CN1396224A - Solvent-type high-solid paint containing rheologically modified resin - Google Patents
Solvent-type high-solid paint containing rheologically modified resin Download PDFInfo
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Abstract
A solvent-type high-solid paint containing rheologically modifying resin features that its main filming substance is prepared from base resin (30-65%), cross-linking resin (15-40%) and rheologically modifying resin (20-40%) which is prepared from the solution of diisocyanate and the solution of amine compound through adding them to the base resin, reacting at 0-80 deg.C for 0.5-4 hr while stirring, and holding the temp. for 0.5-1 hr. The paint containing this modifying resin has advantages of thixstropy, and uniform coated layer.
Description
Technical field
The present invention relates to a kind of solvent-borne type high solid coating that contains rheology modified resin.
Background technology
In recent years, people's environmental consciousness improves constantly, and coatings industry circle more and more tends to use the lower coating of organic volatile (being called for short VOC), as high solid coating, water-borne coatings, powder coating, radiation curable coating etc.For be coated with in related in vehicle and the general industry application and the finish paint system to use maximum be the solvent-borne type high solid coating, it is ornamental at paint film appearance, mechanical property and have many advantages of not replacing at the aspects such as use continuity of coating material production, coating application equipment.The film forming matter molecular weight and the viscosity of high solid coating are much smaller than the film forming matter of common coating of the same type, during construction, only need to add a small amount of solvent and just can reach working viscosity, therefore evaporateing into airborne organism in the coating film process significantly reduces, pollution on the environment also significantly reduces, and has also reduced simultaneously energy consumption and to the infringement of human body.But,, in construction and film process, easily produce the sagging phenomenon because solvent is low.The method of control sagging mainly is to solve by adding anti-sagging agent at present.The anti-sagging agent that is adopted in traditional solvent based coating such as organic wilkinite, gas phase carbon dioxide, hydrogenated castor oil, polyethylene wax etc., because it is they are bigger to the influence of construction solids constituent and coating film gloss, inapplicable in the solvent-borne type high solid coating.Be usually used in the organic microgel of anti-sagging agent, nonaqueous dispersion, the little glue of alkaline sulfoacid calcium of solvent-borne type high solid coating etc., but their package stability is not so good, still need in use and be distributed in the binder resin once more, if not only troublesome poeration but also disperse badly also has certain influence to the outward appearance (as levelling property, gloss) and the mechanical property of filming.For this reason, two kinds of resins that contain sagging control agents have been developed abroad again, the first is in solvent, the compound that will contain polyisocyanates makes the polyureas solid particulate with monobasic that contains primary amine or the reaction of binary amine compound, then this solid particle melting is scattered in the resin that obtains containing sagging control agents in the binder resin.But in preparation process, because primary amine and the reaction of isocyano in solvent are too fast, even control is reaction at low temperatures, still be difficult to the particle diameter of the polyureas make, like this, when making its fusion be scattered in binder resin under comparatively high temps, the fineness of resin that contains sagging control agents is often not ideal; It two is respectively with aminated compounds and binder resin, and solidifying agent mixes with polyisocyanate compound, then these two kinds of mixtures is mixed by vigorous stirring, makes the reaction of amine and polyisocyanates make the resin that contains sagging control agents.Though adopt this method that speed of response is slightly slowed down, but still wayward, thereby gained contains the resin of sagging control agents, its fineness and thixotropic property are often unstable.Therefore, still can not satisfy the demand with the appearance of film (as levelling property, gloss) and the mechanical property of the solvent-borne type high solid coating of the above-mentioned this resin preparation that contains sagging control agents.
Summary of the invention
The objective of the invention is to, a kind of solvent-borne type high solid coating that contains rheology modified resin is provided, this coating application performance is good, no sag.Rheology modified resin contained in the coating prepares easily, easy to use, do not influence the outward appearance and the mechanical property of filming.
Realize the technical scheme of the object of the invention: a kind of solvent-borne type high solid coating that contains rheology modified resin, form by main film forming matter, auxiliary film forming matter, color stuffing and auxiliary agent, it is characterized in that:
A, main film forming matter are made up of binder resin, cross-linked resin and rheology modified resin, and in resin solid weight, binder resin accounts for 30～65%, and cross-linked resin accounts for 15～40%, and rheology modified resin accounts for 20～40%;
B, auxiliary film forming matter consumption are 0～40% of main film forming matter total weight of solids;
C, color stuffing are (0～1) with main film forming matter and auxiliary film forming matter total weight of solids ratio: (1～3);
D, auxiliary dosage are 0.2～5% of main film forming matter and auxiliary film forming matter total weight of solids;
E, described rheology modified resin are the resins that contains the urea key, and this resin has thixotropic behavior, measure viscosity at 25 ℃ with the Brookfield cone-and-plate viscometer, are that shearing rate is 1s at low-shearing power
-1The time, viscosity is 10000～50000mPas, is that shearing rate is 100s at high shear force
-1The time, viscosity is 300～2000mPas, and the full-bodied viscosity recovery time that the low viscosity under above-mentioned high shear force returns under the low-shearing power is 60～200s, and the fineness of this rheology modified resin is less than 5 μ m;
F, described rheology modified resin are in the presence of the resin identical with binder resin, the solution of diisocyanate cpd and the solution of aminated compounds, mix, react 0.5～4h while stirring at 0～80 ℃, and then be incubated that 0.5～1h makes, the solution of used diisocyanate cpd and the solution of aminated compounds, the equivalence ratio of its isocyano and primary amino is 0.5: 1～1.5: 1, its total weight of solids account for the rheology modified resin that is generated solid weight 2～8%;
G, grinding and also adding solvent during construction, its dosage is so that grind and construction is as the criterion.
In the above-mentioned coating, the binder resin in the described main film forming matter is a kind of with in Synolac, vibrin, acrylic resin, polyester polyol resin or the acrylic polyol resin of ordinary method preparation.
In the above-mentioned coating, described auxiliary film forming matter be with main film forming matter in binder resin other film-formable resins inequality.The resin that can be used as auxiliary film forming matter is Resins, epoxy, Nitro cellulose resin, ethyl cellulose resin, butyl cellulose resin or cellaburate resin.
In the above-mentioned coating, the cross-linked resin in the described main film forming matter is aminoresin of using always or the cross-linked resin that contains isocyanate compound.
In the above-mentioned coating, when preparing described rheology modified resin, the solution of used diisocyanate cpd is the vulcabond of choosing any one kind of them from aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate, the solution that forms with a kind of solvent in varsol, ketones solvent, esters solvent, ether solvent or the solvent of ether ester type; The solution of used aminated compounds, be from aliphatics amine, aromatic amine, alcamines or ether amine, to choose any one kind of them or the various kinds of amine compounds, the solution that forms with a kind of solvent in varsol, ketones solvent, esters solvent, alcoholic solvent, ether solvent or the solvent of ether ester type.
In the above-mentioned coating, aromatic diisocyanate as diisocyanate cpd is 2,4-Xylene Diisocyanate, 2,6-Xylene Diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate or tetramethylxylylene diisocyanate; Aliphatic diisocyanate as diisocyanate cpd is methylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or trimethylammonium hexamethylene diisocyanate; Alicyclic diisocyanate as diisocyanate cpd is isophorone diisocyanate, dicyclohexyl methane diisocyanate or hexahydrotoluene vulcabond.Aliphatics amine as aminated compounds is benzylamine, ethamine, Tri N-Propyl Amine, secondary propylamine, butylamine, sec-butylamine, TERTIARY BUTYL AMINE, n-amylamine, Alpha-Methyl butylamine, α-ethyl propylamine, β-ethyl butyl amine, hexylamine, octylame, decyl amine, hexamethylene-diamine, hexahydroaniline or stearylamide; Aromatic amine as aminated compounds is an aniline; Hydramine as aminated compounds is a thanomin; As amine bonded ether amine is 4-Methoxybenzylamine, methoxy propanamine, 3,4-dimethoxyphenyl ethyl amine, 2,5-dimethoxyaniline, chaff amine or tetrahydrofurfuryl amine.Described varsol is hexane, hexanaphthene, octane, oil mixed solvent, toluene, dimethylbenzene, 100#, 150# or 200# high boiling point aromatic hydrocarbons mixed solvent; Ketones solvent is acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl amylketone, pimelinketone, diacetone alcohol or isophorone; Esters solvent is vinyl acetic monomer, propyl acetate, isobutyl acetate, isoamyl acetate, the DBE of Du Pont, first promise DME or first all DME-1 high boiling point mixed ester kind solvents; Alcoholic solvent is ethanol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, isooctyl alcohol or phenylcarbinol; Ether solvent is ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monobutyl ether; Solvent of ether ester type is ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate.
Above-mentioned coating can be used as middle japanning, true qualities finish paint and metallized finish.
In the above-mentioned coating, described color stuffing is the general inorganic color stuffing of solvent-borne type high solid coating, pigment dyestuff or effect pigment.
In the above-mentioned coating, described auxiliary agent is one or more in wetting agent, anticrater agent, flow agent, siccative, anti-skinning agent, matting agent, slip(ping)agent, slipproofing agent, anti-settling agent, photostabilizer, defoamer, static inhibitor, the conductive agent.
Technique effect of the present invention: 1. in the main film forming matter of coating of the present invention, because the rheology modified resin that contains the urea key is arranged, this resin utilizes the hydrogen bond action power of the interlaminar resin of this urea key and solvent and film forming matter, forms a kind of reversible network structure.When paint spay-coating, shearing force increases, and this network structure is destroyed, and dope viscosity reduces, and is convenient to construction; After applying, because shearing force disappears, above-mentioned network structure can restore to the original state again, the very fast increase of viscosity.So just prevent that high solid coating from easily producing the disadvantage of sagging.2. employed rheology modified resin in the technical solution of the present invention, in the preparation, because diisocyanate cpd and aminated compounds all make solution in advance in appropriate solvent before reaction, when above-mentioned two kinds of compounds reacted, the temperature of reaction of control was lower, the reaction while mixing, and there be the resin identical to exist with binder resin, therefore, controlled the speed of response between isocyano and the primary amino well, resins is easy.In addition, reaction process is another directly under agitation carries out, and therefore, the fineness that can guarantee the rheology modified resin of gained is less than 5 μ m.Employing contains the high solid coating of this rheology modified resin, and its appearance of film and mechanical property all are not subjected to the influence of used rheology modified resin; 3. coating process for preparation of the present invention is simple, and rheology modified resin is made the lacquer method with adopting routine mixing of other components, does not need other specific installations.
Embodiment
Below in conjunction with example the present invention is further described in detail, but is not limited to this.
Following viscosity number is 25 ℃ and adopts the Brookfield cone-and-plate viscometer to record.
A, raw material
(1) preparation of binder resin
1, vibrin (PE-1)
In the four-hole bottle that stirring, thermometer, water trap, fractional column, inert gas entrance are housed, add TriMethylolPropane(TMP) 56.9g, hydroxypivalic acid neopentyl glycol monoesters 84.4g, phthalic anhydride 67.0g, hexanodioic acid 52.7g, tertiary carbonic acid glycidyl ester (Cardura E-10, shell chemical) 21.6g, phenylformic acid 21.9g, dimethylbenzene 45g.Logical rare gas element; under its protection, slowly heat up; add Dibutyltin oxide 0.1g to 120 ℃; continue the temperature rising reflux reaction, be warming up to 220 ℃ with 4～5 hours, and under this temperature, be incubated 2～3 hours; react to acid value be terminal point less than 10mgKOH/g; be cooled to vacuumize below 180 ℃ and remove residuary water and small molecular alcohol, continue to be cooled to below 140 ℃, add dimethylbenzene 80g, N-BUTYL ACETATE 30g.The gained resin solid content: 70%, viscosity (shearing rate 60s
-1): 1024mPas.
2, vibrin (PE-2)
In the four-hole bottle that stirring, thermometer, water trap, fractional column, inert gas entrance are housed, add C
9Lipid acid 50g, C
12-18Lipid acid 70.8g, TriMethylolPropane(TMP) 179.2g, neopentyl glycol 37.6g, m-phthalic acid 212.4g, hexanodioic acid 20.8g, phenylformic acid 32.8g, dimethylbenzene 90g.Logical rare gas element; under its protection, slowly heat up; add Dibutyltin oxide 0.2g to 120 ℃; continue the temperature rising reflux reaction, be warming up to 220 ℃ with 4～5 hours, and under this temperature, be incubated 2～3 hours; react to acid value be terminal point less than 15mgKOH/g; be cooled to vacuumize below 180 ℃ and remove residuary water and small molecular alcohol, continue to be cooled to below 140 ℃, add dimethylbenzene 225g.The gained resin solid content: 70%, viscosity (shearing rate 60s
-1): 2391mPas.
3, Synolac (CA-1)
In the four-hole bottle that stirring, thermometer, water trap, fractional column, inert gas entrance are housed, add Viscotrol C 63.66g, TriMethylolPropane(TMP) 66.45g, neopentyl glycol 41.42g, tetrahydrophthalic anhydride 117.03g, hexanodioic acid 12.51g, dimethylbenzene 45g.Logical rare gas element; under its protection, slowly heat up; add Dibutyltin oxide 0.1g to 120 ℃; continue the temperature rising reflux reaction, be warming up to 220 ℃ with 4～5 hours, and under this temperature, be incubated 2～3 hours; react to acid value be terminal point less than 15mgKOH/g; be cooled to vacuumize below 180 ℃ and remove residuary water and small molecular alcohol, continue to be cooled to below 140 ℃, add dimethylbenzene 100g.The gained resin solid content: 70%, viscosity (shearing rate 60s
-1): 2857mPas.
4, acrylic resin (B-1)
Stirring is being housed, thermometer, dropping funnel, prolong, in the four-hole bottle of inert gas entrance, add Cardura E-1050g, 1000# high boiling solvent 30g, dimethylbenzene 20g, logical rare gas element, after being warming up to backflow (about 175 ℃), to drip monomer mixture solution (the butyl acrylate 100.43g prepare in advance in 4～5 hours, vinylformic acid 18.72g, Propylene glycol monoacrylate 20.36g, vinylbenzene 48.39g, methyl methacrylate 12.1g, di-tert-butyl peroxide ether 3.2g), temperature of reaction remains between 170～180 ℃ during this time, after dripping, continued insulation reaction 1 hour, add initiator solution (the di-tert-butyl peroxide ether 0.8g for preparing in advance, 1000# solvent 10g), after having added, insulation reaction 2～3 hours, make monomer reaction complete, be cooled to below 140 ℃, add dimethylbenzene 45g.The gained resin solid content: 70%, viscosity (shearing rate 60s
-1): 3644mPas.
(2) cross-linked resin
Select Xinhua Resin Factory, Shanghai's system butyl ether aminoresin for use, solid content 60%, the trade mark are 582-2.Certainly also can select other all kinds of butyl etherization, methyl-etherified and the complex etherified aminoresin that contains for use, the cross-linked resin (for example the N-75 of Beyer Co., Ltd's system, Desmodur N, Desmodur RC, Desmodur RU or Desmodur TT) that perhaps contains isocyanate compound.
(3) preparation of rheology modified resin
1、RCRPE-1
In a suitable vessel, the PE-1 binder resin 109.29g that adding makes by above-mentioned binder resin preparation method, room temperature fully stirs down the amine aqueous solution (benzylamine 3.2g, dimethylbenzene 19.47g) that adding prepares in advance, after fully stirring evenly, in 1h, add hexamethylene diisocyanate (HDI) solution (HDI2.8g, dimethylbenzene 15.24g) for preparing in advance, continue to stir insulation reaction 0.5h then and make oyster white thickness resin, its solid content 55%.As shearing rate 1s
-1When (low-shearing power), viscosity is 15728mPas, shearing rate 100s
-1When (high shear force), viscosity is 589.8mPas.Viscosity recovery time 65s, resin fineness 4 μ m.The equivalence ratio 1: 0.9 of used isocyano and primary amino during preparation; HDI and benzylamine account for 7.27% (by solid) in the rheology modified resin RCRPE-1 of gained.
2、RCRPE-2
In a suitable containers, the PE-2 binder resin 122.14g that adding makes by above-mentioned binder resin preparation method, room temperature fully stirs down, add the amine aqueous solution (benzylamine 2.4g, dimethylbenzene 12.85g) for preparing in advance, after fully stirring evenly, in 1h, add the HDI solution (HDI2.1g, dimethylbenzene 10.51g) for preparing in advance, continue then to stir insulation reaction 0.5 hour, make oyster white thickness resin, its solid content 60%.When shearing rate is 1s
-1When (low-shearing power), viscosity is 11010mPas, and shearing rate is 100s
-1When (high shear force), viscosity is 668.4mPas.Viscosity recovery time 70s, resin fineness 5 μ m.The equivalence ratio of used isocyano and primary amino is 1: 0.9 during preparation; HDI and benzylamine account for 5% (pressing solid weight meter) in the rheology modified resin RCRPE-2 of gained.
3、RCRCA-1
In a suitable vessel, the binder resin CA-183.43g that adding makes by above-mentioned binder resin preparation method, room temperature fully stirs down the amine aqueous solution (benzylamine 1.12g, aniline 0.49g, dimethylbenzene 9g) that adding prepares in advance, after fully stirring evenly, in 0.5h, add the HDI solution (HDI1.47g, dimethylbenzene 7.16g) for preparing in advance, continue to stir insulation reaction 1h, obtain white thickness resin, its solid content 60%.When shearing rate is 1s
-1The time, viscosity is 11796mPas, shearing rate is 100s
-1The time, viscosity is 660.6mPas.The viscosity recovery time is 65s, resin fineness 4 μ m.The equivalence ratio of used isocyano and primary amino is 1: 0.9 during preparation, and HDI and benzylamine, aniline account for 5% (in solid) in the rheology modified resin RCRCA-1 of gained.
4、RCRB-1
In a suitable vessel, the binder resin B-1 82.51g that adding makes by above-mentioned binder resin preparation method, room temperature fully stirs down the amine aqueous solution (benzylamine 1.11g, aniline 0.48g, dimethylbenzene 8g) that adding prepares in advance, fully stir evenly the back and in 0.5 hour, add the HDI solution (HDI1.45g, dimethylbenzene 7.78g) for preparing in advance, continue insulation reaction 1h then, obtain oyster white thickness resin, its solid content is 60%.When shearing rate is 1s
-1When (low-shearing power), viscosity is 14942mPas, and shearing rate is 100s
-1When (high shear force), viscosity is 1376mPas.Viscosity recovery time 75s.Resin fineness 5 μ m.The equivalence ratio of used isocyano and primary amino is 1: 0.9 during preparation, and HDI and benzylamine, aniline account for 5% (with solid weight meter) in the rheology modified resin RCRB-1 of gained.
(4) auxiliary film forming matter
Select kind according to actual needs from Resins, epoxy, Nitro cellulose resin, ethyl cellulose resin, butyl cellulose resin or cellaburate resin, used resin is that commercially available product comprises imported product.
(5) color stuffing
Select from following color stuffing according to reality prescription needs:
Mineral dye comprises titanium white, carbon black, iron oxide yellow, red iron oxide, molybdenum red, medium chrome yellow medium yellow, light chrome yellow, ultramarine;
Effect pigment comprises pearly pigment, aluminium powder, copper powder;
Pigment dyestuff comprises azo class pigment, phthalocyanines, quinacridine ketone, isoindoline series pigments etc.
Filler comprises mineral fillers such as talcum powder, kaolin, process white, lime carbonate, aerosil, wilkinite.
(6) auxiliary agent
Determine auxiliary agent kind, the adjuvant used commercially available product (comprising imported product) that is according to actual needs.
B, formulation for coating material, preparation and performance
(1) example 1 (as middle japanning)
1, prescription sees Table 1
Table 1
Annotate: do not contain auxiliary film forming matter in a, the prescription;
| Coating composition | Consumption (g) |
| Main film forming matter binder resin CA-1, solid content 70% cross-linked resin 582-2, solid content 60% rheology modified resin RCRCA-1, solid content 60% | 45.00(45％) 35.00(30％) 29.17(25％) |
| Color stuffing titanium dioxide R-902 (E.I.Du Pont Company's system) talcum powder 1250 order kaolin 1250 order blanc fixes 1250 order bentonites 1250 orders | ????49.00 ????7.00 ????7.00 ????7.00 ????0.70 |
| Auxiliary agent flow agent EFKA-777 (EFKA corporate system) | ????0.28 |
Numeral in the b, table 1 bracket is in main film forming matter total weight of solids shared hundred
Mark;
In c, table 1 prescription, the ratio of color stuffing and main film forming matter is (to press solid weight at 50: 50
Meter);
In d, table 1 prescription, auxiliary dosage is 0.4% (pressing solid weight meter) of main film forming matter.
2, preparation
In sand mill, add whole color stuffings and part binder resin (42.86g) in the table 1, add an amount of dimethylbenzene (15g) again, fully grind with sand mill and to be dispersed to fineness≤20 μ m, add surplus binder resin, whole cross-linked resin, rheology modified resin and auxiliary agent again, dispersed with stirring evenly gets final product, and its solid content is 78.3%.
3, performance
The above-mentioned coating that makes (is coated with-4 glasss with the suitable solvent latting drown to working viscosity 18～22s, 25 ℃), be sprayed on the tinplate or steel plate with 400 order sand paperings, solidify 20min or 130 ℃ at 140 ℃ and solidify 30min, promptly get build and be 30～45 μ m in be coated with and film.This is filmed and tests by the method for GB regulation, and its result is as follows: the 60 ° of gloss 85% of filming, 0 grade of sticking power, shock strength 50kgcm, 1 grade of snappiness, pendulum-rocker hardness＞0.6.
With the paint spay-coating of this example 1 time, build is at 50 μ m sagging not still; And when not adding rheology modified resin, its dry film is existing sagging when 35 μ m.
(2) example 2 (as the true qualities finish paint)
1, prescription sees Table 2
Table 2
Annotate: do not contain auxiliary film forming matter in a, this prescription;
| Coating composition | Consumption (g) |
| Main film forming matter binder resin PE-2, solid content 70% cross-linked resin 582-2, solid content 60% rheology modified resin RCRPE-2, solid content 60% | ?83.57(45％) ?65.00(30％) ?54.17(25％) |
| Color stuffing titanium dioxide R-902 (E.I.Du Pont Company's system) aerosil R-972 (Degussa Corporation's system) | ????70.00 ????0.35 |
| Auxiliary agent flow agent BYK-320 (Bi Ke corporate system) | ????0.52 |
Numeral shared percentage in main film forming matter total weight of solids in b, table 2 bracket
Number;
In c, table 2 prescription, the ratio of color stuffing and main film forming matter is (to press solid weight at 35: 65
Meter);
In d, table 2 prescription, auxiliary dosage is 0.4% (pressing solid weight meter) of main film forming matter.
2, preparation
In sand mill, add whole color stuffings and part binder resin (42.86g) in the table 2, add an amount of dimethylbenzene (10g) again, be ground to fineness≤15 μ m with sand mill, add surplus binder resin, whole cross-linked resin, rheology modified resin and auxiliary agent again, dispersed with stirring evenly gets final product.The solid content of this coating is 73.4%.
3, performance
The above-mentioned coating that makes (is coated with-4 glasss with the suitable solvent latting drown to working viscosity 18～22s, 25 ℃), be sprayed on the tinplate or steel plate with 400 order sand paperings, perhaps be sprayed on example 1 in film on, solidify 20min at 140 ℃, or 130 ℃ of curing 30min, the white finish paint that promptly obtains build and be 30～45 μ m is filmed, this is filmed and tests by the method for GB regulation, its result is as follows: 60 ° of gloss＞95% of filming, 0 grade of sticking power, shock strength 50kgcm, 1 grade of snappiness, pendulum-rocker hardness＞0.7.
With the paint spay-coating of this example 2 time, its build is in 55 μ m still not sagging, also disadvantage such as free of pinholes, foaming; And when not adding rheology modified resin, build is in the existing sagging phenomenon of 35 μ m.
(3) example 3 (, forming) by flash metal luster priming paint and coating varnish as metallized finish
1, prescription
1. flash metal luster priming paint sees Table 3
Table 3
Annotate: the numeral in a, table 3 bracket is shared percentage ratio in main film forming matter total weight of solids; In b, table 3 prescription, color stuffing is 1: 3 (pressing solid weight meter) with the ratio of main film forming matter and auxiliary film forming matter; In c, table 3 prescription, auxiliary dosage is 0.42% (pressing solid weight meter) of main film forming matter and auxiliary film forming matter; In d, table 3 prescription, auxiliary film forming matter consumption is 25% of a main film forming matter total weight of solids.
| Coating composition | Consumption (g) |
| Main film forming matter binder resin PE-1, solid content 70% cross-linked resin 582-2, solid content 60% rheology modified resin RCRPE-1, solid content 55% | ?2.57(37.50％) ?2.00(37.49％) ?3.27(25.01％) |
| Auxiliary film forming matter cellaburate resin CAB381-2 (solid content 15%, Yi Shi Man system) | ????8 |
| Color stuffing aluminium powder 601 (EKA AB's system) | ????2.00 |
| Auxiliary agent flow agent BYK-320 (Bi Ke corporate system) | ????0.02 |
2. coating varnish sees Table 4
Table 4
Annotate: do not contain auxiliary film forming matter in a, this prescription;
| Coating composition | Consumption (g) |
| Main film forming matter binder resin B-1, solid content 70% cross-linked resin 582-2, solid content 60% rheology modified resin RCRB-1, solid content 60% | ?57.14(40％) ?58.33(35％) ?41.67(25％) |
| Auxiliary agent flow agent BYK-320 (Bi Ke corporate system) | ????0.30 |
Numeral in the b, table 4 bracket is in main film forming matter total weight of solids shared hundred
Mark;
In c, table 4 prescription, do not use color stuffing;
In d, table 4 prescription, auxiliary dosage is 0.3% (pressing solid weight meter) of main film forming matter.
2, preparation
With each coating composition of the coating varnish of the flash metal luster priming paint of table 3 and table 4, mix respectively according to a conventional method, being uniformly dispersed gets final product, and the solid content of flash metal luster priming paint is 40.0%, and the solid content of coating varnish is 63.7%.
3, performance
With flash metal luster priming paint and coating varnish respectively latting drown (be coated with-4 glasss to viscosity 13～18s and 18～24s, 25 ℃), earlier above-mentioned flash metal luster priming paint is sprayed on tinplate or surface of steel plate with 400 order sand paperings, or be sprayed on scribbling on painted is filmed in the example 1 with 1200 order sand paperings, dodge and did several minutes, after making the surface drying of filming, the wet wet spray coating varnish that bumps, dodge and do after several minutes, 130 ℃ solidify 30min, or 140 ℃ solidify 20min, and promptly obtaining by build is that the flash metal luster primer coating film of 10～20 μ m and coating varnish that build is 30～40 μ m metallized finish of forming of filming is filmed.This is filmed and tests by the method for GB regulation, and its result is as follows: film 60 ° of gloss more than 95%, 0 grade of sticking power, shock strength 50kgcm, 1 grade of snappiness, pendulum-rocker hardness＞0.75.
With the flash metal luster priming paint of this example 3 with coating varnish is wet when bumping wet spray, the dry film total thickness is at 45～55 μ m sagging not still, and appearance of film is smooth, and the aluminium powder orientation is good, guide number 14.6, free of pinholes, non-foaming; And when not adopting rheology modified resin, build 35 μ m sagging has appearred and the aluminium powder orientation bad, guide number is 13.2.
The spray-finishing construction method of coating of the present invention in adopting each example, also electrostatic spraying can be adopted, also brushing, roller coat, showering, blade coating can be adopted.Coating of the present invention is applicable to coated steel, aluminium, plastic component.Be particularly suitable as middle japanning, true qualities finish paint and metallized finish in vehicle and the general industry application.
Claims (10)
1, a kind of solvent-borne type high solid coating that contains rheology modified resin is made up of main film forming matter, auxiliary film forming matter, color stuffing and auxiliary agent, it is characterized in that:
A, main film forming matter are made up of binder resin, cross-linked resin and rheology modified resin, and in resin solid weight, binder resin accounts for 30～65%, and cross-linked resin accounts for 15～40%, and rheology modified resin accounts for 20～40%;
B, auxiliary film forming matter consumption are 0～40% of main film forming matter total weight of solids;
C, color stuffing are (0～1) with main film forming matter and auxiliary film forming matter total weight of solids ratio: (1～3);
D, auxiliary dosage are 0.2～5% of main film forming matter and auxiliary film forming matter total weight of solids;
E, described rheology modified resin are the resins that contains the urea key, and this resin has thixotropic behavior, measure viscosity at 25 ℃ with the Brookfield cone-and-plate viscometer, are that shearing rate is 1s at low-shearing power
-1The time, viscosity is 10000～50000mPas, is that shearing rate is 100s at high shear force
-1The time, viscosity is 300～2000mPas, and the full-bodied viscosity recovery time that the low viscosity under above-mentioned high shear force returns under the low-shearing power is 60～200s, and the fineness of this rheology modified resin is less than 5 μ m;
F, described rheology modified resin are in the presence of the resin identical with binder resin, the solution of diisocyanate cpd and the solution of aminated compounds, mix, react 0.5～4h while stirring at 0～80 ℃, and then be incubated that 0.5～1h makes, the solution of used diisocyanate cpd and the solution of aminated compounds, the equivalence ratio of its isocyano and primary amino is 0.5: 1～1.5: 1, its total weight of solids account for the rheology modified resin that is generated solid weight 2～8%;
G, grinding and also adding solvent during construction, its dosage is so that grind and construction is as the criterion.
2, coating according to claim 1 is characterized in that, the binder resin in the described main film forming matter is a kind of with in Synolac, vibrin, acrylic resin, polyester polyol resin or the acrylic polyol resin of ordinary method preparation.
3, coating according to claim 1 is characterized in that, described auxiliary film forming matter be with main film forming matter in binder resin other film-formable resins inequality.
4, coating according to claim 3 is characterized in that, the resin that can be used as auxiliary film forming matter is Resins, epoxy, Nitro cellulose resin, ethyl cellulose resin, butyl cellulose resin or cellaburate resin.
5, coating according to claim 1 is characterized in that, the cross-linked resin in the described main film forming matter is aminoresin of using always or the cross-linked resin that contains isocyanate compound.
6, coating according to claim 1, it is characterized in that, when preparing described rheology modified resin, the solution of used diisocyanate cpd is the vulcabond of choosing any one kind of them from aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate, the solution that forms with a kind of solvent in varsol, ketones solvent, esters solvent, ether solvent or the solvent of ether ester type; The solution of used aminated compounds, be from aliphatics amine, aromatic amine, alcamines or ether amine, to choose any one kind of them or the various kinds of amine compounds, the solution that forms with a kind of solvent in varsol, ketones solvent, esters solvent, alcoholic solvent, ether solvent or the solvent of ether ester type.
7, coating according to claim 6, it is characterized in that, aromatic diisocyanate as diisocyanate cpd is 2,4-Xylene Diisocyanate, 2,6-Xylene Diisocyanate, '-diphenylmethane diisocyanate, xylylene diisocyanate or tetramethylxylylene diisocyanate; Aliphatic diisocyanate as diisocyanate cpd is methylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or trimethylammonium hexamethylene diisocyanate; Alicyclic diisocyanate as diisocyanate cpd is isophorone diisocyanate, dicyclohexyl methane diisocyanate or hexahydrotoluene vulcabond.
8, coating according to claim 6, it is characterized in that, be benzylamine, ethamine, Tri N-Propyl Amine, secondary propylamine, butylamine, sec-butylamine, TERTIARY BUTYL AMINE, n-amylamine, Alpha-Methyl butylamine, α-ethyl propylamine, β-ethyl butyl amine, hexylamine, octylame, decyl amine, hexamethylene-diamine, hexahydroaniline or stearylamide as the aliphatics amine of aminated compounds; Aromatic amine as aminated compounds is an aniline; Hydramine as aminated compounds is a thanomin; As amine bonded ether amine is 4-Methoxybenzylamine, methoxy propanamine, 3,4-dimethoxyphenyl ethyl amine, 2,5-dimethoxyaniline, chaff amine or tetrahydrofurfuryl amine.
9, coating according to claim 6 is characterized in that, described varsol is hexane, hexanaphthene, octane, oil mixed solvent, toluene, dimethylbenzene, 100#, 150# or 200# high boiling point aromatic hydrocarbons mixed solvent; Ketones solvent is acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl amylketone, pimelinketone, diacetone alcohol or isophorone; Esters solvent is vinyl acetic monomer, propyl acetate, isobutyl acetate, isoamyl acetate, the DBE of Du Pont, first promise DME or first all DME-1 high boiling point mixed ester kind solvents; Alcoholic solvent is ethanol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, isooctyl alcohol or phenylcarbinol; Ether solvent is ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monobutyl ether; Solvent of ether ester type is ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate.
10, according to the described coating of one of claim 1～9, it is characterized in that, can be used as middle japanning, true qualities finish paint and metallized finish.
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| CNB021381135A CN1175072C (en) | 2002-08-12 | 2002-08-12 | Solvent-type high-solid paint containing rheologically modified resin |
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| CNB021381135A CN1175072C (en) | 2002-08-12 | 2002-08-12 | Solvent-type high-solid paint containing rheologically modified resin |
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