CN101469245B - Coating composition and method of preparing the same - Google Patents
Coating composition and method of preparing the same Download PDFInfo
- Publication number
- CN101469245B CN101469245B CN2007103013747A CN200710301374A CN101469245B CN 101469245 B CN101469245 B CN 101469245B CN 2007103013747 A CN2007103013747 A CN 2007103013747A CN 200710301374 A CN200710301374 A CN 200710301374A CN 101469245 B CN101469245 B CN 101469245B
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- weight
- coating composition
- monomer
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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 organic solvent type coating of having a white phase adopts white titanium pigment as its pigment.Because white titanium pigment 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 white titanium pigment content height in the coating causes, thereby the impact resistance of paint film layer is reduced.In addition, the price of white titanium pigment is high, and is 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 white titanium pigment in a large number, reduces the base-material adhesive consumption simultaneously, reduces cost remarkable in economical benefits significantly.Therefore, being applied in the coating nano-calcium carbonate 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 Triple Pressed Stearic Acid and its esters mostly, is applied in the coating, has following defective: particle surface energy is high, is in the thermodynamic instability state, very easily reunites; Dispersing property in organic medium is also bad, is prone to form 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 SE (PVC), Vestolen PP 7052 (the PP)/Vilaterm plastics such as (PE); At coating industry, then mainly concentrate on a building type 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 white titanium pigments that use and cause resistant impact property difference and nano-calcium carbonate to be used for the shortcoming that organic solvent type coating is prone to take place reunion, 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 said 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, When mixing, also add modified nano calcium carbonate, said modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer.
In the said 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 said 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 is that interlude couples together with thermosetting resin with carboxylic acrylic ester polymer just, and nano-calcium carbonate is also just wrapped up by the thermosetting resin molecule, and 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 white titanium pigment is that the amine baking varnish of pigment is compared, and the impact resistance of coating composition of the present invention is excellent, 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 said 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, be benchmark with the gross weight of this coating composition; The content of said thermosetting resin can be 15-50 weight %, and the content of said aminoresin can be 5-30 weight %, and the content of said filler can be 2-25 weight %; The content of said solvent can be 10-50 weight %; The content of said auxiliary agent can be 0-6 weight %, is preferably 0.2-5 weight %, and the content of said modified nano calcium carbonate can be 8-40 weight %.
Wherein, said nano-calcium carbonate can be traditional nano-calcium carbonate with Triple Pressed Stearic Acid or resinous acid and their salt coating processing, also can be the nano-calcium carbonate that uncoated is handled.
Said carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomers 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; Said acrylate monomer is selected from methyl acrylate, ethyl propenoate, n-butyl acrylate, one or more in NSC 20949, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate and the glycidyl acrylate; Said methacrylate monomers is selected from TEB 3K, Jia Jibingxisuanyizhi, n-BMA, one or more in N-Hexyl methacrylate, vinylformic acid n-octyl, methylacrylic acid laurate, methylacrylic acid 18 carbon esters, methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, SY-Monomer G and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
Number-average molecular weight to said carboxylic acrylic ester polymer does not have special qualification, and under the preferable case, the number-average molecular weight of said carboxylic acrylic ester polymer is 5000-25000.In above-mentioned preferred molecular weight range, said carboxylic acrylic ester polymer easy and coating resin chain generation molecular attraction or winding, and easily by organic solvent dissolution.
Acid number to said carboxylic acrylic ester polymer does not have special qualification, 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, said 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.
Said carboxylic acrylic ester polymer can carry out copolymerization with above-mentioned monomer through the polymerization method of routine and make, and also can be commercially available.
Do not limit each the monomeric mol ratio that forms said carboxylic acrylic ester polymer is special; 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 said modified nano calcium carbonate, do not limit the content of carboxylic acrylic ester polymer is special.Under the preferable case, be benchmark with the nano-calcium carbonate of 100 weight parts, the content of said carboxylic acrylic ester polymer is the 2-20 weight part.
Said thermosetting resin can be used for the thermosetting resin of organic solvent type coating for any routine; The present invention is not special to be 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 FS-2050, the FS2970 of CY430, CY468 and the modest chemical company of moral of DSM N. V., 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.
Said solvent can be this area any organic solvent commonly used; For example, can be in toluene, ETHYLE ACETATE, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, YLENE, hexone, acetone, methylethylketone, butyl glycol ether, the Ucar 35 butyl ether one or more.
Said 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 special to be 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 first promise BM-5901 of company and the L-127 of DIC company, the L-117.
Said filler is this area filler commonly used, mainly plays filling effect, can reduce the cost of coating simultaneously, can be selected from talcum powder, permanent white, weight matter lime carbonate, kaolin, mica powder and the magnesiumcarbonate one or more.
Said auxiliary agent can comprise dispersion agent, and the selectivity flow agent and the anti-settling agent that contain.The kind of said 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, When mixing, also add modified nano calcium carbonate, said 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, and is benchmark with the gross weight of this coating composition, and the content of said thermosetting resin is 15-50 weight %; The content of said aminoresin is 5-30 weight %; The content of said filler is 2-25 weight %, and the content of said auxiliary agent is 0-6 weight %, is preferably 0.2-5 weight %; The content of said solvent is 10-50 weight %, and the content of said modified nano calcium carbonate is 8-40 weight %.
Said modified nano calcium carbonate contacts 5-60 minute and makes through 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 said carboxylic acrylic ester polymer is the 2-20 weight part.
Said nano-calcium carbonate can be traditional nano-calcium carbonate with Triple Pressed Stearic Acid or resinous acid and their salt coating processing, also can be the nano-calcium carbonate that uncoated is handled.
Said carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomers 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; Said acrylate monomer is selected from methyl acrylate, ethyl propenoate, n-butyl acrylate, one or more in NSC 20949, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate and the glycidyl acrylate; Said methacrylate monomers is selected from TEB 3K, Jia Jibingxisuanyizhi, n-BMA, one or more in N-Hexyl methacrylate, vinylformic acid n-octyl, methylacrylic acid laurate, methylacrylic acid 18 carbon esters, methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, SY-Monomer G and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
Number-average molecular weight to said carboxylic acrylic ester polymer does not have special qualification, and under the preferable case, the number-average molecular weight of said carboxylic acrylic ester polymer is 5000-25000.In above-mentioned preferred molecular weight range, said carboxylic acrylic ester polymer easy and coating resin chain generation molecular attraction or winding, and easily by organic solvent dissolution.
Acid number to said carboxylic acrylic ester polymer does not have special qualification, 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, said 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.
Said carboxylic acrylic ester polymer can above-mentioned monomer be carried out polymerization through the polymerization method of routine or copolymerization makes, and also can be commercially available.
Do not limit each the monomeric mol ratio that forms said carboxylic acrylic ester polymer is special; 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.
Said filler is this area filler commonly used, mainly plays filling effect, can reduce the cost of coating simultaneously, can be selected from talcum powder, permanent white, weight matter lime carbonate, kaolin, mica powder and the magnesiumcarbonate one or more.
Said solvent can be this area any organic solvent commonly used; For example, can be in toluene, ETHYLE ACETATE, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, YLENE, hexone, acetone, methylethylketone, butyl glycol ether, the Ucar 35 butyl ether one or more.
Under the preferable case, practical implementation step of the present invention is following:
(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) is 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 through embodiment.
Embodiment 1
Present embodiment is used for explaining 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 TEB 3Ks, 30 gram NSC 20956s, 3 gram Hydroxyethyl acrylates, 0.5 gram BPO (concentration 71%) and 0.5 gram isopropyl benzene hydroperoxide (concentration 80%) thorough mixing, and filter.48 gram YLENE and 45 gram butanols are mixed as solvent, under nitrogen protection, stir and be warming up to 115 ℃, under this temperature, above-mentioned filtrating 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 14.8Pas, 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 "), the acid number of solution is 48.3 milligrams of KOH/ grams.Adopt GPC (GPC) determining molecular weight about 12000.
(2) get nano-calcium carbonate (median size is 60 nanometers for Guangdong Enping Gavin Chemical Industrial Enterprise Co., Ltd., CC-R) 100 weight parts and 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, mixed at high speed (1200 rev/mins) 25 minutes; And, be cooled to room temperature (23 ℃) with mixed slurry taking-up.
(3) get mixture 18 weight parts, saturated polyester (DSM N. V. that step (2) obtains; 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 permanent white, 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 YLENE 5.6 weight parts; (the mechanical ltd of the diligent industry in Jiangsu in a mixing bowl TSO.75), was mixed 25 minutes with 600 rev/mins at 25 ℃ to join high speed dispersor;
(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 explaining 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 methylacrylic acids, 4.3 gram acrylic amides, 25 gram YLENE and 20 gram butanols; B component: 12 gram vinylbenzene, 11.5 gram ethyl propenoates, 15 gram methylacrylic acids, 1.5 gram Diisopropyl azodicarboxylates and 0.8 gram peroxo-uncle butyryl.
Be heated to 90 ℃ to the A component, in 30 minutes, drip the B component to enter then, 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, and temperature is 100 ℃, mixed at high speed 15 minutes.The coating composition note that obtains is made A2.
Embodiment 3
Present embodiment is used for explaining 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 TEB 3Ks, 30 gram NSC 20956s, 3 gram Hydroxyethyl acrylates, 0.5 gram BPO (concentration 71%) and 0.5 gram isopropyl benzene hydroperoxide (concentration 80%) thorough mixing, and filter.48 gram YLENE and 45 gram butanols are mixed as solvent, under nitrogen protection, stir and be warming up to 120 ℃, under this temperature, above-mentioned filtrating 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, and temperature is 120 ℃, mixed at high speed 10 minutes.The coating composition note that obtains is made A3.
Embodiment 4
Present embodiment is used to explain 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, YLENE 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 explaining 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 white titanium pigment (U.S. outstanding company of Australia section, the mixture that CR826) replaces said embodiment 1 step (2) to obtain.The coating composition note that obtains is made C1.
Comparative Examples 2
This Comparative Examples is used for explaining 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 said 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 explain that prior art is used as the preparation of the coating composition of priming paint.
White titanium pigment (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, YLENE 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 electrocoating paint (Northwest, Hunan company cathode electrodip painting, HB-2000) electrophoresis 2-3 minute, voltage was 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 composition 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 sticking power and impact resistance and test.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 above that.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 above that.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 that with 1000g ± 1g weight vertical drop paint film destructive height (cm of unit) is an 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 can find out, use be made into nano paint with the contacted nano-calcium carbonate instead of titanium white powder of carboxylic acrylic ester polymer after, 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 have excellent in impact resistance can, outward appearance is good, and it is constant to keep the ply adhesion of paint film layer.
Claims (12)
1. 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; Said modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer, and the acid number of said carboxylic acrylic ester polymer is a 20-160 milligram KOH/ gram; Gross weight with this coating composition is a benchmark; The content of said thermosetting resin is 15-50 weight %; The content of said aminoresin is 5-30 weight %, and the content of said filler is 2-25 weight %, and the content of said auxiliary agent is 0.2-5 weight %; The content of said solvent is 10-50 weight %, and the content of said modified nano calcium carbonate is 8-40 weight %.
2. 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, is benchmark with the nano-calcium carbonate of 100 weight parts, and the consumption of said carboxylic acrylic ester polymer is the 2-20 weight part.
3. coating composition according to claim 1 and 2; Wherein, Said carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomers 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.
4. coating composition according to claim 3, wherein, the number-average molecular weight of said carboxylic acrylic ester polymer is 5000-25000.
5. coating composition according to claim 3; Wherein, said acrylate monomer is selected from one or more in methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate and the glycidyl acrylate; Said methacrylate monomers is selected from one or more in TEB 3K, Jia Jibingxisuanyizhi, n-BMA, N-Hexyl methacrylate, vinylformic acid n-octyl, methylacrylic acid laurate, methylacrylic acid 18 carbon esters, methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, SY-Monomer G and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
6. coating composition according to claim 1, wherein, said thermosetting resin is one or more of hydroxyl acrylic resin, thermosetting acrylate resin, saturated polyester resin and Synolac; Said solvent is selected from one or more in toluene, ETHYLE ACETATE, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, YLENE, hexone, acetone, methylethylketone, butyl glycol ether and the Ucar 35 butyl ether.
7. the preparation method of the said coating composition of claim 1; This method comprises thermosetting resin, aminoresin, filler and solvent; It is characterized in that; When mixing, also add modified nano calcium carbonate, said modified nano calcium carbonate is the product that nano-calcium carbonate contacts with carboxylic acrylic ester polymer, and the acid number of said carboxylic acrylic ester polymer is a 20-160 milligram KOH/ gram; 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 %.
8. method according to claim 7; Wherein, The temperature that nano-calcium carbonate contacts with carboxylic acrylic ester polymer is 50-150 ℃; Be 5-60 minute duration of contact, is benchmark with the nano-calcium carbonate of 100 weight parts, and the consumption of said carboxylic acrylic ester polymer is the 2-20 weight part.
9. according to claim 7 or 8 described methods; Wherein, Said carboxylic acrylic ester polymer contains the structural unit of acrylate monomer and/or methacrylate monomers 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.
10. method according to claim 9, wherein, the number-average molecular weight of said carboxylic acrylic ester polymer is 5000-25000.
11. method according to claim 9; Wherein, said acrylate monomer is selected from one or more in methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949, vinylformic acid n-octyl, ethyl acrylate, senecioate-hydroxyl ethyl ester, senecioate-hydroxypropyl acrylate, the glycidyl acrylate; Said methacrylate monomers is selected from one or more in TEB 3K, Jia Jibingxisuanyizhi, n-BMA, N-Hexyl methacrylate, vinylformic acid n-octyl, methylacrylic acid laurate, methylacrylic acid 18 carbon esters, methylacrylic acid-beta-hydroxy ethyl ester, methylacrylic acid-β-hydroxypropyl acrylate, SY-Monomer G and the trimethylammonium vinylformic acid trishydroxymethyl propyl ester.
12. method according to claim 7, wherein, said blended temperature is 10-35 ℃, and the blended time is 20-40 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007103013747A CN101469245B (en) | 2007-12-25 | 2007-12-25 | Coating composition and method of preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007103013747A CN101469245B (en) | 2007-12-25 | 2007-12-25 | Coating composition and method of preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101469245A CN101469245A (en) | 2009-07-01 |
| CN101469245B true CN101469245B (en) | 2012-03-28 |
Family
ID=40827060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007103013747A Expired - Fee Related CN101469245B (en) | 2007-12-25 | 2007-12-25 | Coating composition and method of preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101469245B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112144285B (en) * | 2020-09-27 | 2023-04-07 | 江苏利田科技有限公司 | EB (Epstein-Barr) curing textile size and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1462773A (en) * | 2002-05-31 | 2003-12-24 | 北京化工大学 | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate |
| CN1473898A (en) * | 2003-08-08 | 2004-02-11 | 中国化工建设总公司常州涂料化工研究 | Finish for pre-coating coiled material |
| CN1807519A (en) * | 2006-01-27 | 2006-07-26 | 华南理工大学 | Modified nanometer calcium carbonate and method for making same and uses |
| 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 |
-
2007
- 2007-12-25 CN CN2007103013747A patent/CN101469245B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1462773A (en) * | 2002-05-31 | 2003-12-24 | 北京化工大学 | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate |
| CN1473898A (en) * | 2003-08-08 | 2004-02-11 | 中国化工建设总公司常州涂料化工研究 | Finish for pre-coating coiled material |
| 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 |
| CN1807519A (en) * | 2006-01-27 | 2006-07-26 | 华南理工大学 | Modified nanometer calcium carbonate and method for making same and uses |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101469245A (en) | 2009-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4753829A (en) | Opalescent automotive paint compositions containing microtitanium dioxide pigment | |
| CN101469245B (en) | Coating composition and method of preparing the same | |
| CN101613434B (en) | Alcohol soluble polyacrylate resin and preparation method and application thereof | |
| JP4942294B2 (en) | Metallic pigment and paint containing the same | |
| JPWO2006057241A1 (en) | COMPOSITE POWDER COATING, ITS MANUFACTURING METHOD, AND POWDER COATING METHOD | |
| CN1132773A (en) | Pacification of optically variable pigments for use in waterborn coating compositions | |
| DE10361437A1 (en) | Metal pigments with crosslinkable binder coating, coating composition, process for the preparation of the coated metal pigments and their use | |
| CN102002306B (en) | Water-based precoated coiled material coating primer and preparation method thereof | |
| DE102005032346A1 (en) | Pearlescent pigments with crosslinkable binder coating, coating composition, process for the preparation of the coated pearlescent pigments and their use | |
| CN101203577A (en) | Process of preparation of specific color effect pigments | |
| CN102086332B (en) | Coating composition for polyolefin substrate and coating and product thereof | |
| CN102241932B (en) | Colorful paint | |
| CN104726014A (en) | Ultraviolet curing coating raw material and coating prepared from same | |
| CN103911057B (en) | A kind of aqueous covercoat coating for three painting one bakings and preparation method thereof | |
| CN109535909A (en) | Aqueous anti-settling metallic paint and preparation method thereof | |
| CN1626586A (en) | Water born paint in use for plastic painting dressing and preparation method | |
| JPH08170034A (en) | Metallic coating composition and formation of film | |
| CN115895371A (en) | Anti-fingerprint antibacterial spray paint composition | |
| JP2829813B2 (en) | Metallic coating composition and method for forming metallic coating film | |
| JPS63317695A (en) | Coating method | |
| KR100678792B1 (en) | Powder coating compositions | |
| JPH0689279B2 (en) | Super jet black coating composition | |
| CN102796452A (en) | Antifouling self-cleaning nano functional paint and preparation method thereof | |
| CN102181216B (en) | Apple green paint | |
| JPH101625A (en) | Coating material composition, formation of coated film and coated material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191225 Address after: 314411 Jianshe East Road, Guodian, Yanguan Town, Haining City, Jiaxing City, Zhejiang Province Patentee after: Haining Yanguan Industrial Investment Co., Ltd Address before: 518119 BYD Industrial Park, Yanan Road, Kwai Chung Town, Longgang District, Guangdong, Shenzhen Patentee before: Biyadi Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120328 Termination date: 20191225 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |