TW446737B - Metallic material with organic composite coating excellent in corrosion resistance and coatability and reduced in finger mark adhesion and process for producing the same - Google Patents

Abstract

A metallic material having a surface excellent in corrosion resistance and coatability and reduced in finger mark adhesion. The coated metallic material comprises a metallic material having on a surface thereof: a first coating layer obtained from (A) a silane coupling agent ingredient having a reactive functional group such as an amino group having active hydrogen or an epoxy group and (B) a polymer ingredient comprising a water-soluble polymer represented by formula (I) having an average degree of polymerization of 2 to 50; and formed on the first layer, a second coating layer made of a resin composition comprising 100 parts by weight of a resin and 5 to 70 parts by weight of silica.

Description

A7 446 7 3 7 B7_ V. Description of the invention (1) [Detailed description of the invention] The invention relates to the ability to impart excellent corrosion resistance, coating properties, and resistance to fingerprint dirt on the surface of metal materials, and can be used for Metal materials for home appliances and building materials. [Previous Technology] Generally, metal materials such as zinc-plated steel plates and aluminum plates are used in a wide range of fields related to automobiles, building materials, and home appliances. However, zinc and aluminum corrode in the atmosphere and produce rotten uranium products (so-called white rust), which degrades the appearance of metal materials and adversely affects coatability, and there is a concern that products need to be manufactured through various operations at home. It is easy to bear fingerprints and other dirt through the operation of the operator, which significantly reduces the price of goods. Therefore, in order to improve the corrosion resistance, coating properties of the above-mentioned metal material surface, and the difficulty of bearing fingerprints, it is generally used in After the surface of the metal material is treated with chromate using chromic acid, dichromic acid, or a salt thereof as the main treatment liquid, the upper layer is coated with a metal material containing a polyolefin-based resin having a carboxyl group containing colloidal silica. However, in recent years, with increasing awareness of environmental protection, hexavalent chromium in the chromate treatment liquid used to treat the surface of metal materials has a direct adverse effect on the human body. Therefore, chromate treatment is far away. Also, the drainage of hexavalent chromium must undergo special treatment required by the Water Pollution Prevention Law, which increases the overall cost. In addition, the metal materials treated with chromate become industrial waste containing chromium, which has the major disadvantage of being unable to be recycled. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _:- --1 .------ install --------- order 1! ------- line- " 1 (Please read the precautions on the back before filling this page) Ministry of Economy The Intellectual Property Bureau employee consumer cooperative printed A7 446737 B7 V. Invention Description (2), and it became a big problem in society. On the other hand, as a surface treatment method other than chromate, a surface treatment agent using a tannic acid containing a polyvalent phenolcarboxylic acid is well known. When a metal material is treated with a tannic acid aqueous solution, a protective film is formed through the reaction of the tannic acid and the metal material. Since it becomes a barrier against the intrusion of corrosive substances, it is considered that it can improve the corrosion resistance of the aforementioned metal material. However, in recent years, with the improvement of the quality of products, the high corrosion resistance of the film itself is required. Therefore, the chromate alone or the film with an inorganic component is not sufficiently resistant to corrosion, and the status quo is impossible. Practical. Therefore, a treatment method for improving the corrosion resistance of a metal material is disclosed in Japanese Patent Application Laid-Open No. Sho 5 3-1 2 1 0 3 4 and coating a metal surface with a water-dispersible stone, an alkyd resin, and a trialkoxy group. Method of aqueous solution composed of silane compound. Also> A surface treatment method using a water-soluble resin composed of a hydroxypyridone compound derivative for the purpose of imparting resistance to metal materials, and a water-soluble or water-dispersible polymer using a hydroxystyrene compound to metal The method for imparting resistance to materials is disclosed in Japanese Patent Application Laid-Open No. 5 7 _ 4 4 7 5 1 and Japanese Patent Application Laid-Open No. 1-177380. However, "any of the above methods cannot form a film with excellent corrosion resistance that can replace the chromate film on the surface of the metal material", and the aforementioned problems of the actual problem have not been solved at all. Therefore, the current situation is that non-chromium-based surface treatment agents and surface treatment methods for metal materials with excellent corrosion resistance cannot be obtained = This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) I -Γ-- -^ ---- I · I --- I --- ^ · 111 ----- I-(Please read the precautions on the back before filling out this page) Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 446 7 3 7 __B7______ 5. Description of the invention (3) [Questions to be solved by the invention] (Please read the precautions on the back before filling out this page) The present invention is to solve the problem 1 of the previous technology to provide corrosion resistance Non-chromium organic composite coated metal materials with excellent properties, coating properties and fingerprint resistance are not easy for this purpose. [Means to Solve the Problem] In order to solve the problems of the prior art, the present inventors and the like have made repeated efforts to study. As a result, the first layer on the surface of the metal material has a silane coupling agent component and a specific component. A composition composed of chemically constructed polymer components is used as a film, and the second layer is on top of the first layer, which is covered with a silica-containing resin composition and found to have excellent corrosion resistance and coating properties, and Organic composite coated metal material that is not easy to bear fingerprint dirt, and its manufacturing method, and the present invention has been completed. The organic composite coated metal material of the present invention is on the surface of the metal material, and has the following components as the first layer: (A) an active hydrogen-containing amine group, an epoxy group, a vinyl group, a hydrogen thio group, and a methacryloxy group Silane coupling agent components composed of selected one or more silane coupling compounds having at least one reactive functional group and printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy (B) One or more of the following general formula (I) Polymer, one or more polymer components with an average degree of polymerization of 2 to 50: 〇 Η

X Υ 1 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 Gongchu) 4 46 7 3 7 A7 B7 V. Description of the invention (4) [However, in the formula, the X bonded to the benzene ring is Hydrogen atom, hydroxyl group, C! ~ C5 alkyl group, Ci-Cs hydroxyalkyl group, c6 ~ c12 aryl 'benzyl group, benzylidene group, unsaturated hydrocarbons condensed to the aforementioned benzene ring and forming naphthalene ring Family or the base of the following formula (II): Λ〇 (II) Υ 2 (Please read the precautions on the back before filling this page) Ν Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇 之 in formula (II) R1 and R2 each independently represent a hydrogen atom, a hydroxyl group,

Ci ~ C5 alkyl group, or (:: ~ (: " hydroxyalkyl group, in formulas (I) and (ϊ I), Y 1 and Y 2 bonded to a benzene ring each independently represent a hydrogen atom, or The Z group shown by formulae (III) and (IV): R 3 (ΠΙ) C Η R 4 R 5 CH 2 — Ν —R 6

• R 7 In the formulae (III) and (IV), R 6 and R 7 each independently represent a hydrogen atom and C (IV)

R 3, R 4, R This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A7 '4467 3 7 ____B7_ 5. Description of the invention (5) ~ Ci. Hydroxyalkyl, X, Y1, and Y2 bound to each benzene ring in the aforementioned polymer molecule may be the same as or different from each X, Y1, and Y2 bound to another benzene ring, and the aforementioned polymer molecule A film composed of an average number of substitutions of the aforementioned Z group in each benzene ring of 0.2 to 1.0], and the second layer is a layer above the first layer, and will contain 100 parts by weight of the resin and contains silica. It is characteristic that the resin composition is coated in a proportion of 5 to 70 parts by weight. The weight ratio (A) / (B) of the aforementioned silane coupling agent component (A) to the polymer component (B) used in the organic composite coated metal material of the present invention is preferably 1:10 to 10: 1. The aforementioned silane coupling agent component (A) used in the organic composite-coated metal material of the present invention is preferably a silane coupling agent composed of (a) one or more silane coupling agent compounds having one or more active hydrogen-containing amine groups, Silane coupling agent composed of (b) one or more silane coupling compounds having more than one epoxy silane group. The active hydrogen-containing amine group contained in the aforementioned silane coupling agent (a) used in the organic composite-coated metal material of the present invention is better than the equivalent of the epoxy group contained in the aforementioned silicon courtyard coupling agent (b). It is 3: 1 ~ 1: 3. The total amount of the aforementioned silicon courtyard coupling agent (a) and the aforementioned silane coupling agent (b) used in the organic composite-coated metal material of the present invention with respect to the aforementioned polymer component (B) [(a) + ( b)] / (B) is preferably 1: 5 to 5: 1. This paper size is in accordance with China Store Standard (CNS) A4 (210 X 297 mm) Ϊ l · -------- Packing---- Order_ Ί --Ί ---- I ^) / Ί (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4467 3 7 a? B7 V. Description of the invention (6) [Invention of Embodiment] The first film used in the organic composite-coated metal material of the present invention is a silane coupling agent component (A) composed of one or more silane coupling agent compounds having specific reactive functional groups, and contains a special amine Polymerization component (B) composed of one or more phenol resin-based polymers. If the silane coupling compound contained in the silane coupling agent component (A) used in the present invention contains at least one molecule selected from the group consisting of an active hydrogen-containing amine group, an epoxy group, a vinyl group, a hydrogen thio group, and a methyl group, Those having a propyleneoxy group as a reactive functional group are not particularly limited in their structure. If specific examples are listed, those having the following composition ① to ⑤ can be used. ① N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane with N- (aminoethyl) 3-aminopropyltrimethoxysilane, 3-trimethylpropyltriamine Ethoxysilane ② those with epoxy groups 3-reduced glyceryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl ) Ethyltrimethoxysilane ③ Vinyltriethoxysilane with vinyl group ④ 3 -Hydroxythiopropyltrimethoxysilane with oxythio group ⑤__ I ^ --- -^ ------ 装 -------- Order i, ------- Ί ^.) 1 (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) -9-446 73 7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (7) 3_Methacryloxypropyltrimethoxy Silane, 3-methylpropyloxypropylmethyldimethoxysilane The silane coupling agent component (A) used in the present invention is preferably one or more silanes having one or more amine groups containing active hydrogen. Coupling Silane coupling agent (a) composed of the composition, and having a silane-coupling agent (b) consisting of more than one kind of one or more epoxy groups Silane coupling compounds formed. In addition, the silane coupling agent component (A) used in the present invention is a silane coupling agent composed of a silane coupling compound having an amine group containing an active hydrogen! (a) When composed with an epoxy-containing silane coupling agent (b), the active hydrogen-containing amine group contained in the silicon courtyard coupling agent is preferably equivalent to the epoxy group's equivalent of 3: 1 ~ 1: 3 range. If the equivalent ratio of the active hydrogen-containing amine group to the epoxy group exceeds 3: 1, the film-forming property of the obtained film is poor, and the corrosion resistance and coatability are insufficient. When it is less than 1: 3, the anticorrosiveness and coatability of the treated film become saturated. Next, the polymer component (B) used in the present invention is an oligomer or polymer containing a polymerization unit represented by the aforementioned formula (I), and the average degree of polymerization of the polymerization unit of the formula (I) is 2 to 50. In formula (I), X bonded to a benzene ring is a hydroxyl group, a ci ~ C 5 group such as methyl, ethyl, propyl, etc., and a C 1 ~ C 5 hydroxy group such as hydroxymethyl, Hydroxyethyl, hydroxypropyl, etc., C 6 ~ C i 2 aryl groups such as phenyl and naphthyl, such as 'benzyl and benzylidene', are condensed to the aforementioned benzene ring and form an unsaturated hydrocarbon family of naphthalene rings, ie -CH = CH_CH = CH —, or = CH—C = CH—C = group, or a group of the aforementioned formula (II). R1 and R2 in formula (II) are each independently a hydrogen atom, and the size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 1 l · IIIII ^----- ί — ^ Order ------ IJ ί (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-4467 3 7 7 A7 ____ B7 V. Description of the Invention (8) Hydroxyl, Ci- Examples of the Cio alkyl group include methyl, ethyl, and propyl, and examples of the hydroxyalkyl group of Ci to Ci Q include hydroxymethyl, hydroxyethyl, and hydroxypropyl. In formulae (I) and (II), Y1 and Y2 bonded to a benzene ring are each independently a hydrogen atom, or have a Z group represented by formula (III) or (IV), and formula (:! II) And (IV), R3, R4, R5, R6, and R7 are independent of each other as (:! ~ (: &Quot;, such as methyl, ethyl, propyl, etc., and C 1 ~ C 5 hydroxyalkyl For example, via methyl, hydroxyethyl, hydroxypropyl, etc. X, Y 1 in formula (I) and Y 2 in formula (II) which are bonded to each benzene ring in the aforementioned polymer molecule may be respectively different from other benzenes. The X, Y1, and Y2 bound by the rings are the same or different. In addition, the average number of substitutions of the Z group of each benzene ring in the polymer molecule is 0.2 to 1 · 0. The average number of Z group substitutions値 refers to the number average of the Z groups introduced into the all benzene ring in the polymer molecule. For example, in formula (I), n = 10, and X is a benzene ring-containing group of formula (II) When the number of benzene rings per molecule of the polymer is 20, and one Z group is introduced into 10 benzene rings per one molecule of the polymer, the average number of Z group substitutions of the polymer molecule is 値Is [(lxio) + (〇χ10)] / 20 = 0 .5 ° If the average number of this Z group substitution is less than 0.2, the obtained polymer has insufficient adhesion to metal materials and the coating properties become poor. If it exceeds 1.0, the obtained polymer has The hydrophilicity is increased, and the uranium resistance of the obtained film is insufficient. R3 in the z group shown in formula (III) and formula (IV) ~ This paper's reverse degree applies to China National Standard (CNS) A4 (210 X 297) Mm) -11-I r .--- LI —--- pack .--- I --- r order ·! ----- line} 1 (Please read the precautions on the back before filling this page ) 446 7 3 7 A7 B7 V. Description of the invention (9) R7 represents an alkyl group of Ci ~ C1D, a hydroxyalkyl group of Ci-Ci. If the carbon number is 11 or more, the film is formed. The second layer used in the present invention is preferably coated with silica in an amount of 5 to 70 parts by weight relative to 100 parts by weight of the resin. More It is preferably 10 to 50 parts by weight. When the proportion is less than 5 parts by weight, there is no effect of improving the corrosion resistance of the upper layer coating, improving the effect of not easily attaching fingerprint dirt, and reducing the resistance of the resist to being difficult to adhere to fingerprints. . The colloidal silica used can be commercially available colloidal silica, organic silica gel, fumed silica, silica powder, and the like. Examples include Snowtex O, C, 〇S, N, and Japan Aerosil Co., Ltd. Aerosil 100, 200, 300, etc. Alas, its particle size is not particularly limited. The resin used in the coating of the second layer is preferably a resin having a hydroxyl group and / or a carboxyl group. Examples of such resins include commercially available epoxy resins, alkyd resins, acrylic resins, urethane resins, acrylic-modified polyester resins, phenol-modified alkyd resins, polyvinyl butyral resins, and phenol resins. , Melamine resin, ethylene acrylic resin, etc. The structure and molecular weight of these resins are not particularly limited, but must be within a range in which silica can be uniformly dispersed and contained. The second layer is covered with a coating weight of 0 ‘1 to 5. Og / m2 is preferred. When the upper layer coating is less than 0.1 g / m2, the touch resistance and the resistance to adhesion are not sufficient. The fingerprints are not sufficiently soiled. When it exceeds 5.0 g / m2, the paintability is particularly insufficient and the adhesiveness is insufficient. If necessary, the coating of the second layer can contain radon, and can also provide lubricity. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) ---- ^-J ----- 一Install i I (Please read the precautions on the back before filling this page) "SJ · line, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 446737 A7 ___B7 V. Description of the invention (10) In addition, the second layer of the cover is used for To the resin, if necessary, ordinary anti-casting pigments such as molybdic acid-based pigments, phosphate-based pigments, and anti-casting agents (for example, phenolic carboxylic acids such as tannic acid and gallic acid) may be added for corrosion resistance The multiplication effect is increased. In the surface treatment agent used in the manufacturing method of the present invention, the weight ratio (A) / (B) of the silane coupling agent component (A) to the water-soluble polymer component (B) is 1: 10 to 10: 1 as Good, and more preferably 1: 5 to 5: 1. When the weight ratio is less than 1:10, that is, if the ratio of the Shayuan coupling agent component (A) is low, the adhesive force with the surface of the substrate is reduced, so the corrosion resistance and coatability are insufficient. When it exceeds 10: 1 ', that is, when the ratio of the silane coupling agent component (A) is high, the film-forming property of the film is lowered, so that the obtained film has insufficient corrosion resistance and coatability. Next, a method for manufacturing the organic composite-coated metal material of the present invention will be described. In the manufacturing method of the present invention, an aqueous surface treatment liquid containing the above-mentioned surface treatment agent composition as the first layer and adjusted to a pH ranging from 2.0 to 6.5 is applied to the surface of a metal material and dried, and The amount after drying is set to 10 to 50 mg / m2, preferably 5 to 5 mg / m2. At this time, the aqueous treatment liquid is allowed to contact the surface of the metal material at a temperature of 10 to 60 ° C for 0.1 to 30 seconds, and it is preferable to heat and dry. P Η of the aqueous surface treatment liquid of the first layer is adjusted to a range of 2.0 to 6.5 using phosphoric acid, acidic phosphate, fluoride, bifluoride, sulfuric acid, nitric acid, and organic acid. A more preferred PH 値 is 3.0 ~ 5,0. When P Η is less than 2.0, the reactivity between the composition in the obtained treatment solution and the surface of the substrate becomes excessively high, so a bad film occurs, and the resistance of the obtained film to the paper standard applies to the national standard (CNS) A4 specification (210 X 297 mm); --- I ------ "One Pack. 1 — (Please read the precautions on the back before filling out this page) ij ·-Line, Economic Village Intellectual Property Bureau Staff Printed by the consumer cooperative 1 446 7 3 7 A7 _ B7 V. Description of the invention (11) (please read the precautions on the back before filling in this page) The corrosion and coating properties are not sufficient. If it exceeds p Η 6. 5, the water-soluble polymer component (B) itself is liable to precipitate the sinking source from the aqueous surface treatment liquid, and the life of the aqueous treatment liquid is shortened. Moreover, there is no method for using the surface treatment agent and treating the surface of metal materials. It is particularly limited, and for example, a dipping method, a spray method, a roll coating method, and the like can be applied. There is also no particular limitation on the processing temperature and processing time, but generally, the processing temperature is preferably 10 to 60 t, and the processing time is It is preferably 0 · 1 to 20 seconds. Furthermore, the metal material to be treated is preferably The heating port is thermally dried. The heating temperature is preferably 50 ~ 2 0 0 t: When the surface treatment composition used in the manufacturing method of the present invention is brought into contact with a metal material, the metal ions eluted from the metal material are mixed with The water-soluble polymer component (B) forms a complex and may precipitate. In this case, a metal chain-blocking agent may also be added to the surface treatment agent composition. Examples of the metal chain-blocking agent include EDTA and Cy-DTA. , Triethanolamine, gluconic acid, heptogluconic acid, oxalic acid, tartaric acid, malic acid, etc. There is no particular limitation on the processing method, processing temperature, and processing time of the aqueous resin composition used in the second layer, but generally, processing The temperature is printed in the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at 10 ~ 60 ° C for 0.1 ~ 10 seconds, and it is better to heat and dry. The metal material used in the present invention can be iron plate, plated It is selected from zinc-based steel plates, staggered plates, staggered alloy plates, stainless steel plates, etc. [Examples] The present invention will be specifically described with reference to the following examples, but the scope of the present invention does not apply to this paper standard. National Standard (CNS) A4 Specification (210 X 297 mm) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperation Du printed 446737 A7 _B7_ V. Description of the Invention (12) Not limited to each other's examples. 1 * Test material ① Commercially available cold-rolled steel sheet thickness 0.6mm JIS G 3 1 4 1 ② Galvanized steel plate with commercially available sheet thickness 0.6mm hot-dip galvanized steel sheet (GI material) Commercially available sheet thickness 0.6mm Electro-galvanized steel sheet (EG material) ③ Commercial thickness of aluminum sheet 0.6mm JIS A 5 0 5 2 2. Cleaning method of steel sheet Use the surface of the above metal material with a medium alkaline degreaser (registered trademark: 戸 丨 116 (1163 ) 16 『4 3 3 6, Japan? 6 ^ 5}] 1 £ (manufactured) Chemical concentration: 20 g / l, spray treatment under the conditions of processing temperature: 60 ° C, processing time: 20 seconds, to make garbage on the surface And oil removed. Secondly, the alkaline components remaining on the surface were washed with tap water, so that the surface of the test material became purified. 3. The composition of the first layer surface treatment liquid < Processing liquid A > The silane coupling agent component (A) is 3-hydrothiopropyltrimethoxysilicone, and the water-soluble polymer component (B) is η = 5, X = hydrogen, Y 1 = Z = _CH2N (CH3) 2 and adjusted to the average number of Z-based substitutions. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15- i: —— l · ------ ο Install -------- Order ------------ 4J. C Please read the notes on the back before filling this page) 446737 V. Description of the invention (13) 値 = 1, (A): (B) p p is adjusted to 3 · 0 to 10% by weight. Α7 Β7: 1: 8. Then dilute it with deionized water with Η 2 S i F 6, and the solids will be separated into a mixture of components > Β hospital liquid silicon processing will be < amine-2 / IV I Ν divided into a polymerizable soluble water 4 and Η 6 alkane C diyl Η oxo C methyl 一 il yl X propyl, amine 5 Υ 、 Ζ ZO

Β B C 3 η Ν ο 2 5 Η. C ο

Η C

\ ly A / «IV 値 Equivalently take the base Z into whole B 5 Zhou Yan Η 将 P Η F Η 1 and then solidify and release the dilute after the water leaves ο ο 4% weight (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs &lt; Processing liquid c &gt; 3-Aminopropyltriethoxysilicone, a silane coupling agent component (A) + 3 _glycidyloxypropylmethyldimethoxysilane (equivalent ratio of epoxy groups of active hydrogen in amine group = 1: 2), and n = 5 of water-soluble polymer component (B), X--CH2-C6H4-OH, Y 1-Z = — CH2N (CH3) 2, adjusted to the average number of 2-group substitutions 値 = ◦ .75, (A): (3) = 1: 1 ° and then 幵 21 '1 卩 6 After adjusting to pH 4.0, it was diluted with deionized water, and the solid content was 10% by weight. &lt; Processing liquid D &gt; This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -It)-A7 44673 7 B7_____ 5. Description of the invention (14) (Please read the precautions on the back before (Fill in this page) N- (2-aminoethyl) -3-aminopropyltrimethoxysilane + 3-glycidyloxypropylmethyldimethoxysilane (amine) Active hydrogen in the group: equivalent ratio of epoxy group = 1: 2), η = 5, X = -CH2— CsH4 — OH, Y1 = Z = -CH2N (CHS) of water-soluble polymer component (B) 2. Adjust to the average Z-substitution number 値 = 0.75, (A) :( B) = 1: 1. After adjusting the pH to 3.0 with phosphoric acid, it was diluted with deionized water, and the solid content was 10% by weight. &lt; Treatment liquid E &gt; N- (2-aminoethyl) -3 monoaminopropyltrimethoxysilane + 3-glycidyloxypropylmethyldimethoxy group of silane coupling agent component (A) Silane (equivalent ratio of active hydrogen in epoxy group: epoxy group = 1: 1), n = 5, X = hydrogen, Yl = Zn--C Η 2 N (CH3 ) 2. Adjust to the average Z group substitution number 値 = 0.3, (A): (B) = 1: 1. Then H2TiFe and phosphorus were used to print the acid by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to adjust PΗ to 4.0, and then diluted with deionized water, and the solid content was 10% by weight. &lt; Example 1 &gt; A molten zinc-plated steel plate (GI) washed in advance by the method described in (2) was applied by a roll coating method with a treatment solution A at 25 ° C to obtain a dry weight. 3 g / m2, and dried at a plate temperature of 80 ° C. At -17: This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) A7 B7 4 46 7 3 4 46 73 V. Description of the invention (15) The upper layer will be modified with acrylic acid 100 parts by weight of the resin, containing an aqueous resin composition containing silica powder (produced by Aerosil Co., Ltd., trademark: Aerosil 2 0) and 30 parts by weight, was applied by a roll coating method to a dry weight of 2 g. / m2, and dried at a plate temperature of 100 ° C. &lt; Example 2 &gt; An aluminum plate (A 1) washed in advance by the method described in (2) was applied by a roll coating method with a treatment liquid B of 15 ° C to a dry weight of 0.1 g / m 2 and dried at a plate temperature of 150 ° C. On the upper layer, an aqueous resin composition containing silica powder (made by Japan Aerosil Co., Ltd., ·····························) in an amount of 100 parts by weight based on 100 parts by weight of the phenol-modified alkyd resin, It was applied by a roll coating method to a dry weight of 1 g / m 2 and dried at a plate temperature of 150 ° C. &lt; Example 3 &gt; A molten zinc-plated steel plate (GI) which was previously washed in the method described in (2), was coated with a treatment solution B at 30 ° C by a roll coating method to a dry weight of 0. 0.5 g / m2, and dried at a plate temperature of 100 t. On the upper layer, an aqueous resin composition containing silica powder (manufactured by Japan Aerosil Corporation, trademark: Aerosil 2000) in an amount of 50 parts by weight relative to 1,000 parts by weight of the acrylic resin was applied by a roll coating method. The cloth has a dry weight of 3 g / m2, and is dried at a board temperature of 100 ° C. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------ ^- --I --- One-pack i Ϊ {Please read the notes on the back before filling out this page) * · Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Ministry of Economic Affairs 4467 3 7 A7 B7 V. Description of Invention (16) & lt Example 4 &gt; I: --- l · ------, ρ Install i_ V. '. (Please read the precautions on the back before filling this page) The method described in (2) Washed electro-galvanized steel sheet (EG), coated with treatment liquid C at 20 ° C by roller coating method to dry weight of 0 * 0 5 g / m2, and reach plate temperature at 180 ° C Allow to dry. On the upper layer, an aqueous resin composition containing 70 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trademark: Snowtex N) was applied in a roll coating method with respect to 1,000 parts by weight of ethylene acrylic resin. The dry weight is 1 g / m 2 and it is dried at the board temperature of 1000 t. <Example 5> Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and will be washed in advance by the method described in (2). The molten zinc-plated steel plate (GI) is coated with a treatment liquid D at 20 ° C by a roll coating method to a dry weight of 0 _lg / m2, and dried at a plate temperature of 80 ° C. On the upper layer, an aqueous resin composition containing colloidal silica (manufactured by Nissan Chemical Co., Ltd., trademark: Snowtex N) 2 based on 1,000 parts by weight of ethylene acrylic resin was applied by a roll coating method. The resulting dry weight is 2 g / m2 and is dried at a plate temperature of 180 ° C. &lt; Example 6 &gt; A molten zinc-plated steel sheet (GI) which was previously cleaned by the method described in (2) was coated with a treatment solution E of 20 C in accordance with a light coating method and dried to a dry weight of 0.03. g / m 2 and dried at a plate temperature of 80 ° C. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -19-

4467 3 T Α7 Β7 V. Description of the invention (17) The upper layer contains 100 parts by weight of ethylene acrylic resin and contains colloidal silica (manufactured by Nissan Chemical Co., Ltd., trademark: Snowtex 0) 100 parts by weight A proportion of the aqueous resin composition was applied by a roll coating method to a dry weight of 1 g / m2, and dried at a plate temperature of 8 Ot. &Lt; Example 7 &gt; Rinse in advance by the method described in (2). The steel plate (GI) of molten zinc is coated with a treatment liquid E at 20 ° C by a roll coating method to a dry weight of 5 g / m2 'and dried at a plate temperature of 80 ° C. On the upper layer, an aqueous resin composition containing 1000 parts by weight of urethane-modified epoxy resin and containing 70 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trademark: Snowtex 0) is contained. , Coated by a roller coating method to a dry weight of 0.3 g / m2, and dried at a plate temperature of 180 ° C. &lt; Example 8 &gt; A cold-rolled steel sheet (SPC) washed in advance by the method described in (2) was coated with a treatment liquid E at 20 ° C by a roll coating method to a dry weight of 0.5 g. / m 2 and dried at a plate temperature of 80 ° C. On the upper layer, an aqueous resin composition containing 70 parts by weight of colloidal sandstone (manufactured by Nissan Chemical Co., Ltd., trademark: Snowtex N) in an amount of 1,000 parts by weight based on the urethane-modified epoxy resin. , Coated by roller coating to a dry weight of 4 g / m 2, and dried at a board temperature of 1000 ° C. This paper is sized to Chinese National Standard (CNS) A4 (210 X 297 mm) ( Please read the precautions on the back before filling out this page): ^ 一 装 ------- &quot; Order iu--l · ---- — ^) i. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 44673 7 A7 B7 V. Description of the invention (18) 〇 (Please read the precautions on the back before filling out this page) &lt; Comparative Example 1 &gt; The molten zinc-plated steel plate washed in the method described in (2) in advance ( GI), with a treatment liquid C at 20 ° C, and coated with a dry weight of 0.3 g / m2 according to a roll coating method, and dried at a plate temperature of 180 ° C. &lt; Comparative Example 2 &gt; An electrogalvanized steel sheet (EG) washed in advance by the method described in (2) was coated with a treatment liquid A at 20 ° C by a roll coating method to a dry weight of 0.05. g / m2, and dried at a plate temperature of 80 ° C. On the upper layer, an aqueous resin composition containing only a urethane resin was applied by a roll coating method to a dry weight of 1 g / m2, and dried at a plate temperature of 100 ° C. &lt; Comparative Example 3 &gt; Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, aluminum (AL) washed in advance by the method described in (2), and coated with a treatment liquid B at 30 ° C by a roller coating method The resulting dry weight was 0 g / m 2 and dried at a plate temperature of 180 ° C. On the upper layer, an aqueous resin composition containing 90 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trademark: Snowiex N) based on 100 parts by weight of ethylene acrylic resin was applied by a roll coating method. The resulting dry weight is 1 g / m 2 and drying is performed at a plate temperature of 1000 ° C. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 46 73 7 A7 _B7___ V. Description of the Invention (19) &lt; Comparative Example 4 &gt; The galvanized steel sheet (EG) washed in advance by the method described in (2) was coated with a treatment solution D at 20 ° C by a roll coating method to a dry weight of 0.5 g / m2 'and reached The plate was dried at 180 ° C. On the upper layer, an aqueous resin composition containing 50 parts by weight of silica powder (manufactured by Japan Aerosil Corporation, trademark: Aerosil 200) with respect to 1,000 parts by weight of ethylene acrylic resin was applied by a roll coating method to The dry weight was 0.05 g / m2, and drying was performed at a plate temperature of 100 ° C. &lt; Comparative Example 5 &gt; The galvanized steel sheet (e G) 'washed in advance by the method described in (2) contains colloidal silica (100 parts by weight based on vinyl acrylate resin) (Nissan Chemical Co., Ltd.) (Trademark: Snowtex N) 50 parts by weight of an aqueous resin composition is applied to a dry weight of 1 g / m2 by a roll coating method, and dried at a board temperature of 1000 ° C. 3. Evaluation test method Evaluation was performed by the evaluation method shown below. The results are shown in Table 1. This paper size is applicable to China National Standard (CNS) A4 specifications (2〗 0 X 297 issued) I: ——l · ------ ο installed -------- order i, —— h- --- Line} 1 (Please read the precautions on the back before filling in this page) 4467 3 7 A7 _____B7 V. Description of the invention (2〇) [Table 1] N 〇 Anti-corrosive coating and adhesive coating It is not easy to wear fingerprints once and once for corrosion resistance and dirt. 1 GI ◎ ◎ ◎ ◎ 2 AI ◎ ◎ ◎ ◎ ◎ 3 GI ◎ ◎ ◎ ◎ ◎ 4 EG ○ ◎ ◎ ◎ Example 5 GI ◎ ◎ ◎ ◎ ◎ 6 G 〇 ◎ ◎ ◎ 7 G 〇 ◎ ◎ ◎ ◎ 8 SPC 〇 ◎ ◎ ◎ ◎ 1 GI X ◎ ◎ Δ Δ 2 EG X 〇 Δ XX Example 3 AI 〇 Δ Δ Δ ◎ 4 EG X 〇〇X 〇 5 EG XXXX ◎ I ------ ---- Install i! (Please read the notes on the back before filling this page) Order ---- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3.1. Corrosion resistance was performed for the test material for 240 hours: a salt water spray test prescribed by IS-Z2371 ^ The white rust resistance was visually measured and evaluated. The evaluation criteria are as follows. ◎ The incidence of white rust is less than 5%. 〇: The incidence of white rust is more than 5% and less than 10%. △: The incidence of white rust is more than 10% and less than 50%. The paper size is in accordance with Chinese national standards (CNSM4). Specification ⑵〇X 297mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 46 7 3 7 A7 B7 V. Description of the invention (21) X: The incidence of white rust is 50% or more 3 · 2 · Coating close The test surface-treated metal material was coated under the following conditions, and a coating film adhesion test was performed. Coating conditions Coating: Amirac # 1 0 〇〇 (trademark) (white coating) manufactured by Kansai Paint Co., Ltd. Coating method: Bar coating method Baking: 140 ° C, 20 minutes Film thickness: 2 5 em 3 · 2 1. Sub-adhesiveness Using an NT art knife, the coating film was cut into a square of 1 mm and a checkerboard of 1000, and this test material was extruded by an Eriksson testing machine for 5 mm. For the convex portion, a peeling test was performed with an adhesive tape, and the number of peeled coating films was evaluated. Evaluation criteria are shown below. ◎: No peeling 〇: Number of peeling 1 or more, less than 10 pieces △: Number of peeling 11 or more, less than 50 pieces X: White rust occurrence rate of 51 or more, less than 1,000 pieces 3.2.2.2. Secondary Adhesion The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) -24-(Please read the precautions on the back before filling this page) Packing --- --- Wire, 44673 7 A7 B7 V. Description of the invention (22) After immersing the test plate in boiling water for 2 hours, the same test as the one adhesion test was performed and evaluated. 3.3 Corrosion resistance after coating The coating film was cut to the texture of the steel plate with an acrylic resin knife, and the salt water spray test specified in JIS-Z2371 was performed for 240 hours. After the implementation, the cut portion was peeled off with an adhesive tape, and the peeling width was evaluated. The judgment criterion is the measurement of the peeling width (mm) of the coating film at the beginning of the cutting section. ◎: less than 3 mm 〇: 3 mm or more and less than 5 mm △: 5 mm or more and less than 10 mm X: 10 mm or more 3.4. Fingerprints are not easy to adhere to, and the finger is pressed against the test panel, and the state of the fingerprints is evaluated visually. Alas, the judgment criteria are as follows. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) ◎: No fingerprint traces remain at all 〇: Very few fingerprint traces remain △: The fingerprint traces are slightly residual X: The fingerprint traces are As clearly shown in the results of Table 1, Examples 1 to 8 using the surface treatment agent composition of the present invention show good anti-starvation, coating properties, corrosion resistance after coating, and are not easy to bear. Fingerprint dirtiness. However, the upper film is not used. The paper size is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm). A7 ^ 7 g 7__ V. Description of the invention (23) Comparative example 1 of the treatment is resistant and not easy Poor fingerprints have poor dirtiness. In addition, Comparative Example 2 which does not contain silica in the upper layer resin is resistant to corrosion, and is not easily affected by fingerprints. Comparative Example 3, which contains silica outside the scope of the present invention, shows a decrease in adhesion. In Comparative Example 4 in which the amount of the upper layer film was outside the scope of the present invention, satisfactory corrosion resistance could not be obtained. The ratio without the head layer treatment of Comparative Example 5 was poor in corrosion resistance and adhesion. [Effects of the Invention] The organic composite coated metal material formed by using the manufacturing method of the present invention can obtain high corrosion resistance, coating adhesion, and resistance to fingerprints and dirt, as in previous products, without using chromate. Therefore, according to future drainage regulations, it can be applied to the industry without chromium. Furthermore, because there is no selectivity for metallic materials, the characteristics of the materials can still be used, and the rust prevention and coating properties are also improved. It is also very effective as a countermeasure to social issues such as environmental protection and recycling, and it is also practically effective. ---------- Λ &gt; Install il — i-Order (Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperatives The paper is printed in accordance with Chinese national standards ) A4 size (2i0 X 297 mm)

Claims (1)

Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives ¾ Patent Application No. 88 1 04858 Chinese Application for Patent Scope Amendment 1. Revision 1 of the Republic of China in January 1990 1. An organic that is resistant to corrosion, has good coating properties and is difficult to bear fingerprints and dirt The composite coated metal material is characterized in that the surface of the metal material has the following components as a first layer: (A) an active hydrogen-containing amine group, an epoxy group, a vinyl group, a hydrogen thio group, and a methacryloxy group; Silane coupling agent components composed of one or more silane coupling compounds having at least one reactive functional group and (B) one or more polymers represented by the following general formula (I) are selected, with an average degree of polymerization of 2 to 50 Contains more than one polymer component: 〇 Η 〇ΛΛ X Υ 1 LJ [However, in the formula, X bonded to a benzene ring represents a hydrogen atom or -CH2—CeH. »— 〇.Η, and Y1 bonded to a benzene ring in formula (I) is expressed as A film consisting of CH2N (CH3) 2 'wherein the average number of substitutions of Y1 is 0.3 to 1.0]' and the second layer is a layer above the first layer. 0 parts by weight, a resin composition containing 5 to 70 parts by weight of silica is coated. The paper size is quickly used in China. CNS &gt; Λ4 size (210X297mm) (Read the precautions on the back before filling in this page) 446 7 3 7 A8 B8 C8 _ D8 VI. Application for patent scope 2. The organic composite coated metal material described in item 1 of the scope of patent application 'wherein the aforementioned silane coupling agent component (A) is relative to the polymer component --- l · J --------- 1 Order (please read the precautions on the back before filling this page) (B) The weight ratio (A) / (B) is 1: 10 to 10: 1 . 3. The organic composite coated metal material according to item 1 of the scope of the patent application, wherein the aforementioned silane coupling agent component (A) is composed of one or more silane coupling compounds containing (a) one or more amine groups containing active hydrogen. A silane coupling agent, and a silane coupling agent composed of (b) one or more silane coupling compounds having one or more epoxy groups. 4. The organic composite coated metal material as described in item 3 of the scope of the patent application, wherein the active hydrogen-containing amine group contained in the aforementioned silane coupling agent (a) is relative to the epoxy contained in the aforementioned silane coupling agent (b) The base equivalent ratio is 3: 1 to 1: 3. 5. The organic composite-coated metal material as described in item 3 or 4 of the scope of the patent application, wherein the total amount of the aforementioned silane coupling agent (a) and the aforementioned silane coupling agent (b) is relative to the aforementioned polymer component (B ) Has a weight ratio of 1: 5 to 5: 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs C8 D8 446737 VI. Patent application scope (B) The following general formula (1)-more than one polymer, with an average degree of polymerization of 2 to 50-more than one Polymer composition (埼 Please read the meaning of back-¾ first and then fill in ί 0 C Η 2__ (I) [However, in the formula, the X bonded to the benzene ring represents a hydrogen atom or -CH2 — C6H4 — 0H, in formula (I) Y1 bound to a benzene ring is represented as —CH2N (CH3) 2 where the average number of substitutions of Y1 is 30 ~ 3 ~ 1.0] and the pH is adjusted to an aqueous composition of 2.0 ~ 6.5, The surface of the metal material is coated with a coating weight of 10 to 500 mg / m2 after drying. After drying, the upper layer will be used as a second layer to 100 parts by weight with respect to an aqueous resin having a hydroxyl or carboxyl structure. Water-based resin composition containing 5 to 70 parts by weight of silica is coated and dried with a dry weight of 0.1 to 5. Og / m2. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs- 3-This paper size uses China National Standard (CNS) Α4 size (2ι〇 × 297 public envy) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives ¾ Patent Application No. 88 1 04858 Chinese Application for Patent Scope Amendment 1. Revision 1 of the Republic of China in January 1990 1. An organic that is resistant to corrosion, has good coating properties and is difficult to bear fingerprints and dirt The composite coated metal material is characterized in that the surface of the metal material has the following components as a first layer: (A) an active hydrogen-containing amine group, an epoxy group, a vinyl group, a hydrogen thio group, and a methacryloxy group; Silane coupling agent components composed of one or more silane coupling compounds having at least one reactive functional group and (B) one or more polymers represented by the following general formula (I) are selected, with an average degree of polymerization of 2 to 50 Contains more than one polymer component: 〇 Η 〇ΛΛ X Υ 1 LJ [However, in the formula, X bonded to a benzene ring represents a hydrogen atom or -CH2—CeH. »— 〇.Η, and Y1 bonded to a benzene ring in formula (I) is expressed as A film consisting of CH2N (CH3) 2 'wherein the average number of substitutions of Y1 is 0.3 to 1.0]' and the second layer is a layer above the first layer. 0 parts by weight, a resin composition containing 5 to 70 parts by weight of silica is coated. The paper size is quickly used in China. CNS &gt; Λ4 size (210X297mm) (Read the precautions on the back before filling in this page)