CN115368813B - Scratch-resistant bi-component polyurethane varnish - Google Patents
Scratch-resistant bi-component polyurethane varnish Download PDFInfo
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- CN115368813B CN115368813B CN202110548405.9A CN202110548405A CN115368813B CN 115368813 B CN115368813 B CN 115368813B CN 202110548405 A CN202110548405 A CN 202110548405A CN 115368813 B CN115368813 B CN 115368813B
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- 239000004972 Polyurethane varnish Substances 0.000 title claims abstract description 25
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 51
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000003085 diluting agent Substances 0.000 claims abstract description 17
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000004814 polyurethane Substances 0.000 claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000004611 light stabiliser Substances 0.000 claims abstract description 8
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 6
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 6
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 6
- 239000008158 vegetable oil Substances 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 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 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 206010024229 Leprosy Diseases 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000002966 varnish Substances 0.000 abstract description 18
- 239000000377 silicon dioxide Substances 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 5
- 239000003973 paint Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- HAIZPCLVGBYWBK-UHFFFAOYSA-N leptoside Chemical compound O1C(C)C(O)C(OC)CC1OC1CC(CC2C3C4C(=O)C(O)C5(C)C(C=6OCC(=O)C=6)CC(C35O)O2)C4(C)CC1 HAIZPCLVGBYWBK-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- -1 silane modified silica Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000013112 stability test 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
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- 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
- C09D7/68—Particle size between 100-1000 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
- 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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a scratch-resistant bi-component polyurethane varnish, which comprises the following components in parts by weight: and (3) a component A: 40-60 parts of hydroxyl-terminated polyurethane resin, 15-25 parts of hydroxyl acrylic resin, 3-6 parts of nano silicon dioxide, 1-3 parts of light stabilizer, 1-2 parts of flatting agent and 60-80 parts of main agent diluent; and the component B comprises the following components: 80 parts of aliphatic polyisocyanate and 20 parts of curing agent diluent. The invention adopts hyperbranched polyurethane modified nano silicon dioxide with a core-shell structure to modify the bi-component polyurethane varnish, wherein the silicon dioxide takes hydroxyl end-capped hyperbranched polyurethane as shell varnish resin, has strong acting force, and can be uniformly dispersed in the bi-component polyurethane varnish. Secondly, nano silicon dioxide is added into the varnish to increase the surface hardness of the varnish, meanwhile, the silicon dioxide is spherical with uniform particle size and has a diameter of 80-120nm, and the addition into the varnish does not negatively affect the gloss of the varnish.
Description
Technical Field
The invention relates to scratch-resistant varnish, in particular to scratch-resistant varnish modified by nano silicon dioxide with a core-shell structure.
Background
With the continuous development of the automobile industry, the automobile paint not only needs to meet the requirements of protection and corrosion resistance, but also has the performances of color, appearance, scratch resistance and the like. The two-component polyurethane varnish has the advantages of high fullness, high glossiness and the like, and is favored by automobile host factories. However, compared with the traditional acrylic amino type single-component varnish paint, the double-component polyurethane varnish paint film is softer and has poorer scratch resistance, and the automobile is inevitably scratched during running, so that scratches or reduced gloss appear on the automobile varnish layer. In order to improve the scratch resistance of polyurethane varnishes, application No. 201680052362.2 discloses the addition of a polyisocyanate containing silane groups as a crosslinking agent to increase the crosslinking density of the varnish, thereby increasing the hardness and scratch resistance. Increasing the crosslink density increases the hardness, but the impact resistance decreases. Application number 201910094774.8 discloses a preparation method of a silicon modified two-component waterborne polyurethane composite coating, silane modified nano silica particles are added in varnish, but only silane modified silica has poor compatibility with coating groups.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and discloses a method for preparing hyperbranched modified nano silicon dioxide modified polyurethane varnish with a core-shell structure.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the scratch-resistant two-component polyurethane varnish comprises the following components in parts by weight:
and (3) a component A:
40-60 parts of hydroxyl-terminated polyurethane resin,
15-25 parts of hydroxy acrylic resin,
3-6 parts of nano silicon dioxide,
1-3 parts of light stabilizer,
1-2 parts of leveling agent,
60-80 parts of main agent diluent;
and the component B comprises the following components:
75-85 parts of aliphatic polyisocyanate,
15-25 parts of a curing agent diluent;
the preparation method of the nano silicon dioxide comprises the following steps:
s1, adding tetraethyl orthosilicate and hydrochloric acid into an ethanol solution, and stirring for 1-3 hours at the temperature of 22-28 ℃;
s2, adding an amino silane coupling agent and hydrochloric acid into an ethanol solution, and stirring for 1-3 hours at 38-42 ℃;
s3, uniformly stirring and mixing the solutions obtained in the steps S1 and S2, wherein the temperature is 23-28 ℃, and filtering, washing with ethanol and drying the reaction mixture to obtain aminated nano silicon dioxide;
s4, adding the aminated nano silicon dioxide obtained in the step S3 into diisocyanate, stirring for 1-3 hours at 58-62 ℃, filtering, washing with ethyl acetate, adding a filter cake into vegetable oil-based polyol, adding an organotin catalyst, stirring for 1-3 hours at 78-82 ℃, filtering, washing with ethyl acetate, and drying in a protective gas atmosphere;
s5, repeating the step S4 for three times to obtain the nano silicon dioxide.
Preferably, in the step S1, the weight ratio of the tetraethyl orthosilicate to the hydrochloric acid is 9-11:1; in the step S2, the weight ratio of the silane coupling agent with amino to the hydrochloric acid is 9-11:1; the weight ratio of the silane coupling agent with amino to the tetraethyl orthosilicate is 0.5-2:1.
Preferably, in the step S4, the weight ratio of the aminated nano silicon dioxide to the diisocyanate is 1:3-5; the weight ratio of the aminated nano silicon dioxide to the vegetable oil-based polyol is 1:3-5.
Preferably, in step S1 and step S2, the stirring speed is 800-1500 rpm.
Preferably, in the step S1, the weight ratio of the tetraethyl orthosilicate to the ethanol is 1:15-25; in the step S2, the weight ratio of the silane coupling agent with amino to the ethanol is 1:15-25.
Preferably, the silane coupling agent with amino group is at least one of KH-550, KH-602 and KH-792; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane-4, 4' -diisocyanate; the vegetable oil-based polyol is at least one of castor oil-based polyol and leprosy resin oil-based polyol; the organotin catalyst is at least one of dibutyl tin dilaurate, dibutyl tin oxide and stannous octoate.
Preferably, the light stabilizer is at least one of Tinuvin788, tinuvin900 and Tinuvin 5151; the leveling agent is at least one of BYK320, BYK322 and BYK 310.
Preferably, the main diluent is at least one of ethyl acetate, butyl acetate, propylene glycol dimethyl ether and methyl isobutyl ketone.
Preferably, the aliphatic polyisocyanate is at least one of Desmodur N3300, desmodur N75, and SUMIDUR N3300.
Preferably, the curing agent diluent is at least one of butyl acetate and a high boiling point petroleum solvent SO-1000.
The two-component polyurethane varnish requires an A component and a B component according to 3: mixing at a ratio of 0.9-1.1, adding diluent, and adjusting viscosity to 23+ -1 s (25 deg.C).
The invention has the beneficial effects that: firstly, hyperbranched polyurethane modified nano silicon dioxide with a core-shell structure is adopted to modify the bi-component polyurethane varnish, and the silicon dioxide takes hydroxyl end-capped hyperbranched polyurethane as shell varnish resin, so that the acting force is strong, and the silicon dioxide can be uniformly dispersed in the bi-component polyurethane varnish. Secondly, nano silicon dioxide is added into the varnish to increase the surface hardness of the varnish, meanwhile, the silicon dioxide is spherical with uniform particle size and has a diameter of 80-120nm, and the addition into the varnish does not negatively affect the gloss of the varnish.
Drawings
The nano-silica having a core-shell structure as described in example 1 of fig. 1.
Detailed Description
Example 1
The scratch-resistant two-component polyurethane varnish composition comprises the following components in parts by weight:
and (3) a component A:
| hydroxyl-terminated polyurethane resin | 50 parts of, |
| Hydroxy acrylic resin | 20 parts of, |
| Nano silicon dioxide | 1 part of, |
| Light stabilizer Tinuvin788 | 2 parts of, |
| Leveling agent BYK320 | 2 parts of, |
| Main agent diluent equal mass ethyl acetate and methyl isobutyl ketone mixture | 70 parts; |
and the component B comprises the following components:
| aliphatic polyisocyanate SUMIDUR N3300 | 80 parts of, |
| Curing agent diluent equal mass butyl acetate SO-1000 | 20 parts; |
the preparation method of the silicon dioxide comprises the following steps:
s1, adding 5 parts by weight of tetraethyl orthosilicate and 0.5 part by weight of hydrochloric acid into 100 parts by weight of ethanol solution, stirring for 2 hours at 1000 revolutions per minute, wherein the temperature is 25 ℃;
s2, adding 5 parts by weight of silane coupling agent KH550 with amino groups and 0.5 part by weight of hydrochloric acid into 100 parts by weight of ethanol solution, stirring for 2 hours at 1000 revolutions per minute, wherein the temperature is 40 ℃;
s3, mixing the solutions obtained in the steps S1 and S2, stirring at the temperature of 25 ℃, filtering the reaction mixture, washing with ethanol, and drying to obtain aminated nano silicon dioxide;
s4, adding 5 parts by weight of the aminated nano silicon dioxide obtained in the step S3 into 20 parts by weight of hexamethylene diisocyanate, stirring for 2 hours at 60 ℃, filtering, washing with ethyl acetate, adding the filter cake into 20 parts by weight of leptoside oil-based polyol, adding 0.2 part by weight of dibutyltin dilaurate catalyst, stirring for 2 hours at 80 ℃, filtering, washing with ethyl acetate, and drying in a protective gas atmosphere;
s5, repeating the step S4 for three times to obtain the nano silicon dioxide with hyperbranched polyurethane as a shell and nano silicon dioxide as a core, wherein the obtained silicon dioxide with a core-shell structure is nano-scale and has a diameter within the range of 80-150 nm.
Example 2
The scratch-resistant two-component polyurethane varnish composition comprises the following components in parts by weight:
and (3) a component A:
| hydroxyl-terminated polyurethane resin | 50 parts of, |
| Hydroxy acrylic resin | 20 parts of, |
| Nano silicon dioxide | 3 parts of, |
| Light stabilizer Tinuvin788 | 2 parts of, |
| Leveling agent BYK320 | 2 parts of, |
| Main agent diluent equal mass ethyl acetate and methyl isobutyl ketone mixture | 70 parts; |
and the component B comprises the following components:
| aliphatic polyisocyanate SUMIDUR N3300 | 80 parts of, |
| Curing agent diluent equal mass butyl acetate SO-1000 | 20 parts; |
the preparation method of the silicon dioxide comprises the following steps:
s1, adding 5 parts by weight of tetraethyl orthosilicate and 0.5 part by weight of hydrochloric acid into 100 parts by weight of ethanol solution, stirring for 2 hours at 1000 revolutions per minute, wherein the temperature is 25 ℃;
s2, adding 5 parts by weight of silane coupling agent KH-602 with amino and 0.5 part by weight of hydrochloric acid into 100 parts by weight of ethanol solution, stirring for 2 hours at 1000 revolutions per minute, wherein the temperature is 40 ℃;
s3, mixing the solutions obtained in the steps S1 and S2, stirring at the temperature of 25 ℃, filtering the reaction mixture, washing with ethanol, and drying to obtain aminated nano silicon dioxide;
s4, adding 5 parts by weight of the aminated nano silicon dioxide obtained in the step S3 into 20 parts by weight of toluene diisocyanate, stirring at 60 ℃ for 2 hours, filtering, washing with ethyl acetate, adding the filter cake into 20 parts by weight of leptose resin oil-based polyol, adding 0.2 part by weight of dibutyltin dilaurate catalyst, stirring at 80 ℃ for 2 hours, filtering, washing with ethyl acetate, and drying in a protective gas atmosphere;
s5, repeating the step S4 for three times to obtain the nano silicon dioxide with hyperbranched polyurethane as a shell and nano silicon dioxide as a core, wherein the obtained silicon dioxide with a core-shell structure is nano-scale and has a diameter within the range of 80-150 nm.
Example 3
The scratch-resistant two-component polyurethane varnish composition comprises the following components in parts by weight:
and (3) a component A:
| hydroxyl-terminated polyurethane resin | 50 parts of, |
| Hydroxy acrylic resin | 20 parts of, |
| Nano silicon dioxide | 3 parts of, |
| Light stabilizer Tinuvin788 | 2 parts of, |
| Leveling agent BYK320 | 2 parts of, |
| Main agent diluent equal mass ethyl acetate/methyl isobutyl ketone | 70 parts; |
and the component B comprises the following components:
| aliphatic polyisocyanate Desmodur N75 | 80 parts of, |
| Curing agent diluent equal mass butyl acetate SO-1000 | 20 parts; |
the preparation method of the silicon dioxide comprises the following steps:
s1, adding 5 parts by weight of tetraethyl orthosilicate and 0.5 part by weight of hydrochloric acid into 100 parts by weight of ethanol solution, stirring for 2 hours at 1000 revolutions per minute, wherein the temperature is 25 ℃;
s2, adding 5 parts by weight of silane coupling agent KH-602 with amino and 0.5 part by weight of hydrochloric acid into 100 parts by weight of ethanol solution, stirring for 2 hours at 1000 revolutions per minute, wherein the temperature is 40 ℃;
s3, mixing the solutions obtained in the steps S1 and S2, stirring the mixture 2 at room temperature, filtering the reaction mixture, washing the reaction mixture with ethanol, and drying the reaction mixture to obtain aminated nano silicon dioxide;
s4, adding 5 parts by weight of the aminated nano silicon dioxide obtained in the step S3 into 20 parts by weight of toluene diisocyanate, stirring for 2 hours at 60 ℃, filtering, washing with ethyl acetate, adding a filter cake into 20 parts by weight of castor oil-based polyol, adding 0.2 part by weight of dibutyltin dilaurate catalyst, stirring for 2 hours at 80 ℃, filtering, washing with ethyl acetate, and drying in a protective gas atmosphere;
s5, repeating the step S4 for three times to obtain the nano silicon dioxide with hyperbranched polyurethane as a shell and nano silicon dioxide as a core, wherein the obtained silicon dioxide with a core-shell structure is nano-scale and has a diameter within the range of 80-150 nm.
Comparative example 1
This comparative example differs from example 1 only in that no nanosilica was added and replaced with commercially available silica having a conventional particle size D50 of 100 nm.
Example 4
And (3) spraying a middle coating of 20 micrometers on an electrophoresis board, spraying a black finish paint of 15 micrometers, baking at 80 ℃ for 5-10 minutes until the paint reaches finger dryness, spraying the varnish of examples 1-3 on the black finish paint, spraying the varnish to a thickness of 40 micrometers, leveling for 5 minutes, and finally baking at 140 ℃ for 30 minutes to prepare the composite coating.
Morphology testing: observing the nano silicon dioxide structure of the core-shell structure by using a transmission electron microscope; FIG. 1 is a transmission electron microscope image of the silica described in example 1.
And (3) paint storage stability detection: according to the method of GB-T6753.3-1986 paint storage stability test, the paint is stored for 6 months under natural conditions, and the sedimentation condition of the paint is observed.
And (3) detecting scratch resistance of the paint: FLTM161-01, 2 μm polishing paper from 3M company was used. The test results are shown in Table 1.
TABLE 1
| Storage stability | Scratch front gloss (20 degree) | Post scratch gloss | |
| Example 1 | Completely suspended without change from the original state of the paint | 93.2 | 89.6 |
| Example 2 | Completely suspended without change from the original state of the paint | 92.8 | 90.6 |
| Example 3 | Completely suspended without change from the original state of the paint | 92.6 | 90.3 |
| Comparative example 1 | Completely suspended without change from the original state of the paint | 93.3 | 80.2 |
It can be seen from fig. 1 and table 1 that the nano-silica of the examples has a core-shell structure, is spherical particles with regular shape, and has a uniform particle size of between 80 and 120 nm. The nano silicon dioxide with the core-shell structure has good storage stability in the main agent of the bi-component polyurethane varnish, and the addition of the nano silicon dioxide particles has little influence on the glossiness of the bi-component polyurethane varnish, but can greatly improve the scratch resistance of the bi-component polyurethane varnish.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. The scratch-resistant bi-component polyurethane varnish is characterized by comprising the following components in parts by weight:
and (3) a component A:
40-60 parts of hydroxyl-terminated polyurethane resin,
15-25 parts of hydroxy acrylic resin,
3-6 parts of nano silicon dioxide,
1-3 parts of light stabilizer,
1-2 parts of leveling agent,
60-80 parts of main agent diluent;
and the component B comprises the following components:
75-85 parts of aliphatic polyisocyanate,
15-25 parts of a curing agent diluent;
the preparation method of the nano silicon dioxide comprises the following steps:
s1, adding tetraethyl orthosilicate and hydrochloric acid into an ethanol solution, and stirring for 1-3 hours at the temperature of 22-28 ℃;
s2, adding an amino silane coupling agent and hydrochloric acid into an ethanol solution, and stirring for 1-3 hours at 38-42 ℃;
s3, uniformly stirring and mixing the solutions obtained in the steps S1 and S2, wherein the temperature is 23-28 ℃, and filtering, washing with ethanol and drying the reaction mixture to obtain aminated nano silicon dioxide;
s4, adding the aminated nano silicon dioxide obtained in the step S3 into diisocyanate, stirring for 1-3 hours at 58-62 ℃, filtering, washing with ethyl acetate, adding a filter cake into vegetable oil-based polyol, adding an organotin catalyst, stirring for 1-3 hours at 78-82 ℃, filtering, washing with ethyl acetate, and drying in a protective gas atmosphere;
s5, repeating the step S4 for three times to obtain nano silicon dioxide taking hyperbranched polyurethane as a shell and nano silicon dioxide as a core, wherein the diameter of the nano silicon dioxide with the core-shell structure is in the range of 80-150 nm;
in the step S1, the weight ratio of tetraethyl orthosilicate to hydrochloric acid is 9-11:1, and the weight ratio of tetraethyl orthosilicate to ethanol is 1:15-25; in the step S2, the weight ratio of the silane coupling agent with amino to the hydrochloric acid is 9-11:1, and the weight ratio of the silane coupling agent with amino to the ethanol is 1:15-25; the weight ratio of the silane coupling agent with amino to the tetraethyl orthosilicate is 0.5-2:1; in the step S4, the weight ratio of the aminated nano silicon dioxide to the diisocyanate is 1:3-5; the weight ratio of the aminated nano silicon dioxide to the vegetable oil-based polyol is 1:3-5; the silane coupling agent with amino is at least one of KH-550, KH-602 and KH-792; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane-4, 4' -diisocyanate; the vegetable oil-based polyol is at least one of castor oil-based polyol and leprosy resin oil-based polyol; the organotin catalyst is at least one of dibutyl tin dilaurate, dibutyl tin oxide and stannous octoate.
2. The scratch-resistant two-component polyurethane varnish according to claim 1, wherein in the step S1 and the step S2, the stirring speed is 800-1500 rpm.
3. The scratch resistant two-component polyurethane varnish of claim 1, wherein the light stabilizer is at least one of Tinuvin788, tinuvin900 and Tinuvin 5151; the leveling agent is at least one of BYK320, BYK322 and BYK 310.
4. The scratch resistant two-component polyurethane varnish of claim 1, wherein the main diluent is at least one of ethyl acetate, butyl acetate, propylene glycol dimethyl ether and methyl isobutyl ketone.
5. The scratch resistant two-component polyurethane varnish of claim 1, wherein the aliphatic polyisocyanate is at least one of Desmodur N3300, desmodur N75, and SUMIDUR N3300.
6. The scratch-resistant two-component polyurethane varnish according to claim 1, wherein the curing agent diluent is at least one of butyl acetate and a high boiling point petroleum solvent SO-1000.
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