JPS5937347B2 - Manufacturing method of metal plating 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 of obtaining a high-brightness metal plated body by forming a metal plating layer on a metal surface by vacuum evaporation or sputtering. A method is already known in which metals such as aluminum, copper, chromium, nickel, or alloys thereof are used on the surface of a metal molded product, and metal plating is performed by vacuum evaporation, sputtering, or the like.

However, 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, there is a risk of scratches on the surface and poor smoothness. The appearance was extremely poor due to the shortage, and furthermore, the adhesion between the bare surface of the adherend and the metal plating layer was extremely poor, resulting in the metal plating layer often coming off. Therefore, in order to compensate for these defects, a thermosetting resin film with a thickness of about 30 to 50 microns is interposed as a base coat layer between the bare surface of the adherend and the metal plating layer, and a metal plating layer is applied to the surface of the resin film. It is commonly adopted to allow the formation of

However, in the case of known resin clears, it is difficult to obtain a thick film with the same amount of resin, and it is necessary to apply at least two coats to obtain a film thickness of about 50 microns, and even more coats if the material surface is in poor condition. Two coats were necessary.

However, in order to obtain multiple layers with the current high-temperature baking resin clear mentioned above, it requires high energy and a long time each time, which is not only undesirable in terms of production efficiency, but also causes the lower layer film to heat up due to overbaking. It also caused deterioration and decreased adhesion between layers.

The present invention aims to solve the above-mentioned problems and provide a method for manufacturing a metal plated body with high production efficiency, which can be processed in a short time and eliminate the para-polishing step.

That is, the present invention provides (a) a resin liquid whose basic component is a polymerizable polymer and/or a polymerizable oligomer containing a phosphorus element in one molecule, or (11) a polymerizable polymer, on the metal surface. A step of applying a resin liquid whose basic components are a polymer and/or a polymerizable oligomer and a polymerizable monomer containing a phosphorus element in the molecule and solidifying it by irradiating ultraviolet rays to obtain a primer coat layer; (b) applying a thermosetting resin liquid on the primer coat layer and heating and solidifying it to obtain a base coat layer; and (c) forming a metal plating layer on the surface of the base coat layer by vacuum evaporation or sputtering. The present invention relates to a method for manufacturing a metal-plated body, which comprises a step of applying.

The present invention will be explained in more detail below. The resin liquid used in the primer coat of the present invention has (1) a polymerizable polymer and/or a polymerizable oligomer having a phosphorus element as a basic component, and optionally a polymerizable monomer having a phosphorus element, etc. (Ii) a polymerizable polymer and/or a polymerizable oligomer and a polymerizable monomer containing the phosphorus element as basic components; It is a composition formed by mixing other polymerizable monomers, organic solvents, other photosensitizers, etc. as necessary.

Polymerizable herein means having at least one unsaturated group in the molecule. The composition (Ii) is most preferred in view of adhesion to active metal surfaces such as chromate-treated bare surfaces and galvanized bare surfaces.

(g) When the polymerizable polymer and/or polymerizable oligomer containing the phosphorus element is used as a basic component, 50% by weight or less of the phosphorus element-containing polymerizable monomer and /or other polymerizable monomers may be contained.

However, when a phosphorus element-containing polymerizable monomer is used in combination, the amount of this monomer is in the range of 1 to 30% by weight based on the total composition of the resin liquid. In addition, when the basic components are (11) the polymerizable polymer and/or polymerizable oligomer a and the polymerizable monomer b containing the phosphorus element, the ratio of the two is a/b = 99/1 to 7
0/30 (wt%), preferably 95/5 to 80/20
(wt%), and if necessary, other polymerizable monomers may be added so that the total monomer amount (total of phosphorus element-containing polymerizable monomer and other polymerizable monomers) in the entire resin liquid composition is 50% by weight.
It can be added within the following range.

More specifically, the polymerizable polymer and/or 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 acrylics, urethane-modified acrylics, 4111-alkyd-modified acrylic resins, unsaturated group-containing polyolefin resins, and drying oils.

Specific examples of the unsaturated polyester resin include commercially available Rigorak 2460uv (Showa Kobunshi) and Polylite C.
H-303 (Dainippon Ink), etc. Specific examples of the unsaturated acrylic resin include commercially available Diabeam K-8303 (Mitsubishi Rayon), and specific examples of the polyester modified acrylic resin include &ζ Commercially available Aronix M8O3O, Aronix M8O6O (Toagosei Chemical Industry Co., Ltd.), and the like can be mentioned. In addition, as an epoxy-modified acrylic resin, commercially available UcOat2Ol (Toho Chemical Industry Co., Ltd.)
, Ditzkreit UE8lOO, Ditzkreit UE8
2OO (Dainippon Ink & Chemicals), and commercially available urethane-modified acrylic resin XP-1077-40-
2 (Nippon Gosei), XP-51-37-70-2 (Nippon Gosei), 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 the phosphorus element include mono(2-hydroxyethyl acrylate) acid phosphate, mono(2-hydroxyethyl methacrylate) acid phosphate, and mono(3-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-hydroxypropyl methacrylate) acid phosphate, phosphoric acid esters of acrylic acid or methacrylic acid containing a hydroxyl group, acrylic alcohol acid phosphate ,
One or a mixture of two or more of vinyl phosphate, vinylphosphonic acid, mono(2-hydroxyethyl acrylate) acid phosphite, di(2-hydroxyethyl methacrylate) acid phosphite, etc., and their salts and esters. Yes, especially preferably mono (2
- Phosphate esters of acrylic acid or methacrylic acid containing a hydroxyl group, such as hydroxyethyl acrylate) acid phosphate, mono(2-hydroxyethyl methacrylate) acid phosphate, and di(2-hydroxyethyl acrylate) acid phosphate. . Furthermore, examples of the polymerizable polymer (or polymerizable oligomer) containing the phosphorus element include polymers or oligomers obtained from the phosphorus element-containing polymerizable monomer, or polymers obtained by modifying these with epoxy or polyester. In the present invention, by using a resin liquid containing phosphorus element, the adhesion of the film obtained from the resin liquid to the metal material can be significantly improved, and as a result, physical and chemical properties such as corrosion resistance are improved. It is possible.

On the other hand, other polymerizable monomers used as optional components include monomers having at least one unsaturated group in the molecule, such as (a) (meth)acryloyl group-containing monomers, and (b) aromatic monomers. A vinyl group-containing monomer or (iii) an aliphatic vinyl group-containing monomer.

Specific examples of the monomer (a) include hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; )
Etherification products of the above-mentioned hydroxyl group-containing monomers such as acrylate and tetrahydrofurfuryl acrylate with alkyl alcohols or cyclic alkyl alcohols: methyl (meth)acrylate, butyl (meth)acrylate, neopentyl glycol di(meth)acrylate, 1 -6 Hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and other esters of (meth)acrylic acid and alkyl alcohol. 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 group (a), which are ether compounds of a hydroxyl group-containing monomer and an alkyl alcohol, ether compounds of a hydroxyl group-containing monomer, and (meth)acrylic acid and an alkyl alcohol. It is an ester compound. These above-mentioned polymerizable polymers and/or oligomers and polymerizable monomers are not limited to only one type, but it is also possible to use two or more types in combination to bring out the characteristics of each.

The "resin liquid" used in the primer coat layer of the present invention has a polymerizable polymer and/or oligomer as a basic component, and may be mixed with the polymerizable monomer as appropriate depending on the difficulty of the coating work, the surface condition of the coating film, etc. They are combined to adjust the viscosity and properties of the resin liquid. In particular, when a low viscosity resin liquid is required, an organic solvent is also used. Furthermore, in the present invention, since ultraviolet rays are used as an energy source for solidifying the resin liquid, it is necessary to add a photosensitizer to the resin liquid.

Examples of the photosensitizer include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzyl, benzophenone, anthraquinone, naphthoquinone, chloranthraquinone, tetramethylthiuram disulfide,
Examples include diphenyl disulfide, 2,2-diethoxyacetophenone, benzoine peroxide, azobisisobutyronitrile, 2,2'-azobispropane, etc., and the amount used depends on the resin solution. The amount is 0.05 to 15 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable polymer and/or oligomer and the polymerizable monomer.

The resin liquid used in the primer coat layer of the present invention may optionally contain a leveling agent, a polymerization prevention agent, and an anti-sagging agent. Raw materials used in known paints, such as pigments, may be added.

In particular, if a composition containing pigments is used as a primer coat layer, it is extremely effective to obtain a thick film in one coat. Pigments used in the primer coat layer of the present invention include extender pigments commonly used in paints such as talc, calcium carbonate, magnesium carbonate, bentonite, silica, barium sulfate, barium silicate, and other rust-preventive pigments; Any material may be used as long as it does not inhibit the solidification of the coating film when irradiated with ultraviolet rays, such as colored pigments.

In the present invention, since ultraviolet rays are used to cure the primer coat, taking this point into consideration, I@. Extender pigments such as talc, silica, barium sulfate, and calcium carbonate are preferred.

These pigments are more preferable because they have a large effect of imparting thixotropy. It is not particularly limited as it varies depending on the mixing ratio of the resin liquid and pigment and the oil absorption amount (bulk specific gravity) of the ζ pigment, but preferably 5 to 200 parts by weight of pigment per 100 parts by weight of resin liquid. This is the percentage of

In order to obtain a mixture of the resin liquid and the pigment, they are mixed using a known dispersing machine such as a roll mill, a dispersion mill, a sand mill, or a ball mill.

In the present invention, it refers to a thermosetting resin used in the base coat layer and a resin or a combination of resins that forms a crosslinked structure or promotes the formation of a crosslinked structure by heating.

Therefore, a composition formed by mixing a thermosetting resin liquid, a synthetic resin containing groups necessary to react with each other and form a crosslinked structure by heating, a solvent (organic solvent, water, etc.), other additives, etc. It is a thing. The groups necessary to react with each other to form a crosslinked structure include carboxyl group (including acid anhydride group) to epoxy group, carboxyl group (including acid anhydride group) to hydroxyl group, hydroxyl group to epoxy group, hydroxyl group -isocyanate group (including block isocyanate group), epoxy group -amino group, hydroxyl group -methylol group, hydroxyl group -etherified methylol group, etc. More specifically, melamine-alkyd resin, acrylic-alkyd resin, acrylic-melamine resin, self-curing acrylic resin,
Typical examples include epoxy to phenol resins, epoxy to polyamide resins, and polyester to isocyanate resins. In order to obtain a primer coat layer in the method for producing 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, a spray coater, a curtain flow coater, or a brush coater to obtain a desired film thickness, preferably Apply to a thickness of about 30 to 50 microns, and if necessary, after setting, irradiate with ultraviolet rays. At this time, if an even thicker film is required, the adhesive can be applied multiple times and solidified using the above method each time. Next, the thermosetting resin liquid is applied to the surface of the brimer coat layer in the same manner as described above to a desired film thickness, preferably about 20 to 30 microns, and then the thermosetting resin is coated with the liquid as necessary to solidify the thermosetting resin. Heat and solidify under certain conditions.

It is usually heated at about 120 to 220°C for about 15 to 40 minutes. In the method of the present invention, a metal plating layer with a thickness of about 1 micron or less made of metals such as aluminum, chromium, nickel, copper, and alloys thereof is then formed on the surface of the base coat layer by vacuum evaporation or sputtering. do.

The thus obtained product is a metal-plated body and has excellent heat resistance, with no occurrence of multicolored rainbow patterns, wrinkles, cracks, etc. even when heated.

In addition, since the metal plating layer of the metal plating body obtained by the present invention is an extremely thin film, in order to protect the plating layer and prevent surface contamination, the metal plating layer used in the primer coat layer of the present invention is applied to the surface of the metal plating layer for the purpose of protecting the plating layer and preventing surface contamination. Either apply the same resin liquid and solidify it by irradiating it with active energy from commonly used ionizing radiation and/or electromagnetic waves, or apply the same thermosetting resin liquid used as the base coat layer. Then, the final product can be made by heating and curing or by applying a cold-setting resin liquid such as acrylic lacquer and solidifying it. Next, the present invention and its specific effects will be explained by giving examples.

Note that "parts" or "%" indicate "parts by weight" or "% by weight." The above resin liquid A-1 for primer coat layer was applied to the surface of a cold-rolled steel sheet that had been polished and cleaned so that the dry film thickness was 30 microns. After spray painting and setting for 10 minutes at room temperature,
A primer coat layer was obtained by irradiating for 60 seconds at an irradiation distance of 20 (V7!) using one high-pressure mercury lamp with a lamp input of 80 W/(177!).

Next, Solbetsuso #100 was applied on the primer coat layer.
The base coat layer resin solution B-1 whose viscosity was adjusted with a mixed solvent consisting of 90:10 parts by weight of butyl cellosolve (Food cup 414, measured viscosity 30 seconds) was dried to a film thickness of 2.
The base coat layer was coated with a spray coating so as to have a thickness of 0 microns, set at room temperature for 20 minutes, and then left in a hot air drying oven at 200° C. for 20 minutes to solidify the base coat layer. After it was taken out from the furnace and cooled, it was immediately subjected to vacuum evaporation at a vacuum degree of 1×10 −4 T0rr to obtain an aluminum metal film of 500A. Spray the above primer coat layer resin solution A-2 onto the surface of a polished and cleaned cold-rolled steel sheet to a dry film thickness of 30 microns, and after setting it in a hot air drying oven at 50°C for 5 minutes, turn on the lamp. 80W/? With one high-pressure mercury lamp,
Irradiation distance 20? was irradiated for 60 seconds to obtain a primer coat layer.

Next, the base coat layer resin solution B-2 was applied onto the primer coat layer in the same manner as in Example 1, and after setting, the base coat layer was left in a hot air oven at 140 DEG C. for 30 minutes to solidify the base coat layer. After taking it out of the furnace and cooling it, it is immediately vacuum evaporated under the conditions of vacuum degree 1X10-4T0rr,
A 500A aluminum metal film was obtained. Spray the above resin liquid A-3 for primer coat layer onto the surface of a polished and cleaned cold-rolled steel sheet to a dry film thickness of 30 microns, and after setting in a hot air drying oven for 50'C x 5 minutes, lamp power is 80W. Irradiation distance is 20CI with one /Cm high pressure mercury lamp! A primer coat layer was obtained by irradiating with L for 60 seconds.

Next, the base coat layer resin solution B-3 was applied onto the primer coat layer in the same manner as in Example 1, and after setting, the base coat layer was left in a hot air drying oven at 150 DEG C. for 30 minutes to solidify the base coat layer. After being removed from the furnace and cooled,
Immediately, vacuum evaporation was performed at a vacuum degree of 1×10 −4 T0rr to obtain a 500A aluminum metal film. Example 4 [Resin liquid A-4 for primer coat layer] Same as the resin liquid A-1 for primer coat layer [Resin liquid B-4 for base coat layer] (1) Acrydic A-8
01: Manufactured by Dainippon Ink and Chemicals Co., Ltd. (2) Takenate D-110N: Manufactured by Takeda Pharmaceutical Co., Ltd. The above resin liquid A-4 for the primer coat layer was applied to the surface of a cold rolled steel sheet that had been polished and cleaned in Example 1. A primer coat layer was obtained by coating and curing in the same manner as above.

Next, the resin solution B-4 for the base coat layer was spray coated onto the primer coat layer to a dry film thickness of 20 microns, and after setting for 30 minutes at room temperature, it was left in a hot air drying oven at 140° C. for 30 minutes to form a base coat. The layer was allowed to solidify. Immediately after taking it out of the furnace and cooling it, the vacuum level is 1X10.
Vacuum deposition was performed under the condition of -4T0rr to obtain a 500A aluminum metal film. Example 5 The above composition A-5 for a primer coat layer, whose viscosity was adjusted (viscosity measured by food cup #4 for 40 seconds) with the same mixed solvent of equal amounts of xylol trimethyl isobutyl ketone as the resin liquid B-1 for a base coat layer, was subjected to hub polishing. Spray paint the surface of the automobile headlamp reflector material that omitted it to a dry film thickness of 80 microns, and after setting it at room temperature for 30 minutes, use a lamp input of 160 W/one of my high-pressure mercury lamps, and an irradiation distance of 20 cm for 30 cm. A primer coat layer was obtained by irradiating for seconds.

Next, Solbetsuso #10 was applied on the primer coat layer.
The base coat layer resin solution B-5 whose viscosity was adjusted with a mixed solvent of 90:10 parts of butyl cellosolve (Food cup #4, Okiyodo viscosity 30 seconds) was spray-coated to a dry film thickness of 25 microns, and the mixture was allowed to cool to room temperature. After setting for 20 minutes, the base coat layer was left in a hot air drying oven at 200° C. for 20 minutes to solidify the base coat layer.

Immediately after taking it out of the furnace and cooling it, the vacuum level is 1X10-4T.
Vacuum deposition was performed under the condition of 0rr to obtain a 500A aluminum metal film. Example 6 [Resin liquid B-6 for base coat layer] The same composition A-6 for primer coat layer as the resin liquid B-3 for base coat layer was applied to the surface of the same material as in Example 5 in the same manner as in Example 5. Apply it. It solidified.

Next, resin solution B-6 for base coat layer was applied by the same method as for the base coat layer of Example 5, and after setting,
The base coat layer was left to solidify in a hot air drying oven at .degree. C. for 30 minutes. After being taken out from the furnace and cooled, vacuum evaporation was performed at a vacuum degree of 1×10 −4 T0rr to obtain a 500A aluminum metal film. Comparative Example 1 Resin liquid B-4 for base coat layer was applied on the primer coat layer obtained by applying and solidifying resin liquid A-4 for base coat layer in the same manner as in Example 4 using resin liquid A-4 for base coat layer. The film was spray coated to a thickness of 20 microns, dried and solidified at room temperature for 7 days, and then vacuum evaporated at a vacuum degree of 1 x 10-4 T0rr to obtain a 500A aluminum metal film.

Comparative Example 2 On the primer coat layer obtained by applying and solidifying in the same manner as in Example 2, the base coat layer resin liquid B-
Spray paint 7 to 15 microns and apply 3 at room temperature.
After setting for 0 minutes, place it in a hot air drying oven at 120℃ for 20 minutes.
Leave it for a minute.

Immediately after removing from the furnace and cooling, the vacuum level is 1 x 10-4T.
Vacuum deposition was performed at 0rr to obtain a 500A aluminum metal film. The effects of the metal plating bodies obtained in Examples 1 to 6 and Comparative Examples 1 to 2 were comparatively evaluated.

The results are shown in Table-1.

Test method (1) Appearance: Visually judge the brightness and smoothness of the surface of the metal plating layer of the metal plating body.

(2) Heat resistance: The metal-plated body is left in a circulating hot-air electric furnace at 180°C for 60 minutes, and after a specified period of time, the test piece is taken out of the furnace, allowed to cool naturally, and then the condition of the surface of the metal-plated layer is visually judged. It is clear from the comparative test result table that the test specimen obtained by the method of the present invention has excellent appearance and heat resistance, and therefore is suitable for lighting reflectors where deterioration of the metal plating layer due to heat is a particular problem. It is very useful as

Claims (1)

[Claims] 1(a) A resin liquid whose basic component is a polymerizable polymer and/or a polymerizable oligomer containing a phosphorus element in the molecule, or (ii) a polymerizable polymer and/or a polymerizable polymer, is applied to the metal surface. (b) a step of applying a resin liquid whose basic components are a polymerizable monomer containing a phosphorus element in its molecules and irradiating it with ultraviolet rays to obtain a primer coat layer; (b) the primer coat; A metal comprising the steps of: applying a thermosetting resin liquid onto the layer and heating and solidifying it to obtain a base coat layer; and (c) forming a metal plating layer on the surface of the base coat layer by vacuum evaporation or sputtering. Method of manufacturing plated bodies.