JPS5911664B2 - Manufacturing method of metal plated body - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for manufacturing a metal plated body.

More specifically, the present invention relates to a method for obtaining a thin metal-plated body with metallic luster by forming a metal plating layer on a metal surface, particularly a metal surface that has been subjected to chromate treatment, by vacuum evaporation or sputtering. A method is already known in which metal plating is performed on the surface of a metal molded product using metals such as aluminum, copper, chromium, nickel, etc., or alloys thereof, by vacuum evaporation or sputtering.

By the way, according to such conventional methods, a metal plating layer is formed directly on the surface of the metal adherend, but since the thickness of the metal plating layer is extremely thin, less than 1 micron, scratches on the surface, The appearance is extremely poor due to lack of smoothness, etc., and the adhesion between the bare surface of the adherend and the metal plating layer is extremely poor.
Separation of the metal plating layer often occurred. 30 Therefore, in order to compensate for these defects, a resin film with a thickness of about 30 to 50 microns is interposed as a base coat layer between the surface of the adherend and the metal plating layer, and a metal plating layer is formed on the surface of the resin film. is commonly adopted.

However, the base 35 coating layer has raw materials such as melamine-alkyd resin, melamine-acrylic resin,
A resin liquid made by dissolving acrylic resin etc. in an organic solvent is used, and it is spray-painted and heated at 150 to 180°C for 30 minutes.
The layers were solidified by heat treatment for about 0 minutes. However, since such a method requires heat treatment at high temperature for a long time, it requires a huge amount of thermal energy and is not preferred from the viewpoint of production efficiency. Furthermore, since it contains a large amount of organic solvent, it is difficult to obtain a thick film, which results in poor finished appearance of the metal plated body, and in addition, it is wasteful in terms of resource conservation. In recent years, from the viewpoint of solving the above-mentioned problems, many attempts have been made to apply a resin liquid of an organic compound having an unsaturated group and treat it quickly and efficiently using ionizing radiation or electromagnetic wave energy. There is.

However, due to various problems, it has hardly reached the stage of practical use. One of the problems will be described using the headlamp reflector of an automobile as an example.

First of all, the reflecting surface of this type of reflecting mirror usually consists of an aluminum plating layer formed by vacuum evaporation. In the process of attaching the reflector to the vehicle body, it is necessary to solder one end of an electric circuit cord to the back surface of the reflector, or to apply waterproof sealing or adhesive sealing. In this case, it is of course inevitable that the product will be heated locally or in its entirety. As a result, a multicolored rainbow pattern or wrinkles appear on the surface of the aluminum plating layer on the opposite side, and the original shine of the aluminum plating disappears.
In other words, it causes diffuse reflection, which makes it unable to function as a headlamp reflector. Another problem is that chromate treatment is applied to the surface of the metal adherend to improve its corrosion resistance, which may inhibit the adhesion of the undercoat layer and cause the coating layer to fall off. It is. The present invention relates to a novel manufacturing method that solves these problems. The purpose of this project is to bring the use of ultraviolet energy to a practical stage, and to propose a method for manufacturing metal-plated bodies that requires short processing time, has good production efficiency, and has good adhesion to chromate-treated bare surfaces. That is, the present invention provides a method for producing a metal plated body in which a resin liquid is applied to a metal surface, cured by ultraviolet irradiation, and then a metal plating layer is provided thereon, in which (a) the resin liquid is (D-polymerized) A resin liquid whose basic components are a polymerizable polymer and/or a polymerizable oligomer and a polymerizable monomer containing a phosphorous element in the molecule, or (11) a polymerizable monomer containing at least one phosphorus element in the molecule; Immediately before forming the metal plating layer (b) using a resin liquid containing a polymer and/or a polymerizable oligomer as a basic component and using a vacuum evaporation method or a sputtering method,
The present invention relates to a method for manufacturing a metal-plated body, which comprises performing a heat treatment for 10 minutes.

