WO2022147864A1 - 一种适于eb固化的光致变色组合物制品及制备方法 - Google Patents
一种适于eb固化的光致变色组合物制品及制备方法 Download PDFInfo
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- WO2022147864A1 WO2022147864A1 PCT/CN2021/074178 CN2021074178W WO2022147864A1 WO 2022147864 A1 WO2022147864 A1 WO 2022147864A1 CN 2021074178 W CN2021074178 W CN 2021074178W WO 2022147864 A1 WO2022147864 A1 WO 2022147864A1
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- WIPO (PCT)
- Prior art keywords
- curing
- photochromic
- photochromic composition
- polyol
- added
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001723 curing Methods 0.000 title abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001227 electron beam curing Methods 0.000 claims abstract description 30
- -1 acrylate diol Chemical class 0.000 claims abstract description 29
- 230000005855 radiation Effects 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims abstract description 5
- 239000004814 polyurethane Substances 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 238000003847 radiation curing Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 47
- 239000004417 polycarbonate Substances 0.000 claims description 29
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 15
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 15
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- 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 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 5
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000006378 damage Effects 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 3
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 31
- 239000008199 coating composition Substances 0.000 description 23
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 14
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 14
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 8
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 238000005562 fading Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical group CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 208000025174 PANDAS Diseases 0.000 description 1
- 208000021155 Paediatric autoimmune neuropsychiatric disorders associated with streptococcal infection Diseases 0.000 description 1
- 240000000220 Panda oleosa Species 0.000 description 1
- 235000016496 Panda oleosa Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
- G02C7/102—Photochromic filters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Definitions
- the invention belongs to the field of optical films, in particular to a photochromic composition product suitable for EB curing and a preparation method, which are mainly applied to the production and processing of color-changing glasses and color-changing films.
- Coating color-changing technology is a process in which the lens has been cured, and a layer of color-changing coating is applied on the surface, and the film is cured under certain conditions. This process perfectly solves the three defects of the substrate discoloration technology.
- this technology has been monopolized by the foreign giant Essilor.
- Domestic glasses manufacturers have imitated Essilor's coating color-changing technology for many years, and the degree of imitation of this technology has reached 80%. Heating at a temperature of about 120°C for 2 hours is cured to form a film.
- the technology is time-consuming, energy-intensive, and has low production efficiency and product yield.
- Many domestic eyewear manufacturers have tried to develop coating color-changing photo-curing technology, but all ended in failure. The main reason is that photochromic powder has a certain lifespan. Loss of the ability to fade.
- the object of the present invention is to firstly provide a photochromic composition suitable for EB curing.
- This photochromic composition can be widely used in the technical field of lens coating, and the use of EB curing technology can effectively solve the problem in the UV curing process.
- the problem of damage to the photochromic powder can also improve production efficiency and product qualification rate, thereby reducing production costs.
- a photochromic composition suitable for EB curing the following components, in parts by weight, include:
- the molecular formula of the acrylate diol is as follows:
- Described catalyst A is any one in tin ethylhexanoate, dibutyltin dilaurate or stannous octoate.
- the catalyst B is any one of 2,4,6-tris(dimethylaminomethyl)phenol, boron trifluoride ether, dimethylimidazole or triphenylphosphine.
- a preparation method of the above-mentioned photochromic composition suitable for EB curing is provided, and the dosage of each component is according to the above-mentioned parts by weight, comprising the following steps:
- the temperature is lowered to 60°C, acrylate diol is added, catalyst A, diluent, and diisocyanate are added, and the temperature is kept at 60-80°C.
- a preparation method of a product comprising the above-mentioned photochromic composition suitable for EB curing is provided, and the consumption of each component comprises the following steps according to the above-mentioned parts by weight:
- the temperature is lowered to 60°C, acrylate diol is added, catalyst A, diluent, and diisocyanate are added, and the temperature is kept at 60-80°C.
- the base material is any one of polycarbonate material, polyurethane material, polyacrylic acid material.
- the EB curing is carried out under the condition of 120kv voltage and 50KGy radiation dose.
- an article comprising at least a coating layer made from the above-mentioned photochromic composition suitable for EB curing, which is made by the above-mentioned method.
