WO1999062962A1 - Novel photoinitiators and applications therefor - Google Patents
Novel photoinitiators and applications therefor Download PDFInfo
- Publication number
- WO1999062962A1 WO1999062962A1 PCT/US1999/012104 US9912104W WO9962962A1 WO 1999062962 A1 WO1999062962 A1 WO 1999062962A1 US 9912104 W US9912104 W US 9912104W WO 9962962 A1 WO9962962 A1 WO 9962962A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photoinitiator
- alkyl group
- photoinitiators
- present
- radiation
- Prior art date
Links
- 230000005855 radiation Effects 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 33
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 29
- 239000000835 fiber Substances 0.000 claims description 13
- WQINSVOOIJDOLJ-UHFFFAOYSA-N 2-(1,3-dioxoisoindol-2-yl)acetic acid Chemical compound C1=CC=C2C(=O)N(CC(=O)O)C(=O)C2=C1 WQINSVOOIJDOLJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 9
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 7
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 7
- 235000005513 chalcones Nutrition 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- UIYCHXAGWOYNNA-UHFFFAOYSA-N vinyl sulfide Chemical compound C=CSC=C UIYCHXAGWOYNNA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 4
- 239000000203 mixture Substances 0.000 abstract description 38
- 239000000178 monomer Substances 0.000 abstract description 24
- 238000010030 laminating Methods 0.000 abstract description 4
- -1 dichlorocarbene, diphenylcarbene Chemical class 0.000 description 30
- 238000001723 curing Methods 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 17
- 230000001070 adhesive effect Effects 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 16
- 150000003254 radicals Chemical group 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000006862 quantum yield reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 206010073306 Exposure to radiation Diseases 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 0 Cc(cc1)ccc1N(*)* Chemical compound Cc(cc1)ccc1N(*)* 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- PGRNEGLBSNLPNP-UHFFFAOYSA-N 1,6-dichloro-3-methylhex-1-ene Chemical compound ClC=CC(C)CCCCl PGRNEGLBSNLPNP-UHFFFAOYSA-N 0.000 description 1
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- MNTFMEKKNFHJGV-UHFFFAOYSA-N 2,2-diphenylethenylsulfanylbenzene Chemical compound C=1C=CC=CC=1SC=C(C=1C=CC=CC=1)C1=CC=CC=C1 MNTFMEKKNFHJGV-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
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000012958 Amine synergist Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- YQHHCMVUMULAPZ-UHFFFAOYSA-N C[CH2+] Chemical compound C[CH2+] YQHHCMVUMULAPZ-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000003211 polymerization photoinitiator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- WTXMTPLATLKWQS-UHFFFAOYSA-N propane Chemical compound CC[CH2+] WTXMTPLATLKWQS-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940080262 sodium tetrachloroaurate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- ZLUSCZLCHQSJRU-UHFFFAOYSA-N thallium(1+) Chemical compound [Tl+] ZLUSCZLCHQSJRU-UHFFFAOYSA-N 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/32—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to an acyclic carbon atom of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
Definitions
- the present invention relates to novel photoinitiators and methods for generating a reactive species using the photoinitiators.
- the present invention further relates to methods of polymerizing or photocuring polymerizable unsaturated material using the above-mentioned photoinitiators.
- polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beginning of the 20th century.
- Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives.
- chain polymerization is initiated by a reactive species which often is a free radical.
- the source of the free radicals is termed an initiator or photoinitiator.
- Improvements in free radical chain polymerization have focused both on the polymer being produced and the photoinitiator. Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.
- a free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule.
- a photoinitiator i.e., an initiator which absorbs light energy, may produce free radicals by either of two pathways: (1) the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals; or
- the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and/or former compound(s).
- R ⁇ , R2 and R 3 each independently represent H-, an alkyl group, a chalcone, phthaloylglycine, HSO 3 -,
- R 4 and R 5 each independently represent an alkyl group; x represents an alkyl group or
- z represents an alkyl group, an alkylaryl
- yi, y 2/ y 3 , y 4 and y 5 each independently represent H-, HSO 3 -,
- wavelength selective photoinitiators are produced having a desired absorption maximum varying from about 222 ran to about 390 ran.
- the present invention is directed to the above-described ⁇ -amine enol ether photoinitiators, compositions containing the same, and methods for generating a reactive species which includes providing one or more of the photoinitiators and irradiating the one or more photoinitiators.
- One of the main advantages of the photoinitiators of the present invention is that they efficiently generate one or more reactive species under extremely low energy lamps, such as excimer lamps and mercury lamps, as compared to prior art photoinitiators. Further, the photoinitiators of the present invention are as much as five times faster than the best prior art photoinitiators.
- the present invention is further directed to methods of using the above-described ⁇ -amine enol ether photoinitiators to polymerize and /or photocure a polymerizable material.
- the photoinitiators of the present invention result in rapid curing times in comparison to the curing times of prior art photoinitiators, even with relatively low output lamps.
- the present invention includes a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious wavelength specific photoinitiator composition described above. When an unsaturated oligomer/ monomer mixture is employed in place of the unsaturated monomer, curing is accomplished.
- the present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more ⁇ -amine enol ether photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition.
- the admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same.
- the present invention is also directed to an adhesive composition comprising an unsaturated polymerizable material admixed with one or more ⁇ -amine enol ether photoinitiators of the present invention.
- the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition, in which at least one layer is a nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
- the present invention is directed to energy-efficient, reactive, ⁇ -amine enol ether photoinitiators and methods for utilizing the same. More particularly, the present invention is directed to new photoinitiators having the following general formula:
- R 7 R and R 3 each independently represent
- H- an alkyl group, a chalcone, phthaloylglycine, HSO 3 -
- R and R 5 each independently represent an alkyl group; x represents an alkyl group or
- z represents an alkyl group, an alkylaryl group or ; wherein y l y 2 , y 3 , y 4 and y 5 each independently represent H-, HSO 3 -,
- NaS0 3 -, HOOC-, NaOOC- and an alkyl group NaS0 3 -, HOOC-, NaOOC- and an alkyl group.
- the present invention also includes a method of polymerizing an unsaturated polymerizable material by exposing the unsaturated material to radiation in the presence of one or more of the ⁇ -amine enol ether photoinitiators described above. Further, the present invention is directed to a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more of the ⁇ -amine enol ether photoinitiators described above, into a film and irradiating the film with an amount of radiation sufficient to polymerize the admixture.
- the present invention is further directed to an adhesive composition comprising an unsaturated polymerizable material admixed and one or more ⁇ -amine enol ether photoinitiators of the present invention.
