CN115368813A - Scratch-resistant double-component polyurethane varnish - Google Patents
Scratch-resistant double-component polyurethane varnish Download PDFInfo
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- CN115368813A CN115368813A CN202110548405.9A CN202110548405A CN115368813A CN 115368813 A CN115368813 A CN 115368813A CN 202110548405 A CN202110548405 A CN 202110548405A CN 115368813 A CN115368813 A CN 115368813A
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- 239000004972 Polyurethane varnish Substances 0.000 title claims abstract description 29
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 19
- 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 37
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 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
- 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
- 239000000203 mixture Substances 0.000 claims description 17
- 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
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 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
- 238000002156 mixing Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 239000012974 tin catalyst Substances 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
- 241000221089 Jatropha Species 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
- 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
- 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
- 239000000377 silicon dioxide Substances 0.000 abstract description 27
- 239000002966 varnish Substances 0.000 abstract description 18
- 239000011258 core-shell material Substances 0.000 abstract description 11
- 239000004814 polyurethane Substances 0.000 abstract description 8
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000003973 paint Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001048891 Jatropha curcas Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005536 corrosion prevention 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003839 salts 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
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- 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)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a scratch-resistant double-component polyurethane varnish, which comprises the following components in parts by weight: the component A comprises: 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 B component: 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 two-component polyurethane varnish, and the silicon dioxide takes hydroxyl-terminated hyperbranched polyurethane as the shell varnish resin, has strong acting force and can be uniformly dispersed in the two-component polyurethane varnish. Secondly, the nano silica is added into the varnish to increase the surface hardness of the varnish, and meanwhile, the silica is spherical with uniform particle size and the diameter of the silica is between 80 and 120nm, so that the nano silica does not have negative influence on the gloss of the varnish when being added into the varnish.
Description
Technical Field
The invention relates to a scratch-resistant varnish, in particular to a scratch-resistant varnish modified by nano silica with a core-shell structure.
Background
With the continuous development of the automobile industry, the automobile coating not only needs to meet the requirement of protection and corrosion prevention, but also has more and more attention paid to the color, appearance, scratch resistance and other performances of the automobile coating by consumers. 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 coating, the two-component polyurethane varnish coating has the advantages that a varnish film is softer, the scratch resistance is poorer, and an automobile is difficult to avoid scratch in the running process, so that the scratch or the gloss of the automobile varnish layer is reduced. In order to improve the scratch resistance of polyurethane varnishes, application No. 201680052362.2 discloses the addition of polyisocyanates containing silane groups as crosslinking agents to increase the crosslinking density of the varnish and thus the hardness and scratch resistance. Increasing the crosslink density increases the hardness, but decreases the impact resistance. 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 into a varnish, but silica modified by silane only has poor compatibility with coating groups.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and adopts a method for preparing hyperbranched modified nano silicon dioxide modified polyurethane varnish with a core-shell structure.
In order to achieve the purpose, the invention adopts the technical scheme that: a scratch-resistant two-component polyurethane varnish comprises the following components in parts by weight:
and (2) 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 leveling agent,
60-80 parts of a main agent diluent;
and B component:
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 a silane coupling agent with amino and hydrochloric acid into an ethanol solution, and stirring for 1 to 3 hours at the temperature of 38 to 42 ℃;
s3, stirring and mixing the solution obtained in the S1 and the solution obtained in the S2 uniformly at the temperature of 23 to 28 ℃, filtering the reaction mixture, washing the reaction mixture 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 1-3h at 58-62 ℃, then filtering, washing with ethyl acetate, adding a filter cake into vegetable oil-based polyol, adding an organic tin catalyst, stirring for 1-3h at 78-82 ℃, filtering, washing with ethyl acetate, and then drying in a protective gas atmosphere;
and S5, repeating the step S4 for three times to obtain the nano silicon dioxide.
Preferably, in the step S1, the weight ratio of tetraethyl orthosilicate to hydrochloric acid is 9 to 11; in the step S2, the weight ratio of the silane coupling agent with amino groups to hydrochloric acid is 9 to 11; the weight ratio of the silane coupling agent with amino groups to tetraethyl orthosilicate is 0.5 to 2.
Preferably, in the step S4, the weight ratio of the aminated nano silica to the diisocyanate is 1; the weight ratio of the aminated nano silicon dioxide to the vegetable oil-based polyol is 1 to 3-5.
Preferably, in the step S1 and the step S2, the rotation speed of the stirring is 800 to 1500 revolutions per minute.
Preferably, in the step S1, the weight ratio of the tetraethyl orthosilicate to the ethanol is 1; in the step S2, the weight ratio of the silane coupling agent with amino groups to the ethanol is 1.
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 jatropha curcas oil-based polyol; the organic tin catalyst is at least one of dibutyltin dilaurate, dibutyltin oxide and stannous octoate.
Preferably, the light stabilizer is at least one of Tinuvin788, tinuvin 900 and Tinuvin 5151; the leveling agent is at least one of BYK320, BYK322, and BYK 310.
Preferably, the primary 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 is used by the following steps of A component and B component according to the ratio of 3:0.9-1.1, adding diluent to adjust the viscosity to 23 + -1 s (second cup of salt field, 25 ℃).
The invention has the beneficial effects that: firstly, the hyperbranched polyurethane modified nano silicon dioxide with a core-shell structure is adopted to modify the two-component polyurethane varnish, and the silicon dioxide takes hydroxyl-terminated hyperbranched polyurethane as the shell varnish, has strong acting force and can be uniformly dispersed in the two-component polyurethane varnish. Secondly, the nano silica is added into the varnish to increase the surface hardness of the varnish, and meanwhile, the silica is spherical with uniform particle size and the diameter of the silica is between 80 and 120nm, so that the nano silica does not have negative influence on the gloss of the varnish when being added into the varnish.
Drawings
Fig. 1 nanosilica with core-shell structure as described in example 1.
Detailed Description
Example 1
The scratch-resistant two-component polyurethane varnish composition described in the present example comprises the following components in parts by weight:
the component A comprises:
| hydroxyl terminated polyurethane resin | 50 portions of, |
| Hydroxy acrylic resin | 20 portions of, |
| Nano silicon dioxide | 1 part of, |
| Light stabilizer Tinuvin788 | 2 portions of, |
| Leveling agent BYK320 | 2 portions of, |
| Mixture of ethyl acetate and methyl isobutyl ketone with equal mass of main agent and diluent | 70 parts of (B); |
and B component:
| aliphatic polyisocyanate SUMIDUR N3300 | 80 portions of, |
| Curing agent diluent equal mass butyl acetate SO-1000 | 20 parts of a binder; |
the preparation method of the silica described in this embodiment includes 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, and stirring for 2 hours at 1000 revolutions per minute at the temperature of 25 ℃;
s2, adding 5 parts by weight of silane coupling agent KH550 with amino and 0.5 part by weight of hydrochloric acid into 100 parts by weight of ethanol solution, and stirring for 2 hours at the temperature of 40 ℃ at 1000 r/min;
s3, mixing the solutions obtained in the S1 and the S2, stirring at 25 ℃, filtering the reaction mixture, washing with ethanol, and drying to obtain aminated nano-silica;
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 ℃, then filtering, washing with ethyl acetate, adding a filter cake into 20 parts by weight of jatropha 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 then drying in a protective gas atmosphere;
and S5, repeating the step S4 for three times to obtain the nano silicon dioxide taking the hyperbranched polyurethane as the shell and the nano silicon dioxide as the core, wherein the obtained silicon dioxide with the core-shell structure is in the nano level, and the diameter of the silicon dioxide is within the range of 80-150 nm.
Example 2
The scratch-resistant two-component polyurethane varnish composition described in the present example comprises the following components in parts by weight:
the component A comprises:
| hydroxyl terminated polyurethane resin | 50 portions of, |
| Hydroxy acrylic resin | 20 portions of, |
| Nano silicon dioxide | 3 portions of, |
| Light stabilizer Tinuvin788 | 2 portions of, |
| Leveling agent BYK320 | 2 portions of, |
| Mixture of ethyl acetate and methyl isobutyl ketone with equal mass of main agent and diluent | 70 parts of (B); |
and the component B comprises:
| aliphatic polyisocyanate SUMIDUR N3300 | 80 portions of, |
| Curing agent diluent equal mass butyl acetate SO-1000 | 20 parts of (1); |
the preparation method of the silica described in this embodiment includes 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, and stirring for 2 hours at 1000 revolutions per minute at the temperature of 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, and stirring for 2 hours at the temperature of 40 ℃ at 1000 r/min;
s3, mixing the solutions obtained in the S1 and the S2, stirring at 25 ℃, filtering the reaction mixture, washing with ethanol, and drying to obtain aminated nano-silica;
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 jatropha 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;
and S5, repeating the step S4 for three times to obtain the nano silicon dioxide taking the hyperbranched polyurethane as the shell and the nano silicon dioxide as the core, wherein the obtained silicon dioxide with the core-shell structure is in a nano level, and the diameter of the silicon dioxide is within the range of 80-150 nm.
Example 3
The scratch-resistant two-component polyurethane varnish composition described in the present example comprises the following components in parts by weight:
and (2) component A:
| hydroxyl terminated polyurethane resin | 50 portions of, |
| Hydroxy acrylic resin | 20 portions of, |
| Nano silicon dioxide | 3 portions of, |
| Light stabilizer Tinuvin788 | 2 portions of, |
| Leveling agent BYK320 | 2 portions of, |
| Main agentDiluent equal mass ethyl acetate/methyl isobutyl ketone | 70 parts of (B); |
and B component:
| aliphatic polyisocyanate Desmodur N75 | 80 portions of, |
| Curing agent diluent equal mass butyl acetate SO-1000 | 20 parts of a binder; |
the preparation method of the silica described in this embodiment includes 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, and stirring for 2 hours at 1000 revolutions per minute at the temperature of 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, and stirring for 2 hours at 1000 revolutions per minute at the temperature of 40 ℃;
s3, mixing the solutions obtained in the S1 and the S2, stirring the mixture for 2 at room temperature, and filtering, 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;
and S5, repeating the step S4 for three times to obtain the nano silicon dioxide taking the hyperbranched polyurethane as the shell and the nano silicon dioxide as the core, wherein the obtained silicon dioxide with the core-shell structure is in a nano level, and the diameter of the silicon dioxide is within the range of 80-150 nm.
Comparative example 1
This comparative example differs from example 1 only in that no nanosilica is added, and is replaced by commercially available, conventional silica having a particle size D50 of 100 nm.
Example 4
20 microns of middle coat is sprayed on the electrophoresis plate, 15 microns of black finish coat is sprayed on the electrophoresis plate, the mixture is baked for 5 to 10 minutes at 80 ℃ until the coating is dry, then the varnish described in the example 1~3 is sprayed on the black finish coat, the spraying thickness is 40 microns, the leveling is carried out for 5 minutes, and finally the mixture is baked for 30 minutes at 140 ℃ to prepare the composite coating.
And (3) morphology testing: observing the nano silicon dioxide structure with the core-shell structure by using a transmission electron microscope; FIG. 1 is a transmission electron micrograph of the silica described in example 1.
And (3) detecting the storage stability of the coating: according to the GB-T6753.3-1986 paint storage stability test method, the paint is stored for 6 months under natural conditions, and the paint settlement condition is observed.
Detecting the scratch resistance of the coating: FLTM161-01, 2 micron polished paper from 3M company was used. The test results are shown in Table 1.
TABLE 1
| Stability in storage | Gloss before scratching (20 degree) | Gloss after scratching | |
| Example 1 | Completely suspended and unchanged from the original state of the paint | 93.2 | 89.6 |
| Example 2 | Completely suspended and unchanged from the original state of the paint | 92.8 | 90.6 |
| Example 3 | Completely suspended and unchanged from the original state of the paint | 92.6 | 90.3 |
| Comparative example 1 | Completely suspended and unchanged from the original state of the paint | 93.3 | 80.2 |
As can be seen from FIG. 1 and Table 1, the nanosilicon dioxide of the examples has a core-shell structure, is spherical particles with regular shapes, and has uniform particle size of 80-120 nm. The nano-silica with the core-shell structure has good storage stability in a main agent of the bi-component polyurethane varnish, and the addition of the nano-silica particles hardly affects 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 used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The scratch-resistant two-component polyurethane varnish is characterized by comprising the following components in parts by weight:
the component A comprises:
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 leveling agent,
60-80 parts of a main agent diluent;
and B component:
75-85 parts of aliphatic polyisocyanate,
15-25 parts of 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 a silane coupling agent with amino and hydrochloric acid into an ethanol solution, and stirring for 1 to 3 hours at the temperature of 38 to 42 ℃;
s3, stirring and mixing the solution obtained in the S1 and the solution obtained in the S2 uniformly at the temperature of 23 to 28 ℃, filtering the reaction mixture, washing the reaction mixture 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 1-3h at 58-62 ℃, then filtering, washing with ethyl acetate, adding a filter cake into vegetable oil-based polyol, adding an organic tin catalyst, stirring for 1-3h at 78-82 ℃, filtering, washing with ethyl acetate, and then drying in a protective gas atmosphere;
and S5, repeating the step S4 for three times to obtain the nano silicon dioxide.
2. The scratch-resistant two-component polyurethane varnish composition according to claim 1, wherein in step S1, the weight ratio of tetraethylorthosilicate to hydrochloric acid is 9 to 11; in the step S2, the weight ratio of the silane coupling agent with amino groups to hydrochloric acid is 9 to 11; the weight ratio of the silane coupling agent with amino groups to tetraethyl orthosilicate is 0.5 to 2.
3. The scratch-resistant two-component polyurethane varnish composition according to claim 1, wherein in step S4, the weight ratio of the aminated nanosilica to diisocyanate is 1 to 3 to 5; the weight ratio of the aminated nano silicon dioxide to the vegetable oil-based polyol is 1 to 3-5.
4. The scratch-resistant two-component polyurethane varnish composition according to claim 1, wherein in steps S1 and S2, the stirring speed is 800 to 1500 rpm.
5. The scratch-resistant two-component polyurethane varnish composition according to claim 1, wherein in step S1, the weight ratio of the tetraethyl orthosilicate to the ethanol is 1 to 15-25; in the step S2, the weight ratio of the silane coupling agent with amino groups to the ethanol is 1.
6. The scratch-resistant two-component polyurethane varnish composition according to claim 1, wherein the amino group-containing silane coupling agent 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 jatropha oil-based polyol; the organic tin catalyst is at least one of dibutyltin dilaurate, dibutyltin oxide and stannous octoate.
7. The scratch-resistant two-component polyurethane varnish composition of claim 1, wherein the light stabilizer is at least one of Tinuvin788, tinuvin 900 and Tinuvin 5151; the leveling agent is at least one of BYK320, BYK322 and BYK 310.
8. The scratch resistant two-component polyurethane varnish composition of claim 1, wherein the host diluent is at least one of ethyl acetate, butyl acetate, propylene glycol dimethyl ether, and methyl isobutyl ketone.
9. The scratch resistant two-component polyurethane varnish composition of claim 1, wherein the aliphatic polyisocyanate is at least one of Desmodur N3300, desmodur N75, and SUMIDUR N3300.
10. The scratch resistant two-component polyurethane varnish composition of claim 1, wherein the curing agent diluent is at least one of butyl acetate and a high boiling point petroleum based solvent SO-1000.
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| CN117964313A (en) * | 2024-02-06 | 2024-05-03 | 江苏美标家居科技有限公司 | Multifunctional fireproof and antiriot plate and preparation method thereof |
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