WO2022147865A1 - 一种基于环氧改性的光致变色组合物、制品及制备方法 - Google Patents
一种基于环氧改性的光致变色组合物、制品及制备方法 Download PDFInfo
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- WO2022147865A1 WO2022147865A1 PCT/CN2021/074182 CN2021074182W WO2022147865A1 WO 2022147865 A1 WO2022147865 A1 WO 2022147865A1 CN 2021074182 W CN2021074182 W CN 2021074182W WO 2022147865 A1 WO2022147865 A1 WO 2022147865A1
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- photochromic composition
- photochromic
- epoxy
- polyol
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- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004593 Epoxy Substances 0.000 title claims abstract description 9
- 238000012986 modification Methods 0.000 title claims abstract description 6
- 230000004048 modification Effects 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 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
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- -1 olefin anhydride Chemical class 0.000 claims abstract description 7
- 238000003847 radiation curing Methods 0.000 claims abstract description 7
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 37
- 229920000515 polycarbonate Polymers 0.000 claims description 19
- 239000004417 polycarbonate Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- OEMSKMUAMXLNKL-UHFFFAOYSA-N 5-methyl-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical group C1C(C)=CCC2C(=O)OC(=O)C12 OEMSKMUAMXLNKL-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 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 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-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
- 239000013530 defoamer Substances 0.000 claims description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 3
- 229940044119 2-tert-butylhydroquinone Drugs 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
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 229940014800 succinic anhydride Drugs 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000008199 coating composition Substances 0.000 description 15
- 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 10
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 10
- 150000002009 diols Chemical class 0.000 description 10
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 8
- 239000010408 film Substances 0.000 description 5
- 238000005562 fading Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 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
- 238000001227 electron beam curing Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- UYCICMIUKYEYEU-ZHACJKMWSA-N 3-[(e)-dodec-2-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCC\C=C\CC1CC(=O)OC1=O UYCICMIUKYEYEU-ZHACJKMWSA-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
- 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
- 239000002202 Polyethylene glycol Substances 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
- 230000032683 aging Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011241 protective layer Substances 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
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated 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
-
- 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
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/10—Epoxy resins modified by unsaturated compounds
Definitions
- the invention belongs to the field of optical films, and in particular relates to an epoxy-modified photochromic composition, a product and a preparation method, which are mainly applied to the production and processing of color-changing glasses and color-changing films.
- the other is the coating discoloration technology, which is a process in which the lens has been cured, and a layer of color-changing coating is applied on the surface, which is cured to form a film under certain conditions.
- This process perfectly solves the three defects of the substrate discoloration technology.
- due to the difficult development of this process the long R&D cycle and the harsh process requirements, this technology has been monopolized by foreign giants. After years of imitation by domestic eyewear manufacturers, the imitation of this technology has reached 80%.
- the coating color changing technology is a thermosetting technology. The coating color changing liquid is coated on the lens substrate and heated at a temperature of about 120 degrees for 2 hours to cure to form a film.
- the technology takes a long time, consumes high energy, and has low production efficiency, and the product qualification rate is only about 50%.
- 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. In the case of fading ability.
- the LED with a wavelength of 405 nm is radiated for 1 min and then thermally cured for 1 hour. Although the time of this process is shortened by half, it still has high energy consumption and low production efficiency, and cannot realize intelligent mechanized production.
- the object of the present invention is to firstly provide a photochromic composition based on epoxy modification.
- the photochromic composition can effectively solve the problem of damage to photochromic powder caused by ultraviolet light, and can also greatly shorten the discoloration of the coating. Glasses production time, and improve product yield, thereby reducing production costs.
- a photochromic composition based on epoxy modification the following components, in parts by weight, include:
- the catalyst is any one or more of 2.4.6-tris(dimethylaminomethyl)phenol, boron trifluoride ether, dimethylimidazole or triphenylphosphine; the polymerization inhibitor It is any one or more of hydroquinone, 2-tert-butyl hydroquinone, methyl hydroquinone and 4-methoxyphenol.
- a preparation method of the above-mentioned epoxy-modified photochromic composition is provided, and the dosage of each component is according to the above-mentioned weight portion, comprising the following steps:
- a preparation method of a product comprising the above-mentioned epoxy-modified photochromic composition, wherein the consumption of each component is according to the above-mentioned parts by weight, comprising the following steps:
- the base material is any one of polycarbonate material, polyurethane material or polyacrylic acid material.
- the EB radiation curing is carried out under the conditions of 110-120kv voltage and 30-50KGy radiation dose, preferably 120kv voltage and 50KGy radiation dose.
- an article comprising the above-mentioned epoxy-modified-based photochromic composition, which is prepared by the above-mentioned preparation 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 olefinic acid anhydride is any one or a combination of two or more in 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 2-dodecenyl-succinic anhydride, maleic anhydride ;
- Described alicyclic epoxy resin is any one in TTA21, TTA26, TTA2081;
- Described oxetane is any one in TCM101, TCM102, TCM201, TCM204;
- Described photoinitiator is any one in 6976M, 6992M, YQ-II-65, LSR-IV-020;
- antioxidant is 2,6-di-tert-butyl-p-cresol, bis(3,5-tertiary butyl-4-hydroxyphenyl) sulfide, tetra[beta-(3,5-tertiary) A kind of butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, thiodipropionic acid diester species;
- the ultraviolet light absorber is any one of LOWILITE22, LOWILITE26, LOWILITE28 or LOWILITE234;
- Described photochromic powder is any one or a combination of two or more of midnight grey, volcanic grey and misty grey of Weiman Company;
- Described leveling agent is any one or a combination of two or more in Levaslip8629, Levaslip839, Levaslip837 or Levaslip810;
- the defoamer is any one or a combination of two or more in Defom2700, Defom5500, Defom8700 or Defom6500;
- the voltage used in the EB curing can be 100kv or 110kv or 120kv, and the dose can be 40KGy or 50KGy or 60Kgy; preferably, the voltage is 120kv, and the radiation dose is 50KGy.
- the principle of the present invention is: the present invention introduces the unsaturated carbon-carbon double bond of the olefinic anhydride and the flexible segment of the polyol into the epoxy system, and introduces the olefinic anhydride, which can not only provide a method for free radical curing, but also provide hardness after curing. and solvent resistance; the introduction of polyol flexible segments can improve the toughness after curing, and can also improve the discoloration speed and fading speed of the color-changing coating; at the same time, epoxy groups can provide a cationic curing method to form a dual curing system.
- the interpenetrating network structure is formed, which further improves the solvent resistance, reduces the shrinkage rate, improves the adhesion of the coating on the lens, and achieves the purpose of 100 grid 0.
- the high-energy electron beam bombards the carbon-carbon double bond in the polymer molecule to break it and generate free radicals. It is not necessary to add a free radical initiator, and the conversion rate of the double bond can be increased to more than 95%, the maximum The crosslinking density and solvent resistance are improved to a certain extent, so that the photochromic composition can be well adhered to the surface of the transparent substrate.
- the damage of ultraviolet light to the photochromic powder is avoided, the photochromic composition can be cured and formed into a film within a few seconds, the production efficiency and the qualified rate of finished products are improved, and the energy consumption and production cost are reduced.
- the preparation of the photochromic composition of the present invention and the implementation method thereof enable the photochromic coating composition to have good light transmittance, fastness, aging resistance and corrosion resistance on the substrate, and at the same time have good color depth and fading speed.
- PEG1000 polyethylene glycol (molecular weight 1000)
- PCD1000 Polycarbonate diol (molecular weight 1000)
- PCL1000 Polycaprolactone diol (molecular weight 1000)
- PDA1000 polyester diol (molecular weight 1000)
- PTMEG1000 polytetrahydrofuran diol (molecular weight 1000)
- Antioxidant BHT 2,6-di-tert-butyl-p-cresol
- the photochromic coating composition was sprayed on the surface of a polycarbonate (PC) lens, rotated at 800 rpm for 20 seconds, under the protection of nitrogen, cured by EB, using a voltage of 110kv and a dose of 30KGy, and finally obtained a PC color-changing lens .
- PC polycarbonate
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800rpm for 20 seconds, under the protection of nitrogen, cured by EB, using a voltage of 120kv and a dose of 50KGy to obtain a PC color-changing lens.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800rpm for 20 seconds, under the protection of nitrogen, cured by EB, using a voltage of 120kv and a dose of 50KGy to obtain a PC color-changing lens.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800rpm for 20 seconds, and cured by EB under the protection of nitrogen, using a voltage of 110kv and a radiation dose of 30KGy to obtain a PC color-changing lens.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800rpm for 20 seconds, under the protection of nitrogen, cured by EB, using a voltage of 120kv and a radiation dose of 50KGy to obtain a PC photochromic lens.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800rpm for 20 seconds, under the protection of nitrogen, cured by EB, using a voltage of 120kv and a dose of 50KGy to obtain a PC color-changing lens.
- the photochromic coating composition was sprayed on the surface of the PC lens, rotated at 800rpm for 20 seconds, under the protection of nitrogen, cured by EB, using a voltage of 120kv and a dose of 50KGy to obtain a PC color-changing lens.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Eyeglasses (AREA)
- Optical Filters (AREA)
Abstract
本发明提供了基于环氧改性的光致变色组合物、制品及制备方法，该组合物包含多元醇、烯烃酸酐、催化剂、脂环族环氧、氧杂环丁烷、光致变色粉、光引发剂、抗氧剂、紫外光吸收剂、流平剂和消泡剂。本发明将碳碳不饱和双键和多元醇的柔性链段引入环氧体系中，复配氧杂环丁烷，形成双重固化体系，环氧基的引入可以降低收缩率，提升附着力，然后通过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，实现光致变色组合物在几秒钟内固化成膜，提高生产效率和成品合格率，降低能耗和生产成本。
Description
本发明属于光学膜领域，具体涉及一种基于环氧改性的光致变色组合物、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。
另一种是涂层变色技术，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垄断。国内眼镜生产企业通过多年模仿，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度左右的温度下加热2小时固化成膜。该技术耗时长、能耗高、生产效率低，产品合格率仅为50％左右。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。现有技术中有提到采用波长为405nm的LED辐射1min后再热固1小时的工艺，该工艺虽然时间缩短一半，但是仍然能耗较高、生产效率低，无法实现智能机械化生产。
发明内容
本发明的目的首先是提供一种基于环氧改性的光致变色组合物，所述的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，还可以大大缩短涂层变色眼镜的生产时间，并提高产品良率，进而降低生产成本。
具体技术方案：一种基于环氧改性的光致变色组合物，以下各组分按重量份计，包括：
所述的催化剂为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或几种；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或几种。
作为本发明的第二个方面，提供一种上述基于环氧改性的光致变色组合物的制备方法，各组分用量按照上述的重量份，包括以下步骤：
先将多元醇在100～130℃下，优选120℃，抽真空1～2小时后，降温至60～80℃加入烯烃酸酐，80～100℃，优选90℃，保温搅拌均匀；加入催化剂、阻聚剂和脂环族环氧树脂，再升温至100～130℃，优选120℃，保温搅拌1～2小时；加入氧杂环丁烷和光致变色粉，在60～90℃下，优选80℃，保温搅拌1～2小时；再加入光引发剂、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，提供一种包含上述基于环氧改性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：
先将多元醇在120℃下抽真空1～2小时后，降温至60～80℃，加入烯烃酸酐，90℃保温搅拌均匀；加入催化剂、阻聚剂和脂环族环氧树脂，再升温至120℃，保温搅拌2小时；加入氧杂环丁烷和光致变色粉，在80℃下保温搅拌1～2小时；再加入光引发剂、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，在氮气的保护下，经过EB辐射固化形成薄膜，得到所述制品。
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。
进一步地，所述EB辐射固化是在110～120kv电压，30～50KGy辐射量条件下进行，优选120kv电压，50KGy辐射量。
作为本发明的第四个方面，提供一种制品，包含上述基于环氧改性的光致变色组合物，是由上述制备方法制备的。
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；
所述的烯烃酸酐为4-甲基-4-环己烯-1,2-二甲酸酐、2-十二烯基-丁二酸酐、马来酸酐中的任意一种或者两种以上的组合；
所述的脂环族环氧树脂为TTA21、TTA26、TTA2081中的任意一种；
所述的氧杂环丁烷为TCM101、TCM102、TCM201、TCM204中的任意一种；
所述的光引发剂为6976M、6992M、YQ-II-65、LSR-IV-020中的任意一种；
所述的抗氧剂为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；
所述的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；
所述的流平剂为Levaslip8629、Levaslip839、Levaslip837或者Levaslip810中的任意一种或者两种以上的组合；
所述的消泡剂为Defom2700、Defom5500、Defom8700或者Defom6500中的任意一种或者两种以上的组合；
所述的EB固化采用的电压可以是100kv或者110kv或者120kv，剂量可以是40KGy或者50KGy或者60Kgy；优选为120kv电压，50KGy辐射量。
本发明的原理是：本发明将烯烃酸酐的不饱和碳碳双键和多元醇的柔性链段 引入环氧体系中，引入烯烃酸酐，既可以提供自由基固化的方法，又提供固化后的硬度和耐溶剂性能；引入多元醇柔性链段可以提升固化后的韧性，又可以提升变色涂层的变色速度和褪色速度；同时环氧基团可以提供阳离子固化的方法，形成双重固化体系，固化后形成互穿网络结构，进一步提升耐溶剂性能，又可以降低收缩率，提升涂层在镜片上的附着力，达到百格0级的目的。采用EB辐射固化的方式，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，可以不用添加自由基引发剂，还可以提升双键的转化率达到95％以上，最大程度的提升交联密度和耐溶剂性能，使得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，实现光致变色组合物在几秒钟内固化成膜，提高生产效率和成品合格率，降低能耗和生产成本。
本发明的这种光致变色组合物的制备及其实施方法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、耐老化性能和耐腐蚀性能，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。
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)：
PEG1000：聚乙二醇(分子量1000)
PCD1000：聚碳酸酯二元醇(分子量1000)
PCL1000：聚己内酯二元醇(分子量1000)
PDA1000：聚酯二元醇(分子量1000)
PTMEG1000：聚四氢呋喃二元醇(分子量1000)
催化剂TPP：三苯基膦
阻聚剂MEHQ:4-甲氧基苯酚
江苏泰特尔脂环族环氧树脂：TTA21
江苏强力氧杂环丁烷：TCM102
浙江杨帆光引发剂：6976M
德谦消泡剂Defom8700
德谦流平剂Levaslip810
亚帝凡特紫外光吸收剂LOWILITE22
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
实施例1
实施例1.1
向容器中加入30.8g PEG1000，在120℃下抽真空2h，降温至70℃，加入10.4g 4-甲基-4-环己烯-1,2-二甲酸酐，90℃保温搅拌2小时，再加入38.85g TTA21、0.24g TPP和0.02g HEMQ，120℃保温搅拌2小时，然后加入15g TCM102、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02gBHT、0.02g LOWILITE22、0.1g Defom8700、0.1g Levaslip810、1g 6976M，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聚碳酸酯(PC)镜片表面，在800rpm转速下旋转20秒，在氮气的保护下，经过EB固化，采用电压110kv，剂量30KGy，最后得到PC变色镜片。
实施例1.2
向容器中加入30.8g PEG1000，在120℃下抽真空2h，降温至70℃，加入10.4g 4-甲基-4-环己烯-1,2-二甲酸酐，90℃保温搅拌2小时，再加入38.85g TTA21、0.24g TPP和0.02g HEMQ，120℃保温搅拌2小时，然后加入15g TCM102、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02gBHT、0.02g LOWILITE22、0.1g Defom8700、0.1g Levaslip810、1g 6976M，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，在氮气的保护下，经过EB固化，采用电压120kv，剂量50KGy，最后得到PC变色镜片。
实施例2：
向容器中加入30.8g PCD1000，在120℃下抽真空1.5h，降温至70℃，加入10.4g 4-甲基-4-环己烯-1,2-二甲酸酐，升温至90℃保温搅拌2小时，再加 入38.85g TTA21、0.24g TPP和0.02g HEMQ，120℃保温搅拌2小时，然后加入15g TCM102、2.5g midnight grey和2.5g misty grey，80℃保温搅拌1小时后，加入0.02gBHT、0.02g LOWILITE22、0.1g Defom8700、0.1g Levaslip810、1g 6976M，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，在氮气的保护下，经过EB固化，采用电压120kv，剂量50KGy，最后得到PC变色镜片。
实施例3：
实施例3.1
向容器中中加入30.8g PCL1000，在120℃下抽真空2h，降温至80℃，加入10.4g 4-甲基-4-环己烯-1,2-二甲酸酐，80℃保温搅拌2小时，再加入38.85g TTA21、0.24g TPP和0.02g HEMQ，120℃保温搅拌2小时，然后加入15g TCM102、2.5g midnight grey和2.5g misty grey，70℃保温搅拌1小时后，加入0.02gBHT、0.02g LOWILITE22、0.1g Defom8700、0.1g Levaslip810、1g 6976M，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，在氮气的保护下，经过EB固化，采用电压110kv，辐射剂量30KGy，最后得到PC变色镜片。
实施例3.2
