TW201120244A - Surface treatment agent for use on a pre-coated metal sheet, coated and surface treated metal sheet whereon the surface treatment agent has been applied, and pre-coated metal sheet with excellent film adhesion during processing and which uses the sur - Google Patents

Abstract

Disclosed is a surface treatment agent, with a pH from 2.0-6.5, for use on a pre-coated metal sheet. In water, the surface treatment agent contains as solids: polyester resin of which the particle diameter ranges from 50-150nm, the glass transition temperature (Tg) is from 0-30 DEG C and the hydroxyl number is from 5-13; tannins or tannic acid; a silane coupling agent; and silica particulate. The disclosed surface treatment agent, which does not generate deposits during the lengthy stationary state during the actual production of a pre-coated metal sheet, is a stable surface treatment agent for use on a pre-coated metal sheet.

Description

201120244 ^ VI. Description of the invention: 'Technical field to which the invention pertains FIELD OF THE INVENTION The present invention relates to a substrate treatment agent for a precoated metal sheet which is not considered to be toxic chromium, and a coated substrate coated therewith A metal plate and a precoated metal sheet having excellent adhesion to the film using the same. BACKGROUND OF THE INVENTION In place of the conventional coated products coated after processing, especially in the industrial fields such as home appliances, building materials, automobiles, etc., pre-coated metal sheets coated with previously colored organic coatings are being widely used instead of The technique of manufacturing products only by adding _ to the painting. The precoated metal sheet is a metal sheet which is subjected to substrate treatment and an electroplated metal sheet which is coated with an organic film, and has both aesthetic and 0-processability and has excellent resistance to surnames. For example, Patent Document 1 discloses a technique of obtaining a precoated steel sheet having excellent workability, stain resistance, and hardness by defining a structure of a film. Patent Document 2 discloses a precoated steel sheet having improved end surface corrosion resistance by using a specific chromic acid treatment liquid. The purpose of these pre-coated steel sheets is to improve the productivity or improve the quality by the chromic acid treatment and the composite effect of the organic film, which has the property of being "avant-garde, workability, and paint adhesion" and omitting the coating after processing. However, the toxicity of the hexavalent chromium which is likely to be eluted by the organic film containing the complex acid-treated film and the complex anti-recording pigment is high, and the demand for the chromium-free rust-proof treatment and the chromium-free organic film is increased. A non-chromium-based rust-preventing treatment method which replaces the complex acid treatment, and has a treatment technique of % 201120244 which is disclosed in Patent Document 3 and which contains an aqueous solution of sulfur gland and tannin or tannic acid, but is produced by using the anti-recording treatment method. There are (4) the application of the jade shape is severe (4), and the coating film adhesion between the pre-coated metal electrode and the processing part is not a problem. Specialized, automotive use, etc., by containing tannins gt; ^ combined with water into the 彳 = outside reveals the technology of white rust and coating adhesion, but two-sided treatment, so that the method ensures pre-coating Covering metal & required processing adhesion. 14 methods are still not specific: in the literature 5, the pre-coated metal sheet containing tannin or tannic acid, agent and micro-particles of oxidized stone is not disclosed. The substrate treatment agent is now being used as a processing seal. Sexually, in addition to the above-mentioned essential components, the document also contains a chemical agent, and the addition of the polyester resin contributes to the processing adhesion of the metal plate. Japanese Patent Application Laid-Open No. Hei. No. 723-A No. PCT Publication No. pp. [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei 59-U638 No. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. For the purpose of the nature, the inventor of the present application has applied the essential components of the patent document 5 (tannin or tannic acid 'Shi Xi 201120244 burnt light mixture, and micro-diode) to the treatment agent containing the (4) resin. After the actual operation of the pre-coated metal sheet production, the problem of the sinking of the treatment agent is encountered during the long-term use in the state of the shirt. In a constant state, a sinking occurs in the treating agent, causing various problems in operation. Firstly, the coating material accumulated in the paint tray and the treatment agent are coated on the metal plate by the applicator, or sprayed and mixed with the treatment agent of the sinking object, the solid material will be metal The board becomes a foreign object and the angle is not damaged. In addition, the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In addition, the composition ratio of the "supernatant" (actual treatment agent) will be greatly changed from the original treatment agent, and the performance as the treatment agent itself may not be exhibited. SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate treatment agent for precoated metal sheets which solves the problems of the prior art described above. Another object of the present invention is to provide a polyester resin which, in addition to tannin or tannic acid, a decane coupling agent and particulate cerium oxide, even if it also contains a processing resin which contributes to improving the processing adhesion of the precoated metal sheet. A substrate treatment agent for precoated metal sheets which does not precipitate and is stable in actual operation in the long-term constant state in which a precoated metal sheet is produced. Still another object of the present invention is to provide a coated substrate treated metal sheet coated with such a treating agent, and a precoated metal sheet having excellent coating film processing adhesion using the same. Means to solve the problem 5 201120244 Application. The inventor of the case is committed to research and review, and the results

After having a specific solid type in the water, brother, and Q & i 77 particle diameter, glass transition temperature (10)), and m base price of the grease, constitute a treatment agent, and set the treatment agent After the news, the money turned to the subject of the rainbow. The present invention is based on the above-observed knowledge, and more specifically, the invention relates to a substrate treatment agent for pre-coated metal sheets, which comprises tannin or tannic acid as a solid component, Wei Ling agent, and The particle size of the fine particles of the oxidized stone is 5G to 15 () nm, and the glass transition temperature (Tg) is (4). The base price is 5 to 13 of a polyester resin, and the treatment agent has a pH of 2_0 to 6.5. In the present invention, the reason why the above-described excellent effects can be obtained is based on the knowledge obtained by the present inventors. In other words, in addition to tannin or tannic acid, Wei light mixture, and particulate dioxane 2, there is also a patent document 5 which is made into a polysyl resin which contributes to the improvement of the processing adhesion of the precoated metal sheet. The described treatment agent is applied to the actual operation of pre-coated metal sheet production, but it is faced with the problem of precipitation during processing in the long-term constant state of use. In this case, the applicant is constantly engaged in research and review. , get the knowledge gained as observed below. In the manufacture of precoated metal sheets, generally when a substrate treating agent is used on a continuous production line, the treating agent is circulated and coated on a metal plate by a roll coater or a nozzle. The treatment agent of the above-mentioned conventional technique (Patent Document 5) exhibits an acidity of about 4, so when it is operated for a long time, for example, when applied to a galvanized steel sheet, the surface of the metal sheet is one by one. Dissolve at a point to increase the concentration of rhythm in the treatment agent. Further, usually, the metal sheet is subjected to the coating step of the base treatment agent immediately after degreasing, 201120244 water washing, and hot air drying step, so that the temperature of the metal sheet entering the coating step is substantially high, and the temperature of the treating agent is gradually increased. Since the treatment agent is applied to the metal plate at a certain speed, and the new treatment agent is supplied to the circulation system in an amount corresponding thereto, the concentration of the metal in the treatment agent is in a state of being commensurate. Or the temperature is a fixed value. Although it is also affected by the operating conditions, the temperature is about 4 于 in a constant state. Oh, the concentration of metallic sweat (when zinc) is about 100 ppm. According to the above observations, the present inventors have found that no precipitation occurs when a treatment agent containing a polyester resin is used, and no precipitation occurs at a temperature of the metal contamination or the rise of the above-mentioned constant enthalpy state, so that the treatment agent is present. The steady state is extremely important. Further, in the operation as described above for a long period of time, zinc is dissolved as an ion and dissolved in the treating agent. Since the hydrogen ions in the treatment agent are consumed due to the ionization of zinc, there will be a treatment agent as the concentration of zinc ions increases. 