TW200427795A - Method for coated composite film - Google Patents

Abstract

Disclosed is a method for producing a coated composite film, comprising forming an electrocoated film on a substrate, and then successively applying an intermediate paint, a base paint and a clear paint in a wet-on-wet manner, followed by baking and curing the applied three layers at once, wherein said intermediate paint contains, on the basis of a resin solid content, (a) 5 to 30% by weight of a urethane-modified polyester resin having a number average molecular weight of 1,500 to 3,000, obtained by reacting an aliphatic isocyanate compound with a hydroxy group-containing polyester resin having a glass transition point (Tg) of 40 to 80 DEG C, the polyester being obtained by polycondensation of an acid component containing 80 mol% or more of isophthalic acid and a polyhydric alcohol, (b) 30 to 60% by weight of a polyolefin elastomer having an acid group and/or a hydroxy group, and c 10 to 30% by weight of a blocked isocyanate compound. The method provides with a coated composite film excellent in anti-chipping property by a three-coat one-bake method.

Description

200427795 发明 Description of the invention: The technical field of the invention is: 3 Field of the invention The present invention relates to a method for forming a coated composite film, and in particular 5 relates to a method for forming a coated layer through a three-coat film drying method. Method for covering composite film. L Prior Art 3 Background of the Invention There are two ways to form a coated composite film. One method 10 is to dry and harden each coating film individually after coating. Another method is to form a coated composite film by applying two or more coatings without hardening, and then hardening it once. For example, a two-layer baking method is usually used to form a metal coating film. JP-A No. 11-114489 discloses a method for forming a coated composite film, which comprises continuously forming a color base coating film, a metal 15-base coating film, and a transparent coating film, and then baking and hardening three layers simultaneously , 俾 promotes the appearance of the film. When the intermediate coating film, the base coating film and the transparent coating film are formed by baking the three coating films once, the oven for curing the intermediate coating film can be eliminated. In this way, energy consumption can be reduced and operating time can be shortened, which has important advantages in terms of economics and environmental protection. However, the three-coat film drying method has the following problems, for example. In some cases, the peeling of the coating film occurs by a so-called dicing wafer, and the dicing wafer occurs when a moving vehicle hits a cobblestone and the cobblestone hits the coating film. In the conventional method of forming a coated composite film, for example, an individual baking method for each application of coating and a one-time baking method for two coating films, a base coating film and an intermediate coating film are respectively baked and hardened. Therefore, the strategy for cutting-resistant wafers can be achieved by forming a cutting-resistant wafer coating film above or below the intermediate coating film, or by adjusting the degree of the top film and the brightness of the base coating film to form an intermediate coating film that has not yet been peeled off. 5 For example, Jp-A No. 2002 · 249699 and JP-A No. 9-208882 describe a wafer cutting primer coating composition, and the wafer coating film is cut only after the coated composite film is formed. In addition, in JP-A No. 6-256714 or JP-A No. 6-254482, the improvement of cut-resistance wafer properties is studied from the viewpoint of an intermediate coating composition, but the improvement degree of 10 degrees is not sufficient for a three-coat film baking method. In addition, the car body has many uneven parts. When the entire surface of the car body is coated by the three-coat film once, there is a problem that it is easy to cause the appearance to deteriorate. [Akimoto 3 15 Summary of the Invention The present invention can solve the aforementioned conventional problems, and the object of the present invention is to provide a method for forming a coated composite film with excellent cut-resistant wafer properties by a two-coat film and one-time baking method. The present invention provides the intermediate coating based on the resin solid content of 20, containing (a) 5 to 30% by weight of a urethane-modified polyester resin having a number average molecular weight of 1, 500 to 3,000, which is obtained by reacting an aliphatic isocyanate compound with a hydroxyl-containing polyester resin having a glass transition point (Tg) of 40 ° C to 80 ° C, and the polyester is obtained by containing 80 mol% or more 6 200427795 Obtained by polycondensation of phthalic acid and polyhydroxy alcohol, (b) 30 to 60% by weight of polyolefin elastomers having acid groups and / or hydroxyl groups, and 10 to 30% by weight of block isocyanate compounds . 5 [Embodiment] Detailed description of the preferred embodiment The intermediate coating film is formed in the coating film forming method of the present invention. The intermediate coating material for forming the intermediate coating film contains a urethane-modified polyester resin (a), Polyolefin elastomer 10 (b) and block isocyanate compound (c). If necessary, the intermediate coating may further contain a melamine resin (d), a non-aqueous dispersion resin (e) having a core-shell structure, and a flake pigment (f). The amino resin-modified polyester resin (a) can be obtained by reacting a hydroxyl-containing polyester resin with an aliphatic isocyanate compound. 15 In general, polyester resins are prepared by polycondensation of an acid component such as a carboxylic acid, an anhydride, and an acid gas with a monohydric alcohol or a polyhydric alcohol. The hydroxyl-containing polyester resin used in the present invention contains an acid component used in the polycondensation reaction of phthalic acid at 80 mol% or more based on the total molar number of acid components. When the content of isophthalic acid in the acid component is less than 80 mol%, the glass transition temperature (Tg) of the obtained hydroxyl-containing polyester resin 20 becomes lower than a desired range. Acid components other than isophthalic acid include, for example, phosphophthalic acid, phosphophthalic anhydride, tetrahydrophosphophthalic acid, tetrahydrophosphophthalic anhydride, hexahydrophosphophthalic acid, and hexahydrophosphoxylene Anhydride, methyltetrahydrophosphophthalic acid, methyltetrahydrophosphophthalic anhydride, himic acid anhydride, trimellitic acid, trimellitic anhydride 7 200427795, pyromellitic acid, pyromellitic acid Anhydride, terephthalic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, succinic anhydride, ten Dicarbenyl succinic acid, dodecenyl succinic anhydride, and the like. In addition, as for the acid component, an acid other than polyvalent pentavalent acid and polyvalent retarding anhydride, which are commonly used in the preparation of polyester resins, may be contained. Such acids include, for example, monoweilic acid and hydroxycarboxylic acids. As the acid used for preparing the hydroxyl-containing polyester resin, isophthalic acid may be used alone, or other acids may be used in combination. Polyhydric alcohols include, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-10 butanediol, 1 4,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-ammonium adipase, 2,2-dimethyl-3 -Technyl propyl-2,2-dimethyl-3 -caproyl propionate, 2,2,2-trimethylidene-1,3-pentanediol, polytetramethylene ether glycol, poly Caprolactone polyol, glycerol, sorbitol, annitol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol 15 tetraol, Dipentaerythritol and so on. In the preparation of the hydroxyl-containing polyester resin, in addition to the acid component and the polyhydric alcohol, other components that can react with these components can also be used. These other components include, for example, acid chlorides, acid derivatives of lactones, epoxy compounds, and dry and semi-dry oils and fatty acid derivatives thereof. The intrinsic moieties can form graft chains through ring-opening addition of polyester resins formed from 20 to polyvalent carboxylic acids and polyhydric alcohols. Lactones include, for example, cold-propiolactone, dimethylpropiolactone, butyrolactone, T-valerolide, ε-caprolactone, caprolactone, caprylic vinegar, crotonide, 5 -Valerolactone, ά -caprolactone, etc. Particularly, ε-caprolactone is most preferable. Specific examples include an epoxy compound such as Carjula E (manufactured by Shell Chemical Co., Ltd. 8 200427795) caprolactones. The hydroxyl-containing polyester resin has a glass transition temperature (Tg) of 4 (rc to 85 1 and preferably 45 ° C. to 75X :. When the glass transition temperature (Tg) is lower than 40.0, the film hardness decreases. When Tg is higher than 80 ° C, the chip-cutting resistance is reduced. 5 Aliphatic isocyanate S compounds include, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane-丨, 'Diisocyanate, monocyclohexyl-4,4-diisocyanate, methylcyclohexyl diisocyanate, and isophor S with diisocyanate g. In particular, the chip-resistant performance of the coated composite film And 10 points of weather resistance, hexamethylene diisocyanate or trimethyl hexamethylene diisocyanate is preferably used. Biuret, isocyanurate, and adducts thereof can be used. The purpose of the polymer containing the radical The reaction between the resin and the aliphatic isocyanate g can be carried out by a method known to those skilled in the art. The amino resin modified polyester resin (a) has a number average molecular weight 15 (Mn) of 150 to 3000. And preferably from 1700 to 2500. When the molecular weight is less than 1500, workability and hardenability are insufficient. When the molecular weight is When it exceeds 3,000, the non-volatile content at the time of coating is too low, but the working ability is inferior. The number average molecular weight here is determined by GPC method using polystyrene as a standard. 20 Carbamate The modified polyester resin (a) has a hydroxyl value (0HV) of preferably 30 to 180 and more preferably 40 to 160. When the hydroxyl value exceeds 180, the water resistance of the coated composite film decreases. When the value is less than 30, the hardenability of the coated composite film is reduced. In addition, the resin has an acid value (AV) of preferably 3 to 30 mg KOH / g, more preferably 5 to 25 mg KOH / g. When the acid value exceeds 9 200427795 30 mg KOH / g, the water resistance of the coated composite film decreases. When the acid value is less than 3 mg KOH / g, the hardenability of the coated composite film decreases. Contained in the intermediate coating The content of the urethane-modified polyester resin (a) is 5 based on the solid content of the resin, and the content is 5 to 30% by weight and preferably 10 to 30% by weight. When the content is less than When the weight ratio is 5%, the cut-resistant wafer performance becomes insufficient. When the content exceeds 30% by weight, the coated composite film The degree of reduction is considered. By including a polyester resin modified with urethane as an intermediate 10 coating component, the elasticity of the coated composite film is improved, and the properties of the coated cut-resistant wafer are also improved. Polyolefin elastomer ( b) Usually a polyolefin-based graft polymer. The polyolefin elastomer (b) is prepared, for example, by copolymerizing a polyolefin-based macromonomer with an ethylenically unsaturated compound. 15 Polyolefins are The main macromonomer means a polymer monomer having an ethylenically unsaturated group at the end of the polyolefin chain. The macromonomer mainly consisting of a polyolefin is, for example, via a polyolefin having a hydroxyl group and having an ethylenically unsaturated group. The acid or anhydride of the group is obtained by reaction. Polyolefins having a hydroxyl group include, for example, polyolefin-based resins such as polyethylene, polypropylene, polybutene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, EPDM, etc. The remaining ends have hydroxyl groups. It preferably has a number average molecular weight of 200 to 5000, and more preferably 500 to 4000. Commercially available polyolefins having a hydroxyl group include, for example, the following: 10 200427795 [Table i] Trade name manufacturer compound Mη G-1000 Saibon Soda Corporation α, ω-polybutadiene glycol about 15,00 G-2000 Yuan Caoda Corporation α, ω-polybutadiene glycol approximately 2,000 G-3000 Caoda Corporation Japan α, ω-polybutadiene glycol approximately 29,00 G-1000 Butadiene glycol approximately 15,00 G-2000 Alpha, omega-hydrogenated polybutadiene glycol from Japan's Soda Corporation approximately 21,000 G-3000 Alpha, omega-hydrogenated polybutadiene glycol from Japan's Soda Corporation 3,000 R-15HT α-polybutadiene glycol from effluent petrochemical company, about 1,200 R-45HT α, ω-polybutadiene glycol from effluent petrochemical company, about 2,800 LIR-506 polyisoprene from Kuraray Pentaol is about 25,000 acid anhydrides having a rare unsaturated group, and examples include maleic anhydride, itaconic anhydride, succinic anhydride, and the like. Among them, the use of maleic anhydride is particularly preferred. 5 The reaction of a polyolefin having a hydroxyl group with an acid or an anhydride having an ethylenically unsaturated group can be performed by a method known to those skilled in the art. Polyolefin-based macromonomers can be obtained by reacting a polyolefin having a hydroxyl group, a diisocyanate compound, and an alcohol having an ethylenically unsaturated group. The alcohol having an ethylenically unsaturated group includes, for example, a hydroxyl-containing acrylic monomer. 10 As for the diisocyanate compound, an aliphatic diisocyanate for preparing a urethane-modified polyester resin can be used. Particularly preferred is isophorone diisocyanate. As the hydroxyl-containing acrylic monomer, for example, hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxy 15-propyl methacrylate (HPMA), hydroxypropyl acrylate (HPA), and Hydroxybutyl acrylate (BBA). These monomers can be used alone or by mixing two or more kinds. Among these hydroxyl-containing acrylic monomers, it is particularly preferable to use hydroxyethyl (meth) acrylate. The reaction of a hydroxyl-containing polyolefin, a diisocyanate compound, and an alcohol having an ethylenically unsaturated group can be performed by methods known to those skilled in the art. The ethylenically unsaturated compounds to be copolymerized with the polyolefin-based macromonomer include ethylenically unsaturated monomers, unsaturated acrylic resins, unsaturated polyester resins, and the like. 5 Ethylenically unsaturated monomers include, for example, acrylic monomers such as methyl acrylic acid, methyl methacrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate, methyl ethyl acrylate, Butyl and n-butyl methacrylate. These acrylic monomers may be used alone or in combination of two or more. In addition, other monomers copolymerizable with acrylic monomers, such as styrene and vinyl acetate, can be used. The unsaturated acrylic resin is introduced into the acrylic resin as an unsaturated bond. For example, unsaturated acrylic resins can be obtained by addition of glycidyl acrylate to carboxyl groups of acrylic resins; obtained by addition of anhydrides having unsaturated bonds to hydroxyl groups of acrylic resins; or additions having unsaturated bonds of 15 It is obtained from carboxylic acid to ethylene oxide group of acrylic resin. As for the unsaturated acrylic resin, it is preferable to have an acid value of 0 to 200 mg KOH / g, and more preferably 0 to 150 mg KOH / g, an M base value of 10 to 300 and more preferably 10 to 200, and a number average molecular weight of 1 0.00 to 50,000 and more preferably 2000 to 5000, and iodine value of 0.5 to 100 and more preferably 0.5 to 70. 20 The unsaturated polyester resin can be obtained by a conventional method such as the reaction of a polyol compound with a polyacid compound having an unsaturated group. For unsaturated polyester resins, it is preferred to have an acid value of 0 to 200 mg of KOH / g, and more preferably 0 to 150 mg of KOH / g, a hydroxyl value of 10 to 300, and more preferably 10 to 200. The number The average molecular weight is from 1,000 to 5,000 and more preferably from 1,000 to 40,000, 12 and the iodine value is from 0.5 to 100 and more preferably from 0 to 5 and 70. The copolymerization of polyolefin-based macromonomers and ethylenically unsaturated compounds can be carried out by a method known to those skilled in the art. For example, according to the solution polymerization method, the macromonomer mainly containing olefins is dissolved in an appropriate solvent, the temperature is increased, and then the ethylenically unsaturated compound and an appropriate polymerization initiator are added dropwise thereto while stirring. Suitable solvents for the reaction include, for example, aliphatic hydrocarbons such as kerosene, ethylcyclohexane, and Shellzole TH (trade name, manufactured by Shell Corporation of Japan), aromatic hydrocarbons such as toluene, dimethylbenzyl, and Swadzu. (Swazole) 100 (trade name, manufactured by Maru #Petrochemical Co., Ltd.), esters such as butyl acetate and eucalyptus Ester) EEP (trade name, manufactured by Yong Bei Corporation), and alcohols