CN115785330A - Acrylic acid aqueous dispersion and application thereof - Google Patents
Acrylic acid aqueous dispersion and application thereof Download PDFInfo
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- CN115785330A CN115785330A CN202211586417.1A CN202211586417A CN115785330A CN 115785330 A CN115785330 A CN 115785330A CN 202211586417 A CN202211586417 A CN 202211586417A CN 115785330 A CN115785330 A CN 115785330A
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- acrylic acid
- polyamide
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- aqueous dispersion
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000006185 dispersion Substances 0.000 title claims abstract description 55
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 239000004952 Polyamide Substances 0.000 claims abstract description 29
- 229920002647 polyamide Polymers 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000003973 paint Substances 0.000 claims description 45
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002966 varnish Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 239000006184 cosolvent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 abstract description 9
- 150000002513 isocyanates Chemical class 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 150000003141 primary amines Chemical group 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 239000002585 base Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 15
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000007665 sagging Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 5
- 238000001962 electrophoresis Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000002987 primer (paints) Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- 229920007019 PC/ABS Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- -1 ethylene glycol ethers Chemical class 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses an acrylic acid aqueous dispersion and application thereof, wherein the acrylic acid aqueous dispersion is obtained by copolymerizing styrene, acrylic acid monomers and micromolecular polyamide; the molecular weight of the micromolecule polyamide is 600-1100. According to the acrylic acid aqueous dispersion, small molecular polyamide molecules are introduced into a polymer structure, and before the acrylic acid aqueous dispersion is in contact with isocyanate for crosslinking, because amide bonds and primary amine functional groups of the small molecular polyamide have strong hydrophilicity, hydrogen bonds with water molecules are beneficial to improvement of rheological property of a coating. Meanwhile, all H atoms connected with N on the polyamide bond can further react with isocyanate, so that the residue of active hydrogen after crosslinking is reduced, and the medium resistance of the coating is further improved. The acrylic acid aqueous dispersion can adapt to various substrates, can meet the coating requirements of an automatic coating line of an automobile factory, and provides a new path for cost optimization of the automobile factory finished automobile coating.
Description
Technical Field
The invention relates to an acrylic resin, in particular to an acrylic acid aqueous dispersion and application thereof.
Background
In order to improve the production efficiency of automatic spraying of an automobile coating line, the basic targets of vehicle coating are to adopt as few drying processes as possible and as low baking temperature as possible in the coating process, so that the energy consumption can be saved, and the optimization of coating time in unit time can be realized. However, in the coating process of the water-based paint, the defects (shrinkage cavity, interlayer adhesion and sagging) of interlayer matching caused by a long moisture volatilization process (relative to a solvent) and an excessively high surface tension of water in the coating process are usually limited, and the sagging resistance of the paint and the surface state and performance of the finish after coating are directly influenced by the volatility of a dispersion medium of the water-based base coat resin, the rheological property of the polymer and the reaction rate of the resin.
In addition, the technical innovation of automobile factories always aims at 'energy saving, quality improvement and efficiency improvement'. The baking temperature and the baking time in the automobile coating are reduced, and the baking temperature and the baking time occupy very important positions in the control process of the coating cost. Therefore, the normal-temperature self-drying process and the low-temperature drying process are the primary choices of the whole automobile coating line of an automobile factory, and the isocyanate-cured waterborne acrylic polyurethane system not only can meet the automobile protection requirements in performance, but also can meet the matching requirements between the whole automobile coating energy-saving coating process and other coatings. However, the commercially available aqueous polyurethane systems all use hydroxy acrylate or epoxy acrylate (containing hydroxyl group), and when the resin systems with these structures are crosslinked by using the isocyanate aqueous dispersion, the acid value content in the resin is high (which is beneficial to water dispersion after neutralization), and the water resistance of the coating film after curing is insufficient; however, if the water resistance is improved by increasing the crosslinking density, the inherent defect that the hardness of the water-based system is increased (due to complete crosslinking and solidification and micro-domain crystallization) along with the extension of the curing time is revealed, and how to meet the use durability and interlayer matching of the automobile coating material is always a focus of attention in the coating technical field.
Disclosure of Invention
The invention aims to provide an acrylic acid aqueous dispersion which has good adhesion to various substrates and can improve the durability of a primer coating, and a preparation method and application thereof.
The technical scheme for realizing the first purpose of the invention is that the acrylic acid aqueous dispersion is obtained by copolymerizing styrene, acrylic acid monomers and micromolecular polyamide.
The softening point of the acrylate part in the acrylic acid aqueous dispersion is 15-50 ℃.
Optionally, the molecular weight of the small-molecule polyamide is 600-1100.
The acrylic acid aqueous dispersion is prepared according to the following method:
(1) adding cosolvent and low molecular weight polyamide with molecular weight of 600-1100 into a reactor with a stirring and heating device, starting stirring, heating to 60 +/-5 ℃, and waiting until the polyamide is completely dissolved.
(2) And continuously heating to 130-140 ℃, beginning to drop a mixture of styrene, acrylic monomer and initiator, then preserving heat, measuring the content of free monomer, and finishing the heat preservation when the content of the free monomer is controlled within 0.1%.
(3) Removing free monomers and part of cosolvent by reduced pressure distillation, dropwise adding N, N-dimethylethanolamine for neutralization, controlling the neutralization degree to be 85-90%, adding water for stirring uniformly, continuously removing the rest propylene glycol monomethyl ether until the amount of the propylene glycol methyl ether in the system is 10-15% of the amount of the initial addition, and filtering to obtain the acrylic acid aqueous dispersion.
Wherein, the low molecular polyamide accounts for 2 to 5 percent of the effective component of the total formula.
Optionally, the acrylic monomer is a combination of two or more of butyl acrylate, acrylic acid, methyl methacrylate, hydroxypropyl acrylate, and hydroxyethyl acrylate.
The low molecular polyamide is polyamide 650.
The initiator is dicumyl peroxide.
In the step (2), after the mixture of the styrene, the acrylic monomer and the initiator is dripped, the temperature is firstly preserved for 1 to 2 hours, the initiator solution is replenished, and the temperature is preserved for 4 to 5 hours continuously.
The technical scheme for realizing the second purpose of the invention is that the acrylic acid aqueous dispersion is applied to the water-based automobile base paint and is suitable for the 'wet-on-wet' coating process of the finishing section of the automatic automobile production line.
The water-based automobile base paint prepared from the acrylic acid aqueous dispersion is matched with low-temperature baking type finishing varnish, and is suitable for collinear coating of multi-material (PP/EPDM, PC, ABS, SMC, CFRP, cathode electrophoresis and steel) automobile parts.
When different materials of an automobile production line are coated in a collinear way, the water-based automobile base color paint prepared by the acrylic acid aqueous dispersion is firstly sprayed on a substrate, and the base color paint is leveled for 2-3 minutes at room temperature to obtain a first base color paint layer; spraying a second layer of base color paint on the first layer of base color paint, and leveling for 2-3 minutes at room temperature to obtain a second layer of base color paint; spraying the finishing varnish on the second base paint layer, and leveling to obtain a finishing varnish layer; finally drying at 80 +/-5 ℃ to obtain the coating.
The invention has the positive effects that: (1) According to the invention, before the acrylic acid aqueous dispersion is in contact with isocyanate for crosslinking, because amide bonds and primary amine functional groups have strong hydrophilicity, hydrogen bonds with water molecules are beneficial to improving the rheological property of the coating, and the introduction of the anti-sagging auxiliary agent in the coating preparation process is reduced (the small molecular auxiliary agent generally generates strong migration along with the time continuation in the coating material, so that the coating is indirectly gradually hardened and embrittled, the durability of the vehicle coating material is not facilitated, and the reduction of the small molecular auxiliary agent is also beneficial to the full contact permeation of the resin and the base material, and the interaction between the base material and the primer resin is strengthened). In addition, active hydrogen on the amido bond can further react with isocyanate, so that the existence of hydrophilic groups or chain segments of the resin after curing is reduced, the hydrophilic-to-hydrophobic transition of the cured coating is further improved, and the improvement of the water resistance and chemical resistance of the coating is promoted.
(2) In the acrylic acid aqueous dispersion, micromolecular polyamide 650 resin (oligomer obtained by condensation of dimeric vegetable oil acid and fatty amine) is copolymerized with acrylic acid monomer, double bonds in polyamide are copolymerized with the acrylic acid monomer, and primary amine with higher activity than that of hydroxyl and isocyanate reaction is introduced, so that the base paint prepared by the acrylic acid aqueous dispersion can be quickly and partially crosslinked after being coated, and the molecular weight is quickly increased, so that a dispersion medium in the base paint is easier to volatilize in the base paint (the resin supports relatively more pores at the initial stage of partial crosslinking, and the porosity is reduced and the film pores are reduced along with continuous crosslinking).
(3) The acrylic acid aqueous dispersion can adapt to various substrates, can meet the coating requirements of an automatic coating line of an automobile factory, and provides a new path for cost optimization of the automobile factory finished automobile coating.
The base color paint prepared from the acrylic acid aqueous dispersion has good matching performance with low-temperature baking finishing varnish, and can be dried at 80 ℃, so that multi-material collinear coating of an automobile production line can be realized, for example, metal parts and non-metal parts (PP/EPDM, PC, ABS, SMC, CFRP, cathode electrophoresis and steel) of an automobile can be subjected to collinear coating, and the metal parts and the non-metal parts are not respectively coated.
Detailed Description
(example 1)
The aqueous acrylic dispersion of this example was prepared as follows:
(1) in a reactor equipped with a stirring and heating device, 90 parts of propylene glycol monomethyl ether and 3.14 parts of a low-molecular polyamide (polyamide 650 in this example) having a molecular weight of 600 to 1100 were put, and stirring and heating were started to 60. + -. 5 ℃ until the polyamide 650 was completely dissolved.
The cosolvent may be ethylene glycol ethers or propylene glycol butyl ether, other than propylene glycol methyl ether; propylene glycol methyl ether, glycol ethers, and propylene glycol butyl ether can be used alone or in combination as a cosolvent.
The polyamide 650 has the following structural formula:
(2) and continuously heating to 130-140 ℃, dropwise adding a mixture of styrene, acrylic acid monomers and an initiator (24.5 parts of styrene, 40.16 parts of butyl acrylate, 4.5 parts of acrylic acid, 22 parts of methyl methacrylate, 5.7 parts of hydroxypropyl acrylate and 1.3 parts of dicumyl peroxide), uniformly dropping for 3-4 hours, keeping the temperature for 1 hour, continuously replenishing an initiator solution (0.2 part of dicumyl peroxide/10 parts of propylene glycol methyl ether), continuously keeping the temperature for 4-5 hours after dropping for 30 minutes, measuring the content of free monomers, and ending the heat preservation when the content of the free monomers is controlled within 0.1%.
(3) Distilling under reduced pressure to remove free monomers and partial cosolvent (accounting for about 60 percent of the total input amount of the cosolvent), dripping 5.0 parts of N, N-dimethylethanolamine for neutralization (the neutralization degree is controlled to be 85 to 90 percent), stirring for 30min, adding 110 parts of water for stirring, continuously removing the rest propylene glycol monomethyl ether until the propylene glycol methyl ether in the system is equal to the amount of 10 to 15 percent of the initial addition amount, stopping distilling to remove the propylene glycol methyl ether, cooling to below 60 ℃, and filtering to obtain the acrylic acid aqueous dispersion.
The obtained acrylic resin water dispersion is semitransparent liquid, the non-volatile content is 40-45%, the content of active hydrogen (each primary amine in polyamide is 2 active hydrogen, which is equivalent to 2 hydroxyl functional groups) in the acrylic resin water dispersion is 1.0-2.0% (calculated by solid resin), and the softening point of an acrylate part is controlled at 15-50 ℃.
(examples 2 to 6)
The aqueous acrylic dispersions of examples 2 to 6 were prepared by the same method as in example 1 except for the amounts of the polyamide 650, styrene, acrylic acid monomer, initiator, and N, N-dimethylethanolamine, and the amounts of the polyamide 650, styrene, acrylic acid monomer, initiator, and N, N-dimethylethanolamine for each example were as follows:
| examples | 2 | 3 | 4 | 5 | 6 |
| Polyamide 650 | 3.0 | 3.5 | 3.2 | 2.8 | 2.5 |
| Styrene (meth) acrylic acid ester | 24 | 25 | 25.5 | 27 | 27.5 |
| Acrylic acid butyl ester | 40.2 | 32 | 35 | 28 | 24.5 |
| Acrylic Acid (AA) | 4.0 | 4.5 | 4.3 | 4.5 | 4.0 |
| Methacrylic acid methyl ester | 28 | 25 | 30 | 20 | 27 |
| Hydroxypropyl acrylate | 5.7 | —— | 9.6 | 13.5 | 12.8 |
| Acrylic acid hydroxyethyl ester | —— | 5.5 | —— | —— | —— |
| Dicumyl peroxide | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| N，N-dimethylethanolamine | 4.9 | 5.2 | 5.1 | 5.2 | 4.9 |
(example 7)
The water-based automobile base paint comprises a paint component and a curing agent, wherein the curing agent is isocyanate aqueous dispersion (VENCOREX CONRUI XL 600), and the paint component comprises the following components in parts by weight: 40 parts of acrylic acid aqueous dispersion, 15 parts of calcium carbonate, 15 parts of titanium dioxide, 1 part of dispersing agent, 6 parts of defoaming agent, 0.5 part of flatting agent, 2 parts of cosolvent, 0.1 part of anti-sagging agent and 60 parts of deionized water in example 1.
The mass ratio of the paint components to the curing agent is 100.
(test example 1)
Test samples:
sample 1, the waterborne automotive basecoat described in example 7. The water-based automobile base paint comprises paint components and a curing agent, wherein the curing agent is isocyanate aqueous dispersion (VENCOREX CorRui XL 600) and is prepared from the following components in percentage by mass of 100:8. the paint component comprises the following components in parts by weight: 40 parts of acrylic acid aqueous dispersion, 15 parts of calcium carbonate, 15 parts of titanium dioxide, 1 part of dispersing agent, 6 parts of defoaming agent, 0.5 part of leveling agent, 2 parts of cosolvent, 0.1 part of anti-sagging agent and 60 parts of deionized water in example 1.
Sample 2, aqueous automobile basecoat prepared from an aqueous hydroxyacrylic dispersion resin (aqueous hydroxyacrylic dispersion resin from midsea oil ordinary coating chemical research institute, ltd). The water-based automobile base coat comprises paint components and a curing agent, wherein the curing agent is isocyanate aqueous dispersion (Corsichu XP 2655) and is prepared from the following components in percentage by mass of 100:8. the paint component comprises the following components in parts by weight: 40 parts of hydroxyl acrylic acid aqueous dispersion resin, 15 parts of calcium carbonate, 15 parts of titanium dioxide, 1 part of dispersing agent, 6 parts of defoaming agent, 0.5 part of flatting agent, 2 parts of cosolvent, 0.1 part of anti-sagging agent and 60 parts of deionized water.
Test method 1: the test samples 1 and 2 are respectively coated on PP/EPDM, PC/ABS, SMC, CFRP, cathode electrophoresis + steel and other substrates to test the anti-denaturation property and the dispersion medium release property of the base paint.
Test method 2: the method comprises the following steps of (1) adopting a wet-on-wet coating process, sequentially coating a substrate, spraying a first layer of base paint, spraying a second layer of base paint, spraying finishing varnish and drying (80 ℃,30 min), specifically, spraying a test sample on the substrates of PP/EPDM, PC/ABS, SMC, CFRP, cathode electrophoresis + steel and the like, leveling at room temperature for 2-3 min to obtain a first layer of base paint; spraying a second primer layer on the first base color paint layer, and leveling for 2-3 minutes at room temperature to obtain a second base color paint layer; spraying the finishing varnish on the second primer layer, and leveling for 8-10 minutes to obtain a finishing varnish layer; drying at 80 ℃ for 30min to obtain a coating, and testing the gloss, pencil hardness, adhesive force, stone impact resistance, cupping, impact strength, chemical resistance (gasoline, engine oil, wind window cleaning liquid, acid and alkali), temperature change resistance, water resistance, moisture resistance, salt spray resistance and artificial aging resistance of the coating (2000 h).
Wherein the matched second layer of base paint is base paint with the brand number WBA-01 produced by Wucheng optical metallic paint company Limited in Changzhou city.
The matching varnish is a low-temperature baking finishing varnish which is produced by Wucheng Chenguang metallic paint Co., ltd of Changzhou city and has the mark of DSC-01G.
The test results for sample 1 are as follows:
the detection results of sample 2 were as follows:
during detection, the sagging property is detected according to GB 9264; the release of the dispersion medium is related to surface dryness and detected according to GB 1728; the water resistance of the coating is detected according to GB/T1733; detecting the attachment aging according to GB/T9286; the gloss of the coating was measured according to GB 9754; the pencil hardness is detected according to GB 6739; the stone impact resistance is detected according to ISO 20567-1; cupping was detected as GB 9753; the impact strength is detected according to GB 1732; the chemical resistance (gasoline, engine oil, acid, alkali and air window cleaning liquid) is detected according to GB 9274; temperature resistance was measured as per Table 6.3 of QC/T966-2014; moisture resistance was tested according to GB 13893; the salt spray resistance is detected according to GB 1771; resistance to artificial ageing (2000 h) was determined according to GB 1865.
As can be seen by detection, the performance of the acrylic acid aqueous dispersion is obviously superior to that of the common hydroxyl acrylic acid aqueous dispersion resin sold in the market, the prepared base paint has good matching performance with low-temperature baking finish varnish, the prepared coating has good water resistance and good sagging resistance, the interlayer adhesion to various substrates is good, and the coating protection of various substrates such as PP/EPDM, PC, ABS, SMC, CFRP, cathode electrophoresis and steel is considered.
The base paint prepared from the acrylic acid aqueous dispersion has good matching property with low-temperature baking finishing varnish, and can be dried at 80 +/-5 ℃, so that multi-material collinear coating of an automobile production line can be realized, for example, automobile metal parts and non-metal parts can be coated in a collinear way instead of being coated respectively.
Claims (12)
1. An aqueous acrylic dispersion characterized by: obtained by copolymerizing styrene, acrylic monomers and micromolecular polyamide.
2. The aqueous acrylic dispersion according to claim 1, wherein: the softening point of the acrylate moiety is from 15 ℃ to 50 ℃.
3. The aqueous acrylic dispersion according to claim 1, wherein: the molecular weight of the micromolecule polyamide is 600-1100.
4. The aqueous acrylic dispersion according to claim 1, wherein the acrylic dispersion is prepared by the following method:
(1) adding cosolvent and low molecular weight polyamide with molecular weight of 600-1100 into a reactor with a stirring and heating device, starting stirring, heating to 60 +/-5 ℃, and completely dissolving the polyamide;
(2) continuously heating to 130-140 ℃, starting to dropwise add a mixture of styrene, acrylic monomers and an initiator, then preserving heat, measuring the content of free monomers, and finishing the heat preservation when the content of the free monomers is controlled within 0.1%;
(3) removing free monomers and part of cosolvent through reduced pressure distillation, dropwise adding N, N-dimethylethanolamine for neutralization, controlling the neutralization degree to be 85-90%, adding water for stirring uniformly, continuously removing the rest propylene glycol methyl ether until the amount of the propylene glycol methyl ether in the system is 10-15% of the amount originally added, and filtering to obtain the acrylic acid aqueous dispersion.
5. The aqueous acrylic dispersion according to claim 4, wherein: the low molecular polyamide accounts for 2 to 5 percent of the effective component of the total formula.
6. The aqueous acrylic dispersion according to claim 4, wherein: the acrylic monomer is a composition of more than two of butyl acrylate, acrylic acid, methyl methacrylate, hydroxypropyl acrylate and hydroxyethyl acrylate.
7. The aqueous acrylic dispersion according to claim 4, wherein: the low molecular polyamide is polyamide 650.
8. The aqueous acrylic dispersion according to claim 4, wherein: the initiator is dicumyl peroxide.
9. The aqueous acrylic dispersion according to claim 4, wherein: in the step (2), after the mixture of styrene, acrylic monomer and initiator is dripped, the temperature is firstly preserved for 1 to 2 hours, the initiator solution is replenished, and the temperature is preserved for 4 to 5 hours continuously.
10. Use of an aqueous acrylic dispersion according to claim 1 in aqueous automotive base paints.
11. The use of an aqueous acrylic dispersion according to claim 10 in aqueous automotive base paints, characterized in that: the water-based automobile base paint prepared from the acrylic acid aqueous dispersion is matched with low-temperature baking type finishing varnish and is used for collinear coating of different materials in an automobile production line.
12. The use of an aqueous acrylic dispersion according to claim 10 in aqueous automotive base paints, characterized in that: when different materials of an automobile production line are coated in a collinear way, the water-based automobile base color paint prepared from the acrylic acid aqueous dispersion is firstly sprayed on a substrate, and a first base color paint layer is obtained after leveling at room temperature; spraying a second layer of base color paint on the first layer of base color paint, and leveling at room temperature to obtain a second layer of base color paint; spraying the finishing varnish on the second base paint layer, and leveling to obtain a finishing varnish layer; finally drying at 80 +/-5 ℃ to obtain the coating.
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