KR20120032023A - 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 surface treatment agent - Google Patents

Abstract

A polyester resin having a particle diameter of 50 to 150 nm, a glass transition temperature (Tg) of 0 to 30 ° C, and a hydroxyl value of 5 to 13, together with tannin or tannic acid, a silane coupling agent, and fine silica as solids in water. The base treatment agent for precoat metal plate containing and whose pH as a processing agent is 2.0-6.5. There is provided a stable pretreatment sheet for precoat metal sheet, in which precoating sheet metal production does not cause precipitation in the unstable operation in a steady state for a long time.

Description

Substrate treatment agent for precoat metal plate, precoated metal plate coated with it and precoated metal plate excellent in processing adhesiveness of coating film using the same AGENT HAS BEEN APPLIED, AND PRE-COATED METAL SHEET WITH EXCELLENT FILM ADHESION DURING PROCESSING AND WHICH USES THE SURFACE TREATMENT AGENT}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a base coating agent for pre-coated metal plates containing no chromium known to be toxic, a coating base metal sheet coated with the same, and a precoated metal sheet excellent in processing adhesion of a coating film using the same.

Instead of the conventional post-coated products that were coated after processing, especially in the industrial fields such as home appliances, building materials, and automobiles, precoated metal sheets coated in advance with colored organic coatings are used. Manufacturing technology has spread. A precoat metal plate coat | covers an organic film to the metal plate and plated metal plate which carried out the base treatment, and has a beautiful aesthetic, a good workability, and a corrosion resistance. For example, Patent Literature 1 discloses a technique for obtaining a precoated steel sheet excellent in workability, stain resistance and hardness by defining the structure of the coating film. Patent Literature 2 discloses a precoated steel sheet having improved cross-sectional corrosion resistance by using a specific chromate treatment liquid.

These precoated steel sheets have a corrosion resistance, workability and paint adhesiveness due to the combined effect of chromate treatment and organic coating, and omit coating after processing to improve productivity and quality. However, due to the problem of the toxicity of hexavalent chromium that may elute from chromate-treated coatings and organic coatings containing chromium-based rust-preventing pigments, the demand for non-chromium rust-preventing treatments and non-chromium organic coatings is increasing. As a non-chromic antirust treatment method that replaces the chromate treatment, Patent Document 3 discloses a treatment technique using an aqueous solution containing thiourea and tannin or tannic acid. However, when a precoat metal plate is produced using this antirust treatment method. When applied to home appliances, automobiles, etc., where the processing shape is complicated, there is a problem that the coating film adhesion at the processing portion is greatly inferior. Patent Document 4 discloses a technique for improving the whitening resistance and paint adhesion by surface-treating with an aqueous solution containing tannic acid and a silane coupling agent. However, even in this method, the processing adhesion required for the precoat metal sheet cannot be secured.

Patent Document 5 discloses a base treatment agent for a precoated metal sheet containing tannin or tannic acid, a silane coupling agent, and fine silica at the same time, and this base treatment agent is currently practically used to satisfy processing adhesiveness. This patent document also describes a treatment agent containing a polyester resin component in addition to the essential components, but it is explained that the addition of the polyester resin contributes to the improvement of the processing adhesiveness of the precoat metal sheet.

Japanese Unexamined Patent Publication No. Hei 8-168723 Japanese Unexamined Patent Publication No. Hei 3-100180 Japanese Laid-Open Patent Publication No. 53-9238 Japanese Unexamined Patent Publication No. 59-116381 Japanese Unexamined Patent Publication No. 2001-89868

In order to improve the coating film processing adhesion of the precoat metal sheet, the inventors of the present invention have added a treatment agent containing a polyester resin in addition to the essential components (tannin or tannic acid, a silane coupling agent and fine silica) of Patent Document 5 to prepare a precoat metal sheet. In the long-term use at steady state, the problem of precipitation in the treating agent was encountered.

If precipitation occurs in the treatment at steady state, several problems arise in operation. First, by depositing a deposit coater with a treatment agent on the metal plate by spreading the deposit deposited in the paint pan with the treatment agent, or by spraying the treatment agent containing the precipitate, the solid substance becomes foreign matter on the metal plate and adheres, resulting in poor appearance ( Commodity value is significantly impaired). In addition, the sticky deposit adheres to the surface of the roll coater or causes clogging of the spray, so that it is necessary to frequently perform roll replacement or spray maintenance, and workability is significantly reduced. Moreover, when precipitation is severe, the component ratio of a "symbol" liquid (actual treatment agent) changes largely from that of the original treatment agent, and leads to the situation where the original performance as a treatment agent cannot be expressed.

An object of the present invention is to provide a substrate treating agent for a precoat metal sheet which can solve the above-mentioned problems in the prior art.

Another object of the present invention is to add to tannin or tannic acid, a silane coupling agent, and fine silica, in addition to tannic acid, even if it contains a polyester resin which contributes to the improvement of processing adhesion of the precoat metal sheet, It is to provide a stable base treatment agent for a precoated metal sheet in which precipitation does not occur in a working industry.

It is still another object of the present invention to provide a precoated metal sheet excellent in processing adhesion between a coated base metal sheet coated with such a treatment agent and a coating film using the same.

As a result of intensive research and examination, the inventor of the present invention combines a polyester resin having a specific solid content with a specific particle diameter, a glass transition temperature (Tg) and a hydroxyl value in water to form a treatment agent, and the treatment agent is also added to a specific pH range. It turned out that setting to is very effective for solving the said subject.

The present invention is based on the above findings, and more specifically

Polyester resin which has a particle diameter of 50-150 nm, a glass transition temperature (Tg) of 0-30 degreeC, and a hydroxyl value of 5-13, with tannin or tannic acid, a silane coupling agent, and fine silica as solid content in water. And a pH of 2.0 to 6.5 as the treating agent.

In the present invention, the reason why the above excellent effects can be obtained is estimated as follows according to the findings of the present inventors.

That is, in addition to tannin or tannic acid, a silane coupling agent, and a fine silica, the processing agent of patent document 5 containing the polyester resin demonstrated to contribute to the improvement of the process adhesiveness of a precoat metal plate is carried out to the manufacturing industry of precoat metal plate manufacture. As a result, the present inventors have repeatedly studied and examined the present inventors in the face of the problem that precipitation occurs in the treatment agent in the steady state use over a long period of time.

In the production of the precoat metal plate, when the base treatment agent is used in a continuous line, it is common to circulate the treatment agent and apply it onto the metal plate with a roll coater or a spray. Since the treatment agent of the prior art (patent document 5) described above exhibits an acidity of about pH 4, when the operation is carried out for a long time, for example, when applied on a galvanized steel sheet, zinc is eluted little by little from the surface of the metal plate and circulated. The zinc concentration in the processing agent increases. Moreover, since a metal plate usually leads to the application | coating process of a base treatment agent immediately after passing through the degreasing, washing | cleaning, and hot air drying process, the temperature of the metal plate at the time of application | coating process enters substantially high, and the temperature of a processing agent rises gradually. Since the treating agent is applied and consumed on the metal plate at a constant rate, and a balanced amount of new treating agent is supplied to the circulation system, when they are balanced, the contamination concentration or temperature of the metal in the treating agent is normal. Depending on the operating conditions, in steady state, the temperature is usually up to 40 ° C. and the concentration of metal contamination (in the case of zinc) is approximately up to 100 ppm. Based on the above findings, the inventors have found that it is extremely important that the treatment agent is stable without causing precipitation during the use of the treatment agent containing the polyester resin or precipitation under the elevated temperature of the above-mentioned steady state. Revealed.

In the long time operation described above, zinc becomes an ion and is dissolved in the treatment agent. Since hydrogen ions in the treatment agent are consumed for the ionization of zinc, the pH of the treatment agent tends to rise gradually as the zinc ion concentration rises. If the value of the pH exceeds a predetermined value, it will be one of the causes that causes precipitation and adversely affects the operational stability as described later. Therefore, the pH needs to be a treatment agent that is difficult to fluctuate easily. That is, the present inventors have found that it is important that the fluctuation of the pH is sufficiently small in the above-described steady state metal contamination so as not to cause precipitation during the use of the treatment agent containing the polyester resin.

As the precipitation in the treating agent containing polyester becomes high in the presence of metal contamination, components having a coordinating ability such as a silane coupling agent or tannic acid in the treating agent react with the metal ions eluted from the metal plate, thereby making it stable in the treating agent. It became difficult to exist, and the present inventor thought that it precipitates with a polyester resin. However, as the study proceeded, the inventors found that there is a difference in the degree of precipitation easily depending on the type of polyester resin.

Thus, with respect to the cause of the difference in the degree to which precipitation is easy to occur according to the kind of polyester resin, the present inventor estimates as follows based on the combination of said knowledge about the mechanism of precipitation generation in a processing agent. do.

Since the silane coupling agent and the tannic acid are highly reactive compounds, a part of the treatment agent reacts to form a reaction product having poor solubility, which associates and aggregates to precipitate. When Zn ions eluted in the treatment agent are present, the Zn ions react with the reaction product and proceed in a direction in which the charge of the reaction product is further lost, so that the solubility is further lowered to promote the occurrence of precipitation. However, when a specific polyester resin exists in this system, since this reaction product adsorb | sucks by hydrophobic interaction to the hydrophobic part of a polyester resin emulsion, and it prevents the reaction products from being aggregated and aggregates, precipitation is suppressed. The degree of precipitation inhibition effect by the polyester resin depends on the degree of affinity of the reaction product with the polyester resin (easiness of adsorption by hydrophobic interaction) and the stability in the liquid of the polyester resin emulsion. Estimate. That is, based on this mechanism, it is estimated that the base treatment agent for precoat metal sheets of this invention exhibits the outstanding effect mentioned above.

Based on the various findings of the present inventors described above, the present inventors conducted further verification experiments. As the polyester resin, the present inventors have a particle diameter of 50 to 150 nm, a glass transition temperature (Tg) of 0 to 30 ° C, and a hydroxyl value. It is preferable that it is 5-13, and it is preferable that pH as a processing agent is 2.0-6.5, and based on this knowledge, the base treatment agent for the precoat metal plate of this invention which has the structure mentioned above was completed.

The present invention may include the following embodiments, for example.

(1) Poly with a particle diameter of 50 to 150 nm, a glass transition temperature (Tg) of 0 to 30 ° C, and a hydroxyl value of 5 to 13 together with tannin or tannic acid, a silane coupling agent and fine silica as solids in water. It contains ester resin and pH as processing agent is 2.0-6.5, The base treatment agent for precoat metal sheets characterized by the above-mentioned.

(2) When the mass concentration of tannin or tannic acid in the treatment agent is TA, the mass concentration of the silane coupling agent is SC, the mass concentration of fine silica is SI, and the mass concentration of polyester resin is PR: TA: SC = 1: 40 To 40: 1, (TA + SC): SI = 1: 10 to 20: 1, and (TA + SC): PR = 1: 10 to 10: 1 at the same time, and the concentration of each component (TA + SC + SI + PR) is 10-200 g / L, The base treatment agent for precoat metal sheets as described in said (1) characterized by the above-mentioned.

(3) The base treatment agent for the precoat metal sheet according to the above (1) or (2), wherein the silane coupling agent has a glycidyl ether group.

(4) The base treatment agent for the precoat metal sheet according to any one of the above (1) to (3), wherein no precipitation occurs when 100 ppm of zinc ions are mixed.

(5) The variation in pH when the zinc ions are mixed at 100 ppm is 1.5 or less, wherein the base treatment agent for a precoat metal sheet according to any one of the above (1) to (4).

(6) The undercoating-treated metal sheet according to any one of the above (1) to (5) is coated and dried on at least one surface thereof.

(7) The coated base material-treated metal sheet according to the above (6), wherein an adhesion amount of the solid content of the base material for the precoat metal sheet according to any one of the above (1) to (5) is 10 to 500 mg / m 2.

(8) A precoat metal sheet, having an upper coat layer on the uncoated base metal sheet as described in the above (6) or (7).

(9) The precoat metal plate which has a coating layer containing an rustproof pigment as a lower coat layer on the coating base metal plate as described in said (6) or (7), and has an upper coat layer on it further.

According to the present invention, in addition to tannin or tannic acid, a silane coupling agent and fine silica, by containing a polyester resin having a particle diameter of 50 to 150 nm, a Tg of 0 to 30 ° C, and a hydroxyl value of 5 to 13, In addition, it is possible to provide a stable base treatment agent for the precoat metal sheet, in which the production of the precoat metal sheet does not occur in the steady-state operation in a steady state for a long time.

The base treatment agent for the precoat metal plate of the present invention is a combination of a silane coupling agent and fine silica in tannin or tannic acid, thereby providing a base coating film having a base treatment film having a performance inferior to that of the chromate-treated precoat metal plate. It is possible to provide, and at the same time, by using such a specific polyester resin in combination, it is possible to produce a long-term stable precoat metal sheet.

In addition to tannin or tannic acid, a silane coupling agent and fine silica as solids in water, the base treatment agent for the precoat metal sheet of the present invention has a particle diameter of 50 to 150 nm and a glass transition temperature (Tg) of 0 to 30 ° C. It contains a polyester resin whose hydroxyl value is 5-13, The pH as a processing agent is 2.0-6.5, It is characterized by the above-mentioned.

Tannin or tannic acid, a silane coupling agent, and fine silica used for the base treatment agent for a precoat metal plate of this invention should just be normally used for the base treatment agent for a precoat metal plate conventionally.

Tannin or tannic acid may be hydrolyzable, may be condensed tannin, or may be one in which some of these are decomposed. Tannin and tannic acid are not particularly limited, such as hamamelelli tannin, blast tannin, gluttony tannin, miroboran tannin, dividy tannin, algarobivilla tannin, baronia tannin, catechin, etc. Is good at `` tannic acid: AL '' (manufactured by Fujikagaku Kogyo Co., Ltd.).

The silane coupling agent is, for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltri Ethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N- β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, N- β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethyldimethoxysilane, N- β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, N- β- (N -Vinylbenzylaminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmeth Dimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercapto Propyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimeth Oxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, γ-anilino Propylmethyldimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, Octa Decyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (triethoxysilyl) propyl] ammonium chloride, Octadecyldimethyl [3- (methyldiethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and the like. Although the silane coupling agent which has a glycidyl ether group, for example, (gamma)-glycidoxy propyl trimethoxysilane and (gamma)-glycidoxy propyl triethoxysilane which have glycidyl ether group, The processing adhesiveness of is particularly improved. Moreover, when the triethoxy type silane coupling agent is used, the storage stability of a base treatment material can be improved. This is considered to be because triethoxysilane is relatively stable in aqueous solution, and the polymerization rate is slow.

The mass concentration ratio of tannin or tannic acid and silane coupling agent in the treating agent is preferably 1:40 to 40: 1. If it deviates from this range, even if either component is many, the processing adhesiveness of a coating film and an rust prevention effect will fall. The mass concentration ratio of tannin or tannic acid and silane coupling agent is preferably 1:35 to 35: 1, more preferably 1:30 to 30: 1, most preferably 1:20 to 20: 1.

In the present invention, the fine silica is a generic term for silica that can have a stable and water-dispersed state when dispersed in water because of having a fine particle diameter. As particulate silica, for example, "Snotec N", "Snotec C", "Snotec UP", "Snotec PS" (all manufactured by Nissan Kagaku Co., Ltd.), "Adelite AT-200" (Asahiden Commercially available silica gel such as Kakogyo Co., Ltd., or powdered silica such as Aerosil # 300 (Nippon Aerosol Co.). The fine silica may be appropriately selected depending on the required performance. When fine silica is used, such as "Snotech C", which can be stably dispersed even at a pH of 4 or more, the storage stability of the base treatment agent can be improved. It is considered that this is because the pH of the chemical liquid can be adjusted to 4 or more, so that the reaction of the highly reactive silane coupling agent can be suppressed at a low pH.

At this time, in this invention, the advantage of using a silica whose pH is 4 or more and stable is storage stability. Therefore, it is not inconsistent with setting the liquid to pH 2 to 6.5 for operational stability.

With respect to the mass concentration of fine silica in the treatment agent, the mass concentration of the total of tannin or tannic acid and the silane coupling agent is preferably in the range of 1:10 to 20: 1. If it is less than 1:10, the cohesion force of a base treatment layer will fall and the process adhesiveness of a coating film will fall, and when it exceeds 20: 1, the process adhesiveness of a coating film will fall. The ratio of the mass concentration of tannin or the sum of tannic acid and silane coupling agent to the mass concentration of particulate silica is more preferably from 2:10 to 15: 1, and most preferably from 4:10 to 10: 1.

As for the polyester resin used for the pretreatment agent for precoat metal plates of this invention, particle diameter is 50-150 nm, glass transition temperature (Tg) needs to be 0-30 degreeC, and hydroxyl value needs to be 5-13. The presence of such a polyester resin in the base treatment agent prevents the insoluble reaction products resulting from the reaction of a part of the silane coupling agent and the tannic acid, which are highly reactive compounds, coagulate and aggregate to prevent aggregation. This precipitation occurrence suppression effect of a specific polyester resin having a particle diameter of 50 to 150 nm, a glass transition temperature (Tg) of 0 to 30 ° C, and a hydroxyl value of 5 to 13 has a silane coupling agent and tannic acid. It is considered that the reaction product is adsorbed to the hydrophobic portion of the polyester resin emulsion by hydrophobic interaction, and the reaction products prevent the association and aggregation of the reaction products.

First, when Tg of a polyester resin is less than 0 degreeC, the phenomenon which surface hardens arises and stability in the processing agent of a polyester resin falls, As a result, the above-mentioned precipitation suppression effect disappears and precipitation tends to occur.

This explains the phenomenon that the surface hardens. Below the glass transition temperature (Tg), the polyester resin emulsion particles are in a glass state, have hardness, and do not have fluidity on their own. Therefore, even if the emulsion particles collide with each other, they are stably dispersed without fusion. However, when the temperature reaches Tg or more, the emulsion particles become rubbery or liquid, and when the particles collide with each other, they aggregate and fuse. In particular, since the evaporation of water occurs on the surface of the treatment agent entered into the paint pan, the emulsion concentrates, aggregates (fusions), and solidifies. As a result, the situation (surface hardening phenomenon) like polyester film which put the thin film on the liquid surface of a processing agent will become. In addition, although the emulsion particles have charges on the surface and the particles repel each other and are stably dispersed, the charges are neutralized by the Zn ions in the treatment agent, and the repulsive force decreases, making it easier to aggregate and fuse. . That is, surface hardening phenomenon becomes easy to occur.

If the particle diameter of the polyester resin is out of an appropriate range, the surface hardening phenomenon also occurs. If the particle diameter is less than 50 nm, the number of particles adjacent to each other increases, the viscosity is high, and the movement of the particles themselves becomes dull, making them easy to aggregate, and as a result, surface hardening occurs. On the other hand, when the particle diameter exceeds 150 nm, the area of the particles exposed to the air layer is large at the outermost surface of the treatment liquid, and the evaporation of water is promoted at the portion thereof, resulting in easier aggregation and resulted in a surface hardened state. As a result, the stability in the processing agent of a polyester resin falls similarly, the precipitation suppression effect mentioned above disappears and precipitation tends to generate | occur | produce.

When Tg of a polyester resin exceeds 30 degreeC, the performance after film-forming will not come out (process adhesiveness of the film of a precoat metal plate will fall compared with the case of the polyester resin in which Tg exists in the said preferable range).

In Patent Document 5, although the tanning or tannic acid, the silane coupling agent, and the fine silica, the base treatment agent for a precoat metal sheet containing a polyester resin is described as effective for improving the process adhesion of the coating film, the present inventors It has been provided to the working industry that the problem of precipitation in the treating agent in the long term use in the steady state has been already described. At this time, the present inventors used the polyester resin (Finetex ES-650 (made by Dainippon Inkaki Chemical Co., Ltd.)) described in the Example of patent document 5.

Then, the present inventors tried various experiments aiming at solving the said problem, and repeated examination, As a polyester resin, as mentioned above, particle diameter is 50-150 nm and Tg is 0-30. It was also found that certain ones having a hydroxyl value of 5 to 13 should be used. In addition, the polyester resin of the Example of patent document 5 (Finetex ES-650 (made by Dainippon Inky Chemical Co., Ltd.)) was measured by the method described in this specification, The particle diameter is 300 nm and glass transition temperature (Tg) ) Was 40 to 50 ° C. Since the Example of patent document 5 focused on the verification of the adhesion of the coating film to the metal plate which processed the base material, it confirms until the "preservation" stability of the processing agent, but until the presence or absence of precipitation which arises in a processing agent in long-term operation. Did not do it. This indicates that, at the time of filing of Patent Document 5, the phenomenon in which precipitation occurs in the treatment agent in a long period of operation was not recognized.

In the present invention, the Tg of the polyester resin is more preferably 1 to 28 ° C, more preferably 3 to 25 ° C, most preferably 15 to 25 ° C.

In addition, the improvement of the "preservation" stability of the processing agent of patent document 5 is by using the silane coupling agent of a triethoxysilane form, and a stable fine silica of pH 4 or more. The storage stability of the treatment agent depends on the reaction of highly reactive constituents (silane coupling agent, fine silica, tannic acid) during the storage of the treatment agent (before actually used as the treatment agent). Therefore, storage stability of a processing agent is a characteristic before actual use of a processing agent. On the other hand, the problem of precipitation which arises when operating for a long time using the processing agent which this invention tried to solve is encountered at the time of practical use of the processing agent after storage, and it is a problem of a dimension different from the storage stability of a processing agent.

In the substrate treating agent for the precoat metal sheet of the present invention, when the hydroxyl value of the polyester resin is less than 5, the charge on the surface of the emulsion particles is insufficient, and the stability (dispersibility) in the liquid is lowered, thereby easily causing precipitation and sufficient. The effect of precipitation inhibition is not expressed. If the hydroxyl value of the polyester resin is more than 13, it is difficult to obtain hydrophobic interaction, so that the reaction product does not affinity (adsorption) to the polyester resin and precipitation occurs.

As the polyester resin in the base treatment agent for the precoat metal sheet of the present invention, any one can be used as long as it satisfies the conditions of the aforementioned particle diameter, Tg and hydroxyl value. In the case of using a commercially available product, for example, a product that satisfies the conditions is selected from a series such as Toyo Boseki Co., Ltd., Vironal, Dainippon Inky Kagaku Kogyo Co., Ltd. Finetex, and Gao Co. Ltd. NT. Can be used.

The mass concentration of the polyester resin in the treatment agent is preferably 0.1 to 10 times the mass concentration of the total of tannin or tannic acid and the silane coupling agent. If it is less than 0.1 time, the effect of polyester resin addition will not be seen, and if it exceeds 10 times, the process adhesiveness of a coating film will fall rather. More preferably, it is 0.15 to 5 times, most preferably 0.2 to 2 times.

In the base treatment agent of the present invention, the total concentration of the tannin or tannic acid, the silane coupling agent, the fine silica and the polyester resin is preferably 10 to 200 g / L. If the total mass concentration is less than 10 g / L, the desired adhesion amount is difficult to be obtained. On the other hand, if the total mass concentration is more than 200 g / L, the concentration is so high that the stability (preservation stability, preservation and operation stability) of the ground treatment agent is lowered.

The base treatment agent of the present invention preferably has a pH of 2.0 to 6.5, more preferably 3.0 to 6.0. If the pH is less than 2.0, the elution of Zn increases and the concentration of Zn in the treatment liquid increases, so that precipitation tends to occur. On the other hand, in the neutral region exceeding 6.5, the stability of the particulate silica decreases, and gelation tends to occur.

The base treatment agent of the present invention preferably has an increase in pH of 1.5 or less when 100 ppm of zinc ions are mixed. Since the treatment agent whose pH rise fluctuates more than 1.5 when the zinc ions are uniformly dissolved in 100 ppm is inferior in pH buffering capacity, it is easy to cause an extreme pH rise locally in the treatment agent during operation, adversely affecting the stability during operation. There are many cases. It is effective to set the mass concentration (TA) of tannin or tannic acid in the treatment material to 5 g / L or more in order to make the fluctuation in pH rise to 1.5 or less. This is thought to be due to the pH buffering effect by proton dissociation of tannin or tannic acid.

As evaluation of the stability at the time of operation, the presence or absence of precipitation occurrence at the time of Zn contamination was determined by the following method. A predetermined amount of zinc powder (particle diameter: about 0.3 to 1.5 mm (14 to 50 mesh ASTM) was added to the treatment liquid, stirred and dissolved at 40 ° C. for 3 hours to prepare a 100 ppm solution of zinc. 300 ml of this solution was placed in a polyethylene bottle, and left standing for 3 days in a thermostat at 40 ° C. Thereafter, the precipitate was collected by filtration through a # 300 mesh, washed with pure water, and then the precipitate was sufficiently filled in an 1100 ° C. oven. (About 2 hours) After drying, the weight was measured after returning to room temperature in a desiccator, and when the weight of a precipitate was less than 1 mg, it determined with no precipitation.

Next, the measuring method of Tg, hydroxyl value, and particle diameter of the polyester resin (water-dispersion type polyester resin emulsion of 20% of solid content) used for the ground treatment agent of this invention is demonstrated.

<Measurement method of Tg>

Resin has the property that a specific heat changes with a state change in the vicinity of Tg (glass transition temperature). Using this, the DSC method is to measure the specific heat change (endotherm near Tg) of the measurement sample which occurs when the standard material and the measurement sample are heated and subjected to the same temperature raising condition. In the present invention, Tg was measured by the DSC method.

First, about 1 g of polyester resin is taken in a Teflon (Ceflon) chalet of 50 mmφ. This is put into an oven at 50 ° C. for 2 hours to evaporate moisture. Next, it is left to depressurize for 24 hours to make a dry sample. This sample is ground and about 10 mg is taken in the aluminum cup for a thermal analysis apparatus. Also, about 10 mg of the alumina powder is used as a standard substance in an aluminum cup. This is set in a thermal analysis apparatus, cooled at -50 ° C, and the measurement is started. The temperature increase rate at the time of this measurement is 20 degreeC / min. Absorption heat generation data during this period was collected, and the obtained data was analyzed (read the temperature at which the heat change occurred: analysis software attached to the device), and Tg (° C.) of the resin was obtained.

Thermal analyzer used: Seiko Electronics Co., Ltd., DSC-210.

<Measurement method of hydroxyl value>

It measured according to the method A-acetylation method described in JIS K1557-1 plastic-polyurethane raw material polyol test method-Part 1: The method of obtaining a hydroxyl value. The measurement sample used the thing which evaporated water at 50 degreeC similarly to the measurement of Tg, and was left to dry for 24 hours by the pressure reduction desiccator, and dried. In addition, the titration calculated | required the end point by potentiometric titration (at AT420 by Kyoto Denshi Corporation), and the hydroxyl value was computed by the predetermined calculation formula.

<Measurement method of particle diameter>

It is diluted with pure water so that solid content of a polyester resin may be 0.1%. About 500 g of this was put into a 1 L glass beaker and this was ultrasonically dispersed for 1 minute in an ultrasonic cleaner (600 W, 40 kHz). This was carried out as a pretreatment for releasing secondary aggregated particles. The particle diameter was measured by the particle size distribution measuring device using this as a measurement sample. The particle diameter was taken as the average particle diameter computed from the attached analysis software.

A device used: Nike Sok Co., Ltd., nano track UPA-EX150

The pH of the treating agent was measured using a pH meter (Doadikei Kay, pH meter HM-30G).

<PH change when Zn ions are mixed>

The rise change in pH when 100 ppm of zinc ions were mixed was measured by the following method.

First, the initial pH of each treatment agent was measured with a pH meter. Thereafter, a predetermined amount of zinc powder (particle diameter: about 0.3 to 1.5 mm (14 to 50 mesh ASTM)) was added to each treatment agent, stirred and dissolved at 40 ° C. for 3 hours to prepare a 100 ppm zinc solution. The pH of the solution was measured with a pH meter. The initial value measured first was subtracted from this value, and it was set as the rise change of pH.

The coating base treatment metal plate of the present invention is characterized in that the base treatment agent for the precoat metal sheet of the present invention is coated and dried on at least one surface thereof.

In order to form a base treatment layer on a metal plate using the base treatment agent of this invention, a base treatment agent (chemical liquid) is apply | coated to a metal plate, and it heats and dries. You may add acid, an alkali, etc. in chemical liquid in order to adjust pH in the range which does not impair the performance. As heating temperature, 50-250 degreeC is good. If it is less than 50 degreeC, since the evaporation rate of water is slow and sufficient film-forming property cannot be obtained, antirusting power is lacking. When it exceeds 250 degreeC, the tannic acid which is an organic substance, and the alkyl part of a silane coupling agent generate | occur | produce denaturation by thermal decomposition etc., and adhesiveness and corrosion resistance fall. As for heating temperature, 70-160 degreeC is more preferable. Heating and drying methods are not particularly limited. For example, hot air drying can be used, in which case drying for 1 second to 5 minutes is preferable.

The coating method of the ground treatment agent is not particularly limited, and generally, a known coating method such as a roll coat, air spray, airless spray, dipping, or the like can be used.

It is preferable that the adhesion amount with respect to the metal plate of the base treatment agent of this invention is 10-500 mg / m <2> as solid content. If it is less than 10 mg / m <2>, sufficient processing adhesiveness will not be ensured, and if it exceeds 500 mg / m <2>, processing adhesiveness will fall rather.

The precoat metal plate of this invention has an upper coating layer on the coating base metal plate of this invention by which the base treatment agent of this invention was apply | coated and dried on the surface of at least one side, It is characterized by the above-mentioned.

In the precoat metal sheet of the present invention, the base resin of the upper coating layer coated on the underlying treatment layer may be of any type, such as an aqueous system, a solvent system, or a powder system. As a kind of resin, generally well-known thing, for example, polyacrylic-type resin, polyolefin resin, polyurethane-type resin, epoxy-type resin, polyester-based resin, polybutyral-type resin, melamine-type resin etc. are used as it is, or a combination Can be used.

You may add a coloring pigment to an upper film layer. As the coloring pigment, titanium oxide (TiO ₂ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), alumina (Al ₂ O ₃ ), kaolin cray, carbon black, iron oxide _{(Fe 2 O 3, Fe 3} O 4) can generally be a coloring pigment such as a well-known inorganic pigments or organic pigments such as.

In addition to the above-mentioned colored pigment, you may add an rust preventive pigment to an upper coat layer as needed. As the rust preventive pigment, generally known ones, for example, (1) phosphate rust preventive pigments such as zinc phosphate, iron phosphate, and aluminum phosphate, (2) molybdates such as calcium molybdate, aluminum molybdate and barium molybdate Rustproof pigments, vanadium-based rustproof pigments such as (3) vanadium oxide, (4) fine silica such as water dispersible silica and fumed silica, and the like. Chromate antirust pigments such as strontium chromate, zinc chromate, calcium chromate, potassium chromate, barium chromate and the like are not used because they are environmentally toxic.

1-25 micrometers is suitable for the thickness of the upper coat layer containing a coloring pigment and an antirust pigment. If it is less than 1 micrometer, the corrosion resistance of a precoat metal plate will worsen, and if it is more than 25 micrometers, the workability of a coating film will be inferior. However, when the upper coating is used as an organic or inorganic coating such as a lubricating coating or an anti-fingerprint coating, and is used as a surface-treated metal sheet for a so-called post coating or a coating which is not subjected to further coating, the upper coating may be used depending on the purpose of use. What is necessary is just to select suitably the kind and the film thickness, and it does not limit a film thickness to 1-25 micrometers especially.

Application | coating of an upper layer coating can be generally performed by a well-known coating method, for example, a roll coat, a curtain flow coat, an air spray, an airless spray, dipping, a bar coat, brush coating, etc.

In the precoat metal plate of this invention, the coating layer which added the rust preventive pigment can be formed as a lower coating layer between the base treatment layer and the upper coating layer.

The base resin of the lower coat layer may be of any form, such as an aqueous system, a solvent system, or a powder system. Moreover, an adhesive layer may be sufficient. As a kind of resin, generally well-known thing, for example, polyacrylic resin, polyolefin resin, polyurethane resin, epoxy resin, polyester resin, polybutyral resin, melamine resin etc. are used as it is or combining them, Can be used. As the rust-preventive pigment, any one can be used, but generally known ones include, for example, (1) phosphate-based rust-preventive pigments such as zinc phosphate, iron phosphate and aluminum phosphate, (2) calcium molybdate, aluminum molybdate, Molybdate rust-preventive pigments, such as barium molybdate, (3) vanadium rust-preventive pigments, such as vanadium oxide, (4) fine silica, such as water dispersion silica and fumed silica, etc. can be used. Chromate antirust pigments such as strontium chromate, zinc chromate, calcium chromate, potassium chromate, barium chromate and the like are not used because they are environmentally toxic. The addition amount of the rust preventive pigment is suitably 1 to 40% by weight. If it is less than 1 wt%, there is little corrosion resistance effect, and if it exceeds 40 wt%, the workability of a coating film will fall and it is unsuitable.

1-25 micrometers is suitable for the thickness of the lower coat layer containing an rustproof pigment. If it is less than 1 micrometer, the rust prevention effect will be inadequate, and if it exceeds 25 micrometers, the workability of a coating film will be inferior. Application | coating of the coating layer containing an rustproof pigment can be generally performed by a well-known coating method, for example, roll coat, curtain flow coat, air spray, airless spray, immersion, bar coat, application | coating using a brush, etc.

[Example]

EMBODIMENT OF THE INVENTION Below, the Example and comparative example of this invention are given, and this invention is concretely demonstrated to it.

1. Production of Trial

1.1 Test Materials

? Electro Galvanized Steel Sheet (EG)

   Plate thickness 0.6 mm, 20 g / m2 per side of zinc deposit

Hot dip galvanized steel (GI)

   Plate thickness 0.6 mm, 60 g / ㎡ per side of zinc coating weight (both sides plating)

? Cold rolled steel sheet (cold rolled)

   Plate thickness 0.6mm

1.2 Pretreatment

The test material was immersed in an aqueous solution having a concentration of 20 g / L and a temperature of 60 ° C. for 10 seconds using CL-N364S (manufactured by Nippon Park Car Co., Ltd.) of an alkali degreasing agent, washed with pure water, and dried.

1.3 not processed

Treatment with lower limb treatment (Examples 1 to 96, Comparative Examples 1 to 61)

The base treatment agent of the composition (content is g / L unit) shown in the column of the "base treatment layer" of Tables 1-5 is apply | coated to a test material so that it may become a predetermined | prescribed film thickness with a roll coater, and it arrives in a hot air drying furnace. It dried so that plate | board temperature might be 70 degreeC, 150 degreeC, and 220 degreeC. In the solid content of each base treatment agent, the following were used as tannic acid, a silane coupling agent, and a silica.

(a) tannic acid

 Tannic Acid AL (manufactured by Fujikagaku Co., Ltd.)

(b) silane coupling agent

Silane coupling agent A: γ-glycidoxypropyltrimethoxysilane

Silane coupling agent B: γ-mercaptopropyltrimethoxysilane

Silane Coupling Agent C: Methyltrichlorosilane

Silane coupling agent D: γ-glycidoxypropyltriethoxysilane

(c) silica

ST-N: Snow Tech N (made by Nissan Kagaku Kogyo)

Aerosil: Aerosil # 300 (Nippon Aerosil)

ST-C: Snow Tech C (made by Nissan Kagaku Kogyo)

As polyester resin, the thing of Tg and hydroxyl value shown in Tables 1-5 was used.

Coating chromate treatment (Comparative Examples 36 to 38)

As a coating chromate agent, ZM-1300AN (manufactured by Nippon Parkcharizing Co., Ltd.) was applied to the test material by using a roll coater so that the amount of Cr adhered to 40 mg / m 2, and dried so that the temperature reached to 70 ° C. in a hot air drying furnace.

? Electrolytic Chromate Treatment (Comparative Example 39)

In a bath of 50 g / L chromic acid and 0.3 g / L sulfuric acid, an electric current was supplied to the specimen at an electric current density of 10 A / dm 2 so that the amount of Cr was 40 mg / m 2. It dried so that reached plate temperature might be 80 degreeC.

1.4 Undercoat Coating

The coating material shown below as a primer coating material was apply | coated to the substrate-treated test material so that it might become a predetermined | prescribed film thickness with a roll coater, and it hardened | cured-dried so that the reaching board temperature might be 220 degreeC in the induction heating furnace which blown hot air, and the lower coat layer was Formed.

? Polyester A

Zinc phosphite is used as Nippon Paint's P641 primer paint and rust preventive pigment.

? Polyester B

Nippon Paint Co., Ltd. P641 primer paint and anti-corrosive pigment, V / P (vanadic acid / phosphate) system.

? Polyester C

Mop is used as a P641 primer paint and rust preventive pigment from Nippon Paint.

? Polyester D

Calcium silicate system is used as P641 primer paint and rust preventive pigment from Nippon Paint.

? urethane

Zinc phosphite is used as Nippon Paint's P108 primer paint and rust preventive pigment.

? Epoxy

Zinc phosphite is used as Nippon Paint's P304 primer paint and rust preventive pigment.

1.5 upper layer coating

Nippon Paint Co., Ltd. FL100HQ (polyester-based, white in color) was applied to the lower-layer coated test piece so as to have a predetermined film thickness by a roll coater. It hardened | cured and dried so that an upper coat layer might be formed.

2. Evaluation

2.1 Coating Process Adhesion Test 1

The plate after coating was put in a 1 mm square checker plate with a cutter knife on the coated surface, and extruded 7 mm with an Ericsson tester so that the coated surface was convex, and then taped according to the methods described in 8.2 and 8.5 of JIS K 5400. It was provided for the peel test. In addition, in this test, the tape peeling test is performed continuously in the same place twice (hereinafter, referred to as "double tape peeling"). Evaluation of tape peeling is performed based on the drawing of the example of evaluation described in 8.5 of JIS K 5400, and when it is 10 points | pieces, when it is 10 points | pieces, when it is 8 or more and less than 10 points, when it is 6 or more and less than 8 points, when it is △ and less than 6 points It evaluated as x.

2.2 Coating Process Adhesion Test 2

180 degreeC bending process (0T process in 20 degreeC atmosphere) was performed to the board | substrate after coating, the coating film of the process part was observed by 20 times loupe, and the presence or absence of the crack of the coating film was investigated. Moreover, the coating film residual state at the time of sticking an adhesive tape to a process part and peeling this hardly was visually observed. In addition, in this test, tape peeling was performed twice. Evaluation of the crack of the coating film is clear even when there is no coating film crack at all, when there are about 1 to 3 very small cracks in the coating film, when there are very small cracks on the coating film, and when the coating film is visually inspected. When large cracks existed in the whole process part, it evaluated as x. In addition, evaluation of the coating film residual state after tape peeling is a case where the coating film does not peel at all, and remains on a steel plate, (circle) and the case where the coating film is partially peeled off, and the case where the coating film is peeling severely partially is (triangle | delta), and the bending process part is almost completed. The case where peeling of a coating film is recognized over the whole surface was evaluated as x. In addition, after 0T process of the coated steel plate, it was immersed in boiling water for 1 hour, and it took out and left to stand for 24 hours, and the tape peeling of the coating film was performed. The evaluation of the coating film remaining state indicates that the coating film does not peel at all and remains on the plated steel sheet. The case where the coating film is partially peeled off and the case where the coating film is partially peeled off severely are almost over the entire surface of the bent processed portion. The case where peeling of a coating film is recognized was evaluated as x.

2.3 Corrosion Resistance Test

The salt spray test was done about the board | substrate after coating by the method described in 9.1 of JISK5400. The test time was 240 h in the case of an electrogalvanized steel plate, and 360 h in the case of a hot dip galvanized steel plate. Evaluation of the coating film of a cross cut part evaluates as (circle) when the largest inflation width of a cross cut part is less than 1 mm, (circle) when 2 mm or more and less than 3 mm, (triangle | delta), when 3 mm or more and less than 5 mm, and x when it is 5 mm or more. It was.

In addition, the above-described salt spray test was also performed on the flat plate produced so that the end (burr) at the time of cutting was on the evaluation surface side of the coated steel sheet (the upper burr). In the case of less than 2 mm, (circle), when 2 mm or more and less than 3 mm, it evaluated as (circle), and when 3 mm or more and less than 5 mm, it evaluated as (triangle | delta) and 5 mm or more. In addition, the corrosion resistance test was not performed when the original plate is a cold rolled sheet steel.

2.4 Storage Stability Test

After storing the base treatment agent used for each Example in 40 degreeC oven for predetermined time, each coating metal plate was produced on the conditions of this Example using this, and the coating process adhesion test 2 shown in 2.2 was done. Compared with the case where the fresh base treatment agent was used, the maximum storage time which cannot see the fall of coating-film-processing adhesion performance was evaluated as the storage stability of the base treatment agent.

2.5 Operational Stability Test of Lower Limb Treatment Agents (1)

Zinc powder (particle diameter: about 0.3-1.5 mm (14-50 mesh ASTM)) was added to the solution of each base treatment agent of an Example and a comparative example so that concentration might be 100 ppm, and it stirred for 3 hours and made it melt | dissolve at 40 degreeC. Thereafter, 300 ml of the solution was placed in a 500 ml capped polyethylene container and allowed to stand for 3 days in a thermostat at 40 ° C. The solution taken out of the thermostat was filtered through a # 300 mesh to recover the precipitate, and then washed with pure water. The precipitate was dried sufficiently (about 2 hours) in an oven at 110 ° C., then returned to room temperature in a desiccator and weighed, when the weight of the precipitate was less than 1 mg, it was determined that there was no precipitation. After standing for 3 days, the solution was visually inspected, and there was no abnormality. In addition, when there was no precipitation, the solution was slightly cloudy, but when there was no precipitation, ○, there was less than 100 mg of precipitation. In the case of △, when precipitation of 100 mg or more occurred, it was evaluated as x.

2.6 Operational Stability Test of Lower Limb Treatment Agents (2)

 (Assuming that circulation is not sufficient in the piping of the ground treatment agent during operation, and retention occurs.)

In the test method of 2.5, the process of melt | dissolving zinc powder, stirring at 40 degreeC for 3 hours was abbreviate | omitted. That is, 300 ml of the solution of each base treatment agent of the Examples and Comparative Examples was put into a 500 ml polyethylene container with a lid, and the zinc powder (particle diameter: about 0.3 to 1.5 mm (14 to 50 mesh ASTM) was added at a concentration of 100 ppm. The mixture was added as much as possible, and the solution was left still for 3 days in a constant temperature bath at 40 DEG C. After being taken out of the thermostat, the solution was filtered through a # 300 mesh to recover the precipitate, washed with pure water, and then the precipitate was sufficiently washed in a 110 DEG C oven (about 2 Time) After drying, the sample was returned to room temperature in a desiccator and weighed, and when the weight of the precipitate was less than 1 mg, it was determined that there was no precipitation.The evaluation was performed by visual inspection on a solution after standing in a thermostat for 3 days. If there is no abnormality and there is no precipitation, ◎, the solution has some turbidity, but if there is no precipitation, ○, if there is less than 100 mg of precipitation, △, more than 100 mg of precipitation occurs. If hayeoteul has been evaluated as ×.

The evaluation results are shown in Tables 6 to 10.

Claims (9)

A polyester resin having a particle diameter of 50 to 150 nm, a glass transition temperature (Tg) of 0 to 30 ° C, and a hydroxyl value of 5 to 13, together with tannin or tannic acid, a silane coupling agent, and fine silica as solids in water. It contains, and pH as a processing agent is 2.0-6.5, The base treatment agent for precoat metal sheets characterized by the above-mentioned. The mass concentration of tannin or tannic acid in the treatment agent is TA, the mass concentration of the silane coupling agent is SC, the mass concentration of fine silica is SI, and the mass concentration of polyester resin is PR: TA: SC = 1:40 to 40: 1, (TA + SC): SI = 1: 10 to 20: 1, (TA + SC): PR = 1: 10 to 10: 1 are simultaneously satisfied and the sum of each component A base treatment agent for precoat metal sheets, characterized by a concentration (TA + SC + SI + PR) of 10 to 200 g / L. The base treatment agent for a precoat metal sheet according to claim 1 or 2, wherein the silane coupling agent has a glycidyl ether group. The base treatment agent for a precoat metal sheet according to any one of claims 1 to 3, wherein no precipitation occurs when zinc ions are mixed at 100 ppm. The base treatment agent for a precoat metal sheet according to any one of claims 1 to 4, wherein a rise change in pH when 100 ppm of zinc ions are mixed is 1.5 or less. The base treatment agent for the precoat metal plate as described in any one of Claims 1-5 is apply | coated and dried at least on the surface of single side | surface, The coating base metal sheet which is characterized by the above-mentioned. The coating base material-treated metal sheet according to claim 5, wherein an adhesion amount of the solid content of the base treatment agent for the precoat metal sheet according to any one of claims 1 to 5 is 10 to 500 mg / m 2. A precoat metal sheet having an upper coat layer on the coated substrate-treated metal sheet according to claim 6. The precoat metal plate which has a coating layer containing an rustproof pigment as a lower coat layer on the coating base material metal plate of Claim 6, or 7, and further has an upper coat layer on it.