JP5340516B2 - Rust-proof coating agent composition and laminated metal material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent composition for rustproofing excellent in rustproof properties, enabling thin coating, and having alkali resistance, water resistance, solvent resistance, processability and excellent adhesiveness to a metal material, and a laminated metal material. SOLUTION: The coating agent composition for rustproofing is characterized in that it is an aqueous emulsion containing a below-mentioned polyolefin resin, the number average particle size of the polyolefin resin is <=1 &mu;m, and the aqueous emulsion is substantially free from an emulsifier component or a compound having a protective colloid effect. The polyolefin resin is as follows: a copolymer constituted of (A1) an unsaturated carboxylic acid or its anhydride, (A2) an ethylenic hydrocarbon and (A3) at least one kind of compound expressed by any one of formulas (I) to (IV); and the weight ratios of each constituting component (A1) to (A3) satisfy relationship (1): 0.01<=(A1)/ (A1)+(A2)+(A3)}&times;100<5 and relationship (2): (A2)/(A3)=55/45 to 99/1.

Description

  The present invention has not only an excellent antirust effect, but also good alkali resistance of the coating film, and also has water resistance, solvent resistance, good workability, and good adhesion to metal materials, The present invention relates to a rust-preventive coating agent composition that can be easily formed at a low temperature and excellent in transparency of the resulting film, and a laminated metal material having a film obtained therefrom.

  While metal-plated steel sheets such as electrogalvanized steel sheets and hot-dip galvanized steel sheets are widely used in automobiles, home appliances, structures, etc., in recent years, there has been an increasing demand for surface-treated steel sheets having excellent rust prevention properties. Under such circumstances, a chromate treatment using hexavalent chromium has been adopted in order to further enhance the rust prevention property of the galvanized steel sheet. This chromate treatment improves the rust prevention of the galvanized material, but it has been pointed out that there is a problem of chromium contamination in the work environment and installation location due to harmful hexavalent chromium, so-called non-chromate antirust treatment agent that does not use chromium. Development is an urgent need.

  As one of the new non-chromate antirust treatment agents, treatment agents based on various polymer compounds have been studied. For example, as an attempt to coat an olefin-based powder resin on the surface of a steel sheet, Japanese Patent Application Laid-Open Nos. 60-143952, 7-207215, or 11-131259 discloses an ethylene-unsaturated carboxylic acid. It has been disclosed to powder-copolymerize copolymer resin powder with acid.

  However, when painting using such a powder resin, it is very difficult to coat to a thickness of 20 μm or less, and it cannot be used for thin coating applications. Moreover, it is difficult to obtain a coating film with excellent smoothness and uniformity, and in order to improve the smoothness and uniformity of the coating film, the flowability and average particle diameter of the powder resin may be limited. Many.

  As a method for making the coating thin and uniform, a method is known in which a coating agent is prepared by dissolving or dispersing a resin in an organic solvent or an aqueous medium, and coating is performed on a steel plate or the like. In this case, the use of an aqueous medium is more preferable than the use of an organic solvent from the standpoints of environmental protection, resource saving, dangerous goods regulations by the Fire Service Act, and workplace environment improvement.

  From such a point of view, using an ethylene-unsaturated carboxylic acid copolymer having a high unsaturated carboxylic acid content, the carboxyl group in the resin is neutralized with a basic compound to disperse the aqueous protective agent dispersed in the aqueous medium. Rust coating agent is used. For example, JP-B-5-54823, JP-A-6-246229, JP-A-2000-198949, etc. describe an ethylene-unsaturated carboxylic acid copolymer having an unsaturated carboxylic acid content of about 20% by mass. A water-based anticorrosive coating agent composed mainly of coalescence is exemplified.

  However, when a resin having a high unsaturated carboxylic acid content is applied, the alkali resistance of the coating is remarkably lowered, so that it cannot be used for applications requiring alkali resistance.

  Japanese Laid-Open Patent Publication No. 57-187246 discloses a metal coated with an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer resin having a low unsaturated carboxylic acid content. However, in this case as well, it is difficult to make the resin layer 10 μm or less because the film-formed resin is covered with metal.

  When dispersing an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer resin having a low unsaturated carboxylic acid content in an aqueous medium, JP-A-62-252478, JP-A-7-82423, The method described in JP-A-9-296081 requires various emulsifiers or compounds having protective colloid action.

  However, in such a method, the system contains a highly hydrophilic emulsifier and a compound having a protective colloid action, and these remain in the film even after drying, so that the water resistance of the formed film is remarkably high. There exists a problem that it falls and sufficient rust prevention property is not acquired. Furthermore, coatings containing an emulsifier and a compound having a protective colloid action are not preferable from the environmental and hygienic viewpoints because they may bleed out. In addition, when a compound having a protective colloid action or the like is used in combination, the original properties of the polyolefin resin are impaired because they plasticize the resin. That is, it has been required to disperse the polyolefin resin finely and uniformly in the aqueous medium without substantially adding a compound that remains in the coating after drying.

Problems to be solved by the invention

  The inventors of the present invention are capable of thin coating with respect to the above problems, and have excellent rust prevention, alkali resistance, water resistance, solvent resistance, workability, and good adhesion to metal materials. It is intended to provide a rust-preventive coating composition that has excellent properties, can be easily formed at low temperatures, and is excellent in transparency of the resulting film, and a laminated metal material having a film obtained therefrom It is.

Means for solving the problem

[Means for Solving the Problems]
As a result of diligent research, the present inventors applied a coating agent containing a specific resin composition to the surface of a metal material to form a layer composed of the resin composition, thereby forming a number of excellent properties described above. The present inventors have found that the present invention has developed performance and have reached the present invention.
That is, the gist of the present invention is as follows.
(1) An aqueous dispersion containing the following polyolefin resin and an organic amine compound , wherein the polyolefin resin has a number average particle size of 1 μm or less and has an emulsifier component or protective colloid action in the aqueous dispersion The coating agent composition for rust prevention characterized by not containing substantially.
Polyolefin resin:
(A1) unsaturated carboxylic acid or anhydride thereof,
(A2) ethylene hydrocarbon,
(A3) A copolymer composed of at least one compound represented by any one of the following formulas (I) to (IV), wherein the mass ratio of each component (A1) to (A3) is Polyolefin resin satisfying the formulas (1) and (2).
0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 <5 (1)
(A2) / (A3) = 55 / 45-99 / 1 (2)
[Chemical 2]
(2) The rust preventive coating composition according to (1), wherein the polyolefin resin has a melt flow rate at 190 ° C. under a load of 2160 g of 0.1 to 500 g / 10 minutes.
(3) The prevention according to (1) or (2), wherein the unsaturated carboxylic acid or its anhydride (A1) component is at least one selected from maleic anhydride, acrylic acid or methacrylic acid Rust coating composition.
(4) The antirust coating agent composition according to any one of (1) to (3), wherein the ethylene-based hydrocarbon (A2) is ethylene.
(5) The anticorrosive coating composition according to any one of (1) to (4), wherein the compound (A3) is a compound represented by the formula (I).
(6) The polyolefin resin is an ethylene-acrylic acid ester-maleic anhydride terpolymer or an ethylene-methacrylic acid ester-maleic anhydride terpolymer (1) to (5), The coating agent composition for rust prevention according to any one of the above.
(7) The coating agent composition for rust prevention according to any one of (1) to (6), further comprising a polyvalent metal ion.
(8) The coating agent composition for rust prevention according to any one of (1) to (7), further comprising inorganic particles having an average particle diameter of 0.005 to 10 μm.
(9) The coating composition for rust prevention according to any one of (1) to (8), further comprising a phosphate compound.
(10) anti-corrosion according to any of per 100 parts by weight of the resin in the aqueous dispersion, further a crosslinking agent characterized by containing 0.01 to 100 parts by weight (1) - (9) Coating agent composition.
(11) A laminated metal material obtained by providing a film obtained by drying the rust-preventive coating agent composition according to any one of (1) to (10) on a metal material.
(12) The laminated metal material according to (11), wherein the metal material is any one of galvanized steel, copper material, and aluminum material.
(13) The laminated metal material according to (11) or (12), wherein the film thickness is 0.1 to 10 μm.
(14) A method for producing a laminated metal material, comprising applying the rust-preventive coating agent composition according to any one of (1) to (10) to a metal material and then drying at 30 to 250 ° C.

  The present invention will be described in detail below. The anticorrosive coating agent composition is abbreviated as “coating agent composition”.

  The polyolefin resin used in the present invention contains an unsaturated carboxylic acid or its anhydride (A1) component in an amount of 0.01% by mass or more and less than 5% by mass based on the entire resin [(A1) + (A2) + (A3)]. More preferably, it is necessary to contain 0.1% by mass or more and less than 5% by mass, more preferably 0.5% by mass or more and less than 5% by mass, and most preferably 1 to 4% by mass. When the content of the component (A1) is less than 0.01% by mass, it becomes difficult to make the resin aqueous (liquefaction) and it is difficult to obtain a good aqueous dispersion. On the other hand, when the content of the unsaturated carboxylic acid or its anhydride is 5% by mass or more, it becomes easy to make it aqueous, but the mixing stability with other additives may be lowered.

  The unsaturated carboxylic acid or anhydride thereof that can be used as the component (A1) of the polyolefin resin is a compound having at least one carboxyl group or acid anhydride group in the molecule (in the monomer unit), specifically Examples thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, and the like, as well as unsaturated dicarboxylic acid half esters and half amides. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable. Moreover, the unsaturated carboxylic acid should just be copolymerized in polyolefin resin, The form is not limited, For example, random copolymerization, block copolymerization, graft copolymerization etc. are mentioned.

  In the polyolefin resin used in the present invention, the component (A3) represented by any of the following formulas (I) to (IV) is necessary as a constituent component, and this component imparts hydrophilicity to the polyolefin resin. Even if the component (A1) is less than 5% by mass, it can be made aqueous without adding an emulsifier or a protective colloid. The mass ratio (A2) / (A3) between the ethylene-based hydrocarbon (A2) component and the (A3) component must be in the range of 55/45 to 99/1, and 60/40 to 98/2. It is preferably 65/35 to 97/3, more preferably 70/30 to 97/3, and particularly preferably 75/25 to 97/3. When the ratio of the component (A3) to [(A2) + (A3)] is less than 1% by mass, it becomes difficult to make the polyolefin resin aqueous, and it is difficult to obtain a good aqueous dispersion. On the other hand, when the content ratio of the compound (A3) exceeds 45% by mass, the properties as the polyolefin resin by the component (A2) are lost, and the performance such as water resistance and alkali resistance is deteriorated.

  Examples of the ethylene hydrocarbon (A2) component constituting the polyolefin resin of the present invention include alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, and the like. A mixture of these can also be used. Among these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, and ethylene is particularly preferable.

  Examples of the component (A3) represented by any one of the above formulas (I) to (IV) constituting the polyolefin resin of the present invention include, for example, methyl (meth) acrylate represented by the formula (I), (meth) (Meth) acrylic acid esters such as ethyl acrylate and butyl (meth) acrylate, maleic acid esters such as dimethyl maleate, diethyl maleate and dibutyl maleate represented by formula (II), formula (III) (Meth) acrylic acid amides represented by formula (IV), alkyl vinyl ethers represented by formula (IV) such as methyl vinyl ether and ethyl vinyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, etc. Vinyl alcohols obtained by saponifying vinyl esters with basic compounds, etc. These mixtures can also be used. Among these, (meth) acrylic acid esters represented by the formula (I) are more preferable, and methyl (meth) acrylate or ethyl (meth) acrylate is particularly preferable.

  The polyolefin resin used in the present invention is most preferably a terpolymer comprising ethylene, methyl acrylate or ethyl acrylate, and maleic anhydride. Here, the acrylic ester unit may be converted into an acrylic acid unit by hydrolyzing a small part of the ester bond when the resin is made into an aqueous solution described later. It suffices if the ratio of each constituent component taking into account the change is within a specified range.

In addition, unsaturated carboxylic anhydride units such as maleic anhydride units constituting the polyolefin resin in the present invention form an acid anhydride structure in which the adjacent carboxyl group is dehydrated and cyclized in the dry state of the resin. In an aqueous medium containing a basic compound, a part or all of the ring is opened to facilitate the structure of a carboxylic acid or a salt thereof.
In the present invention, when the amount is defined based on the amount of carboxyl groups of the resin, the calculation is performed on the assumption that all acid anhydride groups in the resin are ring-opened to form two carboxyl groups. .

  The polyolefin resin used in the present invention may be copolymerized with a small amount of other monomers. Examples include dienes, (meth) acrylonitrile, vinyl halides, vinylidene halides, carbon monoxide, sulfur disulfide, and the like.

  The polyolefin resin used in the present invention has a melt flow rate of 0.1 to 500 g / 10 min, preferably 0.1 to 400 g / 10 min, more preferably 0.1 to 300 g / 10 min, at 190 ° C. and a load of 2160 g, which is a measure of molecular weight. More preferably 0.5 to 250 g / 10 min, most preferably 1 to 250 g / 10 min can be used. When the melt flow rate of the polyolefin resin is less than 0.1 g / 10 min, it becomes difficult to make the resin water-based and it is difficult to obtain a good aqueous dispersion. On the other hand, when the melt flow rate of the polyolefin resin exceeds 500 g / 10 min, the film obtained from the aqueous dispersion becomes hard and brittle, and the mechanical strength and workability deteriorate.

  The method for synthesizing the polyolefin resin used in the present invention is not particularly limited, but it is preferable not to use an emulsifier or a protective colloid in view of the gist of the present invention. Generally, it is obtained by high-pressure radical copolymerization of a monomer constituting the polyolefin resin in the presence of a radical generator. In addition, the unsaturated carboxylic acid or its anhydride may be graft copolymerized (grafted modification).

  In the aqueous dispersion of the present invention, the above polyolefin resin is dispersed or dissolved in an aqueous medium. Here, the aqueous medium is a medium composed of a liquid containing water as a main component, and may contain a water-soluble organic solvent or a basic compound described later.

  The number average particle diameter of the polyolefin resin particles dispersed in the aqueous dispersion must be 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less, still more preferably 0.2 μm or less, Particularly preferred is less than μm. The particle size distribution is not particularly limited. If it exceeds 1 μm, the particles are liable to settle and storage stability is lowered.

  The resin content in the aqueous dispersion of the present invention can be appropriately selected depending on the film forming conditions, the desired thickness and performance of the resin film, and is not particularly limited. However, the viscosity of the coating composition is kept at an appropriate level. And 1-60 mass% is preferable at the point which expresses favorable film formation ability, 3-55 mass% is more preferable, 5-50 mass% is further more preferable, 10-45 mass% is especially preferable.

The aqueous dispersion of the present invention is characterized by substantially not containing an emulsifier or a compound having a protective colloid action, and can maintain a polyolefin resin stably in an aqueous medium with a number average particle diameter of 1 μm or less without using them. can do. Since the emulsifier and the compound having a protective colloidal action are generally non-volatile, they remain in the polyolefin resin even after the coating is formed, and have a function of plasticizing the coating, with coating properties, particularly rust prevention, water resistance, It causes a decrease in alkali resistance.
Here, “substantially free of an emulsifier or a compound having a protective colloid effect” means that in the production of the aqueous dispersion of the present invention, these non-volatile substances are used for the purpose of promoting aqueous formation and stabilizing the aqueous dispersion. By not actively adding drugs or compounds to the system, this means that they are not contained as a result. The content of such a compound is particularly preferably zero, but may be less than 0.1% by mass with respect to the polyolefin resin component as long as the effects of the present invention are not impaired.

  Examples of the emulsifier referred to in the present invention include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide. Examples thereof include compounds having a polyoxyethylene structure such as copolymers and sorbitan derivatives, and amphoteric emulsifiers include lauryl betai , Lauryl dimethylamine oxide, and the like.

  The compounds having protective colloidal action include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone, polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing Acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less, such as polypropylene wax and carboxyl group-containing polyethylene-propylene wax, and salts thereof, acrylic acid-maleic anhydride copolymers and salts thereof, styrene- (meth) acrylic acid Copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer Carboxyl group-containing polymers having unsaturated carboxylic acid content of 10% by mass or more and their salts, polyitaconic acid and salts thereof, water-soluble acrylic copolymers having amino groups, gelatin, gum arabic, casein, etc. Examples thereof include compounds that are used as fine particle dispersion stabilizers.

  In the aqueous dispersion of the present invention, the carboxyl group in the polyolefin resin is preferably neutralized with a basic compound. Aggregation between the fine particles is prevented by the electric repulsive force between the carboxyl anions generated by neutralization, and stability is imparted to the aqueous dispersion.

  The basic compound used in making the aqueous solution may be any compound that can neutralize the carboxyl group. As the basic compound, in addition to metal hydroxides such as LiOH, KOH, and NaOH, compounds that volatilize during film formation are preferred from the viewpoint of the water resistance of the film, among which the boiling point is 30 to 250 ° C., more preferably 50 to 200. Organic amine compounds at 0 ° C. are preferred. When the boiling point is less than 30 ° C., the rate of volatilization at the time of making the resin aqueous later described increases, and the aqueous formation may not proceed completely. When the boiling point exceeds 250 ° C., it becomes difficult to disperse the organic amine compound from the resin film by drying, and the water resistance of the film may deteriorate.

  Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, and 3-ethoxypropylamine. , 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, N- Examples thereof include ethyl morpholine. The addition amount of the basic compound is preferably 0.5 to 3.0 times equivalent, more preferably 0.8 to 2.5 times equivalent, and particularly preferably 1.01 to 2.0 times equivalent to the carboxyl group in the polyolefin resin. If the amount is less than 0.5 times equivalent, the effect of adding a basic compound is not recognized. If the amount exceeds 3.0 times equivalent, the drying time during film formation may be long, or the aqueous dispersion may be colored.

  In the present invention, it is preferable to add an organic solvent at the time of aqueous formation in order to promote aqueousization of the polyolefin resin and reduce the dispersed particle size. The amount of the organic solvent to be used is preferably 40% by mass or less of the aqueous dispersion, more preferably 1 to 40% by mass, further preferably 2 to 35% by mass, and particularly preferably 3 to 30% by mass. When the amount of the organic solvent exceeds 40% by mass, it cannot be regarded as an aqueous medium substantially and does not deviate from one of the objects of the present invention (environmental protection). Stability may be reduced.

  In general, a part of the organic solvent contained in the aqueous dispersion can be distilled out of the system by an operation called stripping. In the aqueous dispersion of the present invention, the aqueous dispersion can be obtained by this operation. The amount of the organic solvent in the solvent may be appropriately reduced and can be 10% by mass or less, and 3% by mass or less is preferable from the environmental viewpoint. In order to distill off the organic solvent by stripping, it is necessary to take measures in the production process such as increasing the pressure reduction of the equipment or extending the operation time, so the lower limit of the amount of organic solvent considering such productivity is 0.01. It is about mass% (the detection limit of the analytical instrument used for the measurement of the present invention). However, even if it is less than 0.01% by mass, the performance as an aqueous dispersion is not particularly problematic. Even if the amount of the organic solvent is reduced by stripping, the aqueous dispersion of the present invention is not particularly affected in terms of performance and can be used favorably for various applications.

  Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring at normal pressure or reduced pressure to distill off the organic solvent. The organic solvent content can be quantified by gas chromatography. Further, since the solid content concentration is increased by distilling off the aqueous medium, for example, in the case where the viscosity increases and the workability deteriorates, water is added to the aqueous dispersion in advance. You can also.

  As an organic solvent, in order to obtain a good aqueous dispersion, one or more atoms (specifically, oxygen, nitrogen, fluorine, chlorine) having Pauling electronegativity of 3.0 or more are contained in the molecule. It is preferable to use what is doing. Among them, those having a solubility in water at 20 ° C. of 5 g / L or more are preferably used, and more preferably 10 g / L or more.

  Specific examples of the organic solvent used in the present invention include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl. Alcohols such as alcohol, tert-amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and isophorone , Ethers such as tetrahydrofuran, dioxane, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, acetic acid-3-meth Cibutyl, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate, etc., ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate , Glycol derivatives such as diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate Furthermore, 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, and the like are preferable. Among them, those having a boiling point of 30 to 250 ° C. are preferable. Particularly preferred is ~ 200 ° C. These organic solvents may be used in combination of two or more. In addition, when the boiling point of the organic solvent is less than 30 ° C., the ratio of volatilization when the resin is made aqueous increases, and the efficiency of aqueous formation may not be sufficiently increased. An organic solvent having a boiling point exceeding 250 ° C. is difficult to be scattered from the resin film by drying, and the rust prevention and water resistance of the film may be deteriorated.

  Among the above organic solvents, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, and the like are highly effective in promoting the aqueous formation of the resin and are easy to remove the organic solvent from the aqueous medium. Dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether are preferred, and isopropanol is particularly preferred from the viewpoint of low temperature drying properties.

Next, the manufacturing method of the polyolefin resin aqueous dispersion is demonstrated.
The method for obtaining the aqueous polyolefin resin dispersion of the present invention is not particularly limited. For example, the above-described components, that is, a polyolefin resin having a specific composition, a basic compound, an organic solvent, and water can be preferably sealed. A method of heating and stirring in a container can be employed, and this method is most preferred. According to this method, a polyolefin resin having a specific composition can be satisfactorily made into an aqueous dispersion without substantially adding an emulsifier component or a compound having a protective colloid effect.

  Any container may be used as long as it is equipped with a tank into which a liquid can be charged and can appropriately stir the mixture of the aqueous medium and the resin powder or granular material charged into the tank. As such a device, a device widely known to those skilled in the art as a solid / liquid stirring device or an emulsifier can be used, and a device capable of pressurization of 0.1 MPa or more is preferably used. The stirring method and the rotation speed of stirring are not particularly limited.

  The shape of the polyolefin resin used for the aqueous treatment is not particularly limited, but it is preferable to use a granular or powdery particle having a particle diameter of 1 cm or less, preferably 0.8 cm or less from the viewpoint of increasing the aqueousization speed.

  An aqueous medium composed of water, a basic compound and an organic solvent, and a granular or powdery polyolefin resin are put into the tank of this apparatus, and they are preferably stirred and mixed at a temperature of 40 ° C. or lower. Next, while maintaining the temperature in the tank at 80 to 200 ° C., preferably 90 to 200 ° C., more preferably 100 to 200 ° C., the polyolefin resin is sufficiently aqueousized by preferably continuing stirring for 5 to 120 minutes. And then cooling to 40 ° C. or lower, preferably with stirring, to obtain an aqueous dispersion. When the temperature in the tank is less than 80 ° C., it becomes difficult to make the polyolefin resin aqueous. When the temperature in the tank exceeds 200 ° C., the molecular weight of the polyolefin resin may decrease. As a heating method in the tank, heating from the outside of the tank is preferable. For example, the tank can be heated using oil or water, or a heater can be attached to the tank for heating. Examples of the cooling method in the tank include a method of naturally cooling at room temperature and a method of cooling using oil or water at 0 to 40 ° C.

  After this, jet pulverization may be further performed as necessary. The jet pulverization treatment here means that a fluid such as an aqueous polyolefin resin dispersion is ejected from pores such as nozzles and slits under high pressure, and resin particles or resin particles collide with a collision plate or the like. Further, the resin particles are further refined by mechanical energy. Specific examples of the apparatus for this purpose include a homogenizer manufactured by APVGAULIN, a microfluidizer M-110E / H manufactured by Mizuho Industries, Ltd., and the like.

  Examples of a method for adjusting the solid content concentration of the aqueous dispersion thus obtained include a method in which the aqueous medium is distilled off or diluted with water so as to obtain a desired solid content concentration.

  As described above, the aqueous dispersion of the present invention is obtained by preparing a uniform liquid by dispersing or dissolving a polyolefin resin in an aqueous medium. Here, the uniform liquid state means that, in terms of appearance, a portion where the solid content concentration is locally different from other portions such as precipitation, phase separation or skinning is not found in the aqueous dispersion. Say.

Further, the aqueous yield in the production of the aqueous dispersion can be known from the amount of coarse particles remaining in the obtained aqueous dispersion. Specifically, the aqueous dispersion is filtered under pressure (air pressure 0.2 MPa) through a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and the amount of resin remaining on the filter is measured.
Even when the amount of residual resin is large and the yield is low, if the above-mentioned filtration is performed during the production process to remove such coarse particles, it can be used as an aqueous dispersion in the subsequent steps.
Although the aqueous yield in the present invention may be slightly reduced depending on the conditions, it is generally very good, and aqueous formation is achieved with almost no coarse particles remaining.

The aqueous polyolefin resin dispersion thus produced is excellent in low-temperature film-forming properties, and can form a transparent film even under drying conditions below the melting point of the resin.
Here, “haze (cloudiness value)” of a coated film coated with an aqueous polyolefin resin dispersion at room temperature is used as a measure of film forming property and transparency. A PET film having a haze of 2.0 to 5.0 (%) is used as a substrate, and this is coated with a polyolefin resin aqueous dispersion with a coating thickness of 2 μm and dried at 25 ° C. The haze of the entire coated film thus obtained is 20.0 (%) or less. This value is more preferably 15.0 (%) or less, and particularly preferably 10.0 (%) or less.

  Since the coating composition of the present invention has a low unsaturated carboxylic acid content in the resin component, it is excellent in mixing stability with various additives. Therefore, an additive as described below can be added to further improve the rust prevention performance.

  In the present invention, it is preferable to contain polyvalent metal ions, inorganic particles, a phosphate compound, and a crosslinking agent component in the coating agent composition in order to further improve rust prevention.

  Examples of the polyvalent metal ion include alkaline earth metals such as magnesium, calcium and barium, and ions such as zinc, iron, nickel, copper and aluminum. In addition, you may use these in mixture of 2 or more types. The amount of polyvalent metal ions added is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, based on the amount of carboxyl groups in the polyolefin resin. When the addition amount of polyvalent metal ions is less than 10 mol%, the degree of the effect of improving rust prevention is small, and when the addition amount exceeds 90 mol%, the stability of the coating composition may be deteriorated.

  Add inorganic particles such as magnesium oxide, zinc oxide, tin oxide and titanium oxide, inorganic particles such as calcium carbonate and silica, and water-swellable layered inorganic compounds such as vermiculite, montmorillonite and hectorite as inorganic particles. Can do. Of these, silica and water-swellable layered inorganic compounds are preferred from the viewpoint of rust prevention, and silica is particularly preferred. The average particle diameter of these inorganic particles is preferably 0.005 to 10 μm, more preferably 0.005 to 5 μm from the viewpoint of the stability of the aqueous dispersion. In addition, you may use these in mixture of 2 or more types. The added amount of the inorganic particles is preferably 1 to 1000 parts by mass, more preferably 2 to 100 parts by mass, further preferably 3 to 50 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyolefin resin. . When the added amount of inorganic particles is less than 1 part by mass, the degree of the effect of improving rust prevention is small, and when the added amount exceeds 1000 parts by mass, the adhesion to metal is reduced or a uniform film is obtained. There may not be.

  In order to improve the dispersibility of the inorganic particles, the coating composition to which the inorganic particles are added is preferably subjected to a high-pressure dispersion treatment such as a homogenizer treatment, a ball mill treatment, a paint shaker treatment, or the jet pulverization treatment described above.

  As the phosphate compound, a metal phosphate compound is preferable, and from the viewpoint of rust prevention, a polyvalent metal phosphate compound is particularly preferable, and examples thereof include zinc phosphate and aluminum phosphate. Can do. In addition, the phosphate here means the phosphate in a broad sense including orthophosphate, polyphosphate, metaphosphate, etc., and may take any of these phosphate structures. The addition amount of the phosphate compound is preferably 1 to 80 parts by mass, more preferably 3 to 80 parts by mass, further preferably 5 to 70 parts by mass, and 10 to 70 parts by mass with respect to 100 parts by mass of the polyolefin resin. Particularly preferred. When the addition amount of the metal salt compound is less than 1 part by mass, the degree of the effect of improving rust prevention is small, and when the addition amount exceeds 80 parts by mass, the adhesion to metal and the workability tend to be lowered.

  When the solubility of the phosphate compound in the aqueous medium is low, in order to improve the dispersibility of the metal salt compound, the resin aqueous dispersion to which the metal salt compound is added is subjected to a homogenizer treatment, a ball mill treatment, a paint shaker treatment, Alternatively, it is preferable to perform a dispersion process such as the jet pulverization process described above. Among them, it is preferable to perform high-pressure dispersion treatment such as jet pulverization treatment from the viewpoint of improving dispersibility and film transparency.

  The content of the crosslinking agent component is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, and particularly preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin in the resin aqueous dispersion. When the content of the crosslinking agent is less than 0.1 parts by mass, the degree of improvement in rust prevention is small, and when it exceeds 100 parts by mass, not only the physical properties other than the rust prevention property, particularly processability, The properties of the polyolefin resin are lost. Examples of the crosslinking agent include a crosslinking agent having self-crosslinking property, a compound having a plurality of functional groups that react with a carboxyl group in the molecule, a metal capable of forming a complex by coordination of a plurality of carboxyl groups or carboxylate anions, and the like. For example, an isocyanate compound, a melamine compound, a benzoguanamine compound, a urea compound, an epoxy compound, an oxazoline group-containing compound, a carbodiimide compound, a zirconium salt compound, and a silane coupling agent are preferable. Among these, a melamine compound, an epoxy compound, an oxazoline group-containing compound, a zirconium salt compound, and a silane coupling agent are particularly preferable for enhancing the rust prevention property of the coated metal material. These crosslinking agents can be used in combination.

  Furthermore, various agents such as leveling agents, antifoaming agents, anti-waxing agents, pigment dispersants, UV absorbers, pigments such as titanium oxide, zinc white, carbon black, etc. A dye may be added. In addition, organic or inorganic compounds other than those described above can be added to the aqueous resin dispersion as long as the stability of the aqueous resin dispersion is not impaired.

  In the present invention, the metal material on which the resin aqueous dispersion is coated is not particularly limited, but among them, when used for galvanized steel, copper material, or aluminum material, the antirust effect is high, which is preferable. Examples of the galvanized steel plating method include an electroplating method and a hot dipping method, but any method may be used. The surface of the galvanized steel may be subjected to chemical conversion treatment. As the chemical conversion treatment method, the one treated with a chemical conversion solution not containing chromium is preferable in consideration of the environment, but the coating agent using the aqueous resin dispersion of the present invention is used for galvanized steel subjected to chromate treatment. However, rust prevention can be exhibited. The galvanized steel is typically used in the form of a plate, and examples of the copper material include a copper plate and a copper wire, and examples of the aluminum material include an aluminum foil, an aluminum foil, an aluminum sheet, and an aluminum plate. It is done.

  The aqueous resin dispersion of the present invention is excellent in film forming ability and can be easily formed by a known method. For example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc., uniformly coats various substrate surfaces, and at room temperature as required After setting in the vicinity, a uniform resin film can be formed in close contact with the surfaces of various substrates by subjecting it to drying or heat treatment for drying and baking. As a heating device at this time, a normal hot air circulation type oven, an infrared heater, or the like may be used. In addition, the heating temperature and the heating time are appropriately selected depending on the characteristics of the base material to be coated, the type of curing agent described later, the blending amount, etc. The heating temperature is preferably 30 to 250 ° C, more preferably 60 to 230 ° C, particularly preferably 80 to 210 ° C, and the heating time is preferably 1 second to 20 minutes, more preferably 5 seconds to 15 minutes, 10 seconds to 10 minutes is particularly preferable. In addition, when a crosslinking agent is added, in order to sufficiently advance the reaction between the carboxyl group in the polyolefin and the crosslinking agent, it is desirable to appropriately select the heating temperature and time depending on the type of the crosslinking agent.

In addition, since the aqueous resin dispersion of the present invention has a small number average particle diameter and is in a liquid state, it can be applied thinly on the surface of the substrate, for example, 0.1 to 10 μm as a resin film. In consideration of rust prevention, transparency, workability, etc., 0.2 to 8 μm is preferable, and 0.2 to 5 μm is particularly preferable. When the thickness of the resin coating is less than 0.1 μm, the effect of rust prevention becomes small.
In addition, in order to adjust the thickness of the resin film, in addition to appropriately selecting the apparatus used for coating and its use conditions, an aqueous resin dispersion having a concentration suitable for the desired thickness of the resin film is used. It is preferable to do. The concentration at this time can be adjusted by the charged composition at the time of preparation. In addition, the resin aqueous dispersion once prepared may be adjusted by appropriately diluting or concentrating.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
Various characteristics were measured or evaluated by the following methods.
(1) Structure of polyolefin resin It was obtained by performing ¹ H-NMR analysis (manufactured by Varian, 300 MHz) at 120 ° C. in orthodichlorobenzene (d ₄ ).
(2) Residual Amount of Ester Group after Aqueous Treatment After the aqueous polyolefin treatment was dried at 150 ° C., ¹ H-NMR analysis at 120 ° C. in orthodichlorobenzene (d ₄ ) (manufactured by Varian) 300 MHz), and the residual ratio (%) of the ester group was determined with the amount of the ester group of the (meth) acrylic acid ester before being made aqueous as 100%.
(3) Solid content concentration of polyolefin resin aqueous dispersion An appropriate amount of the polyolefin dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight to determine the polyolefin resin solid content concentration.
The rotational viscosity of the aqueous dispersion at a temperature of 20 ° C. was measured using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec.
(5) Average particle diameter of polyolefin resin particles The number average particle diameter was determined using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340) manufactured by Nikkiso Co., Ltd.
(6) Aqueousization yield Resin mass remaining on the filter when the aqueous resin dispersion is hydrofiltered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) (air pressure 0.2 MPa) The yield was calculated from the mass of charged resin.
(7) Appearance of aqueous dispersion The color tone of the aqueous resin dispersion was evaluated by visual observation.
(8) Pot life When the aqueous polyolefin resin dispersion was allowed to stand at room temperature for 90 days, the appearance of the aqueous dispersion was evaluated in the following three stages.
○: No change in appearance.
Δ: Thickening is observed.
X: Solidification, aggregation and precipitation are observed.
(9) Water resistance evaluation method The coated steel sheet was evaluated after being left at room temperature for 1 day. The coating film was rubbed several times with a cloth wetted with water, and the state of the coating film was visually evaluated.
○: No change, Δ: The coating film is cloudy, ×: The coating film is completely dissolved (10) Alkali resistance evaluation method
A NaOH aqueous solution adjusted to pH 12.0 at 20 ° C. was heated to 45 ° C. and stirred, and the coated metal plate was immersed in this aqueous solution for 3 minutes. Then, it washed with water and evaluated the state of the coating film visually.
○: No change, Δ: Coating film is cloudy, ×: Coating film is dissolved or peeled (11) Solvent resistance evaluation method The coated steel sheet was evaluated after standing at room temperature for 1 day. The coating film was rubbed several times with a cloth wetted with ethanol, and the state of the coating film was visually evaluated.
○: No change, Δ: Coating film is cloudy, ×: Coating film is completely dissolved (12) Rust prevention evaluation method The coated steel sheet was evaluated after standing at room temperature for 1 day. Using a salt spray tester of JIS Z-2371 standard, a 5 mass% NaCl aqueous solution was sprayed at 35 ° C., and the coating state after 100 hours was evaluated.
◎: Rust area ratio less than 5%, ○: Rust area ratio 5% or more, less than 10%, △: Rust area ratio 10% or more, less than 50%, ×: Rust area ratio 50% or more (13) Processability evaluation method The coated steel sheet was evaluated after being left at room temperature for 1 day. The coated steel plate was bent so that the surface opposite to the painted surface was in contact, and the presence or absence of cracks in the bent portion was examined.
○: No crack, ×: Crack (14) Adhesion evaluation (I): Cross-cut tape peeling The coated steel sheet was evaluated after standing at room temperature for 1 day. Conforms to JIS K5400 8.5.2. The grid area of 1 mm × 1 mm × 100 pieces was peeled off with an adhesive tape and evaluated by the number remaining without peeling. “N / 100” indicates that n pieces out of 100 grids remain after the test.
(15) Adhesion evaluation (II): Erichsen processing The coated steel sheet was evaluated after standing at room temperature for 1 day. Eriksen processing of 8 mm was performed, and after the adhesive tape was adhered to the processed part, the tape was peeled off vigorously and the state of the coating film was visually evaluated.
○: No peeling, x: peeling (16) Organic solvent content in aqueous polyolefin resin dispersion Shimadzu Corporation gas chromatograph GC-8A [FID detector used, carrier gas: nitrogen, column packing material (GL (Science): PEG-HT (5%)-Uniport HP (60/80 mesh), Column size: Diameter 3 mm x 3 mm, Sample input temperature (injection temperature): 150 ° C, Column temperature: 60 ° C, Internal standard : N-butanol], an aqueous resin dispersion or a solution obtained by diluting this with water was directly put into the apparatus, and the content of the organic solvent was determined. The detection limit was 0.01% by mass.
(17) Haze (cloudiness value)
According to JIS K7105, “Haze (%)” was measured using NDH2000 “turbidity and haze meter” manufactured by Nippon Denshoku Industries Co., Ltd. A haze 2.8% PET film (thickness 12μm) is coated with an aqueous polyolefin resin dispersion using a Meyer bar so that the coating thickness after drying is 2μm, and then left in an atmosphere at 25 ° C for 3 days. And dried to produce a coated film. Thus, the haze of the whole coat film produced was measured.

  Table 1 shows the composition of the resin used. The melting point of the resin described in Table 1 is a value measured by DSC (measuring device: DSC-7 manufactured by Perkin Elmer), and the melt flow rate is a method described in JIS 6730 (190 ° C., 2160 g load). It is a measured value.

(Manufacture of coating agent composition E-1)
3. Using a stirrer equipped with a heat-resistant 1-liter glass container with a heater, 60.0 g of polyolefin resin (Bondaine HX-8210, manufactured by Sumitomo Chemical Co., Ltd.), 60.0 g of isopropanol (hereinafter, IPA); 5 g (1.2 times equivalent to the carboxyl group of maleic anhydride in the resin) of triethylamine (hereinafter TEA) and 175.5 g of distilled water are charged in a glass container and stirred at a rotation speed of 300 rpm. As a result, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a milky white uniform polyolefin resin aqueous dispersion was obtained. This was used as a coating agent composition E-1.
Various properties of the coating composition are shown in Table 2. The number average particle diameter was 0.068 μm, and the distribution was also one peak, and the polyolefin resin was dispersed in a good state in the aqueous medium. Furthermore, the pot life of the aqueous dispersion was 90 days or longer. In addition, the ester group residual ratio of the resin after being made aqueous was 99%, and 1% of ethyl acrylate was hydrolyzed. This ester group residual ratio was 99% at room temperature for 90 days and remained unchanged after standing. The haze of the coated film coated with this coating composition by the above-described method was 2.8%, and the transparency was good.

(Production of coating agent composition E-2)
Using the polyolefin resin (B) (Bondyne TX-8030, manufactured by Sumitomo Chemical Co., Ltd.), except that the amount of IPA was changed as shown in Table 2, the aqueous polyolefin resin dispersion was prepared in the same manner as in the production of the coating composition E-1. This was used as coating agent composition E-2. Various characteristics of this coating agent composition are shown in Table 2.

(Manufacture of coating agent composition E-3)
E-1 250 g and distilled water 85 g were charged into a 0.5 liter 2-neck round bottom flask, a mechanical stirrer and a Liebig condenser were installed, and the flask was heated in an oil bath to distill off the aqueous medium. When about 90 g of the aqueous medium was distilled off, heating was terminated and the mixture was cooled to room temperature. After cooling, the liquid component in the flask was subjected to pressure filtration (air pressure 0.2 MPa) with a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave), and the solid content concentration of the filtrate was measured to be 20.5 mass. %Met. While stirring the filtrate, distilled water was added to adjust the solid content concentration to 20.0% by mass. The obtained aqueous dispersion was designated coating agent composition E-3.
The content of the organic solvent (IPA) in this coating agent composition was 0.3% by mass. Moreover, when the external appearance of this coating agent composition was observed visually, it was a uniform thing in which precipitation and layer separation were not seen, the number average particle diameter was 0.070 micrometer, and the distribution was also 1 mountain. Moreover, even if it was left to stand at room temperature for 90 days, the appearance did not change and was stable. The haze of the coated film coated with this coating composition by the above-described method was 3.3%, and the transparency was good.

(Manufacture of coating agent composition E-4)
Except having used coating agent composition E-2, polyolefin resin aqueous dispersion was obtained by operation according to manufacture of coating agent composition E-3, and this was made into coating agent composition E-4. Various properties of the coating composition are shown in Table 2.

(Manufacture of coating agent composition H-1)
45.0 g of ethylene-acrylic acid copolymer resin (Primacol 5980I, 20% by weight acrylic acid copolymer, manufactured by Dow Chemical) ), 12.6 g (1.0 times equivalent to the carboxyl soot of acrylic acid in the resin) of TEA and 242.4 g of distilled water were charged into a crow container, and stirred at a rotation speed of 300 rpm. However, no sedimentation of resin particles was observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 100 to 105 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) As a result, a slightly cloudy aqueous dispersion was obtained. This was designated coating agent composition H-1. At this time, almost no resin remained on the filter.

Example 1
On hot-dip galvanized steel sheet (made by Nippon Test Panel Osaka Co., Ltd., size 70 mm × 150 mm × 0.8 mm ^t , Examples 2 to 13 and Comparative Examples 1 and 2) Was coated with a Mayer bar and dried and heat treated at 200 ° C. for 2 minutes to obtain a coated steel sheet. The coating thickness after drying was 2 μm. Table 3 shows the performance evaluation results. The alkali resistance was good.

Examples 2-4
A coated steel sheet was prepared by performing the same operation as in Example 1 except that E-2 (Example 2), E-3 (Example 3), and E-4 (Example 4) were used as the coating agent composition. Obtained. Table 3 shows the performance evaluation results.

Example 5
A coated steel sheet was obtained by performing the same operation as in Example 1 except that the drying heat treatment was changed as shown in Table 3 using the coating agent composition E-3. Table 3 shows the performance evaluation results.

Example 6
A coating agent composition was prepared by adding and stirring 20 parts by mass of silica (Aerosil 380, manufactured by Nippon Aerosil Co., Ltd.) with respect to 100 parts by mass of the resin in the coating agent composition E-1. Using this coating agent composition, the same operation as in Example 1 was performed to obtain a coated steel sheet. Table 3 shows the performance evaluation results. Addition of silica improved rust prevention.

Example 7
Using the coating composition prepared in Example 6, the same operation as in Example 1 was performed except that the film thickness after drying was changed as shown in Table 3 to obtain a coated steel sheet. Table 3 shows the performance evaluation results. Various performances were good even if the film thickness after drying was thin.

Example 8
10 parts by mass of an inorganic layered compound (Kunimine Industries, Ltd., Kunipia F (average particle size 0.1 to 0.5 μm), hereinafter abbreviated as KF) was added to 100 parts by mass of the resin in the coating composition E-2 and stirred. Thereafter, 150 MPa × 2 times (Mizuho Kogyo Microfluidizer) was applied to prepare a coating composition. Using this coating agent composition, the same operation as in Example 1 was performed to obtain a coated steel sheet. Table 3 shows the performance evaluation results. When the inorganic layered compound was added, the rust prevention property was improved.

Example 9
After adding 40 parts by mass of aluminum phosphate (Ishizu Pharmaceutical Co., Ltd.) to 100 parts by mass of the resin in coating agent composition E-1, stirring, 150 MPa × twice (Mizuho Kogyo Microfluidizer) treatment To prepare a coating composition. Using this coating agent composition, the same operation as in Example 1 was performed to obtain a coated steel sheet. Table 3 shows the performance evaluation results. Addition of a phosphate compound improved rust prevention.

Example 10
A coating agent composition was prepared by adding 30 mol% of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) to the carboxyl group in the resin in the coating agent composition E-3 and stirring. Using this coating agent composition, the same operation as in Example 1 was performed to obtain a coated steel sheet. Table 3 shows the performance evaluation results. Addition of calcium hydroxide improved rust prevention.

Examples 11-13
10 parts by weight of a melamine compound (Cymel 327, manufactured by Mitsui Cytec, Example 11) as a crosslinking agent with respect to 100 parts by weight of the resin in the coating agent composition E-3, 10 parts by weight of an oxazoline group-containing compound (Epocross WS) -700, manufactured by Nippon Shokubai Co., Ltd., Example 12) 5 parts by mass of an epoxy compound (Denacol EX-313, manufactured by Nagase Kasei Kogyo Co., Ltd., Example 13) were added and stirred to prepare a coating composition. Using this coating agent composition, the same operation as in Example 1 was performed to obtain a coated steel sheet. Table 3 shows the performance evaluation results. Addition of a cross-linking agent improved rust prevention.

Comparative Example 1
A coated steel sheet having a film thickness of 2 μm was obtained after drying by performing the same operation as in Example 1 except that H-1 was used as the coating agent composition. Table 3 shows the performance evaluation results. The performance other than the alkali resistance was almost the same as that of Example 1, but the alkali resistance was very poor.

Comparative Example 2
A coating agent composition was prepared by adding and stirring 20 parts by mass of silica (Aerosil 380, manufactured by Nippon Aerosil Co., Ltd.) with respect to 100 parts by mass of the resin in H-1. Using this coating composition, an operation according to Example 1 was performed to obtain a coated steel sheet having a thickness of 2 μm after drying. Table 3 shows the performance evaluation results. Although the rust prevention property was improved, the alkali resistance was not improved and was very bad.

Examples 14 and 15
A 0.8 mm thick copper plate (Example 14) degreased with coating agent composition E-1 and an aluminum plate (Example 15) were coated with a Mayer bar, dried and heat treated at 200 ° C. for 2 minutes, Obtained. The coating thickness after drying was 2 μm. Table 4 shows the performance evaluation results.

Comparative Examples 3 and 4
A 0.8 mm-thick copper plate (Comparative Example 3) degreased with coating agent H-1 and an aluminum plate (Comparative Example 4) were coated with a Mayer bar and subjected to a drying heat treatment at 200 ° C. for 2 minutes to obtain a coated steel plate. . The coating thickness after drying was 2 μm. Table 4 shows the performance evaluation results.

Effect of the invention

  According to the present invention, a coating agent composition having excellent rust prevention properties is obtained, and at the same time, it has alkali resistance, solvent resistance, workability, and good adhesion to a steel plate. A coating composition and a laminated metal material having a layer comprising the same are provided.

Claims (14)

An aqueous dispersion containing the following polyolefin resin and an organic amine compound , wherein the polyolefin resin has a number average particle size of 1 μm or less, and substantially contains an emulsifier component or a compound having a protective colloid action in the aqueous dispersion. A coating agent composition for rust prevention which is not contained in
Polyolefin resin:
(A1) unsaturated carboxylic acid or anhydride thereof,
(A2) ethylene hydrocarbon,
(A3) A copolymer composed of at least one compound represented by any one of the following formulas (I) to (IV), wherein the mass ratio of each component (A1) to (A3) is Polyolefin resin satisfying the formulas (1) and (2).
0.01 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 <5 (1)
(A2) / (A3) = 55 / 45-99 / 1 (2)
[Chemical 1]
The rust preventive coating composition according to claim 1, wherein the polyolefin resin has a melt flow rate at 190 ° C and a load of 2160 g of 0.1 to 500 g / 10 min.
The antirust coating agent composition according to claim 1 or 2, wherein the unsaturated carboxylic acid or its anhydride (A1) component is at least one selected from maleic anhydride, acrylic acid or methacrylic acid. object.
The coating composition for rust prevention according to any one of claims 1 to 3, wherein the ethylene-based hydrocarbon (A2) is ethylene.
The said compound (A3) is a compound shown by Formula (I), The coating agent composition for rust prevention in any one of Claims 1-4 characterized by the above-mentioned.
The polyolefin resin is an ethylene-acrylic acid ester-maleic anhydride terpolymer or an ethylene-methacrylic acid ester-maleic anhydride terpolymer. Anticorrosive coating agent composition.
Furthermore, a polyvalent metal ion is contained, The coating agent composition for rust prevention in any one of Claims 1-6 characterized by the above-mentioned.
Furthermore, the inorganic particle | grain with an average particle diameter of 0.005-10 micrometers is contained, The coating agent composition for rust prevention in any one of Claims 1-7 characterized by the above-mentioned.
Furthermore, a phosphate compound is contained, The coating agent composition for rust prevention in any one of Claims 1-8 characterized by the above-mentioned.
Per 100 parts by weight of the resin in the aqueous dispersion, further crosslinking agents anticorrosion coat composition according to claim 1, characterized in that it contains 0.01 to 100 parts by weight.
A laminated metal material comprising a metal material provided with a coating obtained by drying the rust-preventive coating agent composition according to any one of claims 1 to 10 .
The laminated metal material according to claim 11, wherein the metal material is any one of galvanized steel, copper material, and aluminum material.
The laminated metal material according to claim 11 or 12, wherein the film has a thickness of 0.1 to 10 µm.
A method for producing a laminated metal material, wherein the rust-proof coating agent composition according to any one of claims 1 to 10 is applied to a metal material and then dried at 30 to 250 ° C.