11 The tendency to rise slowly. When the value of the pH is larger than a predetermined value, as described later, since precipitation occurs, it is one of the causes of adversely affecting the operational stability, and therefore it is necessary to use a treatment agent whose pH is not easily changed. In other words, the inventors have found that in the case of using a treatment agent containing a polyester resin, precipitation does not occur, and in the metal contamination of the above-described constant state, it is important that the pH is sufficiently small. The present inventors believe that the precipitate in the treatment agent containing the polyacetate is formed at a high temperature in the presence of metal contamination and has a coordination energy such as a decane coupling agent or a tannin in the treatment agent, and is formed by a metal plate. The metal ion reaction becomes difficult to stably exist in the treating agent, and it is precipitated together with the polyester resin. With the research, it is easy to precipitate according to the type of the resin 201120244 resin. Degrees also make a difference. Regarding the reason why the ease of precipitation occurs depending on the kind of the polyester resin, the inventors have made the following assumptions about the mechanism of precipitation in the treating agent based on the knowledge obtained by combining the above observations. Since the decane coupling agent and the tannic acid are highly reactive compounds, a part of the treating agent is reacted to become a poorly soluble reaction product, and the aggregates are aggregated and precipitated. When Zn ions eluted in the treating agent are present, the Zn ions react with the above reaction product, and the charge of the reaction product proceeds further in the direction of loss. Therefore, the solubility is further lowered, which contributes to the production of melons. However, when a specific polyester resin is present in such a system, the reaction product adsorbs to the hydrophobic portion of the polyester resin emulsion by a hydrophobic interaction, hinders aggregation after aggregation between the reaction products, and thus inhibits precipitation. . The present inventors presume that the degree of adsorption of the reaction product and the polyester resin by the precipitation inhibition effect of the polyester resin (the ease of adsorption by the interaction of hydrophobicity), and the dissolution of the polyester resin emulsion are presumed. ^中之; Qualitative related. In other words, according to such a mechanism, it is presumed that the base treatment agent for precoated i-metal sheets of the present invention can exhibit the above-described excellent effects. According to the above-observed knowledge of the inventors of the present invention, the Japanese-a/π-cumulative test experiment 'the present inventors identified the polyester resin' 50 to 15 〇 nm, and the glass transition temperature (Tg) was 〇~3 〇χ: Preferably, the hydroxy group is f, and the treating agent has a pH of 2.0 to 6_5, and the pre-treated substrate treating agent of the present invention having the above structure is completed based on the knowledge obtained. "genus: The present invention may, for example, include the following aspects. 8 201120244 (1) A substrate treatment agent for precoated metal sheets, which contains tannin or tannic acid as a solid component, a decane coupling agent, and fine particles in water. Cerium oxide, and a polyester resin having a particle diameter of 5 〇 to i5 〇 nm, a glass transition temperature (Tg) of 0 to 30, and a Zhao base price of 5 to 13, and a treatment agent of 11 is 2 〇. ～5 5. (2) The base treatment agent for precoated metal sheets according to (1) above, wherein the mass concentration of tannin or tannic acid in the treatment agent is TA, the mass concentration of the decane coupling agent When the mass concentration of SC and particulate ceria is SI and the mass concentration of the polyester resin is PR, it also satisfies TA: SC=1: 40~40: 1, (TA+SC): si=l: 10~20 : 1 and (TA+SC) : PR=1 : 10~10 : The total concentration of each component (TA+SC+SI+PR) is 10~200g/L. (3) As above (1) or ( (2) The base treatment agent for precoated metal sheets described in the above, wherein the ruthenium coupling agent has a glycidyl ether group. (4) The precoated metal sheet according to any one of the above (1) to (3) Substrate treatment agent When a zinc ion of 1 〇〇 ppm is mixed, the sinking process does not occur. (5) The base treatment agent for precoated metal sheets according to any one of the above (1) to (4), which is mixed therein. In the case of 〇〇ppm, the change in pH is 1.5 or less. (6) The coated substrate is treated with a metal plate, and the surface of at least one surface is coated and dried to any of the above (1) to (5). (7) The coated base treated metal sheet according to the above (6), wherein the precoated metal described in any one of the above (1) to (5) The solid content of the substrate base treatment agent is from 〇 to 500 mg/m 2 . (8) A precoated metal sheet which is applied to the coating described in the above (6) or (7) 9

S 201120244 The substrate treated metal sheet has an upper film layer. (9) A precoated metal sheet having a film layer containing a rust preventive pigment as a lower layer film layer on the coated substrate treated metal sheet described in the above (6) or (7), and having an upper layer thereon The film layer. Advantageous Effects of Invention According to the present invention, it is possible to provide a Tg of 0 to 30 ° C and a hydroxyl value of 5, in addition to tannin or tannic acid, a decane coupling agent, and particulate cerium oxide, by a particle diameter of 50 to 150 nm. The polyester resin of ～13 is a pre-coated base material treating agent for metal sheets which does not precipitate and is practical in the actual operation under the long-term constant state of producing a precoated metal sheet. The base treatment agent for precoated metal sheets of the present invention is used by combining a decane coupling agent and a particulate cerium oxide in tannin or tannic acid to provide a precoated metal sheet which is treated with a chromic acid substrate. A pre-coated metal sheet of a substrate-treated film of inferior performance, and by using a specific polyester resin as described above in combination, a pre-coated metal plate which is stable for a long period of time can be produced. C. Embodiment 3 Form for Carrying Out the Invention The base treatment agent for precoated metal sheets of the present invention contains water having a particle diameter of 50 in addition to tannin or tannic acid, a decane coupling agent, and particulate cerium oxide. ～150 nm, a polyester resin having a glass transition temperature (Tg) of 0 to 30 ° C and a hydroxyl value of 5 to 13 as a solid component, and a pH of the treating agent of 2.0 to 6.5. The tannin or tannic acid, decane coupling agent, and particulate cerium oxide used in the substrate treating agent for precoated metal sheets of the present invention can be used to date in the pretreatment of a substrate treatment agent for precoated metal sheets 10 201120244 . The tannin or tannic acid may be a hydrolyzable tannin, or may be a condensed tannin, or decomposed from one of the parts. Tannins and tannins can be witch hazel tannin, gallnut tannin, gallnut tannin, tannin of Myrobalan, tannin of Divi-Divi, carob ( The tannins of Algarobilla, the tannins of Valonia, and the catechins are not particularly limited, but from the viewpoint of improving the processing adhesion of the coating film, "tannic acid: AL" (Fuji Chemical) Industrial system) is better. The decane coupling agent may, for example, be γ-(2-aminoethyl)aminopropyltrimethoxy decane, γ-(2-aminoethyl)aminopropyl decyl dimethoxy decane, γ-( 2-Aminoethyl)aminopropyltriethoxylate, γ-(2-aminoethyl)aminopropyl decyldiethoxy decane, γ-(2-aminoethyl)amine Propylmercaptodioxane, γ-methylpropenyloxypropyltrimethoxydecane, γ-methylpropenyloxypropylmethyldimethoxydecane, γ-methylpropenyloxypropyl Triethoxy decane, γ-methyl propylene methoxy propyl fluorenyl diethoxy decane, Ν-β-(Ν-vinylphenylaminoethyl)-γ-aminopropyl dimethyl milk , Ν-β-(Ν-Ethylphenylaminoethyl)-γ-aminopropylmethyldimethoxydecane, Ν-β-(Ν-vinylphenylaminoethyl)_γ-amine Propyl diethoxy oxyphyllin*, Ν-β-(Ν-ethylphenylaminoethyl)-γ-aminopropyl fluorenyl diethoxylate, γ-glycidoxypropyl trimethyl Oxetane, γ-glycidoxypropylmethyldioxanane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxydecane Γ-mercaptopropyl Trioxoxane, γ-mercaptopropylmethyldioxanone, γ-mercaptopropyltriethoxyoxane, γ-mercaptopropyl decyldiethoxy decane, decyltrimethoxy decane, dimercapto曱 矽 曱 曱 曱 曱 三 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 Dimethoxyoxane, γ-chloropropyltriethoxyoxane, γ-gas propylmethyldiethoxy decane, hexamethylene diazoxide, γ-anilinopropyl trioxoxane, γ-aniline Propyl dimethyl dioxane ' γ-anilinopropyl triethoxy decane, γ-anilinopropyl methyl diethoxy decane 'vinyl trimethoxy decane, vinyl methyl dimethoxy decane 'ethylene Triethoxy oxane, vinyl methyl diethoxy decane, dimethyl octadecyl [3-(tridecyloxy decyl) propyl] ammonium hydride, dimethyl octadecyl [3- (methyldimethoxyindenyl)propyl]ammonium chloride, dimethyloctadecyl-(diethoxysulfanyl)propyl] gasification, dimethyloctadecane [3- (methyldiethoxyindolyl)propyl] gasification bond, γ-gas Methyl dioxin, γ-mercaptopropyl dimethyl dimethoxy decane, methyl trichloro decane, dimercapto dioxane, trimethyl gas decane, etc., but when a decane having a glycidyl ether group is used When a coupling agent, for example, γ-glycidoxypropyldioxanane having a glycidyl ether group and γ-glycidoxypropyltriethoxysilane, the coating film can be particularly improved in processing. Sex. Further, when a triethoxy type decane coupling agent is used, the storage stability of the substrate treated material can be improved. This can be considered because the diethyl oxane is relatively stable in an aqueous solution and the polymerization rate is slow. The mass concentration ratio of tannin or tannic acid to the shixi burning mixture in the treating agent is preferably 1:40 to 40:i. When it is outside the range, 'whatever it is - more than two points, the coating film will be sealed or the effect will be low ~ or the tannins (4) mixture will have a mass concentration ratio of 1:35~35:: Ning is better than 1 m. The best one is J: 2〇~2〇: i. Preferably, in the present invention, the particulate sulfur dioxide is collectively referred to as the teaching path 12 201120244 which can stably transfer the water dispersion 1 when dispersed in water. For example, "SnowTEX N", "SNOWTEX C", "SNOWTEX UP", "SNOWTEX PS" (all manufactured by Gifu Chemical Industry Co., Ltd.) and "ADELITE AT-20Q" (manufactured by Gunmetallization Industry Co., Ltd.) can be used. A commercially available cerium oxide gel or a powdered cerium oxide such as AEROSIL #300 (manufactured by Japan AEROSIL). The particulate cerium oxide can be selected as appropriate depending on the desired properties. When the particulate cerium oxide is stably dispersed at a pH of 4 or more as in "SN〇WTEX c", the storage stability of the substrate treating agent can be improved. This is considered to be because the pH of the chemical solution can be adjusted to 4 or more, so that the reaction of the decane coupling agent having high reactivity at a low pH can be suppressed. Here, in the present invention, the advantage of using cerium oxide which is stable at a pH of 4 or more is storage stability. Therefore, there is no contradiction between setting the pH of the solution to 2 to 6.5 for operational stability. The mass concentration of the tannin or tannic acid and the lanthanum coupling agent in the treatment agent is preferably in the range of: 〇1 〇 2 〇 : ^. When it is less than 1:10, the cohesive force of the substrate treatment layer is lowered, so that the processing of the coating film is low, and when it is more than 20:1, the processing density of the coating film is not good. The mass concentration ratio of the tannin or the tannic acid and the decane coupling agent relative to the mass concentration of the particulate TiO2 is preferably 2:1 〇 15 15: 丨, preferably 4: 10 10 10: 1 . The polyester resin used in the substrate treatment agent for precoated metal sheets of the present invention has a particle diameter of 5 〇 15 15 〇 nm, a glass transition temperature (Tg) of 〇 〜 3 〇 ^ and a valence base price of 5 〜 13 . By presenting such a polylysate in the substrate treating agent, aggregation between the poorly soluble reaction products formed by the reaction of the decane coupling agent and a part of the tannic acid of the compound can be inhibited.

S 13 201120244 After agglutination, inhibition of precipitation occurs. By using a specific polyester resin having a particle diameter of 5q to ΐ5" and a glass transition temperature (Tg) of 〇30 and a hydroxyl group of 5 to 13, the precipitation production inhibitory effect can be regarded as __mixture and tannic acid. The reaction product is formed by hydrophobicity _(10) in (4) the hydrophobic portion of the emulsion, and hinders agglomeration between the reaction products. First, when the Tg of the polyester resin is less than (TC, it is caused by skinning phenomenon The stability of the polyester resin in the treating agent is low, and as a result, the above-mentioned precipitation inhibiting effect is lost, and precipitation tends to occur. Here, the skinning phenomenon is described. The polyester resin emulsion particles are glass below the glass transition temperature (Tg). The state is firm and has no fluidity. Therefore, even if the emulsion particles collide with each other, they do not melt and stably disperse. However, when the temperature is above Tg, the emulsion particles are in a rubber state or a liquid. If the particles collide with each other, they will agglomerate and melt. In particular, since the surface of the treatment agent placed on the coating plate evaporates, the emulsion will concentrate and then collapse (melt) to solidify. The surface of the solution of the treatment agent will be covered with a polyester resin (skin phenomenon). Moreover, the emulsion teaches the charge on the surface, and the particles repel each other and stably disperse, but the Zn ion in the treatment agent, the charge Being neutralized, and reducing the power of rejection, it becomes easy to agglomerate and melt. In other words, it becomes easy to cause skinning. When the particle of polyester resin is outside the proper range, it will still cause skinning. When the particle diameter When the thickness is less than 50 nm, the viscosity is high because the number of adjacent particles is increased, and the action of the particles itself becomes slow, so that it is easy to aggregate, and the result is 'crusted. On the other hand, when the particle diameter is larger than 150 nm, the surface of the treatment liquid is The area of the particles exposed to the air layer is large, and this part promotes the evaporation of water, so 14 201120244, 'It becomes easy to aggregate' into a skin. As a result, the stability of the same polyester resin in the treatment agent When it is lowered, the above precipitation inhibiting effect is lost and precipitation tends to occur. When the Tg of the polyester resin is more than 30 ° C, the properties after film formation cannot be exhibited (pre-coated metal sheet film) The processing adhesion is lower than when the Tg is a polyester resin in the above preferred range.) In Patent Document 5, even if it contains tannin or tannic acid, a decane coupling agent, and particulate cerium oxide, and polyester The base treatment agent for pre-coated metal sheets of the resin can effectively improve the processing adhesion of the coating film, but the inventor of the present application is equivalent to the long-term use in a constant state when the treatment agent is applied to practical operation. In the process, the inventors of the present application use the polyester resin (Finetex ES-650 (Daichi Ink) described in the example of Patent Document 5, in the process of the present invention. The inventors of the present application have continued to undergo various experiments and reviews for the purpose of solving the above problems. As a result, it has been found that the specific particle diameter as described above must be 50 to 150 nm, and the Tg is 0 to 1. A polyester resin is used at 30 ° C and a hydroxyl group value of 5 to 13. In addition, the polyester resin (Finetex ES-650 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) of the example of Patent Document 5 was measured by the method described in the present specification, and the particle diameter was 300 nm, and the glass transition temperature (Tg) was 4〇. ~5〇°C. Since the embodiment of Patent Document 5 focuses on the adhesion test of the coated film to the metal sheet treated by the substrate, even if it is confirmed that the "preservation" stability of the treatment agent is not confirmed, the treatment agent for long-term operation cannot be confirmed. Whether or not precipitation occurs. This indicates that at the time of the application of Patent Document 5, the development of precipitation in the agent of the long-term operation was not recognized. : In the case of Ben 1 "Mingzhong, the Tg of the poly-g resin is preferably 1~catch, and the more taut is 3~25t, and the best is 15~2n:. ... another 'special shots of 5 notes to enhance the stability of the treatment program "turn" stability, by using the triethoxy Wei type of money 33 mixture, or in the above _ stable particle dioxo. The storage stability of the treating agent is affected by the reaction between the constituents having high reactivity (actually known as "particles of cerium oxide, tannic acid"). Therefore, the storage stability of the treating agent means the characteristics before the actual use of the treating agent. In contrast, the problem of causing precipitation during long-term operation after the use of the treating agent according to the present invention is a problem that the storage stability of the treating agent is different from that of the treating agent. In the substrate treatment agent for precoated metal sheets of the present invention, when the hydroxyl value of the polyester resin is less than 5, since the charge on the surface of the emulsion particles is insufficient, the stability (dispersibility) in the solution is low, so precipitation is likely to occur, and it is impossible to cause precipitation. A sufficient precipitation inhibition effect is exhibited. When the hydroxyl value of the polyester resin is more than 13, since the hydrophobic interaction is not easily obtained, the reaction product cannot be adsorbed (adsorbed) on the polyester resin and precipitates. The polystyrene resin in the substrate treating agent for precoated metal sheets of the present invention may be used in any case as long as it satisfies the above-mentioned conditions of particle diameter, Tg and base price. When a commercial product is used, it can be used by, for example, "Vyl〇nal" manufactured by Toyobo Co., Ltd., "Finetex" manufactured by Otsuka Ink Chemical Industry Co., Ltd., and "NT" selected from Kao Corporation. The mass concentration of the polyester resin in the treating agent is preferably 0.1 to 1 times the mass concentration of the tannin or tannic acid 16 201120244 and the decane coupling agent. When the film was reported to be 1 times, the effect of the addition of the polyester resin was not observed, and when it was more than 10 times, the processing adhesion of the film was lowered. Preferably, it is 0.15 to 5 times, and the best is 0.2 to 2 times. In the base treatment agent of the present invention, the mass concentration of tannin or tannic acid, decane coupling &amp; θ 丨, particulate nitric oxide, and polyester resin is 1 〇 2 〇〇 g / L It is better. When the total mass concentration is less than 10 §, it is not easy to reach the desired amount of adhesion. On the other hand, when it is larger than fine g/L, the concentration will be too high, and the stability of the substrate treatment agent (storage stability, storage and operation stability) Sexual operation stability) is not good. y The substrate treating agent of the present invention preferably has a pH of from 2 to 6.5, more preferably from 3.0 to 6 Torr. When it is less than pH 2.0, the dissolution of Zn is increased, and precipitation is likely to occur due to an increase in the concentration of 211 in the treatment liquid. On the other hand, when the stability of the fine particle cerium oxide is low in a neutral region of more than 65, gelation is liable to occur. The base treatment agent of the present invention preferably has a pH change of 1.5 or less when mixed with 丨〇〇ppm. When the zinc ion having 1 〇〇ppm is uniformly dissolved, the fluctuation of the pH is larger than that of the treatment agent of 丨5, because the pH buffering ability is poor, so that the treatment agent in the operation tends to locally generate an extreme pH rise, and the operation time is high. There are many cases in which stability has an adverse effect. In order to increase the pH rise by 1,5 or less, it is effective to set the mass concentration (TA) of tannin or tannic acid in the treatment agent to 5 g/L or more. This is considered to be obtained by the pH buffering effect produced by dissociation of protons of tannin or tannic acid. The evaluation of the stability during the operation was carried out by the following method to determine the presence or absence of precipitation at the time of Zn contamination. A predetermined amount of zinc powder is added to the treatment liquid (granule 17 201120244 diameter: about 0.3 to 1.5 mm (14 to 50 mesh ASTM), and is given at 40 ° C; and dissolved for 3 hours to make a zinc solution of 100 ppm. Pour the solution into a 5 〇〇 ml plastic bottle and let it stand for 3 days in a 40 ° C thermostat. After that, filter it with a #300 mesh and collect the precipitate. After washing with pure water, it will be washed. The dried material was sufficiently dried (about 2 hours) in an oven of ll ° ° C, and then returned to normal temperature in a desiccator to measure the weight. When the weight of the precipitate was less than 111 ^, it was judged that there was no precipitation. A method for measuring a hydroxyl value and a particle diameter of a polyester resin (a 20% water-dispersible polyester resin emulsion) used in the substrate treatment agent of the present invention. <Method for measuring Tg> Resin has The specific heat changes with the change in the state near the Tg (glass transition temperature). By using this property, the specific heat change of the measurement sample generated when the standard substance and the measurement sample are heated under the same temperature rising condition is measured (the heat absorption near the Tg) The DSC method is used in the present invention by the DSC method. First, Tg. First, take about lg of polyester resin in a 5〇mm□ Tefl〇n (registered trademark) petri dish. Place it in an oven of 5 〇 ambient gas for 2 hours to evaporate the water. The dried sample was prepared by a vacuum dryer for 24 hours. After pulverizing the sample, about 1 mg was taken in an aluminum cup for a thermal analysis device. Further, alumina powder was used as a standard material, and about 1 〇 mg was similarly taken. In an aluminum cup, it was placed in a thermal analyzer, and the measurement was started after cooling to _5 〇〇 c. The rate of temperature rise during the measurement was performed at 2 (rc/min). The heat absorption data was collected and analyzed. The obtained data (reading the temperature after the thermal change and the analytical software attached to the device), and determining the Tg («»c) of the resin. 18 201120244 Using a thermal analysis device: Seiko Electronics Co., Ltd., dsC-210. Method for measuring valence of hydroxy acid&gt; Measured according to the method of test for the determination of the hydroxyl group of HS-K1557-1 plastic-polyamine phthalate raw material - Part 1: Determination of hydroxy valence. In the same manner as the Tg measurement, the water was evaporated at 50 t: The sample was dried in a vacuum dryer for 24 hours, and the titration was determined by potentiometric drip and AT420 using electrons. The hydroxyl value was calculated by a predetermined calculation formula. &lt;Measurement of particle diameter Method &gt; Dilute with pure water to separate the solid shape of the polyester resin into 〇1%. Place it in a 1L glass beaker of about 500g and immerse it in a ultrasonic cleaner (6〇〇w, 40kHz). Ultrasonic dispersion was performed for 1 minute. This was carried out as a pretreatment for dispersing the particles of the secondary particles. This was used as a measurement sample, and the particle size measurement was performed in a particle size distribution measuring apparatus. The particle size is the average particle diameter calculated from the analytical software attached thereto. Using device: manufactured by Nikkiso Co., Ltd., the pH of the Nanotrac UPA-EX150 treating agent was measured using a pH meter (East Dkk Co., Ltd., pH meter HM-30G). &lt;Change in pH at the time of mixing of Zn ions&gt; The change in pH after the incorporation of zinc ions of 100 ppm was measured by the following method. First, the pH of each treatment agent was measured by a pH meter. After that, a predetermined amount of zinc powder is added to various chemicals (particle size: about mm 5mm (14~5〇mesh)

S 19 201120244 A zinc solution of 100 ppm was prepared, and ASTM)) was dissolved by stirring at 40 ° C for 3 hours to measure the pH of the bribe. The initial value of the new material is changed as the pH rises. The coated substrate-treated metal sheet of the present invention is coated on at least one surface of the single surface to dry the substrate treating agent for a difficult-to-covered metal sheet of the present invention. When a substrate treatment layer is formed on a metal plate using the substrate treatment agent of the present invention, the substrate treatment agent (_) is applied to the metal plate, and g and dried. In the liquid medicine, it is also possible to adjust the pH in the range of money and energy. Heating temperature is 50~25 (rc is better. When it is smaller than thief, because the evaporation rate of water is slow, it can't get sufficient money, so the anti-recording power is insufficient. When it is more than 250° (:, the tannin of the time) The acid-cut portion of the acid-cutting agent is thermally decomposed, etc., causing denaturation, and the adhesion or the impurity is lowered. The heating temperature is 70 to 16 G. (: Preferably, the method of heating and drying is not particularly limited. It can be dried by hot air, and it is preferably dried in the second to 5 minutes. The coating method of the substrate treating agent is not particularly limited, and generally known methods such as roll coating, air spraying, and airless spraying can be used. ^, immersion, etc. 'The adhesion amount of the substrate treating agent of the present invention to the metal plate is preferably 10 to 5 〇Omg/m 2 in terms of solid content. When less than 10 mg/m 2 , sufficient processing adhesion is not ensured. When the thickness is more than 5 〇〇mg/m2, the processing adhesion is low. The precoated metal sheet of the present invention is coated on the surface of at least one side and dried with the substrate treating agent of the present invention. Painted substrate treated metal plate 'with upper film layer 20 201120244 In the precoated metal sheet of the present invention, the basic resin coated on the upper layer coating layer on the underlying treatment layer may be any one of a water type, a solvent system, a powder system, etc. The type of the resin is generally known. For example, a polypropylene resin, a polyolefin resin, a polyamine phthalate resin, an ethoxy resin, a polyester resin, a polybutyraldehyde resin, a melamine resin, or the like can be used as it is. A coloring pigment may also be added to the upper film layer. For the coloring pigment, for example, titanium oxide (Ti〇2), zinc oxide (ZnO), zirconium oxide (Zr02), calcium carbonate (CaC〇3), barium sulfate (BaS〇4) may be used. ), generally known pigments such as alumina (Al2〇3), kaolin, carbon black, iron oxide (Fe203, Fe3〇4), or organic pigments, etc. In addition to the aforementioned color pigments, the upper layer is also Anti-rust pigments may be added as needed. Anti-rust pigments are generally known, and for example, (1) phosphate-based anti-rust pigments such as phosphoric acid, iron phosphate, and aluminum phosphate, calcium lanthanum molybdate, aluminum molybdate, bismuth molybdate, etc. Molybdenum acid anti-rust (3) hunger-proof rust-preventive pigments such as vanadium oxide, (4) particulate cerium oxide such as water-dispersible cerium oxide, fumed silica, etc. chrome-tantalum, chromic acid, calcium chromate, chromic acid The chromic acid-based rust-preventive pigments such as potassium and strontium chromate are not toxic because they are toxic to the environment. The thickness of the coating layer containing the coloring pigment or the rust-preventing pigment is preferably 丨25 μπι. When less than 1 μΓη The corrosion resistance of the coated metal sheet is not good, and when it is more than 25 μm, the workability of the coating film is not good. However, the upper layer film is used as an organic or inorganic film such as a lubricative film or a fingerprint-resistant film, that is, after coating, or When the surface-treated metal sheet of the *% line of the coating material is used, the type or film thickness of the upper layer film may be appropriately selected depending on the purpose of use, and the film thickness is not limited to 1 to 25 μm. The coating of the upper film can be carried out by a coating method generally known, for example, by roll coating, curtain coating, air blasting, airless spraying, dipping, bar coating, brush coating, or the like. In the precoated metal sheet of the present invention, a film layer to which an anti-recording pigment is added may be disposed as a lower layer film layer between the substrate-treated layer and the upper layer. The basic resin of the lower film layer may be any of water, solvent, or powder systems. X ' may also be an adhesive layer. The type of the job is generally known to the public's. For example, a polypropylene resin, a polyolefin resin, a polyurethane resin, an ethoxy resin, a poly S resin, or a polybutylene can be used. A melamine-based resin or the like is used as it is or in combination. The rust preventive pigment may be used in any of the following, but for example, (1) zinc phosphate, iron phosphate, aluminum phosphate A phosphate P pigment, (7), fine (tetra), fine (tetra), etc. Acidified sulphate bismuth pigment, (4) water-dispersed oxidized silica eve: smoked (four) particulate dioxide. The chromic acid-based anti-recording pigments such as chromic acid, zinc chromate, complex acid, potassium, and strontium complex are not toxic to the environment, and the amount of the pigment added to the P-label is the weight of the bud. It is better. When it is less than 1 weight = ', the effect of (4) is small, and when it is more than 4 (% by weight), the coating film is not preferable. # Included: The thickness of the film layer under the scale pigment is not good for one work. When the filling of the film is greater than 25μιη, the coating film with the well-known coating pigment can be used for cloth (4) - the general public threat, ^ Gas = for example: by roller coating, curtain coating, air &quot;, (4) selection, dipping, bar coating, brush coating, and the like. [Embodiment] Hereinafter, the present invention will be specifically described by way of examples and comparative examples of the invention. 1. Production of test plate 1.1 Test material • Electrogalvanized steel sheet (EG) Thickness 0.6mm 'Zinc adhesion amount per side 2〇g/m2 (double-sided plating) • Melt galvanized steel sheet (GI) Thickness 0.6mm 'The amount of reciprocation is 60g/m2 per side (double-sided electric ore) • Cold-rolled steel sheet (cold-rolled) Thickness of 0.6mm 1.2 Pre-treatment uses alkali degreasing agent CL-N364S (made by Japan PARKERIZING) as the δ-type material, The solution was immersed in an aqueous solution having a concentration of 20 g/L and a temperature of 60 C for 10 seconds, washed with pure water, and dried. 1.3 Base treatment • Treatment in the substrate treatment agent (Examples 1 to 96, Comparative Examples 1 to 61) The composition shown in the column of the "base treatment layer" in Tables 1 to 5 was measured by a roll coater (the content was g/L unit). The base treatment agent was applied to the test material to form a predetermined film, and was dried in a hot air drying oven to have an arrjval sheet temperature of 70 ° C and 150. (:, 220. (:: In the solid content of each base treatment agent, the following are used for tannic acid, decane coupling agent, and cerium oxide. (a) Tannic acid tannic acid AL (manufactured by Fuji Chemical Industry Co., Ltd.) 23 201120244 (b) Hydrazine coupling agent decane coupling agent A : γ-glycidoxypropyltrimethoxy decane olefin coupling agent Β : γ-mercaptopropyltrioxane decane coupling agent C: methyl trioxane Shi Xi Burning Light Mixture D : γ-glycidoxypropyl triethoxy sulphate (c) cerium oxide ST-N : SNOWTEXN (made by 曰 化学 化学 AE AE AEROSIL : AEROSIL #300 (Japan Aer〇SIL ST-C : SNOWTEX C (manufactured by Nissan Chemical Industries Co., Ltd.) The polyester resin is Tg and the base price shown in Tables 1 to 5. • Coating chromic acid treatment (Comparative Examples 36 to 38) with a roll coater ZM-1300AN (manufactured by PAR本 PARKERIZING) coated with a chromic acid agent was applied to the test piece to have a Cr adhesion amount of 4 〇mg/m2, and dried in a hot air drying oven until the plate temperature reached 70 °C. • Electrolytic chromic acid treatment (Comparative Example 39) In a bath of chromic acid 50g/L and sulfuric acid 0.3g/L, the current density is 1〇A/dm2, and the amount of Cr is 40mg/m2. After electrolytic chromic acid treatment, it is washed with water, and then dried in a hot air drying oven until the plate temperature is 8 〇〇c. 1.4 The lower layer film is treated on the substrate-treated test material, and the roll coater is applied as the primer coating. The coating material shown was formed to have a predetermined film thickness, and then hardened and dried by an induction heating furnace blown with hot air until the sheet temperature reached 220 ° C to form an underlayer film layer.

• Polyester A 24 201120244 曰本Paint P641 primer coating, using zinc phosphite as a rust preventive pigment.

Polyester B 曰本Paint P641 primer coating, using V/P (vanadate/phosphoric acid) as a rust preventive pigment.

• Poly vinegar C

Sakamoto Paint P641 primer coating, using Mo as a rust preventive pigment. • Polyester D 曰本Paint P641 primer coating, using calcium citrate as a rust-proof pigment. • Amino phthalate 曰 The P108 primer coating made by Paint is made of zinc phosphite as a rust preventive pigment. • Ethoxy Hydroxide This P304 primer is made from Paint and uses zinc phosphite as a rust preventive pigment. 1.5 The upper layer film is treated on the underlayer film for the test material, and the FL100HQ (polyester type, white) made by Pa本Paint is coated with a roll coater to form a predetermined film thickness, and then hardened by an induction heating furnace blown with hot air. Dry to reach a plate temperature of 220 ° C to form an upper film layer. 2. Evaluation 2.1 Coating film adhesion test 1 Cut the square with a side length of 1 mm on the coating surface with a cutting knife, and then apply it after painting with the love S. 25 201120244 ^&quot; After the plate was pressed for 7 mm, the coated surface was protruded. The tape peeling test was carried out according to the method described in 8.2 and 8.5 of JIS K 5400. This test was carried out twice in the same place at the same place. Make "2 times stripping"). The evaluation of the peeling was performed by a graph of the evaluation of JISK 5400 8.5 §, and the evaluation was ◎ when the score was 10 points, 〇 when 8 points or more and less than 1 〇, and 6 points or less and less than 8 minutes. When it is △, it is X when it is less than 6 minutes. 2.2 Coating film adhesion test 2 Apply 18 0 to the coated board. (: Bending processing (20. 〇 under ambient gas, 〇丁加工)' Then observe the coating film of the processing part with a magnifying glass of 20 times, and investigate whether or not the film is broken. Also, attach the adhesive tape to the processing part to visually The residual state of the coating film when the adhesive f was quickly peeled off was observed. In addition, two persons were also subjected to separation in the test. The evaluation of the film rupture was evaluated as ◎ when the coating film was not broken, and the coating film was When the rupture of 1~3 or so is very small, it is 〇, when the coating film has a total small rupture, it is △, and it can be visually recognized that the coating film of the whole processing part has a large rupture and is x. The evaluation of the residual state was evaluated as ◎ when the coating film remained on the electrodeposited steel sheet without peeling, 〇 when the coating film was partially peeled off, and Δ when the coating film was partially peeled off, and was bent. In the case where the coating film was peeled off, it was found to be χ. In addition, after the coated steel sheet was processed, it was 'immersed in boiling water for 1 hour, and the strip was peeled off after being taken out for 24 hours. Evaluation of the residual state of the coating film , the coating film remains in the plating without peeling In the case of the plate, the evaluation was ◎, when the coating film was partially peeled off, it was 〇, when the coating film was partially peeled off, it was Δ, and when the film was peeled off, it was found to be 全面 in the case of peeling of the film. 26 201120244 2.3 Money The method described in the test of κ 54009&gt;1 applies a salt water (four) test to the coated plate. The test time is 鸠 in the case of electroplating of the steel plate, and is in the case of molten steel plate. When the maximum expansion visibility on the lateral slice side is less than hnm, it is evaluated as ◎, when it is less than 3 _, it is 〇, when it is 3 mm or more, it is Δ, and when it is 5 _ or more, it is X. When the hair σ (burr) is located on the evaluation surface side (becoming the upper burr) of the coated steel sheet, the salt spray test is also carried out, and when the expansion width of the coating film of the surface is 2 mm or less, it is evaluated as ◎, When it is 2 mm or more and less than 3 mm, it is 〇, when it is 3 or more, it is Δ when it is less than (7), and when it is 5 mm or more, it is x. When the original plate is a cold steel plate, the corrosion resistance test is not performed. 2 · 4 Storage of the base treatment agent Stability test The base used in each example was stored in an oven at 40 ° C. After the base treatment agent is used for a predetermined period of time, each of the coated metal sheets is produced using the conditions of the examples, and the coating process adhesion test 2 shown in 2.2 is performed. Compared with the case of using a fresh base treatment agent, there will be no The storage time stability of the undercoating agent was evaluated as the storage stability of the underlying treatment agent. 2.5 Operational stability test of the substrate treatment agent (1) In the solutions of the respective substrate treatment agents of the examples and the comparative examples, Add zinc powder (particle size: about 0.3~1.5mm (14~50 mesh ASTM)' to make the concentration lOOppm, then stir at 40 °C for 3 hours and dissolve. Then, pour 300ml of the solution into 500ml plastic container In the thermostat at 40 ° C, it was allowed to stand for 3 days. The solution taken from the constant temperature tank was passed through the #300 sieve, and the sediment was recovered. 27 s 201120244 After washing with pure water, the precipitate was dried in an oven at 11 ° C for about 2 hours. The weight was measured after returning to normal temperature in a desiccator. When the weight of the sinking house is less than 1mg, it is judged as no sinking. In the evaluation, no abnormality was observed in the solution after 3 days of standing in the constant temperature bath, and no precipitation was observed. ◎, when the solution was slightly turbid in the solution but not in the sinking hall, it was 〇, and there was less than l〇〇mg. When the temple is △, it is X when it is precipitated with more than lmg. 2.6 Operational stability test of the substrate treatment agent (magic (the case where the circulation in the piping of the substrate treatment agent is insufficient during the operation, and the occurrence of the retentate is generated.) In the test method of 2.5, the powder is omitted. The step of dissolving in one hour, in other words, pouring 3 ml of the solution of each of the substrate treating agents of the examples and the comparative examples into a covered plastic container of 5 ml, and adding a powder (particle size: about 0.3 to l) .5mm (14~5〇mesh ASTM) to make the concentration lOOppm' and then stand still in the temperature tank of 40 C for 3 days. After the solution is taken out of the strange temperature 4曰, the solution is passed through the #3GG sieve to recover the precipitate. After washing with pure water, the /year-old substance is sufficiently dried (about 2 hours) in a supply box of 11 〇C, and then in a desiccator: the weight is measured after returning to normal temperature. When the weight of the precipitate is less than When lmg is judged as no &quot;iwl again. The evaluation is based on the observation of the static value in the temperature tank for 3 days, 'no difference is found in '' and no precipitation is ◎, when the solution is slightly turbid but no precipitation Naimen Town fishing rod, when there is less than lOOmg precipitation is △, in the production of more than 100mg of precipitation The evaluation results are displayed in Table 6~1〇 as X.. 28 201120244

[II Upper Membrane Thickness (m) V) •r» UJ IT) •λ 1/1 «/*! irj &lt;r&gt;»r&gt; ir» «/*&gt;·/&gt; m io ·/* &gt; l/') in 树脂 Resin Type: Polyester | Polyester | | Polyester | | Polyester | | Polyester | 1 Polyester ι 1 Polyester ι l Polyester ι | Polyester | 1 Polyester ι 1 Polyester ι l polyester ι 1 polyester ι 1 polyester ι 1 polyester! 1 polyester | 1 polyester ι polyester | polyester 1 | polyester 1 | poly si | l polyester ι | polyester | Polyester | | Polyester | | Polyester | Polyester 1 Polyester ι | Polyester! l Polyester ι Lower film thickness _ «Λ ir* in «ο to ΚΓ) ·/-&gt; IT) yn tr> Λ ·/*&gt; «Λ •ο Primer type | Polyester A | Polyester AI 1 Polyester A 1 | Polyester A | | Polyester A | 1 Polyester A 1 Polyester A | Polyester A | | Polyester A | Polyester A | Polyester A ] 1 Polyester A 1 1 Polyester A 1 1 Polyester A 1 1 Polyester A 1 1 Polyester A 1 | Polyester AI | Polyester A | | Polyester A | | Polyester A | | Polyester A | | Polyester AI 1 Polyester A 1 |Polyester A |Polyester A | |Polyester AI 1 Polyester A 1 1Polyester A 1 Polyester A 1 Polyester A 1 Adhesive layer adhesion amount (mg/m2) 〇(N 200 I ο &lt ;N o fS o fN ο &lt;Ν ο soso fN o rN 〇&lt;N ο &lt;Ν 200 ο (Ν ο (Ν |&lt;ι〇(*ΐ)| |&lt;io(*i)| | &lt;io(*i)| 200 i | 200 ; 200 l | 200 : ο &lt;N 1 200 ! | 200 ; 200 ! 1 200 i 200 ; 1 200 丨ο &lt;N lOOppm Zn pH change greater than 1.5 〇〇〇oooo pH (adjusted with acetic acid and ammonia) κη o (N Ο o &lt;&gt; 'O ΙΛ 对 · 对 ' — m W1 Vi VI Vt in V) VI W) V-» u-1 inch' » Yi — inch' — V-&gt; rf — &gt;ri | TA+SC+ SI+PR ο o ο oo Ο oo 1 250 1 (N 1 250 1 200 200 200 1 200 1 m in 〇〇oo cs ON fN a\ &lt;N Os On 〇〇O'» 〇〇Os Oo Ό OO oo Composition ratio 1 PR/ (TA+SC) 0.33 0.33 ο.33 1 J 0.33 | 0.33 I 1 0.33 1 | 0.33 I 0.33 0.33 0.33 0.33 0.50 0.50 0.50 0.50 0.33 0.33 0.33 | 0.33 I | 0.33 I 1 ° ·33 | 0.33 I (N o &lt;N 〇&lt;N 〇t °·15 1 015 | 0.15 Ο 〇SI/ (TA+SC) 0.33 °·33 1 1 0.33 1 | 0.33 | 033 1 °·33 1 0.33 0.33 0.33 | 0.33 0.33 1 0.50 1 0.50 0.50 0.50 1 ο·33 1 0.33 0.33 | 0.33 I | 0.33 I | 0.33 | 1 °·33 1 1 0.33 I 0.33 1 °·33 0.33 1 °·33 0.33 0.33 | I TA / SC Ο ΙΛ om ΙΛ in O ITi O v-. 〇iTi 〇iTi 〇 — — — — 〇 ΙΛo ΙΛ 〇o wj oo ΙΛ o Vi 〇ΙΛ υ-ι in d ui o Polyester resin content SS Ss S ss ο •Τ'» ο ο ΙΤ) ο CM rN fN rN JN (N &lt;N On ON VO hydroxyl price (KOH mg/g) ri m rn rn rn 卜 m V&quot;) m ΙΛ 卜 m in 卜2 W-) rn ΙΛ» rn ·/*&gt; tn ΙΛ ir> ir» omo Ο ir&gt ; 宕o S 〇ir> S 〇o KT\ particle diameter (nm> § ο gso Ο κ 〇κη gogo § § os § 〇 氡 氡 氡 矽 矽 | 含有 sssss - —* &lt;N (N (N ssss 1 kind ST-N I ST-N I ST-N I ST-N I ST-N I ST-N 1 ST-N I ST-N I ST-N ST-N I ST-N ST-N ST-N ST-N ST-N ST-N ST-N ST-N | ST-N I ST-N ST-N ST-N ST-N ST-N ST-N ST-N ST-N ST-N ST-N ST-N decane coupling agent | content ooo O o ο O oooo (N (N &lt;N inch inch oooo 〇oo O type &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&nbsp; Tannin content sss S - (- (N &lt;N (N &lt;N sssssss original board type oo 〇〇o ϋ oo 〇〇〇ϋ Ο Ο ϋ ϋ o oooooooo ϋ ϋ oa | Example i | 1 Example 2 I 1 Example 3 1 丨 Example 4 : 丨 Example 5; 1 Example 6 i | Example 7 | Example 8: | Example 9 | Example io | Example li 1 Example 12 1 Example 13 1 Embodiment 14 1 Embodiment 15 1 Embodiment 16 | Embodiment 17 Example 18 | Example 19 | Example 20 | Example 21 | Example 22 1 Example 23 1 Example 24 | Example 25 | 26 1 Embodiment 27 1 Example 28 | Example 29 Example 30. Forgiveness 3E/2E0l&quot;,'^f^ Y^-^^•峒 銮 (Γ) s 29 201120244 Upper skin Μ film thickness _ κη to w-&gt; m in %n u-) m irj ir&gt; VJ «Λ Vi m in in IT) IT) U-) to resin type polyester polyester I | polyester | | polyester | | polyester | | polyester | | polyester | | polyester | Ester | am • ο | polyester 1 | polyester | | polyester | | polyester | 1 polyester 1 | polyester | | polyester | I polyester | | polyester | | polyester | DS • Q | Ester | 1 polyester 1 | polyester | | polyester I polyester i | polyester | | polyester | polyester underlayer film thickness (μηι) ιτ» ir> w-&gt; trt in in • rgt; Λ *Τί ir&gt; V) •T) *n •Λ ir&gt; ΙΓί in Primer Types of Coatings|Polyester Α | 1 Polyester A 1 |Polyester A | |Polyester AI |Polyester A | 1Polyester A 1 1 polyester A 1 | polyester A | | polyester A | | polyester A | 1 polyester A 1 | polyester A | 1 polyester A 1 1 polyester A 1 | polyester A | 1 polyester A 1 | Polyester A | | Polyester A 1 | Polyester AI | Polyester A 1 | Polyester A 1 | Polyester A | | Polyester A 1 1 Polyester A 1 1 Polyester A 1 | Polyester A | 1 Polyester a ! 1 Polyester A j | Polyester A | 1 Polyester A 1 Adhesive layer adhesion amount (mg/m2) 〇ο fS o &lt;N oo &lt;N Ssoso ΓΊ oso (N o (N ο iS ο N o ο noo rs ο lOOppm Zn pH change is greater than 1.5 0 o 0 o 0 o 0 ooo 0 0 o 0 o ο ooo pH (adjusted with acetic acid and ammonia) a V ~1 — V) ^f· •Λ — τΤ Vl m tj- U-) irj »n V) Vi V) Wi ui Vt in 1/1 &lt;/1 — yn — 1/1 'TA+SC+ | SI +PR 〇0 00 〇〇V-&gt; 00 •n oo sss 00 m 〇〇m OQ m 〇〇SO 00 so 00 SO 〇〇oo OO OO (N &lt;N (N m (N rs (N mr^ &gt; oo &lt;N OO 〇0 s〇CO 00 d0 SO oo Ο Composition ratio PR/ (TA+SC) 2 oogogo CN fN fN VJ V&quot;&gt; ooo 〇1(10) 11.67 11.67 1 〇.24 &lt;N &lt; N 〇i 〇.24 &lt;N iS 〇mdm 〇m 〇m ΓΛ 〇ο 〇1 1167 m ΓΛ ο SV (TA+SC) mmom 〇mm 〇f^J omm O momm O momm 〇ro mo rn m rn C ^i ΓΊ m rn rn m rn rn c^i rn 1 o.24 | 0.22 I 1 〇.24 0.22 sosoo 11.67 r&lt;imom rn 〇mm ο TA/SC ΙΛΪ Vi VI v&gt; «η »r&gt; V) * Rt \n Vi Vi VI W~l | 0.025 | 10.02222| 〇momo 1/1 V» Vi Vi Vt Polyester Resin Content KTt V) »T) &lt;N (N 沄ssss 〇〇〇ssssss &lt;N s 〇s P 'cU) 趔& E «r&gt; 卜 m rn Vi m ir&gt;v&gt; m «Τ) 卜mmmmmmmmmmmmm ί ?Ρ o v&gt; s 〇»/*&gt; s 〇s 〇ΚΠ s 〇u-&gt; s 〇V-&gt; V-) V» ό V) m particle diameter (nm) s § § 〇% 〇 Gogo § so § § gsg § § § cerium oxide content (N (N &lt; N (N &lt; N &lt; N &lt; N &lt; N &lt; N &lt; N (N (N sm &lt; N s 〇(N (N type ST-N ST-N I ST-N ; ST-N ST-N ST-N | ST-N I ST-N 1 ST-N ST-N 1 ST-N I ST-N 1 ST-N | ST-N i ST-N I | ST-N | ST-N | ST-N | | ST-N i | ST-N 1 ST-N i | ST-N i | ST-N ! 1 ST-N | ST-N ST-N | 1 ST-N ST-N | ST-N I ST-N 矽 耦合 coupling agent content ooo 〇o inch inch inch ^r § § (N &lt;N oo inch rf OO type &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; tannic acid content ssss fS is is &lt;N Ν c s r&lt;j (N (N fS (N &lt; N &lt; N g § ss (N &lt; N 1 original plate type 〇oooo 〇o 〇o Ο 〇 〇oaaaaaoaoaooao 〇ao 〇 Example 31 | Example 32 | | Example 33 I | Example 34 | | Example 35 I | Example 36 | | Example 37 I | Example 38 | | Example 39 | 1 Example 40 1 | Example 41 1 | Example 42 | Example 43 | | Example 44 I | Example 45 I | Example 46 I | Example 47 1 | Example 48 | Example 49 | Example 50 | Example 51 | Example 52 | Example 53 | Example 54 | Example 55 Example 56 | | Example 57 | | Example 58 I | Example 59 1 Example 60 30 201120244 Upper film thickness (m) in ID W-) Ό m ·/) «/ &gt; un ΙΛ «Ο V-) V» tr&gt; m w&gt; IT) V) Resin type polyester polyester polyester polyester polyester i polyester polyester 1 polyester polyester polyester polyester polyester Polyester polyester polyester polyester polyester 1 polyester i polyester polyester 1 polyester 1 polyester; polyester polyester polyester polyester polyester polyester polyester film thickness (m) in m Vi m V~) in in «Λ «Λ «Λ « /% yy~i tTi ITt ΙΛ in κγϊ ΙΛ κη »/» «λ primer coating, type i polyai AA | polyester A 1 polyester A polyester B 1 polyester c 1 polyester D 1 amine f acid ethyl ester Ethoxyl 1 • Polyester A | Polyester A Polyester A Polyester A Polyester A Poly S A A Polyester A Polyester A Polyester A Polyester A Polyester A 1 Polyester A Polyester A Polyester A 1 Poly SI A ! 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Claims (1)

201120244 VII. Patent application scope: ι_ A substrate treatment agent for pre-coated metal sheets, characterized in that it contains tannin or tannic acid as a solid component, a decane coupling agent, and a particulate sulfur dioxide in a water and contains particles. a polyester resin having a diameter of 50 to 150 nm, a glass transition temperature (Tg) of 0 to 30 ° C and a hydroxyl value of 5 to 13, and a pH of the treating agent of 2.0 to 6.5 〇 2. A substrate treatment agent for precoating a metal plate, wherein the mass concentration of the tannin or tannic acid in the treatment agent is TA, the mass concentration of the brothel consumption agent is SC, and the mass concentration of the particulate ceria is SI and poly When the mass concentration of the ester resin is PR, it satisfies at the same time TA: SC=1: 40~40 small (TA+SC): SI=1: 10~20: 1 and (TA+SC): PR=1: 1〇~ 10 · 1 ' and the total concentration of each component (TA + SC + SI + PR) is 10 to 200 g / L. 3. The substrate treating agent for precoated metal sheets according to claim 1 or 2, wherein the decane coupling agent has a glycidyl ether group. 4. A substrate treatment agent for a precoated metal sheet according to any one of the items of K3 of the Shenqing Patent No. K3, which does not cause precipitation when zinc ions of 10 Qppm are mixed. 5. The base treatment agent for precoated metal sheets of any of the items of the fourth to fourth aspects of the invention is a rise of 1.5 or less when mixed with zinc ions of bismuth (8) ppm. A coated substrate-treated metal sheet characterized by coating a surface of a precoated metal sheet for a precoated metal sheet according to any one of the first to fifth aspects of the invention. 40 201120244 7. The coated substrate treated metal sheet according to claim 5, wherein the solid content of the base treatment agent for the precoated metal sheet according to any one of claims 1 to 5 is 10~500mg/m2. 8. A precoated metal sheet characterized by having an upper film layer on a coated substrate treated metal sheet as in claim 6 or 7. A precoated metal sheet characterized by having a coating layer containing a rust preventive pigment as a lower layer of a coating layer on a coated substrate treated metal sheet according to claim 6 or 7 of the patent application, and further having thereon Upper layer of film. 41 201120244 IV. Designated representative map: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: