WO2022147863A1 - 一种超支化聚氨酯乙烯基醚的光致变色组合物、制品及制备方法 - Google Patents
一种超支化聚氨酯乙烯基醚的光致变色组合物、制品及制备方法 Download PDFInfo
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- WO2022147863A1 WO2022147863A1 PCT/CN2021/074166 CN2021074166W WO2022147863A1 WO 2022147863 A1 WO2022147863 A1 WO 2022147863A1 CN 2021074166 W CN2021074166 W CN 2021074166W WO 2022147863 A1 WO2022147863 A1 WO 2022147863A1
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- Prior art keywords
- vinyl ether
- add
- photochromic composition
- hours
- photochromic
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 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 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 4
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 78
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 21
- 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 16
- 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 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- 239000004417 polycarbonate Substances 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000000975 dye Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000001227 electron beam curing Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 39
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 15
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 15
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 14
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 13
- 239000008199 coating composition Substances 0.000 description 12
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 238000006845 Michael addition reaction Methods 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
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HXYCHJFUBNTKQR-UHFFFAOYSA-N heptane-1,2,3-triol Chemical compound CCCCC(O)C(O)CO HXYCHJFUBNTKQR-UHFFFAOYSA-N 0.000 description 1
- XYXCXCJKZRDVPU-UHFFFAOYSA-N hexane-1,2,3-triol Chemical compound CCCC(O)C(O)CO XYXCXCJKZRDVPU-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
Definitions
- the invention belongs to the field of optical films, in particular to a hyperbranched polyurethane vinyl ether photochromic composition, a product and a preparation method, which are mainly used in 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.
- the object of the present invention is to firstly provide a kind of hyperbranched polyurethane vinyl ether photochromic composition, this photochromic composition can effectively solve the problem of damage to photochromic powder caused by ultraviolet light, and is used for optical products, which can greatly shorten the The production time of coating color-changing glasses can improve the product qualification rate and reduce the cost.
- the hyperbranched polyurethane vinyl ether photochromic composition is obtained according to the following steps, and the required various substances are by weight:
- a preparation method of the above-mentioned hyperbranched polyurethane vinyl ether photochromic composition is provided, and the dosage of each component is according to the weight portion described above, comprising the following steps:
- polyol is cooled to below 60 °C after vacuum dehydration 1 ⁇ 3 hour at 120 ⁇ 150 °C, first add diisocyanate, organic solvent and catalyzer, continue stirring and be warming up to 70 ⁇ 85 °C, keep stirring for 2 ⁇ 3 hours;
- a kind of preparation method of the article that comprises above-mentioned hyperbranched polyurethane vinyl ether photochromic composition also comprises the following steps:
- the hyperbranched polyurethane vinyl ether photochromic composition obtained above is evenly spin-coated on the base material, irradiated by an infrared lamp for 2 to 3 minutes, and then irradiated by EB under a voltage condition of 80 to 150KV and a radiation amount of 30 to 80KGy. Curing to form a film yields an article containing the hyperbranched polyurethane vinyl ether photochromic composition.
- the base material is any one of polycarbonate material, polyurethane material or polyacrylic acid material.
- a product is provided, which is prepared by the above-mentioned preparation method.
- the polyol is any one or a combination of two or more of polyether polyols, polycarbonate polyols, polycaprolactone polyols, polyester polyols, diols or dihydric mercaptans, A dihydric alcohol is preferred;
- the diisocyanate is dimethylene phenyl diisocyanate (XDI), hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) or Any one or a combination of two or more in 4,4'-dicyclohexylmethane diisocyanate (HMDI);
- the organic solvent is dimethyl carbonate, ethyl acetate, vinyl acetate, propylene glycol methyl ether acetate one or more of the catalyst;
- the catalyst is any one of tin ethylhexanoate, dibutyltin dilaurate or stan
- the principle of the invention is as follows: using diisocyanate and polyol to prepolymerize into oligomer, then using triol and tetraol to polymerize into polyurethane prepolymer with hyperbranched structure, and then sealing with 4-hydroxybutyl vinyl ether end, the hyperbranched polyurethane containing vinyl ether is obtained, and finally it is mixed with mercaptan and photochromic fuel to form a radiation curable composition.
- the reaction between thiol and carbon-carbon double bond is a Michael addition reaction, with low stress, low shrinkage, and very softness, which not only helps to improve the adhesion between the coating and the lens, but also improves the discoloration and fading of photochromic dyes Speed; most importantly, the composition has good anti-oxidative polymerization inhibition properties, and can achieve rapid curing even in the absence of nitrogen, reducing the need for nitrogen in the production line and reducing production costs.
- the photochromic composition of the hyperbranched polyurethane vinyl ether provided by the present invention is bombarded by EB high-energy electron beams.
- the double bond is opened and free radicals are generated to initiate cross-linking curing.
- EB curing can increase the double bond conversion rate to 95%, which is of great help to improve the cross-linking density and solvent resistance. It is the best method for preparing photochromic coatings. One of the best materials.
- PEG400 polyethylene glycol (molecular weight 400)
- PEG600 polyethylene glycol (molecular weight 600)
- PEG800 polyethylene glycol (molecular weight 800)
- PPG400 polypropylene glycol (molecular weight 400)
- PPG600 polypropylene glycol (molecular weight 600)
- PPG800 polypropylene glycol (molecular weight 800)
- IPDI isophorone diisocyanate
- Catalyst DBTDL Dibutyltin dilaurate
- Antioxidant BHT 2,6-di-tert-butyl-p-cresol
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, and then cured by EB, using a voltage of 100kv and a dose of 30KGy to obtain a PU color-changing lens. .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, cured by EB, using a voltage of 120kv and a dose of 50KGy, and finally obtained a PU color-changing lens .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, and then cured by EB, using a voltage of 100kv and a dose of 30KGy to obtain a PU color-changing lens. .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, cured by EB, using a voltage of 120kv and a dose of 50KGy, and finally obtained a PU color-changing lens .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, and then cured by EB, using a voltage of 100kv and a dose of 30KGy to obtain a PU color-changing lens. .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, cured by EB, using a voltage of 120kv and a dose of 50KGy, and finally obtained a PU color-changing lens .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, and then cured by EB, using a voltage of 100kv and a dose of 30KGy to obtain a PU color-changing lens. .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, cured by EB, using a voltage of 120kv and a dose of 50KGy, and finally obtained a PU color-changing lens .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, and then cured by EB, using a voltage of 100kv and a dose of 30KGy to obtain a PU color-changing lens. .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, cured by EB, using a voltage of 120kv and a dose of 50KGy, and finally obtained a PU color-changing lens .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, and then cured by EB, using a voltage of 100kv and a dose of 30KGy to obtain a PU color-changing lens. .
