JPS61264200A - Production of composite organic high-polymer plated metallic material having excellent paint adhesiveness - Google Patents

Abstract

PURPOSE:To produce an electroplated steel sheet having excellent paint adhesiveness, corrosion resistance, press workability and weldability without requiring a surface treatment for painting by subjecting a galvanized steel sheet as a cathode to plating in a plating liquid contg. Zn ions and specific water soluble org. high polymer. CONSTITUTION:The Zn- or Zn alloy-plated steel sheet as the cathode is electroplated in the plating liquid which contains 10-600g/l ions and is added with 0.5-30wt% >=1 kinds of water soluble org. high polymers having 500-500,000 mol.wt. The water soluble org. high polymers to be used are anionic, cationic, nonionic and amphoteric water soluble high polymer materials. The eutectoid layer of An as a metal and 0.6-30wt% org. high polymer is formed on the surface of the galvanized steel sheet and the composite org. high-polymer plated steel sheet having the excellent paint adhesiveness, etc., is obtd. without the surface treatment such as phosphate treatment and chromate treatment.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing an organic polymer composite plated metal material in which an electroplated film is formed that has excellent paint adhesion, corrosion resistance, press workability, and weldability. It is. Specifically, it relates to a method for manufacturing organic polymer composite electroplated metal materials, which has the major feature that it does not require any pre-painting treatment such as phosphate treatment or chromate treatment as in conventional methods. 0 [Prior Art] Conventionally, metal plating such as zinc or zinc alloy plating has been widely used to impart corrosion resistance to metal surfaces, particularly to steel plate surfaces. These plated metal materials are often used by coating on top of the plating for the purpose of increasing corrosion resistance and imparting decorative properties. However, metal-plated surfaces such as zinc and zinc alloy plating may have poor paint adhesion, and therefore, prior to coating, a base treatment such as phosphate treatment or chromate treatment is usually applied. However, in recent years, chemical conversion treatments such as phosphate treatment and chromate treatment are required to be shortened and simplified due to the length of the process (6 to 9 steps) and the complexity of bath management. In particular, for users, it is recommended to avoid the above-mentioned in-house treatment (chemical conversion treatment) due to labor-saving or pollution prevention restrictions such as slang treatment and waste liquid treatment, or to use surface-treated steel sheets that do not require surface treatment for painting. Development is strongly requested.

Various methods have been tried so far to solve these problems. Examples of methods using organic compounds in attempts to create surface-treated steel sheets that do not require chemical conversion treatment include methods of applying polar organic compounds, methods of applying and drying resins such as organic composite silicate, or methods of applying organic compounds in a plating solution. A dispersion plating method in which a water-insoluble resin is dispersed and composite eutectoid has already been proposed (US Pat. No. 343,494).
No. 2 and No. 3461044). However, each method has its advantages and disadvantages, and it has not yet reached the point where it fully satisfies the needs of users.For example, the water-insoluble resin dispersion plating method mentioned last is a technology that deserves attention, but when considering industrialization, It had many shortcomings, including: First, the problems in the process are as follows: (a) It requires the use of a surfactant to stabilize the uniform dispersion of resin particles, and requires special measures for liquid circulation, which involves a complicated process. .

(b) Since the resin particles are strongly negatively charged in the plating bath, the resin particles are deposited on the anode, making it difficult to eutectoid the cathode.

(C) In order to avoid this, it was necessary to alternately plate the objects while reversing their polarity (see U.S. Pat. Nos. 5,454,942 and 341,044, or use a special surfactant to There are many limitations, such as the need to positively charge the particles to facilitate cathodic deposition and prevent anodic deposition of the resin (Japanese Patent Publication No. 52-25375).

(d) This method of using a surfactant requires selection of a surfactant for each type of resin particle, or when considering continuous productivity, it becomes difficult to control the concentration of a small amount of surfactant. Contains complicated issues.

On the other hand, problems related to the physical properties of the resulting plating film include the following.

(e) The film thickness cannot be made smaller than the size of the resin particles used.

(f) Since it precipitates in a form embedded in the metal phase of the particles, pinholes are likely to form, which is disadvantageous in terms of corrosion resistance.

(g) Unless a large amount of resin particles (approximately 5% or more) are eutectoid, paint adhesion will not be effective, and depending on the resin particle size used, adhesion to the base substrate may be poor or the physical properties of the plated metal phase may change, making processing difficult. It easily leads to peeling over time.

The dispersion plating method of insoluble resin particles has had the above-mentioned practical problems.

[Problem that the invention seeks to solve]

As mentioned above, methods for producing electroplated metal materials that have excellent paint adhesion without the need for prepainting treatment (chemical conversion treatment) have been extensively tested, but they are not suitable for continuous production. It is also insufficient in terms of functionality such as heat, corrosion resistance, and press workability, and has not reached a level where the current chemical conversion treatment process can be omitted.

On the other hand, a method of composite plating of zinc and a plastic compound in a molecular state has already been attempted in the physical vapor deposition method (Japanese Patent Publication No. 1185/1985). Although this is intended to impart corrosion resistance, there are many problems in industrial implementation, such as processing in a high vacuum and requiring a large amount of equipment for continuous mass production.

In view of this situation, the present invention aims to solve the above problems by focusing on a technology for combining organic polymers and metals.

[Failure to solve the problem]

The present invention involves simply applying an organic compound, water-insoluble wood,
Moving away from the conventional idea of dispersing and co-depositing fat particles,
By developing a new technology that combines organic polymers and metals at the molecular level (molecular composite),
It is intended to create a high level of multifunctional surfaces that cannot be achieved with conventional techniques.

As a result of intensive studies based on the above points, the present inventors have discovered that the above object can be achieved by applying a water-soluble organic polymer to an electric medical device Φ, and have completed the present invention.

That is, the present invention provides a zinc plating bath containing 10 to 6,000 t/z of zinc ions, or a method in which one or more different metal ions other than zinc are added to the zinc plating bath at 61 to 600 t/z, respectively.
In a zinc alloy plating bath containing 0.05 to 30 wt% of each of one or more water-soluble organic polymers having a molecular weight of 5 million to 5 million as essential components, electroplating is performed using a metal material as an anode. Paint adhesion characterized by eutectoiding a metal and a water-soluble organic polymer on the surface and controlling the proportion of the water-soluble organic polymer to be in the range of 0.06 to 50 wt% based on the total precipitation amount. The present invention provides a method for manufacturing an organic polymer composite plated metal material with excellent properties.

The water-soluble organic polymer used in the present invention is uniformly dissolved and stable even in plating solutions containing large amounts of metal salts, so it is necessary to use a dispersant (surfactant) and special measures for liquid circulation. etc. are not required, and the workability is extremely excellent.

In addition, in the present invention, there is no problem such as resin depositing on the anode to form an insulating film and voltage abnormality, so continuous plating can be performed using a normal direct current method. It has been used for a long time. This is a very small amount (o, oo1
~o, o s%) is used mainly for the purpose of improving decorativeness (brightening agent). Other purposes include mist preventive agent, impurity remover (complex forming agent),
It is used as an antifoaming agent, a coagulating and precipitating agent for insoluble suspended impurities, or a dispersing agent for eutectoid particles in dispersion plating methods. Therefore, in the above case, paint adhesion and corrosion resistance are hardly improved. The purpose of the present invention is significantly different from that of conventional methods.The primary purpose of the present invention is to improve paint adhesion and corrosion resistance, and the secondary purpose is to improve press workability and weldability.Therefore, the method of use is also different. ing. That is, in the present invention, the above-mentioned functions are exhibited by actively eutectoiding and compounding the plating metal and the water-soluble organic polymer.

Examples of water-soluble polymers that can be used in the present invention include s I) anionic water-soluble polymer, ■) cationic water-soluble polymer, m) nonionic water-soluble polymer, and ■
) It is roughly divided into four types of amphoteric water-soluble polymers, and among these, those having a molecular weight of SOO to 50,000 can be used.

Examples of I) include the following.

Carboxylic acids such as acrylic acid, methacrylic acid 1, itaconic acid, maleic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, acrylogine ethyl phosphate, methacrylogine ethyl phosphate, etc. A water-soluble 7-ionic vinyl polymer or oligomer containing at least one monomer having a polymerizable double bond with acid, sulfonic acid or phosphoric acid, and derivatives thereof.

Anionic water-soluble polycrethane resin, water-soluble polyester resin, β-naphthalenesulfonic acid formalin condensate, and derivatives thereof.

Anionic natural polymers such as gum tragacanth, xanthan gum, gum arabic, agar, sodium alginate, and carrageenan, and their derivatized moxibustion carboxymethyl cellulose, carboxymethyl starch lignin, periodic lignin, sulfuric lignin, hydrochloric lignin, chromium lignin, cupric ammonia Anionic semi-synthetic polymers such as lignin, dioxane lignin, thiolignin, thioglycolic acid lignin, syringyl lignin, lignin sulfonic acid, lignin sulfonate, and derivatives thereof.

1 [) is a cationic water-soluble polymer compound containing a cationic or basic nitrogen atom in the molecule, the following a
-%-h.

a A homopolymer or a copolymer of two or more nitrogen-containing monomers or salts thereof represented by the following general formulas (1) to (2).

[R is ■ or CH, R2 and R3 are H or carbon number 1
~3 alkyl group] I CH2=C-000 (CH2CH20) ml (CH2)
nlN〈(■)〔ml is a number from 1 to 5, nl is a number from 1 to 3, R,, R2゜(R, is H or alkyl or alkyl having 1 to 3 carbon atoms [m2 and R2 are 0 to 3 number, R1, R2, R,
is the formula% formula% [A is 10- or -NH-, R1, R2, R,, nl is the same as formula (1) and (If)] (R1 * R2+ Rs, n'' is the formula (r) and (“
) ] R1 (R1 is the same as formula (1). The substitution position of pyridine is 2 or 4
position] R7 (R1, R2 are the same as in formula (I). The substituent position of piperidine is the 2 or 4 position)] R1 (R1, R2, R, is the same as in formula (1)) Diallylamine grade ammonium salt or a derivative thereof.

C Salt or quaternary ammonium salt of a condensation product of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine O d Dihaloalkane-polyalkylene polyamine condensation product.

e Epihalohydrin-amine condensation product.

f Chitosan salt, cationically modified semi-synthetic polymers such as starch or cellulose, and natural polymers.

g A polyether polyol or a polyol polyether derivative having a molecular weight of 1,000 to 600,000, obtained by adding an alkylene oxide to a polyalkylimine having 6 to 20 nitrogen atoms or a derivative thereof.

h Cationic water-soluble polyurethane resin and derivatives thereof.

Examples of m) include nonionic synthetic polymers such as polyvinyl alcohol, polyhydroxyethyl (meth)acrylate, polyethylene oxide, polyvinyl ether, nonionic water-soluble epoxy resins, and derivatives thereof, starch, guar gum, tamarind, and dextrin. , nonionic natural polymers such as pullulan, pectin, and derivatives thereof; nonionic semisynthetic polymers such as hydroxyethyl cellulose, methyl cellulose, and derivatives thereof.

Examples of W) include water-soluble proteins such as gelatin and casein, and derivatives thereof, or copolymers of the anionic monomers mentioned in 7) and the cationic monomers mentioned in π).

In addition, examples may include those in which a lipophilic group is introduced into the compounds listed in sr) to N) by copolymerization or bimolecular reaction to such an extent that water solubility is not impaired. Sara K
Among I) to (ii), organometallic polymers containing metal elements can also be used. It is also possible to select one type or two or more types from the above and use them as a mixture.

The water-soluble organic polymer that can be used in the present invention has a molecular weight in the range of 5 million to 5 million, preferably 1000,000.
Limited to the range of ~1 million. The reason for this is that the molecular weight of the organic polymer affects the effect of the present invention;
A large paint adhesion effect cannot be obtained with low molecular weight substances.
On the other hand, polymers with a molecular weight exceeding 5 million have poor solubility in water, which poses a problem as there is a limit to the concentration added to the plating bath.

In the present invention, there are no particular limitations on the metal material to be plated. For example, metal materials such as steel, copper, brass, and aluminum can be used.

The method of the present invention is particularly effective when zinc ions are included as eutectoid metal ions, that is, for zinc and zinc alloy plating. Examples of galvanizing baths that can be used include known galvanizing baths containing 10 to 6 aa F// of zinc ions. For example, (1) generally known acid baths including a sulfate bath using zinc sulfate, a chloride bath using zinc chloride, a borofluoride bath using zinc borofluoride, or a mixed bath thereof; (2) a bath in which zinc chloride is replaced with ammonia; (3) alkaline baths such as zinc birophosphate baths using zinc birophosphate, zincate baths containing zinc and sodium hydroxide, and (4) zinc cyanide plating baths. There are known galvanizing baths, among which (
1) is preferred. As a zinc alloy plating bath, iron, which is considered as an alloying element, is added to the baths (1) to (4) above.
Nickel, chromium, cobalt, manganese, copper, tin, lead,
One or more of chlorides, sulfides, fluorides, cyanides, oxides, organic acid salts, phosphates, sodium salts, etc. of magnesium, aluminum, etc. was added as a bath component at 61 to 6 oot/i each. A generally known zinc alloy plating bath can be used. Among these, baths based on (1) that are secular are preferred. By using an alloy plating bath, it is possible to improve the corrosion resistance and weldability of the galvanized film.

As the plating bath used in the present invention, a plating bath in which 0.05 to 50 wt% of a water-soluble polymer is added to an aqueous solution containing the above eutectoid metal ions can be used. Preferably, a plating bath containing 0.5 to 30 wt% is preferred. After bath adjustment, since the organic polymer is stably dissolved, there is no need to stir the solution for uniform dispersion. The pg of the plating bath may be acidic or alkaline, but care must be taken as the solubility of the water-soluble organic polymer used may deteriorate depending on the pg and metal ion concentration. Furthermore, corrosion resistance can be improved by adding a rust preventive agent to the plating bath according to the present invention.

Direct current or pulsed current can be used as the plating electrolytic conditions.

The amount of eutectoid water-soluble organic polymer is the polymer concentration.

It is significantly affected by the current density and the charge of the organic polymer. The amount of eutectoid increases with high concentration and high current density. Further, if the molecular skeletons are almost the same, the eutectoid amount is in the following order: cationic polymer>nonionic polymer>anionic polymer.

In the present invention, in the organic polymer composite plating film, 0.06~
It is characterized by eutectoiding 50 wt% of organic polymer in a molecular state. Preferably, 0.6 to 30 wt% is eutectoid. If the amount of organic polymer eutectoid is small, the paint adhesion effect will not appear because it approaches Zn single plating.On the other hand, if it is too large, the plating film will become brittle, making it easier for the plating film to break or peel off during press processing. Since the organic polymer composite plating film according to the present invention uses a water-soluble polymer, it has a major feature in that the composite with the eutectoid metal occurs on the molecular order, and macroscopic dispersion and
In this respect, the present invention differs greatly from dispersion plating of water-insoluble resins, which can only be achieved by forming composites. Therefore, in the method of the present invention, unlike dispersion plating, there is no restriction on the lower limit of plating layer due to the diameter of the resin particles used, and the plating amount can be arbitrarily selected from thin film (thin coating weight) to thick film (thick coating weight) i. . Furthermore, depending on the type of water-soluble organic polymer used, the crystal shape of the composite plated metal may be flat, cubic, acicular, etc.
It is also possible to greatly change the crystal shape, such as spherical or rectangular, and it is also possible to control the crystal size. These phenomena indicate that organic polymers are involved from the stage of crystal growth, and are proof that eutectoid formation with metals occurs at the molecular level. The ability to control the surface morphology using organic polymers in this manner is extremely useful in designing adhesive surfaces, as it allows for the control of anchoring effects and increases in adhesive surface area.

The composite plated metal material according to the present invention is based on the premise that paint is applied on the plating film in order to further improve the corrosion resistance of the metal material, so the ability to adhere to the paint is an essential feature required for organic polymer composite plating. It is a function.

As the paint that can be used, known paints such as a room temperature drying paint, a thermosetting paint, or an electrodeposition paint can be used.

As a coating method, known coating methods such as spray coating, powder coating, roll coating, electrostatic coating, and electrodeposition coating can be applied.

The organic polymer composite plating film according to the present invention has adhesion to paint in the peeled state, so there is no need for chemical conversion treatment (painting base treatment) such as phosphate treatment or chromate treatment. Further, no new special treatment such as heat treatment at 100° C. or higher is required. Therefore, even when a room temperature drying type paint is directly applied to a dried plating film, a sufficient paint adhesion effect can be obtained. When using a thermosetting paint, it is necessary to perform a heat treatment to cure the paint, but the heating temperature in this case is preferably 200°C or less. The reason for this is that at high temperatures of 200° C. or higher, the eutectoid organic polymer is susceptible to oxidation and decomposition, and as a result, the adhesion of the paint tends to decrease. Therefore, in order to maintain the adhesion of the paint over a long period of time, it is necessary to pay attention to the heat history before application.

[Effect]

Although the cause of the improvement in paint adhesion by the method of the present invention has not been completely elucidated, the following factors may be mentioned.

First, it is thought that the affinity of the metal surface for paint increases due to compounding with an organic polymer, or that the effective adhesion area increases due to a change in crystal morphology or that an anchor effect contributes. In addition, since stronger paint adhesion can be obtained by combining a water-soluble polymer with a charge opposite to that of the paint, it is thought that the adhesion effect due to acid-base action or the △ contribution of electrolyte crystals may be involved.

〔Example〕

The present invention will be explained below using Examples.

(1) Plating method After alkali degreasing and water washing, cold rolled steel sheets were plated under the following conditions. The plating bath composition and water-soluble organic polymer used are shown in Tables 1 and 2, respectively. Plating conditions are current density 1~
Using 50A/am Ω DC current, bath temperature 5o~50'C
It was carried out within the range of

The amount of organic polymer eutectoid was controlled by changing the concentration of water-soluble organic polymer added and the current density, and the zero plating film thickness was set to 3 μm in all cases.

For film thickness measurement, an eddy current film thickness meter (Sancora Electronics Co., Ltd., S
L-2L-8M type) was used.

Table 1 (2) Evaluation of paint adhesion The evaluation results of paint adhesion of the products of the present invention and comparative products produced under the above conditions are shown in Tables 3 and 4.

The paint film adhesion evaluations listed in Tables 3 and 4 were performed using cationic epoxy electrodeposition paint (Kansai Paint Co., Ltd.).
Electrodeposition was performed at 150'7 using Nireclone No. 9210), and the coating thickness was adjusted to 30 μm after baking at 180° C. for 25 minutes. It was subjected to an adhesion test as it was without applying an intermediate coat or top coat.

The comparative examples of chromate-treated electrogalvanized steel sheet and zinc phosphate-treated electrogalvanized steel sheet are commercially available Zincoat steel sheet (trade name, manufactured by Nippon Steel Corporation) and Bonde steel sheet (trade name, manufactured by Nippon Steel Corporation), respectively. was used. Dispersion plating of water-insoluble resin was performed by adding vinyl acetate/methyl methacrylate (97:s) copolymer emulsion (particle size 5 μm) (solid content) to the zinc plating bath shown in Table 1, A. Using a bath, the bath temperature is 30°C and the current density is 10A/d.
The test was carried out under conditions of 3 μm in thickness.

Note 1) Metal carbon analyzer (Horiba, Ltd. EM-A-1)
10) to 1350°C, and the generated co2.
Detect the amount of CO and quantify the total amount of carbon in the plating film (
wt%). This value (carbon content) was taken as the eutectoid amount of organic polymer.

Note 2) The goblets reaching the base plated surface are spaced 1MN apart.
00 was drawn and the number of remaining coating films was shown when peeled off with cellophane tape.

Note 3) After drawing 100 goblets at 1 mlR intervals that reach the base plating surface, Erichsen extrusion processing and 7-hole processing were performed, followed by a Sellotape peel test. Evaluation criteria for coating film survival rate ◎... Processing No peeling due to tape peeling after processing is observed.○: Peeling due to tape peeling after processing is slight (1~
5%) Δ... Peeling due to tape peeling after processing is slightly (5-1
5%) Accepted ×01. The peeling caused by peeling off the tape after processing is about the level of a priest (1
5 to 35%) Appeared ×× Most of the peeling is due to tape peeling after processing (6
5%) or more.

Table 3 shows the primary adhesion of various zinc-water-soluble organic polymer composite plating films of the present invention together with comparative examples.

In the coating film adhesion evaluation results by the cross-cut test, no significant difference was observed between the products of the present invention (51-17) and the comparative examples (418-21).

However, it can be seen that there is a significant difference in the results of coating film adhesion evaluation under severe conditions using the Erichsen extrusion test. That is, first, when compared with the single Zn plating film (418) that does not contain any organic polymer, it can be seen that the coating film adhesion of the product of the present invention containing a composite organic polymer is extremely excellent. In addition, when compared with commercially available chemically treated steel sheets, all coating adhesion was better than that of commercially available chemically treated steel sheets, except that Ya 1 was equivalent to zinc phosphate treated steel sheet (boiled 20) and water-insoluble resin dispersion plated steel sheet (A21). showed his sexuality.

From the above results, it can be seen that the paint adhesion of the galvanized surface can be significantly improved by eutectoiding a small amount of water-soluble organic polymer with zinc metal.Table 4 shows that the effect of the present invention can be extended to zinc alloy plating. At the same time, water resistant adhesion was added to the coating adhesion evaluation. As is clear from Table 4, the products of the present invention (Mus. 22 to 25) contain no water-soluble organic polymer at all in Comparative Examples &26 to 29, or the chromate-treated and zinc phosphate-treated steel sheets of 430.31 and water-soluble organic polymers. Compared to the insoluble resin dispersion plated steel plate 32, both exhibited excellent primary adhesion and water-resistant adhesion of the coating film.

These results show that the present invention is not only effective in improving the primary adhesion of zinc plating, zinc alloy plating, and tin plating, but also extremely effective in improving the adhesion of water-resistant coatings.

The products of the present invention in Tables 3 and 4 were added to a 5% aqueous sodium chloride solution 6
When the corrosion resistance of the paint was evaluated by immersion at 0°C, it was found that the corrosion resistance was improved compared to when the coating was coated with a plating film that did not contain a water-soluble organic polymer.

Furthermore, even during press processing, the products of the present invention shown in Tables 3 and 4 exhibited press workability equivalent to or better than a plated film that does not contain a water-soluble organic polymer, and no particular adverse effects due to the organic polymer composite were observed. .

As described above, by applying water-soluble organic polymers to electroplating, it is possible to eliminate the complexity and limitations of conventional water-insoluble resin dispersion plating technology, and the method of the present invention can be used. Q (3) found that plated metal materials with excellent paint adhesion and corrosion resistance can be obtained without applying chemical conversion treatment technology.
)Measurement of good coating film adhesion.Same, zinc-organic polymer composite plating using -polymer 5
After drying, a phthalate resin-based room-temperature drying paint SD Horsu 1000 manufactured by Kansai Paint Co., Ltd. was applied and dried, and the adhesion of the paint film was evaluated by a square eye test. The results are shown in Figure 1.0 As is clear from Figure 1, there is an appropriate range for the amount of organic polymer eutectoid in the composite plating, and the total carbon content is 0.
The coating film adhesion effect becomes remarkable in the range of 06 to 50 wt%, preferably +'! , t2 was found to be in the range of 0.2 to 15vrt%.

〔Effect of the invention〕

As described above, the present invention has a major feature in that a water-soluble organic polymer is used instead of a water-insoluble organic polymer. In the method of the present invention, a composite of plating metal and organic polymer is formed on the order of molecules, so a high level of paint adhesion can be achieved by eutectoiding an extremely small amount of organic polymer (0.06 to several weight percent). It is possible to provide corrosion resistance, press workability, and weldability.

The water-soluble organic polymer composite plating film obtained in this way is not only used as an adhesive surface for paints, but also when laminating resin films, rubber, ceramics, etc. on metal surfaces, or when bonding metals together. Can also be used as an adhesive surface. Furthermore, if a water-soluble organic polymer exhibiting non-adhesive properties, such as a polymer containing a large number of c-y bonds, is eutectoid, a non-adhesive surface can be formed. By eutectoiding a water-soluble organic polymer with excellent lubricity, a composite membrane with excellent lubricity can be produced. This type of plating film can be used as a surface treatment for rotating bodies and sliding bodies that require lubricity. By eutectoiding a magnetic metal and a lubricating organic polymer, it is possible to form a magnetic plating layer with self-lubricating properties.

Although the water-soluble organic polymer composite plating technology described above is based on electrolysis, it can also be directly applied to electroless plating technology.

Furthermore, the water-soluble organic polymer composite plating method according to the present invention can be easily produced using conventional electroplating equipment, does not require expensive equipment or much labor, and has high industrial value.

[Brief explanation of drawings]

FIG. 1 is a graph showing the results of a coating film adhesion evaluation test in Examples. Applicant's agent: Keifu Furuya 1 Figure Organic polymer content [wt%]

Claims (1)

[Scope of Claims] 1. A zinc plating bath containing 10 to 600 g/l of zinc ions, or a zinc alloy plating bath containing 61 to 600 g/l of one or more different metal ions other than zinc in the above zinc plating bath. , each containing one or more water-soluble organic polymers with a molecular weight of 5 million to 5 million as essential components.
Electroplating is performed using a metal material as a cathode in a bath containing ~30 wt%, and the metal and water-soluble organic polymer are eutectoided on the surface, so that the proportion of the water-soluble organic polymer is 0.0 with respect to the total amount deposited.
A method for producing an organic polymer composite plated metal material with excellent paint adhesion, which comprises controlling the content to be in the range of 6 to 30 wt%. 2 Claims in which the amount of the water-soluble organic polymer added is 0.5 to 30 wt%, and the proportion of the precipitated water-soluble organic polymer is controlled within the range of 0.6 to 30 wt% with respect to the total amount of precipitation. The manufacturing method according to item 1. 3. The manufacturing method according to claim 1, wherein the plating bath is an acidic zinc plating bath or an acidic zinc alloy plating bath containing 10 to 600 g/l of zinc ions. 4 Claims in which the amount of the water-soluble organic polymer added is 0.5 to 30 wt%, and the proportion of the precipitated water-soluble organic polymer is controlled within the range of 0.6 to 30 wt% with respect to the total amount of precipitation. The manufacturing method according to item 3.