CN104745062B - A kind of aqueous composite paint and its compelx coating method - Google Patents
A kind of aqueous composite paint and its compelx coating method Download PDFInfo
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- CN104745062B CN104745062B CN201510141276.6A CN201510141276A CN104745062B CN 104745062 B CN104745062 B CN 104745062B CN 201510141276 A CN201510141276 A CN 201510141276A CN 104745062 B CN104745062 B CN 104745062B
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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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- Engineering & Computer Science (AREA)
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Abstract
The present invention discloses a kind of aqueous composite paint, and the aqueous composite paint includes aqueous middle painting coating and aqueous finish paint coating；The aqueous middle painting coating and aqueous finish paint coating all include at least one aqueous polyurethane；Apply in the aqueous composite paint of the present invention and the interlayer conformability between finish paint is good, gained compelx coating flatness, resistance to water and resistance to hitting property of stone are excellent.The invention also discloses a kind of compelx coating method of aqueous composite paint, is obtained the excellent compelx coating of a kind of flatness, resistance to water and resistance to hitting property of stone using the coating process.
Description
Technical field
The present invention relates to the technical field of coating.More particularly, to a kind of aqueous composite paint and its compelx coating side
Method.
Background technology
Three apply one dries (3C1B) technique, in referring to vehicle coating process, on the vehicle body for scribbling electrophoresis film, middle painting, face
Paint, three coatings of varnish are all wet on wet in same spray room to complete application.
Compared with traditional vehicle coating process 3C2B, on surface, 3C1B has simply lacked a baking process (middle coated baking
It is roasting), but, control either in coating film thickness, the control of appearance of coat, there is higher requirement on coating process.With
3C2B is compared, and 3C1B applies cross-linking reaction time and reaction rate and finish paint between in needing strict control so that middle painting and finish paint
Between interlayer conformability it is more preferable；In order to ensure the flatness of film, the thickness of middle painting film must be than 3C2B compelx coating
The middle thickness for applying film is thin, and thus may result in resistance to hitting property of stone reduce, or the stone that splashes in vehicle travel process with
Smearing collision causes compelx coating to destroy, or peeling-off in electrophoresis film and the aqueous middle interface for applying film.
At present, acrylic resin and high-tenacity polyester resin are employed in 3C1B material prescriptions, by what is applied in adjustment
Resin structure and solvent are allowed to have good wet on wet coating performance with finish paint optimizing solidification rate.The technology is viscous to coating
Degree and thixotropy are required greatly, in work progress, higher to paint spray booth's environment temperature and humidity requirement.
Accordingly, it is desirable to provide a kind of aqueous composite paint and its compelx coating method.
The content of the invention
It is an object of the present invention to provide a kind of aqueous composite paint, applies and face in the aqueous composite paint of the present invention
Interlayer conformability between paint is good, and gained compelx coating flatness, resistance to water and resistance to hitting property of stone are excellent.
Further object is that a kind of compelx coating method of aqueous composite paint is provided, using the application side
Method is obtained the excellent compelx coating of a kind of flatness, resistance to water and resistance to hitting property of stone.
To reach above-mentioned purpose, the present invention adopts following technical proposals：
A kind of aqueous composite paint, the aqueous composite paint include aqueous middle painting coating and aqueous finish paint coating；It is described
The aqueous middle raw material for applying coating includes at least one aqueous polyurethane；The raw material of the aqueous finish paint coating includes at least one water
Property polyurethane.
Preferably, the aqueous middle raw material for applying coating includes aqueous polyurethane A and aqueous polyurethane B；
The number-average molecular weight of the aqueous polyurethane A is more than 7000, and hydroxyl value is less than 5；
The number-average molecular weight of the aqueous polyurethane B is 1500-5000, and hydroxyl value is 80-250.
The aqueous polyurethane of HMW and low hydroxyl will not be crosslinked, and film can be made to have a pliability, thus can be with
Obtain the higher film of elongation；And by using HMW body, can also make film that there is tensile strength；But due to not
Can crosslink, so the aqueous polyurethane of the low hydroxyl of HMW is used alone, it may appear that crosslink density is relatively low, water resistance
Poor result；Therefore, by and with the aqueous polyurethane of hydroxyl, guarantee crosslink density, to maintain water resistance.But
That, if the molecular weight of the aqueous polyurethane being crosslinked is also high, film will become stone, resistance to hitting property of stone will under
Drop；Therefore through test of many times, have selected above two aqueous polyurethane.
Preferably, the raw material of the aqueous finish paint coating includes aqueous polyurethane C and aqueous polyurethane D；
The number-average molecular weight of the aqueous polyurethane C is 1500-5000, and hydroxyl value is 20-80；
The number-average molecular weight of the aqueous polyurethane D is 1500-5000, and hydroxyl value is 80-250.
Described two aqueous polyurethanes used in topcoat paint of the present invention, can guarantee that resistance to stone hits performance and resistance to water simultaneously
Higher level can be in.The middle painting coating of the present invention must be used simultaneously with topcoat paint, as the painting design of the present invention is
3C1B, i.e., spray paint in the state of applying in not drying, so the mixed layer with finish paint can be applied in occurring；That is it is contemplated that
Into 1 film.Therefore, middle painting and finish paint must be supporting.
Preferably, in the aqueous middle raw material for applying coating, the consumption of aqueous polyurethane A accounts for aqueous composite paint gross weight
10-20wt%；The consumption of aqueous polyurethane B accounts for the 20-40wt% of aqueous composite paint gross weight.
Preferably, in the raw material of the aqueous finish paint coating, the consumption of aqueous polyurethane C accounts for aqueous composite paint gross weight
5-15wt%；The consumption of aqueous polyurethane D accounts for the 10-30wt% of aqueous composite paint gross weight.
The present invention provides a kind of preparation method of aqueous polyurethane A：
Will with number-average molecular weight Mn 1500-4000, acid value AV (solid content) below 5, hydroxyl value OHV in 20-80 extremely
A kind of few PEPA,
Mixture at least containing 1 dihydroxylic alcohols and trihydroxylic alcohol,
Containing the functional group that anion is formed, additionally needing can be with the functional group of isocyanates reaction containing at least two
Compound,
Non- ring type aliphatic diisocyanate, or alicyclic diisocyanate,
Amine neutralization after above substance reaction, then disperses in water, can be with the sense of isocyanates reaction containing at least 2
Roll into a ball and be obtained more than number-average molecular weight Mn7000 after chain extension, water dispersible of hydroxyl value OHV (solid content) below 5
Polyester modified polyurethane Resin A.
The present invention provides a kind of preparation method of aqueous polyurethane B：
With number-average molecular weight Mn500-2000, acid value AV (solid content) below 5, hydroxyl value OHV in 100-300 at least
A kind of PEPA,
Mixture at least containing 1 dihydroxylic alcohols and trihydroxylic alcohol,
Containing the functional group that anion is formed, additionally needing can be with the functional group of isocyanates reaction containing at least two
Compound,
Non- ring type aliphatic diisocyanate, or alicyclic diisocyanate
Amine neutralization after above substance reaction, obtains number-average molecular weight Mn in 1500-5000, hydroxyl value after then disperseing in water
Water-dispersible polyester modified polyurethane resin Bs of the OHV (solid content) in 80-250.
The present invention provides a kind of preparation method of aqueous polyurethane C：
With number-average molecular weight Mn500-2000, acid value AV (solid content) below 5, hydroxyl value OHV in 100-300 at least
A kind of PEPA,
Mixture at least containing 1 dihydroxylic alcohols and trihydroxylic alcohol,
Containing the functional group that anion is formed, additionally needing can be with the functional group of isocyanates reaction containing at least two
Compound,
Non- ring type aliphatic diisocyanate, or alicyclic diisocyanate,
Amine neutralization after above substance reaction, the water-dispersible polyester modified polyurethane resin obtained after then disperseing in water
C。
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 includes polyester resin, allyl resin and polyethers
Resin.
Curing agent used in the present invention includes amino resins and closure isocyanates etc..
A kind of compelx coating method of aqueous composite paint, comprises the following steps：
(1) it is 10-20 μm to spray aqueous middle painting coating and make the thickness of its dry coating, forms unhardened aqueous middle painting and applies
Film；
(2) spray on film aqueous finish paint coating and make aqueous finish paint coating in step (1) unhardened aqueous middle painting
Dry coating thickness reaches 5-20 μm, forms unhardened aqueous finish paint film；
(3) the unhardened aqueous middle painting film obtained in step (1) and (2) and unhardened aqueous finish paint film are entered
After capable heating, drying, lacquer varnish coating makes the thickness of its dry coating reach 30-50 μm, forms unhardened varnish film；
(4) by unhardened aqueous middle painting film, unhardened aqueous finish paint film and unhardened varnish film once
Property heating, make unhardened aqueous middle painting film, unhardened aqueous finish paint film and the hardening of unhardened varnish, formation includes
The aqueous middle compelx coating for applying film, aqueous finish paint film and varnish film.
Preferably, in the compelx coating described in step (4), the aqueous middle dry film thickness for applying film monofilm is at 15 μm, 20 DEG C
When elongation be 20-40%, tensile strength be 20-40N/mm2, crosslink density be 10-20mmol/ml；Aqueous finish paint film list
The dry film thickness of film elongation in 12 μm, 20 DEG C is 10-20%, tensile strength is 20-40N/mm2, crosslink density be 10-
20mmol/ml。
It is heated to be preheating (predrying) in step (3), heating-up temperature is 80-70 DEG C, as long as heating makes moisture, low boiling
Solvent is vapored away；Be not heating and curing reaction.
Beneficial effects of the present invention are as follows：
The present invention by design 4 kinds of different polyurethane resins, by its it is appropriate be mixed in middle painting and finish paint, just may be used
Obtain required for Physical properties of coating film (elongation, tensile strength, crosslink density), can make simultaneously resistance to hitting property of stone and resistance to water in compared with
It is high-grade.
It is the ammonia ester bond being had concurrently by its inside that people both know about traditional polyurethane resin, and has higher elasticity
Higher hardness and then with excellent tack, in the past, hits grade and mixes in coating especially for resistance to stone is improved
The example for closing polyurethane resin has a lot.These resins are used for middle painting monomer or finish paint monomer, then refer to design 1 again
Polyurethane resin or Physical properties of coating film.The 3C1B painting designs of the present invention are to be respectively directed to middle painting and finish paint to design different poly-
Urethane resin (molecular weight and hydroxyl value).Thus the compelx coating of optimal physical property is obtained, the film of higher grade than ever is obtained
Energy.
Specific embodiment
In order to be illustrated more clearly that the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, and should not limit this with this
The protection domain of invention.
The present invention provides at least one preparation method of part material, the same or like original prepared using other methods
Material is also in the scope of the present invention.
The preparation of Production Example 1, PEPA 1-1 (PE1-1)
Equipped with the reaction vessel of the backflow cooling device of reaction delivery port, thermometer, agitating device and nitrogen ingress pipe
In, neopentyl glycol (7.5 parts), 1,6- hexylene glycol (38.5 parts), (54 parts) inputs of 1,6- adipic acid are warmed up to 120 DEG C of raw materials molten
Xie Hou, persistently stirring are warming up to 160 DEG C.After 160 DEG C are kept for 1 hour, continue to be warmed up to 230 DEG C in 5 hours.It is fixed in 230 DEG C of insulations
When test acid value, until resin acid value is to 1mgKOH/g.Less than 80 DEG C are subsequently cooled to, acid value 1mgKOH/g, hydroxyl value is obtained
36mgKOH/g, the PEPA 1-1 (PE1-1) of number-average molecular weight 3000.
The preparation of Production Example 2, PEPA 1-2 (PE1-2)
Neopentyl glycol (13 parts), 1,6- hexylene glycol (33.5 parts), (53.5 parts) inputs of 1,6- adipic acid, using Production Example 1
Method, obtain acid value 1mgKOH/g, hydroxyl value 55mgKOH/g, the PEPA 1-2 (PE1-2) of number-average molecular weight 2000.
The preparation of Production Example 3, PEPA 2 (PE2)
Neopentyl glycol (5.8 parts), 1,6- hexylene glycol (29.9 parts), trimethylolpropane (13.2 parts), 1,6- adipic acid
(51.1 parts) inputs, using the method for Production Example 1, obtain acid value 1mgKOH/g, hydroxyl value 136mgKOH/g, number-average molecular weight
1500 PEPA 2 (PE2).
The preparation of Production Example 4, PEPA 3 (PE3)
Neopentyl glycol (13.8 parts), 1,6- hexylene glycol (35.5 parts), (50.7 parts) inputs of 1,6- adipic acid, using Production Example
1 method, obtains acid value 1mgKOH/g, hydroxyl value 111mgKOH/g, the PEPA 3 (PE3) of number-average molecular weight 1000.
The manufacture of Production Example 5, water-dispersible polyester modified polyurethane resin 1-1 (PUD1-1)
Equipped with the reaction vessel of the backflow cooling device of reaction delivery port, thermometer, agitating device and nitrogen ingress pipe
In, the PEPA 1-1 (PE1-1) (27.7 parts) obtained using Production Example 1, (2.2 parts) inputs of dihydromethyl propionic acid are continued
Stirring is warming up to 80 DEG C.
80 DEG C of periods are reached, IPDI (10 parts) is being added, 80 DEG C of reactions is persistently being incubated, until NCO
Equivalent obtains the polyether polyols of NCO end-blockings to 1044.
Then 50 DEG C are cooled to, (1.7 parts) neutralizations of triethylamine are added, deionized water (41.6 parts) is added after neutralization, is obtained
Polyurethane prepolymer dispersion liquid.
Ethylenediamine (0.8 part), deionized water (16 parts) is added to be warming up to 60 DEG C and be incubated 1 hour afterwards, performed polymer chain extension is complete
Cheng Hou, is cooled to 40 DEG C, obtains solid content 40.0%, and hydroxyl value 2mgKOH/g, the water-dispersible polyester of number-average molecular weight 12500 change
Property polyurethane resin 1-1 (PUD1-1), polyurethane obtained in this Production Example can be considered aqueous polyurethane A.
The manufacture of Production Example 6, water-dispersible polyester modified polyurethane resin 1-2 (PUD1-2)
Equipped with the reaction vessel of the backflow cooling device of reaction delivery port, thermometer, agitating device and nitrogen ingress pipe
In, the PEPA 1-2 (28 parts) obtained using Production Example 2, (2.2 parts) inputs of dihydromethyl propionic acid, persistently stirring are heated up
To 80 DEG C.
80 DEG C of periods are reached, IPDI (8.9 parts) is being added, 80 DEG C of reactions is persistently being incubated, until NCO
Equivalent obtains the polyether polyols of NCO end-blockings to 4190.
Then 50 DEG C are cooled to, (1.7 parts) neutralizations of triethylamine are added, deionized water (42 parts) is added after neutralization, is gathered
Urethane pre-polymerization dispersion liquid.
Ethylenediamine (0.8 part), deionized water (16.2 parts) is added to be warming up to 60 DEG C and be incubated 1 hour afterwards, performed polymer chain extension
After the completion of, 40 DEG C are cooled to, solid content 40.0%, hydroxyl value 1mgKOH/g, the water-dispersible polyester of number-average molecular weight 20000 is obtained
Modified polyurethane resin 1-2 (PUD1-2), polyurethane obtained in this Production Example can be considered aqueous polyurethane A.
The manufacture of Production Example 7, water-dispersible polyester modified polyurethane resin 2-1 (PUD2-1)
Equipped with the reaction vessel of the backflow cooling device of reaction delivery port, thermometer, agitating device and nitrogen ingress pipe
In, the PEPA 2 (22.9 parts) obtained using Production Example 3, dihydromethyl propionic acid (3.1 parts), trimethylolpropane (7.4
Part) input, persistently stir and be warming up to 80 DEG C.80 DEG C of periods are reached, IPDI (17 parts) is being added, is persistently protected
80 DEG C of reactions of temperature, until absworption peaks of the NCO in IR spectrum disappears.
Then 50 DEG C are cooled to, (0.9 part) neutralization of triethylamine are added, after neutralization, is added deionized water (48.6 parts), insulation 1
After hour, 40 DEG C are cooled to, obtain solid content 40.0%, hydroxyl value 100mgKOH/g, the water dispersible of number-average molecular weight 3500 are gathered
Ester modified polyurethane resin 2-1 (PUD2-1), polyurethane obtained in this Production Example can be considered aqueous polyurethane B or D.
The manufacture of Production Example 8, water-dispersible polyester modified polyurethane resin 2-2 (PUD2-2)
The PEPA 2 (27.8 parts) obtained using Production Example 3, dihydromethyl propionic acid (3.2 parts), trimethylolpropane
(12.3 parts), IPDI (22.5 parts), triethylamine (0.7 part), deionized water (33.6 parts), by Production Example
7 method, obtains solid content 40.0%, hydroxyl value 150mgKOH/g, and the water-dispersible polyester of number-average molecular weight 2000 is modified poly- ammonia
Ester resin 2-2 (PUD2-2), polyurethane obtained in this Production Example can be considered aqueous polyurethane B or D.
The manufacture of Production Example 9, water-dispersible polyester modified polyurethane resin 3-1 (PUD3-1)
Equipped with the reaction vessel of the backflow cooling device of reaction delivery port, thermometer, agitating device and nitrogen ingress pipe
In, the PEPA 3 (37.1 parts) obtained using Production Example 4, dihydromethyl propionic acid (2.3 parts), 1,6- hexylene glycol (2 parts),
(0.1 part) input of trimethylolpropane, persistently stirring are warming up to 80 DEG C.80 DEG C of periods are reached, two isocyanide of isophorone is being added
Acid esters (12.8 parts), is persistently incubated 80 DEG C of reactions, until absworption peaks of the NCO in IR spectrum disappears.
Then 50 DEG C are cooled to, (0.8 part) neutralization of triethylamine are added, after neutralization, is added deionized water (42.6 parts), insulation 1
After hour, 40 DEG C are cooled to, solid content 40.0%, hydroxyl value 30mgKOH/g, the water-dispersible polyester of number-average molecular weight 3800 is obtained
Modified polyurethane resin 3-1 (PUD3-1), polyurethane obtained in this Production Example can be considered aqueous polyurethane C.
The manufacture of Production Example 10, water-dispersible polyester modified polyurethane resin 3-2 (PUD3-2)
Equipped with the reaction vessel of the backflow cooling device of reaction delivery port, thermometer, agitating device and nitrogen ingress pipe
In, the PEPA 3 (37.1 parts) obtained using Production Example 4, dihydromethyl propionic acid (2.7 parts), DEG (1.6 parts), three hydroxyl first
(0.1 part) input of base propane, persistently stirring are warming up to 80 DEG C.80 DEG C of periods are reached, IPDI is being added
(12.1 parts), are persistently incubated 80 DEG C of reactions, until absworption peaks of the NCO in IR spectrum disappears.Then 50 DEG C are cooled to, three are added
(0.8 part) neutralization of ethamine, adds deionized water (43.2 parts), after being incubated 1 hour, is cooled to 40 DEG C, obtains solid content after neutralization
40.0%, hydroxyl value 40mgKOH/g, water-dispersible polyester modified polyurethane resin 3-2 (PUD3-2) of number-average molecular weight 2800, this
Polyurethane obtained in Production Example can be considered aqueous polyurethane C.
The containing admittedly of the PUD of above-mentioned preparation, hydroxyl value and number-average molecular weight Mn the results are shown in Table 1.
Table 1
| PUD1-1 | PUD1-2 | PUD2-1 | PUD2-2 | PUD3-1 | PUD3-2 | |
| Gu contain (%) | 40 | 40 | 40 | 40 | 40 | 40 |
| Hydroxyl value | 2 | 1 | 100 | 150 | 30 | 40 |
| Mn | 12500 | 20000 | 3500 | 2000 | 3800 | 2800 |
The manufacture of 11 pigment dispersed slurry of Production Example
In advance by 1.0 parts of dispersant Disperbyk192 (the nonionic class dispersant of BYK companies manufacture), defoamer
After 0.5 part of BYK-011 (defoamer of BYK companies manufacture), 6.0 parts of ion exchange water, 20.4 parts of titanium dioxide mix, in sand
Bead medium is added in grinding machine, mixing dispersion at room temperature reaches less than 5 μm up to fineness, so as to obtain pigment dispersed slurry.
The aqueous middle modulation for applying coating (1) of Production Example 12
The water dispersible obtained in 27.9 parts of the pigment dispersed slurry obtained in above-mentioned Production Example 11, above-mentioned Production Example 5 is gathered
The water-dispersible polyester modified polyurethane tree obtained in 7.7 parts of ester modified polyurethane resin 1-1 (PUD1-1), above-mentioned Production Example 7
15.3 parts of fat 2-1 (PUD2-1), Setaqua BE 270 (polyester resin aqueous dispersion of Nuplex manufactures, non-volatile part 70%)
2.9 parts, AC-176 (aqueous acrylic resin dispersion of Picassian manufactures, non-volatile part 47.5%) 6.4 parts, and curing agent
After 7.0 parts of mixing of Cymel370 (Allnex manufacture amino resins, non-volatile part 88%), (Basf is manufactured with sticky agent HV-30
Sticky agent) 0.4 part, 0.5 part of surface conditioner BYK-346 (surface conditioner of BYK manufactures), solvent ethylene glycol monobutyl ether 0.6
Part mixes, so as to obtain aqueous middle painting coating (1).
The aqueous middle modulation for applying coating (2)-(7) of Production Example 13
Except by water-dispersible polyester modified polyurethane resin 1-1 (PUD1-1), water-dispersible polyester modified polyurethane resin
2-1 (PUD 2-1), Setaqua B E270 (polyester resin aqueous dispersion of Nuplex manufactures, non-volatile part 70%), AC-176
(Picassian manufacture aqueous acrylic resin dispersion, non-volatile part 47.5%), and curing agent Cymel370 (Allnex is manufactured
Amino resins, non-volatile part 88%) be changed to beyond the material described in table 1 and solid part quality % described in table 1,
Thus other modulation steps modulate aqueous middle painting coating (2)-(7) with Production Example 12.
The elongation of the raw material weight number and prepared middle painting coating of aqueous middle painting coating 1-7, tensile strength, crosslinking
The performance data of density is shown in Table 2, and in table 2, the middle painting formulation for coating material of example 1-4 is the formula in the range of technical solution of the present invention, 5-7
Middle painting formulation for coating material be used for convenience of doing comparative example below.
Table 2
The modulation of 14 aqueous finish paint coating (1) of Production Example
By 62.5 parts of water-dispersible polyester modified polyurethane resin 2-1 (PUD2-1) obtained in above-mentioned Production Example 7 and system
25.0 parts of mixing of water-dispersible polyester modified polyurethane resin 3-1 (PUD3-1) obtained in making example 9, with AC-176
(aqueous acrylic resin dispersion of Picassian manufactures, non-volatile part 47.5%) 73.7 parts, and curing agent Cymel370
34.1 parts of (amino resins of Allnex manufactures, non-volatile part 88%), photoluminescent Aluminum Pigment slurry EMR D7670 (Japan's Aluminums
The aluminium powder pigment of manufacture) 30 parts (solid part 50%, PWC12%), the AQ-330 (acrylic acid of the phosphorous acidic group of nanmu this chemical conversion manufacture
Resin) 3.0 parts, and, 40 parts of 2-Ethylhexyl Alcohol, 6.7 parts of sticky agent HV-30 (sticky agent of Basf manufactures), surface conditioner
1.1 parts of BYK-346 (surface conditioner of BYK manufactures) is uniformly dispersed so as to obtain aqueous finish paint coating (1).
The modulation of 15 aqueous finish paint coating (2)-(5) of Production Example
Except by 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 of Picassian manufactures, non-volatile part 47.5%), and Cymel
Solid described in 370 (amino resins of Allnex manufactures, the non-volatile parts 88%) materials that are changed to described in table 3 and table 3
Beyond part quality %, thus other modulation steps modulate aqueous finish paint coating (2)-(5) with Production Example 14.
Table 3
In table 3, the aqueous finish paint coating of example 1-3 consists of the formula in the range of technical solution of the present invention, example 4-5 it is aqueous
Topcoat paint is consisted of and does comparative example use below.
Embodiment 1
The formation of compelx coating
On the passivation steel plate processed through trbasic zinc phosphate, the painting electrophoresis coating PN-310 (cations of ippon coating manufacture
Electrophoretic coating), painting is attached to till making dry coating thickness up to 20 μm, and the heating at 160 DEG C makes which cool down after solidifying for 30 minutes,
So as to form solidification electrophoresis film.
Under room temperature, it is being formed with the substrate of solidification electrophoresis film, the water obtained in Production Example 12 is being sprayed with spray equipment
Property in apply coating (1), till being sprayed onto the thickness after making to be heating and curing up to 15 μm, thus obtain it is unhardened it is aqueous it is middle apply apply
Film.Then, the aqueous finish paint coating (1) that obtains is sprayed in Production Example 14 until making the thickness after heat drying can with spray equipment
Till reaching 10 μm, then preheat 3 minutes at 80 DEG C.Again on the coated plate, with spray equipment lacquer varnish coating SPO-300
After thickness of the coating varnish amino curing type varnish paint of manufacture (ippon coating) after make heat drying can reach 35 μm,
The heating at 140 DEG C solidifies which in 30 minutes, so as to obtain the sample with compelx coating.
And, aqueous middle painting coating (1), aqueous finish paint coating (1) and varnish paint be carried out using following condition it is dilute
Release, spray.
Aqueous middle painting coating (1)
Retarder thinner：Ion exchange water
No. 4 cup/20 DEG C of 50 seconds/Ford
Aqueous finish paint coating (1)
Retarder thinner：Ion exchange water
No. 4 cup/20 DEG C of 40 seconds/Ford
Varnish paint
Retarder thinner：S-100 (the aromatic series hydrocarbon solvent of Exxon manufacture)/S-150 be (Exxon manufacture
Aromatic series hydrocarbon solvent)=1/1 (mass ratio) mixed solvent
No. 4 cup/20 DEG C of 30 seconds/Ford
With the sample with compelx coating obtained above, following evaluation is carried out.Evaluation result is as shown in table 4.
Embodiment 2-4
As different from Example 1, the aqueous middle selection for applying coating and aqueous finish paint coating, specifically chosen to be shown in Table 4, other
Step is same as Example 1, thus obtains the sample with compelx coating.
Comparative example 1-4
As different from Example 1, the aqueous middle selection for applying coating and aqueous finish paint coating, specifically chosen to be shown in Table 4, other
Step is same as Example 1, thus obtains the sample with compelx coating.
Table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Aqueous middle painting | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 4 |
| Aqueous finish paint | 1 | 1 | 2 | 3 | 1 | 2 | 4 | 5 |
| Resistance to water | ○ | ○ | ○ | ○ | ○ | ○ | × | × |
| Resistance to hitting property of stone | 1 | 1 | 1 | 1 | 3 | 4 | 1 | 1 |
Resistance to water
Sample with compelx coating obtained above is put into after impregnating 10 days in 40 DEG C of warm water and is taken out, existed with blade
Grid (drawing the square grid of 100 2mm × 2mm) is drawn thereon, and the adhesive plaster manufactured with Nichiban carries out disbonded test.Not yet
Have peeling-off sample to be evaluated as zero, there occurs the sample of stripping be evaluated as ×, as a result as shown in table 4.
Resistance to hitting property of stone
With MULTI GRIT TESTER 508VDA (ERICHSEN manufactures) in 5kgf/cm2Air pressure under from apart from 35cm
Sample Chilled Iron Grit (G-9652-X) of 500g got to after -25 DEG C of coolings with 45 ° of angle of position
On compelx coating.After washing and drying, the industrial adhesive tape manufactured with Nichiban companies is peeled off, and removes film fragment, so
Afterwards, the extent of exfoliation of visual valuation film.The exfoliated state of film is evaluated by following metewand.As a result it is as shown in table 4.
1 does not almost peel off
2 only a little peel off but outward appearance have no problem
3 strippings are slightly larger or a little more and problematic in appearance
4 strippings are larger or more
5 strippings are significantly greater or substantially more
Stress-deformation characteristic
<Elongation tensile strength>
The coating just modulated in embodiment and comparative example is sprayed on polypropylene board with spray equipment, being sprayed onto makes heating solid
Till thickness after change can reach 20 μm, then preheat 3 minutes at 80 DEG C, then heating solidify which in 30 minutes at 140 DEG C,
Afterwards, film is stripped down so as to obtain the film of stress-deformation characteristic from polypropylene board.With painting automatically for AGS-G models
Figure instrument and analog meter (Shimadzu Seisakusho Ltd.'s manufacture), measurement length be 50mm, temperature be 20 DEG C, draw speed be 10mm/min
Under the conditions of measure.Tensile strength can be after tension test chart tendency and obtain.Simultaneously, elongation can be by figure
(the axial length of the sample before assuming to test is 50 (mm) to the extended length of the sample read in table, is stretched to sample and breaks
Axial length when splitting is L (mm), then elongation (%)=(L-50) × 100/50) and draw.
<Crosslink density>
The coating just modulated in embodiment and comparative example is sprayed on polypropylene board with spray equipment, being sprayed onto makes heating solid
Thickness after change can reach 20 μm be to.The plate is preheated 3 minutes at 80 DEG C, then after heating 30 minutes at 140 DEG C, will be applied
Film is stripped down so as to obtain independent film from polypropylene board.With II-EA of VIBRON DDV-, (it is viscous that Japan Baldwin is manufactured
Compliance test apparatus, experimental condition：Frequency 11Hz, heat up 2 DEG C/minute) measure the crosslink density of the film.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all of embodiment cannot be exhaustive here, it is every to belong to this
Bright technical scheme it is extended obvious change or change still in protection scope of the present invention row.
Claims (5)
1. a kind of aqueous composite paint, it is characterised in that：The aqueous composite paint includes aqueous middle painting coating and aqueous finish paint
Coating；
The aqueous middle raw material for applying coating includes at least one aqueous polyurethane；
The raw material of the aqueous finish paint coating includes at least one aqueous polyurethane；
The aqueous middle raw material for applying coating includes aqueous polyurethane A and aqueous polyurethane B；
The number-average molecular weight of the aqueous polyurethane A is more than 7000, and hydroxyl value is less than 5；
The number-average molecular weight of the aqueous polyurethane B is 1500-5000, and hydroxyl value is 80-250；
The raw material of the aqueous finish paint coating includes aqueous polyurethane C and aqueous polyurethane D；
The number-average molecular weight of the aqueous polyurethane C is 1500-5000, and hydroxyl value is 20-80；
The number-average molecular weight of the aqueous polyurethane D is 1500-5000, and hydroxyl value is 80-250.
2. aqueous composite paint according to claim 1, it is characterised in that：It is aqueous in the aqueous middle raw material for applying coating
The consumption of polyurethane A accounts for the 10-20wt% of aqueous composite paint gross weight；It is total that the consumption of aqueous polyurethane B accounts for aqueous composite paint
The 20-40wt% of weight.
3. aqueous composite paint according to claim 1, it is characterised in that：It is aqueous in the raw material of the aqueous finish paint coating
The consumption of polyurethane C accounts for the 5-15wt% of aqueous composite paint gross weight；The consumption of aqueous polyurethane D accounts for aqueous composite paint gross weight
10-30wt%.
4. using the compelx coating method of the aqueous composite paint any one of claim 1-3, it is characterised in that include
Following steps：
(1) it is 10-20 μm to spray aqueous middle painting coating and make the thickness of its dry coating, forms unhardened aqueous middle painting film；
(2) spray on film aqueous finish paint coating and make the drying of aqueous finish paint coating in step (1) unhardened aqueous middle painting
Film thickness reaches 5-20 μm, forms unhardened aqueous finish paint film；
(3) the unhardened aqueous middle painting film obtained in step (1) and (2) and unhardened aqueous finish paint film are carried out adding
After hot, dry, lacquer varnish coating makes the thickness of its dry coating reach 30-50 μm, forms unhardened varnish film；
(4) unhardened aqueous middle painting film, unhardened aqueous finish paint film and unhardened varnish are applied membrane disposable and is added
Heat, includes unhardened aqueous middle painting film, unhardened aqueous finish paint film and the hardening of unhardened varnish film, formation
The aqueous middle compelx coating for applying film, aqueous finish paint film and varnish film.
5. method according to claim 4, it is characterised in that：In compelx coating described in step (4), aqueous middle painting film
The dry film thickness of monofilm elongation in 15 μm, 20 DEG C is 20-40%, tensile strength is 20-40N/mm2, crosslink density be 10-
20mmol/ml；The dry film thickness of aqueous finish paint film monofilm elongation in 12 μm, 20 DEG C is 10-20%, tensile strength is
20-40N/mm2, crosslink density be 10-20mmol/ml.
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| 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 |
| 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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| CN103184004B (en) * | 2013-03-14 | 2015-08-12 | 东莞大宝化工制品有限公司 | A kind of water-based crackle paint and preparation method thereof and method of application |
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