JPS6017704B2 - Composite resin coated metal body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite resin-coated metal body, and more specifically, the present invention relates to a composite resin-coated metal body, and more specifically, the metal body is coated with aluminum as an inner layer on the surface of the metal body.
A composite resin coating characterized by providing a composite resin layer containing a metal powder such as tin or manganese, and as an outer layer a composite resin layer containing a compound of metals from group LA or group OA of the periodic table. It concerns metal objects.

BACKGROUND ART Conventionally, various types of surface treatments have been extensively researched and put into practical use in order to improve the corrosion resistance of metal bodies.

Since the corrosiveness of metal objects varies greatly depending on the corrosive environment, it is currently difficult to determine the method for preventing corrosion. As an example, surface-treated steel sheets that are mainly galvanized have been put into practical use as outdoor building materials such as roofing materials and wall materials.

On the other hand, for can members and the like, surface-treated steel sheets mainly having tin plating have been put into practical use. In addition to these, chromium, nickel,
Plating of copper, aluminum, etc. has been widely put into practical use. In recent years, not only has the price of coating metals used for surface treatment of such metal bodies soared due to the problem of resource depletion, but also it has become difficult to form stable supply grooves for some metals.

Against this background, technological improvements have been actively made to convert the conventional thick coating technology to thin coating technology.

In other words, in the field of galvanized steel sheets, there has been a shift from hot-dip galvanized steel sheets to lightly leaded steel sheets, and in the field of tin-plated steel sheets, there has been a shift from thick-gained tin-plated steel sheets to thin-gained tin-plated steel sheets. It began to be widely used.

In addition, since tin is very expensive, tin-free steel plates have rapidly begun to be used as materials for bamboo grass in recent years. As such light weight surface treatment begins to be widely used, chemical conversion treatment as a post-treatment will become more important than secondary treatment.

In other words, in order to maximize the effectiveness of light-weight matte coatings, research on post-forming treatments, etc. has been widely conducted, but still,
It does not have the same corrosion resistance as heavy weight. On the other hand, in fields that require a higher degree of corrosion resistance, so-called painted metal bodies in which a resin layer is provided on the plating have been widely used, but as mentioned above, the basis weight of the plating on the metal body As the corrosion resistance decreases, the specific gravity that contributes to corrosion resistance tends to shift to the resin side, so research on improving coating films has been actively conducted in recent years.

In other words, research has been carried out to improve paint designs that place emphasis on paintability, drying properties, and aesthetics to coating films that place emphasis on corrosion resistance. For example, methods of adding corrosion inhibitors such as strontium chromate to the coating resin, or hardening the coating resin to suppress the penetration of corrosive liquids, have been considered, but these methods are difficult to achieve in a highly corrosive environment. In these days of rapid changes, the reality is that corrosion protection from the side of the coating film is not necessarily sufficient. Furthermore, improvements in coating strength resins as described above generally have the disadvantage that processing corrosion resistance is reduced because processability is reduced. In order to eliminate such drawbacks, the present invention improves processing corrosion resistance, and provides excellent corrosion resistance that maintains sufficient corrosion resistance even for resin layers with poor processing properties, such as thermosetting resins. The object of the present invention is to provide a composite coated metal body having a metal powder of aluminum, zinc, nickel, tin, cobalt or manganese, or one or more of these metals as an inner layer on the surface of the base metal. A composite resin layer containing one or more types of alloy or stainless steel powder is provided, and as an outer layer, an oxide, hydroxide, carbonate, or bicarbonate of a metal from group LA or group Oa of the periodic table is provided. Salt, borate, phosphate, silicate, aluminate, stannate, tungstate, molybdate, chromate "dichromate or organic acid salt with a particle size of less than 10 meters" This is a composite resin-coated metal body characterized by being provided with a composite resin layer containing one or more types of powder.

The contents of the present invention will be explained in detail below.

First, the target base metal is a mild steel plate, or an alloy containing tin, chromium, zinc, nickel, iron, copper, cobalt, manganese, lead, aluminum, or one or more of these metals on the surface of the mild steel plate. The surface of plated or coated steel sheets, European steel sheets, or the surface of said coated steel sheets is coated with chromates, dichromates, phosphates, acid phosphates, molybdates, silicates, borates, and perborates. Examples include chemical conversion treated steel plates treated with acid salts or aluminates, cut plates or strip plates of aluminum plates or aluminum alloy plates, and metal processed products other than plate shapes.

Next, the base resins for the composite resin applied to the base metal include epoxy, phenol, acrylic, nylon, vinyl, alkyd, melamine,
Examples include one or more types of resins such as hurya-based, butadiene-based, ester-based, silicon-based, olefin-based, urethane-based, styrene-based, and xylene-based resins.

Pigments, plasticizers, antistatic agents, light or heat stabilizers, and the like may be added to these resins as necessary. Note that these resins cover the base metal surface to impart corrosion resistance, and also serve as a binder for the metal compound described below.

Next, the metal powder blended into the resin will be explained.

First, the metal powder added to the inner resin layer is one or two of aluminum, zinc, nickel, tin, cobalt, or manganese metal powder, an alloy containing one or more of these metals, or stainless steel powder. It is necessary to contain more than 100% of The shape of these metal powders may be either granular or scaly; however, if the scaly powder is added in the same amount, the corrosion resistance will be improved. A metal powder having a particle size and thickness (when it is granular in shape, it is called the particle size, and when it is scaly in shape, it is called the thickness) is 10 mm or less and has excellent coating properties on the surface of a metal body. Particle size and thickness are 1
If it exceeds 0 m, not only will the shape of the composite resin surface on the metal body become rough, but the composite resin coating will be more likely to have defects, and as a result, the corrosion resistance will also decrease. Next, the metal powder added to the outer resin layer includes oxides, hydroxides, carbonates, bicarbonates, borates, phosphates of metals from group LA or group Oa of the periodic table, silicates, aluminates,
It is necessary to contain one or more powders of stannate, tungstate, molybdate, chromate, or organic acid salt having a particle size of 10 m or less.

When the particle size of these metal powders is 10 rm or less, the coating properties on the surface of the metal body are excellent.

If the particle size exceeds 10 mm, not only will the shape of the composite resin surface of the metal body become rough, but the composite resin coating will be more likely to have defects, resulting in a decrease in corrosion resistance. Next, the amount of metal powder added to the inner and outer resin layers is preferably 1 to 30 parts by weight per 100 parts by weight of each resin solid content. If the amount is less than 1 part by weight, the corrosion resistance is extremely low and it is difficult to add. The effect is practically not observed.

Moreover, if the amount exceeds 300 parts by weight, the coating properties will deteriorate and the corrosion resistance will not improve as much as the amount added, which is uneconomical. In addition, in order to determine the appropriate blending amount, the degree of corrosive environment, the thickness of the composite resin layer, etc. must be taken into consideration. - The thickness of the inner and outer composite resin layers to be applied next to the metal body is preferably in the range of 1 to 100 m.

If the thickness is less than 1 Am, the corrosion resistance will be extremely reduced and the coating will be ineffective, while if it exceeds 100 mm, the coating properties will be reduced. Although some of the metal powders mentioned above are sometimes used as pigments, they are essentially different from pigments because they are not particularly required to have the strict performance of pigments, such as coloring power and hiding power.

Now, an example of the method for obtaining the composite resin-coated metal body of the present invention will be briefly described.

First, a composite resin solution to be applied as an inner layer is applied to the surface of a cut plate or a band-shaped metal body using a coating equipment such as a Rofu coat, and then dried at a temperature of 50 to 200°C, and then a composite resin solution to be applied as an outer layer is applied in the same manner. It is applied using a coating equipment such as a roller coater, and both the inner and outer layers are sufficiently cured at a temperature of 100 to 300°C to completely adhere.

The composite resin-coated metal body produced by the above manufacturing method has excellent processing corrosion resistance, but for applications requiring even higher corrosion resistance, coating the outer layer with a resin has a remarkable effect. The resin layer coated on the upper layer may be in the form of a solution, paste, pellet, or film. The composite resin-coated metal body thus obtained has excellent process corrosion resistance and can be applied to various uses requiring corrosion resistance. The present invention will be described in detail below with reference to examples.

Example 1 A composite resin-coated metal plate was prepared using the following composite resin solution and treatment method on a degreased electrolytically chromic acid-treated steel plate having a thickness of 0.5 mm.

Composite resin solution composition Inner layer resin layer Urethane resin solution 10 parts by weight (Urethane resin 2 parts by weight Ethyl acetate)
8 parts by weight) (Product name: Adcode 7)
691...manufactured by Toyo Morton Co., Ltd.) Curing agent for urethane resin 2. Parts by weight (Product name: Catalyst F manufactured by Toyo Morton Co., Ltd.) Scale-like aluminum powder 5 parts by weight (Thickness: 5 m or less) Outer resin layer Urethane resin solution 10 parts by weight (Product name: Adcode 7691... ...1 Manufactured by Toyo Morton Co., Ltd.) Magnesium oxide powder 5 parts by weight (particle size: 1 to 5 m) Treatment method First, the above composite resin solution was applied as an inner resin layer on one side of the electrolytic chromic acid treated steel sheet to a dry thickness of 5 rm. It was coated with a roll coater so that it would be as follows, and then heated at 150 oo for 1 minute to evaporate the solvent component.

Next, as an outer resin layer, a superimposed composite resin solution was applied using a roll coater to a dry thickness of 5 mm.
Heat treatment was performed at a temperature of 50° C. for 2 minutes to completely fix the inner and outer composite resin layers. The obtained composite resin-coated steel plate was subjected to cup drawing processing (processing so that the composite resin layer with a drawing ratio of 2.0 was on the inner surface of the cup), the cup was filled with edible vinegar, and the filling test was continued for 10 days at 5 p0. As a result, no peeling or deterioration of the composite resin layer was observed, and no iron was leached into the edible vinegar.

On the other hand, when a resin layer with aluminum powder removed from the inner resin layer was used, the corrosion resistance significantly decreased, and in a test of filling a cup with edible vinegar, iron elution of 50% was observed. Example 2 Five coats of chromium were applied to the surface of a clean electrolytically tinned steel plate with a thickness of 0.32 mm (Tin coating amount on one side: 2.8 mm/metre).
A final chromate treatment was performed, and a composite resin-coated metal plate was prepared using the following composite resin solution and treatment method.

Composite resin solution composition Inner layer resin layer Acrylic resin solution 10 parts by weight (water:
7 parts by weight of acrylic resin:
Weight part of 3 Product name: Aron S40
20...manufactured by Toagosei ■) scaly aluminum powder
15 parts by weight (thickness: 5 mm or less) Outer layer resin layer 10 parts by weight of acrylic resin solution (product name:
Aron S4020...manufactured by Toagosei ■) Sodium aluminate powder 15 parts by weight (Grain: 4-8
m) Treatment method: First, the composite resin solution was applied as an inner resin layer to one side of the electrically tinned steel plate using a roll coater so that the dry thickness was 5 m, and then heat treated at 180 qo for 1 minute. was applied to evaporate the solvent components.

Next, the above composite resin solution was applied as an outer resin layer using a roll coater to a dry thickness of 5 mm, and then heat treatment was performed at a temperature of 18 mm to form the inner and outer composite resin layers. The layers were completely set. The obtained composite resin-coated steel plate was subjected to cup drawing processing (processing so that the bag composite resin layer with a drawing ratio of 2. was formed on the inner surface of the cup), filled with edible vinegar, and
As a result of continuing the filling test at 5° C. for 10 days, no peeling or deterioration of the composite resin layer was observed, and no iron was added to the edible vinegar.

On the other hand, when using a resin layer with sodium aluminate powder removed from the outer resin layer, the corrosion resistance was significantly reduced, and as a result of a test filled with edible vinegar into a cup, it was found that cracking occurred under the coating film. The iron elution base into the edible vinegar was 1 string blood. Example 3 Degreased, pickled, surface-clean board thickness 0.
A composite resin-coated metal plate was prepared using the following composite resin solution and treatment method on a 5-skin mild steel plate.

Composite resin solution composition Inner layer resin layer Polyester resin solution 10 parts by weight (Polyester resin 3 parts by weight Methyl ethyl ketone
14 parts by weight Toluene 5 parts by weight Product name: Byron 2$ (manufactured by Toyobo ■) Scale shelf powder 3 parts by weight (thickness: 101 m or less) Outer layer resin layer Polyester resin solution 10 parts by weight (Product name:
Byron 2 eaves...manufactured by Toyobo ■) Calcium hydroxide powder 3 parts by weight (particle size: 1
~5 m) Processing method: First, apply the above composite resin solution as an inner resin layer to one side of the steel plate using a roll coater so that the dry thickness becomes 5 mm, and then heat treat at 100°C for 30 seconds. was applied to evaporate the solvent components.

Next, the above composite resin solution was applied as an outer resin layer using a roll coater to a dry thickness of 5 m, and then heat treated at a temperature of 15 mm for 1 minute to coat the composite resin of the inner and outer layers. The layers were completely set. Subsequently, a pinhole with a diameter of 50 rm was forcibly formed on the upper layer of the composite resin layer using a polyester film (thickness: 16 mm, product name: Lumirror).
(Using films made at a ratio of area/100 areas) were laminated with rolls. Next, in order to improve the interfacial adhesion between the film and the composite resin layer, a re-ripening activation treatment was performed at a temperature of 180° C. for 1 minute, and immediately quenched. The obtained polyester film laminated composite resin-coated steel plate was subjected to cup drawing processing (drawing ratio 2
．． As a result of continuing the filling test at 55℃ for 10 days, no peeling or deterioration of the composite resin layer was observed, and edible vinegar was filled with edible vinegar. There was no iron elution at all.

On the other hand, when using a material in which aluminum powder and magnesium oxide powder were removed from the inner and outer resin layers, the corrosion resistance was significantly reduced, and in a test of filling a cup with edible vinegar, rust occurred all over the inner surface of the cup. At the same time, the amount of iron eluted into edible vinegar was 160 breasts. Example 4 Chromate treatment was applied to the surface of a clean electrogalvanized steel sheet with a thickness of 0.5 (amount of zinc deposited on one side: 10 mm/day) to a ratio of 9/30 as chromium, and then A composite resin-coated metal plate was created using the composite resin solution and treatment method shown in .

Composite resin solution composition Inner layer resin layer Acrylic resin solution 10 parts by weight (methyl ethyl ketone 75 parts by weight Acrylic resin
25 parts by weight Product name: SC4
40...Made by Sony Chemical ■) Stainless steel powder
6 parts by weight (thickness: 10 mm or less) outer resin layer acrylic resin solution 10 parts by weight (product name:
SC440...Manufactured by Sony Chemical ■) Magnesium hydroxide powder 6 parts by weight (
Thickness: 3-8 mm) Processing method First, the composite resin solution was applied as an inner resin layer to one side of the electrogalvanized steel sheet using a roll coater so that the dry thickness was 5 mm, and then 100 qo was applied. A heat treatment was performed for 30 seconds to evaporate the solvent component.

Next, the above composite resin solution was applied as an outer resin layer to a dry thickness of 5 mm, and then heated at a temperature of
The inner and outer composite resin layers were completely fixed by heat treatment for a minute.

The resulting composite resin-coated steel plate was subjected to Eriksen 8 skin extension processing, and in a salt spray corrosion resistance test specified in JISZ 2371, no red rust was observed even after 80 field hours.

On the other hand, stainless steel powder is extracted from the inner and outer resin layers.
In the case where the magnesium hydroxide powder was removed, red rust was observed in the Erichsen-processed area from around 10 q hours, and a large amount of red rust occurred after 20 feeding hours. Example 5 Galvanized steel pipe for water supply with clean internal and external surfaces that has been subjected to pickling treatment (
A composite resin-coated steel pipe with a nominal diameter of 5 mm was prepared using the composite resin solution and treatment method shown below.

Composite resin solution composition Inner layer resin layer Acrylic resin solution 10 parts by weight (water
7 parts by weight acrylic resin
Weight part of 3 Product name: Aron S40
20...manufactured by Toagosei ■) scaly aluminum powder
6 parts by weight (thickness: 5 m or less) outer resin layer acrylic resin solution 10 parts by weight (product name:
Aron S4020 (manufactured by Toagosei ■) Sodium aluminate powder (6 parts by weight) Processing method First, apply the above composite resin solution as an inner resin layer to the inner and outer surfaces of the steel pipe using a dip coating method to a dry thickness of 5 Am. After coating and drying, the same composite resin solution as above was applied as an outer resin layer by dip coating method so that the dry thickness was 5 Am, and then heat treatment was performed at a temperature of 180°C for 10 minutes to evaporate the water component. The composite resin layer was completely fixed.

The obtained composite resin-coated steel pipe was cross-cut and JI
In the salt water fog corrosion resistance test specified in S Z 2371, no red bell formation was observed even after 40 q hours had passed.

Claims (1)

[Scope of Claims] 1. A composite resin layer containing one or more metal powders of aluminum, tin, and stainless steel is provided as an inner layer on the base metal surface, and a composite resin layer containing one or more metal powders of aluminum, tin, and stainless steel is provided as an outer layer. A composite resin-coated metal body provided with a composite resin layer containing one or more of calcium and sodium aluminate powders having a particle size of 10 μm or less. 2 Claim 1 in which the metal powder has a scale-like shape
Composite resin-coated metal body as described in . 3 The base metal is a mild steel plate, and the surface of the mild steel plate is coated with tin, chromium, zinc, nickel, iron, copper,
The surface of a coated steel plate or mild steel plate plated or coated with cobalt, manganese, lead, aluminum, or an alloy containing one or more of these metals, or the surface of the coated steel plate, is coated with chromate, dichromate, or phosphoric acid. salt, acid phosphate,
The composite according to claim 1 or 2, which is a chemical steel plate, an aluminum plate or an aluminum alloy plate treated with molybdate, silicate, borate, perborate or aluminate. Resin metal body. 4. The composite resin-coated metal body according to claims 1 and 2, wherein the base metal is a metal processed product other than plate-shaped.