TWI564276B - Liquid photoinitiator and applications thereof - Google Patents
Liquid photoinitiator and applications thereof Download PDFInfo
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- TWI564276B TWI564276B TW105107755A TW105107755A TWI564276B TW I564276 B TWI564276 B TW I564276B TW 105107755 A TW105107755 A TW 105107755A TW 105107755 A TW105107755 A TW 105107755A TW I564276 B TWI564276 B TW I564276B
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- Prior art keywords
- photoinitiator
- group
- compound
- photopolymerizable
- following formula
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- 239000007788 liquid Substances 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- 229960002130 benzoin Drugs 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000012958 Amine synergist Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- WSFJFIDCQBAQQZ-UHFFFAOYSA-N hydroxy(sulfido)phosphanium Chemical compound S[PH2]=O WSFJFIDCQBAQQZ-UHFFFAOYSA-N 0.000 claims description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 150000002429 hydrazines Chemical class 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000000976 ink Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 229920002101 Chitin Polymers 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- CDPUNDLWVGKZHS-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-[4-[2-hydroxyethyl(methyl)amino]phenyl]butan-1-one Chemical compound C=1C=C(N(C)CCO)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 CDPUNDLWVGKZHS-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000010546 Norrish type I reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- -1 acyl phosphine oxide, Chemical compound 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000012395 formulation development Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000007696 reproductive toxicity Effects 0.000 description 1
- 231100000372 reproductive toxicity Toxicity 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polymerisation Methods In General (AREA)
Description
本發明係關於一種液態光引發劑及其應用，尤其關於該液態光引發劑於低黏度油墨及可光聚合材料中之應用。 This invention relates to a liquid photoinitiator and its use, and in particular to the use of the liquid photoinitiator in low viscosity inks and photopolymerizable materials.
光引發劑(photoinitiator)係一種可吸收例如可見光或紫外光能量而達激發態，並發生羅氏一型(Norrish Type I)光反應，***出自由基，從而引發單體(monomers)或寡聚體(oligomers)交聯聚合，達固化效果的物質。 A photoinitiator is a type that absorbs, for example, visible or ultraviolet light energy to an excited state, and undergoes a Norrish Type I photoreaction to split out free radicals, thereby initiating monomers or oligomers. (oligomers) cross-linking polymerization, a substance that achieves a curing effect.
汽巴-嘉基公司(Ciba-Geigy Corporation)於1990年研發出第一支適用於黑色UV油墨的固態引發劑產品「Irgacure® 369」(相關專利：US 5,077,402)，其化學結構顯示於下方。Irgacure® 369之光引發性能(如光速度)表現優異，但其於一般UV油墨中之溶解度不佳，必須透過長時間研磨等工序來溶解，然而這種操作往往會引發部分聚合或黏度改變，導致必須於油墨中進一步添加阻聚劑，使得配方開發變數增多，而且適用期(pot-life)變短。Irgacure® 369的另一個嚴重缺點是在用量多於4重量%時，存在容易析出的問題(尤其在寒帶地區)，使其在應用上受到限制。 In 1990, Ciba-Geigy Corporation developed the first solid-state initiator product "Irgacure ® 369" for black UV inks (related patent: US 5,077,402), the chemical structure of which is shown below. Irgacure ® 369 exhibits excellent light-initiating properties (such as light speed), but its solubility in general UV inks is poor and must be dissolved by long-term grinding processes. However, this operation often causes partial polymerization or viscosity changes. This has led to the necessity to further add a polymerization inhibitor to the ink, which has led to an increase in formulation development variables and a shorter pot-life. Another serious disadvantage of Irgacure ® 369 is that there is a problem of easy precipitation (especially in cold regions) when the amount is more than 4% by weight, which limits its application.
[Irgacure® 369] [Irgacure ® 369]
為改善溶解度問題，汽巴公司推出第二支固態光引發劑產品「Irgacure® 379」(相關專利：US 7247659 B2)，其化學結構顯示於下方。Irgacure® 379於某些油墨配方中的溶解度有所提升，但缺點是仍然為固體，因此還是必須經過研磨工序才能應用至油墨配方中。 To improve solubility, Ciba launched the second solid photoinitiator product, Irgacure ® 379 (related patent: US 7247659 B2), whose chemical structure is shown below. Irgacure ® 379 has improved solubility in certain ink formulations, but the disadvantage is that it is still solid and must be subjected to a grinding process before it can be applied to the ink formulation.
