CN101469247A - Bicomponent polyurethane coating composition, preparation and coating method thereof - Google Patents
Bicomponent polyurethane coating composition, preparation and coating method thereof Download PDFInfo
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- CN101469247A CN101469247A CNA2007101257183A CN200710125718A CN101469247A CN 101469247 A CN101469247 A CN 101469247A CN A2007101257183 A CNA2007101257183 A CN A2007101257183A CN 200710125718 A CN200710125718 A CN 200710125718A CN 101469247 A CN101469247 A CN 101469247A
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Abstract
The invention discloses a bicomponent polyurethane coating composition. The existence of corresponding relation between the performance of an acrylic acid resin and a corresponding structure is applied, a component A, namely an acrylic acid resin with branched chain carbon number less than 6 and a component B, namely polyisocyanate are taken as basic components, and a solvent and an auxiliary agent are added, wherein the acrylic acid resin comprises a high hydroxyl acrylic acid resin and a low hydroxyl acrylic acid resin, and the polyisocyanate is trimer polyisocyanate. A coating prepared by the coating composition has the advantages of high hardness, high strength, high weather resistance, high flexibility, high glossiness, gloss retention and color retention for a long time, no foaming of a plurality of layers of paint films and so on.
Description
[technical field]
The present invention relates to a kind of two-component polyurethane coating composition and preparation method thereof and the method that forms coated film.
[background technology]
The bi-component acrylic polyurethane coating is high quality, the eco-friendly new coating that development in recent years is got up in the acrylic coating.The bi-component acrylic polyurethane coating generally is made up of A component (Hydroxylated acrylic resin) and B component (isocyanic ester).The hydroxyl of Hydroxylated acrylic resin and isocyanic ester generation crosslinking curing, the C-C long-chain section that contains carbamate groups and acrylic resin in the polyester macromolecule structure that generates simultaneously, thereby have the advantage of urethane and acrylic resin concurrently, the non-common product of its over-all properties can be compared, and is considered to one of the most rising coating variety.The energy that the bi-component acrylic polyurethane coating is consumed when solidifying is very low, is a kind of coating new variety that satisfy requirements of the times.
There are corresponding relation in the performance and the corresponding structure of acrylic resin, because there is certain defective in the application performance of conventional acrylic resin in the specific occasion, thereby structure is carried out modification becomes one of problem that acrylic resin in recent years pays close attention to most in synthetic.In the Hydroxylated acrylic resin molecule, introduce structural unit,, give the polyurethane coating film more function as fluorine-containing, siliceous polymer segment with specific function.Epoxy modified acrylic resin strengthens the mechanical property of acrylic coating.SiO
2, TiO
2, ZrO
2, CaCO
3, nanometer particle such as clay also is that the ideal of modified polyacrylate is selected.Also have polyaniline, acrylamide, polyester, polyurethane modified acrylic resin to wait the performance that strengthens his each side.
It is basal component with acrylic resin (A) and the polyisocyanate prepolymers (C) with short-side chain hydroxyl (a1) and long pendant hydroxyl group (a2) that while CN1891768A discloses a kind of coating, and optionally further comprise polylactone polyol (B), have high anti-zoned property by the coating that recently makes of regulating short-side chain hydroxyl (a1) and the content of long pendant hydroxyl group (a2).Wherein the regulation carbon number is defined as long side chain more than or equal to 6 side chain, and carbon number is defined as short-side chain less than 6 side chain.This patent is introduced the elasticity that long pendant hydroxyl group improves coating in trunk polymer, introduce hardness, intensity and weathering resistance that the short-side chain hydroxyl improves coating.But this coating can not have the long-time simultaneously light guarantor look of protecting of higher glossiness.
And along with growth in the living standard, people are more and more higher to the requirement of outward appearance, daily necessities need have higher glossiness simultaneously, can protect simultaneously light for a long time and protect look, generally adopt on plastic basis material or steel base material multilayer film to reach the effect of high glossiness in the prior art.
But at present used low temperature varnish glossiness is not high, places easy loss of gloss for a long time, and hardness promotes slowly, in the baking of must levelling after the spraying just taking away after for some time.Occur easily when carrying out individual layer or laminated coating on plastic basis material and the steel base material bubbling, form film defect.
[summary of the invention]
Not high in order to solve present low temperature varnish glossiness, easily loss of gloss and hardness promote slowly, occur easily bubbling when carrying out individual layer or laminated coating on plastic basis material and the steel base material, form problems such as film defect.The present invention chooses short-side chain Hydroxylated acrylic resin (A) and polyisocyanate prepolymers (C) prepares coating for basal component.The coating that this coating composition forms, not only have high hardness, intensity, weathering resistance, snappiness, and reach beyond thought effect, have high-luster, the long-time light tint retention of protecting is not easy to occur bubbling, form problems such as film defect when base material is carried out individual layer or laminated coating.
Described high glossiness is meant the known high glossiness of those skilled in the art, that is, glossiness reaches more than the 100GU, is the result who adopts BYK multi-angle glossiness survey meter 60 degree to measure.
The purpose of this invention is to provide a kind of two-component polyurethane coating composition with above-mentioned advantage.
Another object of the present invention provides the preparation method of above-mentioned two-component polyurethane coating composition.
The present invention also provides the coating process of above-mentioned two-component polyurethane coating composition.
A kind of two-component polyurethane coating composition comprises A component and B component, and wherein, the A component comprises acrylic resin, solvent, auxiliary agent; The B component comprises polyisocyanates, it is characterized in that, described acrylic resin is the side chain carbon number less than 6 acrylic resin.
Preferably, acrylic resin comprises high Hydroxylated acrylic resin and low Hydroxylated acrylic resin, and the hydroxy radical content of high Hydroxylated acrylic resin is 110-180mg KOH/g; The hydroxy radical content of the acrylic resin of low hydroxyl is 30-65mg KOH/g.
Preferably, polyisocyanates is the tripolymer polyisocyanates.
A kind of preparation method of coating composition as mentioned above said method comprising the steps of:
(1) acrylic resin is joined mix in the solvent and obtain solution;
(2) solution that auxiliary agent and step (1) are obtained mixes, and obtains former lacquer;
(3 join polyisocyanates in the former lacquer that step (2) obtains, and mix;
(4) mixture that adopts 400 purpose strainer filtering above-mentioned steps (3) to obtain obtains coating composition.
A kind of coating process of coating composition as mentioned above, described coating process comprises single coating and multi-layer coated.
The invention has the beneficial effects as follows that this coating can effectively improve glossiness, protect light for a long time and protect look, and can improve hardness rapidly, shorten the process time.Side chain can react under cold condition with isocyanic ester very soon less than 6 high Hydroxylated acrylic resin, and the moisture that is produced can be absorbed by siccative very soon, the carrying out of accelerated reaction.Hang down the hydroxyl polyacrylic ester then for paint film provides good snappiness, thereby make paint film that certain elasticity be arranged, when being subjected to abrading, can recover scuff mark to a certain extent.And this coating can carry out individual layer or multi-layer coated to base material, and is not easy to occur problems such as foaming, formation film defect.This coating preparation technology is simple, easy to prepare simultaneously.
[embodiment]
Below embodiments of the present invention are elaborated.
The invention provides a kind of two-component polyurethane coating composition, is basal component with A part acrylic resin and B component polyisocyanates.
Wherein A part acrylic resin side chain carbon number is less than 6, and preferred carbon number is less than 3 short-chain branch acrylic resin.Acrylic resin comprises high Hydroxylated acrylic resin and low Hydroxylated acrylic resin.Wherein the hydroxy radical content of high Hydroxylated acrylic resin is 110-180mg KOH/g, the SM515 that concrete optional UCB. S.A. (BE) Bruxelles Belgium produces; CY430, CY474, CY499 that DSM N. V. produces; NUPLEX company produces one or more in 1753 grades.The quality percentage composition that its total amount with composition is a benchmark is 30-60%, preferred 40%-50%.Wherein the hydroxy radical content of the acrylic resin of low hydroxyl is 30-65mg KOH/g, the A760 that concrete optional Beyer Co., Ltd produces; Among CY480, the CY472 that DSM N. V. produces, the SN805 etc. one or more, the quality percentage composition that its total amount with composition is a benchmark is 5-15%, preferred 8%-12%.
The preferred tripolymer polyisocyanates of B component polyisocyanates the present invention wherein, N-3300, the N-3600 that concrete optional Beyer Co., Ltd produces, among N3390, the N3375 etc. one or more.The ratio of the content of its isocyanate group and the hydroxy radical content of acrylic resin be 0.8:1.0 to 1.2:1, preferred 0.95:1 is to 1.05:1.
Two-component polyurethane coating composition provided by the invention also comprises solvent and auxiliary agent.
Solvent wherein of the present invention is this area organic solvent solvent commonly used, be selected from varsol, esters solvent, alcoholic solvent, ketones solvent, in the ether solvent one or more, described varsol is selected from toluene, in the dimethylbenzene one or more, described esters solvent is selected from ethyl acetate, butylacetate, methyl acetate, nylon acid dimethyl ester, ethylene glycol ether acetate, isobutyl acetate, in the propyl acetate one or more, described alcoholic solvent is selected from ethanol, n-propyl alcohol, Virahol, propyl carbinol, in the isopropylcarbinol one or several, described ketones solvent is selected from cyclohexanone, hexone, acetone, in the methylethylketone one or more, described ether solvent is selected from butyl glycol ether, in the propylene glycol butyl ether one or more.Solvent is that the quality percentage composition of benchmark is 30%-45% with the total amount of composition.
Auxiliary agent that wherein the present invention adopts comprises flow agent, siccative and ultraviolet absorbers, is that the quality percentage composition of benchmark is 1%-10% with the total amount of composition, preferred 2-6%.The wherein concrete optional polyether-modified polydimethylsiloxane BYK-310 of flow agent, BYK-331, BYK-333; Among modified urea solution B YK-410, Afcona 3670, the Afcona 3700 one or several, the quality percentage composition that its total amount with composition is a benchmark is 0.5%-5%, preferred 1-2%.The TI, the OF that produce of the concrete optional borchers of siccative company wherein; Among the T-12 that U.S.'s gas companies is produced etc. one or several, the quality percentage composition that its total amount with composition is a benchmark is 0.1%-2%, preferred 0.2-0.8%.Wherein among UV 292, the UV1130, UV384, UV928 or the UV400 that produce of the concrete optional CIBA of ultraviolet absorbers company one or several., the quality percentage composition that its total amount with composition is a benchmark is 0.4%-3%, preferred 1-2%.
The present invention also provides the preparation method of aforementioned coating composition, may further comprise the steps:
(1) acrylic resin is joined in the solvent mixes, obtain solution;
(2) solution that auxiliary agent and step (1) are obtained mixes, and obtains former lacquer;
(3 join polyisocyanates in the former lacquer that step (3) obtains, and mix;
(4) mixture that adopts 400 purpose strainer filtering above-mentioned steps (3) to obtain obtains coating composition.
Wherein, described filter screen for example can be a stainless steel filtering net.
The present invention also provides the coating process with this two-component polyurethane coating composition simultaneously.Method to different base material coatings comprises single coating method and multi-layer coating method.
Wherein, the single coating method may further comprise the steps:
(1) base material of having polished, and clean up, dry;
(2) water transfer substrate is toasted 15min down at 60 ℃;
(3) the thick one deck coating composition of spraying 35-45 μ m on above-mentioned base material toasts 30min down at 70 ℃.
Wherein, described base material is the known plastic basis materials of those skilled in the art, for example ABS plastic (acrylonitrile-butadiene-styrene copolymer) base material, PP material plastic basis material.
Wherein, multi-layer coating method may further comprise the steps:
(1) spraying one deck priming paint on base material, the thickness of described priming paint is 8-10 μ m;
(2) after the oven dry, spraying one deck has mill base, and described the thickness of mill base is arranged is 20-25 μ m;
(3) behind the surface drying, spraying one deck coating composition, the bed thickness of described coating composition is 25-30 μ m, oven dry.
Described base material can be the known various base materials of those skilled in the art, as plastic basis material, steel base material etc.As spraying one deck PP priming paint on the plastic basis material in the step (1); Spraying one deck low temperature retouching paint on the steel base material.Described plastic basis material is the known plastic basis materials of those skilled in the art, for example ABS plastic base material, PP material plastic basis material.The steel base material is the known steel base materials of those skilled in the art, as tinplate.
Described mill base is arranged is the known mill bases of those skilled in the art, and as various mill bases such as silver color, black, redness, bluenesss, wherein the present invention adopts the silver color slurry.
Below by embodiment the present invention is described in more detail.
[embodiment 1]
Make the step of coating composition:
(1) the high Hydroxylated acrylic resin SM515 (solid 70% that 40g UCB is produced, hydroxy radical content 4.5%, unbranched), the low Hydroxylated acrylic resin A870BA (solid 60% that the 10g Bayer is produced, hydroxy radical content 1.8%, the side chain carbon number is less than 3) join in the mixed solvent of forming with ethyl acetate 35g, dimethylbenzene 14g, nylon acid dimethyl ester 10g, propyl carbinol 5g and dissolve, and mix;
(2) in said mixture, add BYK331 flow agent 1.0g, UV292 ultraviolet absorbers 0.5g, UV284-2 ultraviolet absorbers 0.5g, T-12 siccative 0.1g, dissolving mixes and obtains former lacquer.
(3) add the isocyanic ester N3390 (isocyanate group content 19.6% is admittedly contain 90%) that the 20g Bayer is produced in said mixture, dissolving mixes.
(4) adopt 400 purpose stainless (steel) wires to filter, get coating composition.
The step of ABS base material single coating:
(1) polishing ABS base material is used the isopropanol solvent scrub, 60 ℃ of baking 5min.
(2) water transfer printing ABS base material, 60 ℃ of baking 12min.
(3) the thick coating composition of spraying one deck 30 μ m on above-mentioned ABS base material, 70 ℃ of baking 30min.
The step of 3 layers of coating of PP material plastic basis material:
(1) the thick PP priming paint of spraying one deck 12 μ m on PP material plastic basis material, 70 ℃ are toasted 13min down.
(2) on above-mentioned base material, spray the thick silver paint of one deck 18 μ m, surface drying 8min again.
(3) on above-mentioned base material, spray the thick coating composition of one deck 30 μ m again, 70 ℃ of baking 30min.
The step of 3 layers of coating of tinplate base material:
(1) the thick low temperature retouching paint of spraying one deck 12 μ m on the tinplate base material, 70 ℃ are toasted 12min down.
(2) on above-mentioned base material, spray the thick silver paint of one deck 18 μ m, surface drying 8min again.
(3) on above-mentioned base material, spray the thick coating composition of one deck 30 μ m again, 70 ℃ of baking 30min.
[embodiment 2]
Method according to embodiment 1 prepares coating composition, and carries out ABS base material single coating; PP material plastic basis material, 3 layers of coating of tinplate steel base material.Different is, what high Hydroxylated acrylic resin adopted is the CY430 (solid 70% that DSM N. V. produces, hydroxy radical content 4.3%, the side chain carbon number is less than 5), what low Hydroxylated acrylic resin adopted is the CY468 (solid 60% that DSM N. V. produces, hydroxy radical content 1.8%, unbranched), change the T-12 siccative into 0.5g.
[embodiment 3]
Method according to embodiment 1 prepares coating composition, and carries out ABS base material single coating; PP material plastic basis material, 3 layers of coating of tinplate steel base material.Different is not add low Hydroxylated acrylic resin A870BA.
[embodiment 4]
Method according to embodiment 1 prepares coating composition, and carries out ABS base material single coating; PP material plastic basis material, 3 layers of coating of tinplate steel base material.Different is, polyisocyanates is that (isocyanate group content 10.5% contains admittedly: 75%) for the VPLS2253 of Bayer
[Comparative Examples 1]
Method according to embodiment 1 prepares coating composition, and carries out ABS base material single coating; PP material plastic basis material, 3 layers of coating of tinplate steel base material.Different is that what high Hydroxylated acrylic resin adopted is 1715 (solid 4.4%, the hydroxy radical contents 74% of NUPLEX, the side chain carbon number is greater than 15), what low Hydroxylated acrylic resin adopted is 8890 (the side chain carbon number is greater than 8 for solid 70%, hydroxy radical content 2.54%) of DSM.
Performance test
Sticking power: draw 100 2 millimeters * 2 millimeters square lattice at sprayed surface with drawing the lattice device, the model of producing with Minnesota Mining and Manufacturing Company is 600 smooth being bonded on the grid of scotch tape, do not stay a space, vertically uncover with utmost dispatch then, observe cut edge and have or not depainting.Is 5B as the depainting amount between 0～5%, is 4B between 5～10%, is 3B between 10～20%, is 2B between 20～30%, is B between 30～50%, is being 0B more than 50%.
Glossiness: adopt BYK multi-angle glossiness survey meter to measure.
Gloss retention: will be coated with to place and outdoorly carry out glossiness mensuration with BYK multi-angle glossiness survey meter more after two months.
Anti-scratch property: on product, streak (portrayal length: 10mm with the external force of 5N with icking tool (model is Bosch-0.75mm), portrayal speed: 10mm/s), observe cut with twenty-twenty vision, can observe the variation of cut or glossiness, estimate the degree of cut with difference in good.
Excellent: as under 4 power microscopes, to observe no marking;
Very; Visual no marking has cut but observe under 4 power microscopes;
Difference: visual have a cut.
Thickness test: after spray, levelling not, the baking of directly taking away is done sagging and is tested the thickness of paint film when just prickly heat occurring.
Test result
The coating performance test result is shown in table 1-table 3.
The coating property test result is as shown in table 4.
Table 1 is the performance test of ABS base material single coating.
Table 1
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 |
| Glossiness (60 °/GU) | 108 | 101 | 91 | 90 | 92 |
| Place outdoor after two months glossiness (60 °/GU) | 105 | 99 | 85 | 85 | 81 |
| Sticking power | 5B | 5B | 4B | 4B | 5B |
| Anti-scratch property | Excellent | Excellent | Poor | Very | Excellent |
Table 2 is the performance test of 3 layers of coating of tinplate base material.
Table 2
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 |
| Glossiness (60 °/GU) | 104 | 98 | 89 | 88 | 90 |
| Place outdoor after two months glossiness (60 °/GU) | 100 | 97 | 76 | 74 | 81 |
| Sticking power | 5B | 5B | 5B | 4B | 4B |
| Anti-scratch property | Excellent | Excellent | Difference | Very | Very |
Table 3 is the performance test of 3 layers of coating of PP base material.
Table 3
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 |
| Glossiness (60 °/GU) | 103 | 99 | 85 | 89 | 86 |
| Place outdoor after two months glossiness (60 °/GU) | 101 | 97 | 75 | 81 | 74 |
| Sticking power | 5B | 5B | 5B | 4B | 4B |
| Anti-scratch property | Excellent | Excellent | Difference | Poor | Excellent |
As above test result shows, coating of the present invention has higher glossiness, and when adopting BYK multi-angle glossiness survey meter 60 degree to measure, glossiness reaches more than the 100/GU, and outdoor placement glossiness is almost constant after two months.And adopt the long-chain acrylic resin is that the glossiness coating more of the present invention of coating of basal component preparation is low, and outdoor placement after two months glossiness reduce a lot, be less than original 90%.Along with growth in the living standard, obvious coating of the present invention has the better application prospect.We also add low hydroxyl polyacrylic acid as can be seen simultaneously provides good snappiness for paint film, and the coating that coating of the present invention is made has good anti-zoned wiping.Also fine from our ADHESION OF PAINTS power test result of the present invention as can be seen of test result.Coating then of the present invention can to plastic basis material carry out single coating and plastics, steel base material are carried out multi-layer coated, the performance excellent property.
Table 4 is the thickness test result of this coating composition.
Table 4
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 |
| Thickness/μ m | 50 | 48 | 40 | 39 | 30 |
As above test result shows, coating of the present invention is excellent property when carrying out the spraying of high thickness, it is very fast that hardness promotes, thickness can reach 50/ μ m and heat rash appears, be that other paint spay-coatings are incomparable to 30/ μ m, not only shortened the process time, and formed problems such as being not easy to occur bubbling, form film defect when being coated with, had a good application prospect.
The invention provides and a kind ofly can effectively improve glossiness, protect light for a long time and protect look, and can improve hardness rapidly, shorten two group polyurethane coating compositions of process time.The low hydroxyl polyacrylic ester that is added can provide good snappiness for paint film, makes paint film that certain elasticity be arranged, and when being subjected to abrading, can recover scuff mark to a certain extent.And this coating can carry out individual layer or multi-layer coated to base material, and is not easy to occur problems such as foaming, formation film defect.This application of paints is extensive simultaneously, and preparation technology is simple, and is easy to prepare.
Claims (10)
1, a kind of two-component polyurethane coating composition comprises A component and B component, and wherein, the A component comprises acrylic resin, solvent, auxiliary agent; The B component comprises polyisocyanates, it is characterized in that, described acrylic resin is the side chain carbon number less than 6 acrylic resin.
2, a kind of two-component polyurethane coating composition as claimed in claim 1, it is characterized in that, described acrylic resin comprises high Hydroxylated acrylic resin and low Hydroxylated acrylic resin, the hydroxy radical content of described high Hydroxylated acrylic resin is 110-180mg KOH/g, and the hydroxy radical content of the acrylic resin of described low hydroxyl is 30-65mg KOH/g.
3, a kind of two-component polyurethane coating composition as claimed in claim 2, it is characterized in that, total amount with composition is a benchmark, and the quality percentage composition of described high Hydroxylated acrylic resin is 30-60%, and the quality percentage composition of described low Hydroxylated acrylic resin is 5-15%.
4, a kind of two-component polyurethane coating composition as claimed in claim 1 is characterized in that, described polyisocyanates is the tripolymer polyisocyanates.
5, a kind of two-component polyurethane coating composition as claimed in claim 4 is characterized in that, the mol ratio of the isocyanate group content of described tripolymer polyisocyanates and the hydroxy radical content of acrylic resin is 0.8:1.0 to 1.2:1.
6, a kind of two-component polyurethane coating composition as claimed in claim 1, it is characterized in that described solvent is selected from one or more in toluene, dimethylbenzene, ethyl acetate, butylacetate, methyl acetate, nylon acid dimethyl ester, ethylene glycol ether acetate, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, cyclohexanone, hexone, acetone, butyl glycol ether, the propylene glycol butyl ether.
7, a kind of two-component polyurethane coating composition as claimed in claim 6 is characterized in that, described solvent is that the quality percentage composition of benchmark is 30%-45% with the total amount of composition.
8, a kind of two-component polyurethane coating composition as claimed in claim 1, it is characterized in that, described auxiliary agent comprises flow agent, siccative, ultraviolet absorbers, total amount with composition is a benchmark, the quality percentage composition of described flow agent is 0.5%-5%, the quality percentage composition of described siccative is 0.1%-2%, and the quality percentage composition of described ultraviolet absorbers is 0.4%-3%.
9, a kind of preparation method of two-component polyurethane coating composition as claimed in claim 1 said method comprising the steps of:
(1) acrylic resin is joined mix in the solvent and obtain solution;
(2) solution that auxiliary agent and above-mentioned steps (1) are obtained mixes, and obtains former lacquer;
(3 join polyisocyanates in the former lacquer that above-mentioned steps (2) obtains, and mix, filter and obtain coating composition.
10. the coating process of a two-component polyurethane coating composition as claimed in claim 1, described coating process is a single coating or multi-layer coated.
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