- the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition.
- the present invention further provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
- reactive species is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such species.
- carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonylcarbenes, siloxycarbenes, and dicarbenes.
- nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes.
- Cations include, by way of illustration, primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, f-butyl cation, t-pentyl cation, t-hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations.
- Cations also include those formed from various metal salts, such as tetra- ⁇ -butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) inflates.
- metal salts such as tetra- ⁇ -butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) inflates.
- anions include, by way of example, alkyl anions, such as ethyl anion, n-propyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions.
- alkyl anions such as ethyl anion, n-propyl anion, isobutyl anion, and neopentyl anion
- cycloalkyl anions such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion
- allylic anions such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion
- benzylic anions
- organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methylcyclopentadienyl manganese tricarbonyl.
- Organometallic photoinitiators generally produce free radicals or cations.
- quantum yield is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1.
- polymerization is used herein to mean the combining, e.g. covalent bonding, of large numbers of smaller molecules, such as monomers, to form very large molecules, i.e., macromolecules or polymers. The monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
- curing means the polymerization of functional ohgomers and monomers, or even polymers, into a crosslinked polymer network.
- curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents.
- the terms "unsaturated monomer,” “functional oligomer,” and “crosslinking agent” are used herein with their usual meanings and are well understood by those having ordinary skill in the art.
- the singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material.
- the term “unsaturated polymerizable material” is meant to include any unsaturated material capable of undergoing polymerization.
- the term encompasses unsaturated monomers, oligomers, and crosslinking agents. Again, the singular form of the term is intended to include both the singular and the plural.
- the term "fiber” as used herein denotes a threadlike structure.
- the fibers used in the present invention may be any fibers known in the art.
- the term "nonwoven web” as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.
- the present invention is directed to new ⁇ -amine enol ether photoinitiators having the following general formula:
- H- an alkyl group, a chalcone, phthaloylglycine, HSO 3 -
- R 4 and R 5 each independently represent an alkyl group; x represents an alkyl group or
- z represents an alkyl group, an alkylaryl
- wavelength selective photoinitiators are produced having a desired absorption maximum varying from about 222 ran to about 390 ran.
- the term "antennae” refers to a moiety on the ⁇ -amine enol ether photoinitiators of the present invention, which absorbs radiation from a radiation source and transfers the absorbed energy to an excitable portion of the photoinitiator molecule. Further, by selecting one or more ionic substituents, yi/ y 2 , y , y or y 5 , water-soluble photoinitiators may be produced.
- the ⁇ -amine enol ether photoinitiator comprises a compound having the following formula:
- x and z are as defined above.
- This particular photoinitiator contains a single morpholino group (“antenna”) and has an absorption maximum at about 360 ran.
- the ⁇ -amine enol ether photoinitiator comprises a compound having the following formula:
- the photoinitiator comprises a compound having the following formula:
- the photoinitiator comprises a water-soluble photoinitiator having the following structure:
- Ri, R 2 and R 3 each independently represent H-, an alkyl group, a chalcone, phthaloylglycine, HSO 3 -,
- R and R 5 each independently represent an alkyl group; x represents an alkyl group or
- z represents an alkyl group, an alkylaryl group or ; wherein at least one of yi, y 2 , y 3 , y 4 and y 5 represents NaS ⁇ 3 - or NaOOC-.
- the photoinitiator comprises an ⁇ -amino enol ether compound containing a phthaloylglycine antennae and having the following formula:
- This particular photoinitiator contains a phthaloylglycine group ("antenna”) and has an absorption maximum at 222 nm.
- the photoinitiator comprises an ⁇ -amino enol ether compound containing a 2,2-diphenylvinyl phenyl sulfide antennae and having the following formula:
- This particular photoinitiator has an absorption maximum at 308 nm.
- the ⁇ -amino enol ether photoinitiators of the present invention may be prepared by any reaction mechanism known to those of ordinary skill in the art as long as the ⁇ -amino enol ether structure remains intact.
- the resulting ⁇ -amino enol ether photoinitiators are relatively stable at room temperature (from about 15 C to
- the ⁇ -amino enol ether photoinitiators of the present invention have a high intensity of absorption.
- the photoinitiators of the present invention may have a molar extinction coefficient greater than about 5,000 liters per mole per cm (1 mole ⁇ cm -1 ) at an absorption maximum.
- the photoinitiators of the present invention may have a molar extinction coefficient
- the photoinitiators of the present invention may have a molar extinction coefficient (absorptivity) greater than about 20,000 1 mole- i cm -! .
- the photoinitiators of the present invention will have a molar extinction coefficient greater than about 25,000 1 mole -1 cm " .
- the present invention is also directed to a method of generating a reactive species.
- the method of generating a reactive species involves generating a reactive species by exposing one or more of the above-described ⁇ -amino enol ether photoinitiators to radiation. The exposure of the photoinitiators to a radiation source triggers a photochemical process.
- the term "quantum yield” is used herein to indicate the efficiency of a photochemical process. More particularly, quantum yield is a measure of the probability that a particular molecule (photoinitiator) will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed.
- quantum yields may vary from zero (no absorption) to 1.
- the ⁇ -amino enol ether photoinitiators of the present invention absorb photons having a specific wavelength and transfers the absorbed energy to one or more excitable portions of the molecule.
- the excitable portion of the molecule absorbs enough energy to cause a bond breakage, which generates one or more reactive species.
- the efficiency with which a reactive species is generated with the photoinitiators of the present invention is significantly greater than that experienced with photoinitiators of the prior art as indicated by faster cure times.
- the ⁇ -amino enol ether photoinitiators of the present invention desirably will have a quantum yield greater than about 0.5.
- the quantum yield of the photoinitiators of the present invention will be greater than about 0.6. Even more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.7. Still more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.8, with the most desirable quantum yield being greater than about 0.9.
- the photoinitiators may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/ monomer mixture.
- the unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art.
- the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.
- examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate, vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyether acrylates, such as the reaction product of acrylic acid with an adipic acid/ hexanediol-based polyether, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4'- diisocyanate, and polybutadiene diacrylate oligomer.
- the types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/deconjugation reactions.
- addition reactions including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/deconjugation reactions.
- the present invention also comprehends a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious ⁇ -amino enol ether photoinitiators of the present invention described above.
- an unsaturated oligomer /monomer mixture is employed in place of the unsaturated monomer, curing is accomplished.
- the polymerizable material admixed with the ⁇ -amino enol ether photoinitiators of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material.
