EP0734405A1 - Photocurable composition - Google Patents
Photocurable compositionInfo
- Publication number
- EP0734405A1 EP0734405A1 EP95903615A EP95903615A EP0734405A1 EP 0734405 A1 EP0734405 A1 EP 0734405A1 EP 95903615 A EP95903615 A EP 95903615A EP 95903615 A EP95903615 A EP 95903615A EP 0734405 A1 EP0734405 A1 EP 0734405A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- photocurable composition
- composition according
- group
- acrylate
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 14
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical compound O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 4
- -1 2-ethylhexyl Chemical group 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 claims description 2
- SDFLTYHTFPTIGX-UHFFFAOYSA-N 9-methylcarbazole Chemical compound C1=CC=C2N(C)C3=CC=CC=C3C2=C1 SDFLTYHTFPTIGX-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 description 22
- 239000002932 luster Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 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 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical class FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-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
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052731 fluorine Chemical class 0.000 description 1
- 239000011737 fluorine Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
Definitions
- the present invention relates to a photocurable composition, and in particular, to a photocurable composition preferably employed for a luster agent for coating an automobile body and the like, including, for example, a coated surface of an automobile, a plastic bumper, and a tire.
- a wax such as carnuba wax, polyethylene wax, a silicone such as dimethyl polysiloxane, and a variety of modified silicones, and the like, have been employed as a luster agent for use on the exterior of an automobile.
- these luster agents do not impart sufficient gloss, water repellency and stain resistance, and have poor durability.
- Japanese Patent Kokai Publication No. S51-134794 disclose a visible light curable composition comprising an epoxy resin, an aryl halonium salt and an organic dye.
- the epoxy resin disclosed in the reference may be obtained from a reaction of bisphenol A with epichlorohydrin.
- the epoxy resin itself shows no gloss nor stain resistance, and it hardly be used as a luster agent.
- a UV curable silicone releasing composition having epoxy and/or acrylic functionality which is disclosed in Japanese Patent Kokai Publication S58-213024, cannot be employed as a luster agent, since the resin is designed to function as a releasing agent.
- a UV curable organopolysiloxane composition disclosed in Japanese Patent Kokai Publication H4-33960 comprises a organopolysiloxane having both acrylic and epoxy functionality, and a specific sulfonate photoinitiator. Even though the composition is photocured in the presence of air as a luster agent, oxygen contained in the air affects and makes the surface of the coating tacky, and the resulting coating lacks durability. Further, another problem is presented in that a UV (i.e., ultraviolet light) irradiation apparatus is needed for the composition.
- the present invention overcomes the above described prior art problems while providing a specific photocurable composition which is curable by using a visible as well as UV light.
- the photocurable composition shows remarkably good properties when it is employed as a luster agent.
- the present invention relates to a photocurable composition
- a photocurable composition comprising: (a) a photopolymerizable monomer or oligomer; (b) a photoinitiator; and (c) a photosensitizer, wherein the photosensitizer comprises at least one material selected from the group consisting of sulfolene, sulfolene derivatives, isatin, and isatin derivatives.
- a photopolymerizable monomer or oligomer employed in the present invention includes a monomeric or oligomeric compound having any one or both of an epoxy group and a vinyl group.
- Preferred photopolymerizable monomers or oligomers include organopolysiloxanes having an epoxy group or a vinyl group.
- the organopolysiloxane may be prepared by hydrosilyl-addition of an epoxy compound to an organopolysiloxane having a n-SiH bond.
- the organopolysiloxane may be prepared by hydrosilyl- addition of an ⁇ -haloolefin to an organopolysiloxane having a n-SiH bond, and then, replacing the halogen with an acrylate in the presence of a base, according to a procedure disclosed in Japanese Patent Kokai Publication No. S58-213024.
- an organopolysiloxane having an epoxy group is preferred as the photopolymerizable compound, because it is not affected by oxygen.
