TW200812710A - Process for forming multi layered coating film - Google Patents

Abstract

The present invention is intended to provide a process for forming a multi layered coating film having good finished appearance and reducing a cost of coating equipment and energy of coating. The present invention relates to a process for forming a multi layered coating 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 a cured electrodeposition coating film on the substrate (step 1), and applying a coating composition on the cured electrodeposition coating film to form a multi layered coating film (step 2); wherein the cationic electrodeposition coating composition has a pigment concentration of 2 to 7% by weight based on solid contents of the electrodeposition coating composition, the pigment in the electrodeposition coating composition comprises 95 to 100% by weight of titanium dioxide, the cured electrodeposition coating film has a lightness index (L-value) of 55 or greater on thickness of the cured electrodeposition coating film being 15 μm or greater, and the cured electrodeposition coating film has a dry film density of 1.20 to 1.25.

Description

200812710 IX. INSTRUCTIONS: [Technical Field of Inventions] Field of the Invention [0001] The present invention relates to a method of forming a multilayer coated film having a good finished appearance and reducing the cost and coating energy of the coating equipment.

Γ mT J BACKGROUND OF THE INVENTION [0002] Electrodeposition coating methods include immersing a substrate to be coated in an electrodeposition coating composition and applying a voltage to the substrate. According to the electrodeposition coating method 10, the coated film can be automatically and continuously formed on even narrow portions of the substrate to be coated having a complicated shape. Therefore, the electrodeposition coating method is widely used to apply a primer having a complicated shape and requiring a high degree of rust prevention, such as an automobile body. Moreover, the electrodeposition coating method is superior in terms of corrosion protection and protection of the substrate. [0003] In general, the electrodeposition coating composition contains a large amount of pigment to improve the corrosion resistance and physical properties of the coated film. In the coating composition, the pigments are present in dispersion in an aqueous medium. In general, the pigments are inorganic pigments which have a high specific density, so that such sedimentation is highly likely to occur in the electrodeposition coating composition. For example, a conventional electrodeposition coating composition containing an inorganic pigment is allowed to stand, which causes inorganic pigment to be deposited. The bath or bath of the electrodeposition coating composition needs continuous stirring to avoid the settlement, which imposes the cost and energy of the coating equipment in the field of coating, and has the composition of reducing the electrodeposition coating. The pigment is concentrated to avoid such settlement and reduce the cost of coating equipment and coating energy. 200812710 " Reduce the pigment concentration to avoid pigment settling on the horizontal surface of the coated substrate'. It can improve the cured electrodeposition coating film. The finished look. [0004] Coating provides a good appearance to the substrate and protects the substrate. In general, multilayer coated films having different functions are formed to obtain a good appearance. In the conventional method, each layer of the coated film of the multilayer coating film is separately coated and cured. [0005] However, in recent years, a method of forming a multilayer coating film comprising the following steps has been used: the next coating film is coated on an uncured coated film by a so-called wet-stack wet coating without baking. And baking the 10 layers at the same time, because of the need to save energy and reduce costs. One possible specific example of the method is a three-coat-bake coating method comprising the following steps (three-time wet coating is applied to the cured electrodeposition coating film by wet-wet coating to coat the intermediate coating, the top of the substrate a top coat and a bright top coat; and simultaneously baking and curing the three layers of uncured coated film. 15 Achieving a method of reducing cost and energy Another possible specific example is a three coat two bake comprising the following steps Coating method: coating an intermediate coating on the cured electrodeposition coating enamel film and curing, then coating the top coating of the substrate with the bright top coating by wet-wet coating; and simultaneously baking and curing the Two layers of uncured coated film. 20 Another possible specific example of the method is a coating method comprising the steps of coating a topcoat of a substrate on a cured electrodeposition coated film without a coated intermediate coating [0006] In this type of coating method in which the number of baking times is small, the thickness of the intermediate coating film formed tends to be thinner than that of the conventional intermediate coating film. In this type of 6200812710, an extremely thin intermediate coating film or no intermediate In the case of coating a film The concealing properties of the cured electrodeposition coated film seem to affect the finished appearance and color tone of the resulting multilayer coated film. The concealing properties of the cured electrodeposition coated film depend on the pigment concentration of the electrodeposition coating composition. The electrospray 5 coating composition is superior to avoiding pigmentation, and conversely, the concealing property is poor. Therefore, it is used in the three-coat one baking coating method or the three-coat two baking gold coating method. Electrodeposition coating compositions of low pigment concentration are difficult.

[0007] In the publication of Japanese Patent Publication No. 2〇〇23-231989, a method for coating a topography electrodeposition coating is disclosed, which comprises coating a composition by cationic electrodeposition in a cationic electrodeposition coating composition. A cationic electrodeposition coating composition having a solid content ranging from 1% by weight to the pigment ash content and a cationic electrodeposition coating composition having a solid concentration of 12 Wt%. However, the reduction in the ash content of the pigment in the electrodeposition coating composition lowers the concealing property of the cured electrodepositor film, which results in a large influence on the appearance of the substrate to the finished film. When a substrate having a low brightness index is applied, the brightness index of the resulting coated film becomes lower, which causes a negative influence on the finished appearance of the resulting multilayer coated film. [0008] A method of forming a multilayer coating film comprising a process (1) coating a target object to be coated on which an electrodeposition coating film is formed in advance is disclosed in Japanese Patent Laid-Open No. Hei. a water-based intermediate coating material to form an uncured intermediate coating film; a process (7) coating a water-based substrate coating material on the intermediate coating film to form an uncured base coating film; Process 7 200812710 (3) Coating the substrate a film coated with a bright coating material to form an uncured bright coated film; and a radish 筠 如 & & ( ( ( 同时 同时 同时 同时 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间 中间Brightly coating the film to obtain a multi-layer coating film, wherein the 3 water-based coating material and/or the water-based substrate coating material contains a pigment dispersion in which 5 of the pigments are dispersed (before the pigment is substantially 3 is prepared by dispersing a pigment dispersant of a U-based substance). This method provides a coated film that has an excellent appearance and does not yellow in the wet coating system that is intended to reduce the coating process, cost, and compliance. However, the method of forming a multilayer coating film may reduce the thickness of the intermediate coating film, which may reduce the concealing properties of the coating film. [0009] In the method of forming a two-layer coating film, which is formed by successively forming an inner layer coating film and a base coating on a substrate on which an underlying coating film has been formed, is disclosed in Japanese Laid-Open Patent Publication No. 2-275971. Film and bright coated film 'The method of forming a two-layer coating film comprises forming an inner layer coating film using an inner layer coating 15 device, and in the inner layer coating device, supplying a white coating material in a variable supply amount White coating material supply tool and black coating material supply tool for supplying black coating material in a variable supply, the white coating material supply tool and the black coating material supply tool system are connected to each other independently to the rotary spray type a coating gun wherein the white coating material and the black 20 color coating material have a pigment concentration (PWC) of 2 to 60% by weight, a nonvolatile content of 35 to 60% by weight, and a coating of 0.03 to 0.3 Pa.s. Material viscosity. This publication describes a three coat-bake coating process. In contrast, this publication does not teach the correlation between the brightness of the cured electrodeposition coated film and the finished appearance or the multi-layer coated film. 8 _ [0010] 200812710 Patent Document 1: JP-A-2004-231989 Patent Document 2: JP-A-2002-126627 Patent Document 3: JP-A-2004-275971 5 Object of the Invention [0 011] Main Aspect of the Invention The purpose is to solve the problem of conventional skills. More specifically, the present invention provides a method of forming a multilayer coated film having a good finished appearance and reducing the cost of coating equipment and coating energy. 10 SUMMARY OF THE INVENTION [0012] Accordingly, the present invention provides a method of forming a multilayer coating film, the method comprising the steps of: performing electrodeposition coating on a substrate by cationic electrodeposition coating composition, and then Heating and curing to form a cured electrodeposition coating film on the substrate (step 1), and coating the coating composition on the cured electrodeposition coating film to form a multi-layer coating film (step 2 Wherein the cationic electrodeposition coating composition has a pigment concentration of 2 to 7% by weight based on the solid content of the electrodeposition coating composition, * 20 of the pigments in the electrodeposition coating composition comprises 95 to 100% by weight ^ Titanium oxide, the cured electrodeposition coated film has a brightness index (L-value) of 55 or more on a thickness of a cured electrodeposition coating film of 15 μm or more, and the cured electrodeposition coated film has Dry film density of 1.20 to 1.25 9 200812710 5 degrees. [0013] The present invention also provides the above method of forming a multilayer coating film, wherein the step 2 comprises the steps of: coating an intermediate coating composition on the cured electrodeposition coating film to form an uncured intermediate coating film, A top coat composition of the substrate is coated on the uncured intermediate coating film to form an uncured base coating film, and a bright top coating composition 10 is coated on the uncured base coating film to form an uncured bright The film is coated, and the uncured intermediate coating film, the uncured base top coated film, and the uncured bright coated film are simultaneously heated and cured. [0014] The present invention also provides the above method of forming a multilayer coating film, wherein 15 step 2 comprises the steps of: coating an intermediate coating composition on the cured electrodeposition coating film, then heating and curing to form Curing an intermediate coating film, coating a top coating composition on the curing intermediate coating film to form an uncured base coating film, 20 coating a bright top coating on the uncured base coating film The uncured bright coated film is formed and the uncured base top coated film and the uncured bright coated film are simultaneously heated and cured. [0015] The present invention also provides the above method of forming a multilayer coating film, 10 200812710 wherein the cured intermediate coating film has a thickness of from 10 Å to 4 Å μη. The present invention also provides the above method for forming a multilayer coating film, wherein the 5 step 2 comprises the steps of: coating a substrate top coating composition on the cured electrodeposition coating film to form an uncured substrate coating The film is coated with a bright topcoat composition on the uncured base coated film to form an uncured bright coated film, and 10 simultaneously heats and cures the uncured base top coated film with uncured bright coating film. [0017] The present invention also provides the above method for forming a multilayer coating film, wherein the step 2 comprises the following steps: 15 coating a solidified top coating composition on the cured electrodeposition coating film to form an uncured solid coating film , and A heats and cures the uncured solid coated film. [0018] The present invention also provides the above method for forming a multilayer coating film, wherein the intermediate coating composition is a water-based intermediate coating composition, the top surface of the substrate, and the 20 coating composition is a water-based substrate top coating composition. The intermediate coating composition is an organic solvent-based intermediate coating composition, and the top coating composition of the substrate is an organic solvent-based substrate top coating composition. The present invention also provides a multilayer coated film obtainable by the above-described method of forming a multilayer coating film 11 200812710. The present invention can provide the formation of a multi-layer coating film having a good finished appearance and an excellent color tone even if a composition having a low pigment concentration (2 to 7% by weight) is used. In the present invention, the identification of the type and use of the pigment in the electrodeposition coating composition can bring about the above advantages. The present invention can also provide a coating film having a well-finished appearance, even if the coating film is coated by a small number of baking methods (for example)

