利光股份有限公司製造的KPN-3504(含有水解性基的矽氧烷)等。而且，氟樹脂可列舉旭硝子股份有限公司製造的西陶普(CYTOP)系列等。 Examples of the hydrophobic coating agent include a decane compound, a fluororesin, and the like. Examples of the decane compound include a decane coupling agent, a decane, and the like. Commercial products of the decane coupling agent include the OPTOOL series manufactured by Daikin Industries Co., Ltd., the KBM series manufactured by Shin-Etsu Chemical Co., Ltd., and the KBE series. The oxime may be KPN-3504 (a hydroxyl group containing a hydrolyzable group) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Further, examples of the fluororesin include a CYTOP series manufactured by Asahi Glass Co., Ltd., and the like.
硬塗劑可列舉東洋油墨公司製造的LCH系列等。 Examples of the hard coating agent include the LCH series manufactured by Toyo Ink Co., Ltd., and the like.
抗靜電劑可列舉東洋油墨公司製造的LAS系列、YYS系列、TYP系列等。 Examples of the antistatic agent include the LAS series, the YYS series, and the TYP series manufactured by Toyo Ink Co., Ltd.
金屬墨水可列舉金墨水、銀墨水、銅墨水等。 Examples of the metal ink include gold ink, silver ink, and copper ink.
第1組成物的膜形成成分的含量較佳為0.001質量%~20質 量%，更佳為0.01質量%~10質量%。 The content of the film-forming component of the first composition is preferably 0.001% by mass to 20%. The amount % is more preferably 0.01% by mass to 10% by mass.
溶劑若為可溶解膜形成成分者，則並無特別限定。例如可列舉乙酸乙酯、四氯化碳、乙酸、丙二醇-1-單甲醚-2-乙酸酯、苯、環己酮等。藉由使用表面張力大的溶劑，膜形成成分的溶解性良好，可抑制塗佈不均等的產生。而且，亦可提高膜形成成分的濃度。另外，膜形成成分的溶解性良好，因此膜形成成分的選擇的自由度高。第1組成物中所使用的溶劑的25℃的表面張力較佳為24mN/m以上。具體例可列舉乙酸乙酯(24mN/m)、四氯化碳(27mN/m)、乙酸(28mN/m)、丙二醇-1-單甲醚-2-乙酸酯(28mN/m)、苯(29mN/m)、環己酮(35mN/m)等。 The solvent is not particularly limited as long as it is a soluble film-forming component. For example, ethyl acetate, carbon tetrachloride, acetic acid, propylene glycol-1-monomethyl ether-2-acetate, benzene, cyclohexanone, etc. are mentioned. By using a solvent having a large surface tension, the solubility of the film-forming component is good, and the occurrence of coating unevenness can be suppressed. Moreover, the concentration of the film forming component can also be increased. Further, since the solubility of the film-forming component is good, the degree of freedom in the selection of the film-forming component is high. The surface tension at 25 ° C of the solvent used in the first composition is preferably 24 mN/m or more. Specific examples thereof include ethyl acetate (24 mN/m), carbon tetrachloride (27 mN/m), acetic acid (28 mN/m), propylene glycol-1-monomethyl ether-2-acetate (28 mN/m), and benzene. (29 mN/m), cyclohexanone (35 mN/m), and the like.
第1組成物的25℃的表面張力因膜形成成分與溶劑的組合而異，較佳為超過23mN/m。藉此，膜形成成分的溶解性良好，可抑制塗佈不均等的產生。 The surface tension at 25 ° C of the first composition varies depending on the combination of the film forming component and the solvent, and is preferably more than 23 mN/m. Thereby, the solubility of the film formation component is good, and the occurrence of coating unevenness can be suppressed.
再者，於現有的方法中，隨著凹凸圖案上所應用的組成物的表面張力變大，存在於組成物的乾燥時產生圖案崩塌，於圖案表面產生粗糙的傾向，根據本發明的方法，即使將表面張力大的組成物應用於凹凸圖案上，亦可抑制所述問題的產生。 Further, in the conventional method, as the surface tension of the composition applied to the uneven pattern becomes large, there is a tendency that the pattern collapses during drying of the composition, and the surface of the pattern tends to be rough. According to the method of the present invention, Even if a composition having a large surface tension is applied to the uneven pattern, the occurrence of the problem can be suppressed.
第1組成物的25℃的黏度較佳為0.1mPa．s~2000mPa．s，更佳為1mPa．s~1000mPa．s。黏度若為所述範圍，則塗佈性良好。 The viscosity of the first composition at 25 ° C is preferably 0.1 mPa. s~2000mPa. s, more preferably 1mPa. s~1000mPa. s. When the viscosity is in the above range, the coatability is good.
第1組成物的應用方法並無特別限定，較佳為塗佈法。塗佈法例如可列舉浸塗法、氣刀塗佈法、簾塗法、線棒塗佈法、凹版塗佈法、擠出塗佈法、旋塗方法、狹縫掃描法、噴墨法等。 The application method of the first composition is not particularly limited, and a coating method is preferred. Examples of the coating method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and ink jet. .
於本發明中，於凹凸圖案的表面應用第1組成物，藉由第1組成物覆蓋凹凸圖案表面的所期望的區域(形成膜的區域)。較佳為藉由第1組成物掩埋圖案凹部，藉由第1組成物包覆凹凸圖案的表面。 In the present invention, the first composition is applied to the surface of the concavo-convex pattern, and the first composition covers a desired region (region where the film is formed) of the surface of the concavo-convex pattern. Preferably, the pattern concave portion is buried by the first composition, and the surface of the concave-convex pattern is covered by the first composition.
於本發明中，亦可於應用第1組成物之後，進行後述的第2步驟之前進行乾燥。藉由進行乾燥，亦可提高生產性。乾燥方法可列舉加熱乾燥、溫風乾燥等。 In the present invention, after the application of the first composition, drying may be performed before the second step described later. Productivity can also be improved by drying. Examples of the drying method include heat drying, warm air drying, and the like.
<第2步驟> <Step 2>
其次，在凹凸圖案的表面自應用的第1組成物露出之前，將表面張力比第1組成物低的第2組成物應用於凹凸圖案上的應用了第1組成物的區域上。 Next, before the surface of the concavo-convex pattern is exposed from the applied first composition, the second composition having a lower surface tension than the first composition is applied to the region of the concavo-convex pattern to which the first composition is applied.
第2組成物的應用在凹凸圖案的表面自應用於凹凸圖案的表面的第1組成物露出之前進行。亦即，於凹凸圖案的表面被第1組成物包覆期間，應用於凹凸圖案上的應用了第1組成物的區域。藉由如上所述地應用第2組成物，在應用於凹凸圖案的表面的組成物乾燥時，可於乾燥時抑制圖案凸部受到第1組成物的毛細管力，其結果可使對圖案凸部所施加的毛細管力變小。再者，於本發明中，所謂的「凹凸圖案的表面自應用的第1組成物露出」是表示作為凹凸圖案上的應用了第1組成物的區域的凹凸圖案的表面存在未被第1組成物覆蓋的部分的狀態。 The application of the second composition is performed before the surface of the concavo-convex pattern is exposed from the first composition applied to the surface of the concavo-convex pattern. In other words, the region to which the first composition is applied is applied to the uneven pattern while the surface of the concave-convex pattern is covered with the first composition. By applying the second composition as described above, when the composition applied to the surface of the uneven pattern is dried, it is possible to suppress the capillary force of the pattern convex portion from being subjected to the first composition during drying, and as a result, the pattern convex portion can be made. The applied capillary force becomes small. In the present invention, the surface of the concave-convex pattern is exposed from the first composition to be applied, and the surface of the concave-convex pattern as the region to which the first composition is applied as the concave-convex pattern is not present in the first composition. The state of the part covered by the object.
第2組成物的應用的時序可一面藉由感測器等觀測凹凸圖案的表面所應用的第1組成物的液面一面進行。而且，按照第1組 成物的種類、塗佈量、乾燥條件(溫度、濕度、風量)預先求出於凹凸圖案的表面應用第1組成物之後，直至凹凸圖案的表面自第1組成物露出為止的時間T0，於同條件下進行第1組成物的應用及乾燥的情況下，亦可於T0以內應用第2組成物。例如較佳為將第1組成物應用於凹凸圖案上之後，於10秒以內將第2組成物應用於凹凸圖案上的應用了第1組成物的區域。 The timing of application of the second composition can be performed while observing the liquid surface of the first composition applied to the surface of the concave-convex pattern by a sensor or the like. In addition, the first composition is applied to the surface of the uneven pattern in accordance with the type, the coating amount, and the drying conditions (temperature, humidity, and air volume) of the first composition, and then the surface of the uneven pattern is exposed from the first composition. At the time T 0 , when the application of the first composition and drying are carried out under the same conditions, the second composition can be applied within T 0 . For example, after the first composition is applied to the uneven pattern, the second composition is applied to the region of the concave-convex pattern in which the first composition is applied within 10 seconds.
第2組成物的應用方法並無特別限定，可使用與所述第1組成物的應用方法同樣的方法。 The application method of the second composition is not particularly limited, and the same method as the application method of the first composition can be used.
於本發明中，第2組成物使用表面張力比第1組成物低的組成物。 In the present invention, the second composition is a composition having a lower surface tension than the first composition.
第1組成物的25℃的表面張力與第2組成物的25℃的表面張力的差較佳為2mN/m以上，更佳為4mN/m以上。藉此可更有效地抑制圖案缺陷的產生。 The difference between the surface tension at 25 ° C of the first composition and the surface tension at 25 ° C of the second composition is preferably 2 mN/m or more, and more preferably 4 mN/m or more. Thereby, the generation of pattern defects can be more effectively suppressed.
第2組成物的25℃的表面張力較佳為23mN/m以下。藉此可更有效地抑制圖案缺陷的產生。另外，可更有效地抑制塗佈後的圖案表面的粗糙。 The surface tension at 25 ° C of the second composition is preferably 23 mN/m or less. Thereby, the generation of pattern defects can be more effectively suppressed. In addition, the roughness of the surface of the pattern after coating can be more effectively suppressed.
第2組成物使用包含溶劑的組成物。 As the second composition, a composition containing a solvent is used.
溶劑可列舉第1組成物中所說明者。較佳為選擇使用表面張力比第1組成物中所使用的溶劑小的溶劑。特佳為25℃的表面張力不足24mN/m的溶劑。具體例可列舉十氟戊烷(14mN/m)、己烷(18mN/m)、乙醇(23mN/m)、甲醇(23mN/m)、丙酮(23mN/m)等。 The solvent can be mentioned as described in the first composition. It is preferred to use a solvent having a surface tension smaller than that used in the first composition. Particularly preferred is a solvent having a surface tension of less than 24 mN/m at 25 °C. Specific examples thereof include decafluoropentane (14 mN/m), hexane (18 mN/m), ethanol (23 mN/m), methanol (23 mN/m), and acetone (23 mN/m).
第2組成物亦可進一步包含膜形成成分。膜形成成分可列舉第1組成物中所說明者。 The second composition may further include a film forming component. The film formation component can be mentioned as described in the first composition.
在第2組成物含有膜形成成分的情況下，膜形成成分的含量較佳為0.001質量%~20質量%，更佳為0.01質量%~10質量%。 When the second composition contains a film-forming component, the content of the film-forming component is preferably 0.001% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass.
第2組成物的25℃的黏度較佳為0.1mPa．s~2000mPa．s，更佳為1mPa．s~1000mPa．s。黏度若為所述範圍，則塗佈性良好。 The viscosity of the second composition at 25 ° C is preferably 0.1 mPa. s~2000mPa. s, more preferably 1mPa. s~1000mPa. s. When the viscosity is in the above range, the coatability is good.
<步驟3> <Step 3>
其次，對凹凸圖案上所應用的第1組成物及第2組成物進行乾燥。如上所述地進行，藉由使溶劑乾燥，獲得如圖1所示般，於凹凸圖案11的表面形成有源自膜形成成分的膜12的圖案形成體。 Next, the first composition and the second composition applied to the uneven pattern are dried. As described above, by drying the solvent, a pattern forming body of the film 12 derived from the film forming component is formed on the surface of the uneven pattern 11 as shown in FIG. 1 .
乾燥方法可列舉加熱乾燥、溫風乾燥等。乾燥條件可根據第1組成物及第2組成物的沸點、塗佈量等而適宜選擇。例如在加熱乾燥的情況下，較佳為於80℃~300℃下進行3秒~30000秒。 Examples of the drying method include heat drying, warm air drying, and the like. The drying conditions can be appropriately selected depending on the boiling point, the coating amount, and the like of the first composition and the second composition. For example, in the case of heat drying, it is preferably carried out at 80 ° C to 300 ° C for 3 seconds to 30,000 seconds.
本發明的圖案形成體的製造方法亦可應用於捲軸式製程中。 The method for producing a pattern forming body of the present invention can also be applied to a roll type process.
所謂「捲軸式製程」是一面將捲繞為卷狀的可撓性基材捲出一面進行處理，將實施了處理的可撓性基材再次捲繞為卷狀的生產系統。 The "roll-type process" is a production system in which a flexible substrate wound in a roll shape is wound up and processed, and the processed flexible substrate is wound again into a roll shape.
例如，於可撓性基材上應用光硬化性組成物而形成圖案形成層，將實施了微細圖案化的卷狀模具擠壓於基材上的圖案形成層上，藉由能量照射而使圖案形成層硬化，藉此可形成無縫隙的無 縫凹凸圖案。形成有凹凸圖案的可撓性基材亦可捲繞為卷狀。而且，亦可不捲繞而繼續進行後述的處理。 For example, a pattern forming layer is formed by applying a photocurable composition to a flexible substrate, and a finely patterned roll mold is pressed onto a pattern forming layer on a substrate, and the pattern is irradiated by energy irradiation. Forming layer hardening, thereby forming a seamless Concave and concave pattern. The flexible substrate on which the uneven pattern is formed may also be wound into a roll shape. Further, the processing described later may be continued without winding.
其次，使形成有凹凸圖案的可撓性基材依序通過應用第1組成物的處理區域1、對第2組成物進行處理的處理區域2、對所應用的第1組成物與第2組成物進行乾燥的乾燥處理區域3後，捲繞為卷狀，藉此可利用捲軸式製程而製造圖案形成體。 Next, the flexible substrate on which the uneven pattern is formed is sequentially applied to the treatment region 1 to which the first composition is applied, the treatment region 2 to which the second composition is treated, and the first composition and the second composition to be applied. After drying the dried processing zone 3, the film is wound into a roll shape, whereby the pattern forming body can be produced by a roll-to-roll process.
在處理區域1、處理區域2的各組成物的應用例如可於填充有各組成物的藥液層中浸漬可撓性基材，藉由浸塗法而將各組成物應用於凹凸圖案表面。而且，可設置各種塗佈裝置(噴墨噴嘴等)，於凹凸圖案表面應用各組成物。 In the application of the respective compositions of the treatment region 1 and the treatment region 2, for example, a flexible substrate can be immersed in a chemical solution layer filled with each composition, and each composition can be applied to the surface of the concave-convex pattern by dip coating. Further, various coating devices (inkjet nozzles, etc.) may be provided to apply the respective compositions to the surface of the concave-convex pattern.
再者，本發明在藉由捲軸式製程等方法而連續地製造圖案形成體的情況下，即使在連續進行的處理中，在一部分凹凸圖案自第1組成物露出之後應用第2組成物，若在其餘凹凸圖案自第1組成物露出之前應用第2組成物，則亦包含於本發明的圖案形成體的製造方法中。 In the case where the pattern forming body is continuously produced by a method such as a roll-to-roll process, the second composition is applied after a part of the uneven pattern is exposed from the first composition even in the continuous processing. The application of the second composition before the remaining uneven pattern is exposed from the first composition is also included in the method for producing the pattern formed body of the present invention.
<光硬化性組成物> <Photocurable composition>
其次，關於本發明的圖案形成體的凹凸圖案的形成中所使用的光硬化性組成物而加以說明。 Next, the photocurable composition used for forming the uneven pattern of the pattern forming body of the present invention will be described.
於本發明中，光硬化性組成物可使用在壓印法中所使用的光硬化性組成物。亦即，光硬化性組成物較佳為壓印用光硬化性組成物。 In the present invention, as the photocurable composition, a photocurable composition used in the imprint method can be used. That is, the photocurable composition is preferably a photocurable composition for imprinting.
光硬化性組成物較佳為包含聚合性化合物及光聚合起始劑。 作為光硬化性組成物的一例，例如較佳為聚合性化合物的含量為70質量%以上、且重量平均分子量超過2000的成分的含量為3質量%以下的組成，更佳為具有乙烯性不飽和雙鍵的聚合性化合物的含量為70質量%以上、且重量分子量超過2000的聚合性化合物的含量為3質量%以下的組成。以下，關於各成分而加以說明。 The photocurable composition preferably contains a polymerizable compound and a photopolymerization initiator. As an example of the photocurable composition, for example, a content of the polymerizable compound is 70% by mass or more, and a content of a component having a weight average molecular weight of more than 2,000 is preferably 3% by mass or less, and more preferably an ethylenic unsaturated layer. The content of the polymerizable compound of the double bond is 70% by mass or more, and the content of the polymerizable compound having a weight molecular weight of more than 2,000 is 3% by mass or less. Hereinafter, each component will be described.
<<聚合性化合物>> <<Polymerized compound>>
聚合性化合物只要不脫離本發明的主旨則並無特別限定。聚合性化合物所具有的聚合性基可列舉含有乙烯性不飽和鍵的基、環氧基、氧雜環丁基等。含有乙烯性不飽和鍵的基可列舉(甲基)丙烯酸酯基、(甲基)丙烯醯胺基、乙烯基、烯丙基、乙烯醚基等。較佳為(甲基)丙烯酸酯基。 The polymerizable compound is not particularly limited as long as it does not deviate from the gist of the present invention. The polymerizable group which the polymerizable compound has may be a group containing an ethylenically unsaturated bond, an epoxy group, an oxetanyl group or the like. Examples of the group containing an ethylenically unsaturated bond include a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, an allyl group, and a vinyl ether group. Preferred is a (meth) acrylate group.
聚合性基數較佳為1~6，更佳為1~3，進一步更佳為1或2。 The polymerizable group number is preferably from 1 to 6, more preferably from 1 to 3, still more preferably from 1 or 2.
聚合性化合物例如可列舉具有1個~6個含有乙烯性不飽和鍵的基的化合物；環氧化合物、氧雜環丁烷化合物；乙烯醚化合物；苯乙烯衍生物；丙烯基醚；丁烯基醚等。聚合性化合物的具體可列舉日本專利特開2011-231308號公報的段落編號0020~段落編號0098中所記載者，其內容可併入至本申請案說明書中。聚合性化合物較佳為(甲基)丙烯酸酯化合物。 Examples of the polymerizable compound include a compound having one to six groups containing an ethylenically unsaturated bond; an epoxy compound, an oxetane compound, a vinyl ether compound, a styrene derivative, a propenyl ether, and a butenyl group. Ether, etc. Specific examples of the polymerizable compound are as described in Paragraph No. 0020 to Paragraph No. 0098 of JP-A-2011-231308, the contents of which are incorporated herein by reference. The polymerizable compound is preferably a (meth) acrylate compound.
聚合性化合物的含量較佳為在除溶劑以外的所有組成物中為70質量%~99.9質量%，更佳為80質量%~99.9質量%，進一步更佳為85質量%~99.9質量%。在使用兩種以上聚合性化合物的情況下，較佳為其合計量為所述範圍。 The content of the polymerizable compound is preferably 70% by mass to 99.9% by mass, more preferably 80% by mass to 99.9% by mass, still more preferably 85% by mass to 99.9% by mass, based on all the components other than the solvent. When two or more types of polymerizable compounds are used, it is preferred that the total amount thereof is in the above range.
關於具有1個~6個含有乙烯性不飽和鍵的基的化合物(1官能~6官能的聚合性化合物)而加以說明。 A compound (1-functional to 6-functional polymerizable compound) having one to six groups containing an ethylenically unsaturated bond will be described.
作為具有一個含有乙烯性不飽和鍵的基的化合物，具體而言可例示(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、N-乙烯基吡咯啶酮(N-vinyl pyrrolidinone)、2-丙烯醯氧基乙基鄰苯二甲酸酯、2-丙烯醯氧基-2-羥基乙基鄰苯二甲酸酯、2-丙烯醯氧基乙基六氫鄰苯二甲酸酯、2-丙烯醯氧基丙基鄰苯二甲酸酯、2-乙基-2-丁基丙二醇丙烯酸酯、(甲基)丙烯酸-2-乙基己酯、2-乙基己基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸-2-羥基丁酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-4-羥基丁酯、丙烯酸二聚物、(甲基)丙烯酸苄酯、(甲基)丙烯酸-1-萘酯或(甲基)丙烯酸-2-萘酯、(甲基)丙烯酸丁氧基乙酯、(甲基)丙烯酸鯨蠟酯、環氧乙烷(以下稱為「EO」)改質甲酚(甲基)丙烯酸酯、二丙二醇(甲基)丙烯酸酯、乙氧基化(甲基)丙烯酸苯酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸月桂酯、甲氧基二丙二醇(甲基)丙烯酸酯、甲氧基三丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、新戊二醇苯甲酸酯(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、壬基苯氧基聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸辛酯、對枯基苯氧基乙二醇(甲基)丙烯酸酯、表氯醇(以下稱為「ECH」)改質苯氧基丙烯 酸酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基六乙二醇(甲基)丙烯酸酯、苯氧基四乙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯、聚乙二醇-聚丙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸硬脂酯、EO改質琥珀酸(甲基)丙烯酸酯、(甲基)丙烯酸三溴苯酯、EO改質(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸三(十二烷基)酯、對異丙烯基苯酚、N-乙烯基吡咯啶酮(N-vinyl pyrrolidone)、N-乙烯基己內醯胺。 As the compound having one group containing an ethylenically unsaturated bond, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and N-vinylpyrrolidone can be exemplified. (N-vinyl pyrrolidinone), 2-propenyloxyethyl phthalate, 2-propenyloxy-2-hydroxyethyl phthalate, 2-propenyloxyethyl hexa Hydrogen phthalate, 2-propenyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate, 2-ethylhexyl (meth)acrylate, 2 -ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, dimer of acrylic acid, benzyl (meth)acrylate, 1-naphthyl (meth)acrylate or 2-naphthyl (meth)acrylate, (methyl) ) Butoxyethyl acrylate, cetyl (meth) acrylate, ethylene oxide (hereinafter referred to as "EO") modified cresol (meth) acrylate, dipropylene glycol (meth) acrylate, B Oxylated phenyl (meth) acrylate, (meth) acrylate Ester, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid Myristyl ester, lauryl (meth)acrylate, methoxydipropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, Methoxy triethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, nonyl phenoxy Polypropylene glycol (meth) acrylate, octyl (meth) acrylate, p-cumyl phenoxy ethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as "ECH") modified phenoxy propylene Acid ester, phenoxyethyl (meth)acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol ( Methyl) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO Modified succinic acid (meth) acrylate, tribromophenyl (meth) acrylate, EO modified tribromophenyl (meth) acrylate, tris (dodecyl) (meth) acrylate, dimorphism Propylene phenol, N-vinyl pyrrolidone, N-vinyl caprolactam.
自光硬化性的觀點考慮，具有一個含有乙烯性不飽和鍵的基的化合物較佳為單官能(甲基)丙烯酸酯化合物。單官能(甲基)丙烯酸酯化合物中，具有芳香族結構及/或脂環式烴結構的單官能(甲基)丙烯酸酯在欲使耐乾式蝕刻性提高的情況下較佳，更佳為具有芳香族結構的單官能(甲基)丙烯酸酯。 From the viewpoint of photocurability, a compound having a group containing an ethylenically unsaturated bond is preferably a monofunctional (meth) acrylate compound. Among the monofunctional (meth) acrylate compounds, a monofunctional (meth) acrylate having an aromatic structure and/or an alicyclic hydrocarbon structure is preferred in order to improve dry etching resistance, and more preferably A monofunctional (meth) acrylate having an aromatic structure.
具有芳香族結構及/或脂環式烴結構的單官能(甲基)丙烯酸酯較佳為(甲基)丙烯酸苄酯、丙烯酸-2-苯氧基乙酯、於芳香環上具有取代基的(甲基)丙烯酸苄酯(較佳的取代基是碳數為1~6的烷基、碳數為1~6的烷氧基、氰基)、(甲基)丙烯酸-1-萘酯或(甲基)丙烯酸-2-萘酯、(甲基)丙烯酸-1-萘基甲酯或(甲基)丙烯酸-2-萘基甲酯、(甲基)丙烯酸-1-萘基乙酯或(甲基)丙烯酸-2-萘基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯，更佳為丙烯酸-2-苯氧基乙酯、(甲基)丙烯酸苄酯、於芳香環上具有取代基的(甲基)丙烯酸苄酯、具有萘結構的單官能(甲基)丙烯酸酯化合物。 The monofunctional (meth) acrylate having an aromatic structure and/or an alicyclic hydrocarbon structure is preferably benzyl (meth) acrylate, 2-phenoxyethyl acrylate, and has a substituent on the aromatic ring. Benzyl (meth)acrylate (preferably the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group), 1-naphthyl (meth)acrylate or 2-naphthyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate or 2-naphthylmethyl (meth)acrylate, 1-naphthylethyl (meth)acrylate or 2-naphthylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (methyl) Adamantyl acrylate, more preferably 2-phenoxyethyl acrylate, benzyl (meth) acrylate, benzyl (meth) acrylate having a substituent on the aromatic ring, a monofunctional group having a naphthalene structure (A) Base) acrylate compound.
於本發明中，聚合性化合物亦較佳為使用具有兩個以上含有乙烯性不飽和鍵的基的化合物。 In the present invention, the polymerizable compound is also preferably a compound having two or more groups containing an ethylenically unsaturated bond.
作為具有兩個以上含有乙烯性不飽和鍵的基的化合物的例子，可例示二乙二醇單***(甲基)丙烯酸酯、二羥甲基二環戊烷二(甲基)丙烯酸酯、二(甲基)丙烯酸基化異氰尿酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、EO改質1,6-己二醇二(甲基)丙烯酸酯、ECH改質1,6-己二醇二(甲基)丙烯酸酯、烯丙氧基聚乙二醇丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、EO改質雙酚A二(甲基)丙烯酸酯、PO改質雙酚A二(甲基)丙烯酸酯、改質雙酚A二(甲基)丙烯酸酯、EO改質雙酚F二(甲基)丙烯酸酯、ECH改質六氫鄰苯二甲酸二丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、EO改質新戊二醇二丙烯酸酯、環氧丙烷(以後稱為「PO」)改質新戊二醇二丙烯酸酯、己內酯改質羥基特戊酸酯新戊二醇、硬脂酸改質季戊四醇二(甲基)丙烯酸酯、ECH改質鄰苯二甲酸二(甲基)丙烯酸酯、聚(乙二醇-丁二醇)二(甲基)丙烯酸酯、聚(丙二醇-丁二醇)二(甲基)丙烯酸酯、聚酯(二)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、ECH改質丙二醇二(甲基)丙烯酸酯、矽酮二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯、新戊二醇改質三羥甲基丙烷二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、EO改質三丙二醇二(甲基)丙烯酸酯、三甘油二(甲基)丙烯酸酯、二丙二醇 二(甲基)丙烯酸酯、二乙烯基伸乙基脲、二乙烯基伸丙基脲、鄰二甲苯二(甲基)丙烯酸酯、間二甲苯二(甲基)丙烯酸酯、對二甲苯二(甲基)丙烯酸酯、1,3-金剛烷二丙烯酸酯、降冰片烷二甲醇二丙烯酸酯。 Examples of the compound having two or more groups containing an ethylenically unsaturated bond include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di(meth) acrylate, and (Meth)acrylated isocyanurate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, EO modified 1,6- Hexanediol di(meth)acrylate, ECH modified 1,6-hexanediol di(meth)acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di(a) Acrylate, EO modified bisphenol A di(meth) acrylate, PO modified bisphenol A di(meth) acrylate, modified bisphenol A di(meth) acrylate, EO modified double Phenol F di(meth)acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate EO modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as "PO") modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate neopentyl glycol, stearic acid Acid-modified pentaerythritol di(meth)acrylate, ECH modification Di(meth)acrylate, poly(ethylene glycol-butanediol) di(meth)acrylate, poly(propylene glycol-butanediol) di(meth)acrylate, polyester (b) Acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ECH modified propylene glycol di(meth)acrylate, anthrone di(meth)acrylate, triethylene glycol Alcohol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, neopentyl glycol modified trimethylolpropane di Methyl) acrylate, tripropylene glycol di(meth) acrylate, EO modified tripropylene glycol di(meth) acrylate, triglycerin di(meth) acrylate, dipropylene glycol Di(meth)acrylate, divinylexylethylurea,divinylpropylpropylurea, ortho-xylene di(meth)acrylate, m-xylene di(meth)acrylate, p-xylene di(a) Acrylate, 1,3-adamantane diacrylate, norbornane dimethanol diacrylate.
該些中，特別是新戊二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、鄰苯二(甲基)丙烯酸酯、間苯二(甲基)丙烯酸酯、對苯二(甲基)丙烯酸酯、鄰二甲苯二(甲基)丙烯酸酯、間二甲苯二(甲基)丙烯酸酯、對二甲苯二(甲基)丙烯酸酯等2官能(甲基)丙烯酸酯可於本發明中適宜地使用。 Among these, especially neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(a) Acrylate, hydroxypivalic acid neopentyl glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, phthalic acid (meth) acrylate, isophthalic (meth) 2-functional (such as acrylate, p-phenylene (meth) acrylate, o-xylene di(meth) acrylate, m-xylene di(meth) acrylate, p-xylene di(meth) acrylate (A) The acrylate) can be suitably used in the present invention.
而且，亦可使用具有芳香族結構及/或脂環式烴結構的2官能~6官能的(甲基)丙烯酸酯化合物。例如可列舉含有芳香族基(較佳為苯基、萘基)，具有2個~4個(甲基)丙烯酸酯基的多官能(甲基)丙烯酸酯化合物。具體例可列舉以下所示的化合物等。 Further, a bifunctional-6 functional (meth) acrylate compound having an aromatic structure and/or an alicyclic hydrocarbon structure can also be used. For example, a polyfunctional (meth) acrylate compound having an aromatic group (preferably a phenyl group or a naphthyl group) and having two to four (meth) acrylate groups may be mentioned. Specific examples thereof include the compounds shown below.
而且，光硬化性組成物亦可含有具有矽原子及/或氟原子 的聚合性化合物。具有矽原子及/或氟原子的聚合性化合物較佳為包含氟原子，更佳為具有碳數為1~9的含氟烷基。 Moreover, the photocurable composition may also contain a ruthenium atom and/or a fluorine atom. Polymeric compound. The polymerizable compound having a halogen atom and/or a fluorine atom preferably contains a fluorine atom, and more preferably has a fluorine-containing alkyl group having 1 to 9 carbon atoms.
碳數為1~9的含氟烷基的氟原子的取代率較佳為40%~100%，更佳為50%~90%，進一步更佳為65%~85%。所謂「氟原子的取代率」是指例如碳數為1~9的烷基中，氫原子被取代為氟原子的比率(%)。碳數為1~9的含氟烷基較佳為包含-CnF2n+1或-CnF2nH，更佳為包含-CnF2n+1。此處，n表示1~9的整數，更佳為表示4~8的整數。 The substitution ratio of the fluorine atom of the fluorine-containing alkyl group having 1 to 9 carbon atoms is preferably from 40% to 100%, more preferably from 50% to 90%, still more preferably from 65% to 85%. The "replacement ratio of a fluorine atom" means, for example, a ratio (%) in which a hydrogen atom is substituted with a fluorine atom in an alkyl group having 1 to 9 carbon atoms. The fluorine-containing alkyl group having 1 to 9 carbon atoms preferably contains -C n F 2n+1 or -C n F 2n H , more preferably contains -C n F 2n+1 . Here, n represents an integer of 1 to 9, and more preferably represents an integer of 4 to 8.
具有矽原子及/或氟原子的聚合性化合物所具有的聚合性基較佳為(甲基)丙烯酸酯基。聚合性基數較佳為1或2，更佳為1。 The polymerizable group of the polymerizable compound having a ruthenium atom and/or a fluorine atom is preferably a (meth) acrylate group. The polymerizable group number is preferably 1 or 2, more preferably 1.
具有矽原子及/或氟原子的聚合性化合物的分子量較佳為100~600，更佳為300~500。具有氟原子的聚合性化合物例如亦可參考國際公開專利2010/137724號公報的段落0022~段落0023的記載，其內容可併入至本申請案說明書中。具有氟原子的聚合性化合物的例子例如可列舉丙烯酸-2-(全氟己基)乙酯。 The molecular weight of the polymerizable compound having a halogen atom and/or a fluorine atom is preferably from 100 to 600, more preferably from 300 to 500. The polymerizable compound having a fluorine atom can be referred to, for example, the description of paragraphs 0022 to 0023 of the International Patent Publication No. 2010/137724, the contents of which are incorporated herein by reference. Examples of the polymerizable compound having a fluorine atom include, for example, 2-(perfluorohexyl)ethyl acrylate.
而且，於本發明中，亦可設為實質上不含具有矽原子及/或氟原子的聚合性化合物的實施方式。 Further, in the present invention, an embodiment in which a polymerizable compound having a ruthenium atom and/or a fluorine atom is substantially not contained may be used.
光硬化性組成物中所含的聚合性化合物中，較佳為具有一個聚合性基的聚合性化合物(較佳為具有一個(甲基)丙烯酸酯基的聚合性化合物)的合計相對於聚合性化合物的總量而言為0質量%~60質量%。上限更佳為50質量%以下。下限可設為5質量%以上，亦可設為10質量%以上。隨著光硬化性組成物中的具有 一個聚合性基的聚合性化合物的含量變多，存在所得的凹凸圖案的彈性係數變大而造成強度降低的傾向。根據本發明的方法，即使對於強度低的圖案，亦可抑制圖案缺陷的產生，且於表面形成膜。 Among the polymerizable compounds contained in the photocurable composition, a total of a polymerizable compound having one polymerizable group (preferably a polymerizable compound having one (meth) acrylate group) is preferred to the polymerizable property. The total amount of the compound is from 0% by mass to 60% by mass. The upper limit is more preferably 50% by mass or less. The lower limit can be 5% by mass or more, and may be 10% by mass or more. With light curable composition The content of the polymerizable compound of one polymerizable group increases, and the elastic modulus of the obtained uneven pattern tends to increase, and the strength tends to decrease. According to the method of the present invention, even for a pattern having low strength, generation of pattern defects can be suppressed, and a film is formed on the surface.
而且，亦可設為實質上不含具有一個聚合性基的聚合性化合物的組成。所謂「實質上不含具有一個聚合性基的聚合性化合物」例如在聚合性化合物的總量中，較佳為1質量%以下，更佳為0.5質量%以下，亦可不含有。 Further, it may be a composition which does not substantially contain a polymerizable compound having one polymerizable group. The "polymerizable compound having one polymerizable group is not substantially contained in the total amount of the polymerizable compound, for example, is preferably 1% by mass or less, more preferably 0.5% by mass or less, and may not be contained.
而且，具有兩個聚合性基的聚合性化合物(較佳為具有兩個(甲基)丙烯酸酯基的聚合性化合物)的合計較佳為相對於聚合性化合物的總量而言為40質量%~100質量%。上限更佳為95質量%以下，進一步更佳為90質量%以下。下限更佳為50質量%以上，進一步更佳為55質量%以上。 Further, the total of the polymerizable compound having two polymerizable groups (preferably a polymerizable compound having two (meth) acrylate groups) is preferably 40% by mass based on the total amount of the polymerizable compound. ~100% by mass. The upper limit is more preferably 95% by mass or less, still more preferably 90% by mass or less. The lower limit is more preferably 50% by mass or more, and still more preferably 55% by mass or more.
光硬化性組成物中所含的聚合性化合物成分中，具有脂環式烴基及/或芳香族基的聚合性化合物的合計較佳為聚合性化合物的總量的30質量%~100質量%，更佳為50質量%~100質量%，進一步更佳為70質量%~100質量%。 In the polymerizable compound component contained in the photocurable composition, the total of the polymerizable compound having an alicyclic hydrocarbon group and/or an aromatic group is preferably 30% by mass to 100% by mass based on the total amount of the polymerizable compound. More preferably, it is 50 mass% - 100 mass%, and further more preferably 70 mass% - 100 mass%.
<<光聚合起始劑>> <<Photopolymerization initiator>>
光聚合起始劑若為藉由光照射而產生使所述聚合性化合物聚合的活性物種的化合物，則可使用任意者。光聚合起始劑較佳為自由基聚合起始劑及陽離子聚合起始劑，更佳為自由基聚合起始劑。而且，於本發明中，亦可併用多種光聚合起始劑。 Any photopolymerization initiator may be any compound which generates an active species which polymerizes the polymerizable compound by light irradiation. The photopolymerization initiator is preferably a radical polymerization initiator and a cationic polymerization initiator, more preferably a radical polymerization initiator. Further, in the present invention, a plurality of photopolymerization initiators may be used in combination.
自由基光聚合起始劑例如可使用市售的起始劑。作為該些的例子，例如可較佳地採用日本專利特開2008-105414號公報的段落編號0091中所記載者。其中，自硬化感度、吸收特性的觀點考慮，較佳為苯乙酮系化合物、醯基氧化膦系化合物、肟酯系化合物。市售品可列舉豔佳固(Irgacure)OXE-01、Irgacure OXE-02、Irgacure 127、Irgacure 819、Irgacure 379、Irgacure 369、Irgacure 754、Irgacure 1800、Irgacure 651、Irgacure 907、路西林(Lucirin)TPO、達羅卡(Darocur)1173等(以上由巴斯夫(BASF)公司製造)。 As the radical photopolymerization initiator, for example, a commercially available initiator can be used. As such an example, those described in Paragraph No. 0091 of JP-A-2008-105414 can be preferably used. Among them, an acetophenone-based compound, a fluorenylphosphine oxide-based compound, and an oxime ester-based compound are preferred from the viewpoint of self-hardening sensitivity and absorption characteristics. Commercially available products include Irgacure OXE-01, Irgacure OXE-02, Irgacure 127, Irgacure 819, Irgacure 379, Irgacure 369, Irgacure 754, Irgacure 1800, Irgacure 651, Irgacure 907, Lucirin TPO. , Darocur 1173, etc. (above by BASF).
光聚合起始劑的含量較佳為在除溶劑以外的所有組成物中為0.01質量%~15質量%，更佳為0.1質量%~12質量%，進一步更佳為0.2質量%~7質量%。光硬化性組成物可僅含有一種光聚合起始劑，亦可含有兩種以上。在含有兩種以上的情況下，較佳為其合計量成為所述範圍。 The content of the photopolymerization initiator is preferably from 0.01% by mass to 15% by mass, more preferably from 0.1% by mass to 12% by mass, even more preferably from 0.2% by mass to 7% by mass, based on all the components except the solvent. . The photocurable composition may contain only one photopolymerization initiator, and may contain two or more kinds. When two or more types are contained, it is preferable that the total amount is the said range.
<<界面活性劑>> <<Interfacial active agent>>
光硬化性組成物可含有界面活性劑。界面活性劑較佳為非離子性界面活性劑。 The photocurable composition may contain a surfactant. The surfactant is preferably a nonionic surfactant.
所謂「非離子性界面活性劑」是具有至少一個疏水部與至少一個非離子性親水部的化合物。疏水部與親水部可分別位於分子的末端，亦可位於內部。疏水部包含選自烴基、含氟基、含Si基的疏水基，疏水部的碳數較佳為1~25，更佳為2~15，進一步更佳為4~10，最佳為5~8。非離子性親水部較佳為具有選自由醇 性羥基、酚性羥基、醚基(較佳為聚環氧烷基、環狀醚基)、醯胺基、醯亞胺基、脲基、胺基甲酸酯基、氰基、磺醯胺基、內酯基、內醯胺基、環碳酸酯基所構成的群組的至少一個基。非離子性界面活性劑可為烴系、氟系、Si系、或氟．Si系的任意非離子性界面活性劑，更佳為氟系或Si系，進一步更佳為氟系。此處，所謂「氟．Si系界面活性劑」是指兼具氟系界面活性劑及Si系界面活性劑此兩者的必要條件者。 The "nonionic surfactant" is a compound having at least one hydrophobic portion and at least one nonionic hydrophilic portion. The hydrophobic portion and the hydrophilic portion may be located at the ends of the molecules, respectively, or may be located inside. The hydrophobic portion comprises a hydrophobic group selected from a hydrocarbon group, a fluorine-containing group and a Si-containing group, and the carbon number of the hydrophobic portion is preferably from 1 to 25, more preferably from 2 to 15, further preferably from 4 to 10, most preferably from 5 to 5. 8. The nonionic hydrophilic portion preferably has an alcohol selected from the group consisting of Hydroxyl group, phenolic hydroxyl group, ether group (preferably polyalkylene oxide group, cyclic ether group), decylamino group, quinone imido group, ureido group, urethane group, cyano group, sulfonamide At least one group of the group consisting of a base, a lactone group, an indolyl group, and a cyclic carbonate group. The nonionic surfactant can be hydrocarbon, fluorine, Si, or fluorine. Any of the Si-based nonionic surfactants is more preferably fluorine-based or Si-based, and more preferably fluorine-based. Here, the "fluorine-Si-based surfactant" means a requirement of both a fluorine-based surfactant and a Si-based surfactant.
氟系非離子性界面活性劑的市售品可列舉住友3M股份有限公司製造的弗洛德(Fluorad)FC-4430、Fluorad FC-4431、旭硝子股份有限公司製造的沙福隆(Surflon)S-241、Surflon S-242、Surflon S-243、三菱綜合材料電子化成股份有限公司製造的艾福拓(Eftop)EF-PN31M-03、Eftop EF-PN31M-04、Eftop EF-PN31M-05、Eftop EF-PN31M-06、Eftop MF-100、歐諾法(OMNOVA)公司製造的波利佛斯(Polyfox)PF-636、Polyfox PF-6320、Polyfox PF-656、Polyfox PF-6520、尼奧斯(Neos)股份有限公司製造的福傑特(Ftergent)250、Ftergent 251、Ftergent 222F、Ftergent 212M DFX-18、大金工業股份有限公司製造的尤尼達因(UNIDYNE)DS-401、UNIDYNE DS-403、UNIDYNE DS-406、UNIDYNE DS-451、UNIDYNE DSN-403N、迪愛生(DIC)股份有限公司製造的美佳法(Megafac)F-430、Megafac F-444、Megafac F-477、Megafac F-553、Megafac F-556、Megafac F-557、Megafac F-559、Megafac F-562、Megafac F-565、Megafac F-567、Megafac F-569、Megafac R-40、杜邦(DuPont)公司製造的卡普斯通(Capstone)FS-3100、藻妮露(Zonyl)FSO-100。 Commercial products of the fluorine-based nonionic surfactant include, for example, Fluorad FC-4430 manufactured by Sumitomo 3M Co., Ltd., Fluorad FC-4431, and Surflon S- manufactured by Asahi Glass Co., Ltd. 241, Surflon S-242, Surflon S-243, Eftop EF-PN31M-03, Eftop EF-PN31M-04, Eftop EF-PN31M-05, Eftop EF manufactured by Mitsubishi Materials Corporation -PN31M-06, Eftop MF-100, Polyfox PF-636, Polyfox PF-6320, Polyfox PF-656, Polyfox PF-6520, Neos by OMNOVA ) Ftergent 250, Ftergent 251, Ftergent 222F, Ftergent 212M DFX-18, UNIDYNE DS-401, UNIDYNE DS-403 manufactured by Daikin Industries, Ltd. UNIDYNE DS-406, UNIDYNE DS-451, UNIDYNE DSN-403N, Megafac F-430, Megafac F-444, Megafac F-477, Megafac F-553, Megafac F-556, Megafac F-557, Megafac F-559, Megafac F-562, Megafac F-565, Megafac F-567, Megafac F-569, Megafac R-40, Capstone FS-3100, Zonyl FSO-100 manufactured by DuPont.
在本發明的光硬化性組成物含有界面活性劑的情況下，界面活性劑的含量較佳為在除溶劑以外的所有組成物中為0.1質量%~10質量%，更佳為0.2質量%~5質量%，進一步更佳為0.5質量%~5質量%。光硬化性組成物可僅含有一種界面活性劑，亦可含有兩種以上。在含有兩種以上的情況下，較佳為其合計量成為所述範圍。 When the photocurable composition of the present invention contains a surfactant, the content of the surfactant is preferably from 0.1% by mass to 10% by mass, more preferably 0.2% by mass, based on all the components other than the solvent. 5质量%, further more preferably 0.5% by mass to 5% by mass. The photocurable composition may contain only one type of surfactant, and may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said range.
而且，於本發明中，亦可設為實質上不含界面活性劑的實施方式。所謂「實質上不含界面活性劑」例如較佳為界面活性劑的含量為0.01質量%以下，更佳為0.005質量%以下，進一步更佳為不含有。 Further, in the present invention, an embodiment in which the surfactant is not substantially contained may be used. The content of the surfactant is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and even more preferably not contained.
<<非聚合性化合物>> <<Non-polymeric compound>>
光硬化性組成物亦可含有具有在末端具有至少一個羥基、或羥基被醚化的聚烷二醇結構，且實質上不含氟原子及矽原子的非聚合性化合物。此處，所謂「非聚合性化合物」是指不具有聚合性基的化合物。而且，所謂「實質上不含氟原子及矽原子」例如表示氟原子及矽原子的合計含有率為1%以下，較佳為完全不含氟原子及矽原子。藉由不含氟原子及矽原子，可提高與聚合性化合物的相容性，特別是在不含有溶劑的組成物中，塗佈均一性、壓印時的圖案形成性、乾式蝕刻後的線邊緣粗糙度變良好。 The photocurable composition may also contain a non-polymerizable compound having a polyalkylene glycol structure having at least one hydroxyl group at the terminal or a hydroxyl group etherified, and substantially free of a fluorine atom and a halogen atom. Here, the "non-polymerizable compound" means a compound which does not have a polymerizable group. In addition, the term "substantially free of fluorine atoms and germanium atoms" means that the total content of fluorine atoms and germanium atoms is 1% or less, and it is preferable that fluorine atoms and germanium atoms are not present at all. By containing no fluorine atom or ruthenium atom, compatibility with a polymerizable compound can be improved, and in particular, coating uniformity, pattern formation property at the time of imprinting, and line after dry etching can be applied to a composition containing no solvent. The edge roughness becomes good.
作為非聚合性化合物所具有的聚伸烷基結構，較佳為包 含碳數為1~6的伸烷基的聚烷二醇結構，更佳為聚乙二醇結構、聚丙二醇結構、聚丁二醇結構、或該些的混合結構，進一步更佳為聚乙二醇結構、聚丙二醇結構、或該些的混合結構，特佳為聚丙二醇結構。 As the polyalkylene structure of the non-polymerizable compound, it is preferably a package The polyalkylene glycol structure having an alkyl group having 1 to 6 carbon atoms, more preferably a polyethylene glycol structure, a polypropylene glycol structure, a polybutylene glycol structure, or a mixed structure of the above, further preferably a polyethylene The diol structure, the polypropylene glycol structure, or a mixed structure of these is particularly preferably a polypropylene glycol structure.
另外，亦可除了末端的取代基以外實質上僅包含聚烷二醇結構。此處所謂「實質上」是指聚烷二醇結構以外的構成要素為整體的5質量%以下，較佳為是指1質量%以下。特別是作為非聚合性化合物而言，特佳為含有實質上僅包含聚丙二醇結構的化合物。 Further, it may contain substantially only a polyalkylene glycol structure in addition to the terminal substituent. The term "substantially" as used herein means that the constituent elements other than the polyalkylene glycol structure are 5% by mass or less, and preferably 1% by mass or less. In particular, as the non-polymerizable compound, it is particularly preferred to contain a compound having substantially only a polypropylene glycol structure.
作為聚烷二醇結構，較佳為具有3個~100個烷二醇結構單元，更佳為具有4個~50個，進一步更佳為具有5個~30個，特佳為具有6個~20個。 The polyalkylene glycol structure preferably has 3 to 100 alkanediol structural units, more preferably 4 to 50, still more preferably 5 to 30, and particularly preferably 6 to 20.
非聚合性化合物較佳為於末端具有至少一個羥基或羥基被醚化。亦可使用在末端具有至少一個羥基或者若羥基被醚化，則即使剩餘的末端是羥基，末端羥基的氫原子亦可經取代的化合物。亦可取代末端羥基的氫原子的基較佳為烷基(亦即聚烷二醇烷基醚)、醯基(亦即聚烷二醇酯)。更佳為所有的末端均為羥基的聚烷二醇。亦可較佳地使用經由連結基而具有多個(較佳為2根或3根)聚烷二醇鏈的化合物，較佳為聚烷二醇鏈未分支的直鏈結構。特佳為二醇型的聚烷二醇。 The non-polymerizable compound preferably has at least one hydroxyl group at the terminal or a hydroxyl group is etherified. It is also possible to use a compound having at least one hydroxyl group at the terminal or, if the hydroxyl group is etherified, the hydrogen atom of the terminal hydroxyl group may be substituted even if the remaining terminal is a hydroxyl group. The group which may also substitute the hydrogen atom of the terminal hydroxyl group is preferably an alkyl group (i.e., a polyalkylene glycol alkyl ether) or a mercapto group (i.e., a polyalkylene glycol ester). More preferably, all of the polyalkylene glycols having a hydroxyl group at the end are used. It is also preferred to use a compound having a plurality of (preferably 2 or 3) polyalkylene glycol chains via a linking group, and preferably a linear structure in which the polyalkylene glycol chain is not branched. Particularly preferred is a glycol type polyalkylene glycol.
非聚合性化合物的較佳的具體例是聚乙二醇、聚丙二醇、該些的單甲醚或二甲醚、單丁醚或二丁醚、單辛醚或二辛醚、單鯨蠟醚或二鯨蠟醚、單硬脂酸酯、單油酸酯、聚氧乙烯甘油醚、聚 氧丙烯甘油醚、該些的三甲醚。 Preferred specific examples of the non-polymerizable compound are polyethylene glycol, polypropylene glycol, monomethyl ether or dimethyl ether, monobutyl ether or dibutyl ether, monooctyl ether or dioctyl ether, and monocetyl ether. Or cetyl ether, monostearate, monooleate, polyoxyethylene glyceryl ether, poly Oxypropylene glyceryl ether, these trimethyl ethers.
非聚合性化合物的重量平均分子量較佳為150~6000，更佳為200~3000，進一步更佳為250~2000，特佳為300~1200。 The weight average molecular weight of the non-polymerizable compound is preferably from 150 to 6,000, more preferably from 200 to 3,000, still more preferably from 250 to 2,000, and particularly preferably from 300 to 1200.
於本發明中，在光硬化性組成物含有非聚合性化合物的情況下，非聚合性化合物的含量較佳為在除溶劑以外的所有組成物中為0.1質量%~20質量%，更佳為0.2質量%~15質量%，進一步更佳為0.5質量%~10質量%。而且，於本發明中，亦可設為實質上不含非聚合性化合物的實施方式。所謂「實質上不含非聚合性化合物」例如較佳為非聚合性化合物的含量為0.01質量%以下，更佳為0.005質量%以下，進一步更佳為不含有。 In the present invention, when the photocurable composition contains a non-polymerizable compound, the content of the non-polymerizable compound is preferably from 0.1% by mass to 20% by mass based on all the components excluding the solvent, and more preferably 0.2% by mass to 15% by mass, and more preferably 0.5% by mass to 10% by mass. Further, in the present invention, an embodiment in which substantially no non-polymerizable compound is contained may be used. The content of the non-polymerizable compound is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and even more preferably no content.
<<溶劑>> <<Solvent>>
在光硬化性組成物中可視需要而含有溶劑。較佳的溶劑是常壓下的沸點為80℃~200℃的溶劑。溶劑的種類若為可溶解各成分者，則可使用任意種類，可列舉與所述下層膜形成用樹脂組成物中所記載的溶劑同樣的溶劑。其中，自塗佈均一性的觀點考慮，最佳為含有丙二醇單甲醚乙酸酯的溶劑。 The photocurable composition may contain a solvent as needed. A preferred solvent is a solvent having a boiling point of from 80 ° C to 200 ° C under normal pressure. When the type of the solvent is such that the respective components can be dissolved, any solvent can be used, and the same solvent as the solvent described in the resin composition for forming the underlayer film can be used. Among them, from the viewpoint of coating uniformity, a solvent containing propylene glycol monomethyl ether acetate is preferred.
光硬化性組成物中的溶劑的含量可根據光硬化性組成物的黏度、塗佈性、目標膜厚而調整為最適宜，自塗佈性改善的觀點考慮，可在光硬化性組成物中以99質量%以下的範圍而含有。在藉由噴墨法將光硬化性組成物塗佈於基材上的情況下，較佳為實質上不含(例如3質量%以下)溶劑。另一方面，在藉由旋轉塗佈等方法而形成膜厚500nm以下的圖案時，可以20質量%~99質量 %的範圍而含有，較佳為40質量%~99質量%，特佳為70質量%~98質量%。 The content of the solvent in the photocurable composition can be adjusted to be optimal depending on the viscosity, coating property, and target film thickness of the photocurable composition, and can be used in the photocurable composition from the viewpoint of improving the coating property. It is contained in the range of 99 mass% or less. When the photocurable composition is applied onto a substrate by an inkjet method, it is preferred that the solvent is substantially not contained (for example, 3% by mass or less). On the other hand, when a pattern having a film thickness of 500 nm or less is formed by a method such as spin coating, it may be 20% by mass to 99% by mass. It is contained in the range of %, preferably 40% by mass to 99% by mass, particularly preferably 70% by mass to 98% by mass.
<<其他成分>> <<Other ingredients>>
光硬化性組成物除了所述成分以外，亦可視需要而含有聚合抑制劑、光敏劑、抗氧化劑、紫外線吸收劑、光穩定劑、抗老化劑、塑化劑、密接促進劑、熱聚合起始劑、光鹼產生劑、著色劑、無機粒子、彈性體粒子、鹼性化合物、光酸產生劑、光酸增殖劑、鏈轉移劑、抗靜電劑、流動調整劑、消泡劑、分散劑、脫模劑等。此種成分的具體例可列舉日本專利特開2008-105414號公報的段落編號0092~段落編號0093、及段落編號0099~段落編號0137中所記載者，該些內容可併入至本申請案說明書中。而且，可參考WO2011/126101號說明書、WO2013/051735說明書、日本專利特開2012-041521號公報及日本專利特開2013-093552號公報的對應的記載，該些內容可併入至本申請案說明書中。 The photocurable composition may contain, in addition to the components, a polymerization inhibitor, a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, a adhesion promoter, and a thermal polymerization initiation. Agent, photobase generator, colorant, inorganic particles, elastomer particles, basic compound, photoacid generator, photoacid proliferator, chain transfer agent, antistatic agent, flow regulator, defoamer, dispersant, Release agent, etc. Specific examples of such a component include those described in paragraph number 0092 to paragraph 0093 of the Japanese Patent Laid-Open Publication No. 2008-105414, and paragraph number 0099 to paragraph number 0137, which can be incorporated into the specification of the present application. in. Further, reference may be made to the corresponding descriptions of the specification of WO2011/126101, the specification of WO2013/051735, the specification of Japanese Patent Laid-Open No. 2012-041521, and the Japanese Patent Laid-Open No. 2013-093552, the contents of which are hereby incorporated herein by reference. in.
光硬化性組成物可將所述各成分加以混合而製備。各成分的混合通常在0℃~100℃的範圍內進行。而且，在將各成分加以混合後，例如較佳為藉由過濾器進行過濾。過濾可於多階段進行，亦可反覆進行數次。而且，亦可對過濾的液體進行再過濾。 The photocurable composition can be prepared by mixing the above components. The mixing of the components is usually carried out in the range of 0 °C to 100 °C. Further, after mixing the components, it is preferably filtered by a filter, for example. Filtration can be carried out in multiple stages or several times. Moreover, the filtered liquid can be refiltered.
過濾器若為自先前便在過濾用途等中所使用者，則可並無特別限定地使用。例如可列舉利用PTFE(聚四氟乙烯)等氟樹脂、尼龍-6、尼龍-6,6等聚醯胺系樹脂、聚乙烯、聚丙烯(PP)等聚烯烴樹脂(包含高密度、超高分子量的樹脂)等的過濾器。該些原 材料中較佳為聚丙烯(包含高密度聚丙烯)及尼龍。 The filter is not particularly limited as long as it is used by a user for filtration or the like. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (PP) may be used (including high density and high density). A filter such as a molecular weight resin). The original Preferred among the materials are polypropylene (including high density polypropylene) and nylon.
過濾器的孔徑例如適合的是0.003μm~5.0μm左右。藉由設為該範圍，可抑制過濾堵塞，變得可確實地除去組成物中所含的雜質或凝聚物等微細的異物。 The pore diameter of the filter is, for example, suitably from about 0.003 μm to about 5.0 μm. By setting it as this range, it is possible to suppress clogging of the filter, and it is possible to surely remove fine foreign matter such as impurities or aggregates contained in the composition.
使用過濾器時，亦可組合不同的過濾器。此時，藉由第1過濾器的過濾可僅為一次，亦可進行兩次以上。在組合不同的過濾器而進行兩次以上的過濾的情況下，較佳為第二次以後的孔徑與第一次的過濾的孔徑相同，或者比第一次的過濾的孔徑小。而且，亦可組合所述範圍內不同孔徑的第1過濾器。此處的孔徑可參照過濾器廠商的標稱值。市售的過濾器例如可自日本頗爾股份有限公司、愛多邦得科東洋股份有限公司、日本英特格股份有限公司(原日本密科里(Mykrolis)股份有限公司)或北澤微濾器股份有限公司等所提供的各種過濾器中選擇。 When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more. In the case where two or more filtrations are performed by combining different filters, it is preferred that the pore diameter after the second time is the same as the pore diameter of the first filtration or smaller than the pore diameter of the first filtration. Further, the first filter having a different pore diameter within the range may be combined. The aperture here can be referred to the nominal value of the filter manufacturer. Commercially available filters are available, for example, from Pall Corporation of Japan, Iddobond Co., Ltd., Japan Inteco Co., Ltd. (formerly Japan Mykrolis Co., Ltd.) or Kitazawa Microfilter Co., Ltd. Among the various filters offered by Ltd., etc.
光硬化性組成物較佳為於23℃下的黏度為100mPa．s以下，更佳為70mPa．s以下，進一步更佳為50mPa．s以下，特佳為30mPa．s以下。下限例如較佳為1mPa．s以上，更佳為2mPa．s以上，特佳為3mPa．s以上。 The photocurable composition preferably has a viscosity of 100 mPa at 23 ° C. Below s, more preferably 70mPa. s below, further preferably 50mPa. Below s, especially good for 30mPa. s below. The lower limit is, for example, preferably 1 mPa. Above s, more preferably 2mPa. Above s, especially good for 3mPa. s above.
而且，在藉由噴墨法而應用光硬化性組成物的情況下，光硬化性組成物的黏度較佳為於23℃下為15mPa．s以下，更佳為12mPa．s以下，進一步更佳為11mPa．s以下，特佳為10mPa．s以下。藉由設為此種範圍，可提高噴墨噴出精度或圖案形成性。 Further, in the case where a photocurable composition is applied by an inkjet method, the viscosity of the photocurable composition is preferably 15 mPa at 23 °C. Below s, more preferably 12mPa. s below, further preferably 11mPa. Below s, especially good for 10mPa. s below. By setting it as such a range, the inkjet discharge precision or pattern formation property can be improved.
而且，於液晶顯示器(LCD)等中所使用的永久膜(結構構 件用抗蝕劑)或電子材料的基板加工中所使用的抗蝕劑中，為了不阻礙製品的動作，理想的是極力避免抗蝕劑中的金屬或有機物的離子性雜質的混入。因此，於所述用途中使用圖案形成體的情況下，光硬化性組成物中的金屬或有機物的離子性雜質的濃度較佳為設為1ppm以下，理想的是設為100ppb以下，進一步更佳為設為10ppb以下。 Moreover, a permanent film (structure) used in a liquid crystal display (LCD) or the like In the resist used for the substrate processing of the resist or the electronic material, it is preferable to avoid the incorporation of the ionic impurities of the metal or the organic substance in the resist in order not to hinder the operation of the product. Therefore, when the pattern forming body is used for the above-mentioned use, the concentration of the ionic impurity of the metal or organic substance in the photocurable composition is preferably 1 ppm or less, preferably 100 ppb or less, and further preferably. It is set to 10 ppb or less.
藉由本發明的圖案形成體的製造方法而所得的圖案形成體例如亦可作為液晶顯示器(LCD)等中所使用的保護層或絕緣膜等永久膜，或半導體積體電路、記錄材料或平面顯示器等的蝕刻抗蝕劑而應用。而且，亦可於樹脂模具、撥水膜、親水膜等中使用。 The pattern forming body obtained by the method for producing a pattern forming body of the present invention can be used, for example, as a permanent film such as a protective layer or an insulating film used in a liquid crystal display (LCD) or the like, or a semiconductor integrated circuit, a recording material, or a flat display. It is applied by etching the resist. Further, it can also be used in a resin mold, a water-repellent film, a hydrophilic film or the like.
以下，列舉實施例而對本發明加以更具體的說明。以下的實施例中所使用的材料、使用量、比例、處理內容、處理順序等只要不脫離本發明的主旨，則可適宜變更。因此，本發明的範圍並不限定於以下所示的具體例。另外，只要無特別說明，則「份」、「%」是質量基準。 Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the treatment contents, the treatment procedures, and the like used in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.
<第1組成物、第2組成物、光硬化性組成物的製備> <Preparation of the first composition, the second composition, and the photocurable composition>
將下述表中所示的原料加以混合，藉由0.1μm的PTFE(聚四氟乙烯)過濾器進行過濾，製備各組成物。 The materials shown in the following tables were mixed, and filtered through a 0.1 μm PTFE (polytetrafluoroethylene) filter to prepare each composition.
再者，第1組成物及第2組成物的表面張力是使用協和界面科學股份有限公司製造的表面張力計SURFACE TENS-IOMETER CBVP-A3，使用鉑板而在25±0.2℃下進行測定。單位以mN/m而表示。 Further, the surface tension of the first composition and the second composition was SURFACE TENS-IOMETER manufactured by Kyowa Interface Science Co., Ltd. CBVP-A3 was measured at 25 ± 0.2 ° C using a platinum plate. The unit is expressed in mN/m.
表3中的記號為以下者。 The symbols in Table 3 are as follows.
(聚合性化合物) (polymerizable compound)
C-1：新戊二醇二丙烯酸酯(光丙烯酸酯(Light acrylate)NP-A共榮社化學公司製造) C-1: Neopentyl glycol diacrylate (Light acrylate NP-A Kyoritsu Chemical Co., Ltd.)
C-2：二羥甲基-三環癸烷二丙烯酸酯(Light acrylate DCP-A共榮社化學公司製造) C-2: Dimethylol-tricyclodecane diacrylate (Light acrylate DCP-A Kyoritsu Chemical Co., Ltd.)
C-3：丙烯酸異冰片酯(Light acrylate IB-XA共榮社化學公司製造) C-3: isobornyl acrylate (Light acrylate IB-XA Kyoritsu Chemical Co., Ltd.)
C-4：丙烯酸芐酯(比斯克特(Viscoat)#160大阪有機化學公司製造) C-4: benzyl acrylate (Viscoat #160 Osaka Organic Chemical Co., Ltd.)
(光聚合起始劑) (photopolymerization initiator)
D-1：Irgacure 819(巴斯夫公司製造) D-1: Irgacure 819 (manufactured by BASF Corporation)
D-2：Irgacure 127(巴斯夫公司製造) D-2: Irgacure 127 (manufactured by BASF Corporation)
(其他成分) (other ingredients)
E-1：Capstone FS-3100(杜邦公司製造) E-1: Capstone FS-3100 (manufactured by DuPont)
E-2：聚丙二醇(Mw=400、和光純藥工業公司製造) E-2: polypropylene glycol (Mw=400, manufactured by Wako Pure Chemical Industries, Ltd.)
<凹凸圖案的製作> <Production of concave and convex pattern>
模具使用線寬30nm、深度60nm的線/間隔(Line/Space)圖案的石英模具。 The mold used a quartz mold of a line/space pattern having a line width of 30 nm and a depth of 60 nm.
使用噴墨裝置(富士膠片迪麥提克斯(FUJIFILM Dimatix)公司製造的DMP-2831)，於矽晶圓上塗佈所述光硬化性組成物(組成物1~組成物4)。液滴尺寸是以6pL塗佈為280μm間隔的正方格子狀。 The photocurable composition (composition 1 to composition 4) was applied onto a tantalum wafer using an inkjet apparatus (DMP-2831 manufactured by FUJIFILM Dimatix Co., Ltd.). The droplet size was a square lattice shape with a spacing of 280 μm coated at 6 pL.
於塗佈區域，於氦環境下壓接所述石英模具，於大氣壓下放置30秒後，藉由高壓水銀燈自石英模具面進行光硬化。照射量設為100mJ/cm2。於曝光後，鬆開石英模具而獲得凹凸圖案。圖案 的殘膜(圖案凹部中的源自光硬化性組成物的膜)為30nm。 In the coating region, the quartz mold was crimped under a helium atmosphere, and after being placed under atmospheric pressure for 30 seconds, the glass mold was subjected to photohardening by a high pressure mercury lamp. The irradiation amount was set to 100 mJ/cm 2 . After the exposure, the quartz mold was loosened to obtain a concave-convex pattern. The residual film of the pattern (the film derived from the photocurable composition in the pattern concave portion) was 30 nm.
<圖案形成體的製造> <Manufacture of Pattern Forming Body>
於藉由所述方法而所得的凹凸圖案的表面旋塗塗佈第1組成物。轉速為1000rpm，旋轉時間設為30s。 The first composition was spin-coated on the surface of the concavo-convex pattern obtained by the above method. The rotation speed was 1000 rpm and the rotation time was set to 30 s.
其次，於應用第1組成物後，於5秒後將第2組成物旋塗塗佈於塗佈有第1組成物的區域上。轉速為1000rpm，旋轉時間設為30s。第2組成物的應用在凹凸圖案被第1組成物覆蓋期間進行。 Next, after applying the first composition, the second composition was spin-coated on the region to which the first composition was applied after 5 seconds. The rotation speed was 1000 rpm and the rotation time was set to 30 s. The application of the second composition is performed while the concavo-convex pattern is covered by the first composition.
再者，僅比較例1-2在應用第1組成物後，於5分鐘後將第2組成物旋塗塗佈於塗佈有第1組成物的區域上。比較例1-2中，在第2組成物的應用時，凹凸圖案自第1組成物露出。 Further, in Comparative Example 1-2, after the application of the first composition, the second composition was spin-coated on the region to which the first composition was applied after 5 minutes. In Comparative Example 1-2, when the second composition was applied, the uneven pattern was exposed from the first composition.
其次，於塗佈後，在室溫(25℃)下進行30分鐘自然乾燥而獲得圖案形成體。 Next, after coating, it was naturally dried at room temperature (25 ° C) for 30 minutes to obtain a pattern formed body.
<塗佈不均的評價> <Evaluation of uneven coating>
藉由光學顯微鏡(×10倍)評價藉由所述方法而所得的圖案形成體的塗佈不均。 Coating unevenness of the pattern formation body obtained by the above method was evaluated by an optical microscope (×10×).
A：於塗佈面無收縮或凝聚，未觀察到塗佈不均 A: no shrinkage or agglomeration on the coated surface, no uneven coating was observed
B：於塗佈面存在收縮或凝聚，觀察到塗佈不均 B: shrinkage or agglomeration on the coated surface, uneven coating was observed
<圖案崩塌的評價> <Evaluation of pattern collapse>
藉由原子力顯微鏡(AFM、布魯克AXS(Bruker AXS)公司製造的Dimension Icon)觀察藉由所述方法而所得的圖案形成體的5μm×5μm的範圍，藉由以下基準進行評價。 The range of 5 μm × 5 μm of the pattern formed body obtained by the above method was observed by an atomic force microscope (AFM, Dimension Icon manufactured by Bruker AXS), and evaluated by the following criteria.
A：遍及観察範圍的整個面，確認良好的圖案轉印 A: Confirm the good pattern transfer throughout the entire surface of the inspection range
B：於観察範圍的不足10%的區域確認到圖案崩塌 B: Pattern collapse is confirmed in an area of less than 10% of the inspection area
C：於観察範圍的10%~70%的區域發現圖案崩塌 C: Pattern collapse occurred in the area of 10% to 70% of the inspection range
D：遍及観察範圍的整個面發生圖案崩塌 D: Pattern collapse occurs throughout the entire surface of the observation range
<圖案粗糙的評價> <Evaluation of pattern roughness>
使用原子力顯微鏡(AFM、布魯克AXS(Bruker AXS)公司製造的Dimension Icon)觀察藉由所述方法而所得的圖案形成體的平坦部的5μm×5μm的範圍而測定表面粗糙度(Ra、單位為nm)，藉由以下基準進行評價。 The surface roughness (Ra, unit of nm) was measured by observing the range of 5 μm × 5 μm of the flat portion of the pattern formed body obtained by the above method using an atomic force microscope (AFM, Dimension Icon manufactured by Bruker AXS). ), evaluated by the following criteria.
A：Ra≦1 A:Ra≦1
B：1≦Ra≦2 B: 1≦Ra≦2
C：2≦Ra C: 2≦Ra
如上述表所示，藉由本發明的方法而所得的實施例的圖案形成體無圖案缺陷。另外，亦無圖案粗糙、及塗佈不均。 As shown in the above table, the pattern forming body of the example obtained by the method of the present invention has no pattern defects. In addition, there is no pattern roughness and uneven coating.
相對於此，藉由比較例的方法而所得的圖案形成體存在圖案缺陷。 On the other hand, the pattern formed body obtained by the method of the comparative example had a pattern defect.
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| JP2001018526A (en) * | 1999-07-07 | 2001-01-23 | Mitsubishi Paper Mills Ltd | Thermosensitive recording material and manufacture thereof |
| US20030190432A1 (en) * | 2000-04-11 | 2003-10-09 | Yasuro Yokota | Process for producing information recording material and coating solutions for use therein |
| WO2010128684A1 (en) * | 2009-05-08 | 2010-11-11 | 新日本製鐵株式会社 | Surface-treated metal plate |
| WO2010134627A1 (en) * | 2009-05-21 | 2010-11-25 | 新日本製鐵株式会社 | Process for producing multilayer-coated metal sheet |
| JP2012200637A (en) * | 2011-03-24 | 2012-10-22 | Seiko Epson Corp | Method of forming processing layer and optical article |
| WO2013024784A1 (en) * | 2011-08-12 | 2013-02-21 | 日本ペイント株式会社 | Method for forming multilayer coating film |
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| WO2001076884A1 (en) * | 2000-04-11 | 2001-10-18 | Mitsubishi Paper Mills Ltd. | Method for producing information recording material and coating liquid for use therein |
| JP2010113761A (en) * | 2008-11-06 | 2010-05-20 | Fuji Electric Device Technology Co Ltd | Spin-coating method and controller of spin-coating apparatus |
| JP5384437B2 (en) * | 2010-06-18 | 2014-01-08 | 東京エレクトロン株式会社 | Application method |
| CN103442813B (en) * | 2011-03-31 | 2016-10-12 | 大日本涂料株式会社 | Multilayer film and the manufacture method of this multilayer film |
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| JP2001018526A (en) * | 1999-07-07 | 2001-01-23 | Mitsubishi Paper Mills Ltd | Thermosensitive recording material and manufacture thereof |
| US20030190432A1 (en) * | 2000-04-11 | 2003-10-09 | Yasuro Yokota | Process for producing information recording material and coating solutions for use therein |
| WO2010128684A1 (en) * | 2009-05-08 | 2010-11-11 | 新日本製鐵株式会社 | Surface-treated metal plate |
| WO2010134627A1 (en) * | 2009-05-21 | 2010-11-25 | 新日本製鐵株式会社 | Process for producing multilayer-coated metal sheet |
| JP2012200637A (en) * | 2011-03-24 | 2012-10-22 | Seiko Epson Corp | Method of forming processing layer and optical article |
| WO2013024784A1 (en) * | 2011-08-12 | 2013-02-21 | 日本ペイント株式会社 | Method for forming multilayer coating film |
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