- the amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiators, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
- the present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more ⁇ -amino enol ether photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition.
- the unsaturated polymerizable material is an unsaturated oligomer/ monomer mixture, curing is accomplished. Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation.
- the admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer- coated nonwoven web or fiber, and a method for producing the same. Any method known in the art of drawing the admixture into a film may be used in the present invention.
- the amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the intensity and wavelength of the radiation, and duration of exposure to the radiation.
- the present invention also includes an adhesive composition comprising an unsaturated polymerizable material admixed with one or more ⁇ -amino enol ether photoinitiators of the present invention.
- the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition.
- a laminate is produced wherein at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
- the adhesive is irradiated to cure the composition.
- any layers may be used in the laminates of the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently.
- any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through.
- the amount of radiation sufficient to polymerize the admixture is readily deterrninable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
- the radiation to which the ⁇ -amino enol ether photoinitiators of the present invention may be exposed generally will have a wavelength of from about 4 to about 1,000 nanometers.
- the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation. Desirably, the radiation will have a wavelength of from about 100 to about 900 nanometers.
- the radiation will have a wavelength of from about 100 to 700 nanometers.
- the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 390 nanometers, and even more desirably will have a wavelength of from 200 to about 390 nanometers. For example, the radiation may have a wavelength of from about 222 to about 390 nanometers.
- the radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp.
- Excimers are unstable excited-state molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond and, while they are dissociating, release their binding energy in the form of ultraviolet radiation.
- the dielectric barrier excimers in general emit in the range of from about 125 ran to about 500 nm, depending upon the excimer gas mixture.
- Dielectric barrier discharge excimer lamps (also referred to hereinafter as "excimer lamp”) are described, for example, by U.
- Excimer lamps were developed by ABB Infocom Ltd., Lenzburg, Switzerland, and at the present time are available from Heraeus Noblelight GmbH, Kleinostheim, Germany.
- the excimer lamp emits incoherent, pulsed ultraviolet radiation.
- Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers.
- the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers.
- the half width wall be of the order of approximately 5 to 15 nanometers.
- the ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve.
- the "half width" of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.
- the emitted radiation of an excimer lamp is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz.
- An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification and the claims.
- excimer lamp radiation is essentially monochromatic.
- the source of radiation used with the ⁇ -amino enol ether photoinitiators of the present invention may be any radiation source known to those of ordinary skill in the art.
- a mercury lamp with a D-bulb which produces radiation having an emission peak of 350 nm is used to produce free radicals from the above- described photoinitiators.
- This radiation source is particularly useful when matched with one or more photoinitiators of the present invention having an absorption maximum of 350 nanometers, corresponding to the emission peak of the mercury lamp.
- Other specialty doped lamps, which emit radiation at about 390 nm, may be used with photoinitiators of the present invention which have an absorption maximum at 390 nm.
- some of the photoinitiators of the present invention will generate one or more reactive species upon exposure to sunlight. Accordingly, these photoinitiators of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source.
- the ⁇ -amino enol ether photoinitiators of the present invention enable the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. These photoinitiators also enable numerous industry applications wherein unsaturated polymerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the photoinitiator is designed, the photoinitiator of the present invention can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light sources are necessary without the photoinitiators of the present invention.
- the effective tuning of the ⁇ -amino enol ether photoinitiators of the present invention for a specific wavelength band permits the photoinitiators of the present invention to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the
- the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp.
- a narrow band emitter such as an excimer lamp.
- an excimer lamp, or other radiation emission source that emits radiation having a wavelength of approximately 222 nm with the phthaloylglycine-containing photoinitiators of the present invention.
- a mercury lamp that emits radiation having a wavelength of approximately 325 nm, 360 nm or 390 ran with the single, double or triple morpholino-containing photoinitiators of the present invention.
- the effectiveness of the photoinitiators of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.
- a major advantage of the ⁇ -amino enol ether photoinitiators of the present invention is that they have rapid curing times in comparison to the curing times of prior art photoinitiators.
- the ⁇ -amino enol ether photoinitiators of the present invention possess rapid curing times from 3-5 times faster than the curing times of the best known photoinitiators.
- Another advantage of the present invention is that the ⁇ - amino enol ether photoinitiators of the present invention are highly sensitive photoinitiators and are beneficially used in situations having lower light levels.
- Ciba Geigy photoinitiator 369 (CGI 369) in the form of a powder was added to a 1 g sample of red flexo ink (Gamma Graphics). The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon-carbon double bonds within the mixture. The curing rate was measured.
- the mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon- carbon double bonds within the mixture.
- the curing rate was measured.
- the KCI 993 photoinitiator had a curing rate relative to the CGI 369 photoinitiator of greater than 220%.
- the mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon-carbon double bonds within the mixture.
- the curing rate was measured.
- the KCI 993 photoinitiator had a curing rate relative to the CGI 369 photoinitiator of greater than
Abstract
The present invention is directed to new, energy-efficient photoinitiators in the form of α-amino enol ether compounds. The present invention is also directed to a method of generating reactive species which includes exposing one or more photoinitiators to radiation to form one or more reactive species. Also described are methods of polymerizing unsaturated monomers, methods of curing an unsaturated oligomer/monomer mixture, and methods of laminating using the photoinitiators of the present invention.
Description
NOVEL PHOTOINITIATORS AND APPLICATIONS THEREFOR
Technical Field
The present invention relates to novel photoinitiators and methods for generating a reactive species using the photoinitiators. The present invention further relates to methods of polymerizing or photocuring polymerizable unsaturated material using the above-mentioned photoinitiators.
Background of the Invention
Polymers have served essential needs in society. For many years, these needs were filled by natural polymers. More recently, synthetic polymers have played an increasingly greater role, particularly since the beginning of the 20th century. Especially useful polymers are those prepared by an addition polymerization mechanism, i.e., free radical chain polymerization of unsaturated monomers, and include, by way of example only, coatings and adhesives. In fact, the majority of commercially significant processes is based on free-radical chemistry. That is, chain polymerization is initiated by a reactive species which often is a free radical. The source of the free radicals is termed an initiator or photoinitiator.
Improvements in free radical chain polymerization have focused both on the polymer being produced and the photoinitiator. Whether a particular unsaturated monomer can be converted to a polymer requires structural, thermodynamic, and kinetic feasibility. Even when all three exist, kinetic feasibility is achieved in many cases only with a specific type of photoinitiator. Moreover, the photoinitiator
can have a significant effect on reaction rate which, in turn, may determine the commercial success or failure of a particular polymerization process or product.