Formed as a three-coat-bake coating method). The multilayer coated film also has an excellent finished appearance on a horizontal surface. The multilayer coated film according to this date has an advantage in that the coated film has a lower density, which is advantageous for reducing the weight of the coated article. The present invention can provide a multi-layer coated film having excellent concealing characteristics, which is formed by a coating method which requires less roasting times to meet the need for saving amount and cost. 15 BRIEF DESCRIPTION OF THE DRAWINGS The figure shows an example of a case for evaluating the throwing power. Figure 2 is a cross-sectional view showing the evaluation for each. A specific example of the method of plating ability [Embodiment] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT [0022] Various types of substrates of seam ratio, such as steel exchange treatment, or may be used in the present invention without the type of shell 0 The conductive substrate can be treated by plating or chemical conversion 12 200812710. Examples of the substrate include, for example, a cold-rolled steel sheet, a rolled steel sheet stainless steel sheet, an electrogalvanized steel sheet, a hot dip-bonded zinc steel sheet, a Le alloy material, a sheet, a zinc-iron alloy plating thin sheet, #4 ^^^ 4 ~ Seeking sheet of zinc-magnesium alloy coated sheet, zinc 5 10 15 20 plating =, film, - Ju Qian alloy coating, tin plating: The ruler. And the cation electrode on the chemical conversion site [〇〇23] and the composition used in the cation electrodeposition coating composition of the present invention contains the solvent to be difficult to bond; the _ cut ^ = blocked isocyanate _ Curing agent; acid for neutralization; organic solvent [0024] The cationic electrodeposition coating composition used in the present invention contains a reference. The (iv) concentration of the cationic electrodeposition coating composition is 2 to 7% by weight based on the solid content of the electrodeposition coating composition. The pigment concentration of 2 to 7% by weight based on the solid content of the electrodeposition coating composition can avoid the sedimentation of the pigment in the electrodeposited coating, which can reduce the mixing time of the electrodeposition bath and reduce the cost of the coating equipment. Coating (4). Moreover, it is avoided to settle on the horizontal surface of the coated substrate, which can improve the finished appearance of the cured electrodeposition coated film. The pigment concentration of the cationic electrodeposition coating composition may preferably be from 3 to 5% by weight based on the solid content of the electrodeposition coating composition. In the electrodeposition coating composition according to the present invention, the pigment in the electrodeposition coating composition contains 95 to 1% by weight of titanium oxide. It is possible to maintain the alum index (L-value) of the cured electrodeposition coating film at 55 or more using a pigment containing 95 to 100% by weight of titanium dioxide, even if the pigment concentration 13 200812710 is low (coated by cationic electrodeposition) The solid content of the coating composition is 2 to 7 畺.) The pigment in the composition after the electrosplitting and k may preferably contain % to 1 (8)% by weight of titanium dioxide, more preferably may contain 6% by weight of dioxane. [6] Useful pigments other than titanium oxide include, for example, the use of machine pigments, for example, coloring pigments, such as carbon black and iron sulphate; exhibiting L pigments such as ridge soil, talc, Shixi acid, strontium carbonate, mica and clay, anti-rust pigments, such as zinc sulphate, iron sulphate, phosphoric acid, phosphoric acid, zinc bismuth, zinc cyanide, zinc oxide, tripolyphosphate, molybdenum Zinc acid, aluminum indium, calcium molybdate, aluminum phosphomolybdate and aluminum zinc phosphomolybdate. 1〇 _7] When the pigment is used as an electrodeposition coating component, a high concentration pigment is usually dispersed in an aqueous solvent in advance in the form of a paste (pigment dispersion). This is because it is difficult to uniformly disperse the low-concentration pigment in one step, which causes the pigment to become powdery. This paste is generally referred to as a pigment dispersion paste. [0028] A pigment dispersion paste is prepared by dispersing a pigment together with a pigment dispersion resin in an aqueous medium. As the pigment dispersion resin, a cationic or nonionic low molecular weight surfactant, or a cationic polymer such as a modified epoxy resin having a quaternary ammonium group and/or a tertiary sulfonium group can be used. As the aqueous medium, deionized water or water containing a small amount of alcohol can be used. Pigment Dispersion Tree Mooncake is generally used as a 20% by weight coating. The pigment dispersion paste can be obtained by dispersing a pigment-dispersed resin varnish and a pigment by using a suitable dispersing device (for example, a ball mill or a sand mill) to obtain a pigment [0]. The cationic epoxy resin used in the present invention includes an amine modification. Epoxy resin. 14 200812710 The cationic resin is usually obtained by ring-opening the entire epoxy ring of the double-aged ring grease with an activated hydrogen compound, allowing the cationic group to be introduced; or by opening a part of the epoxy ring by activating the hydrogen compound with f It is prepared by opening the ring of the remaining epoxy ring with an activated hydrogen compound which can introduce a cationic group. Specific examples of the [coffee] galvanic epoxy resin include a gamma A type epoxy resin and a double _ type epoxy resin. Examples of the bis(10) type epoxy resin (available from Shell Epoxy Co., Ltd.) include Epik〇te Mg (epoxy equivalent)

Value: 9G), EpikGte _ (epoxy equivalent: ton), 攸 1010 (epoxy equivalent: 3__4_) and the like. Examples of the double-type epoxy resin W (available from Yuka Shell EP〇xy c.·, Ltd.) include chat coffee 8〇7 (epoxy equivalent value: 170) and the like D

[0031] The epoxy resin can be modified with suitable resins such as polyester polyols, polyethers = alcohols, and monofunctional filaments. Further, the epoxy resin can extend the chain by reacting the epoxy group with a diol or a dicarboxylic acid. [0032] Desirable is to open the epoxy resin with an activating hydrogen compound, and to have an amine equivalent value of 0.3 to 4.0 meq/g after ring opening, especially 5 to 50% of which is a primary amine group. group. Examples of the activated hydrogen compound to which the cationic group can be introduced include a primary amine, a secondary amine, an acid salt of a tertiary amine, a mixed compound of a sulfide and an acid. Using an amine compound as the activating hydrogen compound, an amine-modified epoxy resin having a tertiary amine group can be obtained to prevent the epoxy resin from reacting with the secondary amine compound. In addition, an amine modified epoxy resin having a secondary amine group can be obtained to prevent the epoxy resin from reacting with the primary amine compound. In addition, an amine-modified epoxy resin having a primary amine group can be obtained to prevent the epoxy resin from reacting with an amine compound having a primary amine 15 200812710 group and a secondary amine group. To prevent the epoxy resin from reacting with an amine compound having a primary amine group and a secondary amine group, the primary amine group of the amine compound is first protected to form a ketimine. The ketimine is deprotected after the epoxy resin and the amine compound are reacted. 5 [0034] Specific examples of the activating hydrogen compound include butylamine, octylamine, and

Ethylamine, dibutylamine, mercaptoamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N,N-dimercaptoethanolamine hydrochloride and monoethyl A monothioether-acetic acid mixture. Further, secondary amines obtained by blocking primary amines, such as ketimine of aminoethylethanolamine and diketimine of diamethylenetriamine, are included. These amines can be used in combination. [0035] An oxazolidinone ring-containing epoxy resin can be used for the cationic epoxy resin, which is described in the Japanese Patent Laid-Open Publication No. Hei. 5 (1993) _ 3 〇 6327 and is known to those skilled in the art. Japanese Patent Publication No. 5 (1993) _3 〇 6 327 is a priority patent application of U.S. Patent No. 5,276,072, which is incorporated herein by reference. The method of introducing an oxazolidinone ring into an epoxy resin includes a method comprising heating a blocked isocyanate curing agent and a polyepoxide blocked with a lower alcohol (for example, methanol) under an inert catalyst and maintaining a constant temperature, and The low, and alcohol as a by-product is removed from the system. Specific examples of the bismuth-containing barium ring-epoxy resin and the preparation method thereof are disclosed in the paragraphs _2] to [(10) 47] of the Japanese Patent Publication No. 20-2. Japanese Patent Publication No. 2000-128959 is a priority shot for the US Patent No., and it is incorporated into the case by reference.

Polyisocyanate of the blocked isocyanate curing agent of the present invention 16 200812710 is a compound having at least a rain-like, cyanate group in the molecule. The polyisocyanate may be an aromatic, cycloaliphatic, aromatic or aromatic-aliphatic group. [〇〇37] Examples of polyisocyanates include aromatic diisocyanates such as benzylidene diisocyanate (TDI), diphenyldecane diisocyanate 5 (MDI), p-phenylene diisocyanate, and naphthalene diisocyanate; Aliphatic diisocyanates of 3 to 12 carbon atoms, such as hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexanyl diisocyanate and diazonic acid diisocyanate; having 5 to A cycloaliphatic diisocyanate of 18 carbon atoms, for example 1, anthracycline diisocyanate, isophorone diisocyanate (IPDI), 4,4,-dicyclohexyl 10 methane diisocyanate (deuterated MDI), methyl Cyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4,-diisocyanate and 1,3-diisocyanate methylcyclohexane (hydrogenated XDI), hydrogenated TDI, 2,5- or 2, 6-bis (isocyanate g methyl)-bicyclo[2.2.1]heptane (==norbornane diisocyanate); aliphatic diisocyanate having an aromatic ring, such as xylene diisocyanate (XDI) and four Methyl xylene diisocyanuric acid (TMXDI); its modified compound (urethane compound, carbosamine, ketone) H〇di〇n), urethonimine, biuret and/or isocyanate-modifying compound; and the like. The polyisocyanate may be used singly or in combination of two or more. [0038] An adduct or prepolymerized 20 compound obtained by reacting a polyisocyanate with a polyol, for example, ethylene glycol, propylene glycol, trihydrocarbyl propane and hexanediol having a ratio of NC0/0H of not less than 2 can be used as a capping Isocyanate curing agent. The capping agent is added to the polyisocyanate group and is amp at room temperature, but can be heated to regenerate the free isocyanate group at a temperature not less than the dissociation temperature. 17 200812710 [0040] Other components of the cationic electrodeposition coating composition may optionally contain a dissociation catalyst, an organotin compound such as dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide; an amine such as N-mercaptomorpholine a metal 5 salt of cerium, cobalt and copper; a blocking agent other than the above components. The amount of the dissociated catalyst is from 01 to 6 parts by weight based on the total solid content of the cationic epoxy resin and the blocked isocyanate curing agent in 100 parts by weight of the cationic electrodeposition coating composition. The cationic electrodeposition coating composition for use in the present invention is obtained by using the above cationic epoxy resin, blocked isocyanate curing agent, and pigment dispersion paste. Prepared in an aqueous solvent. Further, the aqueous medium may contain a neutralizing acid neutralizing the cation% oxygen resin to promote the dispersion of the binder resin emulsion. Examples of the neutralizing acid include inorganic acids or organic acids such as hydrochloric acid, nitric acid, phosphoric acid, 15 formic acid, acetic acid, and lactic acid. [0042] The amount of the neutralizing acid is preferably from 1 〇mg equivalent to 25 ^^ in the 黏g-containing cationic epoxy resin and the blocked isocyanate curing agent, and the lower limit of the neutralizing acid damage is better. It is 15 mg equivalent and the upper limit is more preferably 2 〇 mg when s. When the amount of the neutralized acid is less than 1 〇 mg equivalent, it is not sufficiently mixed with water, and it is difficult to disperse in water, or the stability is greatly lowered. On the other hand, when the amount of acid is more than 25 equivalents, the electric power required for deposition increases, and the deposition of the coating solid content is reduced, which lowers the throwing power. [0043] Desirably, the blocked isocyanate curing agent is present in an amount sufficient to react with an activated hydrogen-containing functional group (eg, a primary amine group, a secondary amine group, and a 18200812710 ☆ hydroxyl group) during curing. To provide a good cured coating film. The amount of blocked isocyanic acid curing agent is expressed as a ratio of the solid content of the cationic epoxy resin to the blocked isocyanate curing agent (cationic epoxy resin/curing agent), preferably between 90/10 and 50/50. Better 80/20 to 65/35. The fluidity and curing rate of the coated film when the film is formed into a film (deposited film) is improved by adjusting the ratio, and the smoothness of the coated film is improved. [0044] Examples of organic solvents for cationic electrodeposition coating compositions include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethylhexyl scale, propylene glycol monobutyl ether, dipropylene glycol monobutyl Ether, propylene glycol monophenyl ether and the like. [0045] The cationic electrodeposition coating composition may contain, in addition to the above components, a coating composition additive such as a plasticizer, a surfactant, an antioxidant, and an ultraviolet light absorber. The cationic electrodeposition coating composition may contain an amino group-containing acrylic resin, an amine group-containing polyester resin, and the like. [0046] The cationic electrodeposition coating composition may preferably have a coating composition solid content of 5 F 5 15 Wt%. If the cationic electrodeposition coating composition has a solid content of the coating composition of #〇·5 to 7 Wt% and is coated on a substrate requiring excellent electron beam homogenization, the cationic electrodeposition may contain a conductivity control agent. The conductivity control agent enhances the homogenous energy of the electrodeposition coating composition. • Examples of conductivity control (4) include acid-neutralization of amine-modified epoxy resins. The acid-neutralizing compound of the amine-modified epoxy resin can be prepared by obtaining an amine modification: an oxy-resin and an acid-neutralized amine-modified epoxy resin. The amine-modified epoxy tree I can be prepared by opening an epoxy ring of an epoxy resin with an activated hydrogen compound. ^ Examples of latex resins include transitional epoxy resins and dual-part epoxy resins. Examples of living and hydrogen compounds include butylamine, octylamine, diethylamine, dibutylamine 'II 19 200812710 methyl butylamine, methyl butylamine, monoethanolamine, diethanolamine, benzyl alcoholamine, diethylamine hydrogen Chlorate, n, n-methylethanolamine acetic acid g, a mixture of diethyldithiol and acetic acid, an amine of an aminoethylethanolamine, a diketimine of an ethylenediamine. The amine-modified epoxy resin is opened with an activated hydrogen compound to have an amine equivalent of 2.0 to 5.0 meq/g. Examples of the acid which neutralizes the amine-modified epoxy resin include organic acids and inorganic acids such as hydrochloric acid, nitric acid, dish acid, formic acid, acetic acid, and lactic acid. Adding the acid neutralizing compound of the obtained amine-modified epoxy resin to the electrodeposition coating composition can provide an adjustment of the cationic electrodeposition coating composition having a conductivity of 1000 to 2000 pS/cm, which can provide 1 for the electric bond. It is excellent in the uniform plating ability even when an electrodeposition coating composition having a low solid content is used. [0047] Electrodeposition Coating The electrodeposition coating system is usually carried out between a substrate serving as a cathode and an anode by applying a voltage of 50 to 450V. When the applied voltage is lower than 5 〇 v, electrodeposition can be insufficient. On the other hand, when the applied voltage is higher than 450 V, the coated film may be broken and its appearance becomes unusual. The temperature of the electrodeposition bath is usually controlled at 10 to 45. (3) [0048] The electrodeposition method includes a step of immersing a substrate to be coated in an electrodeposition coating composition, and applying a voltage between the substrate as a cathode and an anode to cause 20 to deposit a coating film. The period of application of the voltage may generally be 2 to 4 minutes, although it may vary with electrodeposition conditions. [0049] The thickness of the electrodeposition coated film is preferably 5 to 25 μηι, more preferably 20 μηι. When the thickness is greater than 25 μm, the coating composition is wasted. 20 200812710 [0050] The electrodeposition coated film obtained in the above manner is attached to 120. Bake at 260 ° C, preferably 140 to 220 ° C for 1 to 30 minutes to cure directly after the electrodeposition process or after washing, thereby forming a cured electrodeposition coating film. 51] The cured electrodeposition coated film obtainable from the present invention is characterized by a brightness index (L-value) of 55 or more of the cured electrodeposition coated film. The present invention enables curing electrodeposition of 15 μm or more. Cured electrodeposition coating thin on the thickness of the coated film The brightness index (L_value) remains 55 or more to become the month b' even if the pigment concentration is extremely low. 10 Applying the intermediate coating composition and/or the top coating composition on the electrodeposition coating so that the formation has It is possible to complete the multi-layer coating of the appearance without affecting the color of the substrate to be coated. The brightness index (L-value) can be measured according to Jisz 8722 and JIS Z 8730. The brightness index (L-value) can be based on JIS z 8730 The standard light "C" of the spectrometer is used to calculate the X, Y and Z values measured by the transmission method at a wavelength of 380 rnn to 780 nm, and the FIS Z 8722 is the Japanese industrial standard. - Partially developed by the translation ISO 7724·3 without any technical connotation or standard. The visibility index (L_value) is the brightness of the Hunter color difference formula refers to 20 numbers, high L-value Representing high whiteness. [0052] In the present invention, the pigment in the electrodeposition coating composition contains 95 to 1 〇〇 〇 〇 Λ 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与The coating composition can provide a % or greater on a cured electrodeposition coated film having a thickness of 5 μm or more. And the number of core (L value) of the cured electrodeposition coating film, even if the electrodeposition coating 21 200812710 = the rhythm of the object is extremely low (the electrodeposition composition of the electrodeposition composition is determined by the electrodeposition coating ^There is an advantage of having a π value of Μ or more on a cured electrodeposition coated film having a thickness of 15 Å or more, that is, "The deposition coating is formed on a substrate having a low (four) index. (10) such as hot dip steel, in the present invention, the cured electrodeposition coated film has a brightness index _ 2 Γ or greater on the cured electrodeposition coated film.

10, large, regardless of the color or material of the coated substrate. The electrodeposition coating according to the present invention is suitable for multi-layer coating of the undercoating = it reduces the coating film (for example, three-coating - for baking coating, three coating two, coating and inter-coating (four)-like multilayer The thickness of the coating). The cured electrodeposition coated film obtained by the present invention is characterized in that the dry film density of the cured electrodeposition coated film is between (10) and (3). An electrodeposition coating composition having b with a pigment concentration of 2 to 7% by weight of solid thyme and having a % to TG/TiO2 pigment can be provided

Dry film density as described. The advantage of producing a cured electrodeposited coated film having such a light density is to reduce the weight of the coated article. Reducing the weight of the coated object (4) It is very useful to apply a large substrate coating with a large coating area, such as a car. The dry film density of the cured electrodeposition coated film can be measured in accordance with JIS 20 K 7112. [〇〇54] Method of Membrane An exemplary method of forming a multilayer coating film according to the present invention includes a method comprising the steps of: coating an intermediate coating, a substrate top on a cured electrodeposition coating film by wet-wet coating Topcoat and bright top coat; and the same layer of uncured film is baked and cured at 22 200812710 5 •. This method is generally referred to as a three-coat one baking coating method (3C1B). Another exemplary method of forming a multilayer coated film according to the present invention includes a method comprising the steps of: coating an intermediate coating on a cured electrodeposition coated film and curing, and then coating the top surface of the coated substrate by wet-wet coating a layer and a bright top coat; and simultaneously baking and curing the two layers of uncured coated film. This method is generally referred to as a three-coat two-bake coating method (3C2B). Another exemplary method of forming a multilayer coated film in accordance with the present invention includes a method comprising the steps of coating a topcoat and a bright topcoat on a cured electrodeposition coated thin film 10 by wet-wet coating. Without applying an intermediate coating; and simultaneously baking and curing the two layers of uncured coated film (two-coat one baking coating method (2C1B)). Another exemplary method of forming a multilayer coated film in accordance with the present invention includes a method comprising the steps of: coating a solid top 15 on a cured electrodeposition coated film; a topcoat without a coating intermediate; and baking The uncured coated film (a coating-bake coating method (1C1B)) was cured. "00551 A method for forming a multilayer coating film by a three-coat one baking coating method by a three-coat one baking coating method * 20 - which is beneficial for saving energy Step: coating an intermediate coating composition on the cured electrodeposition coating film to form an uncured intermediate coating film, coating a substrate top coating composition on the uncured intermediate coating film to form an uncured base coating Film coating, 23 200812710 Coating a bright topcoat composition on the uncured base coating film to form an uncured alum coating film, and simultaneously heating and curing the uncured intermediate coating film, uncured substrate Top coated film and uncured bright coated film. [0056] The intermediate coating composition of the three-coat-bake coating method for forming a multilayer coating film may be a water-based intermediate coating. a layer composition, or an organic solvent-based intermediate coating composition. The intermediate coating composition contains an intermediate coating resin, a pigment, an aqueous medium, and/or an organic solvent. The intermediate coating resin component is composed of 10 coating trees. In the case where the intermediate coating composition is a water-based intermediate coating composition, the intermediate coating composition may preferably include a pigment obtained by dispersing a pigment and a pigment dispersing agent. Dispersion pastes. Commercially available pigment dispersants can be used in the present invention. Pigment dispersants can include, for example, Disperbyk 190, Disperbyk 15 182, Disperbyk 184, which are commercially available from bYK Japan KK; EFKA Polymer 4550' From EFKA (Ciba Specialty Chemicals); Solsperse 2700 'Solsperse 41000, Solsperse 53095, these are available from Avecia. The pigmented dispersant may preferably have a digital average molecular weight of from 1000 to 100000. When the number average molecular weight is less than 1000, it is possible The No. 2 method provides improved dispersion stability. On the other hand, when the numerical average molecular weight is more than 100,000, the viscosity of the intermediate coating composition may be too high to be coated. The digital average molecular weight of the pigment dispersant may be better. Between 2,000 and 50,000, preferably between 4,000 and 50,000. [0058] The pigment dispersant can be mixed using conventional mixing techniques and pigments and 24 200 812710 obtains a pigment dispersion paste. The pigment dispersant may preferably be present in the pigment 5 10 15 20 2 〇 Cao Dan 77 in the range of 1 to 20 ^ coffee pigment dispersion (tetra) content. On the other hand, when the pigment dispersant The content of the film of the coated film may be deteriorated when the content is more than 里/〇. The pigment dispersion may preferably be between 5 and 15% by weight. [59] The pigment in the intermediate coating composition may be used for the conventional intermediate coating group. ^The pigment in the material is f. The pigment in the intermediate coating composition may preferably be included in the color because the coloring pigment enhances the coating's thin weather resistance and concealing properties. The pigment may preferably comprise titanium dioxide because titanium dioxide has superior white concealing properties and is inexpensive. Examples of the pigment other than titanium dioxide include, for example, organic pigments {column such as azo chelate pigment, insoluble azo pigment, condensed azo pigment titanium pigment, indigo pigment, perinen (peryn〇n) ) pigments, peryl coffee pigments, ditergent pigments, quinodizin g pigments, iso-sigma porphyrin pigments, metal-missing pigments, and inorganic rhymes such as chrome yellow (chromic acid), yellow oxidation Iron, iron, and carbon black. Pigments may in turn include extended pigments such as calcium carbonate, barium sulfate, clay and talc. [0061] The intermediate coating composition may be a light gray intermediate coating composition containing a pigment comprising carbon black and titanium dioxide. The intermediate coating composition may be a predetermined gray intermediate coating composition whose brightness and color are blended with the brightness and color of the top coating composition of the substrate and the so-called colored intermediate coating composition containing various colored pigments. [0062] The pigment concentration 25 of the coating composition solid content of the intermediate coating composition is 200812710 degrees (PW (10) is preferably between 10 and 6% by weight. When the pigment soil is less than _% by mass, the concealing property of the intermediate coating film] It may be deteriorated because of the lack of pigment amount. On the other hand, when the pigment content is more than 6 Gwt%, the fluidity and finished appearance of the intermediate re-film may be deteriorated because an excessive amount of pigment and an increase in viscosity of 5 degrees are involved.

[0063] The water-based intermediate coating composition can be prepared by mixing a pigment dispersion poor, an intermediate coating resin with an intermediate coating curing agent. The pigment dispersant f is present in the intermediate coating composition in an amount of up to 5% by weight based on the solid content of the intermediate coating composition. When the pigment dispersant content is less than G.5% by weight, 10 may not provide improved dispersion stability. On the other hand, when the content of the pigment dispersant is more than 1% by weight, the film properties of the coated film can be deteriorated. The pigment dispersant content may preferably be from 丨 to 5% by weight. The intermediate coating resin in the intermediate coating composition may include, but is not limited to, for example, an acrylic resin, a polyester resin, an alkyd resin, a 15 epoxy resin or a urethane phthalate resin. The intermediate coating curing agent may include, by way of example, a melamine brain, an amine resin or a blocked isocyanide curing agent. A preferred combination of the intermediate coating resin and the intermediate coating curing agent is the following combination: acrylic resin and/or polyester wax, and melamine resin and/or blocked isocyanate curing agent. 20 Each of the intermediate coating resin and the intermediate coating curing agent may be used singly or in combination with two or more to control the film of the intermediate coating film _5] in the case where the intermediate coating μ is a water-based intermediate coating composition Among them, the water-soluble resin can be used as an intermediate coating resin, or, for example, a dispersion-dispersed surface of a fat-removing lining resin: 26 200812710 wherein the intermediate-coating blush can be stably present in the intermediate coating composition. The intermediate coating composition may contain additives such as ultraviolet light absorbers, antioxidants, antifoaming agents, surface conditioners, and microporous preventive agents. [0066] In the case where the intermediate coating composition is an organic solvent-based intermediate coating composition, the intermediate coating composition can be prepared by mixing an intermediate coating resin, an intermediate coating curing agent, and a pigment in an organic solvent. . Preferred parts of the ingredients are as described above.

Examples of the organic solvent may include an aromatic solvent such as toluene and xylene; a ketone solvent such as ruthenium ketone, propylene ketone; an ether solvent such as B-, Isopropyl, decyl isobutyl hydrazine 1 And cyclohexyl, tetrahydrotifuran, dioxazide, ethylene glycol dioxime ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethanol diethyl _, propylene glycol monoterpene ether, benzene _ And stupid ethyl ester solvent 15

For example, ethyl acetate, butyl acetate, isopropyl acetate and ethylene glycol diacetate; guanamine solvents such as dimethyl decylamine, diethylformamide, dimethyl 9 hydrazine and hydrazine-methyl Alkaloids; eell_lve solvents, such as formazone, ethyl cellosolve and butyl cellosolve; alcohol solvents, such as methyl alcohol, with propanol; halogen solvents, such as dichlorocarb. Burning, dichloroethane and chloroform; and the like. The organic solvent may be used singly or in combination of two or more. Further, conventional additives such as a pigment dispersant, a surface conditioner, a viscosity adjusting agent, an ultraviolet light absorber, an antioxidant or the like are used. [0067] Substrate top coat fines The base top coat composition contains a base top coat resin component, a pigment and a solvent. The top coat layer of the substrate may be a water-based base top (four) layer composition of the aqueous dispersion component, or a solvent-based base top coat composition containing the machine-dispersion component. ......

In the case where the top coat composition of the substrate is a water-based base top coat composition, the base top coat composition can be prepared by using a pigment dispersion paste obtained by dispersing a pigment and a pigment dispersant. A pigment dispersant in the intermediate coating group can be used. [0069] The pigment in the top coat composition of the substrate may be a conventional pigment, such as a color pigment and a stretch pigment in the intermediate coating composition. The top surface of the substrate coating composition may in turn comprise a glossy color pigment; in this case, the top coating composition of the substrate is a metal substrate top coating composition. The top coat of the substrate ίο composition may include a coloring pigment such as red, blue or black and/or a stretch pigment and does not include a gloss color pigment; in this case, the top coating composition of the substrate is a solid substrate top surface Coating composition. [0070] Glossy color pigments may include, but are not limited to, for example, uncolored or tinted metallic luster color pigments (eg, metal or metal 15 gold), optical interference mica, pigmented mica, white mica, graphite, uncolored Or colored monochrome pigments or the like. The glossy color pigment may preferably comprise an uncolored or tinted metallic luster color pigment, such as a metal or metal alloy, which has good dispersion and may include a translucent coated film. Metallic luster Color pigments may include, for example, aluminum, alumina, steel, zinc 'iron, 2 镍 nickel, tin or the like. [0071] The glossy color pigments can have a variety of shapes and can be colored. The gloss color pigment may preferably have a scale shape having an average particle diameter of 2 to 50 μm of 1 minute) and a thickness of 〇" to 5 μm. More preferably, the gloss color pigment is a gloss color pigment having an average particle diameter of 1 to 35 μm (DW, which has an excellent brightness of 28 200812710 [0072] the pigment may be used alone or in combination with two or more color pigments, Spreading pigments and optional gloss color pigments and shell pigments. In the case of gloss pigments, the first step can be coated with a pigmented base top coating composition, and the second step can be coated with gloss. A further substrate topcoat composition of color pigments, which may provide a topcoat film for the substrate. The present invention includes such a topcoat film of the substrate. 10 15 20 [Lake] pigment dispersant may preferably Between 3 and 5 重量% by weight (based on the pigment dispersion f solid content of the water-based base top coat composition, it is written in the pigment dispersion paste. When the content of the pigment dispersant is less than 3% by weight, it may not be (4) Dispersion stability. On the other hand, when the content of the pigment dispersant is more than 50% by weight, the film properties of the coating film may deteriorate. [Difficult] The top surface of the water-based substrate may be dispersed by (4) pigment. Reading the top surface of the substrate The resin component (consisting of the base top coating resin and the base top coating curing agent) is injured. The pigment concentration (PWC) based on the solid content of the top coating composition of the substrate is as follows: the weight is 0.5 to 40. % by weight, more preferably 〇 / ^, 3% by weight. When the pigment concentration is more than 50% by weight, the finished appearance of the coated film may be deteriorated. [0075] The pigment dispersant may be present in the range of 1 to 20% by weight. The top coating composition of the substrate, which is the solid content of the coating composition from the top surface of the substrate. When the content of the pigment dispersant is less than 1%, it may not provide improved dispersion stability. Because of the lack of material for the first time, the sputum is more than 2 〇 heavy jin 0 / neck: live " 里里 / 〇 4, film properties of coated enamel film may be 29 200812710 [0076] Each of the base top coat resin and the base top coat curing agent is not limited, and may include the components described by the intermediate coat resin and the intermediate coat curing agent. The preferred combination of resin and substrate topcoat curing agent is the following group Combination: 5 Acrylic resin and/or polyester resin, and dimeric gas amine resin. The combination is superior to the pigment dispersion stability and the coating composition operability. [0077] Water-based substrate top coating The layer composition can be prepared in the same manner as the water-based intermediate coating 1 〇 composition. The organic solvent-based substrate top coating composition can also be prepared in the same manner as the organic solvent-based substrate top coating composition. [0078] Bright top The top coat of the top coat contains a bright top coat resin composition, various additives and solvents. The bright top coat resin consists of a bright top coat of 15 layers of resin and optional Bright top coat curing agent. Bright top coat resin composition (bright top coat resin and optional bright top coat curing agent) contained in the bright top coat composition, various types The additives and solvents may be the same as those described for the intermediate coating composition. [0079] A preferred combination of a bright topcoat resin and a bright topcoat curing agent as a topcoating resin component comprises a combination of an acrylic resin and a melamine resin. In this combination, the acrylic resin may preferably have an acid value of from 1 Torr to 200, a hydroxyl value of from 30 to 2 Torr, and a numerical average molecular weight of 〇(10) to 5 Å, 〇〇〇. [0080] The bright topcoat composition may preferably contain a viscosity modifier as an additive, as the bright topcoat composition is typically applied to the uncured base topcoat film in the present invention. The viscosity modifier prevents bleed and floating between the top coated film and the bright top coated film, as well as the bright page and the k-coated film. The viscosity modifier may preferably be present in the bright topcoat composition in a range of from 〇 to 1 〇 ^ 5 , , , , , , , , , , , , , , , , , , , 明亮 明亮 明亮 明亮 明亮 明亮 明亮 明亮 明亮 明亮 明亮 明亮 明亮. The content may be more preferably from 0.02 to 8 cc., preferably from 3 to 6 parts by weight. When the content of the viscosity modifier is more than 10 parts by weight, the finished appearance of the coated film may be deteriorated. When the content of another m-viscosity agent is less than the read weight%, it may not be possible to prevent slack because of less viscosity adjustment. [〇〇81] The top coat composition may be an organic solvent-based bright top coat composition, a water-based bright top coat composition (eg, a water-soluble coating composition, a water-dispersible coating composition) And an emulsified coating composition), a non-water dispersible bright top coating composition or a powdered bright top coating composition. The bright 15 top coat composition may contain, in addition to the above ingredients, an optional curing catalyst or Φ surface conditioner. The bright topcoat composition may contain a colored pigment and a glossy color pigment in an amount to maintain the transparency of the bright topcoat composition. The bright top coating composition may contain other additives such as curing accelerators, leveling agents, ultraviolet light absorbers, and light stabilizers. -20 [_] The bright top coat composition can be prepared by a method of coating a silk with a water-based intermediate coating group - silk or money. The bright top coat composition can be prepared by the same method as the Japanese Patent Publication No. 613, which is well known. The powdery bright top coat composition may contain an acrylic resin or a polysulfide resin having a radical group and a compound reactive with 31 200812710 〜1 (for example, an amine resin, a polyisocyanate, a 'blocking/cyanide' A combination of an acid ester) or an acrylic resin having an epoxy group in combination with a polycarboxy- or phthalic anhydride, wherein the powdery bright topcoat composition is substantially free of water or an organic solvent. • 5 [0083] Method of forming a multilayer coating film • Method of forming a multilayer coating film by a three-coat one baking coating method The intermediate coating composition is coated on a cured electrodeposition coating film to An uncoated intermediate coating film was formed. The method of applying the intermediate coating layer may include, for example, a spray coating method. A preferred example of the coating method may include an empty 10-air electrostatic sprayer, which is a so-called "reaction grab"; a rotary electrostatic sprayer, which is a so-called "pico (μμ) bell", "micro (μ) 钤" And "Change Bell (4) a)" and the Applicant. A more preferable example or coating method may be a method using a rotating static electricity or a spray coater. [〇〇84] The intermediate coated film may preferably have a dryness of 10 to 80 μm, more preferably 10 to 50 μm; j; In the three-coat-baked coating method, the intermediate coating may preferably have a dry thickness of from 1 G to 4 G Å, more preferably from 15 Å. When the thickness of the intermediate coating film of the three-coat-bake coating method is more than 4 〇 μΠ1, the film may be slack or microporous after coating, which may deteriorate the appearance of the resulting film. When the thickness of the intermediate coating film is less than 10 μηιττ, the finished appearance, color tone or cutting property of the layer coating film can be deteriorated. A step of forming a film on the top surface of the substrate without heating or curing the intermediate coating film is carried out. The intermediate coated film can be preheated at a temperature below the processing temperature of heating and curing (bake 32 200812710 bake) prior to forming the top surface of the substrate. ...

[0086] The top coat film of the substrate can be obtained by coating a top coat composition of the substrate on the intermediate coat film. In the three-coat one baking coating method, the top coat composition of the substrate is coated on the uncured 5 intermediate coated film by wet-wet coating. The method of coating the top coating composition of the substrate is not limited, but includes the method described for the method of coating the intermediate coating composition. When the base top coating composition is applied to a vehicle body, it can be applied in multiple stages by a rotary electrostatic sprayer, preferably in a two-stage coating to impart high refinement to the coated film. The coating method can also be a combination of an air electrostatic sprayer and a rotary 10 electrostatic sprayer. The formation of the top coat film of the substrate can add design characteristics to the coated film and ensure adhesion of the intermediate coated film formed in the previous step and ensure adhesion of the top coat film of the substrate formed in the next step. The top coat film of the substrate may preferably have a dry thickness of 5 to 5 Å μm, more preferably 10 to 30 μηη per coating. After the formation of the film on the top surface of the substrate, the next step of forming a bright top coated film is carried out without heating and curing. In forming a bright top surface k retanning film 4, the top surface coated film can be preheated at a temperature below the heating and curing (baking) processing temperature. 2〇 [〇〇88] A bright top coated film is obtained by coating a bright top coat composition coating on a top coating film of a substrate. The bright topcoat composition is applied to the top surface of the uncured substrate by wet wet coating. [0089] The method of forming a bright top coated film is not limited, but is preferably a coating method, a method, and a method. Desirably, the bright top coated film has a dry thickness of from 20 to 5 Å μηι, preferably from 25 to 4 Å μηη per coating. The formation of a bright top coated film provides substrate topcoat film protection and adds a deep feel to the resulting multilayer coated film. [0090] In the three-coat-bake coating method of one embodiment of the present invention, after forming a bright top-coating film, a three-layer coating film (5 coat films, base tops in uncured) The topcoat film and the bright top coat film are tied to 120 to 160. 〇 Better 14〇i150〇C is baked and cured for a predetermined period of time to obtain a multilayer coated film. In the process of the present invention, the intermediate coating composition, the top coat composition of the substrate, and the bright top coat composition are separately coated in this order by wet wet coating. That is, the uncured coated film is formed first. The term "uncured" as used in this case refers to the state in which the coated film is not completely cured, and includes the state in which the coated film is preheated. The term "preheating" as used in this context refers to room temperature to 100 as a temperature lower than the heating and curing (baking) treatment temperature. (: The temperature is left or the coating film is heated for up to 忉 minutes. The coated film having a better finished appearance can be preheated by applying a film to the top surface of the substrate after forming the intermediate coating film, respectively. The film is obtained. [0091] In the three-coat-bake coating method, a preferred combination of the intermediate coating composition and the top coating composition of the substrate is a water-based intermediate coating composition and a top surface of the water-based substrate. a combination of layer compositions, or a combination of an organic solvent-based intermediate coating composition and an organic solvent-based substrate topcoat composition. The combination of the two methods can include a multilayer coated film having a well-finished appearance. The combination is a combination of a water-based intermediate coating composition and a water-based base top coating composition, which is superior in terms of environmental protection and coating method safety. [0092] Layer coating method 34 200812710 ▲ Another method of forming a multilayer coating film by a three-coat two-bake coating method is beneficial to Langyo Energy. - The following steps are included. · The intermediate coating composition is coated on the cured electrodeposition coating film, and then It heats and cures To form a cured intermediate coating film, 5 coating a substrate top coating composition on the cured intermediate coating film to form an uncured base coating film, coating a bright top coating on the uncured base coating film The layer composition forms an uncured bright coated film, and the same 5% of the uncured base top coated film and the uncured 1 〇 bright coated film are heated and cured. [0093] The three-coat two-bake coating method In the above, the water-based intermediate coating composition or the organic solvent-based intermediate coating composition may be used. Similarly, the above-described water-based base top coating composition or organic solvent-based substrate top coating composition may be used, and The above bright top coat composition can be used. [0094] The intermediate coated film can preferably have a dry thickness of from 10 to 80 μm, more preferably from 1 to 50 μη, in a three-coat two-bake (3C2B) coat. In the coating method, the intermediate coating film may preferably have a dry thickness of from 1 to 40 μm, more preferably from 15 to 3 μm. When the thickness of the intermediate coating film of the three-coat two-bake coating method is greater than 40 μm, The film may be slack or slightly It may deteriorate the appearance of the resulting multi-layer coating film. When the thickness of the intermediate coating film is less than 10 μm, the finished appearance, color tone or planing characteristics of the resulting multilayer coating film may be deteriorated. [0095] Three-coating The method of forming a multi-layer coating film by the two-bake (3C2B) coating method can be carried out in the same manner as the two-coat one-bake coating method except that the two-bake coating method of the coating is applied on the top surface of the coated substrate. The layer composition is preceded by a heating and curing process of the uncured intermediate coating film. The heating and curing process of the uncured intermediate coating film can be heated by 100 to 250 ° C, preferably 130 to 180 ° C for 5 to 60 minutes, Preferably, it is carried out for 30 to 40 minutes. [0096] Another method for forming a multilayer coated film by a two-coat one baking coating method by a two-coat one baking coating method The method comprises the steps of: coating a top coat composition on a cured electrodeposition coating film to form an uncured base coating film, and coating a bright top coating composition on the uncured base coating film Uncured Coating a thin film, and while heating and curing the uncured base coating film and the top surface of the bright coating film uncured. [0097] In the two-coat one baking coating method, the above water-based substrate top coating composition or organic solvent-based substrate top coating composition may be used, and may be composed of the above bright top coating layer. Things. [0098] The two-coat one-bake coating method for forming a multi-layer coated film can be carried out in the same manner as the three-coat one-bake coating method except that the top coat composition of the coated substrate 20 is coated with a bright top coat. The layer composition is not coated with the intermediate coating composition. Method for forming a multilayer coated film by a coating-bake coating method Another method for forming a multilayer coated film by a coating-bake coating method. The method of 2008/0710 includes the following steps: A solid top coating composition is coated on the deposited coating film to form an uncured solid coating film, and the uncured solid coating film is heated and cured. [0100] In a coating one baking coating method, various solid top coating compositions can be used. Examples of the solid top coating composition include a water-based solid top coating composition comprising: (i) a water-soluble polymer compound or a water-dispersible polymer compound, for example, an amine-containing acrylic acid having a hydroxyl group and a carboxyl group; An acrylic resin solution of the resin, and (ii) another polymer compound reactive with the polymer compound (i) 10, such as a water-soluble or water-dispersible amine-based resin or a blocked isocyanate resin. [0101] Examples of the solid top coating composition include an abrasive core-based solid top coating composition comprising: (1) a polymer compound soluble in an organic solvent, such as a hydroxyl group-containing acrylic resin, and (ii) Another polymer compound which can react with the polymerized 15-port (1), such as an amine-based resin or a blocked isocyanate resin. [〇 102] The solid top coating composition includes a pigment. The pigment may include a pigment that can be used for the intermediate coating composition, and/or a pigment that can be used for the top coating composition of the substrate. For example, conventional organic or inorganic colored pigments such as, for example, titanium moon and titanium oxide The solid top coating composition may include a stretching pigment, or an additive such as a curing accelerator, a leveling agent, an ultraviolet light absorber, and a light stabilizer. [0103] A multilayer coating-coating method is formed The method of coating a film can be carried out by coating a solid top coating composition on a cured electrodeposition coating 37 200812710 film to form an uncured solid coating film, and heating and curing the uncured solid coating film. The coated solid top coating composition can be applied by spraying to produce a solid two-coated film having a dry thickness of 30 to 100 μm. The coated solid top coating composition can also be coated multiple times. , Example 5, such as two-stage coating implementation. Spraying can be carried out using a conventional coating machine, such as a gas sprayer, an airless sprayer, an air atomizer, or a rotary atomizer. Solidified solid coating The heating and curing conditions of the film may preferably be from 100 to 250. More preferably from 130 to 180. The temperature at 〇 is from 5 to 6 minutes, more preferably from 30 to 40 minutes. 10 EXAMPLES [0104] The present invention will The invention is not limited by the following examples, however, the invention is not limited to the embodiments. In the examples, "parts" are based on weight unless otherwise indicated. [0105] Preparation Example 1 15 Preparation of cation eprecipitate by fine-tuning of the bismuth preparation Example 1-1 Emperor amine modification 璟筚. Tree compensation 92 parts of 2,4-/2,6-tolyl diisocyanate (weight ratio = 8/2) 95 parts of methyl isobutyl ketone (hereinafter referred to as mibk) and 〇·5 part February 20 20 dibutyl tin laurate filled with a stirrer, cooling tube, nitrogen inlet tube, thermometer - flask with dropping funnel Add 21 parts of methanol while stirring the reaction mixture. Start at room temperature, heat the reaction mixture to 6 ° C by exotherm, keep the reaction for 30 minutes, and remove 5 parts of ethylene glycol from the dropping funnel. Ethylhexidide is added dropwise. In addition, '53 part of bisphenol A-propylene oxide 5 mol adduct is added to 38 200812710 The reaction is carried out mainly at a temperature of from 60 to 65 ° C and continues until the absorption of the isocyanate groups measured by the Han spectrum disappears. [0106] Next, the 365 part synthesized from bisphenol a and epichlorohydrin according to a conventional method will be used. An epoxy resin (epoxy equivalent 188) is added to the reaction mixture and heated to 5 to 125 ° C. After that, a portion of the benzyl dimethyl dimethylamine is added and allowed to react at 130 ° C until the epoxy equivalent After changing to 410, 61 parts of bisphenol a and 33 parts of octanoic acid were added and allowed to react at 120 QC to reach an epoxy equivalent of 1190. Then, the reaction mixture was allowed to cool, 11 parts of diethanolamine, 24 parts of N- Ethylethanolamine was added to a solution of 25 parts of 79% by weight of ketimiminated aminoethylethanolamine dissolved in 10 MIBK, and reacted at 110 ° C for 2 hours. Then, the reaction mixture was diluted with MIBK until the nonvolatile solid content became 80% to obtain an amine-modified epoxy resin (resin solid content: 80%). Preparation Example 1-2

15 Preparation of blocked polyisocyanate HU Bu A 1250 part of diphenylnonane diisocyanate and 266.4 part of MIBK were charged into a reaction vessel, and after heating to 80 ° C, a part of 2.5 parts of dilauroquinone dibutyltin was added. A portion of the 226 part ε-hexidine solution dissolved in 944 part of butyl cellosolve was added dropwise at 80 ° C for 2 hours. The reaction was maintained at 1 Torr. When the total of 4 hours was 20, it was confirmed that the absorption of the isocyanate group measured by the IR spectrum disappeared and stood still; 336.1 part of MIBK was added and thus obtained with 0. The blocked isocyanate curing agent is converted into a warm sound. Preparation Example 1-3 Preparation of Pigment Dispersion Resin_ 39 200812710 A 222.0 part of isophorahydrate isophorone (hereinafter referred to as IPDI) was charged into a reaction having a stir bar, a cooling tube, a nitrogen introducing tube and a thermometer. In the container, after diluting with 39.1 parts of MIBK, a portion of bismuth dibutyltin dilaurate was added. Then, the reaction mixture was heated to 50 ° C, and 131.5 parts of 2-ethylhexanol was added dropwise for 2 hours while stirring 5 in a dry nitrogen atmosphere. Cool down to maintain the reaction temperature at 50 °C if necessary. As a result, 2-ethylhexanol half-blocked ipdi (resin solid content: 90.0%) was obtained. [0110] 87.2 parts of dimethylethanolamine, 117.6 parts of 75% lactic acid aqueous solution, and 39.2 parts of ethylene glycol monobutyl ether were added to a suitable reaction vessel, and the 10 reaction mixture was given at 65 C for half an hour to prepare a fourth stage. Money agent. Thereafter, 710.0 parts of EPON 829 (bisphenol A type epoxy resin available from Shell Chemical Company, epoxy equivalent 193-203) and 289.6 parts of bisphenol A were charged into the reaction vessel. The reaction mixture was heated to 15 (M 60 ° C in a nitrogen atmosphere, the initial exothermic reaction took place. Continue 15 with heating for about 1 hour, the reaction mixture was then cooled to i2 〇〇C, and the 49.8% partially prepared 2-ethylhexanol was added. Block 1?〇1(]^161^ solution). [〇112] The reaction mixture was maintained at 110_120 〇c for about 1 hour, 463.4 parts of ethylene glycol monobutyl ether was added, and the mixture was cooled to homogenization, and 196.7 A partially prepared quaternizing agent is added to the mixture. The reaction mixture is maintained at 85e95 ° C until the acid value becomes 1, and 964 part of deionized water is added to terminate the quaternization of the epoxy-bisphenol A resin. Acting and obtaining a pigment dispersion resin having a quaternary ammonium salt portion (resin solid content: 50%) [〇H3] Reproducible Example 1-4 Disperse and cationic electrodeposition by coating composition m 40 200812710 100 parts The pigment dispersion resin obtained in Preparation Example 1-3, 100.0 part of titanium oxide, and a part of ion-exchanged water of 1 〇〇·〇 were filled and dispersed until the particle size was not more than 10 μη1, and a pigment dispersion paste (solid content: 50%) was obtained. [0114] Preparation Example 1-1 was obtained The amine modified epoxy resin and the blocked isocyanate curing agent obtained in the preparation of the shell example 1-2 are uniformly mixed in a solid content of S of 8 〇 / 2 。. The mixture is added with glacial acetic acid, and the resin is bonded to 1 〇〇g. The solid content MEQ (A) had an acid milliequivalent value of 3 Torr, and was slowly added by ion-exchanged water to be diluted. The VqBK was removed under reduced pressure to obtain an emulsion having a solid content of 36%. 291 parts of the emulsion, 1 part of the pigment dispersion resin obtained above, 1890 part of ion-exchanged water, 2·6 part of 10% aqueous solution of ruthenium acetate, and 1.6 part of dibutyltin oxide were mixed to obtain a cation having a solid content of 5% by weight. Electrodeposition coating composition. The pigment concentration of the electrodeposition coating composition solid content 15 was 3% by weight. The solid content of the electrodeposition coating composition was determined as follows, according to JIS-K5601: solid content II (in 180. (: weight of residue of the composition for heating for 30 minutes) / (weight of coating composition) Χ 100 [0116] Preparation Example 1-5 Recombination of pigment dispersion enthalpy and cation dynamite coating composition (2 , obtained in 100 parts of Preparation Examples 1-3 The pigment dispersion resin, 98 〇 part of titanium dioxide, 2 parts of carbon black and ΐ〇〇·〇 partial ion exchange water were filled and dispersed until the particle size was not more than 10 μηι, and a pigment dispersion paste (solid content: 50%) was obtained. 41 200812710 The amine-modified epoxy resin obtained in Preparation Example 1-1 was uniformly mixed with the blocked isocyanate curing agent obtained in Preparation Example 1-2 at a solid content ratio of 80/20. The mixture was added with glacial acetic acid, and the acid equivalent weight value of 30 g of the resin solid content MEQ (A) was adjusted to 30, and slowly added to the exchange water to dilute. The MIBK was removed under reduced pressure to obtain an emulsion having a solid content of 36%. [0118] 291 parts of the emulsion, 10 parts or more of the pigment dispersion resin obtained, 1920 parts of ion-exchanged water, 2.6 part of 10% aqueous solution of ruthenium acetate, and 1.6 part of dibutyltin oxide were mixed to obtain 1 with a solid content of 5% by weight. The ruthenium cation electrodeposition coating composition. The pigment concentration based on the solid content of the electrodeposition coating composition was 3% by weight. Preparation Example 1-6 Preparation of Pigment Dispersion Paste Cerium Electrodeposition Coating Composition (3) 100 parts of the pigment dispersion resin obtained in Preparation Example 1-3, 100.0 15 part of titanium oxide and 100.0 part of ion-exchanged water were filled. And dispersed until the particle size is not more than 10 μm, obtaining a pigment dispersion paste (solid content: 50%) 〇 [〇12 0 ] The amine-modified epoxy resin obtained in Preparation Example 1-1 and Preparation Example 1 - 2 The blocked isocyanate curing agent obtained was uniformly mixed in a ratio of 20/20 solids. To the mixture, glacial acetic acid was added, and the acid equivalent weight value of 30 g of the resin solid content MEQ (A) of 100 g of the resin was slowly added to the ion exchange water to be diluted. The MIBK was removed under reduced pressure to obtain an emulsion having a solid content of 36%. [0121] 282 parts of the emulsion, 16 parts or more of the pigment obtained 42 200812710 dispersed resin, 1892 part of ion-exchanged water, 2.6 part of 10% aqueous solution of barium acetate and 1.6 part of dibutyltin oxide were mixed to obtain a solid content of 5% by weight. The cationic electrodeposition coating composition. The pigment concentration based on the solid content of the electrodeposition coating composition was 5% by weight. [Preparation Example 1-7] Preparation of Pigment Bifurcation Cation Radon Coating Composition (4) 100 parts of the pigment dispersion resin obtained in Preparation Example 1-3, 100.0 part of titanium oxide, and 100·0 Part of the ion-exchanged water was filled and dispersed until the particle size was not more than 10 μηη, and a pigment dispersion paste (solid content: 10 50%) was obtained. [0123] The amine-modified epoxy resin obtained in Preparation Example 1-1 was prepared and prepared. The blocked isocyanate curing agent obtained in Example 1-2 was uniformly mixed at a solid content ratio of 80/20. To the mixture, glacial acetic acid was added, and the acid equivalent weight value of the acid solid content MEQ (A) of 100 g of the resin was 3 Torr, and the distilled water was gradually added to be diluted. The MIBK was removed under reduced pressure to obtain an emulsion having a solid content of 36%. [0124] 272 parts of the emulsion, 23 parts or more of the pigment dispersion resin, 1892 part of ion-exchanged water, 2.6 part of 1% aqueous solution of cerium acetate, and 1.5 parts of dibutyltin oxide were mixed to obtain a solid content of 5% by weight. 20 cationic electrodeposition coating composition. The pigment concentration based on the solid content of the electrodeposition coating composition was 7% by weight. Preparation Example 1-8 Separation of Pigment Dispersion Paste and Cationic Coating Composition (5) Partial Preparation of (10) Partial Preparation of Pigment Dispersion Resin, 〇43 200812710 - Partial Titanium Dioxide, Partial Ion Exchange with 100.0 The water was filled and dispersed until the particle size was not more than 10 μηη, and a pigment dispersion paste (solid content: 50%) was obtained. [0126] The amine-modified epoxy resin obtained in the preparation of Example ι_ι and the preparation of 5 The blocked isocyanate curing agent obtained in -2 was uniformly mixed at a solids ratio of 80/20. The mixture was added with glacial acetic acid, and the acid equivalent weight value of the resin solid content MEQ (A) of 3 〇〇 g was 3 Torr, and slowly added to the ion parent water for dilution. The [yQBK] was removed under reduced pressure to obtain an emulsion having a solid content of 36%. 10 [0127] 1122 part of the emulsion, 40 parts or more of the pigment dispersion resin, 811 part of ion-exchanged water, 2·6 part of 1%% aqueous solution of cerium acetate, mixed with 6.4 part of dibutyltin oxide to obtain 2% by weight Solid content cationic electrodeposition coating composition. The pigment concentration in the solid content of the electrodeposition coating composition was 3% by weight. 15 [0128] Preparation of Fen Citation Example 1-9 1 Preparation conductivity chelating agent 295 parts of methyl isobutyl ketone, 37.5 part of methyl ethanolamine and 52.5 part of diethanolamine were filled into the flask equipped with reflux condenser and stirrer in. The temperature of the mixture was maintained at 100 ° C while stirring. 2〇5 part of phenolic phenolic aldehyde type 2 epoxy resin (available under the trade name YDCN_7〇3 from T〇ht〇 Kasei c〇·,

Ltd·)^: Add to the mixture. After the resin was completely added, the reaction was allowed to proceed for 3 hours. The obtained amino-based modified resin has a molecular weight of 21 Å and an amine value of 34 〇 mmol/100 g (MEQ (B)) 〇 [0129] Adding 5·5 part of formic acid and 1254.5 part of deionized water to 140 44 200812710 part The above-mentioned amine-based modified pepper furnace and six pairs of known/present liquids 9 were stirred for 3 minutes to maintain the temperature of the mixture at 80. (11. In the straight space φ child team, Τ remove the organic solvent to form a conductivity modifier (solid content: 7.0%). t〇13°] 5 rabbit desert pigment-free nitrogen 3Ajt_^ sub-drain deposition coating The pigment dispersion resin obtained in 100 parts of Preparation Example 13 and (10)·shovel-titanium oxide 舆1〇〇·〇 part of ion-exchanged water were filled and dispersed until the particle size was not more than 10 μηι to obtain a pigment dispersion paste. (solid content: 50%). 10 [G131] The amine-modified epoxy resin obtained by the preparation of Qin 1 and the blocked isocyanate curing agent obtained in Preparation Example 1-2 were uniformly distributed in a solid content of 8 〇 / 2 Torr. Mixing. Add glacial acetic acid to the mixture, and make the equivalent value of the acid equivalent of 3 〇〇 § of the binder resin solid content MEQ (A) to 3 〇, slowly add ion-exchanged water to dilute. Move MIBK under reduced pressure. In addition, an emulsion having a solid content of 36% was obtained. [0132] 280 parts of the emulsion, 1 part of the pigment dispersion resin obtained above, 1845 part of ion-exchanged water, 2.6 part of 1% aqueous solution of ruthenium acetate, 1· 5 parts of dibutyltin oxide and 54 parts of the guide of preparation examples 1-9 The conductivity adjuster was mixed to obtain a cationic electrodeposition coated 2 〇 composition having a solid content of 5% by weight. The pigment concentration based on the solid content of the electrodeposition coating composition was 3% by weight. The cationic electrodeposition coating composition was The conductivity was 1000 pS/cm. [0133] Comparative Preparation Example_1-1 Preparation of Pigment Dispersion Paste and Cationic Electrodeposition Coating of Ghosts (7) 100 parts of the pigment dispersion resin obtained in Preparation Examples 1-3 1〇部45 200812710 Divided stone and black, 40.0 part of kaolin, 5〇·〇 part of titanium dioxide, 9.〇 part of aluminum phosphomolybdate and 100.0 part of ion-exchanged water filled and dispersed until the particle size is not more than 10 μηι Pigment Dispersion Paste (solid content: jo%) [0134] The amine-modified epoxy resin obtained in Preparation Example 1-1 and the blocked isocyanate curing agent obtained in the preparation of Example 2-1 were 80/20. The solid is shy and the proportion is evenly mixed. Add glacial acetic acid to the mixture, and make the acid equivalent weight of the Ε bond resin solid content MEQ (A) to 3 〇, slowly add ion exchange water to dilute. MIBK removed, get 36% Body content emulsion. 10 [0135] 199 parts of the emulsion, 76 parts of the pigment dispersion resin obtained, 1912 part of ion-exchanged water, 2.6 part of 10% aqueous solution of barium acetate, and 1 part of 3 parts of dibutyltin oxide were mixed. A cationic electrodeposition coating composition having a solid content of 5% by weight. The pigment concentration of the composition solid content of § 10 by electrodeposition coating was 23% by weight. [Comparative Example 1-2 Preparation of Pigment Dispersion Ethylene and Electrodeposition Coating Composition The amine-modified epoxy resin obtained in Preparation Example 与 and the blocked isocyanate curing agent obtained in Preparation Example 1-2 were uniformly mixed at a solid content ratio of 80/20. To the mixture, glacial acetic acid was added, and the acid equivalent value of the acid was determined to be 3 Torr in an amount of 1 〇〇 g of the binder resin MEQ (A), and ion-exchanged water was slowly added to dilute. The MIBK was removed under reduced pressure to obtain an emulsion having a solids content of 36%. [0137] A portion of the emulsion, 1883 portion of ion-exchanged water, 2.6 part of a 10% aqueous solution of cesium acetate, and 1.6 part of dibutyltin oxide were mixed to obtain a cationic electrodeposition coating composition having a solids content of 5% by weight in 46 200812710. [0138]Comparative preparation of the composite disk & material dispersion - paste ^ electrodeposition coating group of the material rQ, 100 parts of the preparation of the pigment dispersion resin obtained in Example 丨 3, 100.0 part of titanium dioxide, and 100.0 part of ion-exchanged water Filled in and dispersed until the particle size is not more than 10 μπι, to obtain a pigment dispersion paste (solid content: 50%) 〇[〇13 9 ] The amine modified epoxy resin obtained by the preparation of the example 丨 _ _ The blocked isocyanate curing agent obtained in Example 1-2 was uniformly mixed in a ratio of 10 Å / 2 Torr of solids. To the mixture, glacial acetic acid was added, and the acid equivalent weight value of the resin solid content MEQ (A) was adjusted to 3 Torr, and the ion exchange water was slowly added to dilute. The MIBK was removed under reduced pressure to obtain an emulsion having a solid content of 36 〇/〇. [0140] 259 parts of the emulsion, 33 parts or more of the pigment obtained were divided into 15 parts of resin, 1895 part of ion-exchanged water, 2.6 part of 10% aqueous solution of acetic acid, and 1.5 parts of dibutyltin oxide to obtain a solid content of 5% by weight. The cationic electrodeposition coating composition. The pigment concentration based on the solid content of the electrodeposition coating composition was 1% by weight. Comparative Preparation Example 1-4 20 f by Yan Yan oblique dispersion paste and cationic electrodeposition conversion composition ΠΟ) 100 parts of the pigment dispersion resin obtained in Preparation Example 1-3, 9 〇. 〇 part of titanium dioxide 10.0 part of carbon black and part of ion-exchanged water were filled and dispersed until the particle size was not more than 10 |1111 to obtain a pigment dispersion paste (solid content: 50%). 47 200812710 The amine-modified epoxy resin obtained in Preparation Example M and the blocked isocyanate curing agent obtained in Preparation Example 1-2 were uniformly mixed at a solid content ratio of 8 〇 / 2 Torr. The mixture was added with glacial acetic acid, and the g1 〇〇g was bonded. The acid equivalent content of the resin solid content MEQ (A) was 3 Torr, and the mixture was slowly added to exchange water for dilution. The MIBK was removed under reduced pressure to obtain an emulsion having a solid content of 36%. 914 parts of the emulsion, 1 part of the pigment dispersion resin obtained above, 1889 part of ion-exchanged water, 2.6 part of 10% aqueous solution of ruthenium acetate, and 1.6 parts of dibutyltin oxide were mixed to obtain 5 wt% solids. A 10 cation electrodeposition coating composition of the content. The pigment concentration based on the solid content of the electrodeposition coating composition was 3% by weight. Comparative Preparation Example us _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 0 part of ion-exchanged water was filled and dispersed until the particle size was not more than 10 μm, and a pigment dispersion paste (solid content: 50%) was obtained. The amine-modified epoxy resin obtained in Preparation Example 与 was uniformly mixed with the blocked isocyanate curing agent obtained in Example 1-2 in a ratio of 20% by weight of 80/20 solid. To the mixture, glacial acetic acid was added, and the acid equivalent value of the acid solid content MEQ (A) of 1 〇〇 g was adjusted to 3 Torr, and ion-exchanged water was slowly added to dilute. The MIBK was removed under reduced pressure to obtain an emulsion having a solid content of 36%. [0146] 268 parts of the emulsion, 26 parts or more of the obtained pigment were divided into 48 200812710 dispersed resin, 1893 part of ion-exchanged water, 2.6 part of 10% aqueous solution of barium acetate, mixed with 1.5 part of dibutyltin oxide to obtain 5 wt% solids. The composition is coated with a cationic electrodeposition composition. The pigment concentration based on the solid content of the electrodeposition coating composition was 8% by weight. 5 Preparation Example 2 Preparation of Water-Based Intermediate Coating Composition Preparation Example 2-1 Preparation of Water-Soluble Polyester Rotary 200.0 Part of Isophthalic Acid, 179.0 Partially Azainic Anhydride, 176.0 10 Partially Acid, 150.0 part of trimethylolpropane, 295·〇 part of neopentadiene, 2 parts of oxidation "monobutyltin loaded into the reaction Valley d'heated mixture in nitrogen to dissolve the ingredients, slowly stirred and heated to 170 °C. After three hours, the mixture was heated to 220 ° C to dehydrate and esterify. When the acid value of the mixture reached 1 Torr, the mixture was cooled to 150 °C. To the mixture was added 114.0 parts of hexahydrophthalic acid 15 ester and reacted for one hour, and then the reaction was terminated. The mixture was cooled to 100 ° C, and 112.0 parts of butyl cellosolve was added to obtain a polyester resin. The obtained polyester resin had an acid value of 50, a hydroxyl value of 65, and a numerical average molecular weight of 10,000 (measured by GPC). The polyester resin was cooled to 6 〇〇c, and 8 〇 part of diethanolamine and ion-exchanged water were added to obtain a water-soluble polystyrene resin having a 5% by weight non-volatile content of 20. [0148] Preparation and Preparation of Polyester Resin Latex [For 94 parts of ion-exchanged water dispersion 33.4 part Newcole i i2〇 (available from Nippon Nyukazai Co., Ltd.) and 6 parts of ethylene glycol mono-n-hexyl solubilization 49 200812710 surname. The polyester resin obtained in the preparation of Example 2-1 was dropped into the dispersion and stirred at the same time to obtain a polyester resin emulsion having a nonvolatile content of 47.5%, which was coated with a nonionic dispersant. . PREPARATION EXAMPLE 2_3 5 Preparation of coloring pigments Extravagant 9.4 parts of pigment dispersant (DiSperbyk 19〇, available from βΥΚ Japan KK, 40% by weight solids content), 36·8 part of ion-exchanged water, % 8 part of titanium dioxide ( Rutiles, 0.03 part of carbon black and 〇〇7 part of yellow iron oxide were added and premixed. Then, the glass beads were added at room temperature and stirred in a paint-adjusting container until the particle diameter of the mixture measured by the grind meter was 5 μm, and the coloring pigment I was obtained. The mixing time of the 5 μηι grind meter was adjusted to minutes. Preparation Example 2-4 Huangshui-based intermediate coating composition The above-mentioned colored pigment paste obtained in Example 2-3 was prepared in part 121.2, and the above-mentioned polyester obtained in Example 2-1 was prepared in 152.8. Resin emulsion, 190.2 part of the polyester resin obtained in Preparation Example 2-2, 33.8 part of cymel 235 (available from Mitsui Cytec, Inc.) and 2U part of ion-exchanged water were added and mixed to obtain an aqueous solvent-based intermediate coating composition. Things. Preparation Example 3 20 Preparation of Organic Solvent-Based Intermediate Layer Fine Preparation Example 3-1 Preparation of Polyester Resin Solution Will be equipped with degree, stirrer, temperature controller, reflux condenser, nitrogen-inducing tube and dropping solution The funnel reactor was filled with 258 parts of hexahydrophthalic anhydride, 50 200812710 184 part of isophthalic acid, 213 parts of methyl propyl ketone, (10) part of neopentyl glycol, 72 parts of hydroxypivalic acid neopentyl glycol Monoester, 94 part Carjular E-10 (special decahydrate glycidol _, available from Shell (:hemieais, (d), and heated to 180. 〇:. 菖whai special knife is dissolved by heating, so that the mixture can be stirred 0.2, the sulphur-oxidized monobutyltin was added to the mixture, and stirring was started. The temperature of the reaction mixture was slowly increased from 18 to 22 Torr. The condensate was distilled off for 3 hours. The system was distilled off from the reactor. When the temperature reached 22 〇 cC, the mixture was maintained at this temperature for one hour 10 and 17 parts by 5 minutes was slowly added to the reaction mixture to carry out the condensation reaction in the presence of a solvent. When the acid value of the mixture reached 10 Cool the mixture to I5 at mg KOH/g 0 C, 182 parts of Placcel® (ε-caprolactone, available from Daicel Chemical Industries, LTD) were added to the mixture and stirred for one hour, then 15 was allowed to cool to i〇〇〇c. Xylene was added to the mixture to obtain a polyester resin having a solid content of 79% solids, a molecular average molecular weight of 14 Å (measured by Gpc), an acid value of 8 mg KOH/g, and a hydroxyl value of 21 Å. [〇152] Childhood implementation You π^ 20 Shame _ 僙 Non-aqueous mash (a) Manufacture of dispersion stabilizer The vessel with temperature, stirrer, temperature controller, reflux condenser and nitrogen inlet tube is filled into 90 parts of butyl vinegar. Prepared by mixing 38.9 parts of methyl methacrylate, 38.8 part 51 200812710 octadecyl methacrylate, 22·3 part of 2-hydroxypropanoic acid ethyl ester and 5.0 part azobisisobutyronitrile. 20 parts of solution (solubility parameter (calculated value): 9·5) was added, and the mixture was heated to 8 Torr while stirring. The remaining 85 parts of the above mixture were added dropwise to the mixture of the above 5 while stirring. 3 hours 'then will contain 0.5 part azobisisobutyronitrile with 10 part B A solution of butyl ester was added dropwise to the resulting mixture for several minutes. The reaction solution was further stirred at 80 ° C for 2 hours, and then the reaction was terminated to obtain a solid content of 50% and a numerical average molecular weight of 56 〇〇 (by 61 >(:; measured) Acrylic resin. 10 [0153] (b) Manufacture of non-aqueous dispersion. Fill in 35 parts with temperature, stirrer, temperature controller, reflux condenser and nitrogen-inducing tube. Butyl acetate and (9) part of the above ("Hooking Dispersion Stabilizing Resin" obtained acrylic resin, and heated to 1 〇〇 QC. Next, it will contain 7.0 parts of styrene, u part of methyl methic acid, 12 〇 part of methyl propyl hexaenoate, 8.5 parts of acryl s, 4 () · 7 part 2 _ propyl acrylate A solution of ethyl ester and 1.4 parts of azobisisobutyronitrile (solubility parameter (calculated value " 11.8) was added dropwise to the above mixture for 3 hours. Then, the azo-containing azo-isobutyronitrile and the i-part acetic acid were contained. A solution of butyl ester was added to the above mixture for 30 minutes. 2〇 The reaction solution was further stirred for 1 hour and diluted with butyl acetate to obtain a viscosity of 300 cps (25. 〇 and 18 〇 nm particle size, 4% by weight a non-aqueous dispersion of butyl acetate vinegar dispersion. The non-aqueous dispersion resin has a value of 23 〇 C and 162, respectively. 77 [0154] Preparation Example 3-3 52 200812710 Preparation of a coloring pigment paste... 328 parts of the polyester resin solution obtained in Preparation Example 3-1 was added with 981·7 part of titanium dioxide (rutile), 0.39 part of carbon black, 0.92 part of yellow iron oxide, 159 part of butyl acetate and 82 parts of dinonylbenzene. Premixed. Then add 5 part of the glass beads and stir with a sander for 3 hours. When the dispersion operation was terminated, the particle diameter measured by fineness was 5 μηι or less. 81.8 parts of xylene was added to the mixture and the glass beads were removed by filtration to obtain a pigment paste. [0155] Preparation Example 3 4 children's solvent-based intermediate coating 厝 fine cum & 10 pairs 83. 丨 part of the preparation of the above-mentioned coloring paste obtained in Example 3_3 was added to 21.0 part of the above-mentioned polyester resin obtained in Preparation Example 3-1, 87.5 part preparation implementation Example 3-2 obtained non-aqueous dispersion, 37 · 5 parts cymeL 254 (available from

Mitsui Cytec, Inc.) and 5.2 parts PTMG (polybutylene glycol, available from Mitsubishi Chemicals, Inc.) were mixed and obtained to obtain an organic solvent-based intermediate coating 15 layer composition. Example 1 Cationic electrodeposition coating composition obtained using Preparation Examples 1-4 (1) Hot-dip galvanized steel sheet treated with zinc phosphate (jjS G 3302 standard product, 150 X 70 x 0.8 mm Electrodeposition coating was carried out to obtain an electrodeposition coated film having a dry thickness of 15 2 . Then, the obtained electrodeposition coated film was baked at 160 ° C for 30 minutes to obtain a cured electrodeposition coated film. On the obtained cured electrodeposition coated film, the water-based intermediate coating composition obtained in Example 2 was prepared by air spraying to obtain an intermediate coating film having a dry thickness of 2 μm, and preheated at 8 Å. 5 minutes. Then, 53 200812710 An Aquarex(R) 2000 pearl mica substrate (water-based pearl mica base top coating composition, available from Nippon Paint Co., Ltd.) was coated thereon by air spraying to obtain The top surface of the substrate was dried at a thickness of 13 μηη and preheated at 80 °C for 3 minutes. Next, the Macflow-O-1800W-bright (acid 5 / epoxy cured bright topcoat composition, available from Nippon Paint Co.,

Ltd.) was coated thereon to obtain a substrate top coat film having a dry thickness of 35 μm, and preheated at 140 ° C for 30 minutes to obtain a test piece with a multilayer coated film. The water-based intermediate coating composition used in Example 1, the water-based substrate top surface coated with 10 layers of composition (Aquarex (R) 2000 pearl mica substrate) and the bright top coating composition (Macflow-CM800W-bright) system Diluted and diluted with the following conditions: ion exchange water, 40 seconds / 4 Ford Cup / 20. (1: (water-based intermediate coating composition) 15 Thinner: ion-exchanged water, 45 sec / 4 Ford cup / 20. (3 (water-based base top coating composition) Thinner: ethoxy propylene Ethyl Ethyl Ester (EEP) / S-150 (Aromatic Hydrocarbon Solvent from Exon Corporatm) =: 1/1, 3 sec / 4 Ford Cup / 2 〇 ° C (Bright Top Coating Composition) 20 [0158] The dry film of the electrodeposited coating film was subjected to electrodeposition coating on a tin plate (JIS G 3303 standard product, 150 X 70 X 〇·8 mm) using a cationic electrodeposition coating composition, A dried electrodeposition coated film having a thickness of 15 μm was obtained, and the obtained electrodeposition coated film was baked at 160 ° C for 30 minutes. The obtained coated plate was immersed in mercury to release a curing electric 54 200812710 u product; 4 film. Cut the cured electrodeposition coating film into each side of the wrist (five) of the positive I is in the square (four) difficult to work as a job #. To measure the film density of the potassium telluride solution root fine K7112 (sink and float method) measurement curing electricity The density of the dried film of the deposited film test piece was deposited. The results are shown in the woman. • 5 [0159] Inviting arithmetic mean sorrel - According to JIS_B 0601 (2001) The surface roughness tester (SURFTEST SJ-201P, available from Mitutoyo Corporation) measures the Ra value of the cured electrodeposition coated film. The measurement system uses seven to 10 times using a 2·5 mm width (subdivided by 5 times) dicing. The Ra value is determined by the average obtained by removing the upper and lower values. The smaller the Ra value, the better the appearance of the coated film because the coated film has a surface with less roughness. [0160] Logic L-cured electrodeposition coating film The brightness index (L-value) of the T---cured electrodeposited coating film is measured using the color difference Lu Min (Minolta CR300 ' can be said from Minolta Corporation). 15 [0161] Multi-layer frost film Evaluation of hue In the evaluation of the hue of the multilayer coated film, the L-value, the a-value and the b-value were measured using a color difference meter (Minolta CR300, available from Minolta Corporation), and the ΔΕ was obtained by using Comparative Example 1. The test piece was calculated as a standard color. The results are shown in Table 1. The smaller the ΔΕ, the better the appearance of the multilayer coated film, '20 because the difference between the multilayer coated film and the standard color is extremely small. The lanthanum is calculated by the following number When ΑΕ exceeds 1, Determining the apparent change in hue. Equation AE = V! Sl} + L 55 values listed in [0162] 200 812 710 [〇163] above Δα2 -f Ab2, a- and b- values according to a value based JIS z 8.722

10 is the chroma index based on the Hang characteristic difference formula. In general, the upper limit of the 'L_ value is the value of the touch. An increase in the L value indicates that the material to be tested is white, and a decrease in the L-value indicates that the material to be tested is close to black. The standard value of the chroma index (4) is 0. In the case where the a• value becomes a negative value, the a· value represents that the material to be tested is close to the green b. In the case where the a-value becomes a positive value, the a_ value represents that the material to be tested is close to red. The chroma index b__ standard value is also a value. In the case where the b_ value becomes a negative value, the b value represents that the material to be tested is close to blue. In the case where the b. value becomes a positive value, the b-value represents that the material to be tested is close to yellow. Embodiment 2

The cationic electrodeposition coating composition (1) obtained by the preparation of each of Examples 1-4 was carried out on a hot dip galvanized steel sheet (JIS G 33〇2 standard product, 150 X 70 X 0.8 mm) treated with phosphoric acid. Electrodeposition coating was performed to obtain an electrodeposition coated film having a thickness of 15 Å dry. Then, the obtained electrodeposition coated film was baked at 160 ° C for 30 minutes to obtain a cured electrodeposition coated film. The organic solvent-based intermediate coating composition obtained in Example 3 was prepared by air-spraying on the obtained cured electrodeposition coating film to obtain an intermediate coating film having a dry thickness of 20 μm, and was allowed to stand at room temperature. Set for 1 minute. 20 Then, a Superlac®-1300 pearl mica substrate (melamine-curable acrylic resin-based organic solvent-based base top coating composition, available from Nippon Paint Co., Ltd.) was coated in the middle of uncured by air spray. The film was coated to obtain a substrate top coat film having a dry thickness of 13 μm to form an uncured base top coat film, which was allowed to stand at room temperature for 20 minutes. 56 200812710, Next, use Air Spray to bring Macflow-0-1800W-bright (available from

An acid/epoxy-cured bright top coat composition of Nippon Paint Co" Ltd. was applied thereon to obtain a dried base top coated film having a thickness of 35 μm, and was at 140. (: heating for 30 minutes) , 5 test piece with multi-layer coated film was obtained. The organic solvent-based intermediate coating composition of Example 2, the organic solvent-based substrate top coating composition (Superlac®-1300 pearl mica substrate) and bright The top coat composition (Macflow-(M800W-bright) was diluted and coated under the following conditions. Diluent: Ethyl ethoxypropionate (EEP) / xylene = 9/11, 19 10 seconds / 4 Ford Cup/2〇°C (Organic Solvent-Based Intermediate Coating Composition) Thinner: Toluene/Butyl Acetate/Methyl Ethyl Ketone=40/50/10, 15 sec/4 Ford Cup/20QC (Organic Solvent-Based Substrate Top Surface) Coating composition) Thinner: Ethyl ethoxy propionate (EEP) / S_i5 〇 (Aromatic hydrocarbon solvent available from Ex〇n Corporatin) = yi, 3 〇 / 4 Ford Cup / 2 〇〇 c (Bright 15 top coat composition) The obtained cured electrodeposition coated film and the multilayer coated film were evaluated in the same manner as in Example 1. It is shown in Table 1. [0167] The cationic electrodeposition coating composition (1) obtained by using the preparation example 丨4 was carried out in a hot dip plated steel plate (JIS G 3302 standard) treated with scalyric acid. Electrodeposition coating was carried out on the product, 150 X 7 〇χ〇·8 mm) to obtain an electrodeposition coated film having a dry thickness of 15 Å. Then, the resulting electrodeposition coated film was applied at 160. 0: baked for 30 minutes. A cured electrodeposition coated film was obtained. [0168] On the resulting cured electrodeposition coated film, air spray was used 57 200812710 Intermediate coat composition Olga P-5 071 (melamine-curable polyester resin type white intermediate coat) The composition, available from Nippon Paint Co., Ltd., to obtain an intermediate coated film having a dry thickness of 20 μm, heated at i4 〇〇C for 3 minutes and cooled to obtain a test with a cured intermediate coated film. Then, 5, an Aquarex(R) AR-2000 pearl mica substrate (a water-based pearl mica base top coating composition available from Nippon Paint Co., Ltd.) was applied thereto by air spraying. Obtaining a top surface of the substrate having a dry thickness of 13 μη The coated film was preheated at 80QC for 3 minutes. Then, using air spray

Macflow-〇-1800W-2 bright (10 acid/epoxy cured bright top coat composition available from Nippon Paint Co., Ltd.) was applied thereon to obtain a substrate top having a dry thickness of 35 μm The film was coated on the surface and heated at 14 ° C for 3 minutes to obtain a test piece with a multilayer coated film. The organic solvent-based intermediate coating composition (Olga p_5 〇 71) used in Example 3, the water-based base top coating composition (Aquarex (R) 2000 pearl mica substrate) and the bright top coating group 15 (Macflow-0_1800w_2 bright) was diluted and coated under the following conditions. Diluent: Ethyl ethoxypropionate (EEp) / xylene = 9/11, 19 seconds / No. 4 Ford Cup / 20. (3 (organic solvent-based intermediate coating composition) Thinner: ion-exchanged water, 45 sec / 4 Ford cup / 20 ° C (water-based base top coating composition) 20 Thinner: ethoxypropionic acid Ethyl Ester (EEP) / S-150 (purchased from Εχ: 〇η Corporatm's aromatic hydrocarbon solvent) = 1 / 丨, 3 〇 / 4 Ford Cup / 2 〇〇 c (bright top coating composition) The resulting cured electrodeposition coated film and the multilayer coated thin tanning system were evaluated as described in Example 1. The results are shown in Table 1. 58 200812710 [0170] f Example 4 obtained by using Preparation Examples 1-5 A cured electrodeposition coating film and a multilayer coating film were obtained as described in Example 1, except for the cationic electrodeposition coating composition (2). The resulting cured electrodeposition coating film and the multilayer coating film system 5 were as implemented. The evaluation was carried out in the manner of Example 1. The results are shown in Table 1. Example 5 A curing electric power was obtained as described in Example 1, except that the cationic electrodeposition coating composition (3) obtained in Preparation Example 1-6 was used. The coated film and the multilayer coated film were deposited. The resulting cured electrodeposition coated film and the multilayer coated film system 10 were as in the case of Example 1. The evaluation was carried out. The results are shown in Table 1. Example 6 A cured electrodeposition coating was obtained as described in Example 1, except that the cationic electrodeposition coating composition (4) obtained in Preparation Examples 1 - 7 was used. Film and multilayer coated film. The resulting cured electrodeposition coated film and multilayer coated film system 15 were evaluated in the same manner as in Example 1. The results are shown in Table 2. Example 7 Except using Preparation Examples 1-8 The obtained electrodeposition coating composition (5) was obtained, and a cured electrodeposition coating film and a multilayer coating film were obtained as described in Example 1. The obtained cured electrodeposition coating film and the multilayer coating film were 20 as The evaluation was carried out in the manner of Example 1. The results are shown in Table 2. Example 8 Curing was carried out as described in Example 1, except for the cationic electrodeposition coating composition (6) obtained using Preparation Examples 1-9. The electrodeposition coated film and the multilayer coated film were obtained. The obtained cured electrodeposition coated film and the multilayer coated film were evaluated in the same manner as in Example 1 as in WO 2008 5912710. The results are shown in Table 2. [0175] Evaluation of Preparation and Implementation Example 99 obtained cationic electricity The uniform plating ability of the deposited coating composition (6) confirmed that the fineness of the coating was extremely similar. The evaluation of the uniformity of the ability was carried out as follows. [0176] The non-plating ability of the cation-positive electrodeposition coating composition was uniform. The so-called Siping 1槐钿 method is flattened. Specifically, as shown in Figure 1, it will be labeled with phosphoric acid.

(SURFDINE SD-5000, available from Nipp0n Paint κ.κ·) Four sheets of steel sheets 11 to 14 (Jis G 3141 SPCC_SD) are placed vertically at 10 mm intervals at 10 mm intervals, and the lower side plates are insulated from the lower portion of the bottom plate. A material such as a sticky tape is coated to prepare the chassis 10. The steel plate other than the plate 14 has an opening 15 of 8 mm phi on the lower side. 15 20 [0177] 4 liters of the cationic electrodeposition coating composition was filled into a vinyl chloride container to obtain a first electrodeposition bath. As shown in Fig. 2, a case lGe as an object to be coated is placed in an electrodeposition container containing the electrodeposition coating composition 21. Here, the coating composition 21 is only infiltrated into the casing 1 by π 15 . [0178] The coating composition 21 was stirred with a magnetic stirrer (not shown in Fig. 2). The steel plates U to 14 are electrically connected, and the reference electrode 22 is placed at a position far from the nearest steel plate 11 by 150 faces. A voltage was applied to the steel sheet as a cathode and between the anode and the reference electrode batch, whereby the steel sheet was subjected to cationic electrodeposition coating. The electric coating was applied for 5 seconds after the application of the voltage so that the coating thickness formed on the surface a of the steel sheet η was 15 _. Then, a potentiation deposition process was carried out in which the applied voltage was maintained for 175 seconds. [0Π9] After electrodeposition coating, the steel sheets were rinsed with water, and the coating was cured at 60 200812710 170 ° C for 25 minutes and then cooled in air. The thickness of the coating layer formed on the surface a of the steel sheet 11 closest to the reference electrode 22 was measured. Then, the thickness of the coating formed on the surface G of the steel sheet 14 farthest from the reference electrode 22 was measured. The throwing power of the cationic ion-deposited coating composition was evaluated in the following ratios: Table 5 Coating thickness on face 0 / Coating thickness on surface A (G/A ratio). The evaluation criteria are as follows. Excellent: G/A > 50% (represented by group A) Poor: G/A = 50% or G/A < 50% (indicated by group B) [0180] Comparative Example 1 1 A cured electrodeposition coating film and a multilayer coating film were obtained as described in Example 1, except for the cationic electrodeposition coating composition (7) obtained in Example 1-1. The resulting cured electrodeposition coated film and multilayer coated film were evaluated in the same manner as in Example 1. The results are shown in Table 3. The evaluation results of Comparative Example 1 were established for the evaluation of the color of the multi-layer coating thin film. Comparative Example 2 A cured electrodeposition coated film and a multilayer coated film were obtained as described in Example 1, except that the cationic electrodeposition coating obtained by Comparative Preparation Example 1 was used. The resulting cured electrodeposition coated film and multilayer coated film 20 were evaluated in the same manner as in Example 1. The results are shown in Table 3. fchM Example 3 A cured electrodeposition coated film and a multilayer coated film were obtained as described in Example 1, except that the cationic electrodeposition coating composition (9) obtained in Comparative Preparation Example U was used. The resulting cured electrodeposition coated film and multilayer coated film 61 200812710 were evaluated in the same manner as in Example 1. The results are shown in Table 3. Comparative Example 4 A cured electrodeposition coating film 5 and a multilayer coating film were obtained as described in Example 1, except that the cationic electrodeposition coating composition (10) obtained by Comparative Preparation Example 1-4 was used. . The resulting cured electrodeposition coated film and multilayer coated film were evaluated in the same manner as in Example 1. The results are shown in Table 3. Comparative Example 5 A cured electrodeposition coating film 10 and a multilayer coating were obtained as described in Example 1, except that the cationic electrodeposition coating composition (11) obtained by Comparative Preparation Example 1-5 was used. film. The resulting cured electrodeposition coated film and multilayer coated film were evaluated in the same manner as in Example 1. The results are shown in Table 3. Table 1 | Example 1 Circle _ 1 Example 2 Example 3 Example 4 Example 5 Titanium Dioxide 100 100 100 ~"98 Pigment Kaolin Combined Aluminum Molybdenum Phosphate Carbon Black 2 Pigment Concentration in Solid Content (wt %) 3.0 3.0 3.0 3.0 5.0 Dry film density of cured electrodeposition coated film 1.21 1.21 1·21 1.21 1.22 L-value of cured electrodeposition coated film 57.6 57.6 57.6 56.2 58.0 Solid content of coating composition (wt%) 5.0 5.0 5.0 5.0 5.0 Ra value of the electrodeposited coating film (horizontal surface) 0.18 0.18 0.18 0.18 0.19 Method of forming a multilayer coating film (Step 2) 3C1B (w/w/o) 3C1B (o/o/o 3C2B (o/w/o) 3C1B (w/w/o) 3C1B (w/w/o) Thickness of intermediate coating film 20 20 20 20 20 J Thickness of surface-coated film (mm) 13 13 13 13 13 Color tone evaluation of multilayer coated film △L 0.09 0.08 0·07 -0.22 0.02 Aa 0.06 0.07 0.06 -0.04 -0.10 △b -0.08 -0.05 -0.01 0.09 •0.05 ΔΕ 0.13 0.12 0.09 0.24 0.11 62 200812710

Table 2 Example 6 Example 7 Example 8 Titanium dioxide 100 100 100 Pigment kaolin combined with aluminum phosphomolybdate carbon black Pigment concentration in terms of solid content (Wt%) 7.0 3.0 3.0 Curing film of cured electrodeposition coated film Density 1.25 1.21 1.21 L-value of cured electrodeposition coated film 60.2 57.6 57.6 Solid content of coating composition (wt%) 5.0 20 5.0 Ra value of cured electrodeposition coated film (horizontal surface) 0.20 0.18 0.17 Multi-layer coating Film coating method (Step 2) 3C1B (w/w/o) 3C1B (w/w/o) 3C1B (w/w/o) ----- Thickness of the intermediate coating film (μπι) —-— 20 20 20 Thickness of top substrate coated film (μπι) 13 13 13 AL 0.10 0.08 0.10 Color of multilayer coated film △a -0.11 0.12 0.08 △b -0.09 0.08 -0.06 ΔΕ 0.17 0.16 0.14 • (10) Cationic electricity of Example 8 The throwing ability (ratio G/A) of the deposited coating composition was excellent (66%). 63 200812710 [0187] Table 3

------ Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Pigment Combination----- Titanium Dioxide 50 100 90 100 Kaolin 40 Asbestos Aluminum Molybdate 9 Carbon Black 1 10 Pigment of W solid content meter __edgeness (wt%) 23.0 0 10.0 3.0 8.0 Puncture electrodeposition coating film dry film density 1·40 1.20 1.30 1.21 1.27 solid-state electrodeposition coating film ____ L- Value 56.8 49.6 73.2 54.0 64.8 Solid content of the coating grade - (-% by weight) 5.0 5.0 5.0 5.0 5.0 Ra value of the cured electrodeposition coating film) 0.29 0.17 0.28 0.18 0.27 Multilayer coated film -^ method (step 2) 3C1B (w/w/o) 3C1B (w/w/o) 3C1B (w/w/o) 3C1B (w/w/o) 3C1B (w/w/o) + between Film thickness----- (am) 20 20 20 20 20 Top surface coating degree (film-coated μιη) 13 13 13 13 13 Color evaluation of enamel coating ^ film ^^ AL L=86.79* - 1.01 0.28 -0.77 0.18 Δα a=0.56* 0.18 0.06 0.15 0.14 Ab b=0.79* 0.11 0.00 0.18 0.08 ΔΕ 1.03 0.29 0.80 0.24 : In the evaluation of the hue of the multilayer coated film, the L-value of the comparative example 1 and a- Value and b -f is used as a standard color, and AL, Aa, Ab, and ΔΕ are differences between Comparative Example 1 and each of Examples and Comparative Examples. As shown in the above table, the multilayer coated film obtained according to the embodiment of the present invention has an excellent color tone as obtained in Comparative Example 1, even though the embodiment according to the present invention has the pigment concentration as compared with Comparative Example 1. The low pigment concentration (0. 1 to 〇 2 times of Comparative Example 1). Moreover, the cured multi-layer coated film according to the invention of 2008 20081010 has an excellent finish on a smaller Ra and horizontal surface. The cured electrodeposition coated film according to the present invention also has a small dry tantalum film twist. The cationic electrodeposition coating composition containing the conductivity control agent of Example 8 had excellent throwing ability' even though the coating composition had a lower coating composition solid content (5 wt%). On the contrary, the multilayer coated film obtained in Comparative Example 2 had a ΔΕ of more than 1, and its color tone was different from that of the multilayer coated film obtained in Comparative Example 1. It is attributed to the influence of the substrate hue caused by the low concealment characteristics. The cured electrodeposition coated film obtained in Comparative Examples 3 and 5 had a Ra-like large ruler & compared with Example 1, which deteriorated the appearance of the finish on the horizontal surface, and a large dry film density. The multilayer coated film obtained in Comparative Example 4 had a large ΔΕ (0·80) and its color tone was different from that of the film of Comparative Example 1. Industrial Applicability [0189] The present invention can provide a cured electrodepositor 15 having a L_ value of 55 or more and a coated film, even if the electrodeposition coating composition contains a low pigment concentration, and can provide excellent Formation of a multi-layer coated film of hue. The present invention can also provide the formation of a multilayer coating film having good concealing properties, even if the multilayer coating film is formed by a coating method with a small number of baking times, which satisfies the need for energy saving and cost reduction. 20 The present invention also provides a weight-reducing coated article. [Picture ^ Simple ^ Children] Figure 1 is a perspective view showing an example of a chassis for evaluating the average key capability. Fig. 2 is a cross-sectional view schematically showing a specific example of a method for evaluating the average clock ability. 65 200812710 [Explanation of main component symbols] 10···Chassis 20...electrodeposition container 11-14···Steel plate treated with sulphuric acid 21...electrodeposition coating composition 15...opening 22...reference electrode 66

Claims (1)

200812710 - 5 X. Patent application scope: 1. A method for forming a multilayer coating film, the method comprising the steps of: performing electrodeposition coating on a substrate by cationic electrodeposition coating composition, then heating and curing Forming a cured electrodeposition coating film on the substrate (step 1), and coating the coating composition on the cured electrodeposition coating film to form a multilayer coating film (step 2); wherein the cation The electrodeposition coating composition has a pigment concentration of 2 to 7% by weight based on the solid content of the electrodeposition coating composition, and 10 the pigment in the electrodeposition coating composition contains 95 to 100% by weight of titanium oxide, and the cured electrodeposition coating The film has a brightness index (L-value) of 55 or more on the thickness of the cured electrodeposition coating film of 15 μm or more, and 15 • The cured electrodeposition coated film has a temperature of 1 · 2 0 to 1.2 5 Dry film density. 2. The method of forming a multilayer coating film according to claim 1, wherein the step 2 comprises the following steps: • 20 • coating the intermediate coating composition on the cured electrodeposition coating film to form an uncured intermediate Coating a film, coating a top coating composition on the uncured intermediate coating film to form an uncured base coating film, coating a bright top coating layer on the uncured base coating film 67 200812710 The composition forms an uncured bright coated film, and simultaneously heats and cures the uncured intermediate coated film, the uncured base top coated film and the uncured bright coated film. 3. The method of forming a multilayer coating film according to claim 1 of the patent application, 5 wherein the step 2 comprises the steps of: coating an intermediate coating composition on the cured electrodeposition coating film, then heating and curing the same To form a cured intermediate coating film, coating a top coat composition 10 on the cured intermediate coating film to form an uncured base coating film, and coating a bright top coating on the uncured base coating film The layer composition forms an uncured bright coated film, and simultaneously heats and cures the uncured base top coated film and the uncured bright coated film. The method of forming a multilayer coated film according to the second or third aspect of the patent application, wherein the cured intermediate coating film has a thickness of 10 to 40 μm. 5. The method of forming a multilayer coating film according to claim 1, wherein the second step comprises the step of: coating a top coat composition on the cured electrodeposition coating film to form an uncured substrate. a coated film coating a bright topcoat composition on the uncured base coated film to form an uncured bright coated film, and 68 200812710 simultaneously heating and curing the uncured base top coated film with uncured bright Coating the film. 6. The method of forming a multilayer coating film according to claim 1, wherein the 5 step 2 comprises the steps of: coating a solid top coating composition on the cured electrodeposition coating film to form an uncured solid state The film is coated, and the uncured solid coated film is heated and cured. 7. The method of forming a multilayer coating film according to claim 2, wherein the intermediate coating composition is a water-based intermediate coating composition, and the top coating composition of the substrate is a water-based substrate top surface The coating composition, or wherein the intermediate coating composition is an organic solvent based intermediate coating composition, and the substrate top coating composition is an organic solvent based substrate top surface 15 coating composition. A multilayer coated film obtainable by the method of forming a multi-layer coated film according to any one of claims 1 to 7. 69