CN103796764B - The formation method of multilayer film and multilayer film - Google Patents
The formation method of multilayer film and multilayer film Download PDFInfo
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- CN103796764B CN103796764B CN201280044666.6A CN201280044666A CN103796764B CN 103796764 B CN103796764 B CN 103796764B CN 201280044666 A CN201280044666 A CN 201280044666A CN 103796764 B CN103796764 B CN 103796764B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
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Abstract
The invention provides a kind of technology for coating, wherein, even if coating in discarded, also fully can suppress deterioration and the stripping of the interface of painting film and primary coat film, no matter tone how, all can obtain the film performance of excellence.The formation method of multilayer film of the present invention has following operation: on the coated article implementing electro-deposition coating, coating the 1st base coating forms the 1st base coating film formation process of the 1st base coating film; 1st base coating film is coated with the 2nd base coating film formation process that the 2nd base coating forms the 2nd base coating film; And on the 2nd base coating film, be coated with clear dope to form the transparent coating formation process of transparent coating; Wherein, in the 1st base coating film formation process, be 40 quality % ~ 60 quality % according to the pigment concentration of the 1st base coating film after baking-curing and the mode that thickness is more than 20 μm is coated with above-mentioned 1st base coating to form above-mentioned 1st base coating film; In the 2nd base coating film formation process, the mode being more than 8 μm according to the thickness of the 2nd base coating film after baking-curing is coated with above-mentioned 2nd base coating and forms the 2nd base coating film.
Description
[technical field]
The present invention relates to formation method and the multilayer film of multilayer film.In detail, the present invention relates to formation method and the multilayer film of automobile body-used multilayer film.
[background technology]
In the past, in the coating of car body, by implement on the coated article be coated with as the electro-deposition of primary coat be coated with in such as successively painting process, roasting procedure, on be coated with substrate painting process, preparation heating process, on be coated with transparent painting process and roasting procedure forms multilayer film.Due to must in this wise through the operation of more than 2, thus from reduction CO
2set out in discharge rate, the aspect reduced costs, people require to shorten operation.
Such as someone to propose on coated article and sequentially formed in film, color substrates film and transparent coating these 3 layers are carried out simultaneously to the technology (see patent document 1) of baking-curing (baked I pays け sclerosis).In utilizing this technology to omit, the roasting procedure of film, can reduce costs.
But in recent years, people require discarded middle painting coating itself and shorten operation further.Therefore, such as someone proposes following technology: in discarded while coating, makes in coating containing average grain diameter to be the small organic pigment of less than 0.05 μm and average grain diameter the be inorganic UV shield agent (see patent document 2) of less than 0.10 μm.In the past, when discarded middle coating, there is deterioration in the upper painting film caused by light therethrough and the interface of primary coat film and stripping becomes problem, and utilize this technology, can suppress this problem.
[prior art document]
[patent document]
Patent document 1: Japanese Unexamined Patent Publication 2003-47893 publication
Patent document 2: Japanese Unexamined Patent Publication 2001-38286 publication
[summary of the invention]
[inventing problem to be solved]
But in the technology of patent document 2, the shield effectiveness brought by inorganic UV shield agent has very big-difference according to the difference of tone, particularly low to the shield effectiveness of the light of high-luminance colour.Therefore, the light of high-luminance colour is easily transmitted in film, fully cannot suppress deterioration and the stripping of painting film and primary coat film interface.
In addition, in the technology of patent document 2, the light barrier effect of the inorganic UV shield agent of unit quantity is insufficient, if increase its content, then the content of other composition such as pigment can reduce, and the possibility of result can damage colour rendering or the curability of film.
Further, in the past, show the difference of base coating film according to its tone of tone, its pigment concentration has significantly difference, and (such as, for the white of high brightness, needing is more than 40 mass parts; For the black of low-light level, below 20 mass parts, it is enough.); In the technology of patent document 2, although be coated with coating in discarded, the pigment concentration in base coating film also keeps existing level.Thus, significantly different owing to having according to the pigment concentration in the different base film of tone, thus there is larger variation to stress transfer, i.e. chipping resistance by the impact from outside according to the difference of tone.Particularly when pigment concentration is low, cannot make the stress dispersion inputted by outside, can produce film peeling (Ha ガ レ) or expose the unfavorable situations etc. such as matrix, no matter tone how, also cannot obtain excellent film performance.
The present invention proposes in view of the foregoing, its object is to provide a kind of technology for coating, wherein, even if coating in discarded, also fully can suppress deterioration and the stripping of painting film and primary coat film interface, no matter tone how, all can obtain excellent film performance.
[solving the means of problem]
In order to reach above-mentioned purpose, the invention provides a kind of formation method of multilayer film, the method has following operation: on the coated article of embodiment electro-deposition coating, coating the 1st base coating forms the 1st base coating film formation process of the 1st base coating film; Above-mentioned 1st base coating film is coated with the 2nd base coating film formation process that the 2nd base coating forms the 2nd base coating film; And on above-mentioned 2nd base coating film, be coated with clear dope to form the transparent coating formation process of transparent coating.In the formation method of multilayer film of the present invention, in above-mentioned 1st base coating film formation process, be 40 quality % ~ 60 quality % according to the pigment concentration of the 1st base coating film after baking-curing and the mode that thickness is more than 20 μm is coated with above-mentioned 1st base coating to form above-mentioned 1st base coating film; In above-mentioned 2nd base coating film formation process, the mode being more than 8 μm according to the thickness of the 2nd base coating film after baking-curing is coated with above-mentioned 2nd base coating and forms the 2nd base coating film.
In the formation method of multilayer film of the present invention, as the alternative operation of discarded middle coating, in base coating film formation process, be arranged on the 1st base coating film formation process electrodeposition coating being formed the 1st base coating film and the 2nd base coating film formation process forming the 2nd base coating film on the 1st base coating film.And the pigment concentration of the 1st base coating film is set to 40 quality % ~ 60 quality %, thickness is set to more than 20 μm, the thickness of the 2nd base coating film is set to more than 8 μm.
Utilize the present invention, by the base coating film showing tone being divided into 2 layers, guaranteeing to be formed in the lower floor of the 2nd base coating film the 1st base coating film of the high pigment levels of specific above thickness, positively can shield the light of high-luminance colour thus, excellent chipping resistance can be guaranteed simultaneously.Thus, even if coating in discarded, also can fully suppress and the deterioration of the interface of electrodeposition coating and stripping, no matter tone how, all can obtain excellent film performance.
In addition, the formation method of preferred multilayer film of the present invention has the roasting procedure simultaneously above-mentioned 1st base coating film and above-mentioned 2nd base coating film being carried out to baking-curing further, as the combination of above-mentioned 1st base coating and above-mentioned 2nd base coating, use the combination of solidification temperature lower than the solidification temperature of the 2nd base coating of the 1st base coating.
In the invention, use the solidification temperature of the 1st base coating to form the 1st base coating film and the 2nd base coating film lower than the combination of the solidification temperature of the 2nd base coating, baking-curing is carried out to the 1st base coating film and the 2nd base coating film simultaneously.In the past, when toasting at the same time, when solidification prior to the 1st base coating film of the beginning of the solidification of the 2nd base coating film, along with the cure shrinkage of the 1st base coating film, the 2nd base coating film having started to solidify deforms (askew body), and the unfavorable situation that the flatness of multilayer film is impaired can occur.For this situation, in the present invention, at the same time during baking because the 2nd base coating film after start solidification at the 1st base coating film just starts to solidify, thus can avoid above-mentioned unfavorable situation and improve the flatness of multilayer film, the reflecting feel as appearance characteristics can be improved.
In addition, in the formation method of multilayer film of the present invention, as the combination of above-mentioned 2nd base coating and above-mentioned clear dope, be preferably used in the combination of painting film viscosity lower than the painting film viscosity of the 2nd base coating of clear dope under the solidification temperature of the 2nd base coating.
In the invention, the painting film viscosity being used in clear dope under the solidification temperature of the 2nd base coating forms the 2nd base coating film and transparent coating lower than the combination of the painting film viscosity of the 2nd base coating.
Utilize this invention, because the viscosity of transparent coating, lower than the 2nd base coating film, thus can suppress the 2nd mixed layer between base coating film and transparent coating under the solidification temperature of the 2nd base coating.And the stress of the film shrinkage direction produced when can be released in the cure shrinkage of the 2nd base coating film is (hereinafter referred to " curing deformation (hardening askew) ".), residual solidified distortion in film can be suppressed.Thereby, it is possible to improve the reflecting feel as appearance characteristics, and such stress from outside input of bursting apart can be suppressed, curing deformation release remaining in film can be suppressed simultaneously and peel off.
The multilayer film that the present invention also provides the formation method utilizing above-mentioned multilayer film to be formed.
Utilize multilayer film of the present invention, the effect same with the formation method of above-mentioned multilayer film can be obtained.
[effect of invention]
The present invention can provide a kind of technology for coating, wherein, even if coating in discarded, also fully can suppress deterioration and the stripping of painting film and primary coat film interface, and no matter tone how, all can provide the film performance of excellence.
[accompanying drawing explanation]
Fig. 1 illustrates the temperature of each coating used in embodiment 3 and the figure of the relation of viscosity.
Fig. 2 illustrates the temperature of each coating used in embodiment 1 and the figure of the relation of viscosity.
[detailed description of the invention]
With reference to the accompanying drawings an embodiment of the invention are described in detail.
In the formation method of the multilayer film of present embodiment, the coated article implementing electro-deposition coating is coated with the 1st base coating, the 2nd base coating and clear dope successively, make them carry out baking-curing afterwards simultaneously, thus form the 1st base coating film, the 2nd base coating film and transparent coating.In addition, the multilayer film of present embodiment is the multilayer film utilizing such formation method to be formed.
The formation method of the multilayer film of present embodiment has the 1st base coating film formation process, the 2nd base coating film formation process and transparent coating formation process.
In addition, in the formation method of the multilayer film of present embodiment, between the 2nd base coating film formation process and transparent coating formation process, there is the drying process making dried coating film, there is the roasting procedure simultaneously the 1st base coating film, the 2nd base coating film and transparent coating being carried out to baking-curing after transparent coating formation process.
In the 1st base coating film formation process, form the 1st base coating film by coating the 1st base coating on the coated article implementing electro-deposition coating.
As the coated article implementing electro-deposition coating, advantageous applications implements the car body of cationic electrodeposition coating.
As the 1st base coating, can use containing resinous principle and pigment composition and the coating of the water dispersible such as water-soluble or emulsion.
As resinous principle, use containing the resinous principle as principal component such as mylar, acrylic resin, carbamate resins.
As pigment composition, use general coloring pigment and extender pigment.
As coloring pigment, can enumerate such as: the Chinese whites such as titanium dioxide; The black pigments such as carbon black; The yellow uitramarines such as loess; The red pigment such as iron oxide red, anthraquinone; The blue pigments such as phthalocyanine blue; The viridine greens etc. such as phthalocyanine green.
As extender pigment, the inorganic pigments such as barium sulfate, calcium carbonate, kaolin, silicate (talcum) can be enumerated.
It should be noted that, the 1st base coating also can contain organic solvent or various additive as required.
In 1st base coating film formation process of present embodiment, the pigment concentration of the 1st base coating film after use baking-curing is the 1st base coating of 40 quality % ~ 60 quality %.
Be 40 quality % by the lower limit of the pigment concentration making the 1st base coating film after baking-curing, positively can shield the light of high-luminance colour, fully suppress and the deterioration of the interface of electrodeposition coating and stripping, excellent chipping resistance can be guaranteed simultaneously.In addition, by making higher limit be 60 quality %, the dispersiveness of pigment can be made to stablize, suppress irregular colour, the rupture of membranes of film can be suppressed simultaneously, thus can obtain excellent finished appearance and film performance.
In addition, in the 1st base coating film formation process of present embodiment, be more than 20 μm according to the thickness of the 1st base coating film after baking-curing and be coated with the 1st base coating, form the 1st base coating film.
Be 20 μm by the lower limit of the thickness making the 1st base coating film after baking-curing, positively can shield the light of high-luminance colour, fully suppress and the deterioration of the interface of electrodeposition coating and stripping.It should be noted that, from the viewpoint of avoiding producing after coating sagging, reduce finished appearance, the higher limit of thickness is preferably 40 μm.
In addition, in the 1st base coating film formation process of present embodiment, use solidification temperature lower than the 1st base coating of the solidification temperature of aftermentioned 2nd base coating.That is, the mode occurring to solidify prior to the 2nd base coating film according to the 1st base coating film when carrying out baking-curing to the 1st base coating film and the 2nd base coating film at the same time sets.
Herein, " solidification temperature " refers to the temperature when the decline of temperature rising medium viscosity stops and transferring rising to.Specifically, Measurement of Dynamic Viscoelasticity device is utilized to measure.
In the 2nd base coating film formation process, form the 2nd base coating film by being coated with the 2nd base coating on the 1st base coating film.In the present embodiment, the 1st base coating film touches wet (ウ ェ ッ ト オ Application ウ ェ ッ ト) by wetting and be coated with the 2nd base coating.
As the 2nd base coating, the coating of the water dispersibles such as the water-soluble or emulsion containing resinous principle and pigment composition can be used in the same manner as the 1st base coating.
As resinous principle, use containing the resinous principle as principal component such as mylar, acrylic resin, carbamate resins in the same manner as the 1st base coating film.Wherein, the resin same with the resin-phase of the 1st base coating film is needed not to be.
As pigment composition, use above-mentioned various coloring pigment and extender pigment in the same manner as the 1st base coating film.In addition, the 2nd base coating film is responsible for the effect showing tone, except above-mentioned coloring pigment, also can use photoluminescent pigment.
As photoluminescent pigment, the photoluminescent pigment of mixture in automobile exterior panel coating usually such as aluminum slice, mica, splitting, glass flake can be enumerated.
It should be noted that, the 2nd base coating also can contain organic solvent or various additive as required.
In the 2nd base coating film formation process of present embodiment, the mode being more than 8 μm according to the thickness of the 2nd base coating film after baking-curing is coated with the 2nd base coating and forms the 2nd base coating film.
Be 8 μm by the lower limit of the thickness making the 2nd base coating film after baking-curing, the corrosion resistance after bursting apart can be improved.It should be noted that, from the viewpoint of avoiding producing after coating sagging, reduce finished appearance, the higher limit of thickness is preferably 25 μm.
In the present embodiment, between the 2nd base coating film formation process and transparent coating formation process, there is the drying process making dried coating film.Utilize this drying process to remove the solvent composition in the 1st base coating film and the 2nd base coating film.
In transparent coating formation process, form transparent coating by being coated with clear dope on the 2nd base coating film.
As clear dope, the exterior use coating of general automobile can be used.As curing mechanism, such as acrylic acid-melamine cured, carboxylic acid-glycidyl solidification, hydroxyl-(end-blocking) cured with isocyanates etc. can be enumerated.
Clear dope can use in 1 liquid type or 2 liquid type compoes any one.1 liquid type coating price is cheap, without the restriction of storage period etc., thus from the aspect of the process easiness on automotive painting line for preferably.
It should be noted that, clear dope also can contain organic solvent or various additive as required.
In the transparent coating formation process of present embodiment, to be used under the solidification temperature of the 2nd base coating viscosity lower than the clear dope of the 2nd base coating.That is, when at the same time baking-curing being carried out to the 2nd base coating film and transparent coating, set lower than the mode of the viscosity of the 2nd base coating according to the viscosity of clear dope.
In the present embodiment, there is the roasting procedure simultaneously the 1st base coating film, the 2nd base coating film and transparent coating being carried out to baking-curing after transparent coating formation process.Baking condition is according to the suitable setting of the kind of the 1st base coating, the 2nd base coating and clear dope.
Utilize present embodiment can give play to following effect.
In the formation method of the multilayer film of present embodiment, as the alternative operation of discarded middle coating, in base coating film formation process, be arranged on the 1st base coating film formation process electrodeposition coating being formed the 1st base coating film and the 2nd base coating film formation process forming the 2nd base coating film on the 1st base coating film.And the pigment concentration of the 1st base coating film is set to 40 quality % ~ 60 quality %, thickness is set to more than 20 μm, the thickness of the 2nd base coating film is set to more than 8 μm.
Utilize present embodiment, by the base coating film showing tone is divided into 2 layers, guarantee to form the 1st high base coating film of the pigment concentration of specific above thickness in the lower floor of the 2nd base coating film, positively can shield the light of high-luminance colour, excellent chipping resistance can be guaranteed simultaneously.Thus, even if coating in discarded, also can fully suppress and the deterioration of the interface of electrodeposition coating and stripping, no matter tone how, all can obtain excellent film performance.
In the present embodiment, use the solidification temperature of the 1st base coating to form the 1st base coating film and the 2nd base coating film lower than the combination of the 2nd base coating, baking-curing is carried out to these the 1st base coating films and the 2nd base coating film simultaneously.In the past, when toasting at the same time, when solidification prior to the 1st base coating film of the beginning of the solidification of the 2nd base coating film, along with the cure shrinkage of the 1st base coating film, the 2nd base coating film having started to solidify deforms (askew body), and the unfavorable situation that the flatness of multilayer film is impaired can occur.For this situation, in the present embodiment, just start solidification owing to starting rear 2nd base coating film of solidification at the 1st base coating film during baking at the same time, thus can avoid above-mentioned unfavorable situation, improve the flatness of multilayer film, the reflecting feel as appearance characteristics can be improved.
In addition, in the present embodiment, the painting film viscosity being used in clear dope under the solidification temperature of the 2nd base coating forms the 2nd base coating film and transparent coating lower than the combination of the 2nd base coating.
Utilize present embodiment, because the viscosity of transparent coating, lower than the 2nd base coating film, thus can suppress the 2nd mixed layer between base coating film and transparent coating under the solidification temperature of the 2nd base coating.And the stress of the film shrinkage direction produced when can be released in the cure shrinkage of the 2nd base coating film (curing deformation (hardening askew)), the remaining of curing deformation in film can be suppressed.Thereby, it is possible to improve the reflecting feel as appearance characteristics, and such stress from outside input of bursting apart can be suppressed, curing deformation remaining in film can be suppressed to be released and to peel off simultaneously.
In addition, the multilayer film utilizing present embodiment to improve to utilize the formation method of above-mentioned multilayer film to be formed, can obtain the effect same with the formation method of above-mentioned multilayer film.
It should be noted that, the present invention is not limited to above-mentioned embodiment, and distortion, improvement etc. in the scope of attainable cost goal of the invention comprise in the present invention.
In the above-described embodiment, baking-curing is carried out to the 1st base coating film, the 2nd base coating film and clear dope simultaneously, but be not limited thereto.
[embodiment]
Next, further describe the present invention based on embodiment, but the present invention is not limited to this.
< embodiment 1>
[preparation of the 1st base coating]
In automobile water-based paint (Nippon Paint Co., Ltd manufacture " AQUALEX " (registration mark)), mixture is as titanium dioxide (" CR-90 " (registration mark) that Ishihara Sangyo Kaisha, Ltd. manufactures) 1.79 mass parts, carbon black (" FW200 " (registration mark) that EVONIKDEGUSSA Co., Ltd. manufactures) 0.56 mass parts, talcum (" SG-95 " (registration mark) that Japanese talcum Co., Ltd. manufactures) 17.05 mass parts of pigment composition in advance, thus to be adjusted to the film brightness after baking-curing be 10 ~ 20.Next (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures 17.92 mass parts, mylar (" HMP27 " that Mitsui Chemicals, Inc manufactures) 9.76 mass parts fully stir to add urethane emulsions resin wherein.The pigment concentration obtained thus in the film after by baking-curing is adjusted to the 1st base coating of the embodiment 1 of 40 mass parts.
[preparation of the 2nd base coating]
Urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 14.36 mass parts are added in the automobile water-based paint (" AQUALEXNH731P " (registration mark) that Nippon Paint Co., Ltd manufactures) being adjusted to black pearl color in advance, fully stir afterwards, thus obtain the 2nd base coating of embodiment 1.
[formation of multilayer film]
It the steel plate implementing cationic electrodeposition coating is in advance the 1st base coating prepared in 20 μm of coating the present embodiment of spraying according to the thickness after baking-curing.Next, be 8 μm according to the thickness of film after baking-curing, touch wet spray by wetting and be coated with the 2nd base coating prepared in the present embodiment.Thereafter leaving standstill in the drying oven of 80 DEG C makes it dry for 5 minutes, naturally cools to room temperature afterwards, is then 30 μm of coating clear dopes (" MacFlow-O100 " that Nippon Paint Co., Ltd manufactures) of spraying according to the thickness after baking-curing.Next in the drying oven of 140 DEG C, leave standstill 30 minutes, baking-curing is carried out to the 1st base coating film, the 2nd base coating film and transparent coating simultaneously, thus obtain the multilayer film of embodiment 1.
< embodiment 2>
[formation of multilayer film]
1st base coating of preparation in embodiment 1 is 23 μm according to the thickness after baking-curing and carries out spraying coating, implement the operation identical with embodiment 1 in addition, thus obtain the multilayer film of embodiment 2.
< comparative example 1>
[formation of multilayer film]
1st base coating of preparation in embodiment 1 is 15 μm according to the thickness after baking-curing and carries out spraying coating, implement the operation identical with embodiment 1 in addition, thus obtain the multilayer film of comparative example 1.
< comparative example 2>
[preparation of the 1st base coating]
In the 1st base coating prepared in embodiment 1, mixture is not mixed with the automobile water-based paint (" AQUALEX " (registration mark) that Nippon Paint Co., Ltd manufactures) of pigment, add urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 22.23 mass parts, mylar (" HMP27 " that Mitsui Chemicals, Inc manufactures) 12.1 mass parts simultaneously, fully stir.The pigment concentration obtained thus in the film after baking-curing is adjusted to the 1st base coating of the comparative example 2 of 35 mass parts.
[formation of multilayer film]
Using except not using the 1st base coating of preparation in embodiment 1 except the 1st base coating prepared in this comparative example, obtaining the multilayer film of comparative example 2 by implementing the operation identical with embodiment 1.
< comparative example 3>
[formation of multilayer film]
Carry out, except spraying coating, obtaining the multilayer film of comparative example 3 by implementing the operation identical with embodiment 1 except the 2nd base coating of preparation in embodiment 1 is 5 μm according to the thickness after baking-curing.
< evaluates >
For each multilayer film obtained in embodiment 1 ~ 2 and comparative example 1 ~ 3, implement the evaluation of chipping resistance.Specifically, according to following steps implementation evaluation.
First, according to JASOM104, in slungshot testing machine, the multilayer film of each embodiment and comparative example that are cooled to-20 DEG C is in advance arranged at the position that blasting materials clashes into the angle of 90 degree.As blasting materials, use road No. 7 rubble 50g, with 2kgf/cm
2air pressure spray.After test stops, take out multilayer film, remove destroyed after film and the film part of floating.Thereafter use the visual valuation film peeling such as magnifying glass number and steel plate expose number.
Specifically, about film peeling, from film peeling less, evaluate with ◎ (a little peeling), zero (peeling is few), △ (peeling is slightly many), × (peeling is many), ×× (peeling is too much) these 5 grades successively.In addition, in 50mm × 50mm four directions of damage concentration after the injection, the number of measurement diameter or length to be the number of the film peeling of 0.5mm ~ 1mm and diameter or length the be film peeling of more than 1mm.
Expose about steel plate, from exposing less, evaluate with ◎ (a little exposing), zero (exposing few), △ (exposing slightly many), × (exposing many), ×× (exposing too much) these 5 grades successively.In addition, the multilayer film after spraying is placed 24 hours in brine spray device according to JISZ2371, in 50mm × 50mm four directions of damage concentration, the number of measurement rusty part.
In addition, by based on film peeling and expose film that how many evaluation results is judged as that chipping resistance is good be designated as zero, by be judged as the film of chipping resistance difference be designated as ×, chipping resistance is judged.The results are shown in table 1.
[table 1]
As shown in table 1, in comparative example 1, the thickness of the 1st base coating film is thinner, is 15 μm, is in scope of the present invention (more than 20 μm) outward; In comparative example 2, the pigment concentration in the 1st base coating film is less, is 35 mass parts, is in scope of the present invention (40 mass parts ~ 60 mass parts) outward; And in comparative example 3, the thickness of the 2nd base coating film is thinner, is 5 μm, be in scope of the present invention (more than 8 μm) outward, in above-mentioned comparative example 1, comparative example 2 and comparative example 3, film peeling and steel plate expose all more, are judged as that chipping resistance is poor.
On the other hand, in embodiment 1 and embodiment 2, film peeling and steel plate expose all less, are judged as that chipping resistance is good.
Can being confirmed by these results, by the 1st base coating film being set to pigment concentration is 40 quality % ~ 60 quality %, thickness is more than 20 μm, the 2nd base coating film being set to that thickness is more than 8 μm, excellent chipping resistance can be obtained.
< embodiment 3>
[preparation of the 1st base coating]
The 1st base coating of embodiment 3 is prepared by the melmac composition in the 1st base coating of preparation in embodiment 1 all being replaced with exhaustive methylation melmac (" Cymel303 " (registration mark) that Japanese CytecIndustries Co., Ltd. manufactures).Thus, the solidification temperature of the 1st base coating of the present embodiment is lower than the solidification temperature of the 2nd base coating used in the present embodiment (the 2nd base coating of embodiment 1).
[preparation of clear dope]
By the middle clear dope adding dimethylethanolamine 1.2 mass parts and prepare embodiment 3 of clear dope (" MacFlow-O100 " that Nippon Paint Co., Ltd manufactures) used in embodiment 1.Thus, under the solidification temperature of the 2nd base coating (the 2nd base coating of embodiment 1) used in the present embodiment, the viscosity of the clear dope of the present embodiment is lower than the viscosity of the 2nd base coating used in the present embodiment (the 2nd base coating of embodiment 1).
[formation of multilayer film]
Do not use the 1st base coating of preparation in embodiment 1 and use the 1st base coating prepared in the present embodiment; Do not use the clear dope of use in embodiment 1 and use the clear dope prepared in the present embodiment; Except these 2, obtain the multilayer film of embodiment 3 by implementing the operation identical with embodiment 1.
< evaluates >
For the multilayer film obtained in embodiment 3, implement the evaluation of chipping resistance according to said process.And the evaluation of appearance of film is implemented in the lump when contrasting each multilayer film of embodiment 1 and embodiment 3.
About the evaluation of appearance of film, by visual, from the reflecting feel of film coated surface well, evaluate with ◎ (gloss a little reduces), zero (gloss has few reduction), △ (gloss slightly reduces), × (gloss quite has reduction), ×× (gloss reduces too much) these 5 grades successively.
In addition, WaveScanDOI (manufacture of BYKGardner society) is used to measure the arithmetic average expansion Wa value of film coated surface.The results are shown in table 2.
In addition the section of light microscope to embodiment 1 and each multilayer film of embodiment 3 is used to observe.
[table 2]
As shown in table 2, in embodiment 3, the solidification temperature of the 1st base coating slightly lower than the solidification temperature of the 2nd base coating, under the solidification temperature of the 2nd base coating the viscosity of clear dope lower than the viscosity of the 2nd base coating, compared with embodiment 1, the steel plate of this embodiment 3 exposes few especially, confirms chipping resistance and improves.
Confirm in addition, the Wa of the film coated surface of the multilayer film of embodiment 1 is large, gloss is in a slight decrease; On the other hand, little, the gloss of the Wa of the film coated surface of the multilayer film of embodiment 3 only a little reduces.
In addition, the results verification that section observes is implemented for embodiment 1 and the multilayer film of embodiment 3 and arrives, compared with embodiment 1, the 1st base coating film of embodiment 3 and the sharpness of border of the 2nd base coating film.
Herein, see figures.1.and.2 and the viscosity behavior of each coating used in embodiment 1 and embodiment 3 when baking-curing be described.Fig. 1 is the figure that the temperature of each coating and the relation of viscosity used in embodiment 3 is shown, Fig. 2 is the figure that the temperature of each coating and the relation of viscosity used in embodiment 1 is shown.
In fig. 1 and 2, the viscosity (Pas) that transverse axis represents temperature (DEG C), the longitudinal axis represents each coating.The viscosity of each coating refers to the following complex viscosity measured: use Measurement of Dynamic Viscoelasticity device (" Rheosol-G5000 " that UBM society manufactures), the parallel-plate that use cone diameter is 25mm, spacing (ギ ャ ッ プ) is 1mm, if frequency is 1.6Hz, angular amplitude is 8.23deg, utilize the intensification carried out for 10 minutes till 25 DEG C ~ 140 DEG C, the complex viscosity now measured is the viscosity of this coating.
As indicated by arrows in fig. 1 and fig. 2, be considered to solidification when viscosity starts to rise and start, temperature is now the solidification temperature of each coating.As by Fig. 1 express, in embodiment 3, confirm the solidification temperature of solidification temperature lower than the 2nd base coating of the 1st base coating, under the solidification temperature of the 2nd base coating the viscosity of clear dope lower than the viscosity of the 2nd base coating.
On the other hand, as shown in Figure 2, in embodiment 1, confirm the solidification temperature of solidification temperature higher than the 2nd base coating of the 1st base coating, under the solidification temperature of the 2nd base coating the viscosity of clear dope higher than the viscosity of the 2nd base coating.
By above results verification to, in method of forming layered coating film of the present invention, the solidification temperature of the 1st base coating lower than the viscosity of clear dope under the solidification temperature of the solidification temperature of the 2nd base coating, the 2nd base coating lower than the viscosity of the 2nd base coating, utilize the method, reflecting feel can be improved, can chipping resistance be improved simultaneously.
< embodiment 4>
[preparation of the 1st base coating]
Melmac composition in automobile water-based paint (" AQUALEX " (registration mark) that Nippon Paint Co., Ltd manufactures) is all replaced with exhaustive methylation melmac (Japanese CytecIndustries system " Cymel303 " (registration mark)), simultaneously in advance mixture as titanium dioxide (" CR-90 " (registration mark) that Ishihara Sangyo Kaisha, Ltd. manufactures) 13.16 mass parts of pigment composition, carbon black (" FW200 " (registration mark) that EVONIKDEGUSSA Co., Ltd. manufactures) 0.13 mass parts, talcum (" SG-95 " (registration mark) that Japanese talcum Co., Ltd. manufactures) 6.11 mass parts, thus to be adjusted to the film brightness after baking-curing be 50 ~ 60.Next add urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 17.92 mass parts wherein, mylar (" HMP27 " that Mitsui Chemicals, Inc manufactures) 9.76 mass parts fully stir.The pigment concentration obtained thus in the film after by baking-curing is adjusted to the 1st base coating of the embodiment 4 of 40 mass parts.
[preparation of the 2nd base coating]
Urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 14.36 mass parts are added in the automobile water-based paint (" AQUALEXNH737M " (registration mark) that Nippon Paint Co., Ltd manufactures) being adjusted to silver color in advance, fully stir afterwards, thus obtain the 2nd base coating of embodiment 4.
[formation of multilayer film]
Except the clear dope using in the 1st base coating and the 2nd base coating and embodiment 3 prepared in the present embodiment preparation except not using the 1st base coating of embodiment 1, the 2nd base coating and clear dope, obtain the multilayer film of embodiment 4 by implementing the operation identical with embodiment 1.
< embodiment 5>
[preparation of the 2nd base coating]
Urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 14.36 mass parts are added in the automobile water-based paint (" AQUALEXR540P " (registration mark) that Nippon Paint Co., Ltd manufactures) being adjusted to redness in advance, fully stir afterwards, thus obtain the 2nd base coating of embodiment 5.
[formation of multilayer film]
Except the clear dope using in embodiment 4 preparation in the 2nd base coating and embodiment 3 prepared in the 1st base coating of preparation, the present embodiment except not using the 1st base coating of embodiment 1, the 2nd base coating and clear dope, obtain the multilayer film of embodiment 5 by implementing the operation identical with embodiment 1.
< embodiment 6>
[preparation of the 2nd base coating]
Urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 14.36 mass parts are added in the automobile water-based paint (" AQUALEXB548P " (registration mark) that Nippon Paint Co., Ltd manufactures) being adjusted to blueness in advance, fully stir afterwards, thus obtain the 2nd base coating of embodiment 6.
[formation of multilayer film]
Except the clear dope using in embodiment 4 preparation in the 2nd base coating and embodiment 3 prepared in the 1st base coating of preparation, the present embodiment except not using the 1st base coating of embodiment 1, the 2nd base coating and clear dope, obtain the multilayer film of embodiment 5 by implementing the operation identical with embodiment 1.
< embodiment 7>
[preparation of the 1st base coating]
Melmac composition in automobile water-based paint (" AQUALEX " (registration mark) that Nippon Paint Co., Ltd manufactures) is all replaced with exhaustive methylation melmac (" Cymel303 " (registration mark) that NihonCytecIndustries manufactures), simultaneously mixture is as titanium dioxide (" CR-90 " (registration mark) that Ishihara Sangyo Kaisha, Ltd. manufactures) 26.19 mass parts of pigment composition in advance, thus to be adjusted to the film brightness after baking-curing be 80 ~ 90.Next add urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 17.92 mass parts wherein, mylar (" HMP27 " that Mitsui Chemicals, Inc manufactures) 9.76 mass parts fully stir.The pigment concentration obtained thus in the film after by baking-curing is adjusted to the 1st base coating of the embodiment 7 of 47.4 mass parts.
[preparation of the 2nd base coating]
Urethane emulsions resin (" UcoatUX-310 " that Sanyo Chemical Industries Co., Ltd. manufactures) 14.36 mass parts are added in the automobile water-based paint (" AQUALEXNH578 " (registration mark) that Nippon Paint Co., Ltd manufactures) being adjusted to white in advance, fully stir afterwards, thus obtain the 2nd base coating of embodiment 7.
[formation of multilayer film]
Except the clear dope using preparation in the 1st base coating prepared in the present embodiment, the 2nd base coating prepared in the present embodiment and embodiment 3 except not using the 1st base coating of embodiment 1, the 2nd base coating and clear dope, obtain the multilayer film of embodiment 7 by implementing the operation identical with embodiment 1.
< evaluates >
For each multilayer film of embodiment 3 ~ 7, carry out the evaluation of chipping resistance according to above-mentioned evaluation method.The results are shown in table 3.
[table 3]
As shown in table 3, the silver color multilayer film of known embodiment 4, the red multilayer film of embodiment 5, the blue multilayer film of embodiment 6, the white multi-layer film of embodiment 7 all possess the chipping resistance equal with the black multilayer film of embodiment 3.By this results verification to, utilize the formation method of multilayer film of the present invention, no matter tone is how, all can obtain excellent film performance.
Claims (3)
1. a formation method for multilayer film, it is the formation method of the multilayer film with following operation:
On the coated article implementing electro-deposition coating, coating the 1st base coating forms the 1st base coating film formation process of the 1st base coating film;
Above-mentioned 1st base coating film is coated with the 2nd base coating film formation process that the 2nd base coating forms the 2nd base coating film;
Above-mentioned 2nd base coating film is coated with clear dope to form the transparent coating formation process of transparent coating; And
Described 1st base coating film, described 2nd base coating film and described transparent coating are carried out simultaneously to the roasting procedure of baking-curing,
The method is characterized in that:
In above-mentioned 1st base coating film formation process, be 40 quality % ~ 60 quality % according to the pigment concentration of the 1st base coating film after baking-curing and the mode that thickness is more than 20 μm is coated with above-mentioned 1st base coating to form above-mentioned 1st base coating film;
In above-mentioned 2nd base coating film formation process, the mode being more than 8 μm according to the thickness of the 2nd base coating film after baking-curing is coated with above-mentioned 2nd base coating and forms the 2nd base coating film;
As the combination of above-mentioned 2nd base coating and above-mentioned clear dope, be used in the combination of painting film viscosity lower than the painting film viscosity of the 2nd base coating of clear dope under the solidification temperature of the 2nd base coating.
2. the formation method of multilayer film as claimed in claim 1, is characterized in that,
As the combination of described 1st base coating and described 2nd base coating, use the combination of solidification temperature lower than the solidification temperature of the 2nd base coating of the 1st base coating.
3. a multilayer film, its formation method by the multilayer film described in claim 1 or 2 is formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-199398 | 2011-09-13 | ||
| JP2011199398 | 2011-09-13 | ||
| PCT/JP2012/073196 WO2013039066A1 (en) | 2011-09-13 | 2012-09-11 | Double-layer coating film formation method and double-layer coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103796764A CN103796764A (en) | 2014-05-14 |
| CN103796764B true CN103796764B (en) | 2016-03-02 |
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| CN201280044666.6A Active CN103796764B (en) | 2011-09-13 | 2012-09-11 | The formation method of multilayer film and multilayer film |
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| Country | Link |
|---|---|
| JP (1) | JP5881719B2 (en) |
| CN (1) | CN103796764B (en) |
| BR (1) | BR112014005780A2 (en) |
| WO (1) | WO2013039066A1 (en) |
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| JP5805147B2 (en) * | 2013-07-01 | 2015-11-04 | 本田技研工業株式会社 | Painting method |
| CN107286724B (en) * | 2017-07-06 | 2020-06-05 | 观致汽车有限公司 | Automobile coating structure |
| JP7433853B2 (en) * | 2019-11-19 | 2024-02-20 | トヨタ自動車東日本株式会社 | Formation method of multi-layer coating and multi-layer coating |
| JP2022047724A (en) * | 2020-09-14 | 2022-03-25 | 日本ペイント・オートモーティブコーティングス株式会社 | Multi-layer coating film and method for forming the multi-layer coating film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01210082A (en) * | 1988-02-17 | 1989-08-23 | Kansai Paint Co Ltd | Coating method |
| JP2000281962A (en) * | 1999-03-31 | 2000-10-10 | Kansai Paint Co Ltd | Method for forming multi-layer coated film |
| JP2005177680A (en) * | 2003-12-22 | 2005-07-07 | Nissan Motor Co Ltd | Coating method and apparatus used therefor |
| JP2009177680A (en) * | 2008-01-28 | 2009-08-06 | Nikon Corp | Camera |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU572887B2 (en) * | 1983-11-28 | 1988-05-19 | Basf Corporation | Colour tinted clear coat coating system |
| CA2219303A1 (en) * | 1995-04-27 | 1996-10-31 | Masafumi Kume | Method for formation of multi-layer coating film |
| JPH10277478A (en) * | 1997-04-09 | 1998-10-20 | Nippon Paint Co Ltd | Formation of coating film |
| JP2000317394A (en) * | 1999-05-12 | 2000-11-21 | Kansai Paint Co Ltd | Method for forming coating film |
| JP2005177631A (en) * | 2003-12-19 | 2005-07-07 | Nissan Motor Co Ltd | Coating method |
| US20060121205A1 (en) * | 2004-12-04 | 2006-06-08 | Basf Corporation | Primerless integrated multilayer coating |
| MX2008015710A (en) * | 2006-06-14 | 2008-12-19 | Du Pont | Process for the production of multi-layer coatings. |
| JP2009034668A (en) * | 2007-07-06 | 2009-02-19 | Toyota Central R&D Labs Inc | Coating method, and coated object prepared by the same |
-
2012
- 2012-09-11 JP JP2013533673A patent/JP5881719B2/en active Active
- 2012-09-11 CN CN201280044666.6A patent/CN103796764B/en active Active
- 2012-09-11 BR BR112014005780A patent/BR112014005780A2/en not_active IP Right Cessation
- 2012-09-11 WO PCT/JP2012/073196 patent/WO2013039066A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01210082A (en) * | 1988-02-17 | 1989-08-23 | Kansai Paint Co Ltd | Coating method |
| JP2000281962A (en) * | 1999-03-31 | 2000-10-10 | Kansai Paint Co Ltd | Method for forming multi-layer coated film |
| JP2005177680A (en) * | 2003-12-22 | 2005-07-07 | Nissan Motor Co Ltd | Coating method and apparatus used therefor |
| JP2009177680A (en) * | 2008-01-28 | 2009-08-06 | Nikon Corp | Camera |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103796764A (en) | 2014-05-14 |
| BR112014005780A2 (en) | 2017-03-28 |
| JPWO2013039066A1 (en) | 2015-03-26 |
| WO2013039066A1 (en) | 2013-03-21 |
| JP5881719B2 (en) | 2016-03-09 |
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