- the polyol is any one or a combination of two or more of polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyester polyol, dihydric alcohol or dihydric mercaptan; Described diisocyanate is any one or the combination of two or more in XDI, HDI, MDI, IPDI or HMDI; Described thinner is ethyl acetate, butyl acetate, dimethyl carbonate, toluene, xylene, propylene glycol Any one in methyl ether acetate; Described antioxidant is 2,6-di-tert-butyl-p-cresol, bis(3,5-tertiary butyl-4-hydroxyphenyl) sulfide, tetrakis[ A kind of ⁇ -(3,5-tertiary butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and thiodipropionic
- the present invention introduces the carbon-carbon double bond of acrylate into the polyurethane system, and simultaneously grafts multiple flexible structures and multiple rigid structures on one molecular segment by means of prepolymerization.
- Acrylate diol with phenol A structure can be polymerized with polyol and diisocyanate to form multifunctional urethane acrylate.
- the average functionality of the polymer can reach 10 to 15, so it provides both hardness and solvent resistance.
- grafting a flexible structure on the molecular chain dominated by bisphenol A can also improve the discoloration and fading speed of the photochromic fuel.
- Using EB curing without adding photoinitiator, can increase the conversion rate of double bonds to more than 95%, further improve the hardness and solvent resistance of the film layer, so that the photochromic composition is well attached to the surface of the transparent substrate.
- the damage to the photochromic powder caused by ultraviolet light is avoided, and the curing time of the coating is shortened, thereby improving the qualified rate of finished products and reducing the production cost.
- the invention provides a photochromic composition, a product and a preparation method that are suitable for EB curing.
- EB radiation curing is to use high-energy electron beams to bombard the carbon-carbon double bonds in polymer molecules to break them to generate free radicals, thereby initiating polymerization. , this process does not require ultraviolet radiation and does not generate ultraviolet light, and does not harm the photochromic powder; the photochromic coating composition has good light transmittance, fastness and aging resistance on the substrate, and has Better discoloration depth and fading speed.
- PEG600 polyethylene glycol (molecular weight 600)
- PEG1000 polyethylene glycol (molecular weight 1000)
- PEG800 polyethylene glycol (molecular weight 800)
- HMDI 4,4'-dicyclohexylmethane diisocyanate
- Bisphenol A was purchased from Nanya, Taiwan
- Glycidyl methacrylate was purchased from Mitsubishi, Japan
- IPDI isophorone diisocyanate
- Catalyst A Dibutyltin dilaurate
- Catalyst B Triphenylphosphine
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 100kv, and the amount of radiation 20KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 120kv, the amount of radiation 50KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 100kv, and the amount of radiation 20KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 120kv, the amount of radiation 50KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 100kv, and the amount of radiation 20KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 120kv, the amount of radiation 50KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 120kv, the amount of radiation 50KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 130kv, the amount of radiation 70KGy, and finally get PC color-changing lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 120kv, the amount of radiation 50KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 130kv, the amount of radiation 70KGy, and finally get PC color-changing lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 120kv, the amount of radiation 50KGy, finally get PC photochromic lenses.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, and then irradiated with a 300W infrared lamp for 2 minutes, under the protection of nitrogen, through EB curing, using a voltage of 130kv, the amount of radiation 70KGy, and finally get PC color-changing lenses.
- the maximum discoloration depth of the photochromic glasses that is, the light transmittance when the discoloration is the deepest, is related to the addition ratio of the photochromic powder, independent of the molecular weight and addition amount of the polyol, and also related to the molecular weight of the isocyanate.
- the light transmittance when the photochromic glasses do not change color is only related to the addition ratio of the photochromic powder; but the molecular weight and addition ratio of PEG seriously affect the fading rate of the photochromic glasses, and the molecular weight is not change, the more the proportion added, the faster the fading speed; the more the proportion added, the greater the molecular weight, the faster the fading speed.
