JPH0245503A - Polymeric composite and production thereof - Google Patents

Abstract

PURPOSE:To efficiently provide the subject composite having excellent adhesivity, corrosion resistance, wear resistance, etc., and useful for coating films, etc., by subjecting to an electrolytic treatment an electrolytic solution prepared by dispersing a monomer for electrolytically polymerized polymeric compounds and a specific anionic polymeric compound. CONSTITUTION:Electrodes are immersed in an electrolytic solution wherein a monomer for (A) an electrolytically polymerized polymeric compound (e.g., polythiophene) and (B) an anionic polymeric compound (e.g., acrylic resin) capable of being insolubilized in electrolytic solvents by an electrolytic treatment method are dispersed or dissolved, followed by applying an electric voltage to the electrodes to provide the objective composite comprising the components B and A, the molecules of the component A being placed between the molecules of the component B. The temperature of the electrolytic solution during the electrolysis is preferably 0-40 deg.C and the application of a direct current voltage of 1-500V for 0.5-3600sec is preferable from the aspects of energy and economy.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a polymer that has excellent adhesion performance, rust prevention performance, wear resistance performance, etc. and can be used for coating films, protective films for structural materials, etc. The present invention relates to a compound complex and a method for producing the same.

[Conventional technology]

2. Description of the Related Art Protective films such as coatings on automobiles or coatings on electrode materials are required to have improved characteristics such as rust prevention performance and adhesion performance as the environment in which they are used has deteriorated.

One such film is a film made of aromatic compounds such as 5-membered heterocyclic compounds such as pyrroles and thiophenes, and polycyclic aromatic compounds such as azulene, pyrene, and triphenylene, which have electrical conductivity. Are known. This film is manufactured by dissolving the monomer of the aromatic compound in a solvent containing an electrolyte, and depositing it on an electrode substrate by subjecting this solution to electrolytic oxidation (IBM Journal of Research
& Development, Volume 27, No. 4, P5
30 (1983)). Furthermore, by dissolving phenol or substituted phenol such as allylphenol in an amine aqueous solution and electrolytically polymerizing it, a protective film with anti-rust properties is deposited on the anode plate (Japanese Patent Laid-Open No. 55-160
No. 75, JP-A No. 56-47460, J, EIectr
ochem, Soc, .

Volume 128, No. 11, P2276-P2281 (19
1981)).

However, since these films have a small amount of precipitation per unit of electricity (for example, 0.4 to 0.6 mg/C in JP-A No. 56-47460), they tend to thicken if no current is applied for a long time. However, since the electrolytic polymer is rigid, the adhesion of the film to the substrate is weak, resulting in less flexibility of the film, and the cost of raw material monomers is high.

Further, as another film, there is an electrodeposition coating film. This coating is
It is manufactured by changing the pH near the electrode by electrolyzing water in a solution containing a high molecular polymer and precipitating the high molecular polymer (Progress in Org).
anic chemistry 4 (1976).

P1 to P60). However, even in this electrodeposition coating film, sufficient antirust performance has not yet been obtained.

On the other hand, attempts have been made to enhance the functionality by combining various types of polymer compounds. For example, JP-A-60
In No. 226524, an electrolytically polymerized polymer compound and a polymer latex are combined to impart processability to a conductive polymer. However, even in this case, since a latex emulsion is used in the manufacturing process, it is not possible to obtain a continuous and smooth coating, resulting in a decrease in corrosion resistance and solvent resistance. Furthermore, it is necessary to use a material that is not electrochemically corroded or damaged as an electrode for electrolytic polymerization, and materials such as iron cannot be used.

[Description of the first invention] The first invention (invention set forth in claim (1))
was made in view of the problems of the above-mentioned conventional technology,
The purpose is to provide a composite of polymer compounds with excellent adhesion performance, rust prevention performance, wear resistance performance, etc.

A first aspect of the present invention is a polymer comprising an anionic polymer compound having a property of being insolubilized in an electrolytic solvent by electrolytic treatment, and an electrolytically polymerized polymer compound existing between the anionic polymer compound. It is a complex.

The polymer composite of the first invention has excellent adhesion performance, rust prevention performance, wear resistance performance, etc. This excellent effect is thought to be due to the following reasons.

The electrolytically polymerized polymer compound fills the gaps in the anionic polymer compound and densifies it, thereby improving the water repellency, ion trapping, and oxygen trapping properties of the electrolytically polymerized polymer compound and the adhesion of the anionic polymer compound. By interacting with each other, the above effects are exhibited.

[Description of the second invention] Hereinafter, an invention (referred to as the second invention) that is a concrete example of the first invention will be described.

The polymer composite according to the second invention is composed of an electrolytically polymerized polymer compound and an anionic polymer compound that has the property of becoming insolubilized in an electrolytic solvent by electrolytic treatment.

In the second invention, the electrolytically polymerized polymer compound is a polymer compound polymerized by electrolytic polymerization, and examples include those having a five-membered hetero ring and those having a benzene ring.
One or more of them are used.

For example, as a polymer compound having a 5-membered hetero ring, -
Maximum % formula % (wherein each of R1 and R2 is independently hydrogen, halogen,
A substituent containing at least one of a nitro group, an amino group, an aliphatic group, an unsaturated aliphatic group, and an aromatic group, and X is oxygen, sulfur, nitrogen, or N- (wherein R3 is hydrogen, A substituent containing at least one of an aliphatic group, an unsaturated aliphatic group, and an aromatic group.

) is expressed as at least one repeating unit of Examples include polypyrrole, poly(3-methylpyrrole), polythiophene, and the like.

In addition, as a polymer compound having a benzene ring, -maximum (in the formula, each of R1 to R4 is one of hydrogen, halogen, nitro group, amino group, aliphatic group, unsaturated aliphatic group, aromatic group). ) is a substituent containing at least one type of repeating unit. For example, polyphenylene and the like can be mentioned.

In addition, other polymer compounds having a benzene ring include - maximum (in the formula, each of R1 to R4 is hydrogen, halogen, nitro group, amino group, aliphatic group, unsaturated aliphatic group, aromatic A substituent containing at least one type of group group, X is oxygen, sulfur, -N-1 or -CRS Ra (However, each of R5 and R6 is individually hydrogen, halogen, nitro group, amine group, A substituent containing at least one of an aliphatic group, an unsaturated aliphatic group, and an aromatic group. . Examples include polyaniline, polyphenylene ether, polyphenylene sulfide, and the like.

The weight average molecular weight of the electrolytically polymerized polymer compound is 20
It is preferably within the range of 0 to 50,000.

If the weight average molecular weight is less than 200, the electrolytically polymerized polymer compound will volatilize from the composite when dried, and
If it exceeds 50,000, it is difficult to form a smooth film.

In the present invention, an anionic polymer compound having a property of being insolubilized in an electrolytic solvent by electrolytic treatment is used. Here, the anionic polymer compound has an ionizable functional group,
It is a resin that dissolves in a solvent by neutralizing at least a portion of the ionizable functional group with a counter ion, or a resin that can self-emulsify.

Further, the above-mentioned electrolytic solvent is any type of solvent used in electrolytic treatment, such as water and organic solvents. Here, being insolubilized in an electrolytic solvent does not mean the aggregation and precipitation of the components themselves due to the surfactant adsorbed or coexisting with the coating resin particles losing their active ability, as in the case of aggregation in ordinary emulsions, for example. Rather, it refers to agglomeration and precipitation due to changes in the hydrophilicity or surface activity of the resin itself. In the case of agglomeration and precipitation due to changes in the characteristics of the surfactant adsorbed to the resin itself, such as in latex emulsions, there is no ability to suppress the elution of electrode constituent metals during electrolytic treatment during the manufacturing process, and a large amount of metal may be present in the resulting composite. Since ions are mixed in, a continuous film with excellent rust prevention performance cannot be formed.

Examples of anionic polymer compounds that have the property of becoming insolubilized in electrolytic solvents through electrolytic treatment include acrylic resins, epoxy resins, polyester resins, phenolic resins, alkyd resins, acrylic-urethane resins, acrylic-melamine resins, acrylic-alkyd resins, and epoxy resins. - Those having a basic skeleton of melamine resin, polybutadiene resin, etc., or a mixture thereof.

The weight average molecular weight of the anionic polymer compound is as follows:
It is preferably within the range of 300 to 50,000. If the weight average molecular weight is less than 300, the strength as a protective film cannot be obtained, and if it exceeds 50,000, it is difficult to obtain a film that is smooth enough to protect the object to be coated.

Examples of the composite form of the electrolytically polymerized polymer compound and the anionic polymer compound include the following forms.

First, as shown in the conceptual diagram of the complex of the present invention in FIG.
The electrolytically polymerized polymer compound and the anionic polymer compound are intertwined in molecular units and are uniformly dispersed to form a composite. Or, as shown in the conceptual diagram in Figure 2,
The electrolytically polymerized polymer compound is combined with the anionic polymer compound at the unsaturated bond or the α position of the unsaturated bond.

The composite ratio of the electrolytically polymerized polymer compound and the anionic polymer compound is such that there is no electrolytically polymerized polymer compound in the composite.
．． 01-50% by weight, remainder (99,99-50% by weight)
The range is preferably such that an anionic polymer compound is obtained.

If the proportion of the electrolytically polymerized polymer compound is less than 0.01% by weight, the antirust performance of the composite will be reduced, and if it exceeds 50% by weight, the adhesion to the object to be coated will be reduced.

The composite of the present invention has excellent adhesion performance, rust prevention performance, wear resistance performance, etc., so it can be used as a coating film for automobiles, a protective film for structural materials, etc.
Alternatively, since it has conductivity, it can be applied to conductive films and the like.

In addition, depending on the above-mentioned uses, the composite of the present invention can be used to
Various colorants, inorganic pigments such as extender pigments or antirust pigments, crosslinking agents, etc. may be added.

For example, examples of the above-mentioned inorganic pigments include titanium oxide, metal chromate, Bengara, carbon black, organic pigments, dyes, and the like. Examples of the crosslinking agent include water-dispersible amino resins, phenol resins, blocked isocyanates, and metal salt catalysts. Examples of the water-dispersible amino resin include mononuclear or low-nuclear melamine resins etherified with alcohols having 1 to 4 carbon atoms such as hexamethoxymelamine, urea resins having water solubility and/or water dispersibility, and guanamine resins. and co-condensation resins of these amino compounds. Examples of the phenol resin include phenol and/or alkylated phenol such as resol type phenol resin or novolak type phenol resin.

Examples of the blocked isocyanates include lower alcohols having 8 or less carbon atoms such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and monoalkyl ethers of ethylene glycol or diethylene glycol. Block compounds, etc. Examples of the metal salt catalyst include cobalt naphthenate, manganese naphthenate, vanadyl octylate, vanadium acetylacetonate, cobalt acetate, manganese acetate, lead acetate, and the like.

Among the above additives, water-dispersible amino resins, blocked isocyanate resins, etc. can be added in sufficient amounts to sufficiently crosslink the anionic polymer, but metal oxides can be added in an amount of 0% to the composite. It is preferable to add up to 5% by weight.

[Description of the third invention] The third invention (invention set forth in claim (2))
is an attempt to provide a method for efficiently producing the above-mentioned polymer composite.

In the third invention, an electrode is immersed in an electrolytic solution in which an electrolytically polymerized polymer compound and an anionic polymer compound having a property of being insolubilized in an electrolytic solvent by electrolytic treatment are dispersed or dissolved. This is a method for producing a polymer composite characterized by applying a voltage to the electrode.

According to the third invention, an excellent polymer composite as described above can be produced. Moreover, a polymer composite can be produced with high electrodeposition efficiency per unit electrical quantity angle.

The electrodeposition efficiency (Coulomb efficiency) per unit electrical quantity angle is
This is larger than in the case where a film is formed by depositing an anionic polymer compound and the case where an electrolytically polymerized polymer compound is formed by electrolytic polymerization. This is thought to be because, in addition to the usual electrodeposition coating mechanism, the anionic polymer compound is deposited on the electrode by hydrogen ions released during oxidative polymerization of the monomer of the electrolytically polymerized polymer compound.

On the other hand, since the anionic polymer compound is insolubilized and precipitated in the electrolytic solvent during electrolytic treatment, forming a film that has substantially electrical resistance, materials that are easily corroded or damaged electrochemically are also selected for the electrode. It becomes possible.

[Description of the Fourth Invention] Next, an invention (referred to as the fourth invention) that embodies the third invention will be described.

The method for producing a polymer composite according to the fourth aspect of the present invention includes performing electrolytic treatment using an electrolytic solution containing an electrolytically polymerized polymer monomer and an anionic polymer compound having a property of being insolubilized in an electrolytic solvent by electrolytic treatment. By doing this, a polymer composite is deposited on an electrode immersed in an electrolytic solution.

In the present invention, examples of the electropolymerizable polymer compound include seven polymer compounds that can be electrolytically polymerized, such as those having a five-membered hetero ring and those having a benzene ring. One or more of these are used.

For example, as a monomer having a 5-membered heterocyclic ring, - maximum % formula % N- (where R3 is hydrogen, an aliphatic group, an unsaturated aliphatic group,
It is a substituent containing at least one type of aromatic group.

). ), and
Examples include pyrrole, N-substituted pyrrole, β-substituted pyrrole, thiophene, β-substituted -F-offene, furan, β-substituted furan, indole, carbazole, and the like.

In addition, as a monomer having a benzene ring, -maximum (in the formula, each of R1 and R2 is hydrogen, halogen, nitro group, amino group, aliphatic group, unsaturated aliphatic group, aromatic group). A substituent containing at least one type, X
is oxygen, sulfur, nitrogen or (in the formula, each of R1 to R4 is individually hydrogen, halogen, nitro group, amino group, aliphatic group,
A substituent containing at least one of an unsaturated aliphatic group and an aromatic group; halogen, nitro group, amino group, aliphatic group, unsaturated aliphatic group,
Group II containing at least one aromatic group! :i. ).

), and examples include benzene, aniline, aniline derivatives not substituted at the 4-position, toluene, xylene, phenol, and phenol derivatives not substituted at the 4-position.

Further, examples of the anionic polymer compound include the compounds described above.

The electrolytic solution is one in which the electrolytically polymerized polymer compound 7-mer and the above-mentioned anionic polymer compound are dispersed or dissolved. The solvent for the electrolytic solution may be water or any organic solvent. Examples of organic solvents include methylcyclohexanol, benzalcohol, n-butanol, butyl cellosolve, isopropyl cellosolve, methyl cellosolve, ethyl cellosolve, isopropanol, ethanol, and other organic solvents that can be used for ordinary electrodeposition coating. can also be used.

However, in consideration of environmental pollution and cost, it is preferable to use water or a mixed solvent of water and an organic solvent.

In the case of a mixed solvent, the amount of organic solvent mixed is 0.001 to 3
It is preferably 0%, more preferably 3 to 10%. 3
Mixing more than 0% of organic solvent causes abnormal precipitation of the polymer compound.

Further, the anionic polymer compound also functions as a supporting electrolyte in the electrolytic solution.

In addition, the amount of the monomer of the electrolytically polymerized polymer compound and the anionic polymer compound to be dispersed or dissolved in the electrolytic solution is 0.01 to 50% by weight in the polymer composite to be produced. %, remainder (99,99~50
(% by weight) It is preferable to set the range such that an anionic polymer compound is obtained.

In addition, in the case of the monomer of the electrolytically polymerized polymer compound, the amount of each of the above two components to be dispersed or dissolved in the electrolytic solution is O, OO1 to The range is preferably 30% by weight, more preferably 0.01 to 20% by weight. o, o
If it is less than 1% by weight, it may not develop anti-rust performance when formed into a film, and if it exceeds 30% by weight, precipitation will occur in the electrolytic solution and the stability of the electrolytic solution will deteriorate. Furthermore, the uniformity of the produced composite is impaired.

On the other hand, the amount of the anionic polymer compound added is preferably in the range of 2 to 40% by weight, more preferably in the range of 5 to 30% by weight, based on the entire electrolytic solution.

If it is less than 2% by weight, a film thickness with sufficient protective function cannot be obtained in an economical processing time, and if it exceeds 40% by weight, the viscosity of the electrolyte becomes high and the system of undeposited electrolyte is It is not a good idea to take it outside as it will cause a lot of loss.

Note that a surfactant may be added to the electrolytic solution in order to improve the dispersibility of the electrolytically polymerized polymer compound monomer. The surfactant can be selected from nonionic, anionic, and cationic surfactants.

Furthermore, when the polymer composite to be produced contains additives such as colorants, inorganic pigments, crosslinking agents, etc., it is preferable to add the additives to the electrolytic solution.

The pH of the electrolytic solution is not limited as long as the monomer and anionic polymer compound are stably present.

The electrode may be immersed in the electrolytic solution by immersing both the anode and the cathode in the electrolytic solution, or only the anode may be immersed in the electrolytic solution since the composite is deposited on the anode. That is, the cathode (counter electrode) does not need to be immersed in the same tank that contains the electrolytic solution and in which the anode is immersed. for example,
A diaphragm may be installed between the counter electrode and the anode in order to protect the counter electrode or to prevent impurities eluted from the counter electrode from being mixed into the electrolyte.

Further, the applicable anode and cathode are not particularly limited as long as they are conductive objects. Examples include platinum, gold, stainless steel, chemically treated steel sheets, zinc steel sheets with or without chemical treatment, aluminum sheets, copper sheets,
Examples include tin plates, plated plastic plates, and processed products thereof. The materials of the anode and cathode may be the same or different.

In the present invention, by immersing an electrode in an electrolytic solution and applying a voltage to the electrode, an anionic polymer compound and an electrolytically polymerizable monomer are co-deposited, and at the same time, the electrolytically polymerizable monomer is co-deposited. It polymerizes, forms a complex with an anionic polymer compound, and precipitates on the anode. A voltage is applied to the electrode between the anode and the cathode.

The temperature of the electrolytic solution during the treatment is preferably controlled within the range of 0 to 80°C, more preferably within the range of 0 to 40°C. It is not preferable to manage the electrolytic solution at high temperatures because it impairs the stability of the electrolytic solution. Furthermore, low temperatures that cause the electrolyte to freeze are not preferred.

The conditions for the voltage applied to the electrodes vary depending on the distance between the electrodes or the shape of the polymer composite to be manufactured.
It is preferable from an energy and economical point of view to apply a DC voltage of 500 volts for 0.5 to 3600 seconds. Within this range, dielectric breakdown of the precipitated composite is unlikely to occur during electrolytic treatment.

As the voltage application method, any of the constant voltage method, constant current method, and stepwise pressure increasing method that are used in ordinary electrodeposition coating can be used, and a pulse application method is also possible.

By the above method, an anionic polymer compound is deposited on the anode according to a so-called electrodeposition coating mechanism using the same electric energy, and at the same time a high-level composite is formed of an electrolytically polymerized polymer compound and the precipitated anionic polymer compound by electrolytic polymerization. is formed. Therefore, this treatment can directly coat the composite when the coating is used as an anode. This advanced composite can be isolated from the anode by physical or chemical means depending on the purpose, but by cross-linking the precipitated composite with heat or energy rays, it can be used as an adhesive with a high degree of protective function. A film with good hardness and wear resistance is formed on the anode. In this case, when a room temperature curable anionic polymer is used, it is naturally dried at room temperature.

〔Example〕

The present invention will be explained in detail below.

Example 1 Anionic unsaturated alkynd electrodeposited resin (Dainippon Ink ■
(Mixture of 150 parts by weight of Watersol 141LP and 73 parts by weight of Watersol 193LPA)
After neutralizing 223 parts by weight with 7.8 parts by weight of triethylamine and adding 22 parts by weight of isopropyl alcohol and 1 part by weight of acetofluoride, these were dispersed in 744 parts by weight of water to obtain a water-dispersed varnish. This varnish is ]:l H7,
3. The electrical conductivity was 2000 u s/cm (25°C). In addition, the average particle diameter of the dispersed electrodeposited resin particles is
Photoelastic scattering method (Coulter, model N4 SU
According to B-MICRON Particle analysis), it was approximately 40 mm.

Next, 5 parts by weight of pyrrole was added to 100 parts by weight of the water-dispersed varnish, and dispersed using a stirring disperser. This gave a milky white pyrrole-dispersed varnish. This varnish has a pH of 7.4 and a conductivity of 1730 μs/cm (25°C
), and the average particle diameter of the dispersed electrodeposited resin-pyrrole particles was about 100 mm.

As shown in the schematic diagram of the electrolytic treatment apparatus in Fig. 3, the above varnish is placed in a glass cell l measuring 4 cm wide x 2 cm deep x 8 cm high, and the varnish 2 is filled with a cold rolled steel plate (SCP28).
DY Nippon Kokan ■) 31 and 5US304 sheets (
32 (thickness: 0.1 mm), and a constant voltage of 50 V was applied between the two electrodes for about 30 seconds using the cold rolled steel plate 31 as the anode using the DC power supply 4 connected between the two electrodes. As a result, the surface of the cold rolled steel plate 31 is 3 cm x 6
A cr+ black smooth coating was obtained. This coating is
As a result of the analysis, it was found that the black material was composed of an electrodeposited resin and pyrrole, both of which were present in a weight ratio of about 4=1, and the black material was polypyrrole. In addition, in order to study the combination of the two, we attempted to extract the electrodeposited resin using a Soxhlet apparatus. In the early stage of extraction, some electrocoated resin could be extracted, but
After that, I couldn't extract it at all.

This is because the electrodeposited resin and polypyrrole are composited at the molecular level. Further, FIG. 4 shows the change over time in the infrared absorption (IR) spectrum of the coating. The chart in Figure 4 is the infrared absorption spectrum of the film during the Soxhlet extraction operation, and the peak of 1560CT11-' is the absorption of polypyrrole unsaturated bonds, 1725c++r.
The peak ' is absorption due to expansion and contraction of the carbonyl of the electrodeposited resin (the time in the figure indicates the time for extraction of the solvent (acetone) by Soxhlet). From Figure 4, 1725cm-' and 15
It can be seen that the ratio of 60 cm- remains almost unchanged, indicating that the electrodeposited resin is complexed in such a way that it cannot be extracted by Soxhlet.

Example 2 7 parts by weight of aniline was added to 100 parts by weight of the water-dispersed varnish formed in Example 1 and dispersed using a stirring disperser to obtain a milky white aniline-dispersed varnish.

This varnish has a pH of 7.4 and a conductivity of 1680 μS/c.
m (25°C), and the average particle size of the dispersed electrodeposited resin-aniline particles was about 120 nm (according to photoelastic scattering method).

In the same manner as in Example 1, a pair of electric bridges were immersed in this varnish, and a constant voltage of 75 V was applied between both electrodes. As a result, a brown smooth coating was obtained on the cold rolled steel plate. As a result of analysis, this film was found to be a highly dispersed composite of the electrodeposition resin and polyaniline, and the weight ratio of the two was electrodeposition resin:polyaniline-io:i.

Moreover, the brown substance was polyaniline.

Example 3 460 parts by weight of safflower oil, hydrogenated bisphenol A3
47 parts by weight, 80 parts by weight of isophthalic acid, and 309 parts by weight of varnish obtained from 139 parts by weight of trimethic anhydride, 96 parts by weight of butoxetanol, 20 parts by weight of triethylamine,
9 parts by weight of carbon black and 11 parts by weight of kaolin were added and diluted with 555 parts by weight of dispersed condensate to obtain a water-dispersed varnish. This varnish has a pH of 7.2 and a conductivity of 1600 μs/
cm (25°C).

Next, 5 parts by weight of pyrrole and 1 part by weight of N-methylpyrrole were added to 100 parts by weight of the above water-dispersed varnish, and dispersed using a stirring disperser. This gave a milky white pyrrole-dispersed varnish. This varnish had a pH of 7.4 and a conductivity of 1530 μs/cm (25°C).

In the same manner as in Example 1, a pair of electrodes was immersed in this varnish, and a constant voltage of 10V was applied between both electrodes.

As a result, a smooth black film measuring 3 cm x 6 cm and having a thickness of 20 μm was obtained on the cold rolled steel plate. As a result of analysis, this film was found to be a highly complex composite of polypyrrole, poly-N-methylpyrrole, and electrodeposited resin, and a portion of polypyrrole and poly-N-methylpyrrole were copolymerized.

Example 4 To 70 parts by weight of the same anionic unsaturated alkyd electrodeposition resin as in Example 1, 0.5 parts by weight of a commercially available antifoaming agent, 1.0 parts by weight of anti-aging agent, and 9 parts by weight of carbon black, 40 parts by weight of isopropyl alcohol and 8 parts of triethylamine
．． After adding 5 parts by weight and 16 parts by weight of acetone and stirring and dispersing them, 705 parts by weight of water was further added to obtain a water-dispersed varnish. This varnish has a pH of 7.4 and a conductivity of 1900.
It was μs/cm (25”c).

2 parts by weight of phenol was added to 100 parts by weight of this water-dispersed varnish, stirred and dispersed, and an equivalent amount of triethylamine was added for neutralization to obtain a phenol-dispersed varnish. This varnish has a pH of 7°5 and an electrical conductivity of 1800. c.
zs/cm (25°C).

In the same manner as in Example 1, a pair of electrodes was immersed in this varnish, and a constant voltage of 50 V was applied between both electrodes. As a result, a smooth black film was obtained on the cold rolled steel plate. As a result of analysis, this film was found to be a highly complex composite of polyphenylene oxide, which is a polymer of phenol, and electrodeposited resin.

Comparative Example 1 A pale yellow transparent film was formed on a cold rolled steel plate by treating in the same manner as in Example 1, except that virol was not added to the water-dispersed varnish formed in Example 1. As a result of analysis, this film was found to be an electrodeposited resin.

Comparative Example 2 A cold-rolled steel sheet was produced in the same manner as in Example 3, except that pyrrole and N-methylpyrrole were not added to the water-dispersed varnish formed in Example 3, and the applied voltage was 100 μ. A pale yellow film was formed on top. This coating is
As a result of analysis, it was found to be an electrodeposited resin.

Comparative Example 3 A smooth black film was formed on a cold rolled steel plate by treating in the same manner as in Example 4, except that phenol and triethylamine for neutralization were not added to the water-dispersed varnish formed in Example 4. Formed.

As a result of analysis, this film was found to be an electrodeposited resin.

Comparative Example 4 100 iffi of methanol-water ([1) mixed solvent, 0.5 g of potassium hydroxide, and 2 m of ethyl cellosolve! .

After adding allylamide 76d, 6 ml of orthoallylphenol was added as an electrolytically polymerized monomer.

A pair of electrodes was immersed in this solution in the same manner as in Example 1,
A constant voltage (16V) was applied. However, a platinum wire was used instead of SUS for the counter electrode (cathode).

This treatment formed a brown film on the cold rolled steel plate. As a result of analysis, this film was found to be an electrolytic polymer of allylphenol (polyallylphenol).

Comparative Example 5 First, 410 g of ethyl acrylate, 30 g of sodium acrylate, 5.7 g of azoisobutyronitrile, and 576 g of water.
g and 4.2 g of sodium octadecanoate sulfonate were mixed. 20% of this mixed liquid was placed in a 21 flask equipped with a condenser that had been sufficiently replaced with N2, and while flowing N2,
The remaining 80% was added dropwise and polymerized over 3 hours at 0 to 80'C to obtain a latex emulsion. After that, 80~
Polymerization was completed by stirring at 90"C for 11 hours. This solution was diluted with water to a solid content of 15%. 2 g of virol was added to 100 g of the solution diluted with water.

An attempt was made to deposit a film on a cold rolled steel plate by using this solution in the same manner as in Example 1, but the iron in the steel plate was so eluted that the film could not be formed.

(Evaluation of Coatings) The properties of the coatings formed in Examples 1 to 4 and Comparative Examples 1 to 4 and cured by baking were evaluated as follows.

Corrosion resistance: Cut a 3cm long cant into the coating with a knife.
25°C, 5 wt% Na Ce aqueous solution for a certain period of time (7
2 hours), and the width of rust generation from the cut portion was measured.

The weight (mg) of the deposited film (after drying at 170°C for 50 minutes) per two units of electricity (C) of coulombic efficiency was determined.

The above measurement results are shown in Table 1.

Table 1 As is clear from Table 1, the coating of this example has better corrosion resistance than that of the comparative example, and also has a higher Coulombic efficiency.

Further, the properties of the coatings formed in Examples 1 to 4 and Comparative Example 4 and cured by baking were evaluated as follows.

Adhesion performance: 100 lattice-shaped cuts measuring 1 mm x 1 mm were cut into the film using a knife, and a cellophane adhesive tape was applied to the cut portions and then quickly and quickly peeled off, and the number of remaining burls was measured.

Water resistance: After immersing the coating in warm water at 40°C for 168 hours, use a knife to measure ln++nx1mm cross-cut cant 100.
A cut was made into the piece, cellophane adhesive tape was applied to this part, and when it was rapidly peeled off, the number of remaining holes was measured.

Pencil hardness: The coating was scratched with a Mitsubishi Uni-pencil with a hardness of 6B to 9H, and the hardness one step below the hardness at which scratches were generated was measured.

The above measurement results are shown in Table 2.

Table 2 ■... Electrolytic cell, 2... Electrolyte solution

Claims (2)

[Claims] (1) A polymer composite comprising an anionic polymer compound that has the property of becoming insolubilized in an electrolytic solvent by electrolytic treatment, and an electrolytically polymerized polymer compound existing between the anionic polymer compound. (2) An electrode is immersed in an electrolytic solution in which a monomer of an electrolytically polymerized polymer compound and an anionic polymer compound that has the property of being insolubilized in an electrolytic solvent by electrolytic treatment are dispersed or dissolved, and a voltage is applied to the electrode. 1. A method for producing a polymer composite, comprising: applying an electric current.