The present invention will be explained in more detail below. The "resin liquid" used in the present invention has (i) a tumescent polymer and/or a polymerizable oligomer, and a polymerizable monomer containing a phosphorus element in its molecule as its basic components; A composition obtained by mixing other polymerizable monomers, organic solvents, other sensitizers, etc., or (4) a polymerizable polymer having at least one phosphorus element in the molecule and/or a polymerizable polymer. The composition is composed of the oligomer 1 as a basic component, and optionally mixed with a polymerizable monomer having a phosphorus element, other polymerizable monomers, an organic solvent, and other photosensitizers.

More specifically, the polymerizable polymer and/or
Or the oligomer is a polymer and/or oligomer having at least one unsaturated group in the molecule.

Examples include unsaturated polyester resins, unsaturated acrylic resins, polyester-modified acrylic resins, epoxy-modified acrylic resins, urethane-modified acrylic resins, alkyd-modified acrylic resins, unsaturated group-containing polyolefin resins, and drying oils. Unsaturated polyester resins include Rigolak 2460uv (Showa Kobunshi), Polylite C-303 (Dainippon Ink), unsaturated acrylic resins include Diabeam K-8303 (Mitsubishi Rayon), and polyester-modified acrylic resins include Aronix M8O3O.
l Aronix M8O6O (Toagosei Chemical Industry Co., Ltd.), etc.

Also, as an epoxy modified acrylic resin, UcOat2Ol
(Toho Chemical Industries) Detkulite UE81OO, Deutkulite UE82OO (Dainippon Ink Chemical Co., Ltd.), etc. XP-1077 as urethane modified acrylic resin
-40-2 (Nippon Gosei) XP-51-37-70-
2 (4) Synthetic Chemistry) etc. Examples of alkyd-modified acrylic resins include XP-14-22 (Nippon Gosei Kagaku). Among the above polymers and/or oligomers, particularly preferred are polyester-modified acrylic resins and/or epoxy-modified acrylic resins.

Examples of the polymerizable monomer containing a phosphorus element in the molecule include mono(2-hydroxyethyl methacrylate) acid phosphate, mono(2-hydroxyethyl methacrylate) acid phosphate, and mono(3-hydroxyethyl methacrylate) acid phosphate.
Hydroxypropyl acrylate) acid phosphate, mono(3-hydroxypropyl methacrylate) acid phosphate, di(2-hydroxyethyl acrylate) acid phosphate, di(2-hydroxyethyl methacrylate) acid phosphate, di(3-hydroxypropyl) acrylate) acid phosphate, di(3
- Phosphate esters of acrylic acid or methacrylic acid containing a hydroxyl group such as hydroxypropyl methacrylate) acid phosphate, acrylic alcohol acid phosphate, vinyl phosphate, vinyl phosphonic acid, mono(2-hydroxyethyl acrylate) acylphosphate Phite, di(2-hydroxyethyl acrylate)
One or a mixture of two or more of acidophosphite, di(2-hydroxyethylmethacrylate) acidophosphite, etc., and their salts and esters,
Particularly preferred are acrylic or methacrylic acids containing hydroxyl groups such as mono(2-hydroxyethyl acrylate) acid phosphate, mono(2-hydroxyethyl methacrylate) acid phosphate, and di(2-hydroxyethyl acrylate) acid phosphate. They are phosphoric acid esters. The polymerizable polymer or oligomer containing at least one phosphorus element in the molecule may be a polymer or oligomer obtained from a polymerizable monomer containing phosphorus element in the molecule, or an epoxy or Examples include polymers modified with polyester.

Further, other polymerizable monomers used as optional components for these components include monomers having at least one unsaturated group in the molecule, such as (a) (meth)acryloyl group-containing monomers. (Aromatic vinyl group-containing monomer or ←Makishima aliphatic vinyl group-containing monomer.)

Among the above (a), further hydroxyl group-containing monomers include 2
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Examples of ether compounds of the above-mentioned hydroxyl group-containing monomer and alkyl alcohol or cyclic alkyl alcohol include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and tetrahydrofurfuryl acrylate. Furthermore, ester compounds of (meth)acrylic acid and alkyl alcohol include methyl (meth)acrylate, butyl (meth)acrylate, neopentyl glycol di(meth)acrylate, 1-6 hexanediol di(
There are meth)acrylate, trimethylolpropane tri(meth)acrylate, etc. In addition, examples of the aromatic vinyl group-containing monomer ((b) include styrene, vinyltoluene, etc.), and vinyl acetate, vinylidene chloride, etc. are used as the aliphatic vinyl group-containing monomer (c), respectively. .
Particularly preferred among the above polymerizable monomers are ether compounds of hydroxyl group-containing monomers and alkyl alcohols in group (a), and esters of hydroxyl group-containing monomers and (meth)acrylic acid and alkyl alcohols. It is a compound.

The above-mentioned "resin liquid" of the present invention includes a polymerizable polymer and/or oligomer and a polymerizable monomer having a phosphorus element in the molecule, or a polymerizable polymer and/or a polymerizable polymer containing at least one phosphorus element in the molecule. With oligomers as the basic ingredient,
Depending on the difficulty of the coating work, the surface condition of the coating film, etc., the viscosity and properties of the resin liquid are adjusted by appropriately combining the above-mentioned polymerizable monomers.

In particular, when a low viscosity resin liquid is required, an organic solvent is also used. In the present invention, the resin liquid comprises ([) a polymerizable polymer and/or a polymerizable oligomer (a) and a polymerizable monomer (b?) containing a phosphorus element in the molecule as the basic component. , the ratio of both is (a) Ab) -99/1 ~
70/30 (wt%), preferably 95/5 to 80/20
(wt%), and if necessary, add other polymerizable monomers so that the total amount of monomers in the entire composition of the resin liquid (the sum of the phosphorus element content polymerizable monomer and the other polymerizable monomers) is 50
It can be added within a range of % by weight or less.

In addition, when the resin liquid has (g) a polymerizable polymer and/or oligomer containing at least one phosphorus element in the molecule as a basic component, 50% by weight of the total composition of the resin liquid as necessary. The following phosphorus element-containing polymerizable monomers and/or other polymerizable monomers can be contained.

However, when a polymerizable monomer containing a phosphorus element in its molecule is used, the amount of the monomer is in the range of 1 to 30% by weight based on the total composition of the resin liquid. In the present invention, the above (1>f), which has a large effect of imparting adhesion to the coating film from the viewpoint of activity to the metal surface, is used.
Basic components are more preferred.

However, if the amount of the polymerizable monomer containing the phosphorus element in the molecule is less than 1% by weight, the effect of imparting adhesion to the metal surface is small, and if it exceeds 30% by weight, the water resistance of the coating film decreases. As mentioned above, the resin liquid of the present invention uses an epoxy-modified acrylic resin and/or a polyester-modified acrylic resin as the polymerizable polymer and/or oligomer, and uses a polymerizable resin containing a phosphorus element in the molecule. Mono(2-hydroxyethyl acrylate) acid phosphate, mono(2-hydroxyethyl methacrylate) acid phosphate, di(
Using a phosphoric acid ester monomer of (meth)acrylic acid containing a hydroxyl group such as 2-hydroxyethyl acrylate) acid phosphate and di(2-hydroxyethyl methacrylate) acid phosphate, and if necessary as other polymerizable monomers. Most preferred is a composition containing one or more polymerizable monomers containing (meth)acryloyl groups.

The polymerizable polymer and/or oligomer, the phosphorus element-containing polymerizable monomer, and the other polymerizable monomers are not limited to only one type, but may be used in an appropriate combination of two or more, and each It is also possible to show characteristics. By using a resin liquid containing phosphorus in the present invention, it is possible to significantly improve the adhesion of the film obtained from the resin liquid to metal materials, resulting in improved physical and chemical properties such as corrosion resistance. It is possible to improve the

Furthermore, in the present invention, in order to use ultraviolet rays as an energy source for solidifying the resin liquid, it is necessary to add a photosensitizer to the resin liquid. The photosensitizers include benzoin, benzoin methyl ether, benzoin isophyl ether, benzinole, benzophenone, anthraquinone, naphthoquinone, chloroanthraquinone, tetramethylthiuram disulfide, diphenyl disulfide, 2, 2-diethoxyacetophenone, benzoin peroxide, azobisisobutyronitrile, 2,2
'-Azobispropane, etc., and the amount used is 0.05 to 15 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight of the total amount of polymerizable polymer and/or oligomer and polymerizable monomer in the resin liquid. 5 parts by weight. Other additives such as a leveling agent, a polymerization inhibitor, and an anti-sagging agent may be added to the resin liquid of the present invention as necessary. Furthermore, it is mixed with extender pigments such as talc, calcium carbonate, magnesium carbonate, silica, barium sulfate, coloring pigments, anti-rust pigments, etc.
It can also be used in the same form as known coating compositions. In the method for manufacturing a metal plated body of the present invention, the resin liquid is first applied to the metal surface by a known method such as a roll coater, spray, curtain flow coater, or brush coating to a desired film thickness, preferably about 30 to 50 microns. Then, if necessary, irradiate with ultraviolet rays after setting.

The most distinctive feature of the present invention is the heat treatment after solidification by irradiation with ultraviolet rays, that is, the treatment method before the step of forming a metal plating layer, which will be described later.

To emphasize, this heat treatment significantly improves the heat resistance of the metal plating layer, making it possible to prevent the occurrence of multicolored rainbow patterns, wrinkles, etc. as described above. The heat resistance of the metal-plated body obtained by the conventional method, that is, the process without heat treatment, which is a feature of the present invention, was extremely poor.

This is also the main reason why it has not been practical to use a base coat layer that has been solidified by irradiation with ionizing radiation and/or electromagnetic wave activation energy. To explain further, the present inventor conducted various studies on the causes of defects in conventional methods, and as a result, discovered that the cause was a trace amount of polymerizable monomer remaining in the coating film after solidification. . Therefore, an attempt was made to extend the irradiation time of ultraviolet rays as a method for removing the residual monomer, but no favorable results were obtained. Therefore, they diligently tried various methods and arrived at the unexpectedly simple processing method of the present invention. The heat treatment of the present invention consists of treatment at a temperature of 60 to 180°C for 1 to 10 minutes. Regarding the relationship between heating temperature and time, when the temperature is low, a long time is required;
At high temperatures, heating for a short time is sufficient. Therefore, although there is no intention to uniformly limit the time and temperature, low-temperature and short-time heat treatment is desirable from the viewpoint of saving thermal energy and production efficiency. Furthermore, without being bound by theory, it is believed that this heat treatment mainly involves the dissipation of residual monomers as described above, and also includes partial polymerization and further prevention of moisture absorption in the coating film after heat treatment.

Furthermore, considering this, it is understood that it is preferable to perform the process immediately before vacuum deposition or sputtering. The equipment heat source for the heat treatment may be a commonly known method.

For example, any one of an infrared lamp, kerosene, heavy oil, propane gas, combustion gas such as city gas, and an electric heater may be used. This heat treatment significantly improves the heat resistance of the metal plated body, and also significantly improves the adhesion between the bare metal surface and the film obtained from the resin liquid. In the method of the present invention, a film made of metals such as aluminum, chromium, nickel, copper, and alloys thereof and having a thickness of about 1 micron or less is then deposited on the surface of the film obtained from the resin liquid by nitrogen evaporation or sputtering. Form a metal plating layer.

The metal plated product thus obtained has excellent heat resistance, with no occurrence of multicolored rainbow patterns, wrinkles, cracks, etc. even when heated. The metal plating layer of the metal plating body is extremely thin, so for the purpose of protecting the plating layer and preventing surface contamination,
The same resin liquid as used in the present invention is applied to the surface of the metal plating layer, and the resin liquid is solidified by irradiation with commonly used active energy using ionizing radiation and/or electromagnetic waves as an energy source, or melamine-alkylated resin liquid is applied to the surface of the metal plating layer. A final product can also be obtained by applying and solidifying a thermosetting resin liquid such as a resin liquid, an acrylic-alkyd resin, or an acrylic resin liquid, or a room temperature curing resin liquid such as a polyurethane resin liquid or an epoxy resin liquid. Next, the present invention and its specific effects will be explained by giving examples.

However, "part" or "%" indicates "part by weight" or "% by weight."

Example 1 The above resin liquid was spray-painted on the surface of a cold-rolled steel sheet and chromate-treated steel sheet that had been polished and cleaned so that the dry film thickness was 50 μm, and after setting for 10 minutes at room temperature, a lamp with a manual power of 80 W was applied.
/? 6 at irradiation distance of 20 cTrL with one high-pressure mercury lamp
Irradiated for 0 seconds.

Next, a heat treatment was performed at 150° C. for 3 minutes in a hot air drying oven, and immediately vacuum deposition was performed at a vacuum degree of 1×10 −4 T0rr to obtain an aluminum metal film with a thickness of 500λ. Example 2 The above resin solution was spray-coated on the surface of the polished and cleaned cold-rolled steel plate and chromate-treated steel plate to a dry film thickness of 50 μm, and after setting in a hot air drying oven at 50°C for 5 minutes, a lamp with 80 W of manual power was applied. Irradiation was performed for 60 seconds using a single CTrL high-pressure mercury lamp at an irradiation distance of 20 cTn.

Next, a heat treatment was performed at 100° C. for 5 minutes in a hot air drying oven, and immediately vacuum deposition was performed at a vacuum degree of 1×10 −4 T0rr to obtain 500 aluminum metal films. Example 3 The above resin liquid was spray-coated on the surface of a polished and cleaned cold-rolled steel plate and a chromate-treated steel plate to a dry film thickness of 50μ, and after setting in a hot air drying oven at 50°C for 5 minutes,
Irradiation was performed for 60 seconds at an irradiation distance of 20 CTn using a single high-pressure mercury lamp with a lamp input of 80 W/CTrL.

Next, heat treatment was carried out using a hot air drying furnace for 80TCX for 5 minutes, and immediately vacuum evaporation was performed at a vacuum degree of 1X104T0rr to obtain an aluminum metal film of 500λ. Example 4 The resin solution in Example 1 was spray-coated on the surface of a polished and cleaned cold-rolled steel plate and a chromate-treated steel plate to a dry film thickness of 50 μm, and after setting in a hot air drying oven l trowel at 50°C for 5 minutes, Irradiation was performed for 60 seconds at an irradiation distance of 20 cm using a single high-pressure mercury lamp with a lamp input of 80 W/Cm.

Next, heat treatment was performed at 80°C for 5 minutes in a hot air drying oven, and then true nitrogen was immediately deposited at a vacuum level of 1x10-4T0rr.
500 aluminum metal films were obtained. Example 5 The resin liquid in Example 2 was spray-painted on the surface of a polished and cleaned cold-rolled steel plate and chromate-treated steel plate to a dry film thickness of 50μ, and after setting at room temperature for 10 minutes, a high pressure lamp input of 160W/CTfL was applied. 1 mercury lamp, 6 trowels, irradiation distance 20C! ! It was irradiated with L for 30 seconds.

Next, heat treatment was performed for 5 minutes at 100° C. using a hot air drying oven C trowel, and immediately vacuum deposition was performed at a vacuum degree of 1×10 4 T0rr to obtain an aluminum metal film with a thickness of 500λ. Example 6 The resin solution in Example 3 was spray-painted on the surface of a polished and cleaned cold-rolled steel plate and chromate-treated steel plate to a dry film thickness of 50μ, and after setting at room temperature for 5 minutes at 50°C,
Irradiation distance is 20? with one high-pressure mercury lamp with human power of 160 W/Cm. It was irradiated for 30 seconds.

Next, a heat treatment was performed at 180° C. for 2 minutes in a hot air drying oven, and then straight vapor deposition was immediately performed at a vacuum degree of 1×10 −4 T0rr to obtain an aluminum metal film with a thickness of 500λ. Example 7 The resin solution in Example 2 was spray-painted on the surface of a cold-rolled steel sheet and chromate-treated steel sheet that had been polished and cleaned to a dry film thickness of 50μ, and after setting in a hot air drying oven at 50°C for 5 minutes, the lamp input was 80W/ Irradiation was performed for 60 seconds using a single CTrL high-pressure mercury lamp at an irradiation distance of 20 cTn.

Next, heat treatment was performed for 5 minutes at 100TC in a hot air drying oven, and then immediately sputtering was performed (vacuum degree 8 x 10
-5T0rr, argon pressure 3×10-3T0rr) 10
An aluminum metal film of 00λ was obtained. Example 8 The resin solution from Example 3f was spray-coated onto the surface of a polished and cleaned cold-rolled steel plate and a chromate-treated steel plate to a dry film thickness of 50μ, and after setting at room temperature for 10 minutes, the lamp input was 160W/c! Irradiation distance is 20C with one n high pressure mercury lamp! It was irradiated with IL for 30 seconds.

Next, heat treatment was performed for 2 minutes at 180°C in a hot air drying oven, and immediately after that, the sputtering method (vacuum level 8x10
-5T0rr, argon pressure 3×10-3T0rr) 10
000 aluminum metal films were obtained. Comparative Example 1 Using a composition obtained by removing all mono(2-hydroxyethyl acrylate) and phosphate from the resin solution of Example 1, an aluminum metal film was obtained in the same manner as in Example 1.

Comparative Example 2 A test specimen was obtained in the same manner as in Example 2 using a composition obtained by removing all di(2-hydroxyethyl acrylate) acid phosphate from the resin liquid of Example 2.

Comparative Example 3 A test specimen was obtained in the same manner as in Example 3 using a composition obtained by removing all mono(2-hydroxyethyl methacrylate) acid phosphate from the resin liquid of Example 3.

Comparative Examples 4 to 6 Test specimens were obtained using the resin liquids of Comparative Examples 1 to 3 in the same manner as in Examples 4 to 6, respectively.

Comparative Examples 7-8 Using the resin liquids of Comparative Examples 2-3, test specimens were obtained in the same manner as in Examples 7-8.

Comparative Example 9 The resin solution in Comparative Example 1 was spray-painted on the surface of a cold-rolled steel sheet and chromate-treated steel sheet that had been polished and cleaned to a dry film thickness of 50 μm, and then heated to room temperature (after setting the trowel for 10 minutes, using a lamp with 80 W/? Irradiation distance 2 with one high-pressure mercury lamp
0? Then, it was irradiated for 60 seconds.

Next, using the true vapor deposition method (degree of vacuum 1X104T0rr) 5
An aluminum metal film of 00λ was obtained. Comparative Example 10 The resin liquid in Comparative Example 2 was spray-coated on the surface of a polished and cleaned cold-rolled steel sheet and a chromate-treated steel sheet to a dry film thickness of 50 μm, and after setting in a hot air drying oven at 50°C for 5 minutes, it was manually applied with a lamp. Irradiation distance is 20? with one 80η← high pressure mercury lamp. It was irradiated for 60 seconds.

Next, by vacuum evaporation method (degree of vacuum 1X10-4T0rr)
500 aluminum metal film was obtained. Comparative Example 11 The resin liquid in Comparative Example 3 was spray-painted on the surface of a cold-rolled steel sheet and chromate-treated steel sheet that had been polished and cleaned to a dry film thickness of 50μ, and after setting in a hot air drying oven at 50°C for 5 minutes, a lamp with 800 L of manual power was applied. Irradiation was performed for 60 seconds using a high-pressure mercury lamp at an irradiation distance of 20 CTrL.

Next, by vacuum evaporation method (degree of vacuum 1×10-4T0rr)
500 aluminum metal films were obtained. Comparative Example 12 The resin solution in Comparative Example 1 was spray-painted onto the surface of a cold-rolled steel sheet and chromate-treated steel sheet, which had been polished and cleaned, to a dry film thickness of 50 μm, and after being set at room temperature for 10 minutes, a lamp was applied with a manual power of 80 W/? Irradiation distance 20 with one high-pressure mercury lamp
? It was irradiated for 150 seconds.

Next, by vacuum evaporation method (true nitrogen degree 1 x 104T0rr) 5
An aluminum metal film of 00λ was obtained. Comparative Example 13 The resin solution in Comparative Example 2 was spray-painted on the surface of a cold-rolled steel sheet and chromate-treated steel sheet that had been polished and cleaned to a dry film thickness of 50 μm. Irradiation distance 20c with one lamp
It was irradiated for 30 seconds at m.

Next, by vacuum evaporation method (true nitrogen degree 1 x 104T0rr) 5
000 aluminum metal films were obtained. Comparative Example 14 The resin liquid in Comparative Example 3 was spray-painted on the surface of a polished and cleaned cold-rolled steel plate and chromate-treated steel plate to a dry film thickness of 50μ, and after setting in a hot air drying oven at 50°C for 5 minutes,
Lamp human power 80w/? Irradiation was performed for 20 seconds using a single high-pressure mercury lamp at an irradiation distance of 20 (177!).

Next, by vacuum evaporation method (degree of vacuum 1×10 → TOrr) 5
An aluminum metal film of 00λ was obtained. Comparative Example 15 The resin liquid in Comparative Example 3 was spray-painted on the surface of a polished and cleaned cold-rolled steel plate and chromate-treated steel plate to a dry film thickness of 50μ, and after setting in a hot air drying oven at 50°C for 5 minutes,
Irradiation was performed for 60 seconds at an irradiation distance of 20 CTn using one high-pressure mercury lamp with a lamp power of 80 W/Cm.

Next, using the sputtering method (vacuum degree 8 x 10-5T0
1000 aluminum metal films were obtained. Table 1 shows the results of the first test of heat resistance, adhesion, and appearance.

(Judgment criteria) Heat resistance ○...No rainbow pattern, wrinkles, etc. Δ...Rainbow pattern ×...Rainbow pattern, wrinkles, etc. Adhesion ○...・
・No cracks or peeling ○～△... Some cracks △... Some cracks and peeling ×... Appearance with significant cracks and peeling ○... Brightness, leveling Good property 0 to Δ...Leveling property is poor (test method) 1) Heat resistance...180℃ x 60 in hot air drying oven
Test heat resistance for minutes.

2) Adhesion: Using a cutter knife, cut 11 cutting lines on the surface of the metal plating layer at intervals of 1 m, 71 liters, and 1 m, 1 liter in width to create 100 squares.

After pressing the cellophane tape onto the squares, the cellophane tape is forcibly peeled off, and the remaining base coat layer squares are read and expressed as a percentage. 3) Appearance: Visually judge the appearance of the gold plated surface.

The metal-plated body thus obtained by the method of the present invention is
In addition to being excellent in heat resistance, the adhesion to chromate-treated steel sheets was particularly good.

Claims (1)

[Scope of Claims] 1. A method for producing a metal plated body in which a resin liquid is applied to a metal surface, cured by ultraviolet irradiation, and then a metal plating layer is formed thereon by vacuum evaporation or sputtering, comprising (a) The resin liquid is (i) a resin liquid whose basic components are a polymerizable polymer and/or a polymerizable oligomer and a polymerizable monomer containing a phosphorus element in the molecule, or (ii) at least one phosphorus element in the molecule. A resin liquid containing a polymerizable polymer and/or a polymerizable oligomer having the above phosphorus element as a basic component is used, and (b) immediately before the metal plating layer is provided, the temperature is 60 to 180°C.
1. A method for producing a metal plated body, comprising: performing a heat treatment for 1 to 10 minutes. 2 The resin liquid (i) contains 99% to 70% by weight of a polymer and/or oligomer of an epoxy-modified acrylic resin and/or a polyester-modified acrylic resin having at least one unsaturated group in the molecule, 2. The method for producing a metal plated body according to claim 1, which is a mixture of 1% to 30% by weight of a polymerizable monomer containing at least one phosphorus element in the molecule. 3. The method for manufacturing a metal plated body according to claim 1, wherein the metal plate layer is made of aluminum or an alloy thereof.