向容器中中加入30.8g PCL1000，在120℃下抽真空2h，降温至80℃，加入10.4g 4-甲基-4-环己烯-1,2-二甲酸酐，80℃保温搅拌2小时，再加入38.85g TTA21、0.24g TPP和0.02g HEMQ，120℃保温搅拌2小时，然后加入15g TCM102、2.5g midnight grey和2.5g misty grey，70℃保温搅拌1小时后，加入0.02gBHT、0.02g LOWILITE22、0.1g Defom8700、0.1g Levaslip810、1g 6976M，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，在氮气的保护下，经过EB固化，采用电压120kv，辐射剂量50KGy，最后得到PC变色镜片。
实施例4：
向容器中加入30.8g PDA1000，在120℃下抽真空2h，降温至60℃，加入10.4g 4-甲基-4-环己烯-1,2-二甲酸酐，100℃保温搅拌2小时，再加入38.85g TTA21、0.24g TPP和0.02g HEMQ，120℃保温搅拌2小时，然后加入15g TCM102、2.5g midnight grey和2.5g misty grey，60℃保温搅拌1小时后，加入0.02gBHT、 0.02g LOWILITE22、0.1g Defom8700、0.1g Levaslip810、1g 6976M，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，在氮气的保护下，经过EB固化，采用电压120kv，剂量50KGy，最后得到PC变色镜片。
实施例5：
向容器中加入30.8g PTMEG1000，在120℃下抽真空2h，降温至70℃，加入10.4g 4-甲基-4-环己烯-1,2-二甲酸酐，90℃保温搅拌2小时，再加入38.85g TTA21、0.24g TPP和0.02g HEMQ，130℃保温搅拌2小时，然后加入15g TCM102、2.5g midnight grey和2.5g misty grey，90℃保温搅拌1小时后，加入0.02gBHT、0.02g LOWILITE22、0.1g Defom8700、0.1g Levaslip810、1g 6976M，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，在氮气的保护下，经过EB固化，采用电压120kv，剂量50KGy，最后得到PC变色镜片。
表1实施例1～5制备的光学制品测试结果
从上述实验结果可以得出，相同的二元醇添加比例的条件下，PEG二元醇、PCL二元醇、PTMEG二元醇可以得到更快的褪色速率，其中PEG二元醇性能最佳；具有刚性基团的PDA、PCL、PCD可以得到更高的硬度和更好的耐化性能；耐候性 能没有差别，基本满足光学镜片的标准要求；综上所述，PCL二元醇是最佳选择，可以得到同时满足变色性能、耐化性能和硬度的光致变色镜片，不需要再施加第二层保护层。通过实施例1.1和实施例1.2相比，实施例3.1与实施例3.2对比，EB固化条件选用电压120kv，剂量50KGy时，得到的光学制品铅笔硬度较高，耐化性能较好。
Claims (10)
- 一种基于环氧改性的光致变色组合物，其特征在于，包含以下各组分按重量份计：
所述的催化剂为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或几种；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或几种。 - 一种如权利要求1所述基于环氧改性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：先将多元醇在100～130℃下抽真空1～2小时后，降温至60～80℃，加入烯烃酸酐，80～100℃保温搅拌均匀；加入催化剂、阻聚剂和脂环族环氧树脂，再升温至100～130℃，保温搅拌1～2小时；加入氧杂环丁烷和光致变色粉，在60～90℃下保温搅拌1～2小时；再加入光引发剂、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所述基于环氧改性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：先将多元醇在120℃下抽真空1～2小时后，降温至60～80℃，加入烯烃酸酐，90℃保温搅拌均匀；加入催化剂、阻聚剂和脂环族环氧树脂，再升温至120℃， 保温搅拌2小时；加入氧杂环丁烷和光致变色粉，在80℃下保温搅拌1～2小时；再加入光引发剂、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，在氮气的保护下，经过EB辐射固化形成薄膜，得到所述制品。
- 根据权利要求3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。
- 根据权利要求3所述制品的制备方法，其特征在于，所述EB辐射固化是在110～120kv电压，30～50KGy辐射量条件下进行。
- 根据权利要求3或5所述制品的制备方法，其特征在于，所述EB辐射固化是在120kv电压，50KGy辐射量条件下进行。
- 一种制品，其特征在于，包含由权利要求1所述基于环氧改性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3或4或5所述制备方法制成的。
- 根据权利要求1所述基于环氧改性的光致变色组合物，其特征在于：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。
- 根据权利要求1所述基于环氧改性的光致变色组合物，其特征在于：所述的烯烃酸酐为4-甲基-4-环己烯-1,2-二甲酸酐、2-十二烯基-丁二酸酐、马来酸酐中的任意一种或者两种以上的组合。
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