such as butanol, isopropyl Butanol and ethylene glycol monobutyrate. Polymerization initiators include, for example, peroxides such as tert-butylperoxy-2-ethylhexanoate, benzamidine peroxide and diphenylmethaneperoxide, and azo-based initiators such as azodiffusion Butyl 2,2 ,. Even Mo dimethylvaleronitrile). The reaction temperature is usually adjusted to ⑼ to ⑼, and is preferably 80. (: To 14 ° C. The reaction end point is determined by the stability of the viscosity of the reaction solution. As a result, the polyolefin elastomer having a number average molecular weight of 3,000 to 200,000, and preferably 10,000 to 1〇 〇〇〇〇〇. When the average number of points: the amount is less than 3, the appearance of the coated composite film is inferior. On the contrary, when the average molecular weight of the field number exceeds 20,000, the polyolefin elastomer in the solvent Its solubility is poor. In addition, it is preferred that the dilute hydrocarbon elastomer has a warp group and / or a silk. A better polylean L elastomer has both a carboxyl group and a carboxyl group. By making Xiaohan—or multiple official 200427795 energy groups The polyolefin elastomer can further improve the physical properties and chip-resistant properties of the resulting coated composite film. The acid value of the polyolefin elastomer is preferably 1 to 50 mgKOH / g and more preferably 5 to 30. Mg KOH / g. When the acid value exceeds 50 mg KOH / g, the water resistance of the obtained 5 coated composite film decreases. In addition, the hydroxyl value of the polyolefin elastomer is preferably 1 to 200, and more preferably 50. To 150. When the hydroxyl value exceeds 200, the obtained coated composite film Water resistance is reduced. Based on the weight of the resin solid content, the content of the polyolefin elastomer (d) in the intermediate coating is 30 to 60% by weight and preferably 30 to 40% by weight. When the content is less than 30 %, The physical properties of the obtained coated composite film and the appearance of the coating film are not improved. When the content exceeds 60%, the compatibility of the coating is reduced, resulting in non-uniformity. By including a polyolefin elastomer as an intermediate The composition of the coating, the elongation of the coating film is improved, and the chip resistance of the coating film is also improved. In addition, the compatibility between the middle 15 coating film and the top coating film is reduced, and the base coating film or the transparent coating film will not penetrate into the wet The intermediate coating film can prevent the mixing of phases and improve the appearance, especially the gloss appearance. The block isocyanate compound (c) is used to harden the urethane-modified polyester resin (a) and polyolefin. The component of the elastomer (b). 20 The block isocyanate compound is obtained by adding a block agent to an aliphatic isocyanate or a derivative thereof. When the block isocyanate compound is heated, the block agent dissociates to generate an isocyanate group, different Cyanate groups harden materials by radical reaction with polyester resins modified with urethanes. Aliphatic isocyanates and their derivatives include, for example, those used to prepare polyester resins modified with amine 14 200427795 formate. Blocking agents include, for example, compounds having active methylene groups such as ethoxylated acetone, ethoxylated ethyl acetate, and ethyl malonate. By using a blocking agent, the elasticity of the coated composite film is improved The chip resistance of the coated composite film is also improved. 5 Block isocyanate compounds are sold, for example, by Asahi Chemical Industry Co., Ltd. as active methylene-type block isocyanates "Duranate MF-K60X". Intermediate paint The content of the block isocyanate compound (c) is 15 to 30% by weight and preferably 17 10 to 25% by weight based on the resin solid weight content of the coating. When the content is less than 15% by weight, the hardenability is insufficient; and when the content exceeds 30% by weight, the hardened film is too hard and brittle. The melamine resin (d) is not particularly limited, but includes a methylated melamine resin, a butylated melamine resin, or a methyl-butyl mixed melamine resin. Examples include r Cymel_303 ”,“ Symo 254 ”,“ U ban 128 ”and“ U 15 State 20N60 ”are sold by Mitsui Toyo Co., and the“ Sumimar ”series "Sold by Sumitomo Chemical. The content of the melamine resin (d) in the intermediate coating is at most 20% by weight, and more preferably 5 to 15% by weight based on the content of the resin solid content. When the content of the melamine resin exceeds 20% by weight, the hardened coating film becomes too hard and too brittle. The non-aqueous dispersion liquid resin (e) having a core-shell structure can be prepared by copolymerizing a dispersion stabilizer resin and a copolymerizable monomer in a mixed solution containing an organic solvent, and the copolymer is obtained to obtain non-crosslinked resin particles. Insoluble. Haihe bath. Copolymerization in the presence of political liquid resins is not particularly limited, as long as it is a group-polymerizable unsaturated monomer. In order to synthesize the above-mentioned entry stable resin and non-aqueous dispersion liquid, it is preferable to use a polymerizable monomer having a B group because the non-knife / night with functional group can be combined with a hardener and a dispersion liquid containing a functional group. The stabilization resin reacts to form a three-dimensionally cross-linked coated film. There is no special restriction on dispersion stabilizer resin, as long as it can be stabilized in organic solvents Inflammable ether resins, polycarbonate resins, polyurethane resins, etc., have a base value of 10 to 250 and preferably 20 to 180, and an acid value of 0 to 100 mg KOH / g and preferably. To 50 mg KOH / g and a number average molecular weight of 800 to 100,000 and preferably 1,000 to 20,000. When the foregoing parameters exceed the upper limit, the handling properties of the resin are reduced, and the handling properties of the non-aqueous dispersion are also reduced. When the parameter is lower than the lower limit, the coating film may be desorbed. When formulated into a coated film, the particle stability is reduced. The method for synthesizing stable resins of the knife solution is not particularly limited, but preferably includes a method of obtaining a resin through group polymerization in the presence of a group polymerization initiator, and a method of obtaining a resin through a condensation method or addition reaction. . In addition, the monomers used to obtain the stable resin of the dispersion can be appropriately used according to the properties of the resin, but it is preferable to use monomers having functional groups (such as hydroxyl groups, acid groups, etc.), which are used for synthesis Possibility of polymerizable monomers in non-aqueous dispersion (described later in detail).-If necessary, monomers having functional groups such as glycidyl, isocyanate, etc. can be used. In addition, the weight ratio of the dispersion resin and the polymerizable monomer may be arbitrarily selected according to the purpose of use. For example, based on the total weight of the two components, the dispersion stabilizer resin is 3 to 80% by weight, particularly 5 to 60% by weight, and the blendable monomer is 97 to 20% by weight and particularly 95 to 40. %weight ratio. In addition, based on the total weight, the total concentration of the dispersion stabilizer resin and the polymerizable monomer in the organic / glutarium is preferably 30 to 80% by weight, and particularly 40 to 60% by weight. The non-aqueous dispersion can be obtained by polymerizing a monomer in the presence of a dispersion stabilizer resin. In this non-aqueous dispersion, the preferred hydroxyl value is 50 to 400, preferably 100 to 300, the acid value is 0 to 200 mg KOH / 10 g and preferably 0 to 50 mg KOH / g and the average particle diameter (D50) is from 0.05 to 1 μm and preferably from 0 to 2 μm. When the parameter is below the lower limit, the particle shape cannot be maintained. When the parameter exceeds the upper limit, the stability of dispersion in the coating decreases. Representative examples of polymerizable monomers having a functional group used to synthesize the aforementioned non-aqueous dispersion are as follows. The monomer having a hydroxyl group includes, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxymethyl (meth) acrylate, allyl alcohol, and (fluorenyl) ) Adduct of hydroxyethyl acrylate and ε-caprolactone. On the other hand, the monomer having an acid group includes, for example, a polymerizable monomer having a carboxyl group, a sulfonic acid group, or the like. Examples of the monomer having a carboxyl group include (fluorenyl) acrylic acid, crotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride, fumaric acid, and the like. The polymerizable monomer having a sulfonic acid group includes, for example, tertiary butylacrylamide sulfonic acid and the like. When a polymerizable monomer having an acid group is used, it is preferable that a part of the acid group is a carboxylic acid group. 17 200427795 In addition, polymerizable monomers having functional groups include, for example, unsaturated monomers containing glycidyl groups such as glycidyl (meth) acrylate; and unsaturated monomers containing isocyanate groups such as m-isopropenyl , Α-Difluorenylfluorenyl isocyanate, acrylic isocyanatoethyl s, etc. 5 Other polymerizable monomers include, for example, alkyl (meth) acrylates, such as methyl (fluorenyl) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate Ester, n-butyl (meth) acrylate, third butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate , Lauryl (meth) acrylate, stearyl (meth) propenoate, and tridecyl (fluorenyl) acrylate; oil fatty acids and acrylic or methacrylate monomers with ethylene oxide structures Addition reaction products (such as the addition reaction products of stearic acid and glycidyl methacrylate, etc.); addition reaction products of ethylene oxide compounds containing (: 3 or more alkyl groups and acrylic acid or methacrylic acid, Styrene, α-methylstyrene, o-methylstyrene 15ene, m-methylstyrene, p-methylstyrene, p-third butylstyrene, methacrylate (meth) acrylate, Itaconic acid ester (dimethyl itaconate), maleic acid ester (maleic acid) Acid dimethyl ester), fumarate (dimethyl fumarate); and other polymerizable monomers such as acrylonitrile, methacrylonitrile, methisopropenone, vinyl acetate, Veoba monomer (manufactured by Shell Chemical Company 20, trade name), vinyl propionate, vinyl pivalate, ethylene, propylene, butadiene, N, N-dimethylaminoethyl acrylate , N, N-dimethylaminoethyl methacrylate, acrylamide and vinylpyridine. The polymerization reaction preferably used to obtain a non-aqueous dispersion is carried out in the presence of a group polymerization initiator. Group polymerization Initiators include, for example, azo-based initiators 18 200427795, such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile), peroxide Benzamidine, lauryl peroxide, tert-butyl peroctoate, etc. The amount of such initiator is preferably 0.2 to 10 parts by weight and preferably 0.5 to 100 parts by weight based on the total amount of polymerizable monomers. 5 parts by weight. It is preferred to use 5 for the polymerization of a non-aqueous dispersion obtained from an organic solvent containing a dispersion stabilizer resin. It is usually carried out at a temperature range of about 60 ° C to 160 ° C for 1 to 15 hours. In addition, the non-aqueous dispersion is a particle component in a coating different from the cross-linked polymer particles, but it has a coating composition The film does not form the characteristics of the particle structure. In other words, the difference between the non-aqueous dispersion and the crosslinked polymer particles is that since the particles do not have crosslinked sites, the shape of the particles changes during the baking process and can be a resin component. For example, it is also possible to use resin particles called NAD (non-aqueous dispersion), which is described in Coloring Material No. 48 (1975), pages 28-34, and is used for NAD 15 coatings. Based on the weight of the resin solid content The content of the non-aqueous dispersion resin (e) of the intermediate coating is 15% by weight and preferably 5 to 12% by weight. When the content exceeds 15% by weight, the cut-resistant chip performance decreases. By using the non-aqueous dispersion resin (e), it is possible to prevent miscibility between the coating layers and improve the appearance. As for flake pigments, mica, alumina, talc, and silica can be used. From the viewpoint of chip performance, talc is preferred. Preferred flake pigments ⑴ have a size having a long diameter of 1 to 10 m and a number average particle diameter of 2 to 6 m. When the long diameter is out of this range, 19 200427795, the appearance of the film is inferior, and sufficient cut-resistant wafer performance cannot be obtained. When the diameter of the particles is outside the foregoing range, the appearance of the coated film is deteriorated, and sufficient chip-cutting resistance cannot be obtained. The content of the flake pigment ⑴ 5 is 0.4 to 2 parts by weight based on 100 parts by weight of the resin solid content. It is more preferably 0.5 to 1.5 parts by weight. When the content is outside this range, the adhesiveness with the undercoat film is reduced, and sufficient chip-cutting performance cannot be obtained. Other resins that can be included are not particularly limited, including acrylic resins, polyester resins, alkyd resins, epoxy resins, and the like. These resins can be used alone or in combination of two or more. Colored pigments include, for example, azo-chelated pigments, insoluble azo-based pigments, azo-based pigments, phthalocyanine-based pigments, and benzonaphthone-based pigments. Pigments, pigments based on dinaphthol, pigments based on dioxane, pigments based on fluoracridone, pigments based on iso 15 indololinone, metal complex pigments, etc. As an organic base. As for the inorganic base, chrome yellow, yellow iron oxide, red iron oxide, carbon black, titanium dioxide, and the like can be used. In addition, as for the extender pigment, carbon monoxide, barium sulfate, aluminum powder, kaolin, and the like can be used. As the main pigment, a gray-based coloring pigment containing carbon black and titanium dioxide is used. In addition, coloring pigments having a color tone compatible with that of the top coat, and a combination of various pigments can also be used. In addition, in order to prevent each layer from being compatible with the top coating film and maintain the coating workability, a rheological agent may be added to the aforementioned intermediate coating. Rheological agents include, for example, materials that generally have thixotropic properties, such as polyamine-based chemicals such as 20 200427795 fatty acid amidoamine, fatty acid amidine, long-chain polyamine ammonium phosphate, and swelling dispersions ; Chemical agents mainly based on polyethylenimine + red, such as polyethylene oxide, etc .; Chemical agents based on organic 4 soil such as organic acid smectite, montmorillonite, etc., organic pigments such as Shixi acid shao, sulfuric acid lock, etc .; the viscosity of flake pigments is determined by the shape of the pigment, crosslinked resin particles, etc. The total solid content of the intermediate coating used in this hair month is 30 to 80% by weight and preferably% to ㈣ by weight when applied. When the content is within this range ίο 15

Bu Cai, the main ingredients of the private degree decreased. When the content exceeds the upper limit, the viscosity is too high. When the content is lower than the lower limit, the viscosity is too low, and appearances such as various layers> valley mixing and unevenness appear. In addition to 4 aliquots, other additives commonly added to coatings, such as surface modifiers, defoamers, and defoamers, can also be blended into the intermediate coatings used in the present invention. The mixing amount is in a range known to those skilled in the art. In addition, other resins may be contained in the urethane-modified polyester resin. There are no special restrictions on this resin, but it includes acrylic resins, polyesters

Resin, alkyd resin, epoxy resin, etc. The resin may be used alone or in combination of two or more. A method for preparing the coating composition used in the present invention includes the methods described below and is not limited. Any method well known to those skilled in the art, such as mixing and dispersing pigment compounds with a kneader, roller, and SG mill, is used. Either method can be used. Undercoating film The undercoating film used in the coating film forming method of the present invention is used to form a topcoating film using a clear coating. This primer contains film-forming resins, hardeners, pigments, and pigments, etc., if necessary. The film-forming resin contained in the aforementioned primer is not particularly limited, and examples thereof include acrylic resins, polyesters, alkyd resins, epoxy resins, and urethane resins. These resins may be used alone or in combination of two or more. The aforementioned film-forming resin can be used in combination with a hardener. From various viewpoints of the effectiveness and the cost of the resulting coating film, it is more economical to use silk tree // block isocyanate resin.

Based on the solid content and weight of the film-forming resin, the hardener contains H) in an amount of preferably from 20 to 60% by weight and more preferably from 鄕 to 鄕 by weight. When the content is less than 20% by weight, the hardening ability is insufficient. When the content is higher than 60% by weight, the hardened film is too hard and brittle. The coloring pigment may include, for example, a coloring pigment exemplified for the intermediate coating material. 15 There is no particular limitation on the shape of the metallic pigments optionally contained in the primer

system. Metal pigments can be colored. For example, a metal pigment having an average particle diameter (D1 is 2 to 50 micrometers and a thickness of 0.1 to 5 micrometers is preferred. In addition, a metal pigment having an average particle diameter in the range of 10 to 35 micrometers is excellent in gloss appearance and is suitable for use. The pigment concentration (pwc) of the metallic pigment in the aforementioned coating is usually 20% by weight or less. The concentration is preferably from 0.01 to 18.0% by weight, and more preferably from 0.1 to 15.0% by weight. When metal When the content of the pigment Z exceeds 20.0% by weight, the appearance of the coating film decreases. The aforementioned metallic pigments include, for example, metals or alloys such as aluminum, copper, copper, iron, nickel, tin, and oxides and mixtures thereof. Tinted or 22 200427795 Tinted metallic pigments. In addition, interference mica pigments, muscovite pigments, graphite pigments, and other pigmented or uncolored flake pigments can also be used in combination. In coatings, metallic pigments and all other pigments The total pigment concentration (PWC) 5 is 0.1 to 50% by weight, preferably 0.5 to 40% by weight, and more preferably 1.0 to 30% by weight. When the concentration exceeds the upper limit, the appearance of the coating film decreases. Besides As in the intermediate coating, in order to maintain the coating workability, it is preferable to add a rheological agent to the base coating. The rheological agent is used to form a coating film without unevenness and depression, and usually contains a chemical agent having thixotropic properties. 10 kinds of rheological agent, which may contain the rheological agent exemplified for the aforementioned intermediate coating. In addition to the foregoing components, additives such as surface modifiers, rheological agents, antioxidants, ultraviolet light inhibitors and defoaming agents usually added to coatings It can also be blended with the primer used in the present invention. The blending amount is within the range known to those skilled in the art. 15 The base coating used in the present invention has a total solid content of 10 to 60% by weight when applied. It is preferably 15 to 50% by weight. When the content is higher than the upper limit or lower than the lower limit, the stability of the coating is reduced. When the content exceeds the upper limit, the viscosity is too high and the appearance of the coating film is reduced. When the content is lower than the lower limit, the viscosity is too low In order to form a transparent coating film, a transparent coating is used. The transparent coating is not particularly limited, but it can be used with film-forming heat. Transparent coatings for resins and hardeners. As for transparent coatings, such as solution type, water-based type and powder type. 23 200427795 In terms of transparency and resistance to acid etching, solution type transparent coatings preferably include acrylic resins. And / or a combination of a polyester resin and an amine resin, an acrylic resin and / or a combination of a polyester resin and an isocyanate compound, and an acrylic resin and / or a polyester 5 resin having a carboxylic acid-epoxy curing system. Water-based transparent coatings include, for example, resin-containing coatings, which are obtained by neutralizing the film-forming resin of the aforementioned exemplary solution-type transparent coatings with an alkali, and are not easily water-based. Neutralization can be added before or after polymerization by adding Tertiary amines such as dimethylethanolamine and triethylamine are carried out. 10 Conversely, as the powder type clear coating, conventional powder coatings such as thermoplastic powder coatings and thermosetting powder coatings can be used. Because it contains a coating film with better physical properties, a thermosetting powder coating is preferred. Thermosetting powder coatings include, for example, powder transparent coatings mainly composed of epoxy resins, acrylics and polyester resins, but powder transparent coatings based on acrylics 15 which have better weather resistance are special good. As for the powder-type transparent coating used in the present invention, since it does not contain volatile substances when hardened, it can obtain better appearance and rarely yellowing, so it is based on epoxy resin containing acrylic resin / polyvalent carboxylic acid-based powder coating. Especially good. In addition, as with intermediate coatings, in order to maintain coating workability, it is preferred to add a rheological agent to the clear coating. As for rheological agents, they usually contain chemicals with thixotropic properties. As for the rheological agent, the rheological agent exemplified for the intermediate coating may be contained. If necessary, a hardening catalyst, a surface conditioner, and the like may be contained. Substrate 24 200427795 The coated film forming method of the present invention is preferably used for various substrates, such as metal, plastic, foamed materials, etc., especially metal surfaces and castings. Metals and shaped articles are preferred. This method is particularly suitable for metal products that can be coated with cations. 5 The aforementioned metal products include, for example, iron, copper, metal, tin, zinc, and the like, and alloys containing these metals. Specific embodiments include car bodies and components of automobiles, trucks, motorcycles, buses, and the like. Particularly preferred metals are those that have been chemically treated in advance with phosphates, chromates, and the like. In addition, in the substrate used in the method for forming a metal coating film of the present invention, the electrodeposition coating film can be formed on a chemically-treated steel sheet. As for the electrodeposition coating for forming an electrodeposition coating film, a cationic or anionic type can be used, and a cationic electrodeposition coating composition is preferable, and the coating can obtain a coating film with excellent corrosion resistance. Coating film forming method 15 In the coated thin film forming method of the present invention, the intermediate coating film is formed by the intermediate coating, the base coating film is formed by the base coating, and the transparent coating film is formed by the transparent coating. Formed successively on a substrate in a wet-on-wet manner. When the car body is coated with the intermediate coating according to the present invention, in order to improve the appearance of 20 liters, the film may be formed by multi-stage coating, preferably 2-stage coating by air electrostatic spraying; or by using a rotating mist Electrostatic coating machine [referred to as "micro micro-belt machine (// // (micro micro) bel)", "micro-belt machine (/ (micro) bel)" or "metabel machine (metabel") is formed. The thickness of the dry coating film formed by the intermediate coating of the present invention varies according to the intended use 25 200427795. In many cases, a thickness of 10 microns to 60 microns can be used. When the thickness exceeds the upper limit, the sharpness of the image decreases, and in some cases the Layers have disadvantages such as unevenness and depression; and when the thickness is below the lower limit, the surface may be covered and uneven coating may occur. 5 In the coated film forming method of the present invention, the primer and transparent coating are wet The application method is applied on the unhardened intermediate coating film to form a base coating film and a transparent coating film. The base coating used to form the base coating film in the method of the present invention can be electrostatic sprayed, or a Rutabex machine can be used. , Pico shell machine, pico shell machine, etc. Rotary atomizing electrostatic 10 coater coating. The dry thickness of the coating film is set to 5 to 35 micrometers, and preferably 7 to 25 micrometers. When the thickness of the base coating film exceeds 35 micrometers, the sharpness of the image decreases, in some cases Unevenness or dents appear under the surface. When the thickness is less than 5 micrometers, the surface covering properties are insufficient, and occasionally a non-uniform coating (discontinuous film state) appears. In the coating film forming method of the present invention, when the base coating film is formed, it contains a base 15 When the coating film and the metal pigment are irregular, a transparent coating film is formed, and the coating film is protected by covering the raised portions caused by the irregularity. As for the coating method, the newly described suspicious atomization electrostatic coating is more widely used. Coating machines such as picoshell machines, microshell machines, etc. form thin films. The dry thickness of the transparent coating film formed by the transparent coating is preferably about 10 microns to about 80 microns, and more preferably about 20 microns to 6G microns. When When the thickness exceeds the upper limit, defects such as bursting and dents appear under certain conditions. When the thickness is lower than the lower limit of 0 °, the sharpness of the image is reduced. The coated composite film thus paid receives the formation of the coating film by hardening at the same time. That is the second coating film In this case, 26 ^ υυ427795 < and two-use ovens and drying ovens can be deleted, so it is better from an economic and environmental perspective. Ren. Hai method requires the so-called reliance, the preheating step is between coating The step of removing the volatile material of the wet film with wind between the steps. For example, it can be heated at 40 ° C to 100c for about 1 to 5 minutes. The hardening temperature of the coated composite film Set at 10 0 ° C to 18 0 C 'and preferably 13 (rc to 160 ° C, a hardened coating film with a high degree of crosslinking can be obtained. When the temperature is higher than the upper limit, the coating film becomes hard and brittle. # The temperature is below the lower limit, the sclerosis is insufficient. The hardening time varies with the hardening temperature, but is suitable for 130 ° C to 160. (: Hardened for 10 to 30 minutes. The film thickness of the coated composite film formed by the present invention is usually 30 to 300 microns, and preferably 50 to 25 microns. When the upper limit is exceeded, the film properties (such as Properties such as temperature cycle test) decrease. When the lower limit is lowered, the film strength decreases. According to the present invention, even if the coated composite film is formed by the three coating film drying method at a time, the method includes sequentially wet-wet method Forming the intermediate coating film, the base coating film and the transparent coating film, and then curing the coating film once, can still obtain a coated composite film with excellent chip resistance and coating film appearance. The intermediate coating coating composition of the present invention can The impact when dicing the wafer provides repulsive force and has the property of converting the impact energy into thermal energy to the coating. As such, the coated composite film obtained by the present invention has excellent dicing wafer resistance properties, even after receiving Under severe impact, only a small peeling area is displayed and peeling is less likely to occur. The coated composite film forming method of the present invention includes sequentially forming an intermediate coating film, a base coating film, and Bright coating film, because the baking drying oven step of 27 200427795 coating films can be eliminated, it is very good to say Lin and Huan. In this way, the present invention provides a number of advantages for the obtained coated composite film, such as dicing wafers Excellent properties, enhanced physical properties and good appearance. Example 5 The present invention will be described in detail in the following examples, but the present invention is by no means limited to these examples. The "parts" and "percentages" in the following are based on Preparation Example 1 Preparation of urethane-modified polyester resin (a) 10 440 parts of isophthalic acid, 20 parts of hexahydroophthalic acid, 40 parts of azelaic acid, 300 parts of trihydroxy Methylpropane and 200 parts of neopentyl glycol are placed in a 2 liter reaction vessel; the reaction vessel is equipped with a nitrogen introduction tube, a stirrer, a temperature regulator, an addition funnel, and a cooling tube equipped with a decanter; when the raw materials are dissolved by heating When it becomes stirable, add 0.2 parts of dibutyltin oxide and start stirring. The temperature of the 15 layers of reaction is gradually increased from 180 ° C to 220 ° C for 3 hours. The condensation water produced is removed by distillation of the system. When the temperature reaches 220 ° C, maintain this temperature 1 hour, slowly add 20 parts of xylene to the reaction layer, allowing the condensation reaction in the presence of a solvent. When the resin acid value reaches 10 mg KOH / g, the material is cooled to 100 ° C, and slowly added 1 in 30 minutes. 〇part of hexamethylene diisocyanate. In addition, the temperature was maintained for 1 hour, 200 parts of xylene and 200 parts of butyl acetate were added to obtain a urethane-modified polyester resin having a solid content of 70. %, Average molecular weight 2000, acid value 8 mg KOH / g 'M group value 120 and resin Tg 60 ° C. Preparation Example 2 28 200427795 Preparation of polyolefin elastomer (bl) 650 parts of α, ω-hydrogenated polymer Butadiene glycol ("Gi-io00", manufactured by Soda Corporation, Japan) and 650 parts of toluene were placed in a suitable reaction vessel. The reaction vessel was equipped with a thermometer, stirrer, cooling tube, nitrogen introduction tube, and addition funnel. , 5 The temperature rose to 50 ° C. In the reaction trough, 1% of isophorone diisocyanate and 96 parts of toluene solution were added dropwise over a period of 1 hour, and the temperature was maintained at 50. 〇 1 hour. Then the temperature of the reaction vessel was raised to 85 ° C, 56 parts of methyl propionate and 56 parts of methylbenzyl solution were added dropwise over 1 hour, and maintained at 8 for 1 hour. Cooling to obtain mainly polyolefin Macromonomer solution (solid content 50%). 10 25.6 parts of a monomer solution mainly composed of polyhydrocarbons and 83.2 parts of toluene were placed in a suitable reaction vessel 'and the temperature was raised to 110 ° C. In addition, 20.0 parts of butyl acrylate, 29.0 parts of butyl methacrylate, 2.2 parts of methacrylic acid via butyl acrylate, and 1.5 parts of butyl peroxy-2-ethylhexanoate were mixed to obtain a solution, and the solution was allowed to stand for 3 hours. Time was added dropwise to the reaction vessel while stirring the inside thereof. Subsequently, the reaction vessel was maintained at 110 ° C for 30 minutes. A solution of 0.5 part of tert-butylperoxy-2-ethylhexanoate and 5.0 parts of toluene was added dropwise over a period of 30 minutes. After continuous stirring for 90 minutes, the material was cooled to obtain a polyolefin elastomer (b-1) solution (solid content 40%). The obtained polyolefin elastomer (M) had physical property data: number average 20, molecular weight 20,000, and hydroxyl value 20. Preparation Example 3 Preparation of Polyolefin Elastomer (b-2) 650 parts of α, ω-hydrogenated polybutadiene glycol ("GI-i0000", manufactured by Soda Corporation, Japan), 692.1 parts of toluene and 42.1 parts Maleic anhydride placed in the appropriate reaction 29 200427795

Vessel 'The reaction vessel is equipped with a thermometer, a stirrer, a cooling tube, an inlet tube and an addition funnel. The reaction vessel was pressurized and raised to 130 ° C. Degree until the abnormal peak of acid anhydride (1780 cm-1) measured by FT-IR disappears; ′ The material is cooled to obtain a polyolefin-based macromonomer solution (solid content 50%).

102.9 parts of polyolefin-based comonomer and 0.30 parts of methylbenzyl were placed in a suitable reaction vessel 'and the temperature was raised to 110 ° C. In addition, 9.3 parts of butyl acrylate, 10.0 parts of butyl methacrylate, 10.0 parts of maleic acid, 9.0 parts of hydroxyethyl acrylate, 10.0 hydroxybutyl methacrylate, 3.2 parts of methacrylic acid 10 It was mixed with 1.5 parts of tert-butylperoxy-2-ethyl hexanoate to obtain a solution, which was added dropwise to the reaction container over a period of 3 hours while stirring the inside. The reaction vessel was then maintained at 110 ° C for 30 minutes. A solution of 05 parts of tert-butylperoxy-2-ethylhexanoate and 5.0 parts of toluene was added dropwise thereto over a period of 30 minutes. After continued searching for 90 minutes, the material was cooled to obtain a polyolefin elastomer (b-2) solution (solid content: 40%)

The obtained polyolefin elastomer (b-2) had the following properties: a number average molecular weight of 40,000, a base value of 100, and an acid value of 20 mg κοκ / g. Preparation Example 4 Preparation of Non-Aqueous Dispersion Liquid 20 (a) Preparation of dispersion liquid stabilizer resin 90 parts of butyl acetate was placed in a container equipped with a stirrer, a temperature controller, and a reflux condenser. Then 20 parts of the solution had the following composition: 30 200427795 [Table 2] 38.9 parts of methyl methacrylate, 38.8 parts of stearyl methacrylate, 38.8 parts of 2-hydroxyethyl acrylate, 22.3 parts of azoisobutyronitrile, 5.0 parts were added thereto, Increase the temperature by heating and stirring. 85 parts of the remaining mixed solution was added dropwise at 110 ° C for 3 hours, and then 5 0.5 parts of azobisisobutyronitrile and 10 parts of butyl acetate solution were added dropwise over a period of 30 minutes. The reaction solution was stirred under reflux for 2 hours to increase the rate of change to resin. After the reaction was completed, an acrylic resin was obtained with a solid content of 50%, a number average molecular weight of 5600, and an SP value of 9.5. (b) Preparation of non-aqueous dispersion liquid 10 90 parts of butyl acetate and 60 parts (a) Preparation of dispersion resin stabilized acrylic resin, placed in a container, the container is equipped with a stirrer, condenser and temperature controller . Then a solution with the following composition: [Table 3] Styrene 7.0 parts methacrylic acid 1.8 parts methyl methacrylate 12.0 parts ethyl acrylate 8.5 parts 2-hydroxyethyl acrylate 40.7 parts azoisobutyronitrile 1.4 parts 15 Add dropwise at 100 ° C for 3 hours, and then add 0.1 part of azobisisobutyronitrile and 1 part of butyl acetate solution dropwise over 30 minutes. The reaction solution was continuously stirred for 1 hour to obtain an emulsion having a solid content of 60% and a particle diameter of 180 nm. This emulsion was diluted with butyl acetate to obtain a core-shell type butyl acetate dispersion with a non-aqueous dispersion content of 40%, a viscosity of 300 cps (25 ° C) and particles with a diameter of 31 200427795 and a diameter of 180 nm. This non-aqueous dispersion resin has a Tg of 23 ° C, a base value of 162, and an SP value of 11 · 8; the difference between the SP value of the dispersion-stabilized resin in the shell portion and the overall non-aqueous dispersion resin is 2.3. Example 1 5 Intermediate paint 1 14-3 parts of urethane-modified polyester resin obtained in the previous Preparation Example 1, 1,500 parts of BOR-904 (polyolefin elastomer, manufactured by Sakai Chemical Industry Company) , Ethylene / propylene copolymer, solid content 10%, acid value 4 mg KOH / g), 66.7 parts Duranate MF-K60X (block iso 10 hydrochloride, manufactured by Asahi Chemical Industry Co., Ltd., 60% solid content, 95 parts CR-97 (titanium oxide, manufactured by Ishihara Industries), 5 parts MA-100 (carbon black pigment, manufactured by Mitsubishi Chemical Corporation), and 0.1 part Disparon 4200 -20 (anti-settling agent, manufactured by Kusumoto Chemical Co., Ltd.) was placed in a 1 liter container, mixed with a disperser, and GB503M (glass beads with a particle diameter of 1.6 15 mm) equal to the weight of the mixture was added, and a desktop SG mill was used. The machine disperses at room temperature for 2 hours. When the dispersion is completed, the particle size measured by a grinder is 5 microns or less. The glass beads are filtered to remove the intermediate coating. This coating uses a No. 4 Ford cup with toluene / Swazole- 100 (aromatic hydrocarbon solvent, manufactured by Exxon) = 1/1 mixed solvent diluted to 20 seconds / 20 ° C The solid content of the diluted coating is 25% 20 and the pigment concentration (PWC) is 50%. The base coating is based on acryl melamine-based metal base pigment "Orga TO H600 1 Magic Green Metal" ( Nihon Paint Co., Ltd.) uses a No. 3 Ford cup with 32 daggers of ethoxyethyl propionate / S-100 (aromatic hydrocarbon solvent, manufactured by Exxon Corporation). The mouth is diluted to 17 #, / 2 (rc. The non-volatile content when the coating is applied is 31%. The non-volatile content when it is deposited is 65%. Transparent coatings 5, transparent text [Original ^ oxygen tree month hardening-based transparent coating "Mack" ^ 〇〇 "Transparency" (manufactured by Japan Coatings Co., Ltd.) uses No. 4 Ford Cup, diluted with acetoxy propionate / S "00 (aromatic hydrocarbon solvent, manufactured by Exxon Corporation) to% sec / 20t. When coating is applied The non-volatile matter content is 此外. In addition, the non-volatile matter content at the time of deposition is 61/0. Coated film formation method 10 Cationic electrodeposition coating "Power Top V-20" (Say, manufactured by this coating company) Electrodeposition coating on SPC steel plate, the thickness of the steel plate is 0.8 mm, the length is 30 cm, and the length is 10 cm. It is treated with scaly acid, and is coated by electrodeposition to form a coating film with a dry film thickness of 20 micrometers, followed by ⑽. ◦ Bake and dry for 30 knives and 4 miles. Then the coating plate is adhered to the moving body and is moving. 15 Using a "micro-shell machine" (rotary atomizing electrostatic coating machine) to coat the aforementioned intermediate coating. The dry film thickness became 20 microns, and it was cured in 10 minutes after application. Then, the aforementioned primer was divided into two stages Using the "micro shell machine" and "meta shell machine" in two stages, the dry film thickness became 15 microns. The interval between the two applications was 2.5 minutes. After the second application, it was cured for 8 minutes. Then, the above-mentioned transparent coating was coated with a "micro-shell machine" in one stage, and the dry film thickness was changed to 35 micrometers' for 7 minutes for curing. The resulting coated plate was then dried in a dryer at 140 ° C for 30 minutes. Thin film evaluation method For the obtained coated plate, WS-DOI (thin film appearance measuring device, 33 200427795 manufactured by Bick Chemical Co., Ltd.) was used. Compare the coated eight pairs. Brick film appearance. By WS-DOI, the evaluation of the appearance of the coating film, especially the appearance of the gloss, is expressed by ^ value. As the Wa value becomes smaller, a glossy appearance appears, and the outer I gauge is better. In addition, the cut-resistant wafer properties of the obtained coated plate were evaluated by using a glabero tester (produced by Suga Testing Instrument Co., Ltd.) 3⑼ pieces of No. 7 crushed stone from a distance of 35 cm and an air pressure of 3.0 Kgf / cm2 impacted the film at an angle of 45 degrees. After washing with water and drying, peeling gas was examined using an industrial adhesive tape manufactured by Nichiban, and then the diameter and number of glass were visually observed and evaluated for the degree of peeling. ίο The evaluation of the elongation of the intermediate coating film is as follows: the application of the intermediate coating is also used for polypropylene plates with a thickness of 3 mm. The dry film thickness becomes 40 to 60 microns, and it is cured by biting for about 20 minutes, and then at 140 ° C. Bake for 20 minutes. The obtained film was cut into a free-state film having a drinking part, 5 cm in length and 1 cm in width, and peeled from a polypropylene plate to form a seed and a carrier. For this free-state film, the elongation was measured at a rate of 10 mm / min at 20 ° C using a 15-force tester ("Tensilon", manufactured by Toyo Boldwin Co., Ltd.) at a rate of 10 mm / min. rate. ^ The foregoing results are shown in Table 4. Example 2 Intermediate Coating 2 20 28.6 parts of the urethane-modified resin obtained in the previous Preparation Example 1, 148 parts of PP-2001 (polypropylene-based elastomer, 3 A, manufactured by Yuekai Chemical Co., Ltd., with a solid content of 27%, an acid value of 6.6 mgKOH / g, a light base value of 13,16.7 parts U-128 (melamine resin, made by Mitsui & Sitec Corporation & 60% of content), 33.3 parts of MF-K60X (active methylene block & 34 200427795 ester manufactured by Asahi Chemical Industry Co., solid content of 60%), 25 parts obtained from the previous Preparation Example 4 Non-aqueous dispersion, 39.2 parts of CR-97 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.), 2.9 parts of MA-100 (carbon black pigment, manufactured by Mitsubishi Chemical Co., Ltd.) '0.1 part of Desbaron 4200-20 (anti- Settling agent, manufactured by Kusumoto Chemical Co., Ltd.) 5 and 0.W * LMS-300 (talc, manufactured by Fuji Talc) placed in a 1 liter container. 'Mix with a disperser, add GB503M (having a particle diameter of 1.6 mm) Glass beads), using a desktop sG mill to disperse at room temperature for 2 hours and 0 inches. When the dispersion is complete, use a grinder to measure a particle size of 5 microns or Below. The glass beads were removed by filtration to obtain an intermediate coating. This coating used No. 4 Ford cup and was diluted with 10 曱 ben / Swadzu-100 (aromatic hydrocarbon solvent, manufactured by Exxon) = 1 / i mixed / cereal dilution 20 seconds / 20. (3. The solid content of the coating after dilution is 46% and the pigment concentration (PWC) is 30%. In the same manner as in Example 1, but using the aforementioned intermediate coating 2 instead of the intermediate coating 1, The coated composite film was prepared and evaluated as described above. 15 The results are not shown in Table 4. Example 3 Intermediate coating 3 4.3 parts of the urethane-modified polyester resin obtained in the previous preparation example, 125 parts Polyolefin elastomer (bj) obtained in the previous Preparation Example 2, 66.7 parts of 20 MF_K60x (block isocyanate, manufactured by Asahi Chemical Industry Co., Ltd.), solid matter 60 /. '95 wound CR-97 (titanium oxide, Ishihara Industry Co., Ltd.), 9 parts of Ten-100 (Carbon black pigment, manufactured by Mitsubishi Chemical Corporation) and 4 parts of Disparon 4 Trace 20 (Anti-settling agent, manufactured by Kusumoto Chemical Co., Ltd.) Pigments were prepared in a similar manner to the intermediate coating 1 of Example 1. The solids of the resulting diluted coating 35 200427795 contained The amount was 51%, and the pigment concentration (PWC) of the coating was 50%. According to the same manner as in Example 1 but using the aforementioned intermediate coating 3 instead of the intermediate coating 3, a coated composite film was prepared and evaluated in a similar manner. The results are shown in Table 4. 5 Example 4 Intermediate Coating 4 28.6 parts of the urethane-modified polyester resin obtained in the previous Preparation Example 1 and 99.9 parts of the polyolefin elastomer obtained in the previous Preparation Example 3 (b -2), 16.7 parts U-128 (melamine resin, manufactured by Mitsui Citigroup, solid content 60%) 10, 33.3 parts MF-K60X (reactive methylene block isocyanate, Asahi Chemical Industry Co., Ltd. Manufacturing, solid content 60%) '25 parts of the non-aqueous dispersion obtained in the previous Preparation Example 4, 39.2 parts of CR-97 (titanium oxide, manufactured by Ishihara Industries), 2.9 parts of MA-100 (carbon black pigment, Mitsubishi Chemical (Manufactured by the company), 0.1 parts of Desbaron 4200-20 (anti-settling agent, manufactured by Nanbu Chemical Co., Ltd.) and 0.8 parts of LMS-300 (15 talc, manufactured by Fuji Talc) were placed in a 1 liter container, similar to the implementation of 2 Coating 2 was prepared as a coating method. After dilution, the solid content of the coating is 45%, and the pigment concentration (PWC) is 30%. According to the same manner as in Example 1, but using the aforementioned intermediate coating 2 instead of the intermediate coating 4, a coated composite film was prepared and evaluated in a similar manner. The results are shown in Table 4. Comparative Example 1 Intermediate paint 5 107 parts of urethane-modified polyester resin varnish obtained in the previous Preparation Example 1, 280 parts of CR-97 (titanium oxide manufactured by Ishihara Industries), 13 parts of 36 200427795 MA-100 (Carbon black pigment, manufactured by Mitsubishi Chemical Corporation), 7 parts of MS-100 (scaly talc, manufactured by Fuji Talc), 47 parts of butyl acetate and 47 parts of xylene are placed in a 1 liter container and mixed with a disperser, and placed with The total amount of feed was GB503M (glass beads with a diameter of 1.6 mm), and the material was dispersed at room temperature for 3 hours using a table-type SG mill for 3 hours to obtain a gray pigment paste. When the dispersion was completed, the particle diameter was 5 micrometers or less as measured using a grind meter. The glass beads are filtered to obtain a pigment paste. To 100 parts of this pigment paste, 24 parts of urethane modified urethane resin prepared in Preparation Example 1 and 24 parts of MF-K60X (reactive methylene block isocyanate, manufactured by Asahi Chemical Industry Co., Ltd., solid 60% of content), and 24 parts of 10 U-20N60 (melamine resin, manufactured by Mitsui & Citigroup, solid content of 60%). A mixed solvent of ethoxyethyl propionate / S-100 (aromatic hydrocarbon solvent, manufactured by Exxon) = 1/1 was added thereto, and the material was diluted to 19 seconds / 20 ° C using a No. 4 Ford cup. The solids content of the paint after dilution was 49% and the pigment concentration (PWC) of the paint was 30%. 15 In the same manner as in Example 1, but using the aforementioned intermediate coating 2 instead of the intermediate coating 5, a coated composite film was prepared and evaluated in a similar manner. The results are shown in Table 4. Comparative Example 2 CP-101 (cut wafer primer, manufactured by Japan Coatings Co., Ltd.) was spray-coated on a steel plate that had been subjected to electrodeposition coating and baking hardening, and had a film thickness of 5 micrometers, followed by using Comparative Example 1 with an intermediate coating 5 A coating film is formed. After being cured for 5 minutes, the intermediate coating film 5 described in Comparative Example 1 was used to form an intermediate coating film. Then, the same base coating and clear coating described in the example were used, and the coated composite coating was prepared as in Example i and evaluated in a similar manner. The results are shown in Table 4. 37 200427795 [Table 4] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Appearance ratio (Wa value) 25 21 21 19 21 29 The peeling diameter (mm) of the cut wafer 1.5 1.5 1.2 1.2 2.0 1.5 Number of peelings (block) 10 8 10 9 20 10 Elongation of intermediate coating film (%) 70 100 80 100 30 30 I: Simple explanation of the drawing] (None) Lu 5 [The main components of the drawing represent the symbol table] ( no)

38

Claims (1)

200427795 Scope of patent application: 1. A method for coating a composite film, comprising forming an electrocoating film on a substrate, and then applying an intermediate coating, a primer and a wet coating in a wet-on-wet manner. A clear coating, followed by three layers of baking and hardening, wherein the intermediate coating, based on the resin solid content, contains (a) 5 to 30% by weight of urethane modified It is a polyester resin with a number average molecular weight of 1,500 to 3,000, which is based on an aliphatic isocyanate compound and a hydroxyl-containing polyester resin having a glass transition point (Tg) of 40 ° C to 10 80 ° C. Obtained by reaction, the polyester is obtained by polycondensation of 80 mol% or more of phthalic acid and polyhydroxy alcohol, (b) 30 to 60% by weight of a polyolefin elastomer having an acid group and / or a hydroxyl group And (c) 10 to 30% by weight of a block isocyanate compound. 15 2. The method of claim 1, wherein the intermediate coating further comprises (d) up to 20% by weight of melamine resin based on the resin solid content. 3. The method of claim 1 or 2, wherein the intermediate coating further comprises 20 (e) up to 15% by weight of a non-aqueous dispersion liquid resin having a core-shell structure based on the resin solid content. 4. The method according to any one of claims 1 to 3, wherein the polyolefin elastomer (b) has an acid value of 1 to 50 mgKOH / g and / or a hydroxyl value of 1 to 200. 39 200427795 5. The method according to any one of claims 1 to 4, wherein the block isocyanate compound is a compound in which the hydroxyl group is in the latter stage of the compound having an active methylene group. 40 200427795 (1) Designated representative map: (1) The designated representative map in this case is: (). (None) (II) Brief description of the element representative symbols of this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: