CN112457768B - Photocuring spray paint and preparation method thereof - Google Patents
Photocuring spray paint and preparation method thereof Download PDFInfo
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- CN112457768B CN112457768B CN202011355581.2A CN202011355581A CN112457768B CN 112457768 B CN112457768 B CN 112457768B CN 202011355581 A CN202011355581 A CN 202011355581A CN 112457768 B CN112457768 B CN 112457768B
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- 239000003973 paint Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000007921 spray Substances 0.000 title claims abstract description 24
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 22
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 39
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 21
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 19
- 150000001261 hydroxy acids Chemical class 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 70
- 238000003756 stirring Methods 0.000 claims description 70
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 239000004922 lacquer Substances 0.000 claims description 36
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 229920001451 polypropylene glycol Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 239000004310 lactic acid Substances 0.000 claims description 15
- 235000014655 lactic acid Nutrition 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000011975 tartaric acid Substances 0.000 claims description 15
- 235000002906 tartaric acid Nutrition 0.000 claims description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 13
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 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
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 8
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 8
- 229930195725 Mannitol Natural products 0.000 claims description 8
- 239000000594 mannitol Substances 0.000 claims description 8
- 235000010355 mannitol Nutrition 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000600 sorbitol Substances 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 5
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 238000001723 curing Methods 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical class OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 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 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 28
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 17
- 238000000576 coating method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000007655 standard 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The application discloses a photocuring spray paint and a preparation method thereof. The photocuring paint comprises the following components: 80-90 parts by weight of a polyurethane acrylate prepolymer; 50-60 parts by weight of a (meth) acrylate monomer; 5-8 parts by weight of a silane coupling agent; hydroxy acid modified ZrO225-35 parts by weight; 3-5 parts by weight of a polyol; 2.5-3.2 parts by weight of hydroxyl-terminated polydimethylsiloxane; 0.7-1.2 parts by weight of melamine; 6-9 parts of a photoinitiator; 120-140 parts of a solvent. The photocuring paint has excellent adhesive force, impact strength, weather resistance, flexibility, hardness, abrasion resistance and the like. In addition, the preparation method of the photocuring paint is simple, convenient and quick to operate and high in production efficiency.
Description
Technical Field
The application relates to the field of coatings, in particular to a photocuring spray paint and a preparation method thereof.
Background
The photocuring spray paint is an environment-friendly paint which utilizes ultraviolet irradiation to promote an initiator to decompose to generate free radicals so as to initiate resin to be cured into a film, and can be crosslinked and cured in a short time to form a good paint film. The photocuring paint has the performance of high efficiency, convenience and the like, and is widely applied in various fields, such as paper, woodware, plastics, metal, optical disks, optical fibers, electronic communication, sports goods, automobiles, building coatings, packaging materials and the like, which are indispensable in various industries.
Patent application CN102372935A discloses an ultraviolet light-cured automatic spray paint and a preparation method thereof, wherein the spray paint comprises components such as oligomer, monomer, coupling agent, photoinitiator, propellant and the like. The spray paint can be automatically sprayed by combining with an aerosol technology, and the shrinkage of a thick coating is greatly reduced, so that a paint film with the thickness of more than 0.5mm can be formed by curing, the corrosion prevention effect is excellent, and the spray paint can be particularly applied to the field of heavy corrosion prevention.
However, the paint has room for further improvement in adhesion, impact strength, weather resistance, flexibility, hardness and abrasion resistance.
Disclosure of Invention
[ problem ] to
To overcome the defects in the prior art, the light-cured paint is provided. The paint has excellent adhesion, impact strength, weather resistance, flexibility, hardness, wear resistance and the like.
Another object of the present application is to provide a method for preparing the photo-curing spray paint, which is simple, convenient and fast to operate and has high production efficiency.
[ solution ]
In order to achieve the above object, according to one embodiment of the present application, there is provided a photo-curing lacquer including the following components:
in the application, the light-cured paint with excellent various performances can be prepared by adopting specific components and designing specific component proportion, such as the adhesive force, the impact strength, the weather resistance, the flexibility, the hardness, the wear resistance and the like of a paint film after paint curing are obviously improved.
The photocuring spray paint according to the application can be applied to various spray modes, such as manual spray, mechanical spray, aerosol can automatic spray, and the like, and preferably adopts an aerosol can automatic spray mode, such as sealing in a closed container and pressurizing to fill propellant for use.
Further, the urethane acrylate prepolymer can be prepared by the following method:
(a) mixing polypropylene glycol, isocyanate, acetone and dibutyltin dilaurate in a weight ratio of (30-35) to (60-65) to (0.5-0.7), heating to 70-80 ℃, stirring for reacting for 6-7 hours, and cooling to room temperature; and
(b) and (2) adding hydroxypropyl acrylate with the weight ratio of (45-50): 100 to the polypropylene glycol into the obtained product in the step (1), heating to 50-60 ℃, stirring for reaction for 9-10 hours, and carrying out reduced pressure distillation to remove acetone, thereby preparing the urethane acrylate prepolymer.
In the application, the polyurethane acrylate prepolymer is used as one of main film forming substances for paint spraying, and can bring excellent adhesive force, impact strength, weather resistance, flexibility and the like for paint spraying.
The isocyanate may be at least one selected from diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), or Lysine Diisocyanate (LDI), preferably isophorone diisocyanate (IPDI) or dicyclohexylmethane diisocyanate (HMDI).
The polymerization degree of the polypropylene glycol may be 50 to 100, preferably 60 to 80.
Further, the (meth) acrylate monomer may be at least one selected from the group consisting of isooctyl acrylate, isooctyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol di-methacrylate, pentaerythritol triacrylate, dehydrated glycerol acrylate, dehydrated glycerol methacrylate, 2-hydroxy n-butyl acrylate, 1, 4-butanediol diacrylate, lauryl acrylate, and lauryl methacrylate, preferably, the acrylate is any one selected from the group consisting of 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, dehydrated glycerol acrylate, 2-hydroxy n-butyl acrylate and 1, 4-butanediol diacrylate.
Further, the silane coupling agent may be at least one selected from the group consisting of KH650, KH660 and KH 670.
Further, the hydroxy acid-modified ZrO2The preparation method can be adopted as follows:
(i) dissolving citric acid, lactic acid and tartaric acid in water to prepare a modified solution, wherein the weight ratio of the citric acid to the lactic acid to the tartaric acid to the water is (13-16): 10-12): 5-7): 100; and
(ii) nano ZrO at a weight ratio of (30-35): 1002Mixing the obtained mixture with the modified solution, and stirring and reacting the mixture for 6 to 7 hours at the temperature of between 60 and 70 ℃ to obtain the hydroxy acid modified ZrO2。
In the application, nano-ZrO is modified by a modifying solution prepared by three hydroxy acids in a specific ratio range2Hydroxy acid-modified ZrO prepared thereby2The spray paint can be further liftedImpact strength, weather resistance, hardness, abrasion resistance, and the like.
Further, the nano ZrO2The particle size of (A) may be 20 to 35 nm. When the particle diameter is less than 20nm, the nano ZrO2Has too large surface area and higher surface activity, thereby leading excessive hydroxy acid to be introduced, and leading the nano ZrO to be2The paint has too strong reactivity with other components, thereby influencing the flexibility of the paint; when the particle size is larger than 35nm, too little hydroxy acid is introduced, and the improvement of the spray painting strength is influenced.
Further, the polyol may be at least one selected from sorbitol and mannitol. In the present application, the use of the polyol can increase the degree of crosslinking of the three-dimensional network formed upon curing of the paint, thereby further promoting the improvement of the paint in terms of impact strength, weather resistance, flexibility, and the like.
Further, the polymerization degree of the hydroxyl-terminated polydimethylsiloxane may be 60 to 100, preferably 80 to 100. Under the polymerization degree, the hydroxyl-terminated polydimethylsiloxane can be matched with other components to improve various performances of the spray paint.
Further, the photoinitiator may be at least one selected from the group consisting of α -hydroxyisopropylbenzophenone, α -hydroxycyclohexylbenzophenone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzylphenyl) butanone, and preferably α -hydroxyisopropylbenzophenone or α -hydroxycyclohexylbenzophenone.
Further, the solvent may be at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and propylene glycol dimethyl ether, and is preferably acetone or ethylene glycol diethyl ether.
According to another embodiment of the present application, there is provided a method for preparing the above photo-curing lacquer, comprising the steps of:
(1) mixing a polyurethane acrylate prepolymer, (meth) acrylate monomer, a silane coupling agent, hydroxyl-terminated polydimethylsiloxane and a solvent, and dispersing for 8-10 minutes at a stirring speed of 160-180 r/min;
(2) adding hydroxy acid-modified ZrO to the obtained product of step (1)2Dispersing the polyol and the melamine for 45-50 minutes at a stirring speed of 980-1020 r/min; and
(3) adding a photoinitiator into the product obtained in the step (1), and dispersing for 15-20 minutes at a stirring speed of 130-150 r/min.
In this application, can obtain the photocuring according to this application through stirring the mixture with different components in batches, it is simple and efficient to handle, and production efficiency is high.
[ advantageous effects ]
In summary, the present application has the following beneficial effects:
the photocuring spray paint adopts specific components and designs specific component proportion, thereby having excellent performances such as adhesion, impact strength, weather resistance, flexibility, hardness and abrasion resistance.
In addition, the preparation method of the photocuring paint is simple, convenient and quick to operate and high in production efficiency.
Detailed Description
In order that those skilled in the art can more clearly understand the present application, the present application will be described in further detail with reference to the following examples, but it should be understood that the following examples are only preferred embodiments of the present application, and the scope of the present application as claimed is not limited thereto.
Sources of materials
Polypropylene glycol, purchased from Haian petrochemical plants of Jiangsu province;
isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), available from engorgement industries, germany;
dibutyl tin dilaurate, available from basf, germany;
1, 6-hexanediol diacrylate, 1, 6-hexanediol di-methacrylate, pentaerythritol triacrylate, acrylic acid dehydrated glyceride, 2-hydroxy n-butyl acrylate, 1, 4-butanediol diacrylate, available from Shanghai Michelin Biochemical technology, Inc.;
silane coupling agents KH650, KH660 and KH670, available from Nanjing warp and weft chemical Co., Ltd;
nano ZrO2Purchased from Kjen chemical Co., Ltd of Shanghai;
citric acid, purchased from hui tong chemical ltd, wujiang;
lactic acid, purchased from Shanghai brocade chemical Co., Ltd;
tartaric acid, available from Suzhou Jiaxu chemical environmental protection science and technology Limited;
sorbitol, mannitol, purchased from Jiangsu Yihao Hao Zenith Biotech, Inc.;
hydroxy-terminated polydimethylsiloxanes, available from Shanghai Michelin Biochemical technology, Inc.;
melamine, available from suzhou friend high-definition industries, ltd;
α -hydroxy-isopropylbenzophenone (1173), α -hydroxy-cyclohexylbenzophenone (184), available from Ciba chemistry, Switzerland (China) Inc.;
acetone, available from shanghai engden chemical ltd; and
ethylene glycol diethyl ether, available from Shanghai, Chemicals, Inc.
< example >
Example 1
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 85g of urethane acrylate prepolymer, 55g of 1, 6-hexanediol diacrylate, 6.5g of silane coupling agent KH550, 2.8g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 130g of acetone, and dispersing for 9 minutes at a stirring speed of 170 r/min;
(2) 30g of hydroxy acid-modified ZrO was added to the resultant of step (1)24g of sorbitol and 1.0g of melamine, with stirring at 1000r/min for 47 minutes; and
(3) 7.5 of photoinitiator alpha-hydroxy isopropyl benzophenone was added to the resultant of step (1) and dispersed for 18 minutes at a stirring speed of 140 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with the polymerization degree of 60-80), 33g of isophorone diisocyanate (IPDI), 62g of acetone and 0.6g of dibutyltin dilaurate, heating to 75 ℃, stirring for reacting for 6.5 hours, and cooling to room temperature; and
(b) adding 48g of hydroxypropyl acrylate into the obtained product in the step (1), heating to 55 ℃, stirring for reaction for 9.5 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
The hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving 15g of citric acid, 11g of lactic acid and 6g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 33g of nano ZrO2(particle size of 20-35 nm) and 100g of the modified solution, and stirring and reacting at 65 ℃ for 6.5 hours to obtain the hydroxy acid modified ZrO2。
Thus, a photocured lacquer according to the application is produced.
Example 2
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 80g of urethane acrylate prepolymer, 55g of acrylic acid dehydrated glyceride, 6g of silane coupling agent KH560, 2.5g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 135g of ethylene glycol diethyl ether, and dispersing for 8 minutes at a stirring speed of 180 r/min;
(2) to the resultant of step (1), 25g of a hydroxy acid-modified ZrO was added24.5g of mannitol and 0.9g of melamine, at a stirring speed of 980r/min for 50 minutes; and
(3) 9g of a photoinitiator, alpha-hydroxycyclohexylbenzophenone, was added to the resultant obtained in step (1), and the mixture was dispersed for 20 minutes at a stirring speed of 130 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with the polymerization degree of 60-80), 30g of isophorone diisocyanate (IPDI), 62g of acetone and 0.6g of dibutyltin dilaurate, heating to 70 ℃, stirring for reacting for 7 hours, and cooling to room temperature; and
(b) adding 50g of hydroxypropyl acrylate into the obtained product in the step (1), heating to 60 ℃, stirring for reaction for 10 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
The hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving 15g of citric acid, 10g of lactic acid and 7g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 32g of nano ZrO2(particle size of 20-35 nm) and 100g of the modified solution are mixed and stirred at 65 ℃ for reaction for 6 hours, so that the hydroxy acid modified ZrO is prepared2。
Thus, a photocured lacquer according to the application is produced.
Example 3
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 83g of urethane acrylate prepolymer, 57g of pentaerythritol triacrylate, 7g of a silane coupling agent KH570, 3.2g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 125g of acetone, and dispersing for 8 minutes at a stirring speed of 170 r/min;
(2) 32g of a hydroxy acid-modified ZrO was added to the resultant product of step (1)23.5g of mannitol and 0.8g of melamine, at a stirring speed of 1020r/min for 45 minutes; and
(3) 7g of a photoinitiator, alpha-hydroxycyclohexylbenzophenone, was added to the resultant obtained in step (1), and the mixture was dispersed for 16 minutes at a stirring speed of 145 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with a polymerization degree of 60-80), 35g of dicyclohexylmethane diisocyanate (HMDI), 62g of acetone and 0.5g of dibutyltin dilaurate, heating to 80 ℃, stirring for reacting for 6 hours, and cooling to room temperature; and
(b) adding 45g of hydroxypropyl acrylate into the product obtained in the step (1), heating to 5 ℃, stirring for reaction for 10 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
The hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving 14g of citric acid, 11g of lactic acid and 5g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 33g of nano ZrO2(particle size of 20-35 nm) and 100g of the modified solution, and stirring and reacting at 70 ℃ for 7 hours to obtain the hydroxy acid modified ZrO2。
Thus, a photocured lacquer according to the application is produced.
Example 4
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 90g of urethane acrylate prepolymer, 52g of 2-hydroxy n-butyl acrylate, 8g of silane coupling agent KH560, 2.7g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 130g of acetone, and dispersing for 10 minutes at a stirring speed of 175 r/min;
(2) 30g of hydroxy acid-modified ZrO was added to the resultant of step (1)23.5g of sorbitol and 1.1g of melamine, at a stirring speed of 1000r/min for 45 minutes; and
(3) 8g of a photoinitiator, alpha-hydroxy-isopropylbenzophenone, was added to the resultant of step (1) and dispersed for 18 minutes with a stirring speed of 135 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with a polymerization degree of 60-80), 34g of dicyclohexylmethane diisocyanate (HMDI), 60g of acetone and 0.5g of dibutyltin dilaurate, heating to 70 ℃, stirring for reaction for 7 hours, and cooling to room temperature; and
(b) adding 47g of hydroxypropyl acrylate into the obtained product in the step (1), heating to 55 ℃, stirring for reaction for 9 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
The hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving 13g of citric acid, 12g of lactic acid and 5g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 35g of nano-ZrO2(particle size of 20-35 nm) and 100g of the modified solution, and stirring and reacting at 65 ℃ for 6.5 hours to obtain the hydroxy acid modified ZrO2。
Thus, a photocured lacquer according to the application is produced.
Example 5
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 87g of polyurethane acrylate prepolymer, 50g of 1, 6-hexanediol dimethacrylate, 5g of silane coupling agent KH550, 2.9g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 125g of ethylene glycol diethyl ether, and dispersing for 10 minutes at a stirring speed of 165 r/min;
(2) to the resultant of step (1), 35g of hydroxy acid-modified ZrO was added24.5g of mannitol and 1.1g of melamine, dispersed for 47 minutes at a stirring speed of 980 r/min; and
(3) 9g of a photoinitiator, alpha-hydroxy-isopropylbenzophenone, was added to the resultant of step (1) and dispersed for 15 minutes with stirring at a rate of 150 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with a polymerization degree of 60-80), 34g of dicyclohexylmethane diisocyanate (HMDI), 62g of acetone and 0.7g of dibutyltin dilaurate, heating to 75 ℃, stirring for reacting for 6 hours, and cooling to room temperature; and
(b) adding 45g of hydroxypropyl acrylate into the product obtained in the step (1), heating to 55 ℃, stirring for reaction for 9.5 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
The hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving 13g of citric acid, 11g of lactic acid and 6g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 30g of nano ZrO2(particle size of 20-35 nm) and 100g of the modified solution, and stirring and reacting at 60 ℃ for 6 hours to obtain the hydroxy acid modified ZrO2。
Thus, a photocured lacquer according to the application is produced.
Example 6
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 90g of urethane acrylate prepolymer, 50g of 1, 4-butanediol diacrylate, 5.5g of silane coupling agent KH570, 3.2g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 120g of ethylene glycol diethyl ether, and dispersing for 10 minutes at a stirring speed of 180 r/min;
(2) to the resultant of step (1), 27g of a hydroxy acid-modified ZrO was added23g of sorbitol and 1.2g of melamine, dispersed for 47 minutes at a stirring speed of 980 r/min; and
(3) 6g of a photoinitiator, alpha-hydroxy-isopropyl-benzophenone, was added to the resultant of step (1) and dispersed for 15 minutes with stirring at a speed of 140 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with the polymerization degree of 60-80), 30g of isophorone diisocyanate (IPDI), 62g of acetone and 0.6g of dibutyltin dilaurate, heating to 80 ℃, stirring for reacting for 7 hours, and cooling to room temperature; and
(b) adding 47g of hydroxypropyl acrylate into the obtained product in the step (1), heating to 50 ℃, stirring for reaction for 9.5 hours, and distilling under reduced pressure to remove acetone, thereby obtaining the urethane acrylate prepolymer.
The hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving 16g of citric acid, 12g of lactic acid and 5g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 35g of nano-ZrO2(particle size of 20-35 nm) and 100g of the modified solution, and stirring and reacting at 60 ℃ for 7 hours to obtain the hydroxy acid modified ZrO2。
Thus, a photocured lacquer according to the application is produced.
Example 7
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 85g of urethane acrylate prepolymer, 60g of acrylic acid dehydrated glyceride, 7g of silane coupling agent KH560, 2.5g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 120g of acetone, and dispersing for 9 minutes at a stirring speed of 160 r/min;
(2) to the resultant of step (1), 25g of a hydroxy acid-modified ZrO was added25g of mannitol and 1.2g of melamine, dispersed for 46 minutes at a stirring speed of 1020 r/min; and
(3) 9g of a photoinitiator, alpha-hydroxycyclohexylbenzophenone, was added to the resultant obtained in step (1), and the mixture was dispersed for 16 minutes at a stirring speed of 150 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with a polymerization degree of 60-80), 35g of dicyclohexylmethane diisocyanate (HMDI), 60g of acetone and 0.5g of dibutyltin dilaurate, heating to 70 ℃, stirring for reacting for 6 hours, and cooling to room temperature; and
(b) and (2) adding 48g of hydroxypropyl acrylate into the obtained product in the step (1), heating to 57 ℃, stirring for reaction for 10 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
The hydroxy acid is modifiedZrO2The preparation method comprises the following steps:
(i) dissolving 14g of citric acid, 10g of lactic acid and 5g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 34g of nano ZrO2(particle size of 20-35 nm) and 100g of the modified solution, and stirring and reacting at 60 ℃ for 6 hours to obtain the hydroxy acid modified ZrO2。
Thus, a photocured lacquer according to the application is produced.
Example 8
The following preparation methods were used to prepare the photocured lacquers according to the application:
(1) mixing 90g of urethane acrylate prepolymer, 55g of 1, 6-hexanediol diacrylate, 8g of silane coupling agent KH550, 2.7g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 140g of ethylene glycol diethyl ether, and dispersing for 10 minutes at a stirring speed of 180 r/min;
(2) to the resultant of step (1), 25g of a hydroxy acid-modified ZrO was added24.5g of mannitol and 0.7g of melamine, at a stirring speed of 1000r/min for 48 minutes; and
(3) 7g of a photoinitiator, alpha-hydroxy-isopropyl-benzophenone, was added to the resultant of step (1) and dispersed for 16 minutes with a stirring speed of 135 r/min.
The polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing 100g of polypropylene glycol (with a polymerization degree of 60-80), 35g of dicyclohexylmethane diisocyanate (HMDI), 63g of acetone and 0.6g of dibutyltin dilaurate, heating to 80 ℃, stirring for reaction for 7 hours, and cooling to room temperature; and
(b) adding 50g of hydroxypropyl acrylate into the obtained product in the step (1), heating to 55 ℃, stirring for reaction for 10 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
The hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving 15g of citric acid, 12g of lactic acid and 6g of tartaric acid in 100g of water to prepare a modified solution; and
(ii) 33g of nano ZrO2(particle size of 20-35 nm) and 100g of the modified solution, and stirring and reacting at 65 ℃ for 6.5 hours to obtain the hydroxy acid modified ZrO2。
Thus, a photocured lacquer according to the application is produced.
Comparative example 1
The following preparation method was used to prepare the photocured lacquers:
(1) mixing 75g of urethane acrylate prepolymer, 65g of 1, 6-hexanediol diacrylate, 4g of silane coupling agent KH550, 3.5g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 110g of acetone, and dispersing for 9 minutes at a stirring speed of 170 r/min;
(2) 40g of a hydroxy acid-modified ZrO was added to the resultant of step (1)22g of sorbitol and 1.5g of melamine, with stirring at 1000r/min for 47 minutes; and
(3) 5g of a photoinitiator, alpha-hydroxy-isopropyl-benzophenone, was added to the resultant of step (1) and dispersed for 18 minutes with stirring at a speed of 140 r/min.
Wherein the polyurethane acrylate prepolymer and hydroxy acid modified ZrO2The preparation method of (2) is the same as in example 1.
Comparative example 2
The following preparation method was used to prepare the photocured lacquers:
(1) mixing 95g of urethane acrylate prepolymer, 45g of 1, 6-hexanediol diacrylate, 9g of silane coupling agent KH550, 2.0g of hydroxyl-terminated polydimethylsiloxane (with the polymerization degree of 80-100) and 150g of acetone, and dispersing for 9 minutes at a stirring speed of 170 r/min;
(2) 20g of a hydroxy acid-modified ZrO was added to the resultant of step (1)27g of sorbitol and 0.5g of melamine, with stirring at 1000r/min for 47 minutes; and
(3) 10g of a photoinitiator, alpha-hydroxy-isopropyl-benzophenone, was added to the resultant of step (1) and dispersed for 18 minutes with stirring at a speed of 140 r/min.
Wherein the polyurethane acrylate prepolymer and hydroxy acid modified ZrO2The preparation method of (2) is the same as in example 1.
Comparative example 3
A photo-curable lacquer was prepared in the same manner as in example 1, except that the urethane acrylate prepolymer was prepared by the following method:
(a) mixing 100g of polypropylene glycol (with the polymerization degree of 60-80), 40g of isophorone diisocyanate (IPDI), 55g of acetone and 0.9g of dibutyltin dilaurate, heating to 75 ℃, stirring for reacting for 6.5 hours, and cooling to room temperature; and
(b) adding 40g of hydroxypropyl acrylate into the obtained product in the step (1), heating to 55 ℃, stirring for reaction for 9.5 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer.
Comparative example 4
A photo-curable lacquer was prepared in the same manner as in example 1, except that the urethane acrylate prepolymer was prepared by the following method:
(a) mixing 100g of polypropylene glycol (with the polymerization degree of 60-80), 25g of isophorone diisocyanate (IPDI), 70g of acetone and 0.3g of dibutyltin dilaurate, heating to 75 ℃, stirring for reacting for 6.5 hours, and cooling to room temperature; and
(b) adding 55g of hydroxypropyl acrylate into the product obtained in the step (1), heating to 55 ℃, stirring for reaction for 9.5 hours, and distilling under reduced pressure to remove acetone, thereby obtaining the urethane acrylate prepolymer.
Comparative example 5
Except for using nano ZrO2(particle size of 20-35 nm) to replace hydroxy acid modified ZrO2Except that, a photo-curing lacquer was prepared in the same manner as in example 1.
Comparative example 6
Except that 10g of citric acid, 15g of lactic acid and 3g of tartaric acid were used to prepare a modification solution to modify the nano-ZrO in step (i)2Except that, a photo-curing lacquer was prepared in the same manner as in example 1.
Comparative example 7
Except that in step (i), a modifying solution was prepared using 20g of citric acid, 7g of lactic acid, and 10g of tartaric acid to modify the nano-ZrO2Except that, a photo-curing lacquer was prepared in the same manner as in example 1.
Comparative example 8
Except that nano ZrO with the grain diameter of 5-15 nm is adopted2To prepare the hydroxy acid-modified ZrO2Except that, a photo-curing lacquer was prepared in the same manner as in example 1.
Comparative example 9
Except that nano ZrO with the grain diameter of 40-60 nm is adopted2To prepare the hydroxy acid-modified ZrO2Except that, a photo-curing lacquer was prepared in the same manner as in example 1.
Comparative example 10
A photocurable lacquer was prepared in the same manner as in example 1, except that hydroxy-terminated polydimethylsiloxane having a degree of polymerization of 30 to 50 was used.
Comparative example 11
A photocurable lacquer was prepared in the same manner as in example 1, except that hydroxy-terminated polydimethylsiloxane having a degree of polymerization of 120 to 150 was used.
< test examples >
The photocured lacquers from examples 1 to 8 and comparative examples 1 to 11 were each sprayed onto a sample plate, after which they were leveled for 5 minutes after spraying, cured for 15 seconds with a 365nm uv lamp and, after cooling, the respective sample plates were tested for the following properties, the test results being shown in table 1:
(I) adhesion force: measured according to national standard GB 1720-1979(1989) paint film adhesion determination method;
(II) impact Strength: the (N cm) is measured according to the national standard GB/T1732 + 1993 'paint film impact resistance measurement';
(III) flexibility: the minimum shaft rod diameter of a paint film without cracking is determined by referring to national standard GB/T6742-2007 test for bending paint and varnish (cylindrical shaft);
(IV) salt fog resistance: the time of the damage of the paint film is determined according to the national standard GB/T1771-2007 determination of neutral salt spray resistance of the paint and the varnish;
(V) Pencil hardness: the determination is carried out according to the national standard GB/T6739-2006 paint film hardness determination by the colored paint and varnish pencil method;
(VI) Water resistance: the time of the paint film damage is determined according to the first method (immersion experiment method) by referring to the national standard GB/T1733 + 1993 'paint film water resistance determination method'; and
(VII) abrasion resistance: the measurement is carried out in accordance with the standard ASTM D4060 Standard test method for determining the abrasion resistance of organic coatings using a Taber abrasion tester (1000g/1000r, mg).
[ Table 1]
| I | II | III | IV | V | VI | VII | |
| Example 1 | First stage | 572 | 2mm | 42 days | 6H | 253 days | 11mg |
| Example 2 | First stage | 581 | 2mm | 40 days | 6H | 246 days | 13mg |
| Example 3 | First stage | 569 | 2mm | 45 days | 5H | 262 days | 14mg |
| Example 4 | First stage | 578 | 2mm | 42 days | 6H | 244 days | 10mg |
| Example 5 | First stage | 588 | 2mm | For 44 days | 6H | 251 days | 15mg |
| Example 6 | First stage | 564 | 2mm | 45 days | 5H | 259 days | 12mg |
| Example 7 | First stage | 580 | 2mm | 41 days | 5H | 249 days | 13mg |
| Example 8 | First stage | 574 | 2mm | 40 days | 6H | 253 days | 14mg |
| Comparative example 1 | Second stage | 515 | 3mm | 34 days | 4H | 203 days | 19mg |
| Comparative example 2 | Three-stage | 488 | 2mm | 31 days | 4H | 215 days | 24mg |
| Comparative example 3 | First stage | 420 | 3mm | 25 days | 6H | 175 days | 15mg |
| Comparative example 4 | Second stage | 465 | 4mm | 21 days | 5H | 189 days | 13mg |
| Comparative example 5 | Second stage | 419 | 3mm | 24 days | 3H | 153 days | 29mg |
| Comparative example 6 | First stage | 435 | 3mm | 29 days | 4H | 166 days | 26mg |
| Comparative example 7 | Second stage | 446 | 2mm | 26 days | 4H | 171 days | 24mg |
| Comparative example 8 | Three-stage | 509 | 5mm | 29 days | 4H | 213 days | 15mg |
| Comparison ofExample 9 | First stage | 412 | 3mm | 32 days | 5H | 197 days | 26mg |
| Comparative example 10 | Second stage | 482 | 4mm | 36 days | 5H | 207 days | 20mg |
| Comparative example 11 | Second stage | 494 | 3mm | 33 days | 4H | 219 day | 18mg |
As can be seen from the above Table 1, the photocured lacquers prepared according to examples 1 to 8 of the present application exhibited very good adhesion, all to a first order level; the impact strength is high, and the impact resistance is excellent; the diameter of the mandrel which is not cracked is the lowest, and is the smallest diameter of the mandrel of the measuring device, namely 2mm, so that the flexibility is excellent; the salt spray can last for more than 40 days without damage in the salt spray environment, and the salt spray resistance is very good; the pencil hardness can reach more than 5H, and the paint film hardness is higher; the coating can be soaked in water for more than 240 days without damage, and has excellent water resistance; and low abrasion loss and excellent abrasion resistance.
In contrast, the materials used in comparative examples 1 and 2 are not within the range defined in the present application, and all the properties are significantly reduced; in comparative examples 3 and 4, the adhesion, impact strength, weather resistance, flexibility and other properties of the urethane acrylate prepolymer prepared by the method outside the range defined by the application are obviously reduced; comparative example 5 Using ordinary nano ZrO2Comparative examples 6 and 7 ZrO modified by a method outside the range defined in the present application2The impact strength, weather resistance, hardness, abrasion resistance and other performances of the three materials are obviously reduced; comparative example 8 Using nano ZrO of smaller particle size2The decrease in flexibility is remarkably decreased, and comparative example 9 employs nano ZrO of larger particle size2The impact strength is remarkably reduced; also, comparative examples 10 and 11, which used hydroxyl-terminated polydimethylsiloxanes having a degree of polymerization outside the range defined in the present application, exhibited a decrease in each of the properties.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (6)
1. The photocuring spray paint is characterized by comprising the following components:
80-90 parts by weight of a polyurethane acrylate prepolymer;
50-60 parts by weight of a (meth) acrylate monomer;
5-8 parts by weight of a silane coupling agent;
hydroxy acid modified ZrO225-35 parts by weight;
3-5 parts by weight of a polyol;
2.5-3.2 parts by weight of hydroxyl-terminated polydimethylsiloxane;
0.7-1.2 parts by weight of melamine;
6-9 parts of a photoinitiator;
120-140 parts by weight of a solvent;
the polyurethane acrylate prepolymer is prepared by the following method:
(a) mixing polypropylene glycol, isocyanate, acetone and dibutyltin dilaurate in a weight ratio of (30-35) to (60-65) to (0.5-0.7), heating to 70-80 ℃, stirring for reacting for 6-7 hours, and cooling to room temperature; and
(b) adding hydroxypropyl acrylate with the weight ratio of (45-50): 100 to polypropylene glycol into the product obtained in the step (1), heating to 50-60 ℃, stirring for reaction for 9-10 hours, and removing acetone by reduced pressure distillation to obtain the urethane acrylate prepolymer;
the hydroxy acid modified ZrO2The preparation method comprises the following steps:
(i) dissolving citric acid, lactic acid and tartaric acid in water to prepare a modified solution, wherein the weight ratio of the citric acid to the lactic acid to the tartaric acid to the water is (13-16): 10-12): 5-7): 100; and
(ii) nano ZrO at a weight ratio of (30-35): 1002Mixing the obtained mixture with the modified solution, and stirring and reacting the mixture for 6 to 7 hours at the temperature of between 60 and 70 ℃ to obtain the hydroxy acid modified ZrO2；
The nano ZrO2The particle size of (A) is 20-35 nm;
the polyhydric alcohol is at least one selected from sorbitol and mannitol, and the polymerization degree of the hydroxyl-terminated polydimethylsiloxane is 60-100.
2. The photocurable lacquer according to claim 1, wherein the isocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate,
the polymerization degree of the polypropylene glycol is 50-100.
3. The photocurable lacquer according to claim 1, wherein the (meth) acrylate monomer is at least one selected from the group consisting of isooctyl acrylate, isooctyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, dehydrated glycerol acrylate, dehydrated glycerol methacrylate, 2-hydroxy n-butyl acrylate, 1, 4-butanediol diacrylate, lauryl acrylate, and lauryl methacrylate,
the silane coupling agent is at least one selected from the group consisting of KH650, KH660 and KH 670.
4. The photocurable lacquer according to claim 1, wherein the photoinitiator is at least one selected from the group consisting of α -hydroxyisopropylbenzophenone, α -hydroxycyclohexylbenzophenone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-1-propanone and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzylphenyl) butanone.
5. The photocurable lacquer according to claim 1, wherein the solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and propylene glycol dimethyl ether.
6. A method for producing the light-curing lacquer according to any one of claims 1 to 5, comprising the following steps:
(1) mixing a polyurethane acrylate prepolymer, (meth) acrylate monomer, a silane coupling agent, hydroxyl-terminated polydimethylsiloxane and a solvent, and dispersing for 8-10 minutes at a stirring speed of 160-180 r/min;
(2) adding hydroxy acid-modified ZrO to the obtained product of step (1)2Polyols, and polyols of the formulaDispersing the cyanamide for 45-50 minutes at a stirring speed of 980-1020 r/min; and
(3) adding a photoinitiator into the product obtained in the step (2), and dispersing for 15-20 minutes at a stirring speed of 130-150 r/min.
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| CN102372935A (en) * | 2010-08-11 | 2012-03-14 | 上海颜钛实业有限公司 | Automatically sprayed ultraviolet curing paint and preparation method thereof |
| CN105505197A (en) * | 2015-12-30 | 2016-04-20 | 中物功能材料研究院有限公司 | Ultraviolet curing coating and preparation method thereof |
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| CN102372935A (en) * | 2010-08-11 | 2012-03-14 | 上海颜钛实业有限公司 | Automatically sprayed ultraviolet curing paint and preparation method thereof |
| CN105505197A (en) * | 2015-12-30 | 2016-04-20 | 中物功能材料研究院有限公司 | Ultraviolet curing coating and preparation method thereof |
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