- suitable organopolysiloxanes having an epoxy group are those represented by the following general formulae I, II, and III.
- the group R is a divalent linking group.
- group R can be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.
- the R group is preferably aliphatic. Examples of such alkylene groups for group R include ethylene, ethylene, propylene and butylene, and so forth.
- the compounds of formulae I, II and III can be used solely or in combinations thereof without' limitation.
- the compounds of formulae I, II and III contemplated for the present invention preferably have a viscosity of 10°-10 5 cps at 25°C and an epoxy equivalent of 10 2 -10 4 .
- An alicyclic epoxy-modified organopolysiloxane, such as represented by formulae I, II, and III, is very useful due to its high reactivity.
- suitable compounds include an alkyl ( eth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, n-butyl (meth)acrylate and the like; and another vinyl compound such as styrene, ⁇ -methyl styrene, N-methyl carbazole, isobutyl vinyl ether, vinyl acetate and vinyl pyrrolidone; and the like.
- alkyl ( eth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, n-butyl (meth)acrylate and the like
- another vinyl compound such as styrene, ⁇ -methyl styrene, N-methyl carbazole, isobutyl vinyl ether
- the photoinitiator employed in the present invention is not particularly limited as long as it is a photoinitiator which initiates a polymerization of the above-described epoxy group or vinyl group upon exposure to light.
- a preferred photoinitiator employed in the present invention includes an onium salt, since a cation polymerization can be carried out by using the onium salt. In general, any onium salt conventionally used as a photoinitiator can be employed.
- onium salt examples include triphenylsulfonium hexafluoroantimonate, bis(dodecylphenyl)iodoniu hexafluoroantimonate, diphenyliodonium hexafluorophosphate, di-4,4-dimethylphenyliodonium hexafluoroacetate and the like.
- a particularly preferred onium salt employed in the present invention is triphenylsulfonium hexafluoroantimonate because of its high reactivity.
- the photoinitiator of the present invention is employed in an amount 0.1 to 50 parts, preferably 0.5 to 10 parts, by weight, based on 100 parts by weight of the photopolymerizable monomer or oligomer. if an amount of the photoinitiator is less than 0.1 parts by weight, a durable luster coating may not be provided due to an insufficient initiation of polymerization. If an amount of the photoinitiator is more than 50 parts by weight, a film strength of the resulting cured coating may become poor.
- a photosensitizer employed in the present invention is at least one material selected from the group consisting of sulfolene, sulfolene derivatives, isatin, and isatin derivatives.
- Sulfolene is a compound of the general formula:
- the sulfolene derivatives include a sulfonene compound having at least one of the hydrogen atoms substituted to provide a substituent bonded to the cyclic moiety of the sulfolene.
- substituents include an alkyl group of 1-5 carbon atoms, an alkoxy group of 1-5 carbon atoms, halogen, cyano group, an amino group, a phenyl group, and the like.
- Isatin is a compound of the general formula:
- the isatin derivatives include an isatin compound having at least one of the hydrogen atoms substituted to provide a substituent bonded to the cyclic moiety of the isatin.
- substituents include an alkyl group of 1-5 carbon atoms, an alkoxy group of 1-5 carbon atoms, halogen, a cyano group, an amino group, a phenyl group, and the like.
- the photosensitizer of the present invention such as sulfolene and isatin and derivatives thereof may be employed alone or in combination with each other and/or in combination with additional photosensitizers, such as anthraquinone.
- the photosensitizer of the present invention is employed in an amount 1 to 200, preferably 10 to 50 parts by weight based on 100 parts by weight of a photoinitiator. If an amount of the photosensitizer is less than 1 part by weight, a sensitizing function may become insufficient. If an amount of the photosensitizer is more than 200 parts by weight, latency of the photosensitizer may become poor, a breakage during storage may occur, and a cost of the composition way become high.
- a composition of the present invention itself is a photocurable composition for use in a variety of applications, and exhibits superior curability to visible light irradiation.