[Irgacure® 379] [Irgacure ® 379]
近年來，由於數位印刷(digital printing)、凹版印刷(gravure printing)、柔版印刷(flexographic printing)等印刷技術之蓬勃發展，低黏度油墨的需求日漸增加。低黏度油墨的製造工序中，最佳工藝是將各成分簡單混合後攪拌均勻即可製作完成，毋須研磨工序。因此，上述需經過研磨工序的固態光引發劑並不適合應用於此類低黏度油墨之中，一般多採用具良好混溶 性的液態光引發劑產品。 In recent years, demand for low-viscosity inks has increased due to the booming printing technologies such as digital printing, gravure printing, and flexographic printing. In the manufacturing process of the low-viscosity ink, the optimum process is to simply mix the components and stir them evenly, and the polishing process is not required. Therefore, the above solid photoinitiator which needs to be subjected to a grinding process is not suitable for use in such a low-viscosity ink, and generally has a good miscibility. Sexual liquid photoinitiator products.
關於液態光引發劑，TW I277834B首先介紹如下化學式I所示之α-氨基酮(α-aminoketone)衍生物： Regarding the liquid photoinitiator, TW I277834B first introduces an α-aminoketone derivative represented by the following chemical formula I:
[369N/R-gen® 998] [369N/R-gen ® 998]
[3690/Chivacure® 3690] [3690/Chivacure ® 3690]
US 7,732,504同樣針對α-氨基酮類化合物作了廣泛的衍生物研究，惟並未就於低黏度油墨之適用性進行探討。US 7,732,504說明書中揭露諸多態樣，包括實施例8及實施例10所例示之常溫下為液體的態樣，其化學結構顯示於下方。然而，實施例8及10之光引發成分光速度不佳；尤其，實施例8之光引發成分合成不易，且黏度高，並不適合應用於低黏度油墨，而實施例10之光引發成分更存在會散發氣味且具生殖毒性之缺點。 US 7,732,504 also conducts extensive derivatives studies for α-aminoketones, but does not discuss the suitability of low viscosity inks. A number of aspects are disclosed in the specification of US 7,732,504, including the liquid state at room temperature exemplified in Example 8 and Example 10, the chemical structure of which is shown below. However, the light-initiating components of Examples 8 and 10 have poor light speed; in particular, the photoinitiating component of Example 8 is difficult to synthesize and has high viscosity, and is not suitable for use in a low-viscosity ink, and the photoinitiating component of Example 10 is more present. It will emit odor and has the disadvantage of reproductive toxicity.
[US 7,732,504/實施例8] [US 7,732,504/Embodiment 8]
[US 7,732,504/實施例10] [US 7,732,504/Example 10]
US 5,077,402同樣揭露多種液態之α-氨基酮衍生物，但所揭露之物質仍然存在光速度表現差、容易遷移、會散發臭味等諸多缺點，仍無法滿足業界之需求。 US 5,077,402 also discloses various liquid α-aminoketone derivatives, but the disclosed materials still have many shortcomings such as poor light speed performance, easy migration, and odor emission, and still cannot meet the needs of the industry.
鑒於習知光引發劑存在上述諸多缺點，無法滿足業界需求，本發明提供一種液態光引發劑，於室溫下具有流動性、光速度優異、對低黏度油墨黏度影響低、儲存穩定性高且不釋放氣味，可充分滿足業界對於低黏度油墨之光引發劑要求。 In view of the above-mentioned shortcomings of the conventional photoinitiators, which cannot meet the needs of the industry, the present invention provides a liquid photoinitiator which has excellent fluidity, high light velocity, low viscosity to low viscosity ink, high storage stability and no release at room temperature. Odor can fully meet the industry's requirements for photoinitiators for low viscosity inks.
本發明之一目的在於提供一種液態光引發劑，包含具如下化學式II之化合物作為第一光引發成分： It is an object of the present invention to provide a liquid photoinitiator comprising a compound of the following formula II as a first photoinitiating component:
於本發明之部分實施態樣中，R2為伸乙基，且R3為甲基。 In some embodiments of the invention, R 2 is an exoethyl group and R 3 is a methyl group.
於本發明之部分實施態樣中，該第一光引發成分係如下化學式IIa所表示者：[化學式IIa]
於本發明之部分實施態樣中，上述液態光引發劑更包含選自以下群組之光敏成分(photosensitizing component)：二苯甲酮類(benzophenones)、氧硫類(thioxanthones)、米其勒酮類(Michler’s ketones)及蒽醌(anthraquinone)。 In some embodiments of the present invention, the liquid photoinitiator further comprises a photosensitizing component selected from the group consisting of benzophenones and oxygen sulphur. Classes (thioxanthones), Michler's ketones and anthraquinone.
於本發明之部分實施態樣中，上述液態光引發劑更包含一選自以下群組之第二光引發成分：苯偶姻(benzoin)、醯基膦氧化物(acyl phosphine oxide)、及前述之組合。 In some embodiments of the present invention, the liquid photoinitiator further comprises a second photoinitiating component selected from the group consisting of benzoin, acyl phosphine oxide, and the foregoing The combination.
於本發明之部分實施態樣中，上述液態光引發劑係由具化學式II之化合物所構成。 In some embodiments of the invention, the liquid photoinitiator is comprised of a compound of formula II.
本發明之另一目的在於提供一種上述液態光引發劑於低黏度油墨中的用途，其中該低黏度油墨之黏度係低於1000厘泊(cps)。 Another object of the present invention is to provide a use of the above liquid photoinitiator in a low viscosity ink wherein the viscosity of the low viscosity ink is less than 1000 centipoise (cps).
本發明之又一目的在於提供一種可光聚合的組合物，包含上述液態光引發劑、可光聚合之單體及可光聚合之寡聚體。 It is still another object of the present invention to provide a photopolymerizable composition comprising the above liquid photoinitiator, photopolymerizable monomer and photopolymerizable oligomer.
於本發明之部分實施態樣中，該可光聚合之單體係丙烯酸酯系單體，且該可光聚合之寡聚體係丙烯酸酯系寡聚體。 In some embodiments of the invention, the photopolymerizable single system acrylate monomer, and the photopolymerizable oligomer system acrylate oligomer.
於本發明之部分實施態樣中，該可光聚合的組合物更包含選自以下群組之添加劑：顏料、胺綜效劑(amine synergist)及其組合。 In some embodiments of the invention, the photopolymerizable composition further comprises an additive selected from the group consisting of pigments, amine synergists (amine) Synergist) and its combinations.
為讓本發明之上述目的、技術特徵及優點能更明顯易懂，下文係以部分具體實施態樣進行詳細說明。 The above described objects, technical features and advantages of the present invention will become more apparent from the following detailed description.
以下將具體地描述根據本發明之部分具體實施態樣；惟，在不背離本發明之精神下，本發明尚可以多種不同形式之態樣來實踐，不應將本發明保護範圍解釋為限於說明書所陳述之具體實施態樣。此外，除非另有說明，於本說明書中(尤其是在後述專利申請範圍中)所使用之「一」、「該」及類似用語應理解為包含單數及複數形式。 The invention will be described in detail below with reference to the specific embodiments of the present invention. The invention may be practiced in various different forms without departing from the spirit and scope of the invention. The specific implementation stated. In addition, the terms "a", "an" and "the"
研究發現，本發明之第一光引發成分結構與前述R-gen® 998化合物之差異雖僅在末端係經乙醯化(acetylation)，但卻意外的展現出迥異於R-gen® 998化合物的物化性質，包括：於室溫下即為液態，不需經過加熱或研磨工序即可直接應用，而且不會顯著增加系統的黏度；具有與Irgacure® 369相當的光速度，光引發性能表現優異；以及長時間儲存黏度亦不生明顯變化，儲存穩定性良好。以上諸多優點使得本發明之第一光引發成分非常適用於低黏度UV油墨中作為光引發劑。另須說明者，雖然本發明第一光引發成分之結構與TW I277834及US 7,732,504所揭露之部分態樣相近，但仍存在差異，且該差異出乎意料地使得第一光引發成分在光引發劑應用上具備諸多優點，提供了全方位的改良。 It was found that the difference between the structure of the first photoinitiator component of the present invention and the aforementioned R-gen ® 998 compound is only acetylation at the end, but unexpectedly exhibits a difference from the R-gen ® 998 compound. Physicochemical properties, including: liquid at room temperature, can be directly applied without heating or grinding process, and does not significantly increase the viscosity of the system; has the same speed of light as Irgacure ® 369, excellent photoinitiation performance; And the long-term storage viscosity does not change significantly, and the storage stability is good. Many of the above advantages make the first photoinitiating component of the present invention very suitable for use as a photoinitiator in low viscosity UV inks. It should be noted that although the structure of the first photoinitiator component of the present invention is similar to that of TW I277834 and US 7,732,504, there are still differences, and the difference unexpectedly causes the first photoinitiator component to be photoinitiated. The application has many advantages and provides a comprehensive improvement.
特定言之，本發明之液態光引發劑包含具如下化學
式II之化合物，作為第一光引發成分：
具化學式II之化合物可藉由乙醯化作用(acetylation)合成。詳細合成方式將於後附實施例中說明，於此不另贅述。 Compounds of formula II can be synthesized by acetylation. The detailed synthesis will be described in the following examples, and will not be further described herein.
具化學式II之化合物在室溫下為液態，為本發明液態光引發劑之光引發成分(第一光引發成分)，於受光(如紫外光)照射後可產生自由基，從而引發單體或寡聚體之交聯聚合反應，產生固化效果。除第一光引發成分外，本發明液態光引發劑 亦可視需要包含其他有助於光引發效果之成分，例如光敏成分或其他光引發成分，以提供組合效果。舉例言之，可包含選自以下群組之光敏成分：二苯甲酮類(benzophenones)、氧硫類(thioxanthones)、米其勒酮類(Michler’s ketones)及蒽醌(anthraquinone)，於不受理論限制下，咸信光敏成分可產生奪氫反應(hydrogen abstraction)，而促進光固化反應；另外，亦可包含一選自以下群組之第二光引發成分：苯偶姻(benzoin)、醯基膦氧化物、及前述之組合。於後附實施例之具體實施態樣中，本發明之液態光引發劑可更包含2,4-二乙基氧硫(品名Chivacure® DETX)。 The compound of the formula II is liquid at room temperature, and is a photoinitiator (first photoinitiator) of the liquid photoinitiator of the present invention, which generates a radical after being irradiated by light (such as ultraviolet light), thereby initiating a monomer or The cross-linking polymerization of the oligomer produces a curing effect. In addition to the first photoinitiating component, the liquid photoinitiator of the present invention may optionally contain other components which contribute to the photoinitiating effect, such as photosensitive components or other photoinitiating components, to provide a combined effect. For example, a photosensitive component selected from the group consisting of benzophenones, oxysulfide may be included The thioxanthones, Michler's ketones and anthraquinone, under the theoretical limitation, can produce a hydrogen abstraction and promote a photocuring reaction; A second photoinitiating component selected from the group consisting of benzoin, mercaptophosphine oxide, and combinations of the foregoing may also be included. In a specific embodiment of the following examples, the liquid photoinitiator of the present invention may further comprise 2,4-diethyloxysulfide. (named Chivacure ® DETX).
本發明光引發劑於室溫下為液態，可適合添加於低黏度油墨中作為光引發劑組分。低黏度油墨一般係指黏度低於1000厘泊之油墨而言。本發明液態光引發劑於油墨中的使用量並無特殊限制，可由本領域具通常知識者視需要進行調配。一般而言，為獲致所欲之光固化效果，以油墨之總重計，光引發劑之含量為約1重量%至約15重量%，例如約5重量%至約10重量%，如6重量%、7重量%、8重量%或9重量%，但並不以此為限。 The photoinitiator of the present invention is liquid at room temperature and can be suitably added to a low viscosity ink as a photoinitiator component. Low viscosity inks generally refer to inks having a viscosity of less than 1000 centipoise. The amount of the liquid photoinitiator used in the ink is not particularly limited and can be formulated as needed by those skilled in the art. In general, the photoinitiator is present in an amount of from about 1% by weight to about 15% by weight, such as from about 5% by weight to about 10% by weight, such as 6 weights, based on the total weight of the ink, in order to achieve the desired photocuring effect. %, 7% by weight, 8% by weight or 9% by weight, but not limited thereto.
