JPH0328507B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method of coating various objects. More specifically, a specific resin composition is applied onto a sprayed base material that has not been subjected to physical pretreatment such as blasting or chemical pretreatment such as surface treatment, and then a metal sprayed coating is formed, and then a metal sprayed coating is formed. This invention relates to a coating method for applying resin paint.

(Prior art) For example, when steel is used as the base material of an object to be coated, there are methods of coating metals baser than iron, such as zinc or zinc-aluminum alloy, by electroplating, hot-dip plating, or thermal spraying. It was widely practiced. According to this method, the iron can be protected by the sacrificial anticorrosion effect of the coating metal, which is less base than the iron base material, and because of this feature, it can be used for construction steel materials, thin steel sheets for automobile bodies, various electrical equipment cases, etc. Used for various industrial equipment.

By the way, among the above-mentioned methods, the electroplating method, the melt plating method, etc. cannot be easily implemented except in a specific factory. This is because there is a limit to the size of the object to be coated depending on the size of the plating tank, etc. In particular, the hot-dip plating method has problems with thermal distortion because the object to be coated is immersed in molten metal at a high temperature of 450 to 600 degrees Celsius. This is because there were various restrictions such as the inability to apply it to thin steel sheets.

On the other hand, with the metal spraying method, there is almost no need to heat the material, so there is almost no dimensional deviation, the sprayed coating can be obtained with the desired thickness, and it can be applied on-site even for large substrates. It is used for bridges, steel structures, etc. because of its various characteristics, such as being able to spray paint easily and allowing organic paints to adhere easily to the thermally sprayed coating, and its range of use is expected to continue to expand in the future. It is expected.

However, when metal is coated directly onto a smooth surface such as steel or plastic by thermal spraying, no affinity or chemical bond can be expected between the base material and the metal spray coating, so It was inevitable that the adhesion of the metal sprayed coating would be extremely low.

In order to improve these defects, conventional methods apply blasting treatments such as sandblasting or grit blasting to smooth base materials to create an anchor effect between the base material and the metal sprayed coating (for example, in Japanese Patent Application Laid-open No. 50−
65335, etc.).

However, such pre-treatment blasting work requires a high level of skill and takes a long time, and the large amount of dust generated by blasting is not only hazardous to work safety and hygiene, but also to the environment. This poses a problem of contamination, and therefore requires some kind of preventive treatment, which is not desirable in terms of processing costs.

In addition, when blasting is applied to thin steel plates or plastics with a thickness of about 1 mm or less, the impact force of the abrasive generally causes large distortions, and in extreme cases, the base material often breaks. Therefore, for example, when blasting a thin sheet for automobile bodies with a thickness of about 0.5 to 0.8 mm, a treatment method that specially weakens the impact force must be adopted, and therefore the work is performed based on a reduction in the polishing force. Declining efficiency was a problem.

Also, bouncing abrasive materials flying in a disorderly manner,
Dust scattered during the processing gets into various mechanical parts, etc., causing various undesirable problems.

Furthermore, when performing anti-corrosion metal spraying on welded parts of steel materials, blasting treatment is required beforehand, but this treatment is extremely difficult due to the hardness of the welded parts.

Therefore, a method of performing metal thermal spraying without performing the above-mentioned blasting treatment has also been proposed.

For example, a method of spraying metal onto a thin steel plate plated with a specific metal (Japanese Unexamined Patent Publication No. 60-50156), a method of making the metal surface uneven with a corrosive liquid (Japanese Unexamined Patent Publication No. 60-50156),
50157) and a method of heating a steel plate to form an oxide film of a specific thickness (Japanese Patent Laid-Open No. 61-26763). However, since all of these methods require the substrate to be placed in a special environment, the range of substrates to which they can be applied is extremely limited, making them impractical.

Furthermore, in very specific fields, methods have been proposed to provide special anchor effects.

For example, in the thermal spraying of ceramics, which requires melting at very high temperatures, a method has been proposed in which an undercoat containing an inorganic filler is applied onto a base material that has been previously treated with zinc phosphate or sandblast. (For example, JP-A-61-104060 and JP-A-61-104061). Although this method may provide a sufficient anchoring effect, the disadvantages of the above-mentioned blasting process are Nothing was resolved.

As mentioned above, in the known metal thermal spraying method, the necessity to perform blasting on the base material extremely limits the scope of application of thermal spraying.
Therefore, there is a strong desire in the industry to develop or establish a method for thermal spraying metal without blasting.

Furthermore, in addition to problems related to pretreatment for thermal spraying, there were also problems regarding the stability of the thermal sprayed metal coating itself.

For example, when the base material is iron, by providing a sprayed coating of a metal less noble than iron, the sacrificial anticorrosion effect of the sprayed coating is exhibited, and the base material is protected from corrosion. However, as the corrosion of the sprayed coating progresses, the sprayed metal layer deteriorates, for example, white rust occurs in the case of a zinc coating, and the surface turns black in the case of a zinc-aluminum alloy.

Therefore, it is necessary to protect the surface of the sprayed coating in order to obtain a higher degree of anticorrosion effect and to maintain the aesthetic appearance of the surface.

On the other hand, if the base material is an inorganic material such as concrete, a straight plate, or plastic, the sprayed coating will not have a sacrificial anticorrosion effect, but the thermal sprayed coating will continue to deteriorate, so the coating must be maintained in a stable state for a long period of time. requires surface protection.

Some of the inventors proposed a method of first applying a surface treatment film and then forming a sprayed film.
In this method, it is essential to prevent deterioration of the surface treatment film in order to maintain good adhesion of the sprayed film for a longer period of time. However, according to the method proposed earlier, corrosive substances easily permeate through the porous sprayed coating, and when placed in such an environment, defects such as lifting of the sprayed coating are likely to occur. I understood.

Therefore, it has been found that in order to maintain good adhesion of the sprayed coating for a longer period of time, it is more important to protect the surface treated coating that exists between the object to be coated and the sprayed coating.

(Objective of the Invention) The present invention aims to improve or solve various problems in the conventional metal spraying method as described above, and of course, it is possible to form a metal spray coating without any pre-treatment such as blasting. The present invention aims to provide a method for producing a pretreated coating and a thermally sprayed coating while preventing deterioration of the resulting pretreated coating and thermal spray coating and maintaining them in a stable state for a long period of time.

More specifically, the object of the present invention is to apply a specific resin composition to the surface of various base materials such as metals, plastics, and inorganic materials without any chemical or physical pretreatment, and then perform metal spraying. The objective is to obtain a corrosion-proof coating, a conductive coating, an electromagnetic shielding coating, a durable coating, or a coating with a metallic appearance by coating the surface with a resin.

(Means for Solving the Problems) The above purpose is to blast a resin composition containing 25 to 300% by volume of particles with an average particle size of 10 to 150 μm based on the resin at a rate of 10 to 400 g/m ² . Surface roughness (Rz)
This is achieved by the method of the invention, which consists in spraying the specified metal after obtaining a coating of 30-200 .mu.m and then applying at least one coat of synthetic resin paint.

The present invention will be explained in detail below.

The "base material to be thermally sprayed" (hereinafter simply referred to as base material) used in the method of the present invention includes iron materials such as tin plate, dull steel plate, polished steel plate, blackened steel plate, rusted steel plate, and welded steel plate; aluminum; , nonferrous metals such as zinc; plastics such as ABS, PPO, and vinyl chloride; inorganic materials such as slate boards, calcium silicate boards, and cement; glass, wood, plywood, organic resin films (coatings), etc. Various types can be mentioned.

In the method of the present invention, the "composition" applied before metal spraying contains particles with an average particle size of 10 to 150 μm. Examples of the particles include metals such as copper, nickel, aluminum, zinc, iron, and silicon, or alloys, oxides, nitrides, and carbides.

Specific examples include aluminum oxide, silicon oxide, iron oxide, silicon carbide, and boron nitride.

Depending on the solvent composition of the composition, powders of acrylic resin, styrene resin, epoxy resin, polyethylene, etc. may also be used.

These particles can be used alone or as a mixture of two or more.

The use of silica sand, alumina, silicon carbide, etc. is particularly preferable in consideration of chemical stability with respect to the resin used, not forming a corrosion cell with the thermal spray material, being hard, and not easily precipitated in the composition.

In the present invention, the particle size of the particles is 10 to 150μ.
m range, preferably 30 to 100 μm. In the above range, if the particle size exceeds 150 μm, the particles tend to precipitate in the resin composition, and also tend to cause nozzle clogging when spray coating. Moreover, even if the coating can be applied, the surface roughness becomes too rough, and the surface of the metal sprayed film becomes rough, resulting in a very poor appearance. On the other hand, the particle size is 10μm
If it is smaller, the desired surface roughness cannot be obtained even if the resin composition is applied to the surface of the substrate, and therefore it becomes difficult to obtain a metal sprayed coating with excellent adhesion.

In the present invention, the particles are 25 to 300% by volume [20 to 75% in terms of pigment volume concentration (PVC)], preferably 65 to 150% by volume [pigment volume concentration (PVC)] based on the resin described below. Use within the range of 40 to 60%. In the above range, the amount added to the resin is 25
If it is less than % by volume, the resin content will increase, resulting in a decrease in surface roughness, resulting in a decrease in the adhesion of the metal spray coating. Furthermore, since the amount of resin adhering to the base material increases and an insulating coating is formed, this tends to be inconvenient especially when the thermal spray coating is used for sacrificial corrosion protection.

On the other hand, the amount of particles added to the resin is 300% by volume.
Exceeding this is not preferable because the resin content will be extremely reduced and the bonding force between particles will be weakened, resulting in a decrease in the adhesion of the metal sprayed coating.

Next, the "resin" used in the present invention is:
There is no particular limitation as long as it has a certain degree of dryness, hardness, adhesion, water resistance and durability.

Specific examples include thermoplastic acrylic resins that are one-component room temperature drying resins, vinyl resins, chlorinated rubber, alkyd resins, unsaturated polyester resins that are two-component curing resins, acrylic-urethane resins, polyester-urethane resins, and epoxy resins. Examples include resins and thermosetting resins such as melamine-alkyd resins, melamine-acrylic resins, melamine-polyester resins, acrylic resins, and acrylic-urethane resins.

These can be used alone or as a mixture of two or more.

Particularly preferred are epoxy resins (combined with curing agents such as polyamide resins and amine adducts), acrylic-urethane resins, acrylic resins, etc., which are thermoplastic during metal spraying and allow the sprayed metal particles to enter the coating and harden after the spraying. .

As components other than the resin, an organic solvent, water, etc. for dissolving or dispersing the resin may be added to the composition of the present invention, if necessary.

Furthermore, additives such as dyes, pigments, dispersants, anti-foaming agents, and anti-sag agents (thixotropic agents) can also be used in combination.

The composition may be in any form such as solvent-based, water-soluble, water-dispersed, or solvent-dispersed. However, water-based compositions are preferred when applied to plastics that are not resistant to solvents. Furthermore, when using a water-based resin composition for an iron base material, it is necessary to take measures to prevent rusting.

In the present invention, the composition is prepared by mixing the resin and particles with the addition of a solvent or dispersion medium, various additives, etc., if necessary, using a conventional dispersion and mixing method.

The (resin) composition thus obtained is applied onto a substrate in the same manner as a general coating composition. In particular, it is preferable to employ an air spray method from the viewpoint of ease of controlling the coating amount. However, it goes without saying that brush coating or roll coating is also possible by appropriately adjusting the composition, viscosity, etc., in the same way as ordinary paints.

In the present invention, the coating amount of the composition is 10 to 400 g/
It is necessary to have a proportion of m ² . Particularly preferred is a range of about 20 to 150 g/m ² . In the range of the coating amount, if it is less than 10 g/m ² , the surface roughness becomes small, the thermal spraying efficiency of the metal decreases, and the adhesion of the thermal sprayed coating also decreases, which is not preferable. On the other hand, if the coating amount exceeds 400g/ ^m2 ,
This is undesirable because the surface roughness becomes too rough, or the coating may become too smooth depending on the composition and properties of the composition, resulting in a decrease in the adhesion of the metal sprayed coating. In particular, in the corrosion protection method for base materials that expects the sacrificial corrosion protection effect of the metal spray coating, if the coating amount exceeds approximately 400 g/ ^m2 , an insulating film will be formed between the base material and the metal spray coating. This is not preferable because it becomes difficult to obtain sacrificial anticorrosion effects.

In the present invention, it is necessary that the surface roughness (Rz) of the film after application of the composition be in the range of 30 to 200 μm, preferably 60 to 120 μm. [In the present invention, surface roughness (Rz) is defined in JISB-0601 (1982).
Indicates the ten-point average roughness of "Definition and Display of Surface Roughness",
The surface roughness (Rz) was measured using a surface roughness profile measuring device Surfcom 554A manufactured by Tokyo Seimitsu Co., Ltd. ] If the surface roughness is less than 30 μm, the thermal spraying efficiency will be low and the adhesion of the metal thermal spray coating will be extremely reduced. On the other hand, if the surface roughness exceeds 200 μm, the surface of the sprayed coating will be rough and the appearance will deteriorate significantly, and if the sprayed coating is rubbed, the underlying resin composition coating may be exposed, which is not preferable.

In the method of the present invention, the surface roughness of the coating obtained from the composition is very important. This surface roughness is determined by the particle size and content of particles contained in the composition, and the amount applied to the substrate.

For example, the desired surface roughness can be obtained by applying the above-mentioned specific composition using an air spray method with a slightly dry spray within the above application amount range. Further, for example, the desired surface roughness may be obtained by imparting thixotropic properties to the specific composition as required and applying it with a brush or the like.

In the present invention, a metal is thermally sprayed onto the thus obtained coating having a specific surface roughness.

Note that the coating does not necessarily have to be in a completely dry (hardened) state before the metal is thermally sprayed. That is, it may be semi-dry (hardened). The most preferred method is to thermally spray metal onto a semi-dry coating and then completely cure it.

In the present invention, the thermal spraying method for carrying out the metal thermal spraying includes a gas flame thermal spraying method, an electric arc thermal spraying method, a low-temperature thermal spraying method using a vacuum arc thermal spraying machine, and any of these methods may be used.

Further, the metal used in the thermal spraying method is a metal or alloy selected from copper, copper alloy, zinc, zinc alloy, aluminum, and aluminum alloy.

In the above, copper, zinc, and aluminum are metals themselves, and copper alloy is a metal whose main component is copper.
Small amounts of Ni, Zn, Sn, Al, Fe, Mn, Pb, Co,
It is an alloy obtained by mixing one or more components such as Si, P, etc. Zinc alloy is mainly composed of zinc, with small amounts of Al, Cu, Mg, Pb, Fe, etc.
It is an alloy obtained by mixing one or more components such as Cd, Sn, etc. Aluminum alloy is mainly composed of aluminum, Zn, Mg, Cr, etc.
It is an alloy obtained by mixing small amounts of one or more of Si, Mn, Ni, Pb, Bi, Cu, etc.

In the method of the present invention, the metal thermal spray coating can obtain strong adhesion due to the surface roughness of the coating obtained from the resin composition. It is attached to the base material due to the bonding force of (organic substances). Therefore, it is necessary to avoid conditions in which the resin component in the coating obtained from the resin composition is completely burned out by the temperature of the sprayed metal particles during the implementation of the method of the present invention.

That is, it is desirable that the metal spraying in the present invention be carried out at a relatively low temperature so that the resin component in the coating obtained from the resin composition is not completely burned out. Adoption is preferred.

The low-temperature spraying method uses a low-temperature air stream injected into a cylindrical shape to continuously electrically arc-melt a metal wire in an environment where the pressure in the center is reduced to 0.5 kg/cm ² or less. The molten metal particles are simultaneously sucked into the forward jet air stream, pulverized, rapidly cooled to near room temperature, and molten metal particles are deposited on the substrate in a supercooled liquid state. Therefore, in the case of this method, the amount of thermal spraying per unit time is relatively large,
It is possible to increase the thickness of the sprayed film. On the other hand, in the case of gas flame spraying and electric arc spraying methods, it is necessary to reduce the diameter of the sprayed metal wire, slow the wire speed, make the amount of spraying relatively small, or reduce the thickness of the sprayed film. It is possible to apply the method of the present invention by taking certain measures.

Then, in the method of the present invention, at least one layer of synthetic resin paint is further applied onto the thermally sprayed coating. Metal sprayed coatings usually have surface roughness Rz of about 100 μm and many pores (the pores often reach the underlying surface).

Therefore, in the present invention, in order to protect the pretreatment layer and the sprayed metal layer, it is necessary to fill the recesses and pores with a synthetic resin coating, thereby significantly improving the protective effect of the sprayed coating. Further, depending on the conditions of use, it is also possible to further perform surface coating.

Application of a synthetic resin paint in the present invention includes not only covering the entire surface of the thermally sprayed coating, but also filling and coating (sealing) only the recesses and pores of the thermally sprayed coating.

The latter method is very preferable because a very small amount of paint can prevent excessive exposure of the sprayed coating and also prevent deterioration of the surface treatment layer.

In the method of the present invention, it is possible to directly apply the coating to the surface of the thermal sprayed coating, but if the inside of the pores cannot be coated, air bubbles are likely to occur in the coating, which may reduce the protective effect of the coating. Therefore, special care must be taken when applying thick coats at once. In such cases, use a low-viscosity paint (mist coat) that can penetrate into the fine pores.
It is practical to apply a top coat if necessary.

Furthermore, in order to reduce the unevenness of the sprayed coating as much as possible, it is also a preferable method to polish the sprayed coating before painting.

By doing this, there are no protrusions on the surface of the sprayed coating, no longer exposes the sprayed metal to the surface after the surface is painted, and the surface can be completely protected with a thinner coating, and the appearance and gloss after coating are also improved. It can be greatly improved.

As the polishing method, means commonly used for polishing metal surfaces, such as abrasive paper, abrasive cloth, wire brush, belt sander, and sand grinder, are used.

As the synthetic resin paint used in the coating method of the present invention, any of the known synthetic resin paints that are generally commercially available can be used. For example, amine adducts are added to bisphenol-type epoxy resins, phenol novolac-type epoxy resins, polyglycol-type epoxy resins, ester-type epoxy resins, etc., or to bituminous or urethane-modified versions of these. , polyamine, polyamide resin, or other amino-based curing agent or polyisocyanate curing agent; chlorinated rubber or this together with rosin, coumaron, etc.
Chlorinated rubber paint mixed with indene resin, phenol resin, petroleum resin, plasticizer, etc.; vinyl chloride resin paint using vinyl chloride homopolymer or copolymer of vinyl chloride, vinyl acetate, vinylidene chloride, etc. as a color vehicle ; Acrylic resin paints whose color vehicle is a copolymer of two or more selected from acrylic acid or methacrylic acid, their alkyl esters, monomers such as styrene and vinyltoluene; polybasic acids such as phthalic acid, glycerin, etc. Alkyd resin paint whose color vehicle is the reaction product obtained by the condensation reaction of polyhydric alcohol and fatty acid; polyester resin paint whose color vehicle is the product obtained by the condensation reaction of polybasic acid and polyhydric alcohol. ; Polyurethane resin paint (including bituminous modification) whose main component is a polyol component such as polyester polyol, polyether polyol, or acrylic polyol and polyisocyanate as a curing agent; Room-temperature-curing or heat-curing fluorine resin paints that use isocyanate or melamine resin as a curing agent, fluorine resin paints that use vinylidene fluoride resin, etc. as a coloring agent; silicone resins, silicone-modified alkyd resins, silicone-modified acrylic resins, etc. Silicone resin paint using as a color vehicle;
Other examples include phenol resin and melamine resin.

The synthetic resin paint may contain colored pigments, if necessary.
Various additives such as extender pigments, dyes, and other leveling agents, ultraviolet absorbers, and dispersion stabilizers may be added and mixed. Furthermore, the synthetic resin coating used in the present invention may be a solvent-based coating, a water-soluble coating, a water-dispersion coating, or a solvent-free coating. Further, the synthetic resin paint may be either a room temperature drying type or a forced drying (including heating) type.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

The thermal spraying film thickness, polishing film thickness, and coating film thickness in the following Examples and Comparative Examples are values calculated from the thermal spraying weight, polishing weight, coating weight, and specific gravity.

Example 1 400g of methyl methacrylate, butyl acrylate
500g, 2hydroxyethyl methacrylate 80g,
An emulsion with a monomer composition of 20 g of methacrylic acid, 10 g of sodium dodecylbenzenesulfonate as an emulsifier, and 3 g of ammonium persulfate as an initiator was obtained by emulsion polymerization with a heating residue of 40% by weight. To this was added 306 g of acrylic emulsion resin A (resin solid content volume: 100 cm ³ ) with a heating residue of 36% by weight, to which neutralized amine, film-forming aid, antifoaming agent, and thickener were added.
and 240 g of silica sand (silica sand OS No. 8 manufactured by Okumura Ceramics, specific gravity 2.4) with an average particle size of 100 μm (particle volume 100 cm ³ ,
PCV 50%) was sufficiently stirred to prepare resin composition A.

When 50 g/m ² of this resin composition A is applied by air spray to a 0.8 x 100 x 200 mm dull steel plate,
The surface roughness (Rz) was 100μm. After drying for 1 hour, zinc was low temperature sprayed to a thickness of 50 μm.

The conditions for low temperature thermal spraying are reduced pressure arc thermal spraying machine PA100.
(manufactured by Pan Art Craft), wire diameter 1.1mm
using zinc wire, wire speed 5m/min, voltage
I went with 14V.

On top of this sprayed coating, epoxy resin paint [trade name: Eponics #30, manufactured by Dainippon Toyo Co., Ltd. Undercoat rust color: main agent/curing agent = 85/15 (weight ratio)] was air-sprayed to a dry film thickness of 30 μm. After drying for 1 day, apply an air-dry fluororesin paint [Dainippon Toyo Co., Ltd., product name: V-Flon #100 Topcoat white: Main agent/curing agent =
90/10 (weight ratio)] to a dry film thickness of 90 μm to prepare a test plate.

The vertical tensile strength of this coating was good at 5Kg/ ^cm2 , and a salt water spray test was conducted for 1000 hours and a 50°C warm water immersion test was conducted for 10 days. It was good with no blisters.

Example 2 Epoxy resin [Epicron 4051: Dainippon Ink & Chemicals Co., Ltd. trade name: Epoxy equivalent weight 950] 100 g
Add 80 g of xylene, 60 g of methyl ethyl ketone, and 25 g of butanol to the solution to dissolve polyamide resin (Epicure 892, manufactured by Celanese: active hydrogen equivalent).
133) Epoxy with 40% heating residue added with 10g
275 g of polyamide resin B (resin solid content 100
cm ³ ) and 221 g (particle volume 70 cm ³ , PVC 41%) of silicon carbide [green silicon carbide CG320: manufactured by Nagoya Abrasive Materials Industry Co., Ltd., product name: specific gravity 3.16] with an average particle diameter of 48 μm were thoroughly stirred to form a resin composition. B was produced.

When 30 g/m ² of this resin composition B is applied by air spray to a 2 x 100 x 200 mm SS41 steel plate, the surface roughness (Rz) becomes 60 μm. After drying for 2 hours, algin (13% aluminum zinc -aluminum alloy) was low-temperature sprayed to a coating thickness of 75 μm.

The low-temperature thermal spraying was carried out using a reduced pressure arc spraying machine PA600 (manufactured by Pan Art Craft Co., Ltd.) using an alginic wire with a wire diameter of 1.3 mm at a wire speed of 7.6 m/min and a voltage of 14 V.

The resulting sprayed coating is roughly brushed with an electric wire brush.
After polishing to a thickness of 2 μm, a coating composition prepared by lowering the viscosity of the urethane resin paint shown below with a solvent was applied (mist coating) to a thickness of about 10 μm. Then, after 15 minutes, apply urethane resin paint [Dainippon Toyo Co., Ltd. product name: V Top White: Main agent/
Hardening agent = 80/20 (weight ratio)] was applied so that the dry film thickness was 80 μm.

The vertical tensile strength of this coating was good at 55Kg/ ^cm2 , and it was subjected to a salt spray test for 1,000 hours and a 50°C warm water immersion test for 10 days, but in both cases, the thermal spray coating showed discoloration, lifting, and white rust. It was good with no blisters.

Example 3 To 170 g of acrylic polyol resin (hydroxyl value 100, heating residue 50% by weight), 33 g of isocyanate resin (Sumidyur N75: trade name manufactured by Sumitomo Bayer Urethane: heating residue 75% by weight) was added to produce a heating residue of 54% by weight. Solvent type urethane-acrylic resin 203
(volume 100 cm ³ ), 119 g (particle volume 30 cm ³ , PVC 23%) of aluminum oxide [white fused alumina WA800: Nagoya Abrasive Materials Industry Co., Ltd. product name: specific gravity 3.96] with an average particle diameter of 20 μm were thoroughly stirred. A resin composition C was prepared.

This resin composition C was diluted with thinner and 3x
15g/ by air spray on 200×200mm FRP board
When m ² was applied, the surface roughness (Rz) was 40 μm. After drying for 2 hours, a zinc-aluminum pseudo alloy) was sprayed at a low temperature to a thickness of 40 μm.

The low-temperature thermal spraying was carried out using a vacuum arc spraying machine PA100 using zinc wire and aluminum wire with a wire diameter of 1.1 mm, a wire speed of 4 m/min, and a voltage of 15 V.

On the obtained thermal sprayed coating, a fluororesin clear paint [trade name: V-Flon #200 top coat clear, manufactured by Dainippon Toyo Co., Ltd.: main agent/curing agent = 90/10 (weight ratio)] was air-sprayed to reduce the dry film thickness. It was coated to a thickness of 40 μm, and after drying, it was used as a test piece.

The vertical tensile strength of this coating was good at 50 Kg/cm ² , and the electromagnetic shielding properties were also very good at 60 dB at 500 Hz.

1000 hours salt spray test and 50℃ hot water immersion test
The spraying was carried out for 10 days, and in all cases the sprayed coating remained in good condition with no discoloration, lifting, white rust, or blistering.

Example 4 40 g/m ² of the resin composition B prepared in Example 2 was applied to a 3 x 300 x 300 mm straight plate by air spraying.
After coating, the surface roughness (Rz) was 70 μm.
After drying for 24 hours, 5% red copper was sprayed at a low temperature to a thickness of 120 μm.

The conditions for low-temperature spraying are an arc spraying machine under reduced pressure.
The test was conducted using PA600 red copper wire with a diameter of 1.1 mm and containing 5% zinc at a wire speed of 7.6 m/min and a voltage of 19 V.

[ V Top Clear (trade name, manufactured by Dainippon Toyo Co., Ltd.: main agent/curing agent = 80/20 (weight ratio)) was applied to give a dry film thickness of 60 μm.

This coating has a metallic luster and a vertical tensile strength of 55
Kg/ ^cm2 , which is good, and has been tested for 1000 hours with salt spray.
A 50℃ hot water immersion test was conducted for 10 days, but in both cases,
The sprayed coating was in good condition with no discoloration, lifting, green rust, or blistering.

Example 5 When 50 g/m ² of the resin composition A prepared in Example 1 was applied to a glass plate of 5×300×300 mm by air spray, the surface roughness (Rz) was 100 μm.
After drying for 1 hour, aluminum was low-temperature sprayed to a thickness of 60 μm.

The conditions for low temperature thermal spraying are vacuum arc spraying machine PA600.
Using aluminum wire with a wire diameter of 1.1 mm,
The wire speed was 7.6 m/min and the voltage was 18 V.

[ Manufactured by Dainippon Toyo Co., Ltd. Product name: Eponics #10
Clear: base agent/curing agent = 50/50 (weight ratio)] was applied so that the dry film thickness was 50 μm.

This coating has a metallic luster and a vertical tensile strength of 48
Kg/ ^cm2 , which is good, and has been tested for 1000 hours with salt spray.
A 50℃ hot water immersion test was conducted for 10 days, but in both cases,
The sprayed coating was in good condition with no discoloration, lifting, white rust, or blistering.

Example 6 When the resin composition C prepared in Example 3 was diluted with a solvent and applied to a 2 x 100 x 200 mm SS41 steel plate at 40 g/m ² by air spray, the surface roughness (Rz)
was 60μm. After drying for 12 hours, zinc
Gas flame spraying was performed to a thickness of 60 μm.

The conditions for gas flame spraying are as follows.
Zinc wire with a wire diameter of 3.2 mm is transported at a wire speed of 1 m/min.
LPG and oxygen gas were used as combustion gas.

The resulting sprayed coating is brushed with a wire brush to a thickness of approximately 2 μm.
After polishing, apply approximately 10 μm of a composition made by reducing the viscosity of the epoxy resin paint below (mist coat).
After about 15 minutes, apply epoxy resin paint [Dainippon Toyo Co., Ltd., trade name Eponics #10 Topcoat white: Main agent/hardening agent =
80/20 (weight ratio)] was applied so that the dry film thickness was 60 μm.

The vertical tensile strength of this coating was good at 40Kg/cm ² , and it was subjected to a salt spray test for 1000 hours and a 50°C warm water immersion test for 10 hours. It was good with no blisters.

Example 7 Epoxy resin clear paint [trade name: Eponics #10 Clear, manufactured by Dainippon Toyo Co., Ltd.: main agent/curing agent = 50/50 (weight ratio)] was dried with air spray on a 10 x 100 x 100 mm mortar board. After coating to a film thickness of 50 μm to strengthen the laitance layer and drying for one day, the resin composition B prepared in Example 2 was applied at 100 g/m ² by air spray, and the surface roughness (Rz) was was 200μm. After drying for 12 hours,
Aluminum was low-temperature sprayed to a thickness of 100 μm.

The conditions for low-temperature spraying are vacuum arc spraying machine PA600.
Using aluminum wire with a wire diameter of 1.1 mm,
The wire speed was 7.6 m/min and the voltage was 18 V.

[ dainippon paint
Co., Ltd. (trade name: Rubber Tight #100 Top Coat White) was applied to a dry film thickness of 80 μm.

The vertical tensile strength of this coating film was 15 kg/cm ² and was good, with no cohesive failure in the mortar layer and no interfacial failure.
Salt spray test for 1000 hours, 50℃ warm water immersion test for 10 hours
Although the spraying was carried out for several days, the sprayed coating was in good condition with no discoloration, lifting, white rust, or blistering.

Example 8 Example 1 was applied to a 3 x 300 x 300 mm polyvinyl chloride board.
Resin composition A prepared by air spraying for 20 minutes
When applied with g/ ^m2 , the surface roughness (Rz) is 80μm
It became. After drying for 1 hour, a zinc-aluminum pseudoalloy was low-temperature sprayed to a thickness of 40 μm.

The conditions for low-temperature spraying are vacuum arc spraying machine PA100.
The test was conducted at a wire speed of 4 m/min and a voltage of 19 V using zinc wire and aluminum wire with a wire diameter of 1.1 mm.

After sanding the resulting sprayed coating to a depth of about 2 μm with #400 sandpaper, a composition made by reducing the viscosity of the following fluororesin clear paint was applied to a thickness of about 10 μm (mist coat), and after about 15 minutes, the fluororesin clear paint was applied. A paint [manufactured by Dainippon Toyo Co., Ltd., trade name: V-Flon #200 topcoat clear: main agent/curing agent = 90/10 (weight ratio)] was applied so that the dry film thickness was 30 μm.

This coating has a metallic luster and a vertical tensile strength of 55
Kg/ ^cm2 , which is good, and has been tested for 1000 hours with salt spray.
A 50℃ hot water immersion test was conducted for 10 days, but in both cases,
The sprayed coating was in good condition with no discoloration, lifting, white rust, or blistering.

Example 9 When the resin composition B prepared in Example 3 was applied by air spray at 60 m/m ² onto a 5 x 100 x 300 mm FRP board, the surface roughness (Rz) was 70 μm. After drying for 24 hours, Cypronickel (copper:
Nickel = 90:10 alloy) was low-temperature sprayed to a thickness of 110 μm.

The conditions for low temperature thermal spraying are vacuum arc spraying machine PA600.
The test was carried out using Cypronickel wire with a wire diameter of 1.1 mm, at a wire speed of 5 m/min, and at a voltage of 20 V.

When the resulting thermal sprayed coating was coated with a thin layer of a composition prepared by diluting an epoxy resin paint (same as in Example 6) with a solvent, the coating composition flowed and spread to fill the recesses in the solvent coating. The vertical tensile strength of the coating is 55Kg/cm ²
It was also good in the 50°C warm water immersion test, etc., as described above.

Comparative Example 1 50 g of resin composition A prepared in Example 1 was applied to a 0.8 x 100 x 200 mm dull steel plate by air spraying.
When applying m ² , the surface roughness (Rz) was 100 μm.
After drying for 1 hour, low-temperature spraying was carried out under the same conditions as in the example to give a zinc thickness of 200 μm.

This thermal sprayed coating was subjected to a salt spray test for 1,000 hours without painting, and as a result, due to its sacrificial corrosion protection, red rust did not occur, but overall whiteness occurred and the appearance deteriorated. Furthermore, as a result of a 10-day immersion test in hot water at 50°C, the sprayed film rose above the material, resulting in poor adhesion.

Comparative Example 2 Low-temperature thermal spraying was carried out with the zinc spraying film thickness of 200 μm in Comparative Example 1 being changed to 50 μm, the same as in Example 1.

This 50μm thermal spray coating was tested in salt water spray without painting.
After 50 hours, white rust had formed on the entire surface, but at 1000 hours, due to an insufficient spray coating thickness, red rust accounted for 30% of the entire surface.

Comparative Example 3 A 2 x 100 x 200 mm SS41 steel plate was grit blasted to have a surface roughness (Rz) of 60 μm.

This blast-treated steel sheet was subjected to gas flame spraying with zinc to a film thickness of 60 μm in the same manner as in Example 6.

This 60μm thermal spray coating was tested in salt water without painting.
After 500 hours, white rust had formed on the entire surface, but at 1000 hours, red rust had formed due to an insufficient thermal spray coating thickness, and red rust now accounted for 30% of the entire surface.

Comparative Example 4 Similar to Example 2, Resin Composition B was applied to SS41 measuring 2 x 100 x 200 mm, and algin was sprayed at a low temperature of 75 μm to form a thermally sprayed coating. A salt water spray test was conducted for 1000 hours without painting, and no red rust occurred. However, the sprayed coating turned black and lifted, resulting in poor adhesion.

Comparative Example 5 The urethane resin paint used in Example 2 was
A 100 x 200 mm SS41 steel plate was coated with a dry film thickness of 90μ.

This paint film was subjected to a salt spray test for 1000 hours, but the paint film lifted and red rust appeared on the entire surface. Furthermore, as a result of a 10-day immersion test in salt water at 50°C, blistering occurred on the entire surface.

Test Example In order to confirm the effects of the present invention, the following test was conducted.

The present invention: Epoxy-polyamide composition consisting of 88 g of Epicoat 1001 (epoxy resin), 70 g of xylol, 40 g of methyl ethyl ketone, 40 g of methyl isobutyl ketone, and 22 g of Epicure 892 (polyamide)
250g (resin solid content volume 100cm ³ ) was prepared, and then 520g (particle volume
130cm ³ ) and stir well to prepare resin composition F.
(PVC57%) was obtained.

This resin composition F was diluted with methyl ethyl ketone and air sprayed on a 0.8 x 100 x 200 mm dull steel plate (spray gun: W77- of Iwata Painting Machine Co., Ltd.).
3G, discharge amount: 2 rotations, air pressure: 4Kg/ ^cm2 , painting distance: 20cm, gun speed: 50cm/sec), 100
g/m ² and dried for at least 24 hours.

The surface roughness was Rz: 90 μm.

Using Al wire with a wire diameter of 1.1 mm in a low-temperature spraying machine PA100, wire speed: 5 m/min, voltage: 17 V,
Al spraying was performed under the conditions of current: 130A and air pressure: 6Kg/cm, and the sprayed film thickness was 250μm. As a result of measuring the vertical tensile strength, it was found to be 80 Kg/cm ² , indicating very good adhesion.

(1) Particle size comparison example 6 (particle size smaller than the present application) Epoxy-polyamide composition consisting of 88 g of Epicoat 1001 (epoxy resin), 70 g of xylol, 40 g of methyl ethyl ketone, 40 g of methyl isobutyl ketone, and 22 g of Epicure 892 (polyamide)
250 g (resin solid content volume 100 cm ³ ) was prepared, and then 165 g of alumina powder (particle volume 41
cm ³ ), stir well, and add resin composition A (PVC29
%) was obtained.

This resin composition A was diluted with methyl ethyl ketone and air sprayed onto a 0.8 x 100 x 200 mm dull steel plate (spray gun: W-77- manufactured by Iwata Painting Machine Co., Ltd.).
3G, discharge amount: 2 rotations, air pressure: 4Kg/ ^cm2 ),
It was coated at 100 g/m ² and dried for over 24 hours.

Because the average particle diameter is small, the surface roughness is Rz: 20μ
It was m.

Using a low-temperature spraying machine PA100, using Al wire with a wire diameter of 1.1 mm, wire speed: 5 m/min, voltage: 17 V,
Al spraying was carried out under the conditions of current: 130 A and air pressure: 6 kg/cm, but the sprayed film peeled off when the sprayed film thickness was 150 μm, and the adhesion to the Al sprayed film was very poor.

Comparative Example 7 (Particle size is larger than the present invention) 250 g of the epoxy-polyamide composition prepared in Comparative Example 6 (resin solid content volume: 100 cm ³ ) was added with 520 g of alumina powder (particle volume: 130 cm ³ ) with an average particle size of 170 μm.
Add and stir thoroughly to prepare resin composition B (PVC57%).
However, the particles were so precipitated that it was not possible to form a normal paint.

(2) Particle content comparative example 8 (Particle content is higher than the present application) Alumina powder with an average particle size of 70 μm was added to 250 g of the epoxy-polyamide composition (resin solid content volume 100 cm ³ ) prepared in Comparative Example 6. 1320g (particle volume ^330cm3 )
Add and stir thoroughly to prepare resin composition C (PVC77%).
I got it.

This resin composition C was diluted with methyl ethyl ketone and air sprayed onto a 0.8 x 100 x 200 mm dull steel plate (spray gun: W-77- manufactured by Iwata Painting Machine Co., Ltd.).
3G, discharge amount: 2 rotations, air pressure: 4Kg/ ^cm2 ),
It was coated at 100 g/m ² and dried for over 24 hours.

The surface roughness was Rz: 170 μm.

Using a zinc wire with a wire diameter of 1.1 mm using a low-temperature spraying machine PA100, wire speed: 6 m/min, voltage:
Zinc was sprayed under the conditions of 14V, current: 120A, and air pressure: 6Kg/cm to a coating thickness of 250μm.

The vertical tensile strength of this sprayed film was as low as 25 kg/cm ² . This is because cohesive failure occurred in the resin composition layer due to the large particle content.

Comparative Example 9 (Particle content is lower than the present application) 80 g of alumina powder (particle volume 20 cm 3 ) with an average particle diameter of 70 μm was added to 250 g (resin solid content volume 100 cm ³ ) of the epoxy-polyamide composition prepared in Comparative Example ⁶ . was added and sufficiently stirred to obtain resin composition D (PVC 17%).

This resin composition D was diluted with methyl ethyl ketone and air sprayed onto a 0.8 x 100 x 200 mm dull steel plate (spray gun: W-77- manufactured by Iwata Painting Machine Co., Ltd.).
3G, discharge amount: 2 rotations, air pressure: 4Kg/ ^cm2 ),
It was coated at 100 g/m ² and dried for over 24 hours.

Due to the small content of particles, the surface roughness is Rz:
It was 15 μm.

As in Comparative Example 3, the vertical tensile strength of the sprayed film in which zinc was sprayed to a thickness of 250 μm was extremely low at 15 Kg/cm ² , and delamination occurred between the resin composition layer and the sprayed film.

(3) Surface roughness comparative example 10 (Surface roughness is smaller than the present application) To 250 g of the epoxy-polyamide composition prepared in Comparative Example 6 (resin solid content volume 100 cm ³ ), 520 g of alumina powder with an average particle size of 70 μm ( Particle capacity ^130cm3 )
Add resin composition E (57% PVC) and stir thoroughly.
I got it.

This resin composition E was diluted with methyl ethyl ketone and air sprayed on a 0.8 x 100 x 200 mm dull steel plate (spray gun: W77-
3G, discharge amount: 4 rotations, air pressure: 2Kg/cm ² , painting distance: 5cm, slow gun speed), 100g/cm2
m ² coated and dried for at least 24 hours.

The surface roughness was Rz: 25 μm.

As in Comparative Example 3, the vertical tensile strength of the sprayed film in which zinc was sprayed to a thickness of 250 μm was as low as 20 Kg/cm ² , and delamination occurred between the resin composition layer and the sprayed film.

Comparative Example 11 (Surface roughness is larger than that of the present application) Resin composition E produced in Comparative Example 10 was diluted with methyl ethyl ketone and air sprayed on a 0.8 x 100 x 200 mm dull steel plate (spray gun: W77 manufactured by Iwata Yaiki Kogyo Co., Ltd.) -3G, discharge rate: 1 rotation, air pressure: 6Kg/cm ² , coating distance: 80cm, gun speed increased) to apply 100g/m ² and dry for 24 hours.

Because it is a dry spray, the surface roughness is
Rz: 220 μm.

As in Comparative Example 3, the vertical tensile strength of the sprayed film in which zinc was sprayed to a thickness of 250 μm was as low as 25 Kg/cm ² , indicating cohesive failure of the resin composition layer.

(Effects of the Invention) According to the method of the present invention, it is possible to impart an appropriate surface roughness to a smooth base material without performing blasting treatment as in known methods. Metal spraying becomes possible even on substrates that cannot be blasted because they are thin or have complex shapes. Furthermore, materials that were conventionally thought to be impossible to metal spray can be used. Furthermore, the adhesion of the sprayed coating obtained is extremely excellent.

According to the method of the present invention, high adhesion is achieved by utilizing the plasticity of the sprayed liquid metal particles and by filling the spaces between the particles in the coating obtained from the resin composition, resulting in an anchor effect. It can be demonstrated.

For example, the vertical tensile strength of a zinc sprayed coating on a conventionally blasted surface is around 60 Kg/ ^cm2 , but the vertical tensile strength of the zinc sprayed coating obtained by the method of the present invention is also 50 to 80Kg/ ^cm2 , Shows adhesion that is superior to, but not inferior to, conventional products.

Furthermore, the base material (steel material) can be protected by the sacrificial corrosion protection effect of the metal spray coating. This is an effect caused by contact between the metal sprayed coating and the base material (steel), but even if a thin resin coating is formed on the base material surface, the coating will agglomerate due to the collision force of the sprayed metal particles. Fractures occur and the sprayed particles reach the surface of the base material, so the sacrificial anticorrosion effect can be fully exerted.

In addition, in the method of the present invention, the processing time required for conventional blasting processing can be reduced by 1/10 to 1/20 or more, and therefore, a significant reduction in processing costs can be expected.

In addition, various problems caused by dust generated during blasting, so-called pollution, can be solved all at once.

Furthermore, it not only protects the metal spray coating and improves its appearance, but also prevents water, oxygen, and other corrosive substances from permeating through the porous spray coating and deteriorating the pretreatment layer. It is possible to obtain a coating layer that is stable for a long period of time and has excellent adhesion.

Therefore, it can greatly contribute to the expanded use of metal spraying technology in the future, and its practical industrial value is immeasurable.

Claims (1)

[Scope of Claims] 1. 10 to 400 g of a composition containing 25 to 300 volume % of particles with a particle diameter of 10 to 150 μm based on the resin is applied onto a thermal spraying substrate that is not subjected to pretreatment such as blasting.
Surface roughness (Rz) is 30 to 200 μm when applied at a ratio of m ²
After obtaining the coating, zinc, aluminum, copper, or an alloy thereof is thermally sprayed, and then one or more layers of synthetic resin paint are applied thereon. 2. The coating method according to claim 1, wherein the base material to be thermally sprayed is a steel material, and the thermal sprayed metal is a metal less base than the steel material. 3 Particles with a particle size of 10 to 150 μm are silicon oxide,
The coating method according to claim 1, wherein the coating is at least one selected from the group consisting of alumina and silicon carbide. 4. The coating method according to claim 1, wherein the metal spraying is low-temperature spraying using a vacuum arc spraying machine. 5. The coating method according to claim 1, wherein the surface of the sprayed coating is polished after metal spraying.