- a photocurable composition of the present invention may be formulated as an emulsion by using an emulsifier, however it is most preferable that a photocurable composition of the present invention is used as a luster agent for use in an automobile.
- An emulsifier employed includes a negative ionic, positive ionic, nonionic and amphoteric emulsifiers such as a salt of fatty acid, an ester of fatty acid, and fluorine or silicone class emulsifier.
- An * emulsifier of the present invention is employed in an amount of 1 to 100, preferably 5 to 50 parts by weight based on 100 parts by weight of a photopolymerizable monomer or oligomer.
- An aqueous medium may be employed in combination with an emulsifier.
- a water miscible organic solvent and/or water were generally used as an aqueous medium.
- the aqueous medium include an alcohol such as methanol, ethanol, isopropyl alcohol, glycerol and ethylene glycol, an ether such as dimethyl ether, diethyl ether, methyl cellosolve and ethyl cellosolve, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
- An amount of the aqueous medium employed is not limited, but may be used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of water.
- a luster agent comprising a photocurable composition of the present invention exhibits remarkably good lustering ability, gloss, water repellency and stain resistance and durability, when it is applied in a thickness of 0.01 to 5 ⁇ m on an automobile body or exterior part as the substrate.
- Solvent based photocurable compositions were prepared by blending components indicated in Table 1. The resulting compositions were coated on test-pieces in thickness of 1 ⁇ m by using a buff made of sponge. The test piece was a cold rolled steel panel on which an acrylic urethane paint (Nax BESTA available from Nippon Paint Co., Ltd.) was coated.
- the resulting coatings were photocured by using a halogen lamp of 300 watts in power at a distance of 20 cm for Examples 1 and 2 and Comparative Examples 1 and 2, or with direct sunlight for Example 3 and 4 and Comparative Examples 3 and 4.
- the time to cure for each sample was indicated in Table 1.
- a stain resistance was then evaluated by the following procedure. A sample for evaluating stain resistance was aged outdoor for two weeks at first; the sample was then wiped with a clean cloth; and thereafter a residue of a mud stain was determined.
- organopolysiloxane 1 was an alicyclic epoxy silicone having a viscosity of 8000 cps and an epoxy equivalent of 4000 available from Toray Dow Corning Silicone K.K. under the tradename "BY16-839”
- organopolysiloxane 2 was an alicyclic epoxy silicone having a viscosity of 30 cps and an epoxy equivalent of 600-700 obtained from Shinetsu Chemical Co., Ltd. under the tradename "X-22-169AS”.
- Table 1 Table 1
- organopolysiloxane 1 100 100 - 50 100 100 100 100 100 organopolysiloxane 2 - - 100 50 - - - -
- camphorquinone - - - - 1 - 0.5 - anthraquinone - - - - - 0.5 0.5 - acridine orange - - - - - - - 1
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
A photocurable composition comprising: (a) a photopolymerizable monomer or oligomer; (b) a photoinitiator; and (c) a photosensitizer, wherein the photosensitizer comprises at least one material selected from the group consisting of sulfolene, sulfolene derivatives, isatin, and isatin derivatives.
Description
PHOTOCURABLE COMPOSITION
Technical Field -- The present invention relates to a photocurable composition, and in particular, to a photocurable composition preferably employed for a luster agent for coating an automobile body and the like, including, for example, a coated surface of an automobile, a plastic bumper, and a tire. Background Art
Conventionally, a wax such as carnuba wax, polyethylene wax, a silicone such as dimethyl polysiloxane, and a variety of modified silicones, and the like, have been employed as a luster agent for use on the exterior of an automobile. However, these luster agents do not impart sufficient gloss, water repellency and stain resistance, and have poor durability.
Although employment of a polymerized wax or silicone has been proposed in order to improve durability of a luster agent, such techniques can diminish the waxing processability of the luster composition. Thus, photocurable compositions mentioned below have been proposed. Japanese Patent Kokai Publication No. S51-134794 disclose a visible light curable composition comprising an epoxy resin, an aryl halonium salt and an organic dye. The epoxy resin disclosed in the reference may be obtained from a reaction of bisphenol A with epichlorohydrin. However, the epoxy resin itself shows no gloss nor stain resistance, and it hardly be used as a luster agent.
A UV curable silicone releasing composition having epoxy and/or acrylic functionality, which is disclosed in Japanese Patent Kokai Publication S58-213024, cannot
be employed as a luster agent, since the resin is designed to function as a releasing agent.
A UV curable organopolysiloxane composition disclosed in Japanese Patent Kokai Publication H4-33960 comprises a organopolysiloxane having both acrylic and epoxy functionality, and a specific sulfonate photoinitiator. Even though the composition is photocured in the presence of air as a luster agent, oxygen contained in the air affects and makes the surface of the coating tacky, and the resulting coating lacks durability. Further, another problem is presented in that a UV (i.e., ultraviolet light) irradiation apparatus is needed for the composition.
Description of the Invention
The present invention overcomes the above described prior art problems while providing a specific photocurable composition which is curable by using a visible as well as UV light. The photocurable composition shows remarkably good properties when it is employed as a luster agent.
The present invention relates to a photocurable composition comprising: (a) a photopolymerizable monomer or oligomer; (b) a photoinitiator; and (c) a photosensitizer, wherein the photosensitizer comprises at least one material selected from the group consisting of sulfolene, sulfolene derivatives, isatin, and isatin derivatives.
A photopolymerizable monomer or oligomer employed in the present invention includes a monomeric or oligomeric compound having any one or both of an epoxy group and a vinyl group.
Preferred photopolymerizable monomers or oligomers include organopolysiloxanes having an epoxy group or a vinyl group. The organopolysiloxane may be prepared by hydrosilyl-addition of an epoxy compound to an
organopolysiloxane having a n-SiH bond. Alternatively, the organopolysiloxane may be prepared by hydrosilyl- addition of an ω-haloolefin to an organopolysiloxane having a n-SiH bond, and then, replacing the halogen with an acrylate in the presence of a base, according to a procedure disclosed in Japanese Patent Kokai Publication No. S58-213024. However, an organopolysiloxane having an epoxy group is preferred as the photopolymerizable compound, because it is not affected by oxygen.
Examples of suitable organopolysiloxanes having an epoxy group are those represented by the following general formulae I, II, and III.
III
In formulae I, II, and III, x has a value of 0 to 100; y has a value of 1 to 100; and n has a value of 0 to 100. If x or n is 0, then the molecule has a hydrogen atom or other monovalent substituent bonded to the Si atom in the remaining structure in place
thereof. The group R is a divalent linking group. For example, group R can be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. The R group is preferably aliphatic. Examples of such alkylene groups for group R include ethylene, ethylene, propylene and butylene, and so forth.
The compounds of formulae I, II and III can be used solely or in combinations thereof without' limitation. The compounds of formulae I, II and III contemplated for the present invention preferably have a viscosity of 10°-105 cps at 25°C and an epoxy equivalent of 102-104. An alicyclic epoxy-modified organopolysiloxane, such as represented by formulae I, II, and III, is very useful due to its high reactivity. Alternatively, as the photopolymerizable compound having a vinyl group, suitable compounds include an alkyl ( eth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2- ethylhexyl (meth)acrylate, n-butyl (meth)acrylate and the like; and another vinyl compound such as styrene, α-methyl styrene, N-methyl carbazole, isobutyl vinyl ether, vinyl acetate and vinyl pyrrolidone; and the like.
The photoinitiator employed in the present invention is not particularly limited as long as it is a photoinitiator which initiates a polymerization of the above-described epoxy group or vinyl group upon exposure to light. A preferred photoinitiator employed in the present invention includes an onium salt, since a cation polymerization can be carried out by using the onium salt. In general, any onium salt conventionally used as a photoinitiator can be employed. Specific examples of the onium salt include triphenylsulfonium hexafluoroantimonate, bis(dodecylphenyl)iodoniu hexafluoroantimonate, diphenyliodonium hexafluorophosphate, di-4,4-dimethylphenyliodonium
hexafluoroacetate and the like. A particularly preferred onium salt employed in the present invention is triphenylsulfonium hexafluoroantimonate because of its high reactivity. The photoinitiator of the present invention is employed in an amount 0.1 to 50 parts, preferably 0.5 to 10 parts, by weight, based on 100 parts by weight of the photopolymerizable monomer or oligomer. if an amount of the photoinitiator is less than 0.1 parts by weight, a durable luster coating may not be provided due to an insufficient initiation of polymerization. If an amount of the photoinitiator is more than 50 parts by weight, a film strength of the resulting cured coating may become poor. A photosensitizer employed in the present invention is at least one material selected from the group consisting of sulfolene, sulfolene derivatives, isatin, and isatin derivatives.
Sulfolene is a compound of the general formula:
The sulfolene derivatives include a sulfonene compound having at least one of the hydrogen atoms substituted to provide a substituent bonded to the cyclic moiety of the sulfolene. Examples of such substituents include an alkyl group of 1-5 carbon atoms, an alkoxy group of 1-5 carbon atoms, halogen, cyano group, an amino group, a phenyl group, and the like.
Isatin is a compound of the general formula:
The isatin derivatives include an isatin compound having at least one of the hydrogen atoms substituted to provide a substituent bonded to the cyclic moiety of the isatin. Examples of such substituents include an alkyl group of 1-5 carbon atoms, an alkoxy group of 1-5 carbon atoms, halogen, a cyano group, an amino group, a phenyl group, and the like.
The photosensitizer of the present invention, such as sulfolene and isatin and derivatives thereof may be employed alone or in combination with each other and/or in combination with additional photosensitizers, such as anthraquinone.
The photosensitizer of the present invention is employed in an amount 1 to 200, preferably 10 to 50 parts by weight based on 100 parts by weight of a photoinitiator. If an amount of the photosensitizer is less than 1 part by weight, a sensitizing function may become insufficient. If an amount of the photosensitizer is more than 200 parts by weight, latency of the photosensitizer may become poor, a breakage during storage may occur, and a cost of the composition way become high.
A composition of the present invention itself is a photocurable composition for use in a variety of applications, and exhibits superior curability to visible light irradiation. A photocurable composition of the present invention may be formulated as an
emulsion by using an emulsifier, however it is most preferable that a photocurable composition of the present invention is used as a luster agent for use in an automobile. An emulsifier employed includes a negative ionic, positive ionic, nonionic and amphoteric emulsifiers such as a salt of fatty acid, an ester of fatty acid, and fluorine or silicone class emulsifier. An* emulsifier of the present invention is employed in an amount of 1 to 100, preferably 5 to 50 parts by weight based on 100 parts by weight of a photopolymerizable monomer or oligomer.
An aqueous medium may be employed in combination with an emulsifier. A water miscible organic solvent and/or water were generally used as an aqueous medium. Examples of the aqueous medium include an alcohol such as methanol, ethanol, isopropyl alcohol, glycerol and ethylene glycol, an ether such as dimethyl ether, diethyl ether, methyl cellosolve and ethyl cellosolve, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. An amount of the aqueous medium employed is not limited, but may be used in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of water. A luster agent comprising a photocurable composition of the present invention exhibits remarkably good lustering ability, gloss, water repellency and stain resistance and durability, when it is applied in a thickness of 0.01 to 5 μm on an automobile body or exterior part as the substrate. These and other aspects of the invention are further illustrated by the following nonlimiting examples.
Examples and Comparative Examples Solvent based photocurable compositions were prepared by blending components indicated in Table 1. The resulting compositions were coated on test-pieces in thickness of 1 μm by using a buff made of sponge. The test piece was a cold rolled steel panel on which an acrylic urethane paint (Nax BESTA available from Nippon Paint Co., Ltd.) was coated.
The resulting coatings were photocured by using a halogen lamp of 300 watts in power at a distance of 20 cm for Examples 1 and 2 and Comparative Examples 1 and 2, or with direct sunlight for Example 3 and 4 and Comparative Examples 3 and 4. The time to cure for each sample was indicated in Table 1. A 20° gloss of each sample, which is prepared by coating the resulting composition on a color sample available from Murakami Color Materials Co., was determined according to JIS 8741. A stain resistance was then evaluated by the following procedure. A sample for evaluating stain resistance was aged outdoor for two weeks at first; the sample was then wiped with a clean cloth; and thereafter a residue of a mud stain was determined. In the following summarized examples, "organopolysiloxane 1" was an alicyclic epoxy silicone having a viscosity of 8000 cps and an epoxy equivalent of 4000 available from Toray Dow Corning Silicone K.K. under the tradename "BY16-839", and "organopolysiloxane 2" was an alicyclic epoxy silicone having a viscosity of 30 cps and an epoxy equivalent of 600-700 obtained from Shinetsu Chemical Co., Ltd. under the tradename "X-22-169AS". The results are summarized in Table 1.
Table 1
Examples Comparative Examples
1 2 3 4 1 2 3 4
organopolysiloxane 1 100 100 - 50 100 100 100 100 organopolysiloxane 2 - - 100 50 - - - -
initiator1 3 3 3 3 3 3 3 3
sulfolene 1 - 1 1 - - - -
isatin - 1 - - - - - -
camphorquinone - - - - 1 - 0.5 - anthraquinone - - - - - 0.5 0.5 - acridine orange - - - - - - - 1
methyl cellosolve 25 25 25 25 25 25 25 25
time to cure (min.) 1 1.5 1.5 1 3 3 5 3
20° gloss 68 65 70 65 65 64 65 69 stain resistance2 O O O O O O O O
ø 3SSbF6, where ø means phenyl. "O" means acceptable and "good".
Claims
1. A photocurable composition comprising: (a) a photopolymerizable monomer or oligomer; (b) a photoinitiator; and (c) a photosensitizer, wherein the photosensitizer comprises at least one material selected from the group consisting of sulfolene, sulfolene derivatives, isatin, and isatin derivatives.
2. The photocurable composition according to claim 1, wherein said photopolymerizable monomer or oligomer comprises an epoxy-containing organosiloxane.
3. The photcurable composition according to claim 1, wherein said photopolymerizable monomer or oligomer comprises a compound represented by any one of general formulae I, II, and III:
wherein x and n each independently has a value of 0 to 100; y has a value of 1 to 100; and R is a divalent linking group having 1 to 10 carbon atoms.
4. The photocurable composition according to claim 1, wherein said photopolymerizable monomer or oligomer is selected from the group consisting*of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, styrene, α-methyl styrene, N-methyl carbazole, isobutyl vinyl ether, vinyl acetate, and vinyl pyrrolidone.
5. The photocurable composition according to claim 1, wherein said photosensitizer i contained in an amount of 1 to 200 parts by weight based on 100 parts by weight of said photoinitiator.
6. The photocurable composition according to claim 1, wherein said photoinitiator is contained in an amount 0.1 to 50 parts, by weight, based on 100 parts by weight of said photopolymerizable monomer or oligomer.
7. The photocurable composition according to claim 1, wherein said photoinitiator comprises an onium salt.
8. The photocurable composition according to claim 7, wherein said onium salt is selected from the group consisting of triphenylsulfonium hexafluoroantimonate , bis(dodecylphenyl)iodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and di-4,4-dimethylphenyliodonium hexafluoroacetate.
9. The photocurable composition according to claim 7, wherein said onium salt comprises triphenyl- sulfonium hexafluoroantimonate.
10. The photocurable composition according to claim 1, wherein said photocurable composition further comprises an emulsifier compound, and said photocurable composition is in an emulsion form. •
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP314734/93 | 1993-12-15 | ||
JP31473493A JPH07207188A (en) | 1993-12-15 | 1993-12-15 | Photocurable composition |
PCT/US1994/013638 WO1995016722A1 (en) | 1993-12-15 | 1994-11-28 | Photocurable composition |
Publications (1)
Publication Number | Publication Date |
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EP0734405A1 true EP0734405A1 (en) | 1996-10-02 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP95903615A Withdrawn EP0734405A1 (en) | 1993-12-15 | 1994-11-28 | Photocurable composition |
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EP (1) | EP0734405A1 (en) |
JP (1) | JPH07207188A (en) |
CA (1) | CA2177700A1 (en) |
WO (1) | WO1995016722A1 (en) |
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KR100557553B1 (en) * | 2001-06-29 | 2006-03-03 | 주식회사 하이닉스반도체 | Photoresist monomer, polymer thereof and photoresist composition containing it |
US20030158112A1 (en) | 2002-02-15 | 2003-08-21 | Johns Hopkins University School Of Medicine | Selective induction of apoptosis to treat ocular disease |
WO2021236489A1 (en) * | 2020-05-18 | 2021-11-25 | Bowling Green State University | Biomass derived diketones as efficient visible light photoinitiators |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US3428590A (en) * | 1965-01-22 | 1969-02-18 | Yawata Chem Ind Co Ltd | Process for the production of trioxane copolymers |
BE794482A (en) * | 1972-01-25 | 1973-07-24 | Du Pont | PHOTOPOLYMERISABLE COMPOSITIONS CONTAINING CYCLIC CIS- ALPHA -DICARBONYL COMPOUNDS AND SELECTED SENSITIZERS |
US3847771A (en) * | 1973-03-30 | 1974-11-12 | Scm Corp | Uv and laser curing of pigmented polymerizable binders |
US4172157A (en) * | 1978-09-19 | 1979-10-23 | Celanese Corporation | Aminoplast/alkyd coating composition |
JPS58149042A (en) * | 1982-03-02 | 1983-09-05 | Tokyo Ohka Kogyo Co Ltd | Positive type photosensitive composition |
JPH068402B2 (en) * | 1982-09-27 | 1994-02-02 | ゼネラル・エレクトリック・カンパニイ | Durable silicone emulsion polish |
AU3410584A (en) * | 1983-10-27 | 1985-05-02 | General Electric Company | Durable silicone emulsion polish |
JP2623309B2 (en) * | 1988-02-22 | 1997-06-25 | ユーシービー ソシエテ アノニム | How to get a resist pattern |
US5023140A (en) * | 1988-06-20 | 1991-06-11 | Armstrong World Industries, Inc. | Floor covering having a modified glass wear layer |
DE4124806A1 (en) * | 1991-07-26 | 1993-01-28 | Bayer Ag | PROCESS FOR COATING POLYCARBONATE SHAPING BODIES |
-
1993
- 1993-12-15 JP JP31473493A patent/JPH07207188A/en active Pending
-
1994
- 1994-11-28 EP EP95903615A patent/EP0734405A1/en not_active Withdrawn
- 1994-11-28 CA CA 2177700 patent/CA2177700A1/en not_active Abandoned
- 1994-11-28 WO PCT/US1994/013638 patent/WO1995016722A1/en not_active Application Discontinuation
Non-Patent Citations (1)
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See references of WO9516722A1 * |
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WO1995016722A1 (en) | 1995-06-22 |
CA2177700A1 (en) | 1995-06-22 |
JPH07207188A (en) | 1995-08-08 |
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