本發明之液態光引發劑可促使可光聚合之單體或寡聚體之交聯聚合固化。因此，本發明另提供一種可光聚合的組合物，包含本發明之液態光引發劑、可光聚合之單體及可光聚合之寡聚體。該可光聚合之單體及寡聚體之種類並無特殊限制，可為任何可光聚合之物質，例如是烯鍵系不飽和基團之單體及寡聚體。於本發明之部分實施態樣中，該可光聚合之單體係丙烯酸酯系單體，且該可光聚合之寡聚體係丙烯酸酯系寡聚體。 The liquid photoinitiator of the present invention promotes cross-linking polymerization of photopolymerizable monomers or oligomers. Accordingly, the present invention further provides a photopolymerizable composition comprising the liquid photoinitiator, photopolymerizable monomer and photopolymerizable oligomer of the present invention. The kind of the photopolymerizable monomer and the oligomer is not particularly limited, and may be any photopolymerizable substance such as a monomer and an oligomer of an ethylenically unsaturated group. In some embodiments of the invention, the photopolymerizable single system acrylate monomer, and the photopolymerizable oligomer system acrylate oligomer.
視需要地，可於本發明之可光聚合的組合物中進一步包含一或多種添加劑，以提供所欲之物化性質。例如可添加顏料以賦予產物顏色，或可添加胺綜效劑(amine synergist)，以提升固化表現，例如提高組合物之表面固化速度及乾燥後的鏡面效果。常見顏料之實例包括二氧化鈦、碳黑、鎘紅、鉬紅、鉻黃、鎘黃、鈦黃、氧化鉻、鈦鈷綠、青藍、鈷藍、偶氮系顏料、酞青顏料(phthalocyanine pigments)、煃吖啶酮系顏料(quinacridone based pigments)、異吲哚啉酮系顏料(isoindolinone based pigments)、苝系顏料(perylene based pigments)、硫靛系顏料(thio indigo based pigments)及金屬錯合物顏料。常見之胺綜效劑實例包括甲基二乙醇胺、二丁基乙醇胺、三乙基胺、及三乙醇胺。 Optionally, one or more additives may be included in the photopolymerizable composition of the present invention to provide the desired physicochemical properties. For example, a pigment may be added to impart a color to the product, or an amine synergist may be added to enhance the curing performance, such as increasing the surface curing speed of the composition and the mirror effect after drying. Examples of common pigments include titanium dioxide, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, titanium cobalt green, cyan blue, cobalt blue, azo pigments, phthalocyanine pigments. , quinacridone based pigments, isoindolinone based pigments, perylene based pigments, thio indigo based pigments, and metal complexes pigment. Examples of common amine complexes include methyldiethanolamine, dibutylethanolamine, triethylamine, and triethanolamine.
本發明之可光聚合的組合物亦可視需要包含溶劑，以促進組合物各成分之均勻混合。所述溶劑可為任何可溶解或分散組合物各成分，但不與之反應的溶劑。溶劑之實例包括但不限於：水；脂肪烴系溶劑，例如二氯甲烷、三氯甲烷、四氯甲烷、正己烷及環己烷；芳香烴系溶劑，例如甲苯、苯及二甲苯；酮系溶劑，例如丙酮、甲基乙基酮、異丁酮及環己酮；酯系溶劑，例如乙酸乙酯及乙酸丁酯；醇系溶劑，例如甲醇、乙醇、正丙醇及異丙醇；及醚系溶劑，例如二甲醚、二***及甲基乙基醚。 The photopolymerizable compositions of the present invention may also optionally contain a solvent to promote uniform mixing of the ingredients of the composition. The solvent can be any solvent that does not dissolve or disperse the components of the composition, but does not react with it. Examples of the solvent include, but are not limited to, water; aliphatic hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, n-hexane, and cyclohexane; aromatic hydrocarbon solvents such as toluene, benzene, and xylene; a solvent such as acetone, methyl ethyl ketone, isobutyl ketone or cyclohexanone; an ester solvent such as ethyl acetate and butyl acetate; an alcohol solvent such as methanol, ethanol, n-propanol and isopropanol; Ether solvents such as dimethyl ether, diethyl ether and methyl ethyl ether.
茲以下列具體實施態樣進一步例示說明本發明。 The invention is further illustrated by the following specific embodiments.
實施例Example
[製備例1：具化學式IIa結構之化合物(第一光引發成分)之製備] [Preparation Example 1: Preparation of Compound (Structure of First Photoinitiator) of Structure of Chemical Formula IIa]
取250毫升三頸圓底瓶，於室溫下依序加入30克2-(二甲基氨基)-1-[4-[(2-羥乙基)甲基氨基]苯基]-2-(苯基甲基)-1-丁酮(商品名：R-gen® 998，奇鈦科技股份有限公司)、10.4克醋酸酐及45克甲苯並均勻攪拌之。接著升溫至110℃，回流3小時，以高效能液相層析儀(High Performance Liquid Chromatography，HPLC)確認反應完成後，以50克純水萃取三次。收集有機層並在真空下進行濃縮，獲得具化學式IIa結構之化合物(下稱『化合物IIa』)之棕色黏稠狀液體，產率為80%。 Take a 250 ml three-necked round bottom flask and add 30 g of 2-(dimethylamino)-1-[4-[(2-hydroxyethyl)methylamino]phenyl]-2- (Phenylmethyl)-1-butanone (trade name: R-gen ® 998, Chitin Technology Co., Ltd.), 10.4 g of acetic anhydride and 45 g of toluene and uniformly stirred. Subsequently, the temperature was raised to 110 ° C, refluxed for 3 hours, and after confirming completion of the reaction by High Performance Liquid Chromatography (HPLC), it was extracted three times with 50 g of pure water. The organic layer was collected and concentrated under vacuum to give a brown viscous liquid of the compound of the formula IIa (hereinafter referred to as "compound IIa") in a yield of 80%.
化合物IIa之性質測定： Determination of the nature of compound IIa:
1H NMR(300MHz,CDCl3)：0.65-0.70(t,3H,-COC(CH2CH 3)-),1.82-1.92(m,1H,-COC(CH 2CH3),2.00(s,3H,-N(CH3)CH2CH2OCOCH 3),1.98-2.08(m,1H,-COC(CH 2CH3)-,2.35(s,6H,-COCN(CH 3)2-),3.05(s,3H,-N(CH 3)CH2CH2OCOCH3),3.18-3.19(d,1H,-COC(CH 2ArH)-,3.19-3.20(d,1H,-COC(CH 2ArH)-,3.64-3.68(t,2H,-N(CH3)CH 2CH2OCOCH3),4.25-4.29(t,2H,-N(CH3)CH2CH 2OCOCH3),6.62-6.65(d,2H,-ArHCO-),7.15-7.24(m,5H,-COC(CH2ArH)-),8.34-8.37(d,2H,-ArHCO-)。元素分析：理論值：C%=72.70，H%=8.13，N%=7.06，O%=12.11；實驗值：C%=72.46，H%=8.13，N%=7.08，O%=12.33。高解析度質譜分析(快速原子撞擊)(HRMS(FAB))：理論值：397.52；實際值：397.50。 1 H NMR (300 MHz, CDCl 3 ): 0.65-0.70 (t, 3H, -COC (CH 2 C H 3 )-), 1.82-1.92 (m, 1H, -COC (C H 2 CH 3 ), 2.00 ( s, 3H, -N(CH 3 )CH 2 CH 2 OCOC H 3 ), 1.98-2.08 (m, 1H, -COC(C H 2 CH 3 )-, 2.35 (s, 6H, -COCN (C H 3 2 -), 3.05 (s, 3H, -N(C H 3 )CH 2 CH 2 OCOCH 3 ), 3.18-3.19 (d, 1H, -COC(C H 2 ArH)-, 3.19-3.20 (d, 1H,-COC(C H 2 ArH)-, 3.64-3.68(t,2H,-N(CH 3 )C H 2 CH 2 OCOCH 3 ), 4.25-4.29(t,2H,-N(CH 3 )CH 2 C H 2 OCOCH 3 ), 6.62-6.65 (d, 2H, -Ar H CO-), 7.15-7.24 (m, 5H, -COC(CH 2 Ar H )-), 8.34 - 8.37 (d, 2H, -Ar H CO-). Elemental analysis: Theoretical value: C% = 72.70, H% = 8.13, N% = 7.06, O% = 12.1; Experimental value: C% = 72.46, H% = 8.13, N% = 7.08 , O% = 12.33. High-resolution mass spectrometry (fast atomic impact) (HRMS (FAB)): theoretical value: 397.52; actual value: 397.50.
[實施例1：溶解性測試] [Example 1: Solubility test]
以如下比例配製混合物I至III。接著於混合物I至III中分別添加6重量份的比較化合物Irgacure® 369及化合物IIa，並將所得混合物於室溫下超音波震盪1小時，觀察其溶解情形，並將結果記錄於下表1。 Mixtures I to III were prepared in the following ratios. Next, 6 parts by weight of Comparative Compound Irgacure ® 369 and Compound IIa were separately added to the mixtures I to III, and the resulting mixture was ultrasonically shaken at room temperature for 1 hour, and the dissolution thereof was observed, and the results were recorded in Table 1 below.
混合物I：50重量份1,6-己二醇二丙烯酸酯(1,6-Hexanediol Diacrylate)(商品名：EM221；長興化學工業股份有限公司)與50重量份四官能基聚酯丙烯酸酯(Polyester Tetraacrylate)(商品名：Oligomer 6325-100；長興化學工業股份有限公司)之混合物；黏度為41.2厘泊(cps)。 Mixture I: 50 parts by weight of 1,6-Hexanediol Diacrylate (trade name: EM221; Changxing Chemical Industry Co., Ltd.) and 50 parts by weight of tetrafunctional polyester acrylate (Polyester) Tetraacrylate) (trade name: Oligomer 6325-100; Changxing Chemical Industry Co., Ltd.); a viscosity of 41.2 centipoise (cps).
混合物II：50重量份三羥甲基丙烷三丙烯酸脂(Trimethylolpropane triacrylate)(商品名：EM231；長興化學工業股份有限公司)與50重量份四官能基聚酯丙烯酸酯(商品名：Oligomer 6325-100；長興化學工業股份有限公司)之混合物；黏度為349.5厘泊。 Mixture II: 50 parts by weight of Trimethylolpropane triacrylate (trade name: EM231; Changxing Chemical Industry Co., Ltd.) and 50 parts by weight of tetrafunctional polyester acrylate (trade name: Oligomer 6325-100 ; Changxing Chemical Industry Co., Ltd.) mixture; viscosity is 349.5 centipoise.
混合物III：50重量份乙氧化季戊四醇四丙烯酸酯(Ethoxylated Pentaerythritol Tetraacrylate)(商品名：EM2411；長興化學工業股份有限公司)與50重量份四官能基聚酯丙烯酸酯(商品名：Oligomer 6325-100；長興化學工業股份有限公司)之混合物；黏度為433.0厘泊。 Mixture III: 50 parts by weight of Ethoxylated Pentaerythritol Tetraacrylate (trade name: EM2411; Changxing Chemical Industry Co., Ltd.) and 50 parts by weight of a tetrafunctional polyester acrylate (trade name: Oligomer 6325-100; A mixture of Changxing Chemical Industry Co., Ltd.; viscosity is 433.0 cps.
如表1所示，於室溫下超音波震盪1小時後，僅化合物IIa於各混合物中均為完全溶解，此顯示化合物IIa於低黏度混合物中之溶解性明顯優於固態光引發劑Irgacure® 369。 As shown in Table 1, after supersonic oscillation for 1 hour at room temperature, only Compound IIa was completely dissolved in each mixture, which showed that the solubility of Compound IIa in the low viscosity mixture was significantly better than that of the solid photoinitiator Irgacure ® . 369.
[實施例2：黏度變化測試] [Example 2: Viscosity change test]
於混合物I至III中分別添加4重量份的光引發劑Irgacure® 369、R-gen® 998(光引發劑；奇鈦科技股份有限公司)及本發明化合物IIa，置於0℃的環境下七天，分別量測暴露前後之黏度，並將結果記錄於下表2。 4 parts by weight of photoinitiator Irgacure ® 369, R-gen ® 998 (photoinitiator; Chitin Technology Co., Ltd.) and the compound IIa of the present invention were added to the mixtures I to III, respectively, and placed in an environment of 0 ° C for seven days. The viscosity before and after exposure was measured separately, and the results were recorded in Table 2 below.
如表2所示，化合物IIa對於低黏度混合物之黏度影響甚微，且明顯小於Irgacure® 369與R-gen® 998，且在暴露於0℃環境下七天後，添加化合物IIa之混合物其黏度變化情形大致與未添加光引發劑者一致，且無析出問題。此顯示化合物IIa 的穩定性(尤其在於寒帶地區)優於Irgacure® 369，實用性佳。 As shown in Table 2, compound IIa had little effect on the viscosity of the low viscosity mixture and was significantly smaller than Irgacure ® 369 and R-gen ® 998, and the viscosity of the mixture of compound IIa was changed after seven days of exposure to 0 °C. The situation is roughly the same as that without the addition of photoinitiator, and there is no problem of precipitation. This shows that the stability of compound IIa (especially in the cold zone) is superior to Irgacure ® 369, and it is practical.
