JPS60197773A - Composition for treating metal surface and method for treating metal surface therewith - Google Patents

Abstract

PURPOSE:To privide the titled compsn. which gives a film having excellent corrosion resistance, weldability, electrodepositability, and coatability, consisting of a specified composite resin and an amino resin and/or epoxy resin. CONSTITUTION:95-25wt% org. polymer contg. at least one functional group selected from among hydroxyl, carboxyl and amino groups (e.g. alkyd resin) is reacted with 5-75wt% (in terms of SiO2) di-, tri- or tetra-alkoxy (or alkoxyalkoxy)silane compd. (e.g. divinyl-diethoxysilane) in the presence of an inorg. or org. acid having a pKa of 7 or below in an alcohol solvent at a temp. of not lower than 10 deg.C, but not higher than b.p. to obtain a composite resin (A). 60- 95wt% component A and 40-5wt% amino resin and/or epoxy resin are blended together to obtain a compsn. for treating the surface of metal. A soln. contg. 25-90wt% said compsn. is applied to the phosphate- or chromate-treated metal surface.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves adding an amino resin and/or an epoxy resin to a composite resin consisting of an organic polymer containing a functional group selected from hydroxyl, carboxyl, and amino groups and a reactive silane compound. A metal surface treatment composition comprising a metal surface treatment composition and a metal surface treatment comprising applying the same to a metal surface to form a film that provides high corrosion resistance, weldability, electrodeposition paintability, and coating base properties. Regarding the method.

In recent years, the aim of making the painting process more effective in the metal painting field and reducing manufacturing costs is 1. As a result, the traditional painting method, the so-called "bost-to-paint" method for painting molded objects, is changing. This bleed plate method can omit on-site degreasing, chemical treatment, and painting processes, making it possible to significantly reduce costs. In addition, with the aim of extending the life of steel materials and reducing overall costs by thinning paint films, steel sheets are rapidly being replaced by galvanized copper sheets, alloy galvanized steel sheets, aluminium-plated steel sheets, and alloy aluminium-plated steel sheets, which have even better corrosion resistance. It has now appeared as a product. Furthermore, the rust prevention properties of these metal plates are also improved by painting them.

For example, a composite resin proposed by the present applicant in which an organic polymer and colloidal silica are chemically bonded exhibits an excellent rust-preventing effect (for example, see Japanese Patent Publication No. 54-34406), while a conventional organic resin Compared to the test material, the corrosion resistance is 5 to 10 times higher in the accelerated salt water spray test with the same coating thickness. Furthermore, as a method to further improve rust prevention, a multilayer steel plate has been proposed in which the plated steel plate described above is subjected to a known chromic acid treatment and coated with the composite resin invented by the applicant (for example, (Refer to 1982-108292).

However, the above-mentioned organic polymer invented by the present applicant -
Colloidal silica composite resin is mainly composed of water-soluble organic resin and water-dispersible colloidal silica, so the film formed from this composition has a high affinity for water and has sufficient water resistance, moisture resistance, and alkali resistance. I can't say it,
In a high-humidity environment or under an alkaline atmosphere, the formed film may absorb moisture or swell, resulting in problems such as difficulty in applying the top coat and reduced adhesion.

For example, the above-mentioned organic polymer-colloidal silica composite is used as a coating for surface-treated steel sheets, which are known to exhibit excellent corrosion resistance, and are used in applications such as single-sided coated steel sheets for automatic shell panels and home appliances. . However, when these surface-treated steel sheets are coated with a top coat, for example, degreasing with an alkaline cleaner to remove press oil during press working, or exposure to an alkaline atmosphere during cationic electrodeposition coating for automobiles, may occur. After that, the composite film swells or softens and the treated film changes in quality, which can significantly impair the adhesion of the top coat that is subsequently applied. In addition, for the purpose of high corrosion resistance, single-sided multi-layer treated steel sheets with ROMATE base treatment and water-based composite resin,
Hexavalent chromium may be eluted from the chromate layer by the alkaline cleaner treatment and contaminate the alkaline cleaner.

When such a phenomenon occurs, the surface of the bare steel sheet on the untreated side is treated with hexavalent chromium, so in many cases, the subsequent zinc phosphate chemical conversion treatment of the bare steel sheet can be achieved under specified conditions. As a result, non-uniformity of the chemical conversion coating develops, causing problems in subsequent processes.

Therefore, the present inventors have developed a composite resin that does not have the above-mentioned drawbacks.
As a result of intensive research aimed at developing a metal surface treatment composition consisting of a particularly hydrophobic composite resin, we found that an organic polymer containing at least one functional group selected from hydroxyl, carboxyl, and amino groups and silane were used. A composition consisting of a combination of a hydrophobic composite resin formed by reacting a hydrophobic compound with an amino resin and/or an epoxy resin as a crosslinking agent does not have the above-mentioned drawbacks, and can be further treated with a phosphate or a chromate. The present invention has been completed by discovering that it exhibits particularly remarkable corrosion resistance when applied to a surface-treated metal plate.

Thus, according to the present invention, (2) an organic polymer containing at least one functional group selected from a hydroxyl group, a carboxyl group, and an amino group;
60 to 95% by weight of a composite resin obtained by reacting a tri- or tetraalkoxy (t or alkoxyalkoxy) silane compound in the presence of an inorganic or organic acid at a temperature of lθ°C or higher and lower than the boiling point, and (b) an amino resin. and/or a metal surface treatment composition comprising 5 to 40% by weight of an epoxy resin, and 25 to 9% of the composition.
The organic polymer used to form the composite resin matrix in the present invention provides a metal surface treatment method characterized in that a 0% by weight (solid content) solution is applied to the surface of a metal object. is an organic polymer containing at least one mourning functional group selected from a hydroxyl group (meaning an alcoholic hydroxyl group and a hydroxyl group bonded to glycine, a so-called silanol group), a carboxyl group, and an amino group in the molecule, Those soluble in organic solvents are preferred. For example, acrylic copolymers, alkyd resins, epoxy resins, fatty acid or polybasic acid-modified polygetadiene resins, methylol group-introduced phenol resins, alkanolamine-modified polyurethane resins, polyamine resins, amino resins, polycarboxylic acid resins, polyvinylacecool and mixtures of two or more of these resins, addition condensates, and the like. Among the above-mentioned resins, resins suitable for the present invention are resins containing hydroxyl groups in the molecule, and among them, acrylic copolymers, alkyd resins, epoxy resins, and polyvinyl acecoles are preferable.

The above acrylic copolymer is an acrylic copolymer synthesized by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, etc. using an ordinary unsaturated ethylenic monomer, and a suitable one is essential. It is synthesized from a monomer composition containing an unsaturated vinyl monomer having a hydroxyl group as a component. This can be an acrylic copolymer modified with traps such as alkyd resins, epoxy resins, polybutadiene, polyflex, phenolic resins or amino resins.

The blending ratio of the hydroxyl group-containing unsaturated vinyl monomer can be changed arbitrarily depending on the amount of the silane compound and crosslinking agent used to react with the obtained acrylic copolymer, but it usually requires at least 5% by weight, and It is preferable to adjust to a range in which no hydroxyl group remains in the reaction product of (4) and (2). Such hydroxyl group-containing unsaturated vinyl monomers include 2-hydroxyethyl (meth)acrylate, 2-
Examples include hydroxypropyl (meth)acrylate. In addition to the above essential monomers, unsaturated vinyl monomers can be appropriately blended for the purpose of imparting hardness, flexibility, and crosslinking properties to the resin. . Such monomers include, for example, acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lacryl acrylate; methyl methacrylate, ethyl methacrylate, n- Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate,
Methacrylic acid esters such as lacryl methacrylate, glycidyl methacrylate, etc.; and ethylene, propylene, butadiene, isoprene, chloroprene, etc.1.
Examples include styrene, α-methylstyrene, dimethylstyrene, divinyltoluene, vinyl acetate, vinyl propionate, vinyl ether, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, maleic acid, and the like.

Further, as the alkyd resin used for the same purpose, generally known alkyd resins obtained by ordinary synthesis methods can be used. For example, oil-modified alkyd resin, resin-modified alkyd resin, rosin-modified alkyd resin, phenolic resin-modified alkyd resin, styrenated alkyd resin, acrylic-modified alkyd resin, epoxy resin-modified alkyd resin, silicone resin-modified alkyd resin, oil-free alkyd resin (polyester resin) etc.

Furthermore, as the epoxy resin, fatty acid modified epoxy resin, polybasic acid modified epoxy resin, acrylic resin modified epoxy resin, alkyd resin (or polyester) modified epoxy resin, polybutadiene resin modified epoxy resin, phenol resin modified epoxy resin, amine or Polyamide-modified epoxy resin, Frethane-modified epoxy resin, etc. are used.

The epoxy resin before modification in the above-mentioned modified epoxy resin includes conventionally known organic solvent-soluble epoxy resins, preferably those of the same type as the epoxy resin used as the crosslinking agent described later.

In addition, polyvinyl acecures include polyvinyl esters (polyvinyl acetate, polyvinyl propionate, etc.)
The hydrolyzate of formaldehyde, acetaldehyde,
It is preferable to use a vinyl resin such as polyvinyl formal, polyvinyl acecool, polyvinyl butyral, etc. obtained by 7-cetalization with gtyraldehyde or the like, and a polyvinyl ester having a number average degree of polymerization of 250 to 1500. Acetalization degree Fi55-8
8 mol%, hydroxyl group content h 1o~45 mol%
Preferably.

In the present invention, the di-, tri-, or tetra-alkoxy(alkoxyalkoxy)silane compound (hereinafter simply referred to as "silane compound") reacted with the organic polymer has 2 to 4 silane compounds in the molecule. It is a compound in which an alkoxy group is bonded to a silicon atom, and specifically, compounds having the following structure can be mentioned.

(r) General formula (R1) Alkyl group having 1 to 8 carbon atoms which may contain an alkoxy group or allyl (A11) 11 or Ary
l) group, n represents an integer of 0 or 11 or less) (Tetraalkyl)
Orthosilicates or polyalkyl (or allyl)silicates; specifically, for example, ethyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, n-butyl orthosilicate, n-octylorthosilicate, phenyl orthosilicate, benzyl orthosilicate Silicates, phenethyl orthosilicate, allyl (Aoy+) orthosilicate, methalyl orthosilicate, and polysilicates produced by dehydration condensation of these orthosilicates are also used.

(1) General formula % formula %) (R2 is an alkyl group having 1 to 8 carbon atoms which may contain an alkoxy group t+ is Allyl or tfAr
represents a yυ group; R8 is an alkyl group having 1 to 8 carbon atoms, A
ll) 1m group, Aryl group, vinyl group, r-chloropropyl group, r-aminopropyl group, r-(2-aminoethyl)aminopropyl group, r-mercaptopropyl group, r
-glycidoxypropyl group, β-(3,4-epoxycyclohegycyl)ethyl group, r-methacryloxypropyl group; Alkoxyalkoxy)silane compounds; Specifically, #-TFC examples include divinyljethoxysilane, divinyl-β-methoxyethoxysilane, di(r-glycidoglobyl)dimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltris-
! -Methoxyethoxysilane, r-glycidoglobyltrimethoxysilane, r-methacryloxybrobyltrimethoxysilane, β-(3,4-eboxinechlorohexyl)ethyltrimethoxysilane, r-mercaptopropyltrimethoxysilane You can give things like silane.

That is, if the alkoxyl group in the silane compound has a reaction mechanism in which a silanol group and alcohol are produced by hydrolysis of anti-F3 under specific conditions, it can be used as the silane compound of the present invention.

The blending ratio of the silane compound and organic polymer resin in the present invention is the solid content weight percentage ratio of silica (SI02 equivalent amount) to organic polymer resin in the silane compound, from 5/95 to 75/
25, preferably 1120/80 to 6 o/40.

If the silica content is less than 5% by weight, the desired corrosion resistance cannot be obtained, and if the silica content exceeds 75%, the formed film will not have sufficient flexibility or continuous film properties and will be prone to cracking.
Cohesive failure within the film is likely to occur and sufficient adhesion of the upper eyelid coating cannot be obtained.

When producing the composite resin (4) in the present invention, it is first essential to hydrolyze a silane compound to form a silanol group-containing silane compound. Water and an inorganic or organic acid are required as such hydrolysis catalysts. The effect of the proportion of water in the reaction system on the reaction rate is generally not particularly significant, but if it is extremely small, for example less than 0.1% by weight, hydrolysis will be too slow and impractical. On the other hand, if the amount exceeds 20% by weight, the organic polymer resin or silane compound may precipitate, making it impossible to obtain a uniform composite resin.

The inorganic acid or organic acid used as a hydrolysis catalyst is preferably a water-soluble acid having a dissociation constant value (PKa) of 7 or less.

Specifically, hydrochloric acid, sulfuric acid, nitric acid, chloric acid, phosphoric acid, formic acid,
Examples include acetic acid, propionic acid, acrylic acid, lactic acid, succinic acid, maleic acid, tartaric acid, citric acid, and gallic acid.

In addition, although the reaction is slow, basic catalysts (metal hydroxide,
Ammonia, amines) can also be used.

In the method for synthesizing the composite resin (4) according to the present invention, first, an organic polymer is dissolved in a solvent mainly consisting of an alcohol-based solvent, the solid content is 40% by weight or less, and the mixture is charged into a reaction vessel, and the silane compound is mixed without stirring. drip.

After that, water and an acid catalyst (usually used as an aqueous acid catalyst solution) are added dropwise. This mixed solution is prepared at room temperature, preferably at 10
A composite resin can be obtained by aging at temperatures above ℃, but in order to obtain a tough film, the mixture must be
It is desirable to heat continuously at a temperature of 50 to 90° C. and less than the boiling point, and specifically, heating at 50 to 90° C. sufficiently bonds the image components. As the heating continues, the viscosity of the mixed liquid gradually increases, but eventually it becomes almost constant and no change is observed, so it is sufficient to mark the end point at that point and stop the heating.

Normally, it takes 0.5 to 5 hours to reach the end point.0 The reaction mechanism of the composite resin (2) has not yet been fully elucidated, but it is assumed that the process roughly follows: . When a mixture of alkoxysilane compound, organic resin, acid catalyst, water, and solvent is heated, the alkoxy group of the alkoxysilane compound is hydrolyzed in the presence of water and an acid catalyst in the first step, and the active silanol group (
S(-OH) is generated. The silanol group of this hydrolyzed silane compound immediately forms a covalent bond or a hydrogen bond based on dehydration condensation with a hydroxyl group, carboxyl group, amino group, etc. in the organic resin to form a complex. If the hydrolysis of the alkoxysilane compound does not proceed in the first step, when a composition using this compound is formed into a film, it will not become transparent but will form an opaque, soft and brittle film, and the adhesion of topcoat #IWII will be poor. Since the appearance of the upper eyelid coating is insufficient and many pinholes appear in the upper eyelid coating, it can be inferred that compounding is occurring due to the formation of the covalent bonds or hydrogen bonds.

On the other hand, there are cases where an alkoxysilane compound is hydrolyzed in advance in the presence of an acid catalyst and water, and then mixed with an organic resin. Since self-condensation progresses and siloxane bonds are generated, there is a shortage of silanol groups that form covalent bonds or hydrogen bonds with organic resins, making it impossible to form a composite resin. A metal surface treatment composition using a composite resin obtained in such a system cannot provide excellent metal corrosion protection and paint surface treatment properties, even though they can be described in the present invention.

As is clear from the above results, in the present invention, silanol groups are preferentially reacted with functional groups (especially hydroxyl groups) in the organic resin by self-condensation of active silanol groups generated by hydrolysis of an alkoxysilane compound. There are characteristics.

Furthermore, the reason why the composite resin of the present invention exhibits superior water resistance compared to the water-based composite resin proposed by the present inventors is that the phosphor component in the water-based composite resin is composed of water-softening colloidal silica. When comparing these particles with the organic silica produced by hydrolysis of the silane compound in the solvent-based composite resin of the present invention, it is expected that the absolute amount of water adsorbed on the surface of the silica component of the former is significantly larger. be done. Desorption of this adsorbed water requires a temperature of 150° C. or higher, and it is thought that sufficient dehydration cannot be achieved by low-temperature curing and short-time treatment in the surface treatment step, which is the gist of the present invention.

On the other hand, the solvent-based composite resin of the present invention has almost no adsorbed water and is more hydrophobic than the water-based composite resin, so it has excellent water resistance and alkali resistance.

In the present invention, the composite resin) is composed of a composite resin alone or a composition of a mixture of two or more kinds of composite resins, which contains an amino resin and/or an epoxy resin as an essential component. be done. This resin (Bl) acts as a cross-linking agent through a dehydration bonding reaction or an addition reaction with the remaining functional groups in the composite resin (2), forming a strong and dense film, and exhibiting water resistance and alkali resistance. Such amino resins include conventionally known urea-formaldehyde condensation products modified with methanol or butanol, monomeric and polymeric melamine resins, benzoguanamine resins, etc. In addition, epoxy resins can form a stronger coating through an addition reaction between the epoxy groups in the molecule and the carboxyl groups in the complex reactant.Epoxy resins include conventionally known polyphenols, Typical solvent-soluble epoxy resins include di- or polyglycidyl ethers of aliphatic polyhydric alcohols, dicarboxylic acid diglycidyl esters, epoxy compounds containing a nitrogen-containing heterocycle, and furfuryl glycidyl ether. Among the above-mentioned epoxy resins, preferred specific examples include those having an average molecular weight of at least about 35.
0, preferably about 350-3000 and epoxy equivalent weight 15
0 to 3000, preferably 200 to 2000, such as epoxy resin manufactured by Shell Chemical Co., Ltd.: Ep1kote 828 (bisphenol A type,
Average molecular weight approximately 380, epoxy equivalