CN1647862A - Process for forming multi layered coated film and multi layered coated film - Google Patents

Process for forming multi layered coated film and multi layered coated film Download PDF

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Publication number
CN1647862A
CN1647862A CNA2005100518647A CN200510051864A CN1647862A CN 1647862 A CN1647862 A CN 1647862A CN A2005100518647 A CNA2005100518647 A CN A2005100518647A CN 200510051864 A CN200510051864 A CN 200510051864A CN 1647862 A CN1647862 A CN 1647862A
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China
Prior art keywords
film
uncured
coating
solidified
resin
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Chinese (zh)
Inventor
东井辉三
三原康央
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Nippon Paint Co Ltd
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Nippon Paint Co Ltd
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Publication of CN1647862A publication Critical patent/CN1647862A/en
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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
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47F—SPECIAL FURNITURE, FITTINGS, OR ACCESSORIES FOR SHOPS, STOREHOUSES, BARS, RESTAURANTS OR THE LIKE; PAYING COUNTERS
    • A47F5/00—Show stands, hangers, or shelves characterised by their constructional features
    • A47F5/16—Platform-type show stands with flat, inclined, or curved upper surface
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45B—WALKING STICKS; UMBRELLAS; LADIES' OR LIKE FANS
    • A45B23/00—Other umbrellas
    • 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
    • B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4488—Cathodic paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F13/00—Illuminated signs; Luminous advertising
    • G09F13/04—Signs, boards or panels, illuminated from behind the insignia
    • G09F13/0404—Signs, boards or panels, illuminated from behind the insignia the light source being enclosed in a box forming the character of the sign
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F23/00—Advertising on or in specific articles, e.g. ashtrays, letter-boxes
    • G09F23/06—Advertising on or in specific articles, e.g. ashtrays, letter-boxes the advertising matter being combined with articles for restaurants, shops or offices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
    • B60B2200/00—Type of product being used or applied
    • B60B2200/20—Furniture or medical appliances

Abstract

The present invention provides a process for forming a multi layered coated film having good finished appearance. The present invention relates to a process for forming a multi layered coated film comprising the steps of conducting electrodeposition coating with a cationic electrodeposition coating composition on a substrate, and then heating and curing it to form an cured electrodeposition coated film on the substrate, applying an intermediate coating composition on the cured coated film to form an uncured intermediate coated film, applying a base top coating composition on the uncured intermediate coated film to form an uncured base coated film, applying a clear top coating composition on the uncured base coated film to form an uncured clear coated film, and simultaneously heating and curing the three uncured coated films, wherein the cured electrodeposition coated film has specified ranges of Ra and Pa; or has specified ranges of Tg and crosslinking density.

Description

Form the method and the multilayer film of multilayer film
Technical field
The present invention relates to a kind of method that forms multilayer film, this multilayer film has good covering with paint outward appearance.
Background technology
On the substrate surface of car body, form the multilayer film of various functions, protect ground and give the ground good surface appearance.Yet, in in recent years, because the needs of save energy and minimizing cost have used a kind of like this method that forms multilayer film, it comprises following steps: by so-called wet wet (weton wet) coating process of bumping, use next coating film on uncured filming; And cure this multilayer simultaneously; And after using each layer, not curing the uncured step of filming.
Example as this method, the coating process that a kind of three coatings one are cured (three layers of wet coating) is considered to the most practical method, this method comprises step: on the solidified plating is filmed, by the wet coating process of wet cover, use inter coat, basal surface coating (base top coating) and clear top coat (clear topcoating); And cure simultaneously and solidify this three layers of uncured filming; What this method Fig. 1 represented is a block diagram of this coating process.
Disclose in 277474/1998 at Japanese Patent and to disclose, a kind of method that forms multilayer film comprises following steps: waiting to be coated with on the ground, using the coating and the clear top coat of inter coat, metal in order; And cure these three layers that this is filmed simultaneously.Wherein having described this method can provide and have fabulous boldness and fabulous glossy is filmed.
In the coating process that three coatings one shown in Figure 1 are cured, have been found that solidified electroplates the surface condition film the outward appearance of multilayer film is had very great influence.Reason is considered to, and the number of times of baking step is less in the coating process that this three coating one is cured, as mentioned above.In the method (Japanese Patent discloses 277474/1998) of above-mentioned formation multilayer film, the surface condition that the plating that does not have description can improve the multilayer film outward appearance is filmed.
Disclose at Japanese Patent and to disclose a kind of method that forms multilayer film in 224613/2002, may further comprise the steps:, on ground, form solidified and electroplate and film by the cation electroplating coating composition; By the coating process that three coatings one are cured, on filming, the solidified plating uses three layers of coating; And cure simultaneously and solidify this three layers of uncured filming; Wherein solidified is electroplated the surfaceness (Ra: center line average roughness) that films and have the second-order transition temperature that is not less than 110 ℃ and be no more than 0.3 μ m.In this method, only estimate the parameter of appearance of film, and do not use other parameter with center line average roughness (Ra) conduct.
And in the coating process that three coatings one shown in Figure 1 are cured, the composition that is used for inter coat is used in the solidified plating and films.There is such situation, is used for plating that the solvent that composition contained of inter coat is cured in the process of the using absorption of filming.In curing the above-mentioned stacked process of filming, the solvent evaporates that solidified absorbs in electroplating and filming is filmed in the middle of having influenced etc., has reduced the covering with paint outward appearance of this multi-layer coating film.Have now found that, being applied in solidified electroplates uncured centre on the filming contained solvent of filming solidified is electroplated the very great influence of having filmed, reason is that the number of times of baking step is few, and in the coating process that three coatings one are cured, be laminated into two-layer or uncured the filming of multiwalled cured simultaneously.In the method (Japanese Patent discloses 277474/1998) of above-mentioned this formation multilayer film, not describe and electroplate the physical features of filming, these physical features can improve the outward appearance of multilayer film.
Summary of the invention
Main purpose of the present invention is, a kind of method that forms multilayer film is provided, and can save energy and reduce in the coating process that three coatings one of cost cure, this multilayer film has good covering with paint outward appearance.
In the present invention, have been found that a kind of acquisition has the method for filming of good covering with paint outward appearance.According to method of the present invention, have the multilayer film of good covering with paint outward appearance even can in the coating process that three less coatings one of the number of times of baking step are cured, make.Multilayer film comprise electroplate film, film in the centre, basal surface coating and clear top coat.According to method of the present invention, can save in coating procedure cure and solidify in the needed energy, and reduce product cost.Method of the present invention can be fit to use in such field, and it requires in application process can save energy and obtain good appearance.
With reference to relevant drawings, by following description, to those skilled in the art, above-mentioned purpose of the present invention, other purposes and advantage will become clearer.
Description of drawings
Detailed description by hereinafter and in conjunction with the accompanying drawings can be understood the present invention more fully, yet this is only as explaining, and not represent that the present invention is confined to this, and wherein: Fig. 1 is the schema of illustrating an embodiment of the inventive method.
Embodiment
The invention provides a kind of method that forms multilayer film, this method comprises the steps:
Apply at the enterprising electroplating of ground with the cation electroplating coating composition, heat and solidify this coating then, film on ground, to form the solidified plating,
With the inter coat composition be applied in solidified electroplate film on, film to form uncured centre,
The basal surface coating composition is applied on uncured centre films, films to form uncured bottom (base coated film),
The clear top coat composition is applied on uncured bottom films, forming uncured transparent coating (clear coated film),
Heat and solidify uncured centre simultaneously and film, uncured basal surface is filmed and uncured transparent coating; Wherein
It is 0.05-0.25 μ m that solidified is electroplated the center line average roughness (Ra) that obtains from roughness curve of filming, and the center line average roughness (Pa) that obtains from profilograph is 0.05-0.30 μ m, thereby has realized above-mentioned goal of the invention.
The present invention also provides a kind of method that forms multilayer film, and this method comprises above-mentioned steps, and wherein solidified is electroplated to film and had 37-43mJ/m 2Surface energy, and the composition of inter coat electroplates at solidified and has the contact angle of 10-30 degree on filming, thereby realized above-mentioned goal of the invention.
The present invention also provides a kind of method that forms multilayer film, and this method comprises above-mentioned steps, and wherein to electroplate the center line average roughness (Ra) that obtains from roughness curve film be 0.05-0.25 μ m to solidified; The center line average roughness (Pa) that obtains from profilograph is 0.05-0.30 μ m; With surface energy be 37-43mJ/m 2, and the composition of inter coat electroplates at solidified and the contact angle of 10-30 degree arranged on filming, thus realized above-mentioned goal of the invention.
The present invention also provides a kind of method that forms multilayer film, this method comprises above-mentioned steps, wherein solidified is electroplated 100-130 ℃ the glass transition temperature Tg of filming, 1.2-2.6mmol/cc cross-linking density, more than record, thereby realized above-mentioned goal of the invention by the dynamic viscoelastic measurement.
To at length explain and illustrate the method for the present invention of implementing below.The contriver Japanese Patent disclose proposed in 224613/2002 a kind of by surfaceness (Ra: the method for coming the plating of evaluate cure to film center line average roughness).
By a kind of single method, the outward appearance that very difficult evaluation is filmed because surface morphology, optical signature and color all visually intricately influence outward appearance.In passing through with the ocular estimate of wavelength as the method for estimating appearance of film, for example, the surfaceness relevant with gloss and boldness can be estimated by the short wavelength, and the surfaceness relevant with winding (winding) can be estimated by the long wavelength.In the JIS relevant with surfaceness, be described to appearance curve and be divided into profilograph (P), roughness curve (R) and winding curve (windingcurve) are (W).
The outward appearance of filming can be by being categorized as and the following evaluation to it: slickness, tangerine peel defective and gloss.In the present invention, have been found that the Ra value (center line average roughness in roughness curve) that solidified plating used in traditional evaluation method is filmed, relevant with tangerine peel flaw evaluation item.Have been found that also electroplating the Wa value (center line average roughness in the winding curve) of filming as the solidified of the parameter relevant with winding curve (W) is correlated with the slickness scoring item in the multilayer film outward appearance.In addition, have been found that also the winding of measuring by the long wavelength has influenced the outward appearance of the multilayer film that obtains greatly.And, have been found that now, by using Ra value and Pa value (center line average roughness on profilograph), comprise that Ra value and Wa value come the plating of evaluate cure to film as parameter, controlled surface appearance, improve the covering with paint outward appearance of the multilayer film that obtains, thereby realized one embodiment of the invention.
Think now, electroplate when the composition of middle coating and solidified and to film when having low wettability, even in the forming process of the multilayer film in the coating process that three coatings one of the present invention are cured, electroplate the surface appearance of filming as above-mentioned institute description control solidified, also can't obtain to have the multilayer film of good appearance accidentally.These defectives have influenced the outward appearance of the multilayer film that obtains greatly, because the baking step number of times in the coating process that this three coatings one are cured is less.
In the present invention, have been found that by regulating the surface energy that the solidified plating is filmed, make it a specified scope, can control middle wettability of filming, and can improve the covering with paint outward appearance of the multilayer film that obtains, thereby realize another embodiment of the invention.
In the present invention, have been found that, by regulating a glass transition temperature Tg and cross-linking density to a specified scope, can control solidified and electroplate the solvent resistance of filming, Tg and cross-linking density carry out dynamic viscoelastic and measure by solidified being electroplated film, and can improve the covering with paint outward appearance of the multilayer film that obtains, thereby realize another embodiment of the present invention.
Detailed description of the preferred embodiments
In one embodiment of the invention, selection is included in component and its content in the cation electroplating coating composition, cause to electroplate to film and have the center line average roughness (Pa) of the 0.05-0.30 μ m that obtains by the center line average roughness (Ra) of the 0.05-0.25 μ m that obtains in the roughness curve with from profilograph by the solidified that electroplate to apply forms.The upper limit of center line average roughness (Ra) is preferably 0.20 μ m.The upper limit of center line average roughness (Pa) is preferably 0.25 μ m.Under the prior art level, be difficult to obtain following solidified plating and film, its center line average roughness (Ra) and center line average roughness (Pa) are less than the lower limit of 0.05 μ m.
Used here center line average roughness that obtains from roughness curve (Ra) and the center line average roughness (Pa) that obtains from profilograph are the parameters that defines in JIS B0601.Solidified electroplates the center line average roughness that obtains from roughness curve (Ra) of filming and the center line average roughness (Pa) that obtains from profilograph can be measured by following method, for example according to JIS B0601, by using a kind of evaluation table surface roughness detector to measure, this detector is made by Mitutoyo Corporation.
When Ra value during greater than 0.25 μ m, the outward appearance of multilayer film will variation, especially tangerine peel defective.When Pa value during greater than 0.30 μ m, the outward appearance of multilayer film also can variation, especially smoothness.
Preparation cation electroplating coating composition, have in above-mentioned scope so that obtain, the solidified of center line average roughness that obtains from roughness curve (Ra) and the center line average roughness (Pa) that obtains from profilograph is electroplated the method for filming and is comprised the cation epoxy resin that is adjusted in the cation electroplating coating composition, the type of blocked isocyanate solidifying agent and catalyzer and content.Especially, the type of blocked isocyanate solidifying agent and content are very big to Ra and the influence of Pa value.Can in the process that forms film (deposited film), improve the flowability and the solidification rate of filming by regulating the solid content ratio between cation epoxy resin and the blocked isocyanate solidifying agent, improve the slickness of filming.By the steel plate that uses the surface to handle, to electroplate the slickness of filming and can further improve, this steel plate has less surfaceness.
In another embodiment of the invention, the feasible solidified that forms of employed cation electroplating coating composition and inter coat composition is electroplated to film has 37-43mJ/m 2Surface energy, and the inter coat composition that has been coated with is electroplated the contact angle that the 10-30 degree is arranged on filming at solidified.When solidified is electroplated the surface energy film in above-mentioned scope, and solidified electroplate film and the inter coat composition between contact angle between the 10-30 degree time, the inter coat composition is electroplated the wettability height of filming to solidified so, and the covering with paint good appearance of the multilayer film that obtains.
The lower limit that solidified is electroplated the surface energy of filming is preferably 38mJ/m 2, 39mJ/m more preferably 2, its upper limit is preferably 42mJ/m 2, 41mJ/m more preferably 2Solidified electroplate film and the inter coat composition between the lower limit of contact angle be preferably 10 degree, the upper limit is preferably 25 degree.
When surface energy is lower than 37mJ/m 2, then solidified is electroplated the binding property film between filming with the centre and is just weakened.On the other hand, be higher than 43mJ/m when surface energy 2, then the composition of the inter coat wettability that plating is filmed for solidified just weakens.In addition, when solidified electroplate film and the inter coat composition between contact angle greater than 30 degree, then the inter coat composition is electroplated the wettability of filming for solidified and is just weakened.
The surface energy of filming is the power that puts on free length in vertical direction.In the contact horn cupping, by be determined at film and three types liquid (for example water, methylene iodide, ethylene glycol) between contact angle determine surface energy, this liquid of three types has based on the known γ of Lifshitz-Van der Waals force LWValue, based on the acidic components γ of soda acid power+and based on the basic component γ of soda acid power-, derive equation 1 from poplar-Dupre equation, obtain the γ that films in 1 establishing an equation down LW, γ+and γ-value; And utilize equation 2, calculate (referring to C.J..Van Oss, " J.Protein Chem according to these values ", volume 4,245,1985 and C.J..VanOss, " J.Colloid Interface Sci ", volume 111,378,1986).
Equation 1)
2{(γ i LW·γ j LW) 1/2+?(γ i +·γ j -) 1/2+(γ i -·γ j +) 1/2}
＝(1+cosθ){γ i LW+2(γ i +·γ j -) 1/2}
Equation 2) surface free energy
(γ)＝γ j LW+(γ j +·γ j -) 1/2
γ i LW: based on the mathematical terms of the Lifshitz-Van der Waals force of liquid
γ i +: based on the acidic components of the soda acid power of liquid
γ i -: based on the basic component of the soda acid power of liquid
θ: contact angle
A kind of preparation cation electroplating coating composition and inter coat method for compositions, from these compositions can access solidified in above-mentioned scope electroplate the surface energy film and solidified electroplate film and the inter coat composition between contact angle, this method comprises type and the content that is adjusted in the cation epoxy resin, blocked isocyanate solidifying agent, catalyzer and the surface conditioner that contain in the cation electroplating coating composition.Especially, the type of surface conditioner and content to surface energy and solidified electroplate film and the inter coat composition between contact angle very big influence is arranged.The kind of the surface conditioner of Shi Yonging comprises acryloyl base class, siloxanes base class and vinyl-based in the present invention.
In the process that forms multilayer film of the present invention, more preferably solidified is electroplated to film and have the center line average roughness (Ra) of the 0.05-0.25 μ m that obtains from roughness curve, the center line average roughness (Pa) of the 0.05-0.30 μ m that from profilograph, obtains, and solidified electroplate film and the inter coat composition between contact angle be the 10-30 degree.This is because the multilayer film that can obtain to have better covering with paint outward appearance.
In the present invention, selection is included in component and its content in the cation electroplating coating composition, cause by the solidified that electroplate to apply forms and electroplate film the glass transition temperature Tg (also being expressed as " dynamically Tg " at this) with stated limit and the cross-linking density of stated limit, they obtain by the dynamic viscoelastic measurement.
Here the dynamic Tg of usefulness determines by measuring dynamic glass transition temperature Tg, and it adopts to use sample with the same manner of measuring the ordinary method of measuring Tg by dynamic viscoelastic.The example of employed measuring method comprises a kind of like this method among the present invention, and this method is electroplated and filmed, uses mercury to separate to film and cutting is filmed and made sample by form solidified on ground, uses the sample that makes to carry out dynamic viscoelastic and measures.In the method, with the heat-up rate of 2 ℃ of per minutes sample is heated to 200 ℃ from room temperature, its visco-elasticity is determined in vibration under 11 hertz frequency.Calculating energy storage elasticity (E ')/(ratio of E ") (tan δ), the flex point (temperature at tan δ peak value place) of measuring them is to obtain dynamic Tg for loss elasticity.The example of the measuring apparatus of dynamic viscoelastic comprises, Rheovibron model RHEO 2000,3000 (trade name) for example, and by Orientec Co., Ltd. makes.
In the present invention, electroplating the preferred dynamically Tg that films by the solidified of electroplated coating formation is 100-130 ℃.Dynamically the lower limit of Tg is preferably 110 ℃, and dynamically the upper limit of Tg is preferably 125 ℃.When solidified was electroplated the dynamic Tg film and is lower than 100 ℃, electroplating films can be contained in solvent institute swelling in the inter coat composition, and the covering with paint outward appearance of the multilayer film that makes will variation.On the other hand, when dynamic Tg was higher than 130 ℃, the Young's modulus of the multilayer film of acquisition will reduce, and the shock-resistance of filming also can reduce.
Apply formed solidified and electroplate the dynamic viscoelastic of filming by measuring to measure by electroplating, and be used in the energy storage elasticity that the rubber-like district obtains (E ') according to following equation and calculate, thereby determined cross-linking density in the identical mode of the method for dynamic Tg:
E’＝3nRT
Wherein E ' is an energy storage elasticity; N is a cross-linking density; R is that gas law constant and T are absolute temperature.
In the present invention, the solidified that is formed by the plating coating is electroplated the cross-linking density of filming and is preferably 1.2-2.6mmol/cc.The lower limit of cross-linking density is 1.4mmol/cc more preferably, and the upper limit of cross-linking density is 2.3mmol/cc more preferably.When solidified was electroplated the cross-linking density film and is lower than 1.2mmol/cc, electroplating films can be contained in solvent institute swelling in the inter coat composition, and the covering with paint outward appearance of the multilayer film of acquisition will variation.On the other hand, when solidified is electroplated the cross-linking density film and is higher than 2.6mmol/cc, thereby owing to contain water and be easy to bubble, erosion resistance can reduce.
A kind of method for preparing the cation electroplating coating composition, the solidified that can access the dynamic Tg that has in above-mentioned scope and cross-linking density from this composition is electroplated and is filmed, this method comprises the cation epoxy resin that is adjusted in the cation electroplating coating composition, the type of blocked isocyanate solidifying agent and catalyzer and content.Especially the type of cation epoxy resin and blocked isocyanate solidifying agent and content have very big influence to dynamic Tg and cross-linking density.The example of cation epoxy resin comprises such resin, and these resins obtain by the oxirane ring of opening bisphenol A type epoxy resin or bisphenol f type epoxy resin with the activation hydrogen compound, can introduce cation group in the activation hydrogen compound.The example of blocked isocyanate solidifying agent comprises, 1-hexamethylene diisocyanate (comprising tripolymer), G methylene diisocyanate, trimethylammonium-hexamethylene diisocyanate; Alicyclic diisocyanate is as 4,4 '-methylene-bis (cyclohexyl isocyanate), aromatic diisocyanate such as tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and with the end capped hexamethylene diisocyanate of suitable end-capping reagent (HDI).In addition, dynamically Tg and cross-linking density also can be regulated by the stoving temperature of selecting the blocked isocyanate solidifying agent that the ratio or the plating of cation epoxy resin are filmed.
Used material to be coated with, cation electroplating coating composition, inter coat composition, basal surface coating composition and clear top coat composition and its application method will be described below in the process that forms multilayer film of the present invention.
Ground to be coated with
Ground employed to be coated with can be any ground that can electroplate coating in the process that forms multilayer film of the present invention.The example of ground comprises metal such as iron, steel, aluminium, tin, zinc or the like and its alloy, its plated item or its deposition cell.Its concrete example comprises passenger vehicle, freight truck, motorcycle, bus or the like, forms by using the metal assembly manufacturing.And, the plastics that resin by conductive processing obtains also can be used as ground and use, these resins such as polyvinyl resin, acrylic resin, ethylene-vinyl acetate copolymer resin, polyamide resin, acrylic resin, vinylidene chloride, polycarbonate resin, urethane resin, Resins, epoxy and various FRP.
In the process that forms multilayer film of the present invention, ground can use after carrying out pre-treatment under the former state condition or before plating is filmed, and pre-treatment such as skimming treatment or chemical conversion are handled.
The cation electroplating coating composition
Employed in the present invention cation electroplating coating composition comprises and has water-containing solvent, cation epoxy resin and be dispersed or dissolved in the resin glue of the blocked isocyanate solidifying agent in the water-containing solvent; Be used for neutral acid; Organic solvent.The cation electroplating coating composition can also contain pigment.
Cation epoxy resin
Employed in the present invention cation epoxy resin comprises amine-modified epoxy resin.Cation epoxy resin is known resin, and they disclose in 4978/1979,34186/1981 grade at Japanese Patent description.
Cation epoxy resin is usually made by opening oxirane rings all in the bisphenol-type epoxy resin with the activation hydrogen compound, can introduce cation group in the activation hydrogen compound; Perhaps open a part of oxirane ring, and open remaining oxirane ring and make, can in the activation hydrogen compound, introduce cation group with the activation hydrogen compound by activation hydrogen compound with other.
The object lesson of bisphenol-type epoxy resin comprises bisphenol A type epoxy resin and bisphenol f type epoxy resin.The example of bisphenol A type epoxy resin comprises the Epikote828 (epoxy equivalent (weight): 180-190) that can buy from Yuka Shell Epoxy Co.Ltd., Epikote 1001 (epoxy equivalent (weight): 450-500), Epikote 1010 (epoxy equivalent (weight): 3000-4000) etc.The example of bisphenol f type epoxy resin comprises the EpoxyCo. from Yuka Shell, the Epikote 807 that Ltd. can buy (epoxy equivalent (weight): 170) or the like.
Resins, epoxy with Han oxazolidine ketone ring of following formula:
Formula 1
Figure A20051005186400121
Wherein the R representative is by sloughing the residue that glycidyl obtains from the diglycidyl epoxy compounds, and R ' representative is by sloughing the residue that isocyanate group obtains from diisocyanate cpd, and n represents positive integer,
Can in cation epoxy resin, use, have filming of fabulous temperature capacity and erosion resistance because can make.This is because can obtain to have filming of fabulous solvent resistance (resistance to swelling by solvent).
A kind of method Ba oxazolidone ring introduction Resins, epoxy comprises the steps, heating blocked isocyanate solidifying agent and polyepoxide and maintenance constant temperature under basic catalyst, above-mentioned solidifying agent is with lower alcohol such as methyl alcohol end-blocking, and lower alcohol is distilled out from system as byproduct.
The resin of particularly preferred Resins, epoxy Wei Han oxazolidone ring.This is because can obtain to have filming of excellent solvent-resistance (resistance to swelling by solvent), thermotolerance, erosion resistance and shock resistance.
Everybody knows, and obtains the Resins, epoxy of Han oxazolidine ketone ring by bifunctional Resins, epoxy with the end capped vulcabond of monohydroxy-alcohol (promptly two urethanum) reaction.The object lesson of the Resins, epoxy of Han oxazolidone ring and its preparation method are open in [0012]-[0047] section that Japanese Patent discloses in 128959/2000, and this is known.
Can modified epoxy with appropriate resin, as the alkylphenol of polyester polyol, polyether polyol and single functional group.In addition, by epoxy group(ing) and glycol or dicarboxylic acid reaction, but the Resins, epoxy chainpropagation.
Wish to make the Resins, epoxy open loop so that they are 0.3-4.0meq/g opening the later amine equivalent of ring with the activation hydrogen compound, particularly its 5-50% is a primary amine groups.
The example (can to wherein introducing cation group) of activation hydrogen compound comprises acid salt, sulfide and the acid mixture of primary amine, secondary amine and tertiary amine.In order to prepare the Resins, epoxy that contains primary amine, secondary amine and/or tertiary amine, with the acid salt of primary amine, secondary amine and tertiary amine as the activation hydrogen compound, can be to wherein introducing cation group.
Its concrete example comprises: the acid salt of butylamine, octylame, diethylamine, dibutylamine, methylbutylamine, triethylamine, N, the acid salt of N-dimethylethanolamine, diethyl disulphide-vinegar stock and the secondary amine that obtains by the primary amine end-blocking are as the ketoimine of amino ethyl ethanolamine, the ketoimine of diethylenetriamine.These amine can be used in combination.
The blocked isocyanate solidifying agent
The polymeric polyisocyanate that is used for preparing the present invention's blocked isocyanate solidifying agent is a kind of compound that has 2 isocyanate groups in molecule at least.Polymeric polyisocyanate can be aliphatic, alicyclic, aromatics or araliphatic polymeric polyisocyanate.
The example of polymeric polyisocyanate comprises: the vulcabond of aromatics such as tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), PPDI and naphthalene diisocyanate; Aliphatic vulcabond with 3-12 carbon atom is as hexamethylene diisocyanate (HDI), 2,2,4-trimethyl cyclohexane vulcabond and lysinediisocyanate; Alicyclic diisocyanate with 5-18 carbon atom, as 1,4-cyclohexyl diisocyanate, isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (hydrogenant MDI), methylcyclohexane diisocyanate, different inclined to one side propylidene dicyclohexyl-4,4 '-vulcabond and 1,3-two isocyanato-methylcyclohexanes (hydrogenant XDI), hydrogenant TDI, 2,5-or 2,6-two (isocyanic ester methyl)-two ring [2.2.1] heptane (=norbornene alkyl diisocyanate); Aliphatic vulcabond with aromatic ring is as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI); Its modified compound (urethane compounds, carbodiimide, urethodion, urethonimine, biuret and/or isocyanurate-modified compound) or the like.Polymeric polyisocyanate can use separately or two or more is used in combination.
Being not less than 2 by polymeric polyisocyanate and polyvalent alcohol with the ratio of NCO/OH reacts the addition compound that obtains or prepolymer and can be used as the blocked isocyanate solidifying agent and use this polyvalent alcohol such as ethylene glycol, propylene glycol, TriMethylolPropane(TMP) and hexanetriol.
End-capping reagent added be bonded on the polyisocyanate-based, this end-capping reagent is at room temperature stable, but when heating under being not less than the temperature of dissociation temperature, the free cyano acid ester group can be regenerated.
Pigment
Employed in the method for the invention cation electroplating coating composition can comprise pigment, and described pigment is the pigment that generally is used on the coating.The example of pigment comprises: mineral dye, and colored pigment for example is as titanium dioxide, carbon black and colcother; Pigment extender such as kaolin, talcum, pure aluminium silicate, lime carbonate, mica and clay; Rust-stabilising pigment such as zinc phosphate, tertiary iron phosphate, aluminum phosphate, calcium phosphate, zinc phosphite, zinc cyanide, zinc oxide, aluminium triphosphate, zinc molybdate, molybdic acid aluminium, calcium molybdate, phospho-molybdic acid aluminium and aluminium zinc phosphomolybdate.
When pigment used as component of electroplated coating, pigment is being dispersed in the water-containing solvent with the form high density of slurry (being dispersed with the slurry of pigment) in advance generally.This because of in a step under lower concentration the pulverous pigment of homodisperse be very difficult.Slurry generally is also referred to as pigment disperse sizing agent.
Pigment disperse sizing agent is to be scattered in the water-bearing media together by the resinous varnish with pigment and dispersed color to make.As the resin of dispersed color, can use positively charged ion or non-ionic low molecular weight surfactants, perhaps cationic polymers is as having the modified epoxy of quaternary ammonium group and/or uncle's sulfonium base.As water-bearing media, deionized water or the water that contains a small amount of alcohol all are operable.The resin of dispersed color generally uses with the solid content of 20-100 mass parts, is 100 mass parts in the total amount of filming.Resinous varnish and pigment by dispersed color mix, and can obtain pigment disperse sizing agent, use a suitable diverting device to come dispersed color, diverting device such as ball mill or sand mill then.
The cation electroplating coating composition can randomly comprise dissociation catalyst, organo-tin compound such as dibutyl tin dilaurate, dibutyl tin oxide, oxidation two hot tin; Amine such as N-methylmorpholine, lead acetate; The metal-salt of strontium, cobalt, copper; Purpose is to dissociate end-capping reagent except that mentioned component.The amount of dissociation catalyst is the 0.1-6 mass parts, is 100 mass parts based on the total solid content of cation epoxy resin in the cation electroplating coating composition and blocked isocyanate solidifying agent.
The preparation of cation electroplating coating composition and application
Cation electroplating coating composition of the present invention makes by above-mentioned catalyzer, cation epoxy resin, blocked isocyanate solidifying agent and pigment disperse sizing agent are scattered in the water-containing solvent.In addition, water-bearing media can comprise neutralizing acid, thereby purpose is the dispersiveness that neutralizing cation Resins, epoxy improves the resin glue emulsion.Antacid example comprises mineral acid or organic acid, example hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid.
Antacid amount is preferably 10mg equivalent-25mg equivalent, is 100g based on the resin glue of cation Resins, epoxy and blocked isocyanate solidifying agent.The lower limit of antacid amount is the 15mg equivalent more preferably, and the upper limit of antacid amount is the 20mg equivalent more preferably.When antacid amount is lower than the 10mg equivalent, just can not obtain sufficiently with the compatibility of water, and in water, be difficult to disperse, perhaps stability reduces greatly.On the other hand, when antacid amount was higher than the 25mg equivalent, depositing required electric power increased, and the just reduction of the deposition of the solid content of filming, thereby had reduced throwing power.
The cation electroplating coating composition makes by cation epoxy resin and blocked isocyanate solidifying agent are dispersed in the water-containing solvent.This just wishes in solidification process, with the amount of the blocked isocyanate solidifying agent of the activation reactive hydrogen compound that contains functional group such as primary amine groups, secondary amine, hydroxyl be competent, thereby obtain good cured coating film.The amount of blocked isocyanate solidifying agent is represented by the ratio (cation epoxy resin/solidifying agent) of the solid content of cation epoxy resin and blocked isocyanate solidifying agent, it is preferably 90/10-50/50, be preferably 80/20-60/40 again, most preferably be 80/20-65/35.Can recently improve the flowability and the solidification rate of filming when film forms (deposited film) by regulating this, the slickness of filming simultaneously also is improved.By using surface-treated steel plate (this steel plate has lower roughness), electroplating the slickness of filming can be further improved.In addition, the amount by regulating the blocked isocyanate solidifying agent is perhaps selected stoving temperature to above-mentioned scope, is easy to give needed dynamic Tg of solidified electroplated coating and cross-linking density.
When the resin of synthetic resins component such as cation epoxy resin, blocked isocyanate solidifying agent, dispersed color, can be with an organic solvent as described solvent.The complex process of sloughing solvent fully is necessary.Can improve the flowability of filming when film forms by contain solvent in resin glue, the slickness of film also is improved simultaneously.
The representative examples of organic of using in the cation electroplating coating composition comprises ethylene glycol monobutyl ether, ethylene glycol one hexyl ether, ethylene glycol one ethyl hexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monophenyl ether or the like.
The cation electroplating coating composition can comprise the paint additive except that said components, as softening agent, tensio-active agent, antioxidant and UV light absorber.The cation electroplating coating composition can also comprise the acrylic resin that contains amino, contains amino vibrin or the like.
Apply a voltage between as negative electrode and anodic ground and electroplate coating, this voltage is generally 50-450V.When the voltage that applies is lower than 50V, electroplates and become insufficient.On the other hand, when the voltage that applies is higher than 450V, films and to break, its outward appearance distortion.The plating bath temperature generally is controlled at 10-45 ℃.
Electroplating process comprises following step, and ground to be coated with is immersed in the electroplated coating composition, applies a voltage between as negative electrode and anodic ground to make the deposition of filming.Equally, the time that applies voltage was generally 2-4 minute, though it changes along with the plating condition.
The preferred 5-25 μ of the thickness that plating is filmed m, more preferably 20 μ m.When thickness during less than 5 μ m, resistance to rust just can not effectively obtain.On the other hand, when thickness during greater than 25 μ m, it just causes the waste of coating composition.
Resemble the plating that the method for foregoing description obtains and film at 120-260 ℃, cure 10-30 minute under preferred 140-220 ℃, thereby directly solidify, perhaps water is cured after cleaning electroplating process is finished after, thereby the plating of formation solidified is filmed.
The inter coat composition
The inter coat composition of Shi Yonging comprises inter coat resin Composition, pigment, water-bearing media and/or organic solvent in the present invention.The inter coat resin Composition comprises inter coat resin and optional inter coat solidifying agent.Can use and water-bearing media and organic solvent identical in the cation electroplating coating composition.
The example of inter coat resin comprises, acrylic resin, vibrin, urethane resin, Synolac, fluoro-resin, Resins, epoxy, polyether resin or the like.Preferably acrylic resin, vibrin and urethane resin.The inter coat resin can use separately or two or more is used in combination.
The example of acrylic resin comprises the multipolymer of Acrylic Acid Monomer and other ethylenically unsaturated monomers.The example of the Acrylic Acid Monomer that uses in multipolymer comprises methyl esters, ethyl ester, propyl ester, positive butyl ester, isobutyl ester, the tert-butyl ester, 2-(ethyl hexyl) ester, lauryl, phenylester, benzyl ester and the 2-hydroxypropyl acrylate of acrylic or methacrylic acid; The open loop adduct of the caprolactone of 2-hydroxy ethyl methacrylate or 2-hydroxyethyl meth acrylate; Glycidyl acrylate, glycidyl methacrylate, acrylamide, Methacrylamide and N hydroxymethyl acrylamide, (methyl) acrylate of polyvalent alcohol or the like.Can comprise vinylbenzene, alpha-methyl styrene, methylene-succinic acid, maleic acid, vinyl-acetic ester or the like with other ethylenically unsaturated monomers of above-mentioned monomer copolymerizable.
The example of vibrin comprises saturated vibrin and unsaturated polyester resin, comes the condenses of condensation polyprotonic acid and polyvalent alcohol acquisition as application of heat.The example of polyprotonic acid comprises saturated polybasic acid and unsaturated polyprotonic acid.The example of saturated polybasic acid comprises succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, hexahydro-phthalic acid and 1,4-cyclohexane dicarboxylic acid.The example of unsaturated polyprotonic acid comprises maleic acid, MALEIC ANHYDRIDE, fumaric acid, Tetra hydro Phthalic anhydride, terephthalic acid and m-phthalic acid.The example of polyvalent alcohol comprises dibasic alcohol and trivalent alcohol.The example of dibasic alcohol comprises ethylene glycol, glycol ether, neopentyl glycol, 1,5-pentanediol and 1,6-hexylene glycol.The example of trivalent alcohol comprises glycerol and TriMethylolPropane(TMP).
The example of urethane resin comprises having the resin of urethane bonds, and this key obtains from polyol components such as vinylformic acid, polyester, polyethers, polycarbonate and polyisocyanate compounds.The example of polyisocyanate compounds comprises 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI) and its (TDI) mixture, ditan-4,4 '-vulcabond (4,4 '-MDI), ditan-2,4 '-vulcabond (2,4 '-MDI) and its (MDI) mixture, naphthalene-1,5-vulcabond (NDI), 3,3 '-dimethyl-4,4 '-diphenyl diisocyanate (TODI), xylylene diisocyanate (XDI), dicyclohexyl methane diisocyanate (hydrogenant MDI), isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI), hydrogenant xylylene diisocyanate (HXDI) or the like.
The example of Synolac comprises the Synolac that obtains by polyprotonic acid and polyvalent alcohol and properties-correcting agent reaction, for example fat and oil or its lipid acid (as soybean oil, Toenol 1140, Oleum Cocois, stearic acid or the like), natural resin (as rosin, amber or the like).
The example of fluorine resin comprises, pvdf resin, tetrafluoroethylene resin or its mixture, by the fluorine-based multipolymer that fluoroolefins and monomer copolymerizable obtain, and this monomer contains oxy-compound and other copolymerizable vinyl compounds.
The example of Resins, epoxy comprises the resin that obtains by the reaction of bis-phenol and Epicholorohydrin etc.The example of bis-phenol comprises dihydroxyphenyl propane and Bisphenol F.The example of bisphenol-type epoxy resin comprises Epikote 828, Epikote 1001, Epikote 1004, Epikote 1007, Epikote 1009 (from the commodity of Shell Chemical Co.).In addition, these resins can carry out chainpropagation by a suitable chain propagation agent.
Polyether resin promptly has the polymkeric substance of ehter bond or the example of multipolymer comprises the polyoxyethylene groups polyethers, polyoxypropylene base polyethers or polyoxy butenyl polyethers or in a molecule, have the polyether resin of at least two hydroxyls, as polyethers, as dihydroxyphenyl propane and Bisphenol F derived from aromatic polyhydroxy compounds.In addition, example also comprise logical spiral shell ether resin and reactive derivatives react obtain contain the carboxyl polyether resin, comprise succsinic acid, hexanodioic acid, sebacic acid, phthalic acid, m-phthalic acid, terephthalic acid and trimellitic acid or their acid anhydrides as polycarboxylic acid.
The acid number of wishing the inter coat resin is 3-200, and hydroxyl value is 30-200, and number-average molecular weight is 500-50000.Preferred resin especially acid number is 3-200, and hydroxyl value is 30-200, and number-average molecular weight is the acrylic resin of 2000-50000, and acid number is 3-200, and hydroxyl value is 30-200, and number-average molecular weight is the vibrin of 500-20000.In the situation of preparation as the inter coat composition of the aqueous solution or aqueous dispersion, the acid number of wishing the inter coat resin is 10-200, and hydroxyl value is 30-200.
In the inter coat resin, curable type and lacquer type resin are arranged generally.Preferred curable type resin.If use curable type resin, with inter coat solidifying agent such as blocked isocyanate compounds, oxazolidone compound, carbodiimide compound and melamine compound and the use of inter coat resin-bonded.The curing reaction that contains the inter coat resin Composition of inter coat solidifying agent can carry out under heating or room temperature.In addition, also can use the combination of curable type and non-curable type inter coat resin.
If contain the inter coat solidifying agent, then in the coating solid content, the weight ratio of inter coat resin and inter coat solidifying agent is preferably 90/10-50/50, more preferably 85/15-60/40.When ratio greater than 90/10 and the amount of inter coat solidifying agent during less than 10 weight %, the cross-linking density of coating just can not obtain fully.On the other hand, when ratio less than 50/50 and the amount of inter coat solidifying agent during greater than 50 weight %, the storage stability of coating composition has just reduced, it is big that solidification rate just becomes, the outward appearance of filming has just reduced.
Inter coat composition of the present invention includes pigment.The example of pigment comprises that pigment extender such as barium oxide powder, sedimentary vitriol, barium carbonate, gypsum, clay, silica, talcum, magnesiumcarbonate, vanadine are white etc., and colored pigment.The example of colored pigment comprises pigment dyestuff such as azo lake class pigment, phthalocyanine pigment, indigo class pigment, perylene class pigment, quinophtharone class pigment, dioxazines pigment, quinacridine ketone pigment, isoindoline ketone pigment, metal complex pigment, carbon black; Or mineral dye such as plumbous oxide, Zh 1, colcother, titanium dioxide.Rely on needed performance and tone that the amount of pigment is selected arbitrarily.Pigment can use separately, and perhaps two or more is used in combination.
Based on the coating solid content of inter coat composition, the preferred 10-50 weight % of the concentration of pigment (PWC).The upper limit of concentration is 30 weight % more preferably.
The preferred 35-65 weight of the solid content of inter coat composition %.Lower limit is 40 weight % more preferably, and the upper limit is 60 weight % more preferably.When the lower limit of solid content is lower than 35 weight %, in the application process of coating, sagging can occur, and cover with paint, lacquer, colour wash, etc. outward appearance and can reduce.On the other hand, when the upper limit of solid content is higher than 65 weight %, the mobile reduction in the application process of coating, and cover with paint, lacquer, colour wash, etc. outward appearance and can reduce.
The inter coat composition also can comprise polyamide wax except that mentioned component, it is oilness dispersion, the polyethylene wax of aliphatic acid amides, and it is based on colloidal dispersion, curing catalysts, UV light absorber, antioxidant, levelling agent, surface amendment such as the silicone of polyethylene oxide and organic polymer, anti-sag agent, thickening material, defoamer, lubricant, crosslinkable polymer powder (microgel) or the like.By mixing the above-mentioned additive that consumption is no more than 15 mass parts (with solid content as benchmark), be 100 mass parts based on the total amount of inter coat resin, coating composition and the performance of filming can improve.
Inter coat preparation of compositions and application
By said components being dissolved or being dispersed in the solvent, can make the inter coat composition.Solvent is not limited to, as long as can dissolve and disperse the inter coat resin Composition, but this solvent can be organic solvent and/or water.Organic solvent can be use always in the coating composition field a kind of.The example of organic solvent comprises varsol for example toluene and dimethylbenzene, and ketone is acetone and methyl ethyl ketone for example, and ester is ethyl acetate, butylacetate, cellosolve acetate and ethylene glycol butyl ether for example, alcohol etc.If the reason of taking environmental conservation into consideration, restriction with an organic solvent it is desirable to water so.If so so wherein can comprise the hydrophilic organic solvent of appropriate amount.
In application process, with an organic solvent and/or water and composition thereof, the viscosity of inter coat composition preferably is adjusted to the 10-30 scope of second (Ford cup #4/20 ℃).When viscosity is lower than above-mentioned scope, film and be easy to the basal surface that forms in the application step subsequently molten the mixing of filming in the centre.On the other hand, when viscosity is higher than above-mentioned scope, be difficult to the control coating composition, and the premature setting of filming, and the uniformity coefficient on surface appears at the level that can not be filmed and apply and repair in subsequently the coating step.
Electroplate to film to go up and to obtain the centre and film by the inter coat composition being applied in solidified.Owing to film in the middle of forming, electroplating films has had lighttight character and anti-broken performance.In addition, the bounding force of filming of the basal surface on filming in the middle of being applied in later step has also improved.
Use the method for inter coat and do not limit to, by using the air electrostatic sprayer, just so-called " reaction rifle "; The electrostatic sprayer of rotation, just so-called " micro micro (μ μ) bell ", " micro (μ) bell " and " meta bell "; Deng, can implement this method.Preferable methods is to utilize the electrostatic sprayer of rotation.
The dried thickness of filming in the middle of the ideal is 5-80 μ m, preferably 10-50 μ m.After filming and form in the centre, do not having to carry out the formation step that basal surface is filmed under heating and the solidified situation.Before forming basal surface and filming, the film temperature of preheating of centre is lower than its heating and curing (curing) treatment temp.
The basal surface coating composition
Used basal surface coating composition is gloss paint composition or solid coating composition among the present invention, and it comprises basal surface coating resin component, colour lustre pigments and/or tinting pigment, pigment extender and solvent.The basal surface coating composition is water base or organic solvent based composition, comprises water-dispersion or organic solvent dispersive composition.
The basal surface coating resin component that contains in the basal surface coating composition comprises basal surface coating resin and optional basal surface curable coating agent.Identical with described in the inter coat of the basal surface coating resin component that comprises in the basal surface coating composition (basal surface coating resin and basal surface curable coating agent), tinting pigment, pigment extender, various additive and solvent.By using basal surface coating resin component, colour lustre pigments and optional tinting pigment can be dispersed in the glossiness basal surface coating composition, and tinting pigment is dispersed in the solid-state basal surface coating composition.
The example of used basal surface coating resin comprises that at least a energy forms the resin of filming, and is selected from acrylic resin, vibrin, fluoro-resin, Resins, epoxy, urethane resin, polyether resin and their modified resin.The example of basal surface curable coating agent comprises the solidifying agent of above-mentioned inter coat.The melamine resin of preferred melamine compound, particularly etherificate.The melamine resin of etherificate can be by obtaining as methyl alcohol and butanol etherification trimeric cyanamide with alcohol.Comprise acrylic resin-melamine resin system as the basal surface coating resin of basal surface coating resin component and the preferably combination of basal surface curable coating agent.In this system, the acid number that it is desirable to acrylic resin is 10-200, and hydroxyl value is 30-200, and number-average molecular weight is 2000-50000.
Example as the colour lustre pigments that is included in the pigment in the basal surface coating composition comprises kaolin pigment, painted kaolin pigment, interference pigments, mica, painted pigments, mica, scribbles the glass lamellar pigment of metal oxide, be coated with the glass lamellar pigment of metal, scribble the silica lamellar pigment of metal oxide, metal titanium sheet pigment, graphite pigment, stainless steel sheet pigment, flaky iron oxide pigment, phthalocyanine lamellar pigment and holographic pigment.If with colour lustre pigments and/or tinting pigment, the weight content of all pigment (PWC) is preferably 1-50%, more preferably 5-30%.When PWC less than 1% the time, be not enough in filming, add pattern.On the other hand, PWC was greater than 50% o'clock, and it is bad that the outward appearance of filming becomes.
The preparation of basal surface coating composition and application
The basal surface coating composition is to make by said components is dissolved or is dispersed in the solvent.For solvent without limits, as long as it can dissolve and disperse basal surface coating resin component, but can be organic solvent and/or water.The example of organic solvent comprises hydro carbons for example toluene and dimethylbenzene, and ketone is acetone and methyl ethyl ketone for example, and ester is ethyl acetate, butylacetate, cellosolve acetate and ethylene glycol butyl ether for example, alcohol etc.
The viscosity of basal surface coating composition preferably is adjusted to the 10-30 scope of second (Ford cup #4/20 ℃) with suitable thinner.When viscosity is lower than above-mentioned scope, basal surface film be easy to the transparent surface that forms in the step of applying subsequently film mix mixed.On the other hand, when viscosity is higher than above-mentioned scope, be difficult to the control coating composition, and the premature setting of filming, and the uniformity coefficient on surface appears at the level that can not be coated with film coating and reparation in subsequently the coating step.
Film by obtaining basal surface on filming in the middle of the basal surface coating composition is applied in.Bump wet coating way by wet, the basal surface coating composition is applied on uncured centre films.To the method for using the basal surface coating composition without limits, but comprise the inter coat method for compositions of using described above.When the basal surface coating composition is applied on the car body, implement by multistage coating, preferably carry out the secondary coating with the air electrostatic sprayer, its objective is in order to make coating more attractive in appearance.Air electrostatic sprayer that application process also can be united and rotary type electrostatic spray machine.
Formation that basal surface is filmed allows to increase pattern during filming, guarantee simultaneously with preceding step in film bonding of the centre that forms and with the basal surface that later step is coated with film bonding.
It is desirable to, each thick coating behind the basal surface dried coating film is 5-50 μ m, preferably 10-30 μ m.After basal surface is filmed and formed, do not having to carry out the step that formation transparent surface is subsequently filmed under heating and the solidified situation.Forming before transparent surface films,, heating basal surface in advance and film with the heating that is lower than it and the temperature of curing (curing) temperature.
The clear top coat composition
The clear top coat composition is made up of the clear coating composition that comprises clear top coat resin Composition, various additive and solvent.Transparent surface coating composition is water base and organic solvent based, comprises water-dispersion and organic solvent dispersive composition.
The clear top coat resin Composition that is included in the clear top coat composition comprises clear top coat resin and optional clear top coat solidifying agent.Be included in describe in clear top coat resin Composition (clear top coat resin and clear top coat solidifying agent), multiple additives and solvent and the inter coat in the clear top coat resin combination identical.
Comprise acrylic resin-melamine resin system as the clear top coat resin of clear top coat resin Composition and the preferably combination of clear top coat solidifying agent.In this system, the acid number that it is desirable to acrylic resin is 10-200, and hydroxyl value is that 30-200 and number-average molecular weight are 2000-50000.
As the clear top coat composition, can use following clear coating composition, it comprises the disclosed polymkeric substance that contains the polymkeric substance of carboxyl and contain epoxy group(ing) in the Japanese patent laid-open publication gazette 19315/1996, to bump in the wet coating way wet, by increasing the dissolubility difference of filming with basal surface, guarantee acidproof rain and keep basal surface film in the orientation of colour lustre pigments.The clear top coat composition can be chosen wantonly and comprise additive, for example tinting pigment, pigment extender, properties-correcting agent, UV light absorber, levelling agent, dispersion agent and defoamer.
Clear top coat preparation of compositions and application
Prepare the clear top coat composition in the solvent by said components being dissolved or being dispersed in.Above-mentioned solvent arbitrarily can use.The clear top coat composition is applied in basal surface films to go up to obtain transparent surface and films.Bump wet coating way by wet, the clear top coat composition is applied on uncured basal surface films.
Form the not restriction of method that transparent surface is filmed, but preferable methods comprises spraying method, roller painting etc.It is desirable to, the transparent surface dried bed thickness of every tunic of filming is 20-50 μ m, preferably 25-40 μ m.
The formation that transparent surface is filmed can protect basal surface to film, and is that the multilayer film that obtains is given depth preception.
Cure
Transparent surface film form after, it is three-layer coated to cure that film in uncured centre, basal surface is filmed and transparent surface is filmed, and solidifies the given time down to obtain multilayer film at 120-160 ℃.In the method for the invention, bump wet coating way, use inter coat composition, basal surface coating composition and clear coating composition respectively in order by wet.That is to say that uncured filming is that said sequence forms.Term herein " uncured " is meant to film does not have completely crued state, comprises the state that preheating is filmed yet.The term of Shi Yonging " preheating " is meant under room temperature to 100 ℃ condition and keeps or heating was filmed 1-10 minute herein, and this temperature is lower than the heating and curing (curing) treatment temp of filming.By film in the centre and basal surface film respectively form after preheating film and can obtain to have filming of better covering with paint outward appearance.
Embodiment
According to the following examples, the present invention will be by further detailed explanation, but the present invention is not limited to these embodiment.In these embodiments, except as otherwise noted, " part " is meant weight part.
Preparation embodiment 1
The preparation of amine-modified epoxy resin
With 92 part 2,4-/2,6-tolylene diisocyanate (weight ratio=8/2), 95 parts of mibks (hereinafter being called MIBK) and 0.5 part of dibutyl tin laurate are put into the flask that is equipped with agitator, cooling tube, nitrogen input tube, thermometer and dropping funnel.When stirring reaction mixture, add 21 parts of methyl alcohol.Begin under the room temperature, make reaction mixture be warmed up to 60 ℃ by heat release, reaction kept 30 minutes, with dropping funnel 50 parts of glycol monomethyls-2-ethylhexyl ether was splashed into then.But also add 5 moles of adductss of 53 parts of dihydroxyphenyl propane-propylene oxide.Reaction is mainly carried out under 60-65 ℃ temperature, and lasts till based on being absorbed in the IR spectrometry of isocyanate group and disappear.
Then, be that 188 Resins, epoxy joins in the reaction mixture with 365 parts of epoxy equivalent (weight)s, and be heated to 125 ℃ that epoxy equivalent (weight) wherein is that 188 Resins, epoxy is synthetic by dihydroxyphenyl propane and Epicholorohydrin according to currently known methods.Then, add 1.0 parts of benzyl dimethylamine, and 130 ℃ of reactions down, to becoming 410 to epoxy equivalent (weight).
Thereafter, it is sad to add 61 parts of dihydroxyphenyl propanes and 33 parts, 120 ℃ down reaction to make epoxy equivalent (weight) be 1190.After this, cool off reactant, add the MIBK solution of the ketoimine amino ethyl ethanolamine of 11 parts of diethanolamine, 24 parts of N-ehtylethanolamines, 25 part of 79 weight %, reacted 2 hours down at 110 ℃ again.Then, reaction mixture is diluted to non-volatile solid content with MIBK becomes 80%, thereby the acquisition second-order transition temperature is 2 ℃ an amine-modified epoxy resin (resin solid content: 80%).
Preparation embodiment 2
The preparation of blocked polyisocyanate solidifying agent (1)
1250 parts of diphenylmethanediisocyanates, 266.4 parts of MIBK are put into reactor, add 2.5 parts of dibutyl tin laurates after being heated to 80 ℃.Then, under 80 ℃ of conditions, be dissolved in 944 parts of ε-Ji Neixianan solution in the ethylene glycol butyl ether through 2 hours with 226 parts and splash into.Be reflected at 100 ℃ and kept 4 hours down, affirmation is placed cooling with reactant after disappearing in the IR spectrometry based on being absorbed in of isocyanate group.Add 336.1 parts of MIBK, thereby the acquisition second-order transition temperature is 0 ℃ a blocked polyisocyanate solidifying agent.
Preparation embodiment 3
The preparation of pigment dispersing resin
222.0 parts of isophorone diisocyanates (hereinafter being called IPDI) are put into the reactor that is equipped with agitator, cooling tube, nitrogen input tube and thermometer, after with 39.1 parts of MIBK dilutions, add 0.2 part of dibutyl tin laurate.Then, reaction mixture is heated to 50 ℃,, in 2 hours, splashes into 131.5 parts of 2-Ethylhexyl Alcohols while stirring doing under the nitrogen atmosphere.Temperature of reaction remains on 50 ℃, and the words that need are cooled off.Finally, obtain 2-Ethylhexyl Alcohol half end capped IPDI (resin solid content: 90.0%).
87.2 parts of dimethylethanolamines, lactic acid aqueous solution and 39.2 parts of ethylene glycol monobutyl ethers of 117.6 part 75% are joined in the suitable reaction vessel, under 65 ℃, reaction mixture stirred half hour to make quaternizing agent.
Subsequently, 710.0 parts of EPON829 (by the dihydroxyphenyl propane type of epoxy resin that shell chemical company makes, epoxy equivalent (weight) is 193-203) and 289.6 parts of dihydroxyphenyl propanes are added reactor.Under nitrogen atmosphere, reaction mixture is heated to 150-160 ℃, carries out initial thermopositive reaction.Continue about 1 hour of heating down at 150-160 ℃, reaction mixture is cooled to 120 ℃ then, add 498.8 parts of 2-Ethylhexyl Alcohols that made, half end capped IPDI (MIBK solution).
Reaction mixture kept about 1 hour down at 110-120 ℃, added 463.4 parts of ethylene glycol monobutyl ethers, mixture was cooled to 85-95 ℃ again, after the homogenize, added 196.7 parts of quaternizing agents that made again.Reaction mixture remains on 85-95 ℃ always and becomes 1 up to acid number, 964 parts of deionized waters are added so that stop to epoxy-bisphenol a resin quaternized, obtain to have quaternary ammonium moiety pigment dispersing resin (resin Tg=5 ℃, resin solid content: 50%).
Preparation embodiment 4
The preparation of pigment disperse sizing agent
Pigment dispersing resin, 2.0 parts of carbon blacks, 100 parts of kaolin, 80.0 parts of titanium dioxide, 18.0 parts of phospho-molybdic acid aluminium and 221.7 parts of ion exchanged waters of obtaining among 120 parts of preparation embodiment 3 are put into sand mill, it is distributed to particle diameter is not more than 10 μ m, to obtain pigment disperse sizing agent (solid content: 48%).
Embodiment 1
The formation that the preparation of cation electroplating coating composition and plating are filmed
With the blocked polyisocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 80/20 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of the solid content of 100g resin glue, and slowly adds ion exchanged water and dilute.Remove MIBK under the reduced pressure, the acquisition solid content is 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of this emulsions, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, is the cation electroplating coating composition of 20.0 weight % to obtain solid content.The definite Tg that electroplates film (deposited film) of Tg calculating according to each resin of all resin Compositions in the electroplated coating composition is 15 ℃.The volatile organic compounds matter concentration (VOC) that the electroplated coating composition contains in coating is 0.5%, is 24.2 based on the milligramequivalent value MEQ (A) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, on surface-treated steel plate, electroplate coating with coating composition, so that obtain cation electrodeposition plated coating film (A-1), the dry coating thickness that has 15 μ m after plating is filmed and cured, the surface roughness Ra of used steel plate=0.90 μ m (cutoff value (cutoffvalue): 2.5mm).
Solidified is electroplated the formation of filming
Under 170 ℃, cure the cation electrodeposition plated coating film (A-1) 20 minutes of acquisition, electroplate and film as ground to obtain solidified.
The formation of filming in the centre
With polyester-melamine cured type inter coat composition (" OTO H-880 ", by Nippon Paint Co., Ltd. produce) be applied on the ground, the application device of use is the electrostatic sprayer of rotary gasification type, so that the thickness of dry coating is 20 μ m.After using, preheating at room temperature 8 minutes forms uncured centre and films.
The formation that basal surface is filmed and transparent surface is filmed
With acryl-melamine cured type basal surface coating composition (" OTO H-600 "; by Nippon Paint Co.; Ltd. produce) be applied on middle the filming; so that the thickness of dry coating is 10 μ m; after using; preheating at room temperature 7 minutes forms uncured basal surface and films.Then, with vinylformic acid-epoxy resin cure type clear top coat composition (" MAC O-1600 ", by Nippon Paint Co., Ltd. produces) be applied on basal surface films, so that the thickness of dry coating is 35 μ m.Under 140 ℃, with the centre of using film, substrate surface is filmed and transparent surface is filmed cured 30 minutes, to obtain multilayer film.
The center line average roughness Ra of roughness curve) and the center line average roughness of profilograph (Pa) mensuration
According to JIS-B 0601, utilize the surface roughness instruments of the evaluation type of Mitutoyo company manufacturing to measure Ra and the Pa value that the solidified plating is filmed, this curing is electroplated to film and is obtained by the electroplated coating composition.Utilization contains the wide cutoff value of 2.5mm and makes sample, measures to repeat 7 times, measures Ra and Pa by removing mean value the highest and that Schwellenwert obtains.The result is as shown in table 1.
The mensuration of surface energy
After solvent droplets is dripped 30 seconds, with automatic contact angle instrument (PD-X type, Kyowa InterfaceScience Co., Ltd company makes) solidified of measuring embodiment and comparing embodiment electroplate film and DIW (deionized water), ethylene glycol and methylene iodide between contact angle.By calculating from the observed value that obtains, thereby determine that solidified electroplates the surface energy of filming with above-mentioned equation.
Measurement of contact angle
After the drop of inter coat composition drips 30 seconds, measure (by Kyowa Interface Science Co. with automatic contact angle instrument, Ltd company makes, the PD-X model) embodiment and the curing electroplated coating composition of comparing embodiment and the contact angle between the inter coat composition (" OTO H-880 ").
The visual appearance assessment of multilayer film
After multilayer film cured and solidifies, it was covered with paint, lacquer, colour wash, etc. outward appearance and measures with ripple scanning (Wave-Scan) DOI (BYK-Gardner Co.).In each measured value, " Wa " value is relevant with the gloss scoring item of multilayer film, and " Wc " value is relevant with the tangerine peel flaw evaluation item of multilayer film, and " Wd " value is relevant with the slickness scoring item of multilayer film.Wa, Wc and Wd value are used for carrying out above-mentioned assessment.Be worth more for a short time, visual appearance is good more.
Embodiment 2
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 3 with solid content than 70/30 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 35 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain to have solid content be 36% emulsion.
Mix the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 280 parts of preparation embodiment 4,1560 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 20 part 10%, obtaining solid content is the cation electroplating coating composition of 20 weight %.The definite Tg that electroplates film (deposited film) of Tg calculating according to each resin of all resin Compositions in this electroplated coating composition is 14 ℃.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, is 25.5 based on the milligramequivalent value MEQ (A) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, apply at the enterprising electroplating of surface-treated steel plate with coating composition, so that obtain cation electrodeposition plated coating film (A-2), the surfaceness of used steel plate is a Ra=0.90 μ m (cutoff value: 2.5mm).
With describe among the embodiment 1 the same, film except preparing the cation electroplating coating composition as mentioned above and forming plating, also can obtain multilayer film.The multilayer film that obtains is also estimated with the method for describing among the embodiment 1.The result is as shown in table 1.
Embodiment 3
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 70/30 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mix the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, obtaining solid content is the cation electroplating coating composition of 20 weight %.The definite Tg that electroplates film (deposited film) of Tg calculating according to every kind of resin of all resin Compositions in this electroplated coating composition is 10 ℃.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, is 24.2 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, apply at the enterprising electroplating of surface-treated steel plate with coating composition, so that obtain cation electrodeposition plated coating film (A-3), the surfaceness of used steel plate is a Ra=0.60 μ m (cutoff value: 2.5mm).
With describe among the embodiment 1 the same, film except preparing the cation electroplating coating composition as mentioned above and forming plating, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 1.The result is as shown in table 1.
Embodiment 4
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 80/20 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mix the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 280 parts of preparation embodiment 4,1560 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, obtaining solid content is the cation electroplating coating composition of 20 weight %.The definite Tg that electroplates film (deposited film) of Tg calculating according to every kind of resin of all resin Compositions in this electroplated coating composition is 15 ℃.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, based on the milligramequivalent value MEQ (A) of the acid of 100g resin solid content) be 24.2.Under 30 ℃ of plating bath temperature, apply at the enterprising electroplating of surface-treated steel plate with coating composition, so that obtain cation electrodeposition plated coating film (A-4), the surfaceness of used steel plate is a Ra=0.20 μ m (cutoff value: 2.5mm).
With describe among the embodiment 1 the same, film except preparing the cation electroplating coating composition as mentioned above and forming plating, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 1.The result is as shown in table 1.
Embodiment 5
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 60/40 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mix the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, obtaining solid content is the cation electroplating coating composition of 20 weight %.The definite Tg that electroplates film (deposited film) of Tg calculating by every kind of resin of all resin Compositions in this electroplated coating composition is 4 ℃.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in filming is 0.5%, is 24.2 based on the milligramequivalent value MEQ (A) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, apply at the enterprising electroplating of surface-treated steel plate with coating composition, so that obtain cation electrodeposition plated coating film (A-5), the surfaceness of used steel plate is a Ra=0.60 μ m (cutoff value: 2.5mm).
With describe among the embodiment 1 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 1.The result is as shown in table 1.
The comparative example 1
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 70/30 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, is the cation electroplating coating composition of 20 weight % to obtain solid content.The definite Tg that electroplates film (deposited film) of Tg calculating by every kind of resin of all resin Compositions in this electroplated coating composition is 10 ℃.The volatile organic compounds matter concentration (VOC) that the electroplated coating composition contains in filming is 0.5%, is 24.2 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, apply at the enterprising electroplating of surface-treated steel plate with coating composition, so that obtain cation electrodeposition plated coating film (B-1), the surfaceness of used steel plate is a Ra=0.90 μ m (cutoff value: 2.5mm).
With describe among the embodiment 1 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 1.The result is as shown in table 1.
The comparative example 2
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 70/30 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mix the pigment dispersing resin that obtains among above-mentioned 1500 parts of emulsions, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, obtaining solid content is the cation electroplating coating composition of 20 weight %.The definite Tg that electroplates film (deposited film) of Tg calculating by every kind of resin of all resin Compositions in this electroplated coating composition is 10 ℃.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in filming is 0.5%, is 24.2 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, apply at the enterprising electroplating of surface-treated steel plate with coating composition, so that obtain cation electrodeposition plated coating film (B-2), the surfaceness of used steel plate is a Ra=1.20 μ m (cutoff value: 2.5mm).
With describe among the embodiment 1 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 1.The result is as shown in table 1.
Embodiment 6
The formation that the preparation of cation electroplating coating composition and plating are filmed
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 70/30 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mix the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, obtaining solid content is the cation electroplating coating composition of 20 weight %.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in filming is 0.5%, is 24.2 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, electroplate coating with the cation electroplating coating composition that obtains, thereby obtain the cation electrodeposition plated coating film.The plating of curing acquisition under 160 ℃ is filmed and can be obtained solidified in 20 minutes and electroplate and film (A-6), and this plating is filmed and be can be used as ground.
The formation of filming in the centre
With polyester-melamine cured type inter coat composition (" OTO H-880 ", by Nippon PaintCo., Ltd. produce) be applied on the ground, the application device of use is the electrostatic sprayer of rotary gasification type, so that the thickness of dry coating is 20 μ m.After using, preheating at room temperature formed uncured centre in 8 minutes and films.
The formation that basal surface coating and transparent surface are filmed
With acryl-melamine cured type basal surface coating composition (" OTO H-600 "; by Nippon Paint Co.; Ltd. produce) be applied on middle the filming; so that the thickness of dry coating is 10 μ m; after using, preheating at room temperature formed uncured basal surface coating in 7 minutes.Then, with vinylformic acid-epoxy resin cure type clear top coat composition (" MAC O-1600 ", by Nippon Paint Co., Ltd. produces) be applied on basal surface films, so that the thickness of dry coating is 35 μ m.With the centre of using film, basal surface is filmed and transparent surface is filmed cured under 140 ℃ 30 minutes, to obtain multilayer film.
Solidified is electroplated the mensuration of the dynamic Tg that films
The electroplated coating composition plating that makes among embodiment and the comparative example is coated on the sheet tin that is used for Measurement of Dynamic Viscoelasticity, films to obtain to electroplate.Then, under 170 ℃, cure to electroplate and filmed 20 minutes, film to obtain the solidified plating.With filming that mercury will obtain, and cut the sample that its preparation is used to measure with the sheet tin separation.Sample is heated to 200 ℃ by room temperature, and heat-up rate is 2 ℃ of per minutes, simultaneously with the frequency vibration of 10HZ, and use Orientec Co., Rheovibron model RHEO 2000,3000 (trade(brand)name) the mensuration visco-elasticity that Ltd.. makes.Calculate the ratio (tan δ) of energy storage elasticity (E ') and loss elasticity (E "), thereby definite flex point (temperature at tan δ peak value place) is to obtain dynamic Tg.
Solidified is electroplated the mensuration of the cross-linking density of filming
By above-described equation, calculate by the energy storage elasticity that in dynamically Tg measures, obtains (E '), thereby determine cross-linking density.
The visual appearance assessment of multilayer film
Cure and solidify after the covering with paint outward appearance of multilayer film scan DOI (BYK-Gardner Co.) with ripple and measure.In each measured value, " Wa " value is relevant with the gloss scoring item of multilayer film, and " Wc " value is relevant with the tangerine peel flaw evaluation item of multilayer film, and " Wd " value is relevant with the slickness scoring item of multilayer film.Wa, Wc and Wd value are used for carrying out above-mentioned assessment.Be worth more for a short time, visual appearance is good more.
Embodiment 7
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 3 with solid content than 80/20 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 35 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 20 part 10%, is the cation electroplating coating composition of 20 weight % to obtain solid content.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, is 25.5 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, electroplate coating with the cation electroplating coating composition that obtains, thereby obtain the cation electrodeposition plated coating film.The deposition of curing acquisition under 160 ℃ is filmed and can be obtained solidified in 20 minutes and electroplate and film (A-7), and this plating is filmed and be can be used as ground.
With describe among the embodiment 6 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 6.The result is as shown in table 2.
Embodiment 8
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 80/20 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, is the cation electroplating coating composition of 20 weight % to obtain solid content.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, is 24.2 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, electroplate coating with the cation electroplating coating composition that obtains, thereby obtain the cation electrodeposition plated coating film.The plating of curing acquisition under 180 ℃ is filmed and can be obtained solidified in 20 minutes and electroplate and film (A-8), and this plating is filmed and be can be used as ground.
With describe among the embodiment 6 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 6.The result is as shown in table 2.
Embodiment 9
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 60/40 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIRK, to obtain solid content be 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, is the cation electroplating coating composition of 20 weight % to obtain solid content.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, is 24.2 based on the milligramequivalent value MEQ (A) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, electroplate coating with the cation electroplating coating composition that obtains, thereby obtain the cation electrodeposition plated coating film.The plating of curing acquisition under 180 ℃ is filmed and can be obtained solidified in 20 minutes and electroplate and film (A-9), and this plating is filmed and be can be used as ground.
With describe among the embodiment 6 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 6.The result is as shown in table 2.
The comparative example 3
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 90/10 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, is the cation electroplating coating composition of 20 weight % to obtain solid content.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, is 24.2 based on the milligramequivalent value MEQ (A) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, electroplate coating with the cation electroplating coating composition that obtains, thereby obtain the cation electrodeposition plated coating film.The deposition of curing acquisition under 160 ℃ is filmed and can be obtained solidified in 20 minutes and electroplate and film (B-3), and this plating is filmed and be can be used as ground.
With describe among the embodiment 6 the same, remove as mentioned above this and prepare cation electroplating coating composition and the formation electroplated coating, also can obtain laminated coating.The laminated coating that obtains is estimated with the method for describing among the embodiment 6.The result is as shown in table 2.
The comparative example 4
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 80/20 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 540 parts of preparation embodiment 4,1920 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, is the cation electroplating coating composition of 20 weight % to obtain solid content.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in filming is 0.5%, is 24.2 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, electroplate coating with the cation electroplating coating composition that obtains, thereby obtain the cation electrodeposition plated coating film.The deposition of curing acquisition under 150 ℃ is filmed and can be obtained solidified in 20 minutes and electroplate and film (B-4), and this plating is filmed and be can be used as ground.
With describe among the embodiment 6 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 6.The result is as shown in table 2.
The comparative example 5
With the blocked isocyanate solidifying agent that obtains among the amine-modified epoxy resin that obtains among the preparation embodiment 1 and the preparation embodiment 2 with solid content than 70/30 ratio uniform mixing.Glacial acetic acid is added in the mixture, is 30 so that make the milligramequivalent value MEQ (A) based on the acid of 100g resin glue solid content, and slowly adds ion exchanged water and dilute.Under the reduced pressure, removing MIBK, to obtain solid content be 36% emulsion.
Mixing the pigment dispersing resin that obtains among 1500 parts of above-mentioned emulsion, the 280 parts of preparation embodiment 4,1560 parts of ion exchanged waters, the cerous acetate aqueous solution and 10 parts of dibutyl tin oxides of 40 part 10%, is the cation electroplating coating composition of 20 weight % to obtain solid content.The volatile organic compounds matter content (VOC) that the electroplated coating composition contains in coating is 0.5%, is 24.2 based on the milligramequivalent value (MEQ (A)) of the acid of 100g resin solid content.Under 30 ℃ of plating bath temperature, electroplate coating with the cation electroplating coating composition that obtains, thereby obtain the cation electrodeposition plated coating film.The deposition of curing acquisition under 180 ℃ is filmed and can be obtained solidified in 20 minutes and electroplate and film (B-5), and this electroplated coating can be used as ground.
With describe among the embodiment 6 the same, remove and prepare as mentioned above cation electroplating coating composition and formation plating film, also can obtain multilayer film.The multilayer film that obtains is estimated with the method for describing among the embodiment 6.The result is as shown in table 2.
Measurement result
Table 1
The embodiment numbering Comparative example's numbering
????1 ??2 ??3 ??4 ??5 1 2
????A-1 ??A-2 ??A-3 ??A-4 ??A-5 B-1 B-2
Solidified is electroplated the evaluation of filming
Ra (μ m) (cutoff value 2.5) ????0.25 ??0.23 ??0.23 ??0.05 ??0.19 025 0.3
Pa (μ m) (cutoff value 2.5) ????0.3 ??0.24 ??0.28 ??0.05 ??0.21 0.34 0.44
Surface energy (mJ/m 2) ????37 ??39 ??41 ??37 ??44 41 42
Contact angle (degree) with the inter coat composition ????17 ??20 ??25 ??17 ??36 32 33
The ocular estimate of multilayer film
Wa ????8 ??9 ??8 ??7 ??10 12 15
Wc ????14 ??16 ??16 ??12 ??20 23 27
Wd ????14 ??16 ??17 ??11 ??17 20 23
Table 2
The embodiment numbering Comparative example's numbering
????6 ??7 ??8 ??9 ??3 ??4 ??5
????A-6 ??A-7 ??A-8 ??A-9 ??B-3 ??B-4 ??B-5
Solidified is electroplated the evaluation of filming
Cross-linking density (mmol/cc) ????1.42 ??1.20 ??1.62 ??2.51 ??0.91 ??1.10 ??1.99
Dynamic Tg (℃) ????108 ??100 ??110 ??130 ??110 ??101 ??90
The ocular estimate of multilayer film
??Wa ???O(8) ??O(9) ??O(8) ??O(8) ??X(12) ??X(12) ??X(15)
??Wc ???O(18) ??O(17) ??O(17) ??O(17) ??X(21) ??X(21) ??X(24)
??Wd ???O(16) ??O(16) ??O(16) ??O(17) ??X(22) ??X(21) ??X(22)
Wa O: be no more than 10, X: be not less than 11
Wc O: be no more than 20, X: be not less than 21
Wd O: be no more than 20, X: be not less than 21
Can clearly draw from the result shown in the table 1, the curing that embodiment of the invention 1-5 relates to electroplates to film has the surface of good situation.On the solidified plating is filmed, obtained to have good appearance and do not revealed by three coatings, one baking method from the multilayer film of electroplating the defective of filming.On the contrary, in comparative example 1-2, have macroscopic irregularity, therefore do not obtain having the multilayer film of good appearance owing to electroplate to film.
Can obviously draw from the result shown in the table 2, the multilayer film that obtains on the solidified plating of embodiment of the invention 6-9 is filmed by three coatings, one baking method has good surface appearance.On the contrary, in comparative example 3-5, do not obtain having the multilayer film of good appearance.

Claims (5)

1. a method that forms multilayer film is characterized in that this method comprises the following steps:
Electroplate coating with the cation electroplating coating composition enterprising being about to of ground, heat and solidify this coating then, film on ground, to form the solidified plating,
With the inter coat composition be applied in solidified electroplate film on, film to form uncured centre,
The basal surface coating composition is applied on uncured centre films, films to form uncured bottom
The clear top coat composition is used on uncured bottom films, forming uncured transparent coating, and
Heat simultaneously and solidify that film in uncured centre, uncured basal surface is filmed and uncured transparent coating;
Wherein to electroplate the center line average roughness (Ra) that obtains from roughness curve film be 0.05-0.25 μ m to solidified, is 0.05-0.30 μ m from the center line average roughness (Pa) of profilograph acquisition.
2. a method that forms multilayer film is characterized in that this method comprises the following steps:
Apply at the enterprising electroplating of ground with the cation electroplating coating composition, heat and solidify this coating then, film on ground, to form the solidified plating,
With the inter coat composition be applied in solidified electroplate film on, film to form uncured centre,
The basal surface coating composition is applied on uncured centre films, films to form uncured bottom
The clear top coat composition is used on uncured bottom films, forming uncured transparent coating, and
Heat simultaneously and solidify that film in uncured centre, uncured basal surface is filmed and uncured transparent coating;
Wherein solidify electroplating the surface energy that has of filming is 37-43mJ/m 2, the contact angle that the inter coat composition is electroplated on filming at solidified is the 10-30 degree.
3. a method that forms multilayer film is characterized in that this method comprises the following steps:
Apply at the enterprising electroplating of ground with the cation electroplating coating composition, heat and solidify this coating then, film on ground, to form the solidified plating,
With the inter coat composition be applied in solidified electroplate film on, film to form uncured centre,
The basal surface coating composition is applied on uncured centre films, films to form uncured bottom
The clear top coat composition is used on uncured bottom films, forming uncured transparent coating, and
Heat simultaneously and solidify that film in uncured centre, uncured basal surface is filmed and uncured transparent coating;
Wherein to electroplate the center line average roughness (Ra) that obtains from roughness curve film be 0.05-0.25 μ m to solidified, is 0.05-0.30 μ m from the center line average roughness (Pa) of profilograph acquisition, and surface energy is 37-43mJ/m 2, and the contact angle that the inter coat composition is electroplated on filming at solidified is the 10-30 degree.
4. a method that forms multilayer film is characterized in that this method comprises the following steps:
Apply at the enterprising electroplating of ground with the cation electroplating coating composition, heat and solidify this coating then, film on ground, to form the solidified plating,
With the inter coat composition be applied in solidified electroplate film on, film to form uncured centre,
The basal surface coating composition is applied on uncured centre films, films to form uncured bottom
The clear top coat composition is used on uncured bottom films, forming uncured transparent coating, and
Heat simultaneously and solidify that film in uncured centre, uncured basal surface is filmed and uncured transparent coating;
Wherein to electroplate the glass transition temperature Tg that is obtained by the Measurement of Dynamic Viscoelasticity method of filming be 100-130 ℃ to solidified, and cross-linking density is 1.2-2.6mmol/cc.
5. as the method for each described formation multilayer film among the claim 1-4, wherein the inter coat composition comprises:
The inter coat resin comprises being selected from least a in acrylic resin, vibrin and the urethane resin,
The inter coat solidifying agent, comprise be selected from least a in blocked isocyanate compounds, oxazoline compound, carbodiimide compound and the melamine compound and
Pigment.
CNA2005100518647A 2004-01-26 2005-01-26 Process for forming multi layered coated film and multi layered coated film Pending CN1647862A (en)

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