CN104745062A - Aqueous compound paint and composite coating method thereof - Google Patents
Aqueous compound paint and composite coating method thereof Download PDFInfo
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- CN104745062A CN104745062A CN201510141276.6A CN201510141276A CN104745062A CN 104745062 A CN104745062 A CN 104745062A CN 201510141276 A CN201510141276 A CN 201510141276A CN 104745062 A CN104745062 A CN 104745062A
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- aqueous
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses an aqueous compound paint. The aqueous compound paint comprises the aqueous middle-coating paint and the aqueous top-coating paint, wherein the aqueous middle-coating paint and the aqueous top-coating paint both comprise at least one aqueous polyurethane. The middle coating and the top coating in the aqueous compound paint are excellent in interlayer coordination and the coating obtained by the invention is excellent in smoothness, water resistance and stone-hit resistance. The invention also discloses a composite coating method of the aqueous compound paint. The composite coating method is capable of obtaining a compound coating which is excellent in smoothness, water resistance and stone-hit resistance.
Description
Technical field
The present invention relates to the technical field of coating.More specifically, a kind of aqueous composite paint and compelx coating method thereof is related to.
Background technology
Three are coated with one dries (3C1B) technique, refers in vehicle coating process, and on the vehicle body scribbling electrophoresis film, middle painting, finish paint, varnish three coatings are all wet in same spray room touches application of having wet.
Compared with traditional vehicle coating process 3C2B, 3C1B has just lacked a bake process (middle painting baking) on the surface, but, be all have higher requirement in the control, coating process of the control of coating film thickness, appearance of coat.Compared with 3C2B, 3C1B needs to be coated with cross-linking reaction time and speed of reaction between finish paint in strict control, makes the interlayer conformability between middle painting and finish paint better; In order to ensure the smoothness of film, the thickness of middle painting film must be thinner than the thickness of film in 3C2B compelx coating, and may cause the reduction of resistance to hitting property of stone or the stone splashed in vehicle travel process thus and smear collision causing compelx coating to destroy, or the interface being coated with film in electrophoresis film and water-based is peeled off.
At present, in 3C1B material prescription, have employed acrylic resin and high-tenacity polyester resin, optimize solidification rate by the resin structure that is coated with in adjustment and solvent, make it to have with finish paint and good wetly touch wet coating performance.This technology requires large to dope viscosity and thixotropy, in construction process, to paint spray booth's envrionment temperature and humidity requirement higher.
Therefore, need to provide a kind of aqueous composite paint and compelx coating method thereof.
Summary of the invention
One object of the present invention is to provide a kind of aqueous composite paint, and the interlayer conformability be coated with between finish paint in aqueous composite paint of the present invention is good, gained compelx coating smoothness, water tolerance and resistance to hitting property of stone excellence.
Another object of the present invention is a kind of compelx coating method providing aqueous composite paint, adopts this coating process can obtain the compelx coating of a kind of smoothness, water tolerance and resistance to hitting property of stone excellence.
For achieving the above object, the present invention adopts following technical proposals:
A kind of aqueous composite paint, described aqueous composite paint comprises coating and aqueous finish paint coating in water-based; In described water-based, the raw material of coating comprises at least one aqueous polyurethane; The raw material of described aqueous finish paint coating comprises at least one aqueous polyurethane.
Preferably, in described water-based, the raw material of coating comprises aqueous polyurethane A and aqueous polyurethane B;
The number-average molecular weight of described aqueous polyurethane A is greater than 7000, and hydroxyl value is less than 5;
The number-average molecular weight of described aqueous polyurethane B is 1500-5000, and hydroxyl value is 80-250.
High molecular and the aqueous polyurethane of low hydroxyl can not be cross-linked, and film can be made to have snappiness, thus can obtain the higher film of elongation; And by adopting high molecular body, film also can be made to have tensile strength; But owing to being cross-linked, so be used alone the aqueous polyurethane of the low hydroxyl of high molecular, there will be cross-linking density lower, the result that water resistance is poor; Therefore, by the aqueous polyurethane also with hydroxyl, cross-linking density is guaranteed, to maintain water resistance.But if the molecular weight of crosslinked aqueous polyurethane is also higher, film will become stone, and resistance to hitting property of stone will decline; Therefore through test of many times, have selected above-mentioned two kinds of aqueous polyurethanes.
Preferably, the raw material of described aqueous finish paint coating comprises aqueous polyurethane C and aqueous polyurethane D;
The number-average molecular weight of described aqueous polyurethane C is 1500-5000, and hydroxyl value is 20-80;
The number-average molecular weight of described aqueous polyurethane D is 1500-5000, and hydroxyl value is 80-250.
Use described two kinds of aqueous polyurethanes in topcoat paint of the present invention, can guarantee that resistance to stone hits performance and water resistance is in higher level simultaneously.Middle painting coating of the present invention and topcoat paint must use simultaneously, and because painting design of the present invention is 3C1B, spray paint under the state be namely coated with in not drying, so be coated with and the mixed layer of finish paint in occurring; That is 1 film can be considered to.Therefore, middle painting and finish paint must be supporting.
Preferably, in described water-based coating raw material in the consumption of aqueous polyurethane A account for the 10-20wt% of aqueous composite paint gross weight; The consumption of aqueous polyurethane B accounts for the 20-40wt% of aqueous composite paint gross weight.
Preferably, in the raw material of described aqueous finish paint coating, the consumption of aqueous polyurethane C accounts for the 5-15wt% of aqueous composite paint gross weight; The consumption of aqueous polyurethane D accounts for the 10-30wt% of aqueous composite paint gross weight.
The invention provides the preparation method of a kind of aqueous polyurethane A:
Number-average molecular weight Mn 1500-4000 will be had, acid value AV (solid content) below 5, hydroxyl value OHV at the polyester polyol of at least one of 20-80,
At least contain the mixture of 1 dibasic alcohol and trivalent alcohol,
Containing negatively charged ion formed functional group, need in addition containing at least two can with the compound of the functional group of isocyanate reaction,
Non-ring type aliphatic diisocyanate, or alicyclic diisocyanate,
Amine neutralization after above substance reaction, then disperse in water, functional group containing at least 2 energy and isocyanate reaction and can more than number-average molecular weight Mn7000 be obtained after chain extension, the water-dispersible polyester modified polyurethane resin A of hydroxyl value OHV (solid content) below 5.
The invention provides the preparation method of a kind of aqueous polyurethane B:
There is number-average molecular weight Mn500-2000, acid value AV (solid content) below 5, hydroxyl value OHV at the polyester polyol of at least one of 100-300,
At least contain the mixture of 1 dibasic alcohol and trivalent alcohol,
Containing negatively charged ion formed functional group, need in addition containing at least two can with the compound of the functional group of isocyanate reaction,
Non-ring type aliphatic diisocyanate, or alicyclic diisocyanate
Amine neutralization after above substance reaction, then in water, obtain number-average molecular weight Mn at 1500-5000 after dispersion, hydroxyl value OHV (solid content) is at the water-dispersible polyester modified polyurethane resin B of 80-250.
The invention provides the preparation method of a kind of aqueous polyurethane C:
There is number-average molecular weight Mn500-2000, acid value AV (solid content) below 5, hydroxyl value OHV at the polyester polyol of at least one of 100-300,
At least contain the mixture of 1 dibasic alcohol and trivalent alcohol,
Containing negatively charged ion formed functional group, need in addition containing at least two can with the compound of the functional group of isocyanate reaction,
Non-ring type aliphatic diisocyanate, or alicyclic diisocyanate,
Amine neutralization after above substance reaction, the water-dispersible polyester modified polyurethane resin C then obtained after dispersion in water.
The preparation method of aqueous polyurethane D is identical with the preparation method of aqueous polyurethane B.
Except above-mentioned waterborne polyurethane resin, resin used in the present invention also comprises vibrin, acrylic resin and polyether resin.
Solidifying agent used in the present invention comprises aminoresin and closure isocyanic ester etc.
A compelx coating method for aqueous composite paint, comprises the following steps:
(1) spraying coating in water-based makes the thickness of its dry coating be 10-20 μm, is formed in unhardened water-based and is coated with film;
(2) in step (1) unhardened water-based, film spray aqueous finish paint coating and make the dry coating thickness of aqueous finish paint coating reach 5-20 μm, forming unhardened aqueous finish paint film;
(3) film in the unhardened water-based obtained in step (1) and (2) and unhardened aqueous finish paint film are carried out heat, after drying, spraying varnish coating makes the thickness of its dry coating reach 30-50 μm, forms unhardened varnish film;
(4) by film, unhardened aqueous finish paint film and unhardened varnish film one-time heating in unhardened water-based, film in unhardened water-based, unhardened aqueous finish paint film and unhardened varnish are hardened, forms the compelx coating comprising film in water-based, aqueous finish paint film and varnish film.
Preferably, in the compelx coating described in step (4), in water-based, the dry film thickness of film monofilm elongation 15 μm, 20 DEG C time is 20-40%, tensile strength is 20-40N/mm
2, cross-linking density is 10-20mmol/ml; Dry film thickness elongation 12 μm, 20 DEG C time of aqueous finish paint film monofilm is 10-20%, tensile strength is 20-40N/mm
2, cross-linking density is 10-20mmol/ml.
Be heated to be preheating (predrying) in step (3), Heating temperature is 80-70 DEG C, as long as heating makes moisture, low boiling point solvent vapors away; Be not heating and curing reaction.
Beneficial effect of the present invention is as follows:
The present invention passes through the different urethane resin of design 4 kinds, it suitable is mixed in middle painting and finish paint, just can obtain required Physical properties of coating film (elongation, tensile strength, cross-linking density), resistance to hitting property of stone and water tolerance can be made simultaneously to be in higher level.
People know that traditional urethane resin is the ammonia ester bond had concurrently by its inside, and there is higher elasticity and higher hardness and then there is excellent tack, in the past, especially grade was hit and the example mixing urethane resin in coating has much to improve resistance to stone.These resins are used to middle painting monomer or finish paint monomer, and then refer to design 1 urethane resin or Physical properties of coating film.3C1B painting design of the present invention is, designs different urethane resins (molecular weight and hydroxyl value) respectively for middle painting and finish paint.Obtain the compelx coating of best physical property thus, obtain the film performance that higher grade than ever.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiment, the present invention is described further.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
The present invention provides at least one preparation method of part material, and the identical or close raw material adopting other method to prepare is also in scope.
The preparation of Production Example 1, polyester polyol 1-1 (PE1-1)
The reflux cooling device reflecting the mouth of a river is equipped with, thermometer, in the reaction vessel of whipping appts and nitrogen ingress pipe, neopentyl glycol (7.5 parts), 1,6-hexylene glycol (38.5 parts), 1,6-hexanodioic acid (54 parts) drops into, and after being warmed up to 120 DEG C of material dissolutions, Keep agitation is warming up to 160 DEG C.160 DEG C keep after 1 hour, continue to be warmed up to 230 DEG C in 5 hours.Fixed time test acid value in 230 DEG C of insulations, until resin acid value is to 1mgKOH/g.Then be cooled to less than 80 DEG C, obtain acid value 1mgKOH/g, hydroxyl value 36mgKOH/g, the polyester polyol 1-1 (PE1-1) of number-average molecular weight 3000.
The preparation of Production Example 2, polyester polyol 1-2 (PE1-2)
Neopentyl glycol (13 parts), 1,6-hexylene glycol (33.5 parts), 1,6-hexanodioic acid (53.5 parts) drops into, and uses the method for Production Example 1, obtains acid value 1mgKOH/g, hydroxyl value 55mgKOH/g, the polyester polyol 1-2 (PE1-2) of number-average molecular weight 2000.
The preparation of Production Example 3, polyester polyol 2 (PE2)
Neopentyl glycol (5.8 parts), 1,6-hexylene glycol (29.9 parts), TriMethylolPropane(TMP) (13.2 parts), 1,6-hexanodioic acid (51.1 parts) drops into, use the method for Production Example 1, obtain acid value 1mgKOH/g, hydroxyl value 136mgKOH/g, the polyester polyol 2 (PE2) of number-average molecular weight 1500.
The preparation of Production Example 4, polyester polyol 3 (PE3)
Neopentyl glycol (13.8 parts), 1,6-hexylene glycol (35.5 parts), 1,6-hexanodioic acid (50.7 parts) drops into, and uses the method for Production Example 1, obtains acid value 1mgKOH/g, hydroxyl value 111mgKOH/g, the polyester polyol 3 (PE3) of number-average molecular weight 1000.
The manufacture of Production Example 5, water-dispersible polyester modified polyurethane resin 1-1 (PUD1-1)
The reflux cooling device reflecting the mouth of a river is equipped with, thermometer, in the reaction vessel of whipping appts and nitrogen ingress pipe, use the polyester polyol 1-1 (PE1-1) (27.7 parts) that Production Example 1 obtains, dimethylol propionic acid (2.2 parts) drops into, and Keep agitation is warming up to 80 DEG C.
In 80 DEG C of periods of arrival, add isophorone diisocyanate (10 parts), continue insulation 80 DEG C reaction, until NCO equivalent is to 1044, obtain the polyether polyols with reduced unsaturation of NCO end-blocking.
Then be cooled to 50 DEG C, add triethylamine (1.7 parts) neutralization, add deionized water (41.6 parts) after neutralization, obtain polyurethane prepolymer dispersion liquid.
Add quadrol (0.8 part) afterwards, deionized water (16 parts), be warming up to 60 DEG C of insulations 1 hour, after performed polymer chain extension completes, be cooled to 40 DEG C, obtain solid content 40.0%, hydroxyl value 2mgKOH/g, the water-dispersible polyester modified polyurethane resin 1-1 (PUD1-1) of number-average molecular weight 12500, the urethane that this Production Example obtains can be considered aqueous polyurethane A.
The manufacture of Production Example 6, water-dispersible polyester modified polyurethane resin 1-2 (PUD1-2)
The reflux cooling device reflecting the mouth of a river is equipped with, thermometer, in the reaction vessel of whipping appts and nitrogen ingress pipe, uses the polyester polyol 1-2 (28 parts) that Production Example 2 obtains, dimethylol propionic acid (2.2 parts) drops into, and Keep agitation is warming up to 80 DEG C.
In 80 DEG C of periods of arrival, add isophorone diisocyanate (8.9 parts), continue insulation 80 DEG C reaction, until NCO equivalent is to 4190, obtain the polyether polyols with reduced unsaturation of NCO end-blocking.
Then be cooled to 50 DEG C, add triethylamine (1.7 parts) neutralization, add deionized water (42 parts) after neutralization, obtain polyurethane prepolymer dispersion liquid.
Add quadrol (0.8 part) afterwards, deionized water (16.2 parts), be warming up to 60 DEG C of insulations 1 hour, after performed polymer chain extension completes, be cooled to 40 DEG C, obtain solid content 40.0%, hydroxyl value 1mgKOH/g, the water-dispersible polyester modified polyurethane resin 1-2 (PUD1-2) of number-average molecular weight 20000, the urethane that this Production Example obtains can be considered aqueous polyurethane A.
The manufacture of Production Example 7, water-dispersible polyester modified polyurethane resin 2-1 (PUD2-1)
The reflux cooling device reflecting the mouth of a river is equipped with, thermometer, in the reaction vessel of whipping appts and nitrogen ingress pipe, use the polyester polyol 2 (22.9 parts) that Production Example 3 obtains, dimethylol propionic acid (3.1 parts), TriMethylolPropane(TMP) (7.4 parts) drops into, and Keep agitation is warming up to 80 DEG C.In 80 DEG C of periods of arrival, add isophorone diisocyanate (17 parts), continue insulation 80 DEG C reaction, until the absorption peak of NCO in IR spectrum disappears.
Then 50 DEG C are cooled to, add triethylamine (0.9 part) neutralization, deionized water (48.6 parts) is added after neutralization, be incubated after 1 hour, be cooled to 40 DEG C, obtain solid content 40.0%, hydroxyl value 100mgKOH/g, the water-dispersible polyester modified polyurethane resin 2-1 (PUD2-1) of number-average molecular weight 3500, the urethane that this Production Example obtains can be considered aqueous polyurethane B or D.
The manufacture of Production Example 8, water-dispersible polyester modified polyurethane resin 2-2 (PUD2-2)
Use the polyester polyol 2 (27.8 parts) that Production Example 3 obtains, dimethylol propionic acid (3.2 parts), TriMethylolPropane(TMP) (12.3 parts), isophorone diisocyanate (22.5 parts), triethylamine (0.7 part), deionized water (33.6 parts), by the method for Production Example 7, obtain solid content 40.0%, hydroxyl value 150mgKOH/g, the water-dispersible polyester modified polyurethane resin 2-2 (PUD2-2) of number-average molecular weight 2000, the urethane that this Production Example obtains can be considered aqueous polyurethane B or D.
The manufacture of Production Example 9, water-dispersible polyester modified polyurethane resin 3-1 (PUD3-1)
The reflux cooling device reflecting the mouth of a river is equipped with, thermometer, in the reaction vessel of whipping appts and nitrogen ingress pipe, use the polyester polyol 3 (37.1 parts) that Production Example 4 obtains, dimethylol propionic acid (2.3 parts), 1,6-hexylene glycol (2 parts), TriMethylolPropane(TMP) (0.1 part) drops into, and Keep agitation is warming up to 80 DEG C.In 80 DEG C of periods of arrival, add isophorone diisocyanate (12.8 parts), continue insulation 80 DEG C reaction, until the absorption peak of NCO in IR spectrum disappears.
Then 50 DEG C are cooled to, add triethylamine (0.8 part) neutralization, deionized water (42.6 parts) is added after neutralization, be incubated after 1 hour, be cooled to 40 DEG C, obtain solid content 40.0%, hydroxyl value 30mgKOH/g, the water-dispersible polyester modified polyurethane resin 3-1 (PUD3-1) of number-average molecular weight 3800, the urethane that this Production Example obtains can be considered aqueous polyurethane C.
The manufacture of Production Example 10, water-dispersible polyester modified polyurethane resin 3-2 (PUD3-2)
The reflux cooling device reflecting the mouth of a river is equipped with, thermometer, in the reaction vessel of whipping appts and nitrogen ingress pipe, use the polyester polyol 3 (37.1 parts) that Production Example 4 obtains, dimethylol propionic acid (2.7 parts), DEG (1.6 parts), TriMethylolPropane(TMP) (0.1 part) drops into, and Keep agitation is warming up to 80 DEG C.In 80 DEG C of periods of arrival, add isophorone diisocyanate (12.1 parts), continue insulation 80 DEG C reaction, until the absorption peak of NCO in IR spectrum disappears.Then 50 DEG C are cooled to, add triethylamine (0.8 part) neutralization, deionized water (43.2 parts) is added after neutralization, be incubated after 1 hour, be cooled to 40 DEG C, obtain solid content 40.0%, hydroxyl value 40mgKOH/g, the water-dispersible polyester modified polyurethane resin 3-2 (PUD3-2) of number-average molecular weight 2800, the urethane that this Production Example obtains can be considered aqueous polyurethane C.
The PUD of above-mentioned preparation solid the results are shown in Table 1 containing, hydroxyl value and number-average molecular weight Mn.
Table 1
| PUD1-1 | PUD1-2 | PUD2-1 | PUD2-2 | PUD3-1 | PUD3-2 | |
| Gu containing (%) | 40 | 40 | 40 | 40 | 40 | 40 |
| Hydroxyl value | 2 | 1 | 100 | 150 | 30 | 40 |
| Mn | 12500 | 20000 | 3500 | 2000 | 3800 | 2800 |
The manufacture of Production Example 11 pigment dispersed slurry
In advance by after dispersion agent Disperbyk192 (the nonionic class dispersion agent that BYK company manufactures) 1.0 parts, defoamer BYK-011 (defoamer that BYK company manufactures) 0.5 part, the mixing of ion exchanged water 6.0 parts, titanium dioxide 20.4 parts, granulated glass sphere medium is added in sand mill, at room temperature blending dispersion is until fineness reaches less than 5 μm, thus obtains pigment dispersed slurry.
The modulation of coating (1) in Production Example 12 water-based
By the pigment dispersed slurry 27.9 parts obtained in above-mentioned Production Example 11, the water-dispersible polyester modified polyurethane resin 1-1 (PUD1-1) 7.7 parts obtained in above-mentioned Production Example 5, the water-dispersible polyester modified polyurethane resin 2-1 (PUD2-1) 15.3 parts obtained in above-mentioned Production Example 7, the Setaqua BE 270 (polyester resin aqueous dispersion that Nuplex manufactures, non-volatile part 70%) 2.9 parts, AC-176 (the aqueous acrylic resin dispersion that Picassian manufactures, non-volatile part 47.5%) 6.4 parts, and solidifying agent Cymel370 (Allnex manufactures aminoresin, non-volatile part 88%) after 7.0 parts of mixing, with sticky agent HV-30 (sticky agent that Basf manufactures) 0.4 part, surface conditioner BYK-346 (surface conditioner that BYK manufactures) 0.5 part, solvent ethylene glycol monobutyl ether 0.6 part of mix and blend, thus obtain coating in water-based (1).
The modulation of coating (2)-(7) in Production Example 13 water-based
Remove water-dispersible polyester modified polyurethane resin 1-1 (PUD1-1), water-dispersible polyester modified polyurethane resin 2-1 (PUD 2-1), the Setaqua B E270 (polyester resin aqueous dispersion that Nuplex manufactures, non-volatile part 70%), (Picassian manufactures aqueous acrylic resin dispersion to AC-176, non-volatile part 47.5%), and the solidifying agent Cymel370 (aminoresin that Allnex manufactures, non-volatile part 88%) change to material described in table 1, and beyond solid part quality % described in table 1, other modulation step are with Production Example 12, modulate coating in water-based (2)-(7) thus.
In water-based, the performance data of the elongation of the raw material weight number of coating 1-7 and prepared middle painting coating, tensile strength, cross-linking density is in table 2, in table 2, the middle painting formulation for coating material of routine 1-4 is the formula within the scope of technical solution of the present invention, and the middle painting formulation for coating material of 5-7 is for convenience of the use doing comparative example below.
Table 2
The modulation of Production Example 14 aqueous finish paint coating (1)
By water-dispersible polyester modified polyurethane resin 3-1 (PUD3-1) the 25.0 parts mixing obtained in the water-dispersible polyester modified polyurethane resin 2-1 (PUD2-1) 62.5 parts obtained in above-mentioned Production Example 7 and Production Example 9, with the AC-176 (aqueous acrylic resin dispersion that Picassian manufactures, non-volatile part 47.5%) 73.7 parts, and the solidifying agent Cymel370 (aminoresin that Allnex manufactures, non-volatile part 88%) 34.1 parts, photoluminescent Aluminum Pigment slurry EMR D7670 (aluminium powder pigment that Japan's Aluminum manufactures) 30 parts of (solid parts 50%, PWC12%), AQ-330 (nanmu originally changes into the acrylic resin of the phosphorous acidic group of manufacture) 3.0 parts, and, 2-Ethylhexyl Alcohol 40 parts, sticky agent HV-30 (sticky agent that Basf manufactures) 6.7 parts, surface conditioner BYK-346 (surface conditioner that BYK manufactures) 1.1 parts is uniformly dispersed thus obtains aqueous finish paint coating (1).
The modulation of Production Example 15 aqueous finish paint coating (2)-(5)
Except water-dispersible polyester modified polyurethane resin 2-1 (PUD2-1) and water-dispersible polyester modified polyurethane resin 3-1 (PUD3-1), AC-176 (aqueous acrylic resin dispersion that Picassian manufactures, non-volatile part 47.5%) and Cymel 370 (aminoresin that Allnex manufactures, non-volatile part 88%) are changed to except the material described in table 3 and the solid part quality % described in table 3, other modulation step, with Production Example 14, modulate aqueous finish paint coating (2)-(5) thus.
Table 3
In table 3, the aqueous finish paint coating of routine 1-3 consists of the formula within the scope of technical solution of the present invention, does comparative example and use after the aqueous finish paint coating of routine 4-5 consists of.
Embodiment 1
The formation of compelx coating
On the passivation steel plate through zinc phosphate process, painting electrophoresis coating PN-310 (cation electrophoretic coating that ippon coating manufactures), painting installs to and makes dry coating thickness can reach till 20 μm, cooling after heating makes it solidify in 30 minutes at 160 DEG C, thus forms solidification electrophoresis film.
Under room temperature, on the substrate being formed with solidification electrophoresis film, with coating (1) in the water-based obtained in spray equipment spraying Production Example 12, be sprayed onto and make the thickness after being heating and curing can reach till 15 μm, obtain thus being coated with film in unhardened water-based.Then, with the aqueous finish paint coating (1) that obtains in spray equipment spraying Production Example 14 until make the thickness after heat drying can reach 10 μm, then preheating 3 minutes at 80 DEG C.Again on this coated plate, with spray equipment spraying varnish coating SPO-300 coating varnish (the amino curing varnish colour that ippon coating manufactures) until after making the thickness after heat drying can reach 35 μm, at 140 DEG C, heating makes it solidify in 30 minutes, thus obtains the sample with compelx coating.
And coating (1), aqueous finish paint coating (1) and varnish colour adopt following condition to carry out diluting, spraying in water-based.
Coating (1) in water-based
Diluting solvent: ion exchanged water
50 seconds/Ford No. 4 cup/20 DEG C
Aqueous finish paint coating (1)
Diluting solvent: ion exchanged water
40 seconds/Ford No. 4 cup/20 DEG C
Varnish colour
The mixed solvent of diluting solvent: S-100 (the aromatic series hydrocarbon solvent that Exxon manufactures)/S-150 (the aromatic series hydrocarbon solvent that Exxon manufactures)=1/1 (mass ratio)
30 seconds/Ford No. 4 cup/20 DEG C
With the sample with compelx coating obtained above, carry out following evaluation.Evaluation result is as shown in table 4.
Embodiment 2-4
As different from Example 1, the selection of coating and aqueous finish paint coating in water-based, specifically selects in table 4, and other steps are all identical with embodiment 1, obtains the sample with compelx coating thus.
Comparative example 1-4
As different from Example 1, the selection of coating and aqueous finish paint coating in water-based, specifically selects in table 4, and other steps are all identical with embodiment 1, obtains the sample with compelx coating thus.
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Be coated with in water-based | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 4 |
| Aqueous finish paint | 1 | 1 | 2 | 3 | 1 | 2 | 4 | 5 |
| Water tolerance | ○ | ○ | ○ | ○ | ○ | ○ | × | × |
| Resistance to hitting property of stone | 1 | 1 | 1 | 1 | 3 | 4 | 1 | 1 |
Water tolerance
The warm water dipping sample with compelx coating obtained above being put into 40 DEG C took out after 10 days, draws upper grid (drawing the square grid of 100 2mm × 2mm) thereon, carry out stripping test with the adhesive plaster that Nichiban manufactures with blade.The sample not occurring to peel off is evaluated as zero, and the sample that there occurs stripping is evaluated as ×, result is as shown in table 4.
Resistance to hitting property of stone
With MULTI GRIT TESTER 508VDA (ERICHSEN manufacture) at 5kgf/cm
2air pressure under get to the compelx coating of-25 DEG C of cooled samples from the position of distance 35cm with the Chilled Iron Grit (G-9652-X) of the angle of 45 ° by 500g.After washing and drying, peel off with the industrial adhesive tape that Nichiban company manufactures, remove film fragment, then, the extent of exfoliation of visual valuation film.The stripping state of film is evaluated by following metewand.Result is as shown in table 4.
1 does not almost peel off
2 only a little peel off but outward appearance is no problem
3 strippings are slightly large or slightly more, and have problem in appearance
4 strippings are comparatively large or more
5 strippings are obviously comparatively large or obviously more
Stress-deformation characteristic
< elongation tensile strength >
With spray equipment, the coating just modulated in embodiment and comparative example is sprayed on polypropylene board, be sprayed onto and make the thickness after being heating and curing can reach till 20 μm, then preheating 3 minutes at 80 DEG C, at 140 DEG C, heating makes it solidify in 30 minutes again, afterwards, film peeled from polypropylene board thus obtain the film of stress-deformation characteristic.With autoplotter and the analog meter (Shimadzu Seisakusho Ltd.'s manufacture) of AGS-G model, measurement length be 50mm, temperature is 20 DEG C, draw speed is measured under being the condition of 10mm/min.Tensile strength obtains by the tendency of the chart after tension test.Simultaneously, by the extended length of the sample that reads in chart, (the axial length supposing the sample before testing is 50 (mm) to elongation, axial length when being stretched to sample fracture is L (mm), then elongation (%)=(L-50) × 100/50) and draw.
< cross-linking density >
With spray equipment, the coating just modulated in embodiment and comparative example is sprayed on polypropylene board, is sprayed onto and makes the thickness after being heating and curing can reach 20 μm for extremely.By the preheating 3 minutes at 80 DEG C of this plate, then heat at 140 DEG C after 30 minutes, film is peeled from polypropylene board thus obtains independently film.The cross-linking density of this film is measured with VIBRONDDV-II-EA (the determination of viscoelasticity device that Japan Baldwin manufactures, test conditions: frequency 11Hz, intensification 2 DEG C/minute).
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (7)
1. an aqueous composite paint, is characterized in that: described aqueous composite paint comprises coating and aqueous finish paint coating in water-based;
In described water-based, the raw material of coating comprises at least one aqueous polyurethane;
The raw material of described aqueous finish paint coating comprises at least one aqueous polyurethane.
2. aqueous composite paint according to claim 1, is characterized in that: in described water-based, the raw material of coating comprises aqueous polyurethane A and aqueous polyurethane B;
The number-average molecular weight of described aqueous polyurethane A is greater than 7000, and hydroxyl value is less than 5;
The number-average molecular weight of described aqueous polyurethane B is 1500-5000, and hydroxyl value is 80-250.
3. aqueous composite paint according to claim 1, is characterized in that: the raw material of described aqueous finish paint coating comprises aqueous polyurethane C and aqueous polyurethane D;
The number-average molecular weight of described aqueous polyurethane C is 1500-5000, and hydroxyl value is 20-80;
The number-average molecular weight of described aqueous polyurethane D is 1500-5000, and hydroxyl value is 80-250.
4. aqueous composite paint according to claim 2, is characterized in that: in described water-based coating raw material in the consumption of aqueous polyurethane A account for the 10-20wt% of aqueous composite paint gross weight; The consumption of aqueous polyurethane B accounts for the 20-40wt% of aqueous composite paint gross weight.
5. aqueous composite paint according to claim 3, is characterized in that: in the raw material of described aqueous finish paint coating, the consumption of aqueous polyurethane C accounts for the 5-15wt% of aqueous composite paint gross weight; The consumption of aqueous polyurethane D accounts for the 10-30wt% of aqueous composite paint gross weight.
6. utilize the compelx coating method of the aqueous composite paint according to any one of claim 1-5, it is characterized in that, comprise the following steps:
(1) spraying coating in water-based makes the thickness of its dry coating be 10-20 μm, is formed in unhardened water-based and is coated with film;
(2) in step (1) unhardened water-based, film spray aqueous finish paint coating and make the dry coating thickness of aqueous finish paint coating reach 5-20 μm, forming unhardened aqueous finish paint film;
(3) film in the unhardened water-based obtained in step (1) and (2) and unhardened aqueous finish paint film are carried out heat, after drying, spraying varnish coating makes the thickness of its dry coating reach 30-50 μm, forms unhardened varnish film;
(4) by film, unhardened aqueous finish paint film and unhardened varnish film one-time heating in unhardened water-based, film in unhardened water-based, unhardened aqueous finish paint film and unhardened varnish film are hardened, forms the compelx coating comprising film in water-based, aqueous finish paint film and varnish film.
7. method according to claim 6, is characterized in that: in the compelx coating described in step (4), and in water-based, the dry film thickness of film monofilm elongation 15 μm, 20 DEG C time is 20-40%, tensile strength is 20-40N/mm
2, cross-linking density is 10-20mmol/ml; Dry film thickness elongation 12 μm, 20 DEG C time of aqueous finish paint film monofilm is 10-20%, tensile strength is 20-40N/mm
2, cross-linking density is 10-20mmol/ml.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106680082A (en) * | 2016-12-23 | 2017-05-17 | 佛山市顺德区巴德富实业有限公司 | Method for quickly detecting mechanical properties of elastic building coating |
| CN107099238A (en) * | 2017-06-01 | 2017-08-29 | 万华化学集团股份有限公司 | Coating composition and its preparation method and application is applied in a kind of aqueous automobile |
| CN107118323A (en) * | 2016-06-30 | 2017-09-01 | 惠尔明（福建）化学工业股份有限公司 | A kind of damp curing acrylic resin copolymer |
| CN109627417A (en) * | 2018-10-25 | 2019-04-16 | 湖南湘江关西涂料有限公司 | The aqueous anti-stone of one kind hits dispersions of polyurethanes and preparation method thereof |
| CN111471386A (en) * | 2020-04-01 | 2020-07-31 | 湖南梓先新材料有限公司 | Water-based high-temperature primer surfacer and preparation method thereof |
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| CN103184004A (en) * | 2013-03-14 | 2013-07-03 | 东莞大宝化工制品有限公司 | Water-based crack paint as well as preparation method and application method thereof |
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| CN102585677A (en) * | 2011-11-10 | 2012-07-18 | 江苏海晟涂料有限公司 | Coating for blades of wind generation set |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107118323A (en) * | 2016-06-30 | 2017-09-01 | 惠尔明（福建）化学工业股份有限公司 | A kind of damp curing acrylic resin copolymer |
| CN106680082A (en) * | 2016-12-23 | 2017-05-17 | 佛山市顺德区巴德富实业有限公司 | Method for quickly detecting mechanical properties of elastic building coating |
| CN106680082B (en) * | 2016-12-23 | 2019-03-05 | 佛山市顺德区巴德富实业有限公司 | A kind of method of quick detection elastic building paint mechanical property |
| CN107099238A (en) * | 2017-06-01 | 2017-08-29 | 万华化学集团股份有限公司 | Coating composition and its preparation method and application is applied in a kind of aqueous automobile |
| CN109627417A (en) * | 2018-10-25 | 2019-04-16 | 湖南湘江关西涂料有限公司 | The aqueous anti-stone of one kind hits dispersions of polyurethanes and preparation method thereof |
| CN111471386A (en) * | 2020-04-01 | 2020-07-31 | 湖南梓先新材料有限公司 | Water-based high-temperature primer surfacer and preparation method thereof |
| CN111471386B (en) * | 2020-04-01 | 2022-07-26 | 湖南梓先新材料有限公司 | Water-based high-temperature primer surfacer and preparation method thereof |
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