JPH02279334A - Polymer composite and preparation thereof - Google Patents

Abstract

PURPOSE:To enhance bonding capacity, anticorrosion properties and abrasion- resistant properties by allowing at least a part of the electrolytic polymerization polymer compound of the second layer to be present in the first layer. CONSTITUTION:The first layer composed of a polymer compound and the second layer consisting of an electrolytic polymerization polymer compound and an anionic polymer compound having a property becoming insoluble in an electrolytic solvent by electrolytic treatment are laminated to constitute a composite. At least a part of the electrolytic polymerization polymer compound of the second layer is allowed to be present in the first layer. As the polymer compound of the first layer, any org. or inorg. polymer compound may be used. The electrolytic polymerization polymer compound is a polymer compound obtained by electrolytic polymerization and one having a heterocyclic 5-membered ring or one having a benzene ring is designated and one or more kind of them is used. By this method, a composite of the polymer compounds excellent in bonding capacity, anticorrosion properties and abrasion-resistance and holding these properties in the use under severe environment is obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention can be used for coating films, protective films for electrode materials, etc., which have excellent adhesion performance, rust prevention performance, wear resistance performance, etc.
The present invention relates to a polymer composite in which layers made of polymer compounds are laminated, and a method for producing the same.

[Conventional technology]

So-called anti-corrosion primers are used to protect metal materials, and electrodeposition paints are used as protective coatings for automobiles, industrial machinery, etc. that require particularly high productivity. In order to improve the protective performance of the electrodeposition paint, there has been a demand for a switch from anionic electrodeposition paint to cationic electrodeposition paint, and at present, cationic electrodeposition paint is the mainstream. However, it cannot be said that these products fully satisfy the expanding usage environments of industrial machinery and the demands for long-life and durable performance.

In addition to the protective film made of a metal material, there is a film made of an electrolytically polymerized polymer compound.

This electrolytically polymerized polymer compound coating is used in harsh environments, such as as a protective coating for electrode materials, and is a coating made of five-membered heterocyclic compounds such as pyrroles and thiophenes, as well as polyesters such as azulene, pyrene, and triphenylene. It consists of ring aromatic compounds and the like. This film is produced by dissolving the monomer of the electrolytically polymerized polymer compound in a solvent containing an electrolyte, and depositing it on the electrode substrate by subjecting this solution to electrolytic oxidation (IBM Journal of Re
5earch & development lopment, 27th
Volume, No. 4, P530 (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. 55-16075, No. 1974-474.60, J, Electrochem, Soc, 1st
Volume 28, No. 11, P2276-P2281 (198
1 year)).

However, since these films have a small amount of precipitation per unit electromold (for example, 0.4 to 0.6 mg/C in JP-A No. 56-47460), they become thick if not energized for a long time. In addition, because the electrolytic polymer is rigid, the adhesion of the film to the substrate is weak (the film has little flexibility, and the cost of raw material monomers is high). be.

Therefore, the present inventors solved these problems and developed a composite of polymer compounds suitable for coatings with excellent adhesion performance, rust prevention performance, wear resistance performance, etc.
No. 4). This polymer compound complex is a composite of an anionic polymer compound and an electrolytically polymerized polymer compound. However, even in this composite, the adhesion performance, rust prevention performance, etc. are not satisfactory as a coating used in harsh environments.

[Description of the first invention] The first invention (the invention according to claim (1)) has been made in view of the problems of the prior art described above, and has improved adhesion performance, rust prevention performance, wear resistance performance, etc. The object of the present invention is to provide a composite of a polymer compound that is excellent and maintains the above-mentioned performance even when used in harsh environments.

The polymer composite of the first invention exists between a first layer made of a polymer compound, an anionic polymer compound that has the ability to be insolubilized in an electrolytic solvent by electrolytic treatment, and the anionic polymer compound. and a second layer consisting of an electrolytically polymerized polymer compound, characterized in that at least a part of the electrolytically polymerized polymer compound of the second layer is present in the first layer. It is something.

The polymer composite of the first invention has excellent adhesion performance, rust prevention performance, wear resistance performance, etc. Furthermore, the above performance is guaranteed even when used in harsh environments. This excellent effect is thought to be due to the following reasons.

Regarding adhesion performance, the adhesion of the anionic polymer compound in the second layer is high, and a part of the electrolytically polymerized polymer compound in the second layer is present in the first layer, so it is better than the first layer. Interlayer adhesion with the second layer is excellent. In addition, since the first layer is not likely to be rigid, it has excellent adhesion performance between the first layer and the object to be coated. Therefore, the polymer composite of the present invention has excellent adhesion performance as a whole. Note that the highly composite second layer alone can improve rust prevention, wear resistance, and antistatic performance; however, when this second layer alone is coated on the object, the The coating becomes rigid and its adhesion performance with the object to be coated decreases, making it unable to exhibit its performance as a coating material. In contrast, the polymer composite of the present invention has excellent adhesion performance between the first layer and the object to be coated, even though the first layer is rigid, and therefore the adhesion performance as a whole is improved.

In addition, regarding rust prevention performance, this is because the electrolytically polymerized polymer compound of the second layer has excellent water repellency, ion trapping properties, and oxygen trapping properties.

In addition, the wear resistance performance is due to the fact that the electrolytically polymerized polymer compound fills the gaps between the anionic polymer compounds in the second layer, making the second layer dense.

[Description of other inventions of the first invention] Hereinafter, other inventions that embody the first invention will be described.

The polymer composite of the present invention has a first layer made of a polymer compound, a second layer made of an electrolytically polymerized polymer compound, and an anionic polymer compound that has the property of being made insoluble in an electrolytic solvent by electrolytic treatment. It is formed by laminating layers, and at least a part of the electrolytically polymerized polymer compound of the second layer is present in the first layer.

In the present invention, the first layer polymer compound may be any organic or inorganic polymer compound.

Examples include polymethyl acrylate, polyacrylate ester polymer, modified cellulose, vinyl chloride vinyl acetate polymer, epoxy resin, alkyd resin, modified epoxy resin, polybutadiene resin, and at least one of them.
Use seeds. Among them, polymer compounds used as paint components are desirable. The polymer compound used as this paint component is suitable for supporting the highly functional second layer component and exhibiting its functionality to a high degree while maintaining adhesion performance with the object to be coated. This is because. Examples of the above-mentioned paint components include paints for spray painting, flow painting, curtain flow painting, roller painting, anionic electrodeposition paints, cationic electrodeposition paints, and the like.

Paints for spray painting include amino-acrylic paints, amino-alkyd paints, non-aqueous dispersion (NAD) paints, urethane paints, acrylic lacquers, nitrocellulose lacquers, epoxy resin paints, oil-based paints, water-based paints (oil-based, Examples include solution-based, dispersion-based, or emulsion-based paints such as amino-alkyd and amino-acrylic paints. In addition, as the anionic electrodeposition paint,
Oil-based, epoxy-based, amino-alkyd, amino-
Examples include acrylic type and polybutadiene type.

Further, examples of the above-mentioned cationic electrodeposition paints include epoxy-based, acrylic-based, polybutadiene-based, and polyamine-based paints.

In the case of the above paint components, additives used in ordinary paints, such as pigments, curing catalysts, surfactants, and surface smoothing agents, may be added.

The weight average molecular weight of the polymer compound in this first layer is:
A range of 300 to 50,000 is desirable. If the weight average molecular weight is less than 300, it is too brittle and is not suitable for practical use.

Moreover, if it exceeds 50,000, a uniform film cannot be obtained.

This first layer may contain additives such as pigments, curing catalysts, surfactants, and surface smoothing agents that are used in ordinary paints.

The thickness of the first layer is preferably 1 μm or more. If it is less than 1 μm, the adhesion strength to the object to be coated is insufficient and the composite film cannot function adequately. More preferably, the thickness is within the range of 2 to 20 μm.

Further, the second layer is composed of an electrolytically polymerized polymer compound and an anionic polymer compound that has the property of being made insoluble in an electrolytic solvent by electrolytic treatment.

The electrolytically polymerized polymer compound is a polymer compound polymerized by electrolytic polymerization, and includes those having a five-membered hetero ring, those having a benzene ring, etc., and one or more of them are used.

For example, as a polymer compound having a 5-membered hetero ring, the general formula % (in the formula, each of R1 and R2 is individually 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 an aliphatic group or an aromatic group. (Both are substituents containing one type.) ) 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, a substituent containing at least one type of aromatic group of the general formula (in the formula, each of R1 to R4 is individually hydrogen, halogen, nitro group,
A substituent containing at least one of an amino group, an aliphatic group, an unsaturated aliphatic group, and an aromatic group. ) is expressed as at least one repeating unit of For example, polyphenylene and the like can be mentioned.

In addition, other polymer compounds having a benzene ring include the general formula (where each of R1 to R4 is individually hydrogen, halogen, nitro group, amino group, aliphatic group, unsaturated aliphatic group, however,
Each of R5 and Re individually represents hydrogen, halogen, nitro group,
A substituent containing at least one of an amino group, an aliphatic group, an unsaturated aliphatic group, and an aromatic group. ). ) is expressed as at least one repeating unit of Examples include polyaniline, polyphenylene ether, polyphenylene sulfide, and the like.

The weight average molecular weight of the electrolytically polymerized polymer compound is 30
It is preferably within the range of 0 to 50,000.

If the molecular weight is less than 300, the second layer is too fragile to be of practical use. Moreover, when it exceeds 50,000, it becomes a porous second layer and does not have the function as a protective film.

In addition, anionic polymer compounds that have the property of becoming insolubilized in electrolytic solvents by electrolytic treatment are those that have ionizable functional groups,
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, "insolubilization in the 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 second layer in FIG. 1, the electrolytically polymerized polymer compound and the anionic polymer compound are entangled in molecular units and are uniformly dispersed in a composite state. Furthermore, α of unsaturated bonds in anionic polymer compounds
If it contains hydrogen and the hydrogen can dissociate to form a carbanion, or it has a hydrogen of a carboxyl group and the hydrogen can dissociate to form a carboxylate anion, High degree of compositing is possible through bonding or orientation.

The composite ratio of the electrolytically polymerized polymer compound and the anionic polymer compound is such that the electrolytically polymerized polymer compound is 0 in the second layer.
．． 01-50% by weight, remainder (99,99-50% by weight)
It is preferably within a range that provides an anionic polymer compound. If the proportion of the electrolytically polymerized polymer compound is less than 0.01% by weight, the antirust performance of the polymer composite will decrease, and if it exceeds 50% by weight, the adhesion with the first layer will decrease. Put it away.

Depending on the application, the second layer may contain color pigments such as titanium white, red iron oxide, carbon black, extender pigments such as talc, clay, silica, strontium chromate, ammonium chromate, lead chromate, molybdenum. Oxylate acid-based rust preventive pigments such as potassium acid, etc., and resins in which an alkaline polymer compound uses double bond reactivity as a film-hardening functional group (e.g., drying oil or drying oil-modified alkyd, polybutadiene-based, unsaturated petroleum (resin-based, etc.) in the case of a metal salt dryer such as cobalt or lead, and in the case of isocyanate-curing alkaline polymer compounds, curing catalysts such as tin compounds such as dibutyltin oxide, etc., and ordinary anionic electrodeposition paints. The additives used can be added to allow the second layer to perform its overall function as a membrane.

Further, in the present invention, as shown in FIG. 4, a part of the electrolytically polymerized polymer compound 63 in the second layer 62 has penetrated into the first layer 61 like a chain. Therefore, the adhesion between the first layer and the second layer is stronger than when the first layer and the second layer are bonded only by the normal interfacial adhesion force. Further, examples of the composite form of the electrolytically polymerized polymer compound and the polymer compound in the first layer include the following forms. As shown in FIG. 5, in the first layer, as in the second layer, the electrolytically polymerized polymer compound and the polymer compound are entangled in molecular units and are uniformly dispersed into a composite. A compositional amalgamation having a graded structure is formed between the layers. Furthermore, the polymer compound has an unsaturated bond of α-hydrogen, which can dissociate to form a carbanion, or has a carboxyl group, and the hydrogen can dissociate to form a carboxylate anion. When a vine is included, a high degree of complexation is possible through bonding or coordination.

When the polymer composite of the present invention is applied to an object as a protective coating, it is preferable to arrange the first layer and the object so that they are in contact with each other and the second layer is on the outside.

Further, a third layer made of an anionic polymer compound having a property of being insolubilized in an electrolytic solvent by electrolytic treatment may be further laminated on the second layer of the polymer composite of the present invention. The presence of this third layer can further improve performance such as weather resistance, stain resistance, and water resistance. This third layer and second layer are
They may be bonded only by adhesive force at the interface, as in normal multi-layer coating.

Also, depending on the purpose, the first layer can be placed on top of the first layer and the second layer.
At least one of the second layer and the third layer is laminated repeatedly, or the second layer and the third layer are further stacked on the first layer, the second layer, and the third layer, or It may also be one in which one layer and a second layer are repeatedly laminated. In this case, the bonding relationship between the first layer and the second layer is not only due to the adhesive force at the interface, but also because a part of the electropolymerized polymer crosses the first layer and the second layer. It exists like a chain and strengthens the bond between the first and second layers. The bonding relationship between the other layers may be similar to that described above, or may be bonded only by the adhesive force at the interface. That is, as described below, when producing the polymer composite of the present invention,
Only when the second layer is formed by electrolytic treatment after forming the first layer, the bond is not only due to adhesive force at the interface, but the low molecular weight electrolytically polymerizable monomer invades the first layer during the electrolytic treatment. Together, they form a high molecular weight polymer and are bonded together by forming a compositional amalgamation having a graded structure between the layers. In other cases, the layers are bonded only by adhesive force at the interface.

Furthermore, in order to further improve the appearance of the surface of the polymer composite of the present invention or to color it, the polymer composite may be coated with a coating.

The polymer composite of the present invention has excellent adhesion performance, rust prevention performance, wear resistance performance, etc., so it can be applied to coatings on automobiles, protective films for structural materials, and conductive films because of its conductivity. can do.

[Description of the second invention] The second invention (the invention according to claim (2)) is intended to provide a method for efficiently producing the above-mentioned polymer composite.

The method for producing a polymer composite according to the second aspect of the present invention includes a first step of forming a first layer made of a polymer compound, a monomer of an electrolytically polymerized polymer compound, and an electrolytic solvent by electrolytic treatment. The anionic polymer compound and the anionic polymer compound having the property of being insolubilized are immersed in an electrolytic solution in which the anionic polymer compound and the anionic polymer compound are dispersed or dissolved, and a voltage is applied to the first layer. It is characterized by comprising a second step of forming a second layer consisting of an electrolytically polymerized polymer compound existing between anionic polymer compounds.

According to the second invention, an excellent polymer composite as described above can be produced.

Moreover, in the second invention, a polymer composite having a gradient composition between the first layer and the second layer can be manufactured. In other words, while it is not possible to obtain a composition with a gradient composition by ordinary brush painting, spray painting, etc., this method
In the invention, by applying a voltage to the first layer and forming the second layer by electrolytic treatment, a low molecular electrolytically polymerizable monomer is doped into the first layer and a high molecular polymer is formed. However, a polymer composite having a gradient composition between the first layer and the second layer can be produced.

[Description of other inventions of the second invention] Next, other inventions that make the second invention more specific will be described.

The method for producing a polymer composite of the present invention includes forming a first layer (first step), forming the first layer with an electrolytically polymerized polymer monomer,
A second layer is deposited on the first layer by electrolytic treatment by immersion in an electrolytic solution containing an anionic polymer compound that has the property of being insolubilized in an electrolytic solvent by electrolytic treatment (second step) It is.

Examples of the first layer polymer compound include the compounds mentioned above. However, in the present invention, since the second layer is formed by electrolytic treatment, the polymer compound of the first layer preferably satisfies the following conditions. If this condition is satisfied, the polymer composite of the present invention can be easily produced, and the
A film that is excellent in the required functions of a coating film for coverings and as a composite laminated film can be obtained. The conditions are (1
) It has the electrical conductivity necessary for electrolytic treatment during the formation of the second layer in the second step, (2) It does not dissolve in the electrolytic solution during the electrolytic treatment in the second step, (3) It has sufficient conductivity to support the second layer. It has the ability to form a film.

In the present invention, the second step is to immerse the first layer in an electrolytic solution and apply a voltage to the first layer to electrolytically deposit the second layer on the first layer to form a highly composite layer. It is something to do. Therefore, if the first layer cannot be energized by voltage application, the second layer will not be formed. However, even if the first layer polymer compound itself is insulating,
Conductivity can also be imparted to the first layer by mixing a conductive substance such as graphite or various metal powders into the polymer compound. Furthermore, if the first layer is dissolved by immersion in an electrolytic solution or by electrolytic treatment, a uniform second layer will not be formed, and a polymer composite with excellent properties will not be formed. As such polymer compounds,
Examples include polyvinyl alcohol with a relatively low molecular weight and a high degree of water solubility, or derivatives thereof. Also,
With a polymer compound that cannot support the second layer, it is difficult to obtain a polymer composite with sufficient strength, and especially when the polymer composite of the present invention is used as an isolation protective film, the strength is insufficient. be.

As a method for forming the first layer in the first step, for example, the first layer of the polymer compound is formed by painting, or by applying it in a heated molten state, or by forming it in a solution form using a spin coater. There are other methods. Note that a first layer may be formed on a conductive substrate and the conductive substrate may be used as an electrode in the second step. Furthermore,
When the conductive substrate is used as a coating material for the polymer composite of the present invention, the polymer composite can be easily coated, and the adhesion between the coating material and the polymer composite is high.

When forming the first layer by painting, it is preferable to evaporate most of the non-hydrophilic solvent remaining in the coating film after painting. If the solvent remains, the wettability of the coating film to the electrolytic solution is insufficient, making it difficult to form the second layer. Further, when painting with a water-based paint, it is preferable to evaporate the water (or the solvent if it contains some auxiliary organic solvent) as a solvent after painting. If water remains in the coating film, coating defects such as repellency will occur during the next electrolytic treatment. In addition, when using electrodeposition paints such as anionic electrodeposition paints and cationic electrodeposition paints, the coating film may or may not be washed with water after the electrodeposition coating is performed under normal conditions. .

However, it is preferable to evaporate the droplets adhering to the coating surface. In addition, when the above electrodeposition paint is heated and cured to cause flow of the electrodeposited film during formation, if the thickness of the paint film is 6 μm or more, it becomes an insulating film. It is best to mix in powder.

In addition, when applying a film-forming polymer compound in the form of a solution or a heated solution to an object to be coated, such as the above-mentioned conductive substrate, if the polymer compound does not have adhesion to the object to be coated, It is preferable to add an adhesive to the polymer compound. The amount of the adhesive added is preferably 3 to 200 parts by weight per 100 parts by weight of the polymer compound.

The first layer needs to be electrically conductive because the second layer is formed on its surface by electrolytic treatment during formation of the second layer. The electrical resistance of the first layer in the state of being immersed in the electrolytic solution in the second layer forming process is 100 OKΩ/crt1
The following is desirable.

If it exceeds 1000 Ω/crd, the polymer composite of the present invention that can secure the current necessary for forming the second layer cannot be formed. When using a polymer compound with an electrical resistance exceeding 100 OKΩ/cnf, the layer thickness should be 1 μm.
The electrical resistance can be reduced by making the following or by mixing conductive powder into the polymer compound. The conductive powder includes graphite, copper, steel,
Examples include powders of metals such as stainless steel, zinc, and tin, powders of metal alloys thereof, and at least one of them is used. In the case of the above-mentioned paint, the amount of the conductive powder to be mixed is preferably in the range of 0 to 200 parts by weight per 100 parts by weight of the paint. If it exceeds 200 parts by weight, the strength of the first layer will decrease.

Further, in the case of the film-forming polymer compound, the amount is preferably 0 to 200 parts by weight per 100 parts by weight of the polymer compound. Note that if the thickness of the first layer is less than 1 μm, the electrolytically polymerized polymer compound of the second layer will be doped too much into the first layer during the formation of the second layer, and the bond between the first layer and the second layer will increase. Functional separation disappears. Therefore, in order to adjust the electrical resistance of the first layer, it is better to mix conductive powder rather than reducing the thickness of the first layer.

Note that, if necessary, after forming the first layer, its surface may be polished with sandpaper or the like. In this case, the compositing of the first layer and the second layer is further promoted.

The method for forming the second layer is to immerse the first layer formed above in an electrolytic solution in which a monomer of an electrolytically polymerized polymer compound and an anionic polymer compound are dispersed or dissolved, and apply a voltage to the first layer. is applied. As a result, the anionic polymer compound is deposited on the first layer, and at the same time, the monomer of the electrolytically polymerized polymer compound eutectoid is polymerized and composited in the anionic polymer compound to form a second layer. do. In addition, the electrolytically polymerized polymer compound of the second layer enters between the first layer and the second layer, and adhesion with tight structural fusion is performed. It forms a complex with a polymeric polymer compound at the molecular level.

Formation of such a second layer is performed in a single operation.

Examples of the monomer of the electrolytically polymerizable polymer compound include monomers of a polymer compound that can be electrolytically polymerized and have a 5M hetero ring, a benzene ring, etc.
At least one of them is used.

For example, as a monomer having a 5-membered hetero ring, the general formula %formula% Examples include carbazole.

In addition, as a monomer having a benzene ring, the general formula (in the formula, each of R1 and R2 is hydrogen, a halogen, a nitro group, an amino group, an aliphatic group, an unsaturated aliphatic group, an aromatic group) is used. A substituent containing at least one type, X
is oxygen, sulfur, nitrogen or -N- (where R3 is hydrogen,
A substituent containing at least one of an aliphatic group, an unsaturated aliphatic group, and an aromatic group. ). ), pyrrole, N-substituted pyrrole, β-substituted virol, thiophene, β-substituted thiophene, furan, β-substituted furan, indole, (in the formula R'
-R' each individually represents a substituent containing at least one of hydrogen, halogen, nitro group, amine group, aliphatic group, unsaturated aliphatic group, aromatic group; halogen, nitro group, amino group; It is any one of aliphatic groups, unsaturated aliphatic groups, and aromatic groups (all of which are substituents containing one type).

), 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, the anionic polymer compound has a property of being insolubilized in an electrolytic solvent by electrolytic treatment. Examples of the compound include the compounds described above. Among them, those having functional groups that form anions by ionization such as carboxyl groups, sulfone groups, and phosphonic groups as ionizable functional groups, and a film insoluble in the electrolytic solution is deposited on the first layer by the above electrolytic treatment. A uniform film can be formed as long as the material has the performance to increase the performance. in this case,
The polymeric bone core is not particularly limited.

Products with the above performance include hydrochloric acid, nitric acid,
An electrolyte in which a phenomenon in which a resin substance coagulates or precipitates from an electrolytic solution when a monobasic acid such as acetic acid is added at a pH of 7 to 1 can be applied. If coagulation and sedimentation occur immediately in a pH higher than 7, the stability of the electrolytic solution is poor in the coexistence of electrolytically polymerized polymer compound monomers and is not practical; The anionic polymer compound is not deposited onto the first layer.

The anionic polymer having such properties is preferably a polymer for electrodeposition coatings such as oil-based, alkyd-based, acrylic-based, polybutadiene-based, or unsaturated petroleum resin. Mixed use is also possible.

The anionic polymer compound preferably contains at least one functional group that can be crosslinked by heating or oxygen in the air, such as an unsaturated double bond or a hydroxyl group. Further, these functional groups may be bonded to protective groups in the electrolytic solution and then regenerated in the curing process that follows after electrolysis. Furthermore, in order to effectively crosslink and cure the electrodeposited anionic polymer compound, a water-dispersible amino resin, such as an alcohol-modified low-condensation melamine resin of 04 or less, a guanamine resin, a urea resin, or
A mixture of a curing resin such as a blocked isocyanate compound and a resol type phenolic resin, or a mixture of a curing resin such as a blocked isocyanate compound or a resol-type phenol resin, or a product obtained by grafting or copolymerizing a part or all of them onto an anionic polymer compound may be used. Furthermore, non-electrolytic resins such as petroleum resins, coumaron-indene resins, polybutadiene resins, oils and fats that can be maintained in a dispersed state as surfactant protecting agents that protect the anionic polymer compound in the electrolytic solution, or their heating. Polymerized modified products (polymerized modified products in an inert gas flow or in the presence of oxygen, for example, in the case of oils and fats, boil oil, stand oil, etc. may be added. When such non-electrolytic resins are coexisting, an electrolyte solution may be added. Before adjusting the resin, it is preferable to heat the anionic polymer compound or to mix them together so that the anionic polymer compound is sufficiently adsorbed on the resin.

The acid value of the anionic polymer compound is 30.
A value within the range of ~200 is desirable. The acid value here is the number of potassium hydroxide (KOH) required to neutralize the anionic functional groups (carboxyl group, sulfone group, phosphonic group, etc.) bonded to 1 g of polymer. . If the acid value is less than 30, the electrolytic solution will not have sufficient surface activity to stably retain monomers or additives of the electrolytically polymerized polymer compound in the electrolytic solution, and the electrolytic solution will be unstable. Also,
When the acid value exceeds 200, the amount of second layer deposited per unit quantity of electricity becomes too small to be practical.

The electrolytic solution is one in which the monomer of the electrolytically polymerized polymer compound 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 the organic solvent mixed is preferably 0.001 to 30%, more preferably 3 to 10%. Mixing more than 30% of organic solvents causes abnormal precipitation of anionic polymer compounds.

In order to efficiently disperse or dissolve the monomer of the electropolymerized polymer compound and the anionic polymer compound in the electrolytic solution, the anionic functional group in the anionic polymer compound is neutralized with its counter ion-forming low-molecular compound. It is desirable to harmonize. Examples of the counterion-forming low-molecular compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, and dipropylamine. , diisopropylamine, monobutylamine,
Primary, secondary or tertiary alkylamines having a lower alcohol group having alkyl carbon atoms of 4 or less such as diethylenetriamine; alkanolamines such as monoethanolamine, jetanolamine, triethanolamine;
Examples include alkylalkanolamines such as dimethylamizcanol, and at least one of them is used.Furthermore, as an auxiliary neutralizing agent, cyclohexylamine, octylamine, N-dimethylamine, etc. Relatively high molecular weight aliphatic, ring ring or aromatic amines may also be used.

In such a case, it is preferable to use it together with other low molecular amines in order to form a high quality second layer. Even if the anionic polymer compound is previously neutralized with the neutralizing agent and then dispersed in the electrolytic solution, or the neutralizing agent is added and mixed in the electrolytic solution in advance, the anionic A polymer compound may be added, stirred and dispersed, or dissolved.

When adding an anionic polymer compound and an electrolytic polymer compound monomer to an electrolytic solution, the anionic polymer compound may be first dispersed or dissolved in the electrolytic solution, or the electrolytic polymer compound may be first dispersed or dissolved. Alternatively, both may be dispersed or dissolved at the same time. In either case, it is preferable to thoroughly stir and mix both.

In addition, the amount of each of the above two components to be dispersed or dissolved in the electrolytic solution is from 0.001 to 0.001 to the entire electrolytic solution (containing the above two components) in the case of monomers of electrolytically polymerized polymer compounds. The content is preferably within the range of 30% by weight, and more preferably within the range of 0.01 to 20% by weight. 0.0
If it is less than 0.01% by weight, it may not exhibit antirust performance if formed into a film, and if it exceeds 30% by weight,
Precipitation occurs in the electrolyte, which deteriorates the stability of the electrolyte and further impairs the uniformity of the produced composite.

On the other hand, the amount of the anionic polymer compound added is preferably within the range of 2 to 40% by weight, more preferably within the range of 5 to 30% by weight based on the entire electrolytic solution (containing the two components). . 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 undeposited electrolyte is removed from the system. It is not a good idea as there will be a large loss due to taking it out.

In addition, when forming an additional layer on the second layer, conductive powder for imparting electrical conductivity to the second layer is preferably mixed into the electrolytic solution.

The p I-1 of the electrolytic solution is not limited as long as the monomer and the anionic polymer compound are stably present.

The first layer can be immersed in the electrolytic solution by immersing both the first layer and the counter electrode in the electrolytic solution, or, since the second layer will be deposited on the anode, the first layer can be immersed in the electrolytic solution with only the first layer as the anode. It may also be immersed in For example, if the electrolyte container is conductive, the container may be used as a counter electrode or cathode, or another conductor may be used as an electrode and immersed directly in the electrolyte. Furthermore, even if the so-called diaphragm method is used, in which the counter electrode is isolated with an ion exchange membrane (cation exchange membrane) or a semipermeable membrane, and a so-called diaphragm cathode filled with a basic electrolytic solution is immersed in the electrolyte, it is possible to use a salt bridge electrode. may be used as the opposite. However, when using a diaphragm cathode or a salt bridge as a counter electrode, if the base used in the electrolyte is different from the neutralizing agent in the electrolyte in which the first layer is immersed, the structure prevents the base from migrating into the electrolyte. should be. In the case of migration and contamination, a polymer complex with a fixed composition will not be formed. Note that the first layer may be immersed as is, but
It may be immersed in a form attached to a conductive substrate.

For example, the first layer formed on the conductive substrate by coating or the like in the first step may be immersed as it is.

Furthermore, the applicable conductive object and counter electrode are not particularly limited as long as they are conductive. Examples include platinum, gold, stainless steel, chemically treated steel sheets,
Galvanized steel sheet, aluminum sheet, copper sheet, tin plate, plated plastic sheet, with or without chemical conversion treatment,
Alternatively, processed products thereof can be mentioned. The materials of the conductive object and the counter electrode may be the same or different.

In the present invention, by immersing the first layer in an electrolytic solution and applying a voltage to the first layer, the anionic polymer compound and the electrolytically polymerized polymer compound co-deposit, and at the same time The monomer of the electrolytically polymerized polymer compound is electrolytically polymerized, complexed with the anionic polymer compound, and deposited on the first layer. A voltage is applied to the electrode between the first layer and the counter electrode. The voltage to be applied is a DC voltage. The waveform of the DC voltage to be applied may be a full-wave or half-wave rectified wave from alternating current, or a pulse wave, and is not particularly limited, but the maximum value of the current density is 0. 0
It is preferable to set it to 1 mA/cnr or more. Even if the potential between the first layer and the counter electrode is less than this, the oxidation potential of the electrolytically polymerized polymer compound in the electrolytic solution or the minimum electrodeposition potential of the anionic polymer compound (the potential of the anionic polymer compound The second layer will be formed if the larger potential (potential required to ensure the minimum current density required for electrodeposition on the first layer surface) is secured, but the formation of the second layer at a practical speed is necessary. 0.1 for
mA/crd or more, preferably 0.5 mA/c
It is better to set it to d or more. The voltage application method may be a constant voltage method, a constant current method, or a boost method.

In addition, since the first layer acts as a resistor, in order to ensure a high current density, a higher voltage is applied than when forming the second layer directly on the conductive object by electrodeposition (Japanese Patent Application No. 196364/1983). . The voltage conditions to be applied vary depending on the distance between the first layer and the counter electrode or the shape of the polymer composite to be manufactured, but the voltage is applied within the range of 1 to 750 volts and 0.5 to 6000 seconds. is more preferable from an energy and economic point of view.

The maximum current density can be arbitrarily set in consideration of electrolytic operation efficiency, as long as the first layer does not cause dielectric breakdown. Furthermore, the voltage may be applied to the first layer before the first layer is immersed in the electrolytic solution (by energizing), or after it is immersed in the electrolytic solution (total immersion energizing).

The temperature of the electrolyte during electrolytic operation does not pose a particular problem to the formation of the second layer as long as the electrolyte does not freeze or boil.
Considering decomposition), the temperature is preferably 5 to 50°C. At low temperatures below 5°C, coagulation and sedimentation from the electrolyte tends to occur;
If the temperature exceeds 0°C, the anionic polymer compound tends to decompose.

When forming a polymer composite consisting of only the first layer and the second layer, it is preferable to heat and harden the vaginal polymer composite after the above step to complete the composite lamination.

Furthermore, in the case of forming a multilayered product having three or more layers, the processing operations such as the first step→second step or the second step are repeated. This makes it possible to produce polymer composites that meet various functional objectives. The processing operations when performing this multi-laminate processing may be the same as or different from the first and second steps. This selection can be broadly based on the type of polymeric compound or material that meets the purpose of the laminate. However, when performing the second step, the electrical resistance of the already formed laminate at the end of the previous step is
In the electrolytic treatment solution, the resistance should be 100KΩ/cr& or less. If it exceeds 100 OKΩ/crl, no layer can be formed in the electrolytic operation.

After forming the polymer composite as described above, it is preferable to cure the composite. If the selected composite material consists of a lacquer or a cold-curing material, for example a nitrocellulose lacquer, an acrylic lacquer, a film-forming thermoplastic polymer, a drying oil-modified alkyd resin paint, etc. as a first layer and a cold-curing electrical When a coating material or the like is used for the anionic polymer compound of the second layer, the composite can be cured by forced drying at room temperature or at a low temperature of 100° C. or lower.

However, in order to promote the high degree of compositing between the anionic polymer compound and the electrolytically polymerized polymer compound in the second layer and the fusion adhesion with the first layer, heating at a temperature of 100°C or higher is required. and preferably at a temperature higher than the curing temperature of the anionic polymer compound contained in the electrolytic solution. The upper limit of the heating temperature is not particularly limited, but it is preferably below the temperature at which the main structure of the composite rapidly decomposes, and generally below 350°C. Further, when the first layer is immersed in an electrolytic solution with a conductive base material attached thereto, the curing temperature is limited by the heat resistance of the conductive base material. Further, in cases where the conductive substrate melts or undergoes deformation or foaming that cannot withstand practical use due to heat curing, there are restrictions on the type of polymer composite of the present invention. For example, when forming the composite of the present invention on a resin-plated product, it is preferable to form a composite of a lacquer that can be heat-cured below the melting temperature of the conductive substrate and an air-drying electrodeposition paint.

It is preferable to carry out the above electrolysis operation, take out the polymer composite formed by depositing the second layer from the electrolytic solution, and remove the undeposited electrolyte that has adhered to the polymer composite.

However, if there is no high requirement for uniformity of appearance such as surface smoothness of the polymer composite surface, the performance of the polymer composite is not affected even if the water washing is omitted.

As described above, an excellent polymer composite can be obtained by performing the first and second steps, but especially in selecting the anionic polymer compound and the electrolytically polymerized polymer compound monomer for the second layer, If there is limited affinity between the polymer obtained from the electrolytically polymerized polymer compound monomer and the anionic polymer compound, the electrolytically polymerized polymer is added near the interface between the first layer and the second layer in the second step. A second layer with a two-layer structure containing a large amount of a molecular compound and the other side of the second layer containing only a small amount or no electropolymerized polymer compound is dried by electrolytic operation from the same electrolyte. . This two-layer structure is maintained even during the heat curing operation following the electrolytic operation, and when such a material is selected, the polymer composite consists of an anionic polymer compound and an electrolytically polymerized polymer compound on the first layer. It has a three-layer structure in which a second layer is formed, and a third layer made of an anionic polymer compound is formed thereon. The material forming such a structure is not particularly limited for the first layer, but an anionic polymer compound as an electrolyte component for forming the second layer, a high acid value drying oil-modified alkyd resin, and an alkyl chain of C4 or less ( At least one type of high acid value acrylic resin containing meth)acrylic acid ester as a main component and pyrrole as the electrolytically polymerized polymer compound monomer may be selected.

According to the present invention, it is possible to produce a polymer composite that has excellent adhesion to the surfaces of a wide variety of objects to be coated, as well as excellent rust prevention and wear resistance. Furthermore, in combination with the first layer, it is possible to produce a polymer composite having a wide range of functions that meet the intended use. Moreover, each layer is not bonded only by adhesive force at the interface as in normal multilayer coating, but during electrolytic treatment, the first layer is doped with a low-molecular electrolytically polymerizable polymer compound monomer and the polymer is A compositional amalgamation having a compositional gradient between the layers can be formed. In an ordinary electrolytic operation using only an electrolytically polymerized polymer compound, since the electrolytically polymerized polymer compound to be treated is a macromolecule, the first layer is not doped, and only the interfacial layer is bonded. No compositionally fused laminates are formed.

In the present invention, when forming the polymer composite of the present invention on the surface of a conductive base material, the first layer forming material and the conductive base material are selected in consideration of the adhesion strength between the two and the matching of the intended functions. However, it is also possible to isolate the polymer composite of the present invention and use it by adhering it to a coated object other than the conductive substrate used for forming the composite using an adhesive or the like. In such a case, the polymer composite formed according to the present invention using, for example, a film-forming material in the first layer may be treated with an organic solvent or with chemicals (for example, acid dissolution treatment of a conductive substrate) or treated with a conductive substrate. A polymer complex can be isolated by performing an electrolytic treatment. In such a case, isolation of the complex can be facilitated by performing appropriate treatment (for example, forming a coating layer with weak adhesive strength) on the side of the first layer opposite to the second layer or on the surface of the conductive substrate that does not impede the conduction of electricity. can be done.

If it is necessary to further improve the appearance or color the surface of the polymer composite of the present invention, a known coating can be applied to the polymer composite.

〔Example〕

The present invention will be explained in detail below.

Example 1 Anionic unsaturated alkyd electrodeposited resin (Dainippon Ink)
After neutralizing 223 parts by weight of a mixture of 150 parts by weight of Water Sol 141LpA and 73 parts by weight of Water Sol 193LpA with 7.8 parts by weight of triethylamine, and adding 22 parts by weight of isopropyl alcohol and 7 parts by weight of acetone. These were dispersed in 744 parts by weight of water to obtain a water-dispersed face. This water dispersion festival is
pH7.3, electrical conductivity 2000μs/cm (25°C)
Met. The average particle diameter of the dispersed electrodeposited resin particles was measured using a photoelastic scattering method (Coulter Co., model N4).
SUB-MICRON ParticleAna
lyzer), it was about 40 nm. 5 parts by weight of aniline was added to 100 parts by weight of the above electrolyte solution and dispersed using a stirring disperser. As a result, a milky-white aniline-dispersed varnish was obtained. This aniline dispersion varnish has a pH of 7.4,
The electrical conductivity is 1700 μs/cm (25°C), and the average particle size of the dispersed particles of electrodeposited resin and aniline is about 1
0100n according to photoelastic scattering method).

A polybutadiene type cationic electrodeposition resin (EC-1800-150/100 manufactured by Nippon Petrochemical Co., Ltd.) was neutralized with acetic acid and dispersed. A water-dispersed varnish was thus obtained.

As shown in the conceptual diagram of the electrolytic treatment equipment in Figure 2, the cationic electrodeposition resin water dispersion face is 4cm wide x 2cm deep x 8cm high.
m glass cell 1, and electrolyte 2 consisting of the above-mentioned fess.
Cold pressure is applied to steel plates (JIS standard 5PCD products, Nippon Kokan Co., Ltd.) 31 and 5US304 sheets (thickness 0.1
mm) 32 was immersed, and a constant voltage of 100 V was applied between both electrodes for 5 seconds using the cold rolled steel plate 31 as a cathode using a DC power source 4 connected between both electrodes. As a result, a white coating was obtained on the cold rolled steel plate.

A cold-rolled steel plate (coating-cold-rolled steel plate) in which the above-mentioned coating was formed on the above-mentioned aniline-dispersed varnish in the same manner as above, and 5US
304 sheet was immersed, and at the same time, the coated cold-rolled steel sheet was anodized and a constant voltage of 110 V was applied for about 1 minute. After that, the coated cold-rolled steel plate was removed from the varnish and heated to 180°C.
Bake for 25 minutes. As a result, a smooth brown coating was obtained on the cold rolled steel plate. When the cross-sectional structure of this film was observed with a scanning electron microscope, it was found to have a three-layer structure. Elemental analysis of the three layers reveals that the layer 51 (approximately 2 μm in thickness) near the steel plate 54 is a layer in which polyaniline is composited with a cationic electrodeposited resin (containment of polyaniline in this layer). layer 52 (layer thickness approximately 3 μm)
is a composite layer of anionic electrodeposited resin and polyaniline (the content of polyaniline in this layer is about 13% by weight), and the outermost layer 53 (layer thickness of about 10 μm) is a layer mainly composed of anionic electrodeposited resin only. there were.

Example 2 Styrene, acrylic acid, methyl methacrylate, 2-
A water-dispersed varnish containing 15% of non-volatile components was prepared by adding 10 phr of blocked isocyanate as a curing agent to an acrylic electrodeposition resin consisting of ethylhexyl acrylate and 2-hydroxylethyl acrylate. 5 parts by weight of pyrrole was added to 100 parts by weight of the water-dispersed varnish to obtain a pyrrole-dispersed varnish. Epicote 828 (manufactured by Yuka Shell Ethoxy), linseed oil fatty acid, maleic anhydride,
A linseed oil-modified epoxy electrodeposition resin synthesized from butanol and propylene glycol was neutralized with dimethylethanolamine to obtain a water-dispersed varnish.

A pair of electrodes was immersed in the water-dispersed varnish, and a constant voltage of 50 V was applied to the picture electrode for 5 seconds using a cold rolled steel plate as an anode. This resulted in a pale yellow coating on the cold rolled steel plate.

A cold rolled steel plate on which this coating was formed in the same manner as in Example 1 (coating - cold rolled steel plate) and a 5US304 sheet (thickness 0
．． 1 mm) was immersed in the above-mentioned pyrrole-dispersed varnish in the same manner as in Example 1, and a constant voltage of 70 V was applied between both electrodes for about 1 minute using the coated cold-rolled steel plate as an anode.

After that, the coated cold rolled steel plate was removed from the varnish and 1
Baking was performed at 70°C for 25 minutes. When observed with a scanning electron microscope, a two-layered laminate was formed, and further detailed analysis revealed that from the interface with the steel plate, a linseed oil-modified epoxy electrodeposited resin layer (layer thickness approximately 2 μm), a polypyrrole and acrylic electrodeposited resin (layer thickness approximately 18 μm,
The content of polypyrrole in the layer is about 5% by weight),
It was found that about 2% by weight of polypyrrole was contained in the linseed oil modified epoxy layer.

Example 3 70 parts by weight of graphite was added to 100 parts by weight of an acrylic resin made of styrene, methyl methacrylate, 2-ethylhexyl acrylate, and acrylic acid, and melamine as a crosslinking agent to form a paint. The above paint was spray-painted on a steel plate. In order to evaporate the solvent contained in the coating film, it was placed in a desiccator, and the pressure inside the desiccator was reduced using a vacuum pump. After 1 hour, it was taken out and a coating was obtained on the steel plate.

A modified epoxy resin consisting of Epicor) 1004 (manufactured by Yuka Shell Epoxy), dehydrated castor oil, fatty acids, and maleic anhydride was synthesized, neutralized with dimethylamine, and water was added to obtain a water-dispersed varnish. 3 parts by weight of pyrrole was added to 100 parts by weight of the above varnish and dispersed using a stirring disperser.

A steel plate on which the above acrylic is formed (acrylic-steel plate)
and an SUS 304 sheet (thickness: 0.1 mm), and the acrylic steel plate was used as an anode and an SUS 304 sheet (thickness: 0.1 mm).
A constant voltage of 150 V was applied for 1 minute between both electrodes using the sheet as a cathode. Thereafter, the acrylic steel plate was removed from the varnish and baked at 180°C for 25 minutes. When this film was observed with a scanning electron microscope, it was found to have a two-layer structure. As a result of further detailed analysis, we found that a layer in which polypyrrole is composited with acrylic resin (layer thickness approximately 20 μm) is closer to the steel plate.
m, polypyrrole content in the layer is about 2% by weight), polypyrrole-modified epoxy electrodeposited resin layer (layer thickness about 20 μm)
m, the content of polypyrrole in the layer was 20% by weight).

Comparative Example 1 Polybutadiene type cationic electrodeposition resin used in Example 1 (Nippon Petrochemical Co., Ltd. EC-1800-1, 50/1
00) In the same manner as in Example 1, a SUS 304 sheet was immersed in the dispersion varnish as a counter electrode to the cold rolled steel plate, and a constant voltage of 150 V was applied for 1 minute between both electrodes using the cold rolled steel plate as the cathode.

Baking resulted in a thin orange coating on the cold rolled steel plate due to hardening. As a result of observing the cross-sectional structure with a scanning electron microscope, it was found to be a single layer film (film thickness approximately 20 μm) made of polybutadiene type cationic electrodeposition resin.

Comparative Example 2 A cold-rolled steel plate and a 5O8304 sheet as a counter electrode were immersed in the aniline-dispersed varnish used in Example 1 in the same manner as in Example 1.
A constant voltage of V was applied for about 1 minute. Then change this to 180
By baking at °C for 25 minutes, a smooth film (film thickness: about 20 μm, polyaniline content: about 8% by weight) consisting of a brownish-brown alkyd electrodeposited resin and polyaniline was obtained on a cold rolled steel plate.

Comparative Example 3 A cold rolled steel plate was applied to the linseed oil-modified epoxy dispersion varnish used in Example 2 in the same manner as in Example 2, and SU was added as a counter electrode.
A constant voltage of 60 V was applied for 50 seconds using the cold rolled steel plate as an anode. 170°
An orange coating was obtained on the cold rolled steel plate by baking at C for 25 minutes.

Observation of the cross-sectional structure using a scanning electron microscope revealed that it was a single layer film (film thickness approximately 20 μm) made of linseed oil-modified epoxy resin.
m).

Comparative Example 4 A cold-rolled steel plate and a 5US304 sheet as a counter electrode were immersed in the pyrrole-dispersed varnish used in Example 2 in the same manner as in Example 2, and a constant voltage of 60 V was applied for 70 seconds using the cold-rolled steel plate as an anode. .

By baking at 170°C for 25 minutes, a black coating consisting of acrylic electrodeposited resin and polypyrrole (film thickness approximately 20 μm, polypyrrole content approximately 6
% by weight) was obtained.

Comparative Example 5 The graphite-containing acrylic resin paint used in Example 3 was spray-painted on a cold rolled steel plate in the same manner as in Example 3.

This was baked at 180° C. for 25 minutes to obtain a coating film. Observation using a scanning electron microscope reveals that this coating film is a single layer of homogeneous film (film thickness approximately 20 μm) made of graphite-containing acrylic resin.
Met.

Comparative Example 6 A cold-rolled steel plate and a 5US3Ω4 sheet as a counter electrode were immersed in the pyrrole-dispersed varnish used in Example 3 in the same manner as in Example 3, and 80Ω was applied between both electrodes using the cold-rolled steel plate as an anode.
A constant voltage of V was applied for 50 seconds. Heat this at 180°C for 2
Baking for 5 minutes produces a coating film made of modified epoxy resin and polypyrrole (film thickness approximately 20 μm, polypyrrole content approximately 2
0% by weight).

Comparative Example 7 Conductive glass (IT
5US304 with O glass 3cm x 6cm) as the opposite electrode.
A sheet (0.1 mm thick) was immersed. A constant current of 50 μA/cJ was applied between the two electrodes for 20 minutes to obtain polyaniline on the ITO glass plate. After drying, the cross-sectional structure was observed using a scanning electron microscope, and it was found to be a single layer film (film thickness: about 10 μm) made of polyaniline.

Comparative Example 8 A cold rolled steel plate and a SUS 304 sheet as a counter electrode were immersed in the polybutadiene type cationic electrodeposition resin water-dispersed varnish used in Example 1 in the same manner as in Example 1, and the cold rolled steel plate was used as a cathode between the two electrodes. A constant voltage of 100 V was applied for 5 seconds. As a result, a white film (film thickness: about 20 μm) made of cationic electrodeposition resin was obtained on the cold rolled steel plate.

Alkyd electrodeposition resins used in Example 1 (Watersol L 4.1.L p and Watersol 193L
The mixture of pA) was neutralized with triethylamine, and water was added to adjust the solid content to about 10% by weight. This and pyrrole 1
5g was dispersed to form a paint. This was applied by brush onto the white coating obtained on the cold-rolled steel plate described above. 2 at 180°C
Although it was baked for 5 minutes to form a coating, interlayer peeling occurred between the cationic electrodeposited resin layer and the pyrrole-alkyd electrodeposited resin layer, and it could not be used for testing.

(Evaluation) The properties of the coatings formed in Examples 1 to 3 and Comparative Examples 1 to 6 and cured by baking were evaluated as follows. The results are shown in Table 1.

Corrosion resistance: Make a 3cm long cut in the coating with a knife 3
A 5% by weight NaCn aqueous solution was sprayed at 5 degrees, and the time required for the width of rust to grow from the cut portion to 3 mm was measured.

As is clear from Table 1, it can be seen that the coating of this example has better corrosion resistance than the coating of the comparative example.

Further, the properties of the coatings formed in Examples 1 to 3 and Comparative Examples 2, 4, and 6 and cured by baking were evaluated as follows. The results are shown in Table 2.

Water resistance: After immersing the film in 40°C hot water for 500 hours, use a knife to make 100 cuts of 1 mm x 1 mm, and then apply cellophane adhesive tape to these areas and quickly peel it off. The number of

As is clear from Table 2, it can be seen that the coating of this example has better water resistance than the coating of the comparative example.

Further, the properties of the coatings formed in Example 1 and Comparative Example 7 and cured by baking were evaluated as follows. The results are shown in Table 3.

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 formed was measured.

As is clear from Table 3, it can be seen that the coating of this example has better wear resistance than the coating of the comparative example.

Further, the properties of the coatings formed in Example 1 and Comparative Example 8 and cured by baking were evaluated as follows. The results are shown in Table 4.

Adhesion performance: 100 lattice-like cuts of 1 mm x 1 mm were cut into the film using a knife, and a cellophane adhesive tape was applied to these parts and rapidly peeled off, and the number of burls remaining was measured.

As is clear from Table 4, it can be seen that the film of this example has better interlayer adhesion performance than the film of the comparative example. This is considered to be because the polyaniline of the second layer was precipitated into the first layer.

[Brief explanation of drawings]

FIG. 1 is a conceptual diagram showing the composite form of the second layer of the polymer composite according to the present invention, FIG. 2 is a conceptual diagram of the electrolytic treatment apparatus used in Example 1, and FIG. FIG. 4 is a conceptual diagram showing the relationship between the first layer and the second layer of the polymer composite according to the present invention, and FIG. 5 is a cross-sectional conceptual diagram of the polymer composite according to the present invention. FIG. 2 is a conceptual diagram showing a composite form in the first layer of FIG. DESCRIPTION OF SYMBOLS 1... Electrolytic cell, 2... Electrolyte solution 31... First layer 31, 32, formed on the conductive base layer.
... Electrode, 4 ... DC power supply 51.61 ... First layer 52.62 ... Second layer 53 ... Third layer, 54 ... Steel plate 63 ... Electrolytically polymerized polymer compound

Claims (2)

[Claims] (1) A first layer consisting of a polymer compound, an anionic polymer compound that has the property of becoming insolubilized in an electrolytic solvent through electrolytic treatment, and an electrolytically polymerized polymer compound existing between the anionic polymer compounds. A polymer composite comprising a second layer and a second layer, wherein at least a part of the electrolytically polymerized polymer compound of the second layer is present in the first layer. (2) A first step of forming a first layer made of a polymer compound, and forming the first layer with a monomer of an electrolytically polymerized polymer compound and an anionic polymer compound having the property of being insolubilized in an electrolytic solvent by electrolytic treatment. The above-mentioned anionic polymer compound and
A method for producing a polymer composite, comprising a second step of forming a second layer comprising an electrolytically polymerized polymer compound existing between the anionic polymer compounds.