CN101469245A - Coating composition and method of preparing the same - Google Patents
Coating composition and method of preparing the same Download PDFInfo
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- CN101469245A CN101469245A CNA2007103013747A CN200710301374A CN101469245A CN 101469245 A CN101469245 A CN 101469245A CN A2007103013747 A CNA2007103013747 A CN A2007103013747A CN 200710301374 A CN200710301374 A CN 200710301374A CN 101469245 A CN101469245 A CN 101469245A
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Abstract
The invention discloses a coating composition, which contains a thermosetting resin, an amino resin, a filler and a solvent, and selectively contains an auxiliary agent, wherein the coating composition also contains modified nanometer calcium carbonate, and the modified nanometer calcium carbonate is a product that the nanometer calcium carbonate contacts an acrylic ester polymer containing carboxyl. A method for preparing the coating composition comprises the following steps: the thermosetting resin, the amino resin, the filler and the solvent are mixed, wherein the modified nanometer calcium carbonate is also added into the mixture during the mixing, and is the product that the nanometer calcium carbonate contacts the acrylic ester polymer containing the carboxyl. Compared with the prior amino baking enamel with titanium white added as pigment, the coating composition has excellent shock resistance and low cost, and has strong bonding force with substrates and finishing coats.
Description
Technical field
The present invention relates to a kind of coating composition and preparation method thereof.
Background technology
At present, most hot settings have the organic solvent type coating employing titanium dioxide of white phase as its pigment.Because titanium dioxide is as the pigment of white colored paint, Heat stability is good, strong covering power, the rete of formation is smooth, fine and smooth, and grinability is also fine.But paint film layer hardens, embrittlement owing to the titanium dioxide content height in the coating causes, thereby the impact resistance of paint film layer is reduced.In addition, the price height of titanium dioxide, also unfavorable in the coating cost.
Nano particles of calcium carbonate is a kind of novel ultrafine solids material that grows up the eighties in 20th century.In coatings industry, nano-calcium carbonate plays skeleton function because Heat stability is good is cheap in film forming matter, can replace expensive titanium dioxide in a large number, reduces the base-material adhesive consumption simultaneously, reduces cost remarkable in economical benefits significantly.Therefore, nano-calcium carbonate being applied in the coating in the hope of improving coating property is one of hot issue of paying close attention to of coating circle.
Nano-calcium carbonate belongs to inorganic materials, is applied in the superpolymer to exist the affinity problem between lime carbonate and the superpolymer interface after the blending dispersion, and minimizing along with particle diameter, surface energy increases gradually, and its hydrophilic oleophobic phenomenon is more serious, and agglomeration is serious in organic solvent.Be to reduce the surface energy of nano-calcium carbonate, increase the consistency of itself and high molecular polymer, must carry out surface treatment it.At present, the surface treatment agent of domestic nano-calcium carbonate adopts stearic acid and its esters mostly, is applied in the coating, has following defective: the particle surface energy height, be in the thermodynamic instability state, and very easily reunite; Dispersing property in organic medium is also bad, easily forms boundary defect, causes film performance to descend.Therefore, though nano-calcium carbonate has been realized industrialization in recent years, but the application of nano-calcium carbonate mainly concentrates in polyvinyl chloride (PVC), polypropylene (the PP)/polyethylene plastics such as (PE), at coating industry, then mainly concentrate on and build the class water-borne coatings, that is that all right is ripe for the application in organic solvent type coating.
Summary of the invention
The objective of the invention is to overcome in the prior art a large amount of titanium dioxides that use and cause coating impact resistance difference and nano-calcium carbonate to be used for the shortcoming that organic solvent type coating is easily reunited, provide a kind of add nano-calcium carbonate and do not reunite and film forming after have organic solvent type coating composition of excellent in resistance impact property and preparation method thereof.
The invention provides a kind of coating composition, this coating composition contains thermosetting resin, aminoresin, filler and solvent, and optionally contain auxiliary agent, wherein, this coating composition also contains modified nano calcium carbonate, and described modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer.
The present invention also provides the preparation method of aforementioned coating composition, this method comprises: with thermosetting resin, aminoresin, filler and solvent, wherein, also add modified nano calcium carbonate when mixing, described modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer.
In the described modified nano calcium carbonate, the carboxyl functional group in the carboxylic acrylic ester polymer can react with the lime carbonate molecule, and combines with covalent linkage.After the thermosetting resin in the coating and described modified nano calcium carbonate are mixed for some time, the long-chain organic group in the carboxylic acrylic ester polymer and the thermosetting resin of coating are the high molecular polymers of same nature, so are easy to produce intermolecular attraction or entanglement between them.Like this, Nano particles of calcium carbonate just and thermosetting resin be that interlude couples together with carboxylic acrylic ester polymer, nano-calcium carbonate is also just wrapped up by the thermosetting resin molecule, the high surface energy of particle has obtained greatly reduction.When mixing with other components of coating, be difficult for forming boundary defect, nano-calcium carbonate also just is easy to be dispersed in the organic medium.With traditional interpolation titanium dioxide is that the amine baking varnish of pigment is compared the impact resistance excellence of coating composition of the present invention, with low cost and strong with the bonding force of ground and finish paint.
Embodiment
Coating composition provided by the invention contains thermosetting resin, aminoresin, filler and solvent, and optionally contain auxiliary agent, wherein, this coating composition also contains modified nano calcium carbonate, and described modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer.
According to coating composition provided by the invention, wherein, gross weight with this coating composition is a benchmark, the content of described thermosetting resin can be 15-50 weight %, and the content of described aminoresin can be 5-30 weight %, and the content of described filler can be 2-25 weight %, the content of described solvent can be 10-50 weight %, the content of described auxiliary agent can be 0-6 weight %, is preferably 0.2-5 weight %, and the content of described modified nano calcium carbonate can be 8-40 weight %.
Wherein, described nano-calcium carbonate can be traditional nano-calcium carbonate with stearic acid or resinous acid and their salt coating processing, also can be the nano-calcium carbonate of uncoated processing.
Described carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomer formation and the structural unit of Acrylic Acid Monomer and/or methacrylic acid monomer formation, and optionally contains the structural unit of one or more formation in acrylonitrile monemer, Vinyl Acetate Monomer, acrylamide monomer, methyl acrylamide monomer and the styrene monomer.
Wherein, under the preferable case, described acrylate monomer is selected from methyl acrylate, ethyl propenoate, n-butyl acrylate, one or more in isobutyl acrylate, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate and the glycidyl acrylate; Described methacrylate monomer is selected from methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, one or more in N-Hexyl methacrylate, vinylformic acid n-octyl, methacrylic acid laurate, methacrylic acid 18 carbon esters, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, glycidyl methacrylate and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
There is no particular limitation to the number-average molecular weight of described carboxylic acrylic ester polymer, and under the preferable case, the number-average molecular weight of described carboxylic acrylic ester polymer is 5000-25000.In above-mentioned preferred molecular weight range, described carboxylic acrylic ester polymer easy and coating resin chain generation molecular attraction or winding, and easily by organic solvent dissolution.
There is no particular limitation to the acid number of described carboxylic acrylic ester polymer, and under the preferable case, the acid number of carboxylic acrylic ester polymer is a 20-160 milligram KOH/ gram.In above-mentioned acid number scope, described carboxylic acrylic ester polymer can be better with the Nano particles of calcium carbonate reaction forming covalent bonds, and can not influence the crosslinked of thermosetting resin and aminoresin in the coating.
Described carboxylic acrylic ester polymer can carry out copolymerization with above-mentioned monomer by the polymerization process of routine and make, and also can be commercially available.
Each the monomeric mol ratio that forms described carboxylic acrylic ester polymer is not particularly limited, can change within a large range, under the preferable case, it is 20-160 milligram KOH/ gram that each monomeric mol ratio makes the acid number of the carboxylic acrylic ester polymer that makes.
In described modified nano calcium carbonate, the content of carboxylic acrylic ester polymer is not particularly limited.Under the preferable case, be benchmark with the nano-calcium carbonate of 100 weight parts, the content of described carboxylic acrylic ester polymer is the 2-20 weight part.
Described thermosetting resin can be used for the thermosetting resin of organic solvent type coating for any routine, the present invention is not particularly limited, for example, can be one or more of hydroxyl acrylic resin, thermosetting acrylate resin, saturated polyester resin and Synolac.Wherein, the thermosetting acrylate resin can be the ALMATEX of Mitsui Chemicals company 201, ALMATEX 202, ALMATEX 203, the HR-7000 of Li Yang company of Mitsubishi, HR-7100 and the ACRYDIC T-466 of DIC company, ACRYDIC T-468 etc.Hydroxyl acrylic resin can be CY430, the CY468 of DSM N. V. and FS-2050, the FS2970 of the modest chemical company of moral, and saturated polyester resin can be the 8890-60 of DSM N. V. and Tires1500,1753, the Tires5757 of NUPLEX company.Synolac can be with products such as the AK2070 of moral company, AK2061.
Described solvent can be this area any organic solvent commonly used, for example, can be in toluene, ethyl acetate, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, cyclohexanone, dimethylbenzene, hexone, acetone, methylethylketone, butyl glycol ether, the propylene glycol butyl ether one or more.
Described aminoresin is the solidifying agent of thermosetting resin, can be the solidifying agent of this area thermosetting resin commonly used, the present invention is not particularly limited, for example, can be NUPLEX (Niu Peisi) US138-70, the long Chinese toon resin BR-20SE of company, the UVAN-501 of Mitsui Chemicals company, one or more among the first promise BM-5901 of company and the L-127 of DIC company, the L-117.
Described filler is this area filler commonly used, mainly plays filling effect, can reduce the cost of coating simultaneously, can be selected from talcum powder, barium sulfate, weight matter lime carbonate, kaolin, mica powder and the magnesiumcarbonate one or more.
Described auxiliary agent can comprise dispersion agent, and the selectivity flow agent and the anti-settling agent that contain.The kind of described dispersion agent, flow agent and anti-settling agent and consumption are conventionally known to one of skill in the art.
The preparation method of coating composition provided by the invention comprises: with thermosetting resin, aminoresin, filler and solvent, wherein, also add modified nano calcium carbonate when mixing, described modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer.
Wherein the add-on of each material makes in the coating that makes, gross weight with this coating composition is a benchmark, the content of described thermosetting resin is 15-50 weight %, the content of described aminoresin is 5-30 weight %, the content of described filler is 2-25 weight %, and the content of described auxiliary agent is 0-6 weight %, is preferably 0.2-5 weight %, the content of described solvent is 10-50 weight %, and the content of described modified nano calcium carbonate is 8-40 weight %.
Described modified nano calcium carbonate contacts 5-60 minute and makes by nano-calcium carbonate and carboxylic acrylic ester polymer are mixed down at 50-150 ℃, nano-calcium carbonate with 100 weight parts is a benchmark, and the consumption of described carboxylic acrylic ester polymer is the 2-20 weight part.
Described nano-calcium carbonate can be traditional nano-calcium carbonate with stearic acid or resinous acid and their salt coating processing, also can be the nano-calcium carbonate of uncoated processing.
Described carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomer formation and the structural unit of Acrylic Acid Monomer and/or methacrylic acid monomer formation, and optionally contains the structural unit of one or more formation in acrylonitrile monemer, Vinyl Acetate Monomer, acrylamide monomer, methyl acrylamide monomer and the styrene monomer.
Wherein, under the preferable case, described acrylate monomer is selected from methyl acrylate, ethyl propenoate, n-butyl acrylate, one or more in isobutyl acrylate, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate and the glycidyl acrylate; Described methacrylate monomer is selected from methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, one or more in N-Hexyl methacrylate, vinylformic acid n-octyl, methacrylic acid laurate, methacrylic acid 18 carbon esters, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, glycidyl methacrylate and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
There is no particular limitation to the number-average molecular weight of described carboxylic acrylic ester polymer, and under the preferable case, the number-average molecular weight of described carboxylic acrylic ester polymer is 5000-25000.In above-mentioned preferred molecular weight range, described carboxylic acrylic ester polymer easy and coating resin chain generation molecular attraction or winding, and easily by organic solvent dissolution.
There is no particular limitation to the acid number of described carboxylic acrylic ester polymer, and under the preferable case, the acid number of carboxylic acrylic ester polymer is a 20-160 milligram KOH/ gram.In above-mentioned acid number scope, described carboxylic acrylic ester polymer can be better with the Nano particles of calcium carbonate reaction forming covalent bonds, and can not influence the crosslinked of thermosetting resin and aminoresin in the coating.
Described carboxylic acrylic ester polymer can above-mentioned monomer be carried out polymerization by the polymerization process of routine or copolymerization makes, and also can be commercially available.
Each the monomeric mol ratio that forms described carboxylic acrylic ester polymer is not particularly limited, can change within a large range, under the preferable case, it is 20-160 milligram KOH/ gram that each monomeric mol ratio makes the acid number of the carboxylic acrylic ester polymer that makes.
Described filler is this area filler commonly used, mainly plays filling effect, can reduce the cost of coating simultaneously, can be selected from talcum powder, barium sulfate, weight matter lime carbonate, kaolin, mica powder and the magnesiumcarbonate one or more.
Described solvent can be this area any organic solvent commonly used, for example, can be in toluene, ethyl acetate, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, cyclohexanone, dimethylbenzene, hexone, acetone, methylethylketone, butyl glycol ether, the propylene glycol butyl ether one or more.
Under the preferable case, concrete implementation step of the present invention is as follows:
(1) nano-calcium carbonate is put into high-speed mixer, heat to 60-120 ℃.Nano-calcium carbonate with 100 weight parts is a benchmark, adds carboxylic acrylic ester polymer 2-20 weight part, and (1000-1200 rev/min) mixed 10-30 minute at a high speed, then mixed slurry is taken out cooling;
(2) mixture that thermosetting resin, aminoresin, filler, solvent and step (1) are obtained joins in a mixing bowl of high speed dispersor, mixes 20-40 minute in 10-35 ℃ of middling speed (500-800 rev/min);
(3) said mixture is added in the abrading cylinder of shredder, and add the airtight grinding of grinding bead, test its scraper plate fineness, pour out material when the scraper plate fineness promptly stops to grind less than 20 microns;
(4) adopt 400-600 purpose stainless (steel) wire to sieve, promptly get coating composition of the present invention.
Below, will the present invention will be described in more detail by embodiment.
Embodiment 1
Present embodiment is used for illustrating that the present invention is used as the preparation of painted coating composition.
(1) prepares carboxylic acrylic ester polymer
With 15 gram vinylformic acid, 52 gram methyl methacrylates, 30 gram butyl methacrylate, 3 gram Hydroxyethyl acrylates, 0.5 gram dibenzoyl peroxide (concentration 71%) and 0.5 gram isopropyl benzene hydroperoxide (concentration 80%) thorough mixing, and filter.48 gram dimethylbenzene and 45 gram butanols are mixed as solvent, under nitrogen protection, stir and be warming up to 115 ℃, under this temperature, above-mentioned filtrate was added drop-wise in 2 hours in this solvent, kept 3 hours down, reduce to room temperature (23 ℃) then at 115 ℃.Get product 192 grams, be colourless transparent liquid, viscosity is 14.8Pa.s, and amount of solid content is 51.2%, and (amount of solid content of resin solution is meant that resin is 100-120 ℃ of nonvolatile component down, promptly be called " solid part "), the acid number of solution is 48.3 milligrams of KOH/ grams.Adopt gel permeation chromatography (GPC) determining molecular weight about 12000.
(2) get nano-calcium carbonate (Guangdong Enping Gavin Chemical Industrial Enterprise Co., Ltd., CC-R, median size is 60 nanometers) 100 weight parts put into high-speed mixer (Rugao, Jiangsu machine works, NHG-5), after heating to 70 ℃, add carboxylic acrylate polymer solution 15.6 weight parts that step (1) makes, high-speed mixing (1200 rev/mins) 25 minutes, and, be cooled to room temperature (23 ℃) with mixed slurry taking-up.