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800 rpm for 20 seconds, then irradiated with a 300W infrared lamp for 2 minutes, cured by EB, using a voltage of 120kv and a dose of 50KGy, and finally obtained a PU color-changing lens .
- Table 1 The comparative results of the above embodiments are shown in Table 1 below.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Eyeglasses (AREA)
- Optical Filters (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明提供了一种超支化聚氨酯乙烯基醚的光致变色组合物、制品及制备方法,组合物包括多元醇、二异氰酸酯、溶剂、催化剂、三元醇、四元醇、阻聚剂、4-羟丁基乙烯基醚、流平剂、消泡剂、紫外光吸收剂、抗氧剂、硫醇和光致变色染料,将组合物涂覆在基底材料上,经EB固化做成光学制品。本发明先采用二异氰酸酯与多元醇预聚成低聚物,然后依次采用三元醇、四元醇聚合成超支化结构的聚氨酯预聚物,然后采用4-羟丁基乙烯基醚封端,得到含有乙烯基醚的超支化聚氨酯,最后与硫醇、光致变色燃料混合成可以辐射固化的组合物。该组合物具有较高的折射率、抗氧阻聚和优异的附着力能性能。
Description
本发明属于光学膜领域,具体涉及一种超支化聚氨酯乙烯基醚光致变色组合物、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超支化聚氨酯乙烯基醚光致变色组合物,这种光致变色组合物可以有效解决紫外光对光致变色粉的伤害问题,用于光学制品,可以大大缩短涂层变色眼镜的生产时间,提高产品合格率,降低成本。
具体技术方案:超支化聚氨酯乙烯基醚光致变色组合物,按照如下步骤获得,所需各种物质按重量份计:
向多元醇中加入二异氰酸酯、有机溶剂和催化剂,持续搅拌均匀,再加入三元醇,搅拌均匀后再加入四元醇,测试NCO含量,达到1%~5%后加入阻聚剂和4-羟丁基乙烯基醚,再加入光致变色染料、流平剂、消泡剂、紫外光吸收剂、抗氧剂、硫醇,得到超支化聚氨酯乙烯基醚的光致变色组合物。
作为本发明的第二个方面,提供一种上述超支化聚氨酯乙烯基醚光致变色组合物的制备方法,各组分用量按照上述所述的重量份,包括如下步骤:
S1:将多元醇在120~150℃下真空脱水1~3小时后降温至60℃以下,先加入二异氰酸酯、有机溶剂和催化剂,持续搅拌升温至70~85℃,保温搅拌2~3小时;
S2:降温至55~65℃,缓慢滴加入三元醇,滴加完毕后升温至70~85℃保温搅拌2~3小时;
S3:降温至55~65℃,缓慢滴加入四元醇,滴加完毕后升温至70~85℃保温搅拌2~3小时;
S4:测试NCO含量,达到1%~5%后加入阻聚剂和4-羟丁基乙烯基醚,75~85℃保温搅拌1.5~2小时;
S5:加入光致变色染料,85~95℃保温搅拌1~2小时;
S6:依次加入流平剂、消泡剂、紫外光吸收剂、抗氧剂、硫醇,65~75℃保温搅拌1~2小时,得到超支化聚氨酯乙烯基醚的光致变色组合物。
作为本发明的第三个方面,提供一种包含上述超支化聚氨酯乙烯基醚光致变 色组合物的制品的制备方法,还包括以下步骤:
将上述得到的超支化聚氨酯乙烯基醚光致变色组合物均匀旋涂于基底材料上,经过红外灯辐射2~3min,再在80~150KV电压条件下,30~80KGy辐射量下,经过EB辐射固化形成薄膜,得到含超支化聚氨酯乙烯基醚光致变色组合物的制品。
进一步地,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。
作为本发明的第四个方面,提供一种制品,是由上述制品的制备方法制成的。
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,优选二元醇;所述二异氰酸酯为二亚甲基苯基二异氰酸酯(XDI)、六甲撑二异氰酸酯(HDI)、二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)或者4,4'-二环己基甲烷二异氰酸酯(HMDI)中的任意一种或者两种以上的组合;所述有机溶剂为碳酸二甲酯、醋酸乙酯、醋酸乙烯酯、丙二醇甲醚醋酸酯中的一种或几种;所述的催化剂为乙基己酸锡、二月桂酸二丁基锡或者辛酸亚锡中的任意一种;所述的三元醇为丙三醇、三羟甲基丙烷、1,2,3-庚三醇或者1,2,3-己三醇中的一种或几种;所述的四元醇为季戊四醇或者聚己内酯四元醇的一种;所述的阻聚剂为对苯二酚、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;所述的流平剂为所述的流平剂为BYK330、BYK331、BYK325或者BYK333中的任意一种或者两种以上的组合;所述的消泡剂为BYK053、BYK057、BYK054或者BYK1790中的任意一种或者两种以上的组合;所述的紫外光吸收剂为Tinuvin329、Tinuvin292、Tinuvin312或者Tinuvin326中的任意一种;所述的抗氧剂为BHT、Irganox1010、Irganox1076或者Irgafos168中的任意一种;所述的硫醇为GDMP、BDMP、TMPMP、PETMP的任意一种或者两种以上的组合;所述的光致变色染料为维缦公司的midnight grey、volcanic grey、misty grey的任意一种或者两种以上的组合。
本发明的原理是:采用二异氰酸酯与多元醇预聚成低聚物,依次用三元醇、四元醇聚合成超支化结构的聚氨酯预聚物,再用4-羟丁基乙烯基醚封端,得到含有乙烯基醚的超支化聚氨酯,最后与硫醇、光致变色燃料混合成可以辐射固化 的组合物。硫醇与碳碳双键的反应属于迈克尔加成反应,应力小,收缩率小,非常柔软,既有利于提升涂层与镜片之间的附着力,又可以提高光致变色染料的变色和褪色速度;最重要的是,该组合物具有良好的抗氧阻聚性能,即使在没有氮气的条件下,也可以实现快速固化,减掉生产线对氮气的需求,可以降低生产成本。
本发明的有益效果:通过反复研究调整组合物配方以及电子束辐射固化(EB固化)条件,本发明提供的超支化聚氨酯乙烯基醚的光致变色组合物在EB高能电子束轰击下,碳碳双键打开并产生自由基从而引发交联固化,采用EB固化可以提升双键转化率达到95%,对提高交联密度和提高耐溶剂性能有很大帮助,是制备光致变色涂层的最佳材料之一。
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。
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):
PEG400:聚乙二醇(分子量400)
PEG600:聚乙二醇(分子量600)
PEG800:聚乙二醇(分子量800)
PPG400:聚丙二醇(分子量400)
PPG600:聚丙二醇(分子量600)
PPG800:聚丙二醇(分子量800)
IPDI:异佛尔酮二异氰酸酯
阻聚剂MEHQ:4-甲氧基苯酚
催化剂DBTDL:二月桂酸二丁基锡
消泡剂BYK1790
流平剂BYK333
紫外光吸收剂巴斯夫Tinuvin 329
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BHT:2,6-二叔丁基对甲酚
硫醇:PETMP
实施例1:
实施例1.1:
在向容器中加入10g PEG400,在120℃下抽真空1h,降温至60℃,加入16.67gIPDI、55g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.02g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.76g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.25%,加入0.02g MEHQ和5.2g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、5.46gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压100kv,剂量30KGy,最后得到PU变色镜片。
实施例1.2:
在向容器中加入10g PEG400,在120℃下抽真空2h,降温至60℃,加入16.67gIPDI、55g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.02g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.76g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.25%,加入0.02g MEHQ和5.2g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、5.46gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压120kv,剂量50KGy,最后得到PU变色镜片。
实施例2:
实施例2.1:
向容器中加入10g PEG600,在120℃下抽真空1h,降温至60℃,加入16.67g IPDI、51.2g醋酸乙酯和0.2g DBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.19g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.66季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为3.0%,加入0.02g MEHQ和6.79g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、6.5gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压100kv,剂量30KGy,最后得到PU变色镜片。
实施例2.2:
向容器中加入10g PEG600,在120℃下抽真空2h,降温至60℃,加入16.67g的IPDI、51.2g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.19g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.66季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为3.0%,加入0.02g MEHQ和6.79g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、6.5gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压120kv,剂量50KGy,最后得到PU变色镜片。
实施例3:
实施例3.1:
向容器中加入10g PEG800,在120℃下抽真空1h,降温至60℃,加入16.67g的IPDI、50.23g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时后,降温 至60℃,缓慢滴加1.27g丙三醇,升温至70℃保温搅拌2小时后,降温至60℃,缓慢滴加0.94g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.9%,加入0.02g MEHQ 6.53g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、7.46g PETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压100kv,剂量30KGy,最后得到PU变色镜片。
实施例3.2:
向容器中加入10g PEG800,在120℃下抽真空2h,降温至60℃,加入16.67g的IPDI、50.23g醋酸乙酯和0.2g DBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.27g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.94g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.9%,加入0.02g MEHQ和6.53g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、7.46g PETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压120kv,剂量50KGy,最后得到PU变色镜片。
实施例4:
实施例4.1:
向容器中加入10g PPG400,在120℃下抽真空1h,降温至60℃,加入16.67g的IPDI、55g醋酸乙酯和0.2g DBTDL,升温至70℃保温搅拌2小时后,降温至60℃,缓慢滴加1.02g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.76g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.25%,加入0.02g MEHQ和5.2g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后 加入0.1g BYK1790、0.1g BYK333、5.46gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压100kv,剂量30KGy,最后得到PU变色镜片。
实施例4.2:
向容器中加入10g PPG400,在120℃下抽真空1h,降温至60℃,加入16.67g IPDI、55g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.02g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.76g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.25%,加入0.02gMEHQ和5.2g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、5.46gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压120kv,剂量50KGy,最后得到PU变色镜片。
实施例5:
实施例5.1:
向容器中加入10g PPG600,在120℃下抽真空1h,降温至60℃,加入16.67g的IPDI、51.24g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.19g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.66季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为3.0%,加入0.02g MEHQ和6.74g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、6.5gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压100kv,剂量30KGy,最后得到PU变色镜片。
实施例5.2:
向容器中加入10g PPG600,在120℃下抽真空1h,降温至60℃,加入16.67g的IPDI、51.24g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.19g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.66季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为3.0%,加入0.02g MEHQ和6.74g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、6.5gPETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压120kv,剂量50KGy,最后得到PU变色镜片。
实施例6:
实施例6.1:
向容器中加入10g PPG800,在120℃下抽真空1h,降温至60℃,加入16.67g IPDI、50.23g醋酸乙酯和0.2gDBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.27g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.94g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.9%,加入0.02g MEHQ和6.53g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、7.46g PETMP、0.02gBHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变组合物,折射率为1.554。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,经过EB固化,采用电压100kv,剂量30KGy,最后得到PU变色镜片。
实施例6.2:
向容器中加入10g PPG800,在120℃下抽真空1h,降温至60℃,加入16.67g IPDI、50.23g醋酸乙酯和0.2g DBTDL,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加1.27g丙三醇,升温至70℃保温搅拌2小时,降温至60℃,缓慢滴加0.94g季戊四醇,升温至70℃保温搅拌2小时,测试NCO含量为2.9%,加入0.02g MEHQ和6.53g 4-羟丁基乙烯基醚,升温至80℃保温搅拌2小时后加入3.5g midnight grey和3.5g misty grey,升温至90℃保温搅拌1小时,最后加入0.1g BYK1790、0.1g BYK333、7.46g PETMP、0.02g BHT、0.02g Tinuvin 329,混合均匀后得到超支化聚氨酯乙烯基醚的光致变色组合物,折射率为1.554。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,经过EB固化,采用电压120kv,剂量50KGy,最后得到PU变色镜片。以上各实施例的对比结果参见下表1。
表1 实施例1~6制备的光学制品测试结果
从实施例对比结果可以看出,PEG或PPG的分子量越大,褪色速率越快,即 相同时间隔离光照后的透光率最高;PEG或PPG的分子量大小对耐黄变的影响没有差别,但是选用PPG会产生附着力不好的影响,即使加大电子束EB的电压和剂量,只会提升产品硬度,不会提升附着力。综合上述实验结果,选用PEG800、电子束电压120kv、剂量50KGy,是比较合适的工艺条件。
Claims (10)
- 一种如权利要求1所述超支化聚氨酯乙烯基醚光致变色组合物的制备方法,各物质用量按照权利要求1所述的重量份计,其特征在于,包括以下步骤:S1:将多元醇在120~150℃下真空脱水1~3小时后降温至60℃以下,先加入二异氰酸酯、有机溶剂和催化剂,持续搅拌升温至70~85℃,保温搅拌2~3小时;S2:降温至55~65℃,缓慢滴加入三元醇,滴加完毕后升温至70~85℃保温搅拌2~3小时;S3:降温至55~65℃,缓慢滴加入四元醇,滴加完毕后升温至70~85℃保温搅拌2~3小时;S4:测试NCO含量,达到1%~5%后加入阻聚剂和4-羟丁基乙烯基醚,75~85℃℃保温搅拌1.5~2小时;S5:加入光致变色染料,85~95℃保温搅拌1~2小时;S6:依次加入流平剂、消泡剂、紫外光吸收剂、抗氧剂、硫醇,65~75℃保温搅拌1~2小时,得到超支化聚氨酯乙烯基醚的光致变色组合物。
- 一种包含权利要求1所述超支化聚氨酯乙烯基醚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:将得到的光致变色组合物均匀旋涂于基底材料上,经过红外灯辐射2~3min,再在80~150KV电压条件下,30~80KGy辐射量下,经过EB辐射固化形成薄膜,得到含超支化聚氨酯乙烯基醚光致变色组合物的制品。
- 根据权利要求3所述包含超支化聚氨酯乙烯基醚光致变色组合物的制品的制备方法,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,是由权利要求3或4所述制备方法制成的。
- 根据权利要求1~4任一项所述的超支化聚氨酯乙烯基醚光致变色组合物,其特征在于,所述多元醇为二元醇。
- 根据权利要求1~4任一项所述的超支化聚氨酯乙烯基醚光致变色组合物,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。
- 根据权利要求1~4任一项所述的超支化聚氨酯乙烯基醚的光致变色组合物,其特征在于,所述有机溶剂为碳酸二甲酯、醋酸乙酯、醋酸乙烯酯、丙二醇甲醚醋酸酯中的一种或几种。
- 根据权利要求1~4任一项所述的超支化聚氨酯乙烯基醚的光致变色组合物,其特征在于,所述催化剂为乙基己酸锡、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1~4任一项所述的超支化聚氨酯乙烯基醚的光致变色组合物,其特征在于,所述的阻聚剂为对苯二酚、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。
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