[實施例3：光速度性能(photo speed performance)測試] [Example 3: Photo speed performance test]
將黑色柔版印刷配方(black flexo formulation；含Oligomer 6325-100、EM2411、碳黑；黏度1750cps)與光引發劑混合，以進行光速度測試。具體言之，取100重量份之黑色柔版印刷配方和2重量份Chivacure® DETX(光引發劑；奇鈦科技股份有限公司)，並於所得混合物中分別添加6重量份之Irgacure® 369、Chivacure® 3690(光引發劑；奇鈦科技股份有限公司)、R-gen® 998(光引發劑；奇鈦科技股份有限公司)及化合物IIa，以完成黑色柔版印刷油墨調配；接著將黑色柔版印刷油墨塗佈於可印刷之珠光膜上(濕膜膜厚25.15微米)，並暴露在UV燈系統(Fusion F300；D-bulb；300瓦/英寸)下進行固化，觀察其光速度性能。結果記錄於下表3。 A black flexo formulation (containing Oligomer 6325-100, EM 2411, carbon black; viscosity 1750 cps) was mixed with a photoinitiator for light speed testing. Specifically, 100 parts by weight of a black flexographic printing formulation and 2 parts by weight of Chivacure ® DETX (Photoinitiator; Chitin Technology Co., Ltd.) were taken, and 6 parts by weight of Irgacure ® 369, Chivacure were separately added to the obtained mixture. ® 3690 (photoinitiator; Chitin Technology Co., Ltd.), R-gen ® 998 (photoinitiator; Chitin Technology Co., Ltd.) and compound IIa to complete black flexo printing ink formulation; then black flexo The printing ink was applied to a printable pearlescent film (wet film thickness 25.15 μm) and cured by exposure to a UV lamp system (Fusion F300; D-bulb; 300 W/inch) to observe its light speed performance. The results are reported in Table 3 below.
如表3所示，化合物IIa之光速度性能表現優異，與Irgacure® 369相當，且明顯優於R-gen® 998與Chivacure® 3690。 As shown in Table 3, Compound IIa exhibited excellent light speed performance, comparable to Irgacure ® 369, and was significantly better than R-gen ® 998 and Chivacure ® 3690.
製備例1與實施例1至實施例3之結果顯示，本發明之光引發劑於室溫下為液態且溶解性優異，應用時對系統黏度之影響甚微，具長時間儲存穩定性，且光引發性能表現優異，非 常適用於低黏度UV油墨中作為光引發劑。 The results of Preparation Example 1 and Examples 1 to 3 show that the photoinitiator of the present invention is liquid at room temperature and has excellent solubility, has little effect on system viscosity during application, and has long-term storage stability, and Excellent light-emitting performance, non- Often used as a photoinitiator in low viscosity UV inks.
上述實施例僅為例示性說明本發明之原理及其功效，並闡述本發明之技術特徵，而非用於限制本發明之保護範疇。任何熟悉本技術者在不違背本發明之技術原理及精神下，可輕易完成之改變或安排，均屬本發明所主張之範圍。因此，本發明之權利保護範圍係如後附申請專利範圍所列。 The above embodiments are merely illustrative of the principles and effects of the present invention, and are illustrative of the technical features of the present invention and are not intended to limit the scope of the present invention. Any changes or arrangements that can be easily accomplished by those skilled in the art without departing from the technical principles and spirit of the invention are within the scope of the invention. Accordingly, the scope of the invention is set forth in the appended claims.
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| TW200602808A (en) * | 2004-02-02 | 2006-01-16 | Ciba Sc Holding Ag | Functionalized photoinitiators |
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| US5077402A (en) * | 1987-03-26 | 1991-12-31 | Ciba-Geigy Corporation | Novel alpha-aminoacetophenones as photoinitiators |
| TW200602808A (en) * | 2004-02-02 | 2006-01-16 | Ciba Sc Holding Ag | Functionalized photoinitiators |
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