(3) get mixture 18 weight parts that step (2) obtains, saturated polyester (DSM N. V., 8890-60, amount of solid content 60 weight %) 34 weight parts, aminoresin (Nuplex company, 138-70) 11 weight parts, 1500 order talcum powder, 5 weight parts, organobentonite (Hai Mingsi company, Bentone-38) 0.6 weight part, 3000 order barium sulfate, 13 weight parts, BYK110 dispersion agent 0.6 weight part, BYK333 flow agent 0.2 weight part, butyl glycol ether 4 weight parts, durene 8 weight parts and dimethylbenzene 5.6 weight parts, join high speed dispersor (the mechanical company limited of the diligent industry in Jiangsu, TSO.75) in a mixing bowl, mixed 25 minutes with 600 rev/mins at 25 ℃;
(4) said mixture is added in the abrading cylinder of shredder, and add the airtight grinding of grinding bead, test its scraper plate fineness, pour out material when the scraper plate fineness promptly stops to grind less than 20 microns;
(5) adopt 400 purpose stainless (steel) wires to sieve, the coating composition note that obtains is made A1.
Embodiment 2
Present embodiment is used for illustrating that the present invention is used as the preparation of painted coating composition.
(1) prepares carboxylic acrylic ester polymer
Get the A component respectively: 18 gram vinylbenzene, 28.5 gram ethyl propenoates, 17 gram methacrylic acids, 4.3 gram acrylamides, 25 gram dimethylbenzene and 20 gram butanols; B component: 12 gram vinylbenzene, 11.5 gram ethyl propenoates, 15 gram methacrylic acids, 1.5 gram Diisopropyl azodicarboxylates and 0.8 gram peroxidation uncle butyryl.
The A component is heated to 90 ℃, then the B component was dripped in 30 minutes, and, be warming up to 120 ℃ then, continued insulation reaction 5 hours in 90 ℃ of reactions 30 minutes.Reaction is reduced to room temperature (23 ℃) after finishing, and gets product 138 grams, is colourless viscous liquid, and viscosity is 28.3Pas, and amount of solid content is 71.5%, and the acid number of solution is 128.7 milligrams of KOH/ grams.Adopt GPC method determining molecular weight about 16000.
(2), (3), (4), (5) are according to the method identical with embodiment 1, different is, the carboxylic acrylate polymer solution that adds in the step (2) is the carboxylic acrylate polymer solution that present embodiment step (1) makes, and its add-on is 5.6 weight parts, temperature is 100 ℃, high-speed mixing 15 minutes.The coating composition note that obtains is made A2.
Embodiment 3
Present embodiment is used for illustrating that the present invention is used as the preparation of painted coating composition.
(1) prepares carboxylic acrylic ester polymer
With 19 gram vinylformic acid, 48 gram methyl methacrylates, 30 gram butyl methacrylate, 3 gram Hydroxyethyl acrylates, 0.5 gram dibenzoyl peroxide (concentration 71%) and 0.5 gram isopropyl benzene hydroperoxide (concentration 80%) thorough mixing, and filter.48 gram dimethylbenzene and 45 gram butanols are mixed as solvent, under nitrogen protection, stir and be warming up to 120 ℃, under this temperature, above-mentioned filtrate was added drop-wise in 2 hours in this solvent, kept 3 hours down, reduce to room temperature (23 ℃) then at 120 ℃.Get product 190 grams, be colourless transparent liquid, viscosity is 18.2Pas, and amount of solid content is 53.2%, and the acid number of solution is 65.8 milligrams of KOH/ grams.Adopt GPC method determining molecular weight about 13000.
(2), (3), (4), (5) are according to the method identical with embodiment 1, different is, the carboxylic acrylate polymer solution that adds in the step (2) is the carboxylic acrylate polymer solution that present embodiment step (1) makes, and its add-on is 11.3 weight parts, temperature is 120 ℃, high-speed mixing 10 minutes.The coating composition note that obtains is made A3.
Embodiment 4
Present embodiment is used to illustrate that the present invention is used as the preparation of the coating composition of priming paint.
