CN109971006B - 一种光固型软硬结构可控聚氨酯类防雾薄膜及其制备方法 - Google Patents
一种光固型软硬结构可控聚氨酯类防雾薄膜及其制备方法 Download PDFInfo
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- CN109971006B CN109971006B CN201910257347.7A CN201910257347A CN109971006B CN 109971006 B CN109971006 B CN 109971006B CN 201910257347 A CN201910257347 A CN 201910257347A CN 109971006 B CN109971006 B CN 109971006B
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- Prior art keywords
- soft
- isocyanate
- diisocyanate
- polyurethane prepolymer
- hydroxyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004814 polyurethane Substances 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 19
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 62
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000012948 isocyanate Substances 0.000 claims description 30
- 150000002513 isocyanates Chemical class 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 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 20
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000000016 photochemical curing Methods 0.000 claims description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- -1 acrylate compound Chemical class 0.000 claims description 9
- 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 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001723 curing Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 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 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- 239000013504 Triton X-100 Substances 0.000 claims description 4
- 229920004890 Triton X-100 Polymers 0.000 claims description 4
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical group C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N Isophorone Natural products CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 1
- DFCSFNUXZBPPTD-UHFFFAOYSA-N benzene-1,3-dicarbonyl isocyanate Chemical compound O=C=NC(=O)C1=CC=CC(C(=O)N=C=O)=C1 DFCSFNUXZBPPTD-UHFFFAOYSA-N 0.000 claims 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 1
- 125000006838 isophorone group Chemical group 0.000 claims 1
- 229930193351 phorone Natural products 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000003678 scratch resistant effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 29
- 238000003756 stirring Methods 0.000 description 23
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 13
- 239000012975 dibutyltin dilaurate Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
- 238000006392 deoxygenation reaction Methods 0.000 description 7
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical group C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 3
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- IDOQDZANRZQBTP-UHFFFAOYSA-N 2-[2-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1OCCO IDOQDZANRZQBTP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 229920004929 Triton X-114 Polymers 0.000 description 2
- RAWPGIYPSZIIIU-UHFFFAOYSA-N [benzoyl(phenyl)phosphoryl]-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 RAWPGIYPSZIIIU-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
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- 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
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
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Abstract
本发明提供了一种光固型软硬结构可控聚氨酯类防雾薄膜及其制备方法，属于高分子材料技术领域。所述防雾薄膜包含软结构聚氨酯预聚体、硬结构聚氨酯预聚体与含碳碳双键交联剂，重量比为100:(5～100):(0.5～5)。本发明防雾薄膜的防雾效果持久，表面耐刮擦，耐水性优异且与基材粘附力高，性能与结构可调控，成本低廉，技术成熟，适合生产。
Description
技术领域
本发明属于高分子材料技术领域，特别是涉及一种光固型软硬结构可控聚氨酯类防雾薄膜及其制备方法。
背景技术
透明材料的生产与使用已渗透在人们生活的各个方面，但是透明材料(例如眼镜、面罩、浴室玻璃、汽车前挡玻璃、相机镜头、落地窗、展示柜)在一定环境下会结雾、干扰视线，这种现象给人们带来很多困扰，甚至造成安全隐患和重大的经济损失。
国内市场防雾材料多为喷雾式，其主要成分为表面活性剂类，防雾持效性短，不耐擦拭；通过电加热玻璃升温除雾和除霜需要耗用大量的电和金属；国际市场防雾持久性较好的为美国FSI公司的
Premium系列产品，但其固化温度需高达150℃以上，且其防雾效果在泡水后急剧下降，价格高昂，多数作为高端领域一次性防雾用品使用。
ACS Appl.Mater.Interfaces,2016,8:8737一文中制备了一种具有防雾功能的聚合物涂层，然而其耐水性与附着力差；ACS Appl.Mater.Interfaces,2015,7:1004一文中制备了一种疏水性防雾薄膜，但其成本高昂，且表面不耐磨，防雾持久性差。所以，目前市场开发的防雾涂层材料存在附着力低、生产工艺复杂、防雾时间短、成本高等缺点。
发明内容
为解决现有技术中出现的问题，本发明提供了一种光固型软硬结构可控聚氨酯类防雾薄膜及其制备方法。这种防雾薄膜原料成本低廉，可根据不同生活生产需求调整软、硬预聚体配方，合成技术成熟，固化工艺灵活、简单，具有普适性，适合于工业化生产。
本发明的技术方案：
一种光固型软硬结构可控聚氨酯类防雾薄膜，所述防雾薄膜由软结构聚氨酯预聚体、硬结构聚氨酯预聚体通过光引发剂引发含碳碳双键交联剂固化形成；所述软结构聚氨酯预聚体、硬结构聚氨酯预聚体与含碳碳双键交联剂的重量比为100:(5～100):(0.5～5)。
所述软结构聚氨酯预聚体主要由不含刚性基团的异氰酸酯或异氰酸酯多聚体、直链聚乙二醇、含羟基的丙烯酸酯类化合物与含羟基的表面活性剂制备而成，各组分的重量比为100:(10～80):(10～80):(10～80)。
所述不含刚性基团的异氰酸酯或异氰酸酯多聚体为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体中的一种或两种以上混合；
所述直链聚乙二醇为分子量在200g/mol至1000g/mol范围内的聚乙二醇；
所述含羟基的丙烯酸酯类化合物为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、季戊四醇三丙烯酸酯、聚二季戊四醇五丙烯酸酯中的一种或两种以上混合；
所述含羟基的表面活性剂为OP-4、OP-10、OP-20、OP-50、曲拉通X-100、曲拉通X-114、吐温20中的一种或两种以上混合。
所述硬结构聚氨酯预聚体主要由含刚性基团异氰酸酯或异氰酸酯多聚体、双酚A聚氧乙烯醚与含羟基的丙烯酸酯类化合物制备而成，重量比为100:(10～80):(20～90)。
所述含刚性基团的异氰酸酯或异氰酸酯多聚体为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、萘二异氰酸酯、二苯甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、间苯二异氰酸酯中的一种或两种以上混合；
所述含双酚A聚氧乙烯醚分子量在300g/mol至2600g/mol范围内；
所述含羟基的丙烯酸酯类化合物为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、季戊四醇三丙烯酸酯、聚二季戊四醇五丙烯酸酯中的一种或两种以上混合。
所述含碳碳双键交联剂为季戊四醇四丙烯酸酯、聚二季戊四醇五丙烯酸酯、聚二季戊四醇六丙烯酸酯、季戊四醇三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯中的一种或组合。
所述的光引发剂与含碳碳双键交联剂的质量比为1:(1～1.5)；光引发剂为二苯基乙酮、α,α-二甲氧基-α-苯基苯乙酮、芳酰基膦氧化物、双苯甲酰基苯基氧化膦或二苯甲酮或2,4-二羟基二苯甲酮。
所述的软结构聚氨酯预聚体的制备包括以下步骤：a.将不含刚性基团的异氰酸酯或异氰酸酯多聚体加溶剂稀释，添加直链聚乙二醇后通氮除氧，升温，反应一段时间后加入含羟基的丙烯酸酯类化合物和含羟基的表面活性剂，继续反应一段时间后得到软结构聚氨酯预聚体。
所述的硬结构聚氨酯预聚体的制备包括以下步骤：a.将含刚性基团的异氰酸酯或异氰酸酯多聚体加溶剂稀释，添加双酚A聚氧乙烯醚后通氮除氧，升温，反应一段时间后加入含羟基的丙烯酸酯类化合物和光引发剂，继续反应一段时间后得到硬结构聚氨酯预聚体。
所述溶剂包括丙酮、DMF、二丙酮醇、丁酮、氯仿等。
一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述薄膜的制备包括以下步骤：
a.将软结构聚氨酯预聚体、硬结构聚氨酯预聚体与含碳碳双键交联剂安配比混合均匀；
b.再加入光引发剂，涂膜后进行光固化成膜。
本发明防雾薄膜原料成本低廉，可根据不同生活生产需求调整软、硬预聚体配方，合成技术成熟，固化工艺灵活、简单，具有普适性，适合于工业化生产。
本发明的有益效果：目前市场开发的防雾涂层材料存在附着力低、生产工艺复杂、防雾时间短、防雾持久性差、成本高等缺点。本发明的一种光固型软硬结构可控聚氨酯类防雾薄膜，结构可调控，成本低廉，防雾效果优异，耐磨性好且防雾效果持久，技术成熟，适合生产。
具体实施方式
下面将结合具体实施例对本发明的技术方案进行进一步的说明。
除特殊说明外，其他试剂均购置于国药集团化学试剂有限公司。
一、软结构聚氨酯预聚体的制备
实施例1
将100份异佛尔酮二异氰酸酯置于烧瓶中，加入适量丙酮溶解，10份除水的聚乙二醇200置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入10份丙烯酸羟乙酯与80份OP-10，60℃搅拌反应2h，停止加热反应，得到软结构聚氨酯预聚体1。
实施例2
将100份异佛尔酮二异氰酸酯置于烧瓶中，加入适量丙酮溶解，10份除水的聚乙二醇200置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入45份丙烯酸羟乙酯与45份曲拉通X-100，60℃搅拌反应2h，停止加热反应，得到软结构聚氨酯预聚体2。
实施例3
将100份异佛尔酮二异氰酸酯置于烧瓶中，加入适量丙酮溶解，10份除水的聚乙二醇200置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入80份丙烯酸羟乙酯与10份曲拉通X-114，60℃搅拌反应2h，停止加热反应，得到软结构聚氨酯预聚体3。
实施例4
将100份六亚甲基二异氰酸酯置于烧瓶中，加入适量丙酮溶解，20份除水的聚乙二醇400置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入20份甲基丙烯酸羟乙酯与60份OP-4，60℃搅拌反应2h，停止加热反应，得到软结构聚氨酯预聚体4。
实施例5
将50份异佛尔酮二异氰酸酯、50份赖氨酸二异氰酸酯置于烧瓶中，加入适量丙酮溶解，40份除水的聚乙二醇600置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入30份季戊四醇三丙烯酸酯与10份OP-10、20份OP-20，60℃搅拌反应2h，停止加热反应，得到软结构聚氨酯预聚体5。
实施例6
将100份异佛尔酮二异氰酸酯三聚体置于烧瓶中，加入适量丙酮溶解，60份除水的聚乙二醇600置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入30份聚二季戊四醇五丙烯酸酯与10份OP-50，60℃搅拌反应2h，停止加热反应，得到软结构聚氨酯预聚体6。
实施例7
将100份六亚甲基二异氰酸酯三聚体置于烧瓶中，加入适量丙酮溶解，80份除水的聚乙二醇1000置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入10份甲基丙烯酸羟乙酯与10份吐温20，60℃搅拌反应2h，停止加热反应，得到软结构聚氨酯预聚体7。
二、硬结构聚氨酯预聚体的制备
实施例8
将100份甲苯二异氰酸酯置于烧瓶中，加入适量丙酮溶解，10份除水的双酚A聚氧乙烯醚(分子量约为316g/mol)置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入90份丙烯酸羟乙酯，60℃搅拌反应2h，停止加热反应，得到硬结构聚氨酯预聚体1。
实施例9
将100份二苯基甲烷二异氰酸酯置于烧瓶中，加入适量丙酮溶解，20份除水的双酚A聚氧乙烯醚(分子量约为668g/mol)置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入80份甲基丙烯酸羟乙酯，60℃搅拌反应2h，停止加热反应，得到硬结构聚氨酯预聚体2。
实施例10
将100份二环己基甲烷二异氰酸酯置于烧瓶中，加入适量丙酮溶解，40份除水的双酚A聚氧乙烯醚(分子量约为1020g/mol)置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入30份甲基丙烯酸羟乙酯、30份季戊四醇三丙烯酸酯，60℃搅拌反应2h，停止加热反应，得到硬结构聚氨酯预聚体3。
实施例11
将100份二苯甲烷二异氰酸酯置于烧瓶中，加入适量丙酮溶解，50份除水的双酚A聚氧乙烯醚(分子量约为1548g/mol)置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入50份季戊四醇三丙烯酸酯，60℃搅拌反应2h，停止加热反应，得到硬结构聚氨酯预聚体4。
实施例12
将50份二环己基甲烷二异氰酸酯、50份1,4-环己烷二异氰酸酯置于烧瓶中，加入适量丙酮溶解，60份除水的双酚A聚氧乙烯醚(分子量约为1900g/mol)置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入40份季戊四醇三丙烯酸酯，60℃搅拌反应2h，停止加热反应，得到硬结构聚氨酯预聚体5。
实施例13
将100份间苯二异氰酸酯置于烧瓶中，加入适量丙酮溶解，80份除水的双酚A聚氧乙烯醚(分子量约为2516g/mol)置于恒压滴液漏斗中，通氮除氧，在催化剂二月桂酸二丁基锡作用下，升温50℃并机械搅拌，反应1h；随后加入20份聚二季戊四醇五丙烯酸酯，60℃搅拌反应2h，停止加热反应，得到硬结构聚氨酯预聚体6。
三、防雾薄膜的制备
实施例14
将100份实施例1制备得到的软结构聚氨酯预聚体1与5份实施例8制备得到的硬结 构聚氨酯预聚体1混合，加入交联剂0.5份季戊四醇四丙烯酸酯与0.75份光引发剂二苯基乙酮，涂膜后进行光固化形成防雾薄膜1。
实施例15
将100份实施例2制备得到的软结构聚氨酯预聚体2与10份实施例8制备得到的硬 结构聚氨酯预聚体1混合，加入交联剂0.5份季戊四醇四丙烯酸酯、0.5份聚二季戊四醇六丙烯酸酯与1份光引发剂二苯基乙酮，涂膜后进行光固化形成防雾薄膜2。
实施例16
将100份实施例3制备得到的软结构聚氨酯预聚体3与20份实施例9制备得到的硬 结构聚氨酯预聚体2混合，加入交联剂1份聚二季戊四醇五丙烯酸酯与1.5份光引发剂α,α-二甲氧基-α-苯基苯乙酮，涂膜后进行光固化形成防雾薄膜3。
实施例17
将100份实施例4制备得到的软结构聚氨酯预聚体4与40份实施例10制备得到的硬 结构聚氨酯预聚体3混合，加入交联剂2份季戊四醇三丙烯酸酯与2份光引发剂芳酰基膦氧化物，涂膜后进行光固化形成防雾薄膜4。
实施例18
将100份实施例5制备得到的软结构聚氨酯预聚体5与60份实施例11制备得到的硬 结构聚氨酯预聚体4混合，加入交联剂3份乙氧化季戊四醇四丙烯酸酯与4.5份光引发剂双苯甲酰基苯基氧化膦，涂膜后进行光固化形成防雾薄膜5。
实施例19
将100份实施例6制备得到的软结构聚氨酯预聚体6与80份实施例12制备得到的硬 结构聚氨酯预聚体5混合，加入交联剂2份乙氧化三羟甲基丙烷三丙烯酸酯、2份聚二季戊四醇六丙烯酸酯与4份光引发剂二苯甲酮，涂膜后进行光固化形成防雾薄膜6。
实施例20
将100份实施例7制备得到的软结构聚氨酯预聚体7与100份实施例13制备得到的硬结构聚氨酯预聚体6混合，加入交联剂2.5份季戊四醇四丙烯酸酯、2.5份丙氧化三羟甲基丙烷三丙烯酸酯与7.5份光引发剂2,4-二羟基二苯甲酮，涂膜后进行光固化形成防雾薄膜 7。
对比例1
将100份实施例1制备得到的软结构聚氨酯预聚体1加入1份光引发剂二苯基乙酮，涂膜后进行光固化形成防雾薄膜8。
对比例2
将100份实施例8制备得到的硬结构聚氨酯预聚体1加入1份光引发剂二苯基乙酮，涂膜后进行光固化形成防雾薄膜9。
对比例3
将100份实施例2制备得到的软结构聚氨酯预聚体2与10份实施例8制备得到的硬 结构聚氨酯预聚体1混合，加入1份光引发剂二苯基乙酮，涂膜后进行光固化形成防雾薄膜 10。
对比例4
将100份实施例7制备得到的软结构聚氨酯预聚体7与100份实施例13制备得到的硬结构聚氨酯预聚体6混合，加入1份光引发剂2,4-二羟基二苯甲酮，涂膜后进行光固化形成防雾薄膜11。
将制备的防雾薄膜在70-100℃的蒸汽中放置，并保证温度持续，观察表面是否有起雾现象，放置时间>2min，结果列于表1。
参照GB/T 6739-2006，使用QHQ-A型铅笔硬度计测定涂膜的铅笔硬度，结果列于表1。
参照GB/T 1733-1993，将防雾产品浸泡于去离子水中，观察是否出现起泡、泛白、脱落现象，结果列于表1。
参照GB/T 9286-1998，使用HGQ型漆膜划格器通过划格实验的方法测定涂膜的附着力，结果列于表1。
结果如表1：
表1
从表1可看出，随着软结构聚氨酯预聚体含量的增加，聚合物结构中刚性链增多，致薄膜表面的硬度提高，具有优异的耐磨耐刮性能，本项目所制备的防雾产品经测试后皆不起泡、不泛白、与基材之间无脱落，具有优异的耐水性。
通过本发明获得的防雾薄膜，防雾效果持久，表面耐刮擦，耐水性优异且与基材粘附力高，性能与结构可调控，成本低廉，技术成熟，适合生产。
所属领域的普通技术人员应当理解：以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种光固型软硬结构可控聚氨酯类防雾薄膜，其特征在于，所述防雾薄膜是由软结构聚氨酯预聚体、硬结构聚氨酯预聚体通过光引发剂引发含碳碳双键交联剂固化形成，所述软结构聚氨酯预聚体由不含刚性基团的异氰酸酯或异氰酸酯多聚体、直链聚乙二醇、含羟基的丙烯酸酯类化合物、含羟基的表面活性剂制备而成；所述硬结构聚氨酯预聚体由含刚性基团的异氰酸酯或异氰酸酯多聚体、双酚A聚氧乙烯醚、含羟基的丙烯酸酯类化合物制备而成；所述软结构聚氨酯预聚体、硬结构聚氨酯预聚体与含碳碳双键交联剂的重量比为100:(5～100):(0.5～5)。
2.如权利要求1所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，步骤如下：a.将软结构聚氨酯预聚体、硬结构聚氨酯预聚体与含碳碳双键交联剂按配比混合均匀；b.再加入光引发剂，涂膜后进行光固化成膜。
3.根据权利要求2所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述的软结构聚氨酯预聚体的制备包括以下步骤：a.将不含刚性基团的异氰酸酯或异氰酸酯多聚体加溶剂稀释，添加直链聚乙二醇后通氮除氧，升温，反应一段时间后加入含羟基的丙烯酸酯类化合物和含羟基的表面活性剂，继续反应一段时间后得到软结构聚氨酯预聚体。
4.根据权利要求2或3所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述的硬结构聚氨酯预聚体的制备包括以下步骤：a.将含刚性基团的异氰酸酯或异氰酸酯多聚体加溶剂稀释，添加双酚A聚氧乙烯醚后通氮除氧，升温，反应一段时间后加入含羟基的丙烯酸酯类化合物和催化剂，继续反应一段时间后得到硬结构聚氨酯预聚体。
5.根据权利要求4所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述软结构聚氨酯预聚体中不含刚性基团的异氰酸酯或异氰酸酯多聚体、直链聚乙二醇、含羟基的丙烯酸酯类化合物、含羟基的表面活性剂之间的重量比为100:(10～80):(10～80):(10～80)；所述硬结构聚氨酯预聚体中含刚性基团的异氰酸酯或异氰酸酯多聚体、双酚A聚氧乙烯醚、含羟基的丙烯酸酯类化合物之间的重量比为100:(10～80):(20～90)；所述的光引发剂与含碳碳双键交联剂的质量比为1:(1～1.5)。
6.根据权利要求2、3或5所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述含碳碳双键交联剂为季戊四醇四丙烯酸酯、聚二季戊四醇五丙烯酸酯、聚二季戊四醇六丙烯酸酯、季戊四醇三丙烯酸酯、乙氧化季戊四醇四丙烯酸酯、乙氧化三羟甲基丙烷三丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯中的一种或两种以上混合。
7.根据权利要求3或5所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述不含刚性基团的异氰酸酯或异氰酸酯多聚体为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体中的一种或两种以上混合；所述直链聚乙二醇为分子量在200g/mol至1000g/mol范围内的聚乙二醇；所述含羟基的丙烯酸酯类化合物为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、季戊四醇三丙烯酸酯、聚二季戊四醇五丙烯酸酯中的一种或两种以上混合；所述含羟基的表面活性剂包括OP-4、OP-10、OP-20、OP-50、曲拉通X-100、曲拉通X-114、吐温20中的一种或两种以上混合。
8.根据权利要求6所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述不含刚性基团的异氰酸酯或异氰酸酯多聚体为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、异佛尔酮二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体中的一种或两种以上混合；所述直链聚乙二醇为分子量在200g/mol至1000g/mol范围内的聚乙二醇；所述含羟基的丙烯酸酯类化合物为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、季戊四醇三丙烯酸酯、聚二季戊四醇五丙烯酸酯中的一种或两种以上混合；所述含羟基的表面活性剂包括OP-4、OP-10、OP-20、OP-50、曲拉通X-100、曲拉通X-114、吐温20中的一种或两种以上混合。
9.根据权利要求3、5或8所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，所述含刚性基团的异氰酸酯或异氰酸酯多聚体为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、萘二异氰酸酯、二苯甲烷二异氰酸酯、1,6-己二异氰酸酯、苯二亚甲基二异氰酸酯、1,4-环己烷二异氰酸酯、间苯二异氰酸酯中的一种或两种以上混合；所述双酚A聚氧乙烯醚分子量在300g/mol至2600g/mol范围内。
10.根据权利要求2、3、5或8所述的一种光固型软硬结构可控聚氨酯类防雾薄膜的制备方法，其特征在于，光引发剂为二苯基乙酮、α,α-二甲氧基-α-苯基苯乙酮、芳酰基膦氧化物、双苯甲酰基苯基氧化膦或二苯甲酮或2,4-二羟基二苯甲酮。
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