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Abstract
本发明提供了一种适于EB固化的光致变色组合物制品及制备方法，组合物包含多元醇、丙烯酸酯二醇、二异氰酸酯、催化剂、阻聚剂、稀释剂、光致变色粉、抗氧剂、紫外光吸收剂、流平剂和消泡剂，得到光致变色组合物，将其涂覆于基底材料上，经过红外灯辐射，在氮气的保护下，再经过EB辐射固化成膜。本发明将丙烯酸酯的碳碳双键引入聚氨酯体系中，并以预聚的方法将多个柔性结构和多个刚性结构同时接枝在一个分子链段上，最后通过EB辐射固化使得光之变色组合物良好的附着在透明基材表面。避免了紫外光对光致变色粉的伤害，缩短了涂层固化时间，从而提高成品合格率降低生产成本。
Description
本发明属于光学膜领域，具体涉及一种适于EB固化的光致变色组合物制品及制备方法，主要应用于变色眼镜及变色膜的生产与加工。
目前市面上的变色眼镜分为两种，一种是基材变色，是将光致变色粉溶解在树脂或单体里，然后浇筑在模具里，高温固化成型。该工艺存在以下几个缺陷：1)变色时出现变色深度深浅不一，容易出现熊猫眼的视觉，给客户带来极其不好的视觉体验；2)在制备半成品时，很多变色粉在半成品抛光研磨时被浪费掉，造成极大的成本负担；3)由于原材料限制，该工艺只能制备1.56和1.61镜片，无法制备1.67或1.71高附加值镜片。
涂层变色技术，是镜片已经固化好，在表面涂一层可以变色的涂层，在一定条件下固化成膜的工艺。该工艺完美的解决了基材变色技术的三个缺陷。但是由于该工艺的开发难度较大，研发周期较长，工艺要求苛刻，该技术一直被国外巨头依视路垄断。国内眼镜生产企业通过多年模仿依视路的涂层变色技术，该技术模仿程度已经达到80％，该涂层变色技术为热固技术，是将涂层变色液涂布在镜片基材上，在120℃左右的温度下加热2小时固化成膜。该技术耗时长、能耗高、生产效率和产品合格率低。国内多家眼镜生产企业尝试研发涂层变色光固技术，均以失败告终，主要原因是因为光致变色粉具有一定的寿命，在辐射光强较大的紫外光下，会出现发黄，甚至失去退变色能力的情况。
发明内容
本发明的目的首先是提供一种适于EB固化的光致变色组合物，这种光致变色组合物可被广泛应用于镜片涂层技术领域，使用EB固化技术可以有效解决紫外光固化过程中对光致变色粉的伤害问题，还能提高生产效率、产品合格率，进而降低生产成本。
具体技术方案：一种适于EB固化的光致变色组合物，以下各组分按重量份计，包括：
所述丙烯酸酯二醇的分子式如下：
所述的催化剂A为乙基己酸锡、二月桂酸二丁基锡或者辛酸亚锡中的任意一种。
进一步地，所述丙烯酸酯二醇的制备过程如下：
将双酚A 30～80重量份和甲基丙烯酸缩水甘油酯30～80重量份，加入催化剂B和阻聚剂在90℃温度条件下，反应得到丙烯酸酯二醇；
所述的催化剂B为2,4,6-三(二甲胺基甲基)苯酚、三氟化硼乙醚、二甲基咪唑或者三苯基膦中的任意一种。
作为本发明的第二个方面，提供一种上述适于EB固化的光致变色组合物的制备方法，各组分用量按照上述重量份，包括以下步骤：
将多元醇在100～130℃下抽真空1～2小时后，降温至60℃，加入丙烯酸酯二元醇，再加入催化剂A，稀释剂，二异氰酸酯，在60～80℃温度条件下，保温连续搅拌2小时，得到多官能度聚氨酯丙烯酸酯；再依次加入阻聚剂和光致变色粉，在80℃保温搅拌1小时，再加入抗氧剂、紫外光吸收剂、流平剂、消泡剂，搅拌均匀得到光致变色组合物。
作为本发明的第三个方面，提供一种包含上述适于EB固化的光致变色组合物的制品的制备方法,各组分用量按照上述的重量份，包括以下步骤：
将多元醇在100～130℃下抽真空1～2小时后，降温至60℃，加入丙烯酸酯二元醇，再加入催化剂A，稀释剂，二异氰酸酯，在60～80℃温度条件下，保温连续搅拌2小时，得到多官能度聚氨酯丙烯酸酯；再依次加入阻聚剂和光致变色粉，在80℃保温搅拌1小时，再加入抗氧剂、紫外光吸收剂、流平剂、消泡剂，搅拌均匀得到光致变色组合物；将该光致变色组合物涂覆于基底材料上，经过红外灯辐射2～3分钟，在氮气的保护下，在60～120KV电压条件下，10～80KGy辐射量下，经过EB辐射固化形成薄膜，得到光学制品。
进一步地，所述的基底材料为聚碳酸酯材料、聚氨酯材料、聚丙烯酸材料、的任意一种。
进一步地，所述EB固化是在120kv电压，50KGy辐射量条件下进行。
作为本发明的第四个方面，提供一种制品，至少包含由上述适于EB固化的光致变色组合物制成的涂层，是由上述方法制成的。
其中，所述多元醇为聚醚多元醇、聚碳酸酯多元醇、聚己内酯多元醇、聚酯多元醇、二元醇或者二元硫醇中的任意一种或者两种以上的组合；所述二异氰酸酯为XDI、HDI、MDI、IPDI或者HMDI中的任意一种或者两种以上的组合；所述稀释剂为醋酸乙酯、醋酸丁酯、碳酸二甲酯、甲苯、二甲苯、丙二醇甲醚醋酸酯中的任意一种；所述抗氧剂为2，6-二叔丁基对甲酚、双(3，5-三级丁基-4-羟基苯基)硫醚、四〔β-(3，5-三级丁基-4-羟基苯基)丙酸〕季戊四醇酯、硫代二丙酸双酯种的一种；所述紫外光吸收剂为LOWILITE22、LOWILITE26、LOWILITE28或者LOWILITE234中的任意一种；所述光致变色粉为维缦公司的midnight grey、volcanic grey、misty grey的任意一种或者两种以上的组合；所述流平剂为Levaslip8629、Levaslip839、Levaslip837或者Levaslip810中的任意一种或者两种以上的组合；所述消泡剂为Defom2700、Defom5500、Defom8700或者Defom6500中的任意一种或者两种以上的组合；所述阻聚剂为对苯二酚、2-叔丁基对苯二酚、甲基对苯二酚、4-甲氧基苯酚中的任意一种。
本发明的原理是：本发明将丙烯酸酯的碳碳双键引入聚氨酯体系中并以预聚的方法将多个柔性结构和多个刚性结构同时接枝在一个分子链段上，同时由于采 用双酚A结构的丙烯酸酯二元醇，可以搭配多元醇和二异氰酸酯聚合成多官能度的聚氨酯丙烯酸酯，该聚合物的平均官能度可以达到10～15，因此既提供了硬度又提供了耐溶剂性能，而且在以双酚A为主的分子链上接枝柔性结构，还可以提升光致变色燃料的变色和褪色速度。采用EB固化，可以不用添加光引发剂，还可以提高双键转化率到95％以上，进一步提升膜层的硬度和耐溶剂性能，使得该光致变色组合物良好的附着在透明基材表面。避免了紫外光对光致变色粉的伤害，缩短了涂层固化时间，从而提高成品合格率降低生产成本。
本发明提供的含有适于EB固化的光致变色组合物、制品及制备方法，EB辐射固化是采用高能电子束轰击聚合物分子中的碳碳双键，使其断裂产生自由基，从而引发聚合，该过程不需要紫外光辐射也不产生紫外光，对光致变色粉没有伤害；使得光致变色涂层组合物在基材上具有良好的透光率、牢固度和耐老化性能，同时具有较好的变色深度和褪色速度。
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
以下结合具体实施例对本发明作进一步说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。另外，本发明中提到的喷涂方法是现有技术中公开或已知的技术，在此不再赘述。
下述实施例采用的化合物的名称(下述化合物均为市售原料)：
PEG600：聚乙二醇(分子量600)
PEG1000：聚乙二醇(分子量1000)
PEG800：聚乙二醇(分子量800)
HMDI：4,4’-二环己基甲烷二异氰酸酯
双酚A购于台湾南亚
甲基丙烯酸缩水甘油酯购于日本三菱
IPDI:异佛尔酮二异氰酸酯
HDI:六亚甲基二异氰酸酯
CHDM:环己烷二甲醇
催化剂A：二月桂酸二丁基锡
催化剂B：三苯基膦
阻聚剂:4-甲氧基苯酚
稀释剂：碳酸二甲酯
德谦消泡剂Defom2700
德谦流平剂Levaslip8629
亚帝凡特紫外光吸收剂LOWILITE234
维缦公司光致变色粉midnight grey
维缦公司光致变色粉misty grey
抗氧剂:2，6-二叔丁基对甲酚
实施例1自制丙烯酸酯二元醇：
向容器中加入50g甲基丙烯酸缩水甘油酯、0.05g 4-甲氧基苯酚、0.3g三苯基膦,升温至90℃搅拌均匀后，再将40.12g双酚A分四次加入，全部加入后保温90℃搅拌1小时，得到丙烯酸酯二元醇，分子式如下：
实施例2：
实施例2.1：
向容器中加入26.83g PEG1000、1.16g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入7.94g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.07g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g 2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过 EB固化，采用电压100kv，辐射量20KGy，最后得到PC变色镜片。
实施例2.2：
向容器中加入26.83g PEG1000、1.16g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入7.94g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.07g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g 2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压120kv，辐射量50KGy，最后得到PC变色镜片。
实施例3：
实施例3.1：
向容器中加入26.83g PEG800、0.8g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入7.9g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.76g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g 2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压100kv，辐射量20KGy，最后得到PC变色镜片。
实施例3.2：
向容器中加入26.83g PEG800、0.8g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入7.9g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.76g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g 2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光 致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压120kv，辐射量50KGy，最后得到PC变色镜片。
实施例4：
实施例4.1：
