CN115418144B - Ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material and manufacturing method thereof - Google Patents
Ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material and manufacturing method thereof Download PDFInfo
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- CN115418144B CN115418144B CN202211000416.4A CN202211000416A CN115418144B CN 115418144 B CN115418144 B CN 115418144B CN 202211000416 A CN202211000416 A CN 202211000416A CN 115418144 B CN115418144 B CN 115418144B
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- polyvinyl alcohol
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- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 57
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 57
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 5
- 229920003180 amino resin Polymers 0.000 claims abstract description 4
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 239000000080 wetting agent Substances 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 19
- 238000001723 curing Methods 0.000 claims description 18
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 18
- 239000011118 polyvinyl acetate Substances 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method 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
- C09D129/00—Coating compositions based on homopolymers or 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to an ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material and a manufacturing method thereof. The invention relates to an antifogging coating material, which comprises the following components: 15-20% of polyvinyl alcohol with ultralow alcoholysis degree, 1-10% of curing agent, 60-80% of 1, 4-dioxane, 0.01-0.5% of catalyst, 0-1.0% of auxiliary agent and 5-30% of alcoholysis degree of polyvinyl alcohol. The curing agent is selected from diisocyanate, diisocyanate oligomer and etherified amino resin; the catalyst is selected from dibutyl tin dilaurate and p-toluenesulfonic acid; the auxiliary agent is a defoaming agent and a leveling wetting agent. The antifogging coating material prepared by the invention has good antifogging effect, good water resistance and solvent resistance, and wide application range of base materials.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to an ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material and a manufacturing method thereof.
Background
The fogging of the surface of the material is a normal phenomenon, and the fogging is caused by the temperature difference between the inner side and the outer side of the substrate, so that small water drops gathered on the surface of the substrate can not spread on the whole plane, and light rays are refracted and reflected. Due to the high condensation of water vapor on the surface of the material, fogging can lead to severe light scattering and reduce the transparency of the material, severely limiting their use in humid environments. Currently, there are two main strategies for anti-fog. One is to change the ambient or surface temperature of the substrate to reduce the temperature difference. However, the method has high energy consumption, is not friendly to the environment, and limits the applicability. Another method of anti-fog is by hydrophilic or hydrophobic anti-fog treatment by changing the affinity between the solid surface and the water droplets. With the development of polymer science, polymer coatings using resins as film forming substances have been attracting attention. The resin forms a good film layer through solidification, so that the service life of the anti-fog coating is greatly prolonged. Anti-fog coatings are widely used and can be broadly classified into hydrophobic anti-fog coatings, biomimetic anti-fog coatings and hydrophilic anti-fog coatings. Currently, most of practical anti-fog coatings are hydrophilic anti-fog coatings, and a hydrophilic polymer route is one of preparation methods of the anti-fog coatings.
Polyvinyl alcohol (PVA) has good hydrophilicity, is nontoxic and pollution-free, and is often used for preparing anti-fog coatings or anti-fog agents. However, the water resistance is poor, glutaraldehyde, borate, boehmite and the like are generally added for crosslinking, and even after crosslinking, more hydroxyl groups still remain in the coating, and the coating is easy to foam and fall off in water environment, so that the coating is only used for short-term anti-fog in occasions with low water resistance requirements. At present, the hydrophilic property and the water resistance of PVA-based antifogging coatings are generally solved by adopting a mode of PVA resin, filler addition or substrate surface pretreatment. As in patent 201210553079.1, hydrophilic polymer end groups or side groups, including PVA, are imparted with siloxane groups to enable chemical bonding with the glass substrate, while nanoparticles are incorporated to enhance the mechanical properties of the coating. In patent 201310254464.0, a substrate is first hydroxylated with a strong acid, then treated with 3-aminopropyl triethoxysilane, and maleic anhydride grafted polyethylene and PVA are coated separately to give a PVA hydrophilic coating. In patent 201611156887.9, a primer layer containing hydroxyl acrylic resin and a curing agent is coated on the surface of a substrate, then a finish layer composed of polyvinyl alcohol and nano particles is coated, and the double-layer structure coating is soaked in a cross-linking agent aqueous solution and then cured, so that the super-hydrophilic anti-fog coating with a micro-nano structure on the surface is obtained. In patent 202110216754.0, an ultraviolet light cured hydrophilic semi-interpenetrating network coating is prepared by adopting trehalose modified polyvinyl alcohol, oligomeric ethylene glycol dimethacrylate, benzoin dimethyl ether and deionized water, and has anti-fog and anti-frost properties. In the above patent reports, the surface treatment of the substrate complicates the preparation process of the antifogging coating, the transparency of the coating is possibly reduced due to poor dispersion when the nanoparticles are introduced, and the relationship among adhesive force, hydrophilicity and water resistance is not easily balanced when the resin is modified or compounded. Therefore, the preparation of the hydrophilic PVA antifog coating with good water resistance, good adhesive force and wide application range of the base material still faces challenges.
Disclosure of Invention
The invention aims to provide an ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material with good anti-fog performance, strong adhesive force and good water resistance and a manufacturing method thereof.
The invention provides an ultra-low alcoholysis degree polyvinyl alcohol (PVA) antifogging coating material, which comprises the following components:
ultra low alcoholysis degree PVA: 15-20%;
curing agent: 1-10%;
1, 4-dioxane: 60-80%;
catalyst: 0.01-0.5%;
auxiliary agent: 0-1.0%;
the total amount satisfies 100%.
In the invention, the alcoholysis degree of the PVA with the ultra-low alcoholysis degree is 5-30%.
In the invention, the curing agent is one of diisocyanate, diisocyanate oligomer and etherified amino resin.
Further, the curing agent in the present invention is selected from one of hexamethylene diisocyanate, isophorone diisocyanate, biuret and melamine thereof, a permethlated melamine resin, a partially methylated melamine resin, and a partially butyl etherified melamine resin.
In the invention, the catalyst is one of dibutyl tin dilaurate and p-toluenesulfonic acid.
In the invention, the auxiliary agent is a defoaming agent and a leveling wetting agent.
The invention also provides a manufacturing method of the PVA antifog coating material with low alcoholysis degree, which comprises the following specific steps:
(1) Preparing PVA with ultra-low alcoholysis degree;
dissolving polyvinyl acetate in tetrahydrofuran, slowly adding a certain amount of sodium hydroxide methanol solution (namely alkali alcohol solution) for alcoholysis, and finally adding dilute hydrochloric acid to adjust the pH to 6-7 to obtain PVA with ultra-low alcoholysis degree, wherein the alcoholysis degree range is 5-30%;
(2) Drying the PVA with ultra-low alcoholysis degree obtained in the step (1), dissolving the PVA into 1, 4-dioxane, standing and settling the PVA for more than 24 hours, and removing impurities and insoluble matters;
(3) Mixing the PVA solution with the ultra-low alcoholysis degree prepared in the step (2) with a curing agent according to a certain molar ratio, and adding a catalyst and an auxiliary agent to prepare the PVA anti-fog coating with the ultra-low alcoholysis degree;
(4) Coating the coating prepared in the step (3) on a transparent substrate to form a coating film, and curing the coating film;
(5) Spraying an alkali alcohol solution on the surface of the coating film obtained by curing, or soaking the coating film in the alkali alcohol solution for a certain time;
(6) The surface alkali alcohol solution is washed by clean water.
Further, in the step (1), the molecular weight of the polyvinyl acetate used is in the range of 5000-50000g/mol.
Further, in the step (1), the amount of the alkali alcohol solution added is 3 to 35% of that of the polyvinyl acetate.
Further, in the step (1), the alcoholysis temperature of the polyvinyl acetate is 40-50 ℃ and the alcoholysis time is 2-4 hours.
Further, in the step (4), the transparent substrate is one of polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate (PET) and glass.
Further, in the step (4), the coating film curing condition is room temperature or heat curing.
Further, in the step (5), the alkali concentration in the sprayed or soaked alkali alcohol solution is 1-10%.
Further, in step (5), the alkali in the alkali alcohol solution is sodium hydroxide.
In the invention, polyvinyl acetate is partially alcoholyzed to generate hydroxyl functional groups for crosslinking and curing the coating. After the crosslinked and solidified coating film is treated by alkali alcohol solution, the residual vinyl acetate groups are gradually alcoholyzed from outside to inside, hydroxyl groups with certain concentration gradient distribution are formed on the surface layer of the coating film, and good hydrophilic anti-fog performance is provided for the surface of the coating film. Meanwhile, the non-alcoholysis polyvinyl acetate chain segment at the interface with the substrate provides good adhesion for the coating.
The PVA antifog coating material with ultra-low alcoholysis degree has wide application range, does not need to pretreat the substrate, has good antifog performance (no fogging phenomenon on the surface after steam fumigation for 30 minutes), has excellent adhesive force, and has good solvent resistance (100 times of passing through acetone wiping) and water resistance (no change after 24 hours soaking).
Drawings
FIG. 1 shows the antifogging properties of coating films of ultra-low alcoholysis PVA resins based on alcoholysis degrees of 11% (left) and 17% (right) on the surfaces of PMMA and PET substrates.
Fig. 2 is an anti-fog property of a coating film of an ultra-low alcoholysis degree PVA resin based on an alcoholysis degree of 22% on a glass surface.
Detailed Description
Example 1
204.2g of tetrahydrofuran and 92.8g of polyvinyl acetate are added into a 500mL four-necked flask, 3.0g of sodium hydroxide methanol solution (concentration: 5%) is slowly added after the polyvinyl acetate is completely dissolved at 40 ℃, and after 2 hours of reaction, a proper amount of diluted hydrochloric acid is added to adjust the pH to 6-7, thus obtaining the polyvinyl alcohol with the alcoholysis degree of 11%.
4g of polyvinyl alcohol having an alcoholysis degree of 11% was dried and dissolved in 16g of 1, 4-dioxane at 80℃and left for 24 hours to precipitate and remove impurities and insoluble matters.
10g of the upper layer solution was taken, added with 0.24g of hexamethylene diisocyanate trimer and 0.1g of dibutyltin dilaurate solution (concentration 1%, in 1, 4-dioxane solvent), and after stirring and mixing uniformly, the mixture was coated on PMMA and PET substrates, and cured for 2 hours at 80 ℃.
And (3) soaking the coating film in 5% alkali alcohol solution for 1h at room temperature, taking out, washing with deionized water for several times, airing at room temperature, and ensuring that the optical transmittance of the coating film is 91%.
The prepared coating film is subjected to anti-fog, water-resistant and solvent-resistant tests, and experiments show that the coating film has good anti-fog effect (see figure 1), and simultaneously has good water resistance (no change in 24-hour soaking) and solvent resistance (100 passes of acetone wiping).
Example 2
201.1g of tetrahydrofuran and 91.4g of polyvinyl acetate are added into a 500mL four-necked flask, 7.5g of sodium hydroxide methanol solution is slowly added after the polyvinyl acetate is completely dissolved at 40 ℃, and a proper amount of diluted hydrochloric acid is added after 2 hours of reaction to adjust the pH to 6-7, thus obtaining the polyvinyl alcohol with the alcoholysis degree of 17%.
4g of polyvinyl alcohol having an alcoholysis degree of 17% was dried and dissolved in 16g of 1, 4-dioxane at 80℃and allowed to stand for 48 hours to precipitate and remove impurities and insoluble matters.
10g of the solution was taken, added with 0.38g of isophorone diisocyanate trimer and 0.1g of dibutyltin dilaurate solution (concentration 1%, solvent 1, 4-dioxane), and after stirring and mixing uniformly, coated on PMMA substrate and PET substrate, and cured for 2 hours at 80 ℃.
And (3) soaking the coating film in 5% alkali alcohol solution for 1h at room temperature, taking out, washing with deionized water for several times, airing at room temperature, and ensuring that the optical transmittance of the coating film is 91.5%.
The coating film is subjected to anti-fog, water resistance and solvent resistance tests, and experiments show that the coating film has good anti-fog performance (see figure 1). At the same time, it has good water resistance (no change in 24 hours of soaking) and solvent resistance (100 passes of acetone wiping).
Example 3
195.9g of tetrahydrofuran and 89.1g of polyvinyl acetate are added into a 500mL four-necked flask, 15.0g of sodium hydroxide methanol solution (concentration: 5%) is slowly added after the polyvinyl acetate is completely dissolved at 50 ℃, and after 2 hours of reaction, a proper amount of diluted hydrochloric acid is added to adjust the pH to 6-7, thus obtaining PVA with the alcoholysis degree of 22%.
4g of PVA having an alcoholysis degree of 11% was dried and dissolved in 16g of 1, 4-dioxane at 80℃and allowed to stand for 48 hours to precipitate and remove impurities and insoluble matters.
10g of the upper layer solution is taken, 1.0 g g of fully methylated amino resin, 0.06g of p-toluenesulfonic acid and 0.05 g g of flatting agent are added, and the mixture is uniformly stirred and mixed and then coated on a glass substrate, and the mixture is cured for 2 hours at 160 ℃.
Spraying a layer of 10% alkali alcohol solution on the surface of the cured coating, washing with deionized water for several times after methanol is volatilized, and airing at room temperature, wherein the optical transmittance of the coating is 90%.
The prepared coating film is subjected to anti-fog, water-resistant and solvent-resistant tests, and experiments show that the coating film has good anti-fog effect (see figure 2), and simultaneously has good water resistance (no change in 24-hour soaking) and solvent resistance (100 passes of acetone wiping).
The test method for water resistance, solvent resistance, antifogging property and transparency is as follows:
(1) Water resistance test
The water resistance of the coating was tested by immersing the coating in water for 24 hours according to GB/T1733-1993. Observing whether the coating has the phenomena of color change, foaming, wrinkling, falling off and the like; the coating was rated as water-resistant by no swelling, bubbling, wrinkling, blushing, and peeling.
(2) Solvent resistance test
According to GB/T23989-2009, a one hundred wiping back and forth of the coated surface is performed with cotton wool impregnated with acetone. Observing whether the coating has the phenomena of wrinkling, falling off and the like; the coating was rated solvent resistance as passing without swelling, blistering, wrinkling, blushing, and peeling.
(3) Antifogging property
The coating film was placed 5cm above 80℃water vapor, and the surface of the coating film was observed for fogging.
(4) Transparency of
The transmittance at a wavelength of 550nm was selected to evaluate the transparency.
The above description is merely an embodiment of the present invention, but the scope of the present invention is not limited thereto, and modifications may be made by those skilled in the art without departing from the inventive concept, but these are all within the scope of the present invention.
Claims (4)
1. An ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material is characterized by comprising the following components:
ultra low alcoholysis degree PVA: 15-20%;
curing agent: 1-10%;
1, 4-dioxane: 60-80%;
catalyst: 0.01-0.5%;
auxiliary agent: 0-1.0%;
the total amount satisfies 100%;
the alcoholysis degree of the PVA with the ultra-low alcoholysis degree ranges from 5% to 30%;
wherein: the curing agent is one of diisocyanate, diisocyanate oligomer and etherified amino resin;
the catalyst is one of dibutyl tin dilaurate and p-toluenesulfonic acid; the auxiliary agent is a defoaming agent and a leveling wetting agent;
the polyvinyl alcohol antifogging coating material with the ultra-low alcoholysis degree is prepared by the following steps:
(1) Preparation of polyvinyl alcohol with ultra-low alcoholysis degree
Dissolving polyvinyl acetate in tetrahydrofuran, slowly adding an alkali alcohol solution for alcoholysis, and finally adding dilute hydrochloric acid to adjust the pH to 6-7 to obtain polyvinyl alcohol with ultra-low alcoholysis degree, wherein the alcoholysis degree range is 5-30%;
(2) Drying the ultra-low alcoholysis degree polyvinyl alcohol obtained in the step (1), dissolving the polyvinyl alcohol in 1, 4-dioxane, and standing and settling the polyvinyl alcohol for more than 24 hours to remove impurities and insoluble matters;
(3) Mixing the ultra-low alcoholysis degree polyvinyl alcohol solution prepared in the step (2) with a curing agent according to a certain molar ratio, and adding a catalyst and an auxiliary agent to prepare the ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating;
(4) Coating the coating prepared in the step (3) on a transparent substrate to form a coating film, and curing the coating film;
(5) Spraying an alkali alcohol solution on the surface of the coating film obtained by curing, or soaking the coating film in the alkali alcohol solution for a certain time;
(6) Washing the surface alkali alcohol solution with clear water;
the alkali alcohol solution added in the step (1) accounts for 3-35% of the amount of the polyvinyl acetate;
the alcoholysis temperature of the polyvinyl acetate in the step (1) is 40-50 ℃ and the alcoholysis time is 2-4 hours.
2. A method for preparing an anti-fog coating material of ultra-low alcoholysis polyvinyl alcohol according to claim 1, which is characterized by comprising the following specific steps:
(1) Preparation of polyvinyl alcohol with ultra-low alcoholysis degree
Dissolving polyvinyl acetate in tetrahydrofuran, slowly adding an alkali alcohol solution for alcoholysis, and finally adding dilute hydrochloric acid to adjust the pH to 6-7 to obtain polyvinyl alcohol with ultra-low alcoholysis degree, wherein the alcoholysis degree range is 5-30%;
(2) Drying the ultra-low alcoholysis degree polyvinyl alcohol obtained in the step (1), dissolving the polyvinyl alcohol in 1, 4-dioxane, and standing and settling the polyvinyl alcohol for more than 24 hours to remove impurities and insoluble matters;
(3) Mixing the ultra-low alcoholysis degree polyvinyl alcohol solution prepared in the step (2) with a curing agent according to a certain molar ratio, and adding a catalyst and an auxiliary agent to prepare the ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating;
(4) Coating the coating prepared in the step (3) on a transparent substrate to form a coating film, and curing the coating film;
(5) Spraying an alkali alcohol solution on the surface of the coating film obtained by curing, or soaking the coating film in the alkali alcohol solution for a certain time;
(6) Washing the surface alkali alcohol solution with clear water;
the alkali alcohol solution added in the step (1) accounts for 3-35% of the amount of the polyvinyl acetate;
the alcoholysis temperature of the polyvinyl acetate in the step (1) is 40-50 ℃ and the alcoholysis time is 2-4 hours.
3. The method according to claim 2, wherein the coating film curing condition in step (4) is room temperature or heat curing.
4. The method according to claim 2, wherein the alkali concentration in the sprayed or immersed alkali alcohol solution in step (5) is 1 to 10%; the alkali in the alkali alcohol solution is sodium hydroxide.
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| WO2010062893A1 (en) * | 2008-11-28 | 2010-06-03 | 3M Innovative Properties Company | Antifogging coating composition, antifogging film and article |
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