A free radical-generating photoinitiator may generate free radicals in several different ways. For example, the thermal, homolytic dissociation of an initiator typically directly yields two free radicals per initiator molecule. A photoinitiator, i.e., an initiator which absorbs light energy, may produce free radicals by either of two pathways: (1) the photoinitiator undergoes excitation by energy absorption with subsequent decomposition into one or more radicals; or
(2) the photoinitiator undergoes excitation and the excited species interacts with a second compound (by either energy transfer or a redox reaction) to form free radicals from the latter and/or former compound(s).
While any free radical chain polymerization process should avoid the presence of species which may prematurely terminate the polymerization reaction, prior photoinitiators present special problems. For example, absorption of the light by the reaction medium may limit the amount of energy available for absorption by the photoinitiator. Also, the often competitive and complex kinetics involved may have an adverse effect on the reaction rate. Moreover, commercially available radiation sources, such as medium and high pressure mercury and xenon lamps, emit over a wide wavelength range, thus producing individual emission bands of relatively low intensity. Most photoinitiators only absorb over a small portion of the emission spectra and, as a consequence, most of the lamps' radiation remains unused. In addition, most known photoinitiators have only moderate "quantum yields" (generally less than 0.4) at these wavelengths, indicating that the conversion of light radiation to radical formation can be more efficient. Thus, there are continuing opportunities for improvements in free radical polymerization photoinitiators. Moreover, there is a need in the art for new, energy-efficient photoinitiators for use in a variety of polymerization and photocuring processes.
Summary of the Invention
The present invention addresses some of the difficulties and problems discussed above by the discovery of energy- efficient photoinitiators having the following general formula:
\
O \ / N-R3
C=C
R / \
wherein Rι, R2 and R3 each independently represent H-, an alkyl group, a chalcone, phthaloylglycine, HSO3-,
NaSθ3-, vinyl thioether,
or
group or
; wherein yi, y2/ y3, y4 and y5 each independently represent H-, HSO3-,
NaSCV, HOOC-, NaOOC- and an alkyl group. By selecting particular "R" groups or "antennae," wavelength selective photoinitiators are produced having a desired absorption maximum varying from about 222 ran to about 390 ran.
Further, by selecting one or more ionic substituents, yi, y2, y3, y4 or ys, water-soluble photoinitiators are produced.
The present invention is directed to the above-described α-amine enol ether photoinitiators, compositions containing the same, and methods for generating a reactive species which includes providing one or more of the photoinitiators and irradiating the one or more photoinitiators. One of the main advantages of the photoinitiators of the present invention is that they efficiently generate one or more reactive species under extremely low energy lamps, such as excimer lamps and mercury lamps, as compared to prior art photoinitiators. Further, the photoinitiators of the present invention are as much as five times faster than the best prior art photoinitiators.
The present invention is further directed to methods of using the above-described α-amine enol ether photoinitiators to polymerize and /or photocure a polymerizable material. The photoinitiators of the present invention result in rapid curing times in comparison to the curing times of prior art photoinitiators, even with relatively low output lamps. The present invention includes a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious wavelength specific photoinitiator composition described above. When an unsaturated oligomer/ monomer mixture is employed in place of the unsaturated monomer, curing is accomplished. The present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more α-amine enol ether photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer-coated nonwoven web or fiber, and a method for producing the same.
The present invention is also directed to an adhesive composition comprising an unsaturated polymerizable material admixed with one or more α-amine enol ether photoinitiators of the present invention. Similarly, the present
invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition, in which at least one layer is a nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition.
These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.
Detailed Description of the Invention The present invention is directed to energy-efficient, reactive, α-amine enol ether photoinitiators and methods for utilizing the same. More particularly, the present invention is directed to new photoinitiators having the following general formula:
R-,
\ I "
O N-R3
C=C
R / \
wherein R7 R and R3 each independently represent
H-, an alkyl group, a chalcone, phthaloylglycine, HSO3-
NaS03-, vinyl thioether,
0r
NaS03-, HOOC-, NaOOC- and an alkyl group.
The present invention also includes a method of polymerizing an unsaturated polymerizable material by exposing the unsaturated material to radiation in the presence of one or more of the α-amine enol ether photoinitiators described above. Further, the present invention is directed to a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more of the α-amine enol ether photoinitiators described above, into a film and irradiating the film with an amount of radiation sufficient to polymerize the admixture.
The present invention is further directed to an adhesive composition comprising an unsaturated polymerizable material admixed and one or more α-amine enol ether photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition. The present invention further provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. After the following definitions, the photoinitiators of the present invention will be described in detail, followed by a detailed description of the method of generating reactive species, and the various representative applications of the method.
Definitions
As used herein, the term "reactive species" is used herein to mean any chemically reactive species including, but not limited to, free-radicals, cations, anions, nitrenes, and carbenes. Illustrated below are examples of several of such
species. Examples of carbenes include, for example, methylene or carbene, dichlorocarbene, diphenylcarbene, alkylcarbonylcarbenes, siloxycarbenes, and dicarbenes. Examples of nitrenes include, also by way of example, nitrene, alkyl nitrenes, and aryl nitrenes. Cations (sometimes referred to as carbocations or carbonium ions) include, by way of illustration, primary, secondary, and tertiary alkyl carbocations, such as methyl cation, ethyl cation, propyl cation, f-butyl cation, t-pentyl cation, t-hexyl cation; allylic cations; benzylic cations; aryl cations, such as triphenyl cation; cyclopropylmethyl cations; methoxymethyl cation; triarylsulphonium cations; and acyl cations. Cations also include those formed from various metal salts, such as tetra-π-butylammonium tetrahaloaurate(III) salts; sodium tetrachloroaurate(III); vanadium tetrachloride; and silver, copper(I) and (II), and thallium(I) inflates. Examples of anions (sometimes referred to as carbanions) include, by way of example, alkyl anions, such as ethyl anion, n-propyl anion, isobutyl anion, and neopentyl anion; cycloalkyl anions, such as cyclopropyl anion, cyclobutyl anion, and cyclopentyl anion; allylic anions; benzylic anions; aryl cations; and sulfur- or phosphorus-containing alkyl anions. Finally, examples of organometallic photoinitiators include titanocenes, fluorinated diaryltitanocenes, iron arene complexes, manganese decacarbonyl, and methylcyclopentadienyl manganese tricarbonyl. Organometallic photoinitiators generally produce free radicals or cations.
As used herein, the term "quantum yield" is used herein to indicate the efficiency of a photochemical process. More particularly quantum yield is a measure of the probability that a particular molecule will absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1. As used herein, the term "polymerization" is used herein to mean the combining, e.g. covalent bonding, of large numbers of smaller molecules, such as monomers, to form very large molecules, i.e., macromolecules or polymers. The monomers may be combined to form only linear
macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers.
As used herein, the term "curing" means the polymerization of functional ohgomers and monomers, or even polymers, into a crosslinked polymer network. Thus, curing is the polymerization of unsaturated monomers or oligomers in the presence of crosslinking agents.
As used herein, the terms "unsaturated monomer," "functional oligomer," and "crosslinking agent" are used herein with their usual meanings and are well understood by those having ordinary skill in the art. The singular form of each is intended to include both the singular and the plural, i.e., one or more of each respective material. As used herein, the term "unsaturated polymerizable material" is meant to include any unsaturated material capable of undergoing polymerization. The term encompasses unsaturated monomers, oligomers, and crosslinking agents. Again, the singular form of the term is intended to include both the singular and the plural.
As used herein, the term "fiber" as used herein denotes a threadlike structure. The fibers used in the present invention may be any fibers known in the art. As used herein, the term "nonwoven web" as used herein denotes a web-like matter comprised of one or more overlapping or interconnected fibers in a nonwoven manner. It is to be understood that any nonwoven fibers known in the art may be used in the present invention.
Photoinitiators
The present invention is directed to new α-amine enol ether photoinitiators having the following general formula:
R,
\
0 N -R3
C=C
R Z
wherein Ri, R2 and R3 each independently represent
H-, an alkyl group, a chalcone, phthaloylglycine, HSO3-
N Sθ3-, vinyl thioether,
or
group or
; wherein yλ, y2, y3/ y4 and y5 each independently represent H-, HSO3-, NaS03-, HOOC-, NaOOC- and an alkyl group. By selecting particular "R" groups or "antennae," wavelength selective photoinitiators are produced having a desired absorption maximum varying from about 222 ran to about 390 ran. As used herein, the term "antennae" refers to a moiety on the α-amine enol ether photoinitiators of the present invention, which absorbs radiation from a radiation source and transfers the absorbed energy to an excitable portion of the photoinitiator molecule. Further, by selecting one or more ionic substituents, yi/ y2, y , y or y5, water-soluble photoinitiators may be produced.
In one embodiment of the present invention, the α-amine enol ether photoinitiator comprises a compound having the following formula:
wherein x and z are as defined above. This particular photoinitiator contains a single morpholino group ("antenna") and has an absorption maximum at about 360 ran. In a further embodiment of the present invention, the α-amine enol ether photoinitiator comprises a compound having the following formula:
wherein x and z are as defined above. By adding a second morpholino group to the photoinitiator, the absorption maximum of the photoinitiator shifts to about 380 nm. In yet a further embodiment of the present invention, the photoinitiator comprises a compound having the following formula:
wherein x and z are as defined above. By adding a third morpholino group to the photoinitiator, the absorption maximum of the photoinitiator shifts to about 390 nm.
In yet another embodiment of the present invention, the photoinitiator comprises a water-soluble photoinitiator having the following structure:
X. \ R I 2
O \ / N -R3 C=C
R, / \
wherein Ri, R2 and R3 each independently represent H-, an alkyl group, a chalcone, phthaloylglycine, HSO3-,
NaSθ3-, vinyl thioether,
or
In a further embodiment of the present invention, the photoinitiator comprises an α-amino enol ether compound containing a phthaloylglycine antennae and having the following formula:
wherein x and z are as defined above. This particular photoinitiator contains a phthaloylglycine group ("antenna") and has an absorption maximum at 222 nm.
In yet a further embodiment of the present invention, the photoinitiator comprises an α-amino enol ether compound containing a 2,2-diphenylvinyl phenyl sulfide antennae and having the following formula:
The α-amino enol ether photoinitiators of the present invention may be prepared by any reaction mechanism known to those of ordinary skill in the art as long as the α-amino enol ether structure remains intact.
The resulting α-amino enol ether photoinitiators are relatively stable at room temperature (from about 15 C to
25°C) and normal room humidity (from about 30% to 60%). However, upon exposure to radiation at an appropriate wavelength, the photoinitiators efficiently produce one or more free radicals. The α-amino enol ether photoinitiators of the present invention have a high intensity of absorption. For example, the photoinitiators of the present invention may have a molar extinction coefficient greater than about 5,000 liters per mole per cm (1 mole^cm-1) at an absorption maximum.
As another example, the photoinitiators of the present invention may have a molar extinction coefficient
(absorptivity) greater than about 10,000 l mole^cm-1. As another example, the photoinitiators of the present invention may have a molar extinction coefficient (absorptivity) greater than about 20,000 1 mole-icm-!. As a further example, the photoinitiators of the present invention will have a molar extinction coefficient greater than about 25,000 1 mole-1 cm" .
Method of Generating a Reactive Species and Applications Therefor The present invention is also directed to a method of generating a reactive species. The method of generating a reactive species involves generating a reactive species by exposing one or more of the above-described α-amino enol ether photoinitiators to radiation. The exposure of the photoinitiators to a radiation source triggers a photochemical process. As stated above, the term "quantum yield" is used herein to indicate the efficiency of a photochemical process. More particularly, quantum yield is a measure of the probability that a particular molecule (photoinitiator) will
absorb a quantum of light during its interaction with a photon. The term expresses the number of photochemical events per photon absorbed. Thus, quantum yields may vary from zero (no absorption) to 1. The α-amino enol ether photoinitiators of the present invention absorb photons having a specific wavelength and transfers the absorbed energy to one or more excitable portions of the molecule. The excitable portion of the molecule absorbs enough energy to cause a bond breakage, which generates one or more reactive species. The efficiency with which a reactive species is generated with the photoinitiators of the present invention is significantly greater than that experienced with photoinitiators of the prior art as indicated by faster cure times. For example, the α-amino enol ether photoinitiators of the present invention desirably will have a quantum yield greater than about 0.5. More desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.6. Even more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.7. Still more desirably, the quantum yield of the photoinitiators of the present invention will be greater than about 0.8, with the most desirable quantum yield being greater than about 0.9.
Exposing the α-amino enol ether photoinitiators of the present invention to radiation results in the generation of one or more reactive species. Thus, the photoinitiators may be employed in any situation where reactive species are required, such as for the polymerization of an unsaturated monomer and the curing of an unsaturated oligomer/ monomer mixture. The unsaturated monomers and oligomers may be any of those known to one having ordinary skill in the art. In addition, the polymerization and curing media also may contain other materials as desired, such as pigments, extenders, amine synergists, and such other additives as are well known to those having ordinary skill in the art.
By way of illustration only, examples of unsaturated monomers and oligomers include ethylene, propylene, vinyl chloride, isobutylene, styrene, isoprene, acrylonitrile, acrylic acid, methacylic acid, ethyl acrylate, methyl methacrylate,
vinyl acrylate, allyl methacrylate, tripropylene glycol diacrylate, trimethylol propane ethoxylate acrylate, epoxy acrylates, such as the reaction product of a bisphenol A epoxide with acrylic acid; polyether acrylates, such as the reaction product of acrylic acid with an adipic acid/ hexanediol-based polyether, urethane acrylates, such as the reaction product of hydroxypropyl acrylate with diphenylmethane-4,4'- diisocyanate, and polybutadiene diacrylate oligomer.
The types of reactions that various reactive species enter into include, but are not limited to, addition reactions, including polymerization reactions; abstraction reactions; rearrangement reactions; elimination reactions, including decarboxylation reactions; oxidation-reduction (redox) reactions; substitution reactions; and conjugation/deconjugation reactions.
Accordingly, the present invention also comprehends a method of polymerizing an unsaturated monomer by exposing the unsaturated monomer to radiation in the presence of the efficacious α-amino enol ether photoinitiators of the present invention described above. When an unsaturated oligomer /monomer mixture is employed in place of the unsaturated monomer, curing is accomplished. It is to be understood that the polymerizable material admixed with the α-amino enol ether photoinitiators of the present invention is to be admixed by means known in the art, and that the mixture will be irradiated with an amount of radiation sufficient to polymerize the material. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiators, the identity and amount of the polymerizable material, the intensity and wavelength of the radiation, and the duration of exposure to the radiation.
It is believed that radiation exposure results in the generation of free radicals from the α-amino enol ether photoinitiators of the present invention by one or more of the following: cleavage of a the oxygen-carbon bond resulting in an alkoxy radical; and breakdown of the ether radical to form one or more radicals.
Polymer Films, Coated Fibers and Webs, and Adhesive Compositions
The present invention further includes a film and a method for producing a film, by drawing an admixture of unsaturated polymerizable material and one or more α-amino enol ether photoinitiators of the present invention, into a film and irradiating the film with an amount of radiation sufficient to polymerize the composition. When the unsaturated polymerizable material is an unsaturated oligomer/ monomer mixture, curing is accomplished. Any film thickness may be produced, as per the thickness of the admixture formed, so long as the admixture sufficiently polymerizes upon exposure to radiation. The admixture may be drawn into a film on a nonwoven web or on a fiber, thereby providing a polymer- coated nonwoven web or fiber, and a method for producing the same. Any method known in the art of drawing the admixture into a film may be used in the present invention. The amount of radiation sufficient to polymerize the material is readily determinable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the intensity and wavelength of the radiation, and duration of exposure to the radiation.
The present invention also includes an adhesive composition comprising an unsaturated polymerizable material admixed with one or more α-amino enol ether photoinitiators of the present invention. Similarly, the present invention includes a laminated structure comprising at least two layers bonded together with the above-described adhesive composition. In one embodiment of the present invention, a laminate is produced wherein at least one layer is a cellulosic or polyolefin nonwoven web or film. Accordingly, the present invention provides a method of laminating a structure wherein a structure having at least two layers with the above-described adhesive composition between the layers is irradiated to polymerize the adhesive composition. When the unsaturated polymerizable material in the adhesive is an unsaturated oligomer /monomer mixture, the adhesive is irradiated to cure the composition.
It is to be understood that any layers may be used in the laminates of the present invention, on the condition that at least one of the layers allows sufficient radiation to penetrate through the layer to enable the admixture to polymerize sufficiently. Accordingly, any cellulosic or polyolefin nonwoven web or film known in the art may be used as one of the layers so long as they allow radiation to pass through. Again, the amount of radiation sufficient to polymerize the admixture is readily deterrninable by one of ordinary skill in the art, and depends upon the identity and amount of photoinitiator, the identity and amount of the polymerizable material, the thickness of the admixture, the identity and thickness of the layer, the intensity and wavelength of the radiation, and the duration of exposure to the radiation. The radiation to which the α-amino enol ether photoinitiators of the present invention may be exposed generally will have a wavelength of from about 4 to about 1,000 nanometers. Thus, the radiation may be ultraviolet radiation, including near ultraviolet and far or vacuum ultraviolet radiation; visible radiation; and near infrared radiation. Desirably, the radiation will have a wavelength of from about 100 to about 900 nanometers. More desirably, the radiation will have a wavelength of from about 100 to 700 nanometers. Desirably, the radiation will be ultraviolet radiation having a wavelength of from about 4 to about 400 nanometers. More desirably, the radiation will have a wavelength of from about 100 to about 390 nanometers, and even more desirably will have a wavelength of from 200 to about 390 nanometers. For example, the radiation may have a wavelength of from about 222 to about 390 nanometers. The radiation desirably will be incoherent, pulsed ultraviolet radiation from a dielectric barrier discharge excimer lamp or radiation from a mercury lamp.
Excimers are unstable excited-state molecular complexes which occur only under extreme conditions, such as those temporarily existing in special types of gas discharge. Typical examples are the molecular bonds between two rare gaseous atoms or between a rare gas atom and a halogen atom. Excimer complexes dissociate within less than a microsecond
and, while they are dissociating, release their binding energy in the form of ultraviolet radiation. The dielectric barrier excimers in general emit in the range of from about 125 ran to about 500 nm, depending upon the excimer gas mixture. Dielectric barrier discharge excimer lamps (also referred to hereinafter as "excimer lamp") are described, for example, by U. Kogelschatz, "Silent discharges for the generation of ultraviolet and vacuum ultraviolet excimer radiation." Pure & Appl. Chem., 62, No. 9, pp. 16671674 (1990); and E. Eliasson and U. Kogelschatz, "UV Excimer Radiation from Dielectric-
Barrier Discharges." Appl. Phys. B. 46, pp. 299-303 (1988). Excimer lamps were developed by ABB Infocom Ltd., Lenzburg, Switzerland, and at the present time are available from Heraeus Noblelight GmbH, Kleinostheim, Germany. The excimer lamp emits incoherent, pulsed ultraviolet radiation. Such radiation has a relatively narrow bandwidth, i.e., the half width is of the order of approximately 5 to 100 nanometers. Desirably, the radiation will have a half width of the order of approximately 5 to 50 nanometers, and more desirably will have a half width of the order of 5 to 25 nanometers. Most desirably, the half width wall be of the order of approximately 5 to 15 nanometers.
The ultraviolet radiation emitted from an excimer lamp can be emitted in a plurality of wavelengths, wherein one or more of the wavelengths within the band are emitted at a maximum intensity. Accordingly, a plot of the wavelengths in the band against the intensity for each wavelength in the band produces a bell curve. The "half width" of the range of ultraviolet radiation emitted by an excimer lamp is defined as the width of the bell curve at 50% of the maximum height of the bell curve.
The emitted radiation of an excimer lamp is incoherent and pulsed, the frequency of the pulses being dependent upon the frequency of the alternating current power supply which typically is in the range of from about 20 to about 300 kHz. An excimer lamp typically is identified or referred to by the wavelength at which the maximum intensity of the radiation occurs, which convention is followed throughout this specification and the claims. Thus, in comparison with most
other commercially useful sources of ultraviolet radiation which typically emit over the entire ultraviolet spectrum and even into the visible region, excimer lamp radiation is essentially monochromatic. The source of radiation used with the α-amino enol ether photoinitiators of the present invention may be any radiation source known to those of ordinary skill in the art. In one embodiment of the present invention, a mercury lamp with a D-bulb, which produces radiation having an emission peak of 350 nm is used to produce free radicals from the above- described photoinitiators. This radiation source is particularly useful when matched with one or more photoinitiators of the present invention having an absorption maximum of 350 nanometers, corresponding to the emission peak of the mercury lamp. Other specialty doped lamps, which emit radiation at about 390 nm, may be used with photoinitiators of the present invention which have an absorption maximum at 390 nm.
As a result of the α-amino enol ether photoinitiators of the present invention absorbing radiation in the range of about
250 to about 390 nanometers, some of the photoinitiators of the present invention will generate one or more reactive species upon exposure to sunlight. Accordingly, these photoinitiators of the present invention provides a method for the generation of reactive species that does not require the presence of a special light source.
The α-amino enol ether photoinitiators of the present invention enable the production of adhesive and coating compositions that consumers can apply to a desired object and polymerize or cure upon exposure to sunlight. These photoinitiators also enable numerous industry applications wherein unsaturated polymerizable materials may be polymerized merely upon exposure to sunlight. Therefore, depending upon how the photoinitiator is designed, the photoinitiator of the present invention can eliminate the cost of purchasing and maintaining light sources in numerous industries wherein such light sources are necessary without the photoinitiators of the present invention.
The effective tuning of the α-amino enol ether photoinitiators of the present invention for a specific wavelength band permits the photoinitiators of the present invention to more efficiently utilize the target radiation in the emission spectrum of the radiating source corresponding to the
"tuned" wavelength band, even though the intensity of such radiation may be much lower than, for example, radiation from a narrow band emitter, such as an excimer lamp. For example, it may be desirable to utilize an excimer lamp, or other radiation emission source, that emits radiation having a wavelength of approximately 222 nm with the phthaloylglycine-containing photoinitiators of the present invention. Similarly, it may be desirable to utilize a mercury lamp that emits radiation having a wavelength of approximately 325 nm, 360 nm or 390 ran with the single, double or triple morpholino-containing photoinitiators of the present invention. However, the effectiveness of the photoinitiators of the present invention is not necessarily dependent upon the availability or use of a narrow wavelength band radiation source.
Accordingly, a major advantage of the α-amino enol ether photoinitiators of the present invention is that they have rapid curing times in comparison to the curing times of prior art photoinitiators. The α-amino enol ether photoinitiators of the present invention possess rapid curing times from 3-5 times faster than the curing times of the best known photoinitiators. Another advantage of the present invention is that the α- amino enol ether photoinitiators of the present invention are highly sensitive photoinitiators and are beneficially used in situations having lower light levels.
Although specific antennae are disclosed above in combination with the photoinitiators of the present invention, it should be understood that any antennae may be used with the α-amino enol ether photoinitiators of the present invention.
The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or the
scope of the present invention. In the examples, all parts are by weight, unless stated otherwise.
COMPARATIVE EXAMPLE 1 Photocuring of CGI 369 in Red Flexo Resin
A mixture of Ciba Geigy photoinitiator 369 (CGI 369) in the form of a powder was added to a 1 g sample of red flexo ink (Gamma Graphics). The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon-carbon double bonds within the mixture. The curing rate was measured.
EXAMPLE 1 Photocuring of KCI 993 in Red Flexo Resin A mixture of Kimberly Clark's KCI 993 photoinitiator, having the following structure, in the form of a powder was added to a 1 g sample of red flexo ink (Gamma Graphics).
The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon- carbon double bonds within the mixture. The curing rate was measured. The KCI 993 photoinitiator had a curing rate relative to the CGI 369 photoinitiator of greater than 220%.
COMPARATIVE EXAMPLE 2 Photocuring of CGI 369 in Blue Flexo Resin A mixture of CGI 369 in the form of a powder was added to a 1 g sample of blue flexo ink (Gamma Graphics). The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon-carbon double bonds within the mixture. The curing rate was measured.
EXAMPLE 2 Photocuring of KCI 993 in Blue Flexo Resin A mixture of KCI 993 photoinitiator in the form of a powder was added to a 1 g sample of blue flexo ink (Gamma
Graphics). The mixture was exposed to UV radiation while positioned within an FTIR machine to monitor the decrease in carbon-carbon double bonds within the mixture. The curing rate was measured. The KCI 993 photoinitiator had a curing rate relative to the CGI 369 photoinitiator of greater than
360%.
While the specification has been described in detail with respect to specific embodiments thereof, it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments. Accordingly, the scope of the present invention should be assessed as that of the appended claims and any equivalents thereto.
Claims
1. A photoinitiator having the following formula:
X R2
\ I
O N -R
C=C
/ \ R{ z
wherein Ri, R2 and R3 each independently represent H-, an alkyl group, a chalcone, phthaloylglycine, HSO3-,
NaS03- vinyl thioether, 
or
group or 
; wherein yi, y2/ Y3, y4 a d y5 each independently represent H-, HSO3-,
NaS03-, HOOC-, NaOOC- and an alkyl group.
2. The photoinitiator of Claim 1, wherein the photoinitiator has the following structure:
3. The photoinitiator of Claim 2, wherein the photoinitiator has the following structure:
Q
4. The photoinitiator of Claim 1, wherein the photoinitiator has the following structure:
5. The photoinitiator of Claim 4, wherein the photoinitiator has the following structure:
6. The photoinitiator of Claim 1, wherein the photoinitiator has the following structure:
7. The photoinitiator of Claim 6, wherein the photoinitiator has the following structure:
8. The photoinitiator of Claim 1, wherein the photoinitiator has the following structure:
X R2
\ I
O N -R3
C=C / \ R, z
wherein Ri, R2 and R3 each independently represent
H-, an alkyl group, a chalcone, phthaloylglycine, HSO3-,
NaS╬╕3-, vinyl thioether, 
or
NaS╬╕3-, HOOC-, NaOOC- and an alkyl group; and wherein at least one of yi, ╬│╬╣, Y , Yi and y5 represents NaS╬╕3- or
NaOOC-.
9. The photoinitiator of Claim 1, wherein the photoinitiator has the following structure:
10. The photoinitiator of Claim 9, wherein the photoinitiator has the following structure:
11. The photoinitiator of Claim 1, wherein the photoinitiator has the following structure:
12. The photoinitiator of Claim 11, wherein the photoinitiator has the following structure:
13. A method of generating a reactive species, comprising irradiating the photoinitiator of Claim 1 with radiation.
14. A method of polymerizing an unsaturated polymerizable material, comprising irradiating an admixture of an unsaturated polymerizable material and the photoinitiator of Claim 1.
15. A polymer film, produced by the process of : providing an admixture of an unsaturated polymerizable material and the photoinitiator of Claim 1 that has been drawn into a film; and irradiating the film with an amount of radiation sufficient to polymerize the admixture.
16. A method of coating a nonwoven web comprising: providing a nonwoven web coated with an admixture of unsaturated polymerizable material and the photoinitiator of Claim 1; and irradiating the coating on the web with an amount of radiation sufficient to polymerize the admixture.
17. A method of coating a fiber comprising: providing a fiber coated with an admixture of unsaturated polymerizable material and the photoinitiator of Claim 1; and irradiating the coating on the fiber with an amount of radiation sufficient to polymerize the admixture.
18. A method of making a wavelength specific photoinitiator comprising: attaching one or more antennae to an ╬▒-amine enol ether compound having the following structure:
R2
\
O v N-R'
C=C
R / \
wherein Ri, R2 and R3 each independently represent
H-, an alkyl group, a chalcone, phthaloylglycine, HSU3-,
NaS03-, vinyl thioether, 
or
R4
Rs wherein R4 and R5 each independently represent an alkyl group; x represents an alkyl group or
NaS03-, HOOC-, NaOOC- and an alkyl group.
19. The method of Claim 13, wherein the antennae
one, phthaloylglycine, 
represent an alkyl group, or 
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002298468A CA2298468A1 (en) | 1998-06-03 | 1999-05-28 | Novel photoinitiators and applications therefor |
| BR9906513-4A BR9906513A (en) | 1998-06-03 | 1999-05-28 | New photoinitiators and applications for the same |
| KR1020007001185A KR20010022593A (en) | 1998-06-03 | 1999-05-28 | Novel Photoinitiators and Applications Therefor |
| AU48182/99A AU4818299A (en) | 1998-06-03 | 1999-05-28 | Novel photoinitiators and applications therefor |
| JP2000552171A JP2002517523A (en) | 1998-06-03 | 1999-05-28 | Novel photoinitiator and its use |
| EP99931750A EP1000090A1 (en) | 1998-06-03 | 1999-05-28 | Novel photoinitiators and applications therefor |
| SK155-2000A SK1552000A3 (en) | 1998-06-03 | 1999-05-28 | Novel photoinitiators and applications therefor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8786698P | 1998-06-03 | 1998-06-03 | |
| US60/087,866 | 1998-06-03 |
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| Publication Number | Publication Date |
|---|---|
| WO1999062962A1 true WO1999062962A1 (en) | 1999-12-09 |
Family
ID=22207714
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1999/012104 WO1999062962A1 (en) | 1998-06-03 | 1999-05-28 | Novel photoinitiators and applications therefor |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US6277897B1 (en) |
| EP (1) | EP1000090A1 (en) |
| JP (1) | JP2002517523A (en) |
| KR (1) | KR20010022593A (en) |
| AU (1) | AU4818299A (en) |
| BR (1) | BR9906513A (en) |
| CA (1) | CA2298468A1 (en) |
| PL (1) | PL338379A1 (en) |
| SK (1) | SK1552000A3 (en) |
| WO (1) | WO1999062962A1 (en) |
| ZA (1) | ZA200000315B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19939760A1 (en) * | 1999-08-21 | 2001-03-08 | Schenectady Int Inc | Method and device for isolating electrical components |
| EP2236488A1 (en) | 2001-03-30 | 2010-10-06 | The Arizona Board of Regents on behalf of the University of Arizona | Materials, methods and uses for photochemical generation of acids and/or radical species |
| WO2015088464A1 (en) | 2013-12-13 | 2015-06-18 | Bicak Tugrul Cem | Synthesis of pure diallyl morpholinium monomers in high yields and using antibacterial effect of their spiro polymers |
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- 1999-05-28 KR KR1020007001185A patent/KR20010022593A/en not_active Application Discontinuation
- 1999-05-28 CA CA002298468A patent/CA2298468A1/en not_active Abandoned
- 1999-05-28 PL PL99338379A patent/PL338379A1/en unknown
- 1999-05-28 BR BR9906513-4A patent/BR9906513A/en not_active Application Discontinuation
- 1999-05-28 AU AU48182/99A patent/AU4818299A/en not_active Abandoned
- 1999-05-28 SK SK155-2000A patent/SK1552000A3/en unknown
- 1999-05-28 EP EP99931750A patent/EP1000090A1/en not_active Withdrawn
- 1999-06-03 US US09/325,516 patent/US6277897B1/en not_active Expired - Fee Related
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2000
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Also Published As
| Publication number | Publication date |
|---|---|
| PL338379A1 (en) | 2000-10-23 |
| US6277897B1 (en) | 2001-08-21 |
| CA2298468A1 (en) | 1999-12-09 |
| JP2002517523A (en) | 2002-06-18 |
| EP1000090A1 (en) | 2000-05-17 |
| AU4818299A (en) | 1999-12-20 |
| ZA200000315B (en) | 2000-08-14 |
| KR20010022593A (en) | 2001-03-26 |
| SK1552000A3 (en) | 2000-08-14 |
| BR9906513A (en) | 2001-10-30 |
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