According to the method identical with embodiment 1, different is, step (3) changes into: get mixture 24 weight parts, thermosetting acrylate resin (Li Yang company of Mitsubishi that step (2) obtains, HR-7000, amount of solid content 60 weight %) 49 weight parts, aminoresin (Nuplex company, US138-70) 8.7 weight parts, gas phase SiO
2(Degussa company, R972) 0.3 weight part, EFKA-4010 dispersion agent 0.6 weight part, BYK310 flow agent 0.4 weight part, butylacetate 4 weight parts, propyl carbinol 6 weight parts, dimethylbenzene 5 weight parts and butyl glycol ether 2 weight parts join in a mixing bowl of high speed dispersor, mix 25 minutes with 600 rev/mins at 25 ℃.The coating composition note that obtains is made A4.
Comparative Examples 1
This Comparative Examples is used for illustrating that prior art is used as the preparation of painted coating composition.
According to embodiment 1 step (3), (4) method identical with (5), different is, with titanium dioxide (U.S. outstanding company of Australia section, the CR826) mixture that replaces described embodiment 1 step (2) to obtain.The coating composition note that obtains is made C1.
Comparative Examples 2
This Comparative Examples is used for illustrating that prior art is used as the preparation of painted coating composition.
According to embodiment 1 step (3), (4) method identical with (5), different is, the mixture that replaces described embodiment 1 step (2) to obtain with nano-calcium carbonate (median size is 60 nanometers for Guangdong Enping Gavin Chemical Industrial Enterprise Co., Ltd., CC-R).The coating composition note that obtains is made C2.
Comparative Examples 3
This Comparative Examples is used to illustrate that prior art is used as the preparation of the coating composition of priming paint.
Titanium dioxide (Australia section U.S. outstanding company, CR826) 24 weight parts, thermosetting acrylate resin (Li Yang company of Mitsubishi, HR-7000, amount of solid content 60 weight %) 49 weight parts, aminoresin (Nuplex company, US138-70) 8.7 weight parts, gas phase SiO
2(Degussa company, R972) 0.3 weight part, EFKA-4010 dispersion agent 0.6 weight part, BYK310 flow agent 0.4 weight part, butylacetate 4 weight parts, propyl carbinol 6 weight parts, dimethylbenzene 5 weight parts and butyl glycol ether 2 weight parts join in a mixing bowl of high speed dispersor, mix 25 minutes with 600 rev/mins at 25 ℃.The coating composition note that obtains is made C3.
Paint film is made
The coating composition that embodiment 1-4 and Comparative Examples 1-3 are made before spraying with the dilution proportion of thinner (acetone) according to 1:0.8.
(1) coating composition of embodiment 1-3 and Comparative Examples 1 and 2 preparations is as painting in the automobile
With stainless steel plate alkali cleaning oil removing, phosphatization, put into the electrocoating paint (Northwest, Hunan company cathode electrodip painting, HB-2000) electrophoresis 2-3 minute, voltage is about 300 volts, clean 3 times with ultrafiltrated behind the electrophoresis, use deionized water drip washing again, 170-180 ℃ of baking 20 minutes, obtain the electrocoating paint coating about 30 microns then.
The coating compositions of spray embodiment 1-3 and Comparative Examples 1 and 2 preparations on this electrophoresis ground, then respectively 150 ℃ of bakings 60 minutes down, obtain thickness be about 35 microns in be coated with lacquering, carry out the test of sticking power and impact resistance.Other gets five samples that sprayed aforementioned coating composition respectively, and (Northwest, Hunan company coating MG-100), carries out sticking power test then to spray the amine baking varnish of silver color respectively thereon.Test result is listed in table 1.
(2) coating composition that makes of embodiment 4 and Comparative Examples 3 is as the automobile white primer
In spraying, paint and (paint in the company of the Northwest, Hunan, HS-48B) coating composition that spray embodiment 4 and Comparative Examples 3 make on the material, toasted 60 minutes down at 150 ℃ then, obtain the colored paint coating that thickness is about 35 microns, carry out the test of sticking power and impact resistance.Other gets two samples that sprayed the coating composition that embodiment 4 and Comparative Examples 3 make respectively, and (Northwest, Hunan company varnish K-800), carries out the sticking power test then to spray coating varnish thereon.Test result is listed in table 2.
Performance test
The sticking power test:
The method of inspection: GB/T9286-1998;
Quality index: being divided into is six grades, and 0,1,2 grade is qualified, and 3,4,5 grades is defective.The impact resistance test:
The method of inspection: GB/T1732-1993;
Quality index: do not cause paint film destructive height (cm of unit) with 1000g ± 1g weight vertical drop
Be index, multilayer thickness requirement 〉=30Kgcm is qualified.
Paint film appearance:
The method of inspection: range estimation
Quality index: paint film smooth smooth be qualified.
Table 1
Table 2
Data from last table 1,2 as can be seen, after being made into nano paint with the contacted nano-calcium carbonate instead of titanium white powder of carboxylic acrylic ester polymer, no matter it is as the middle japanning or the colored paint of automobile, its impact resistance all is significantly improved, impact strength is all above 70Kgcm, and its sticking power to electrophoretic primer, middle japanning, coating varnish still remains unchanged, all be reached for 0 grade or 0-1 level, the paint film layer smooth in appearance is smooth;
In Comparative Examples 2, the nano-calcium carbonate non-modified, prepared nano paint impact resistance is pretty good, has surpassed 50Kgcm, but the sticking power of itself and electrophoretic primer is at 3 grades, with the sticking power of colored paint in the 2-3 level, do not meet the industry standard requirement.Therefore, the paint film after the coating composition that is used for body of a motor car protection provided by the invention solidifies has the excellent in impact resistance energy, and outward appearance is good, and it is constant to keep the ply adhesion of paint film layer.
Claims (14)
1, a kind of coating composition, this coating composition contains thermosetting resin, aminoresin, filler and solvent, and optionally contain auxiliary agent, it is characterized in that, this coating composition also contains modified nano calcium carbonate, and described modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer.
2, coating composition according to claim 1, wherein, gross weight with this coating composition is a benchmark, the content of described thermosetting resin is 15-50 weight %, the content of described aminoresin is 5-30 weight %, and the content of described filler is 2-25 weight %, and the content of described auxiliary agent is 0.2-5 weight %, the content of described solvent is 10-50 weight %, and the content of described modified nano calcium carbonate is 8-40 weight %.
3, coating composition according to claim 1, wherein, the temperature that nano-calcium carbonate contacts with carboxylic acrylic ester polymer is 50-150 ℃, be 5-60 minute duration of contact, nano-calcium carbonate with 100 weight parts is a benchmark, and the consumption of described carboxylic acrylic ester polymer is the 2-20 weight part.
4, according to any described coating composition among the claim 1-3, wherein, described carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomer formation and the structural unit of Acrylic Acid Monomer and/or methacrylic acid monomer formation, and optionally contains the structural unit of one or more formation in acrylonitrile monemer, Vinyl Acetate Monomer, acrylamide monomer, methyl acrylamide monomer and the styrene monomer.
5, coating composition according to claim 4, wherein, the number-average molecular weight of described carboxylic acrylic ester polymer is 5000-25000, acid number is a 20-160 milligram KOH/ gram.
6, coating composition according to claim 4, wherein, described acrylate monomer is selected from one or more in methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate and the glycidyl acrylate; Described methacrylate monomer is selected from one or more in methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, N-Hexyl methacrylate, vinylformic acid n-octyl, methacrylic acid laurate, methacrylic acid 18 carbon esters, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, glycidyl methacrylate and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
7, coating composition according to claim 1, wherein, described thermosetting resin is one or more of hydroxyl acrylic resin, thermosetting acrylate resin, saturated polyester resin and Synolac; Described solvent is selected from one or more in toluene, ethyl acetate, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, cyclohexanone, dimethylbenzene, hexone, acetone, methylethylketone, butyl glycol ether and the propylene glycol butyl ether.
8, the preparation method of the described coating composition of claim 1, this method comprises thermosetting resin, aminoresin, filler and solvent, it is characterized in that, also add modified nano calcium carbonate when mixing, described modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer.
9, method according to claim 8, wherein, the add-on of each material makes in the coating that makes, gross weight with this coating composition is a benchmark, and the content of thermosetting resin is 15-50 weight %, and the content of aminoresin is 5-30 weight %, the content of filler is 2-25 weight %, the content of auxiliary agent is 0.2-5 weight %, and the content of solvent is 10-50 weight %, and the content of modified nano calcium carbonate is 8-40 weight %.
10, method according to claim 8, wherein, the temperature that nano-calcium carbonate contacts with carboxylic acrylic ester polymer is 50-150 ℃, be 5-60 minute duration of contact, nano-calcium carbonate with 100 weight parts is a benchmark, and the consumption of described carboxylic acrylic ester polymer is the 2-20 weight part.
11, according to Claim 8 any described method-10, wherein, described carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomer formation and the structural unit of Acrylic Acid Monomer and/or methacrylic acid monomer formation, and optionally contains the structural unit of one or more formation in acrylonitrile monemer, Vinyl Acetate Monomer, acrylamide monomer, methyl acrylamide monomer and the styrene monomer.
12, method according to claim 11, wherein, the number-average molecular weight of described carboxylic acrylic ester polymer is 5000-25000, acid number is a 20-160 milligram KOH/ gram.
13, method according to claim 11, wherein, described acrylate monomer is selected from one or more in methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, the glycidyl acrylate; Described methacrylate monomer is selected from one or more in methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, N-Hexyl methacrylate, vinylformic acid n-octyl, methacrylic acid laurate, methacrylic acid 18 carbon esters, methacrylic acid-beta-hydroxy ethyl ester, methacrylic acid-β-hydroxypropyl acrylate, glycidyl methacrylate and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
14, method according to claim 8, wherein, described blended temperature is 10-35 ℃, the blended time is 20-40 minute.
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Cited By (6)
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| CN102504608A (en) * | 2011-10-20 | 2012-06-20 | 张家界恒亮新材料科技有限公司 | Preparation method of micronano level surface-modified ground limestone and product thereof |
| CN103305043A (en) * | 2013-06-17 | 2013-09-18 | 丹阳市佳美化工有限公司 | Special finishing paint for thermosetting acrylic hubs |
| CN105860786A (en) * | 2016-04-28 | 2016-08-17 | 安徽开林新材料股份有限公司 | Insulation type quick-drying alkyd-amine baking paint |
| CN108359274A (en) * | 2018-02-07 | 2018-08-03 | 广西大学 | Rosin derivative chelates calcium modified Nano or lightweight CaCO3Powder preparation method |
| CN110093069A (en) * | 2019-05-29 | 2019-08-06 | 晔重新材料科技（上海）有限公司 | Nano environmental protection multifunctional water-proof paint |
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| CN1189523C (en) * | 2002-05-31 | 2005-02-16 | 北京化工大学 | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate |
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| CN1986712A (en) * | 2005-12-22 | 2007-06-27 | 佛山市顺德区汉达精密电子科技有限公司 | Fingerprint-proof paint for galvanized steel plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504608A (en) * | 2011-10-20 | 2012-06-20 | 张家界恒亮新材料科技有限公司 | Preparation method of micronano level surface-modified ground limestone and product thereof |
| CN103305043A (en) * | 2013-06-17 | 2013-09-18 | 丹阳市佳美化工有限公司 | Special finishing paint for thermosetting acrylic hubs |
| CN105860786A (en) * | 2016-04-28 | 2016-08-17 | 安徽开林新材料股份有限公司 | Insulation type quick-drying alkyd-amine baking paint |
| CN108359274A (en) * | 2018-02-07 | 2018-08-03 | 广西大学 | Rosin derivative chelates calcium modified Nano or lightweight CaCO3Powder preparation method |
| CN110093069A (en) * | 2019-05-29 | 2019-08-06 | 晔重新材料科技（上海）有限公司 | Nano environmental protection multifunctional water-proof paint |
| CN112144285A (en) * | 2020-09-27 | 2020-12-29 | 江苏利田科技股份有限公司 | EB (Epstein-Barr) curing textile size and preparation method and application thereof |
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| CN101469245B (en) | 2012-03-28 |
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