向容器中加入26.83g PEG600、2.27g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入6.23g实施例1制得的实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.7g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压100kv，辐射量20KGy，最后得到PC变色镜片。
实施例4.2：
向容器中加入26.83g PEG600、2.27g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入6.23g实施例1制得的实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.7g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压120kv，辐射量50KGy，最后得到PC变色镜片。
实施例5：
实施例5.1：
向容器中加入28.02g PEG1000、1.21g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入8.31g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入12.46g的IPDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压120kv，辐射量50KGy，最后得到PC变色镜片。
实施例5.2：
向容器中加入28.02g PEG1000、1.21g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入8.31g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入12.46g的IPDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压130kv，辐射量70KGy，最后得到PC变色镜片。
实施例6：
实施例6.1：
向容器中加入25.25g PEG800、1.37g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入9.35g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.03g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g 2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过 EB固化，采用电压120kv，辐射量50KGy，最后得到PC变色镜片。
实施例6.2：
向容器中加入25.25g PEG800、1.37g CHDM搅拌均匀后，在120℃下抽真空1h，降温至60℃，加入9.35g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入14.03g的HMDI，滴加完毕后，80℃保温连续搅拌2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g 2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压130kv，辐射量70KGy，最后得到PC变色镜片。
实施例7：
实施例7.1：
向容器中加入30.08g PEG1000、1.29g CHDM搅拌匀后，在120℃下抽真空1h，降温至60℃，加入8.84g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入10.04g的HDI，滴加完毕后，80℃保温2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压120kv，辐射量50KGy，最后得到PC变色镜片。
实施例7.2：
向容器中加入30.08g PEG1000、1.29g CHDM搅拌匀后，在120℃下抽真空1h，降温至60℃，加入8.84g实施例1制得的丙烯酸酯二元醇、0.2g二月桂酸二丁基锡和50g碳酸二甲酯，然后缓慢滴加入10.04g的HDI，滴加完毕后，80℃保温2小时，然后加入0.02g 4-甲氧基苯酚、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02g2，6-二叔丁基对甲酚、0.02g LOWILITE234、0.1g Defom2700、0.1g Levaslip8629，混合均匀后得到光致变色 涂层组合物。将该光致变色涂层组合物喷涂在PC镜片表面，在800rpm转速下旋转20秒，然后在300W的红外灯辐射2分钟后，在氮气的保护下，经过EB固化，采用电压130kv，辐射量70KGy，最后得到PC变色镜片。
表1实施例2～7制备的光学制品测试结果
从实施例结果对比可以得出，光致变色眼镜的最大变色深度，即变色最深时透光率与光致变色粉的添加比例有关，与多元醇的分子量和添加量无关，也与异氰酸酯的分子量和组合物的官能团多少无关；光致变色眼镜不变色时的透光率也只与光致变色粉的添加比例有关；但是PEG的分子量和添加比例严重影响光致变色眼镜的褪色速率，分子量不变，添加比例越多，褪色速度越快；添加比例不变，分子量越大，褪色速度越快。电子束的电压越高，辐射量越大，光致变色组合物在PC镜片上面的附着力越好、硬度越高，当达到某个最佳值后，即使再增加电 压或辐射强度，制品的硬度、透光率等性能的变化不明显。采用刚性较强的HMDI可以获得更好的铅笔硬度，但刚性较强，固化后产生的应力较大，导致附着力不好；HDI可以获得更好的附着力，但是柔性较强，无法获得更好的铅笔硬度；对比可以得出，选用IPDI可以平衡附着力和铅笔硬度，达到最佳值。综合实验结果可以得出，选用IPDI和PEG1000，EB电子束电压为120KV，辐射量为50KGy，可以实现附着力、硬度、褪色速度所有性能达到最佳值。
Claims (10)
- 一种适于EB固化的光致变色组合物，其特征在于，包含以下各组分按重量份计：
所述丙烯酸酯二醇的分子式如下：
所述的催化剂A为乙基己酸锡、二月桂酸二丁基锡或者辛酸亚锡中的任意一种。 - 根据权利要求1所述的适于EB固化的光致变色组合物，其特征在于，所述丙烯酸酯二醇的制备过程如下：将双酚A 30～80重量份和甲基丙烯酸缩水甘油酯30～80重量份，加入催化剂B和阻聚剂，反应得到丙烯酸酯二醇；所述的催化剂B为2,4,6-三(二甲胺基甲基)苯酚、三氟化硼乙醚、二甲基咪唑或者三苯基膦中的任意一种。
- 一种如权利要求1或2所述适于EB固化的光致变色组合物的制备方法， 各组分用量按照权利要求1所述的重量份，其特征在于，包括以下步骤：将多元醇在100～130℃下抽真空1～2小时后，降温至60℃，加入丙烯酸酯二元醇，再加入催化剂A，稀释剂，二异氰酸酯，在60～80℃温度条件下，保温连续搅拌2小时，得到多官能度聚氨酯丙烯酸酯；再依次加入阻聚剂和光致变色粉，在80℃保温搅拌1小时，再加入抗氧剂、紫外光吸收剂、流平剂、消泡剂，搅拌均匀得到光致变色组合物。
- 一种包含权利要求1所述适于EB固化的光致变色组合物的制品的制备方法,各组分用量按照权利要求1所述的重量份，其特征在于，包括以下步骤：将多元醇在100～130℃下抽真空1～2小时后，降温至60℃，加入丙烯酸酯二元醇，再加入催化剂A，稀释剂，二异氰酸酯，在60～80℃温度条件下，保温连续搅拌2小时，得到多官能度聚氨酯丙烯酸酯；再依次加入阻聚剂和光致变色粉，在80℃保温搅拌1小时，再加入抗氧剂、紫外光吸收剂、流平剂、消泡剂，搅拌均匀得到光致变色组合物；将该光致变色组合物涂覆于基底材料上，经过红外灯辐射2～3分钟，在氮气的保护下，在60～120KV电压条件下，10～80KGy辐射量下，经过EB辐射固化形成薄膜，得到光学制品。
- 根据权利要求4所述制品的制备方法，其特征在于，所述EB固化是在120kv电压，50KGy辐射量条件下进行。
- 根据权利要求4所述制品的制备方法，其特征在于，所述基底材料为聚碳酸酯材料、聚氨酯材料或聚丙烯酸材料中的任意一种。
- 一种制品，其特征在于，至少包含由权利要求1所述的光致变色组合物制成的涂层。
- 一种制品，其特征在于，是由权利要求4或5所述制备方法制成的。
- 根据权利要求1所述适于EB固化的光致变色组合物，其特征在于，所述的多元醇为聚醚多元醇、聚碳酸酯多元醇、聚己内酯多元醇、聚酯多元醇、二元醇或者二元硫醇中的任意一种或者两种以上的组合。
- 根据权利要求1所述适于EB固化的光致变色组合物，其特征在于，所述的二异氰酸酯为XDI、HDI、MDI、IPDI或者HMDI中的任意一种或者两种以上的组合。
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| US20020136899A1 (en) * | 2001-03-21 | 2002-09-26 | Derojas Agustin Alberto | Lens with photochromic elastomer film and method of making it |
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| CN107216420A (zh) * | 2017-06-06 | 2017-09-29 | 上海甘田光学材料有限公司 | 聚合物多元醇及其组合物和用途 |
| CN107513345A (zh) * | 2017-09-19 | 2017-12-26 | 上海纵港广告器材股份有限公司 | 一种不饱和型聚氨酯涂层的制备方法 |
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| US20020136899A1 (en) * | 2001-03-21 | 2002-09-26 | Derojas Agustin Alberto | Lens with photochromic elastomer film and method of making it |
| US20030193044A1 (en) * | 2002-04-14 | 2003-10-16 | David Henry | Photochromic compositions, preparation thereof and articles made therefrom or coated therewith |
| CN101296963A (zh) * | 2005-09-07 | 2008-10-29 | 光学转变公司 | 包含含封端异氰酸酯粘合促进剂的可固化成膜组合物的光学元件 |
| CN102627910A (zh) * | 2012-03-24 | 2012-08-08 | 吉林建筑工程学院 | 一种光致变色丙烯酸聚氨酯清漆及其制备方法 |
| CN107216420A (zh) * | 2017-06-06 | 2017-09-29 | 上海甘田光学材料有限公司 | 聚合物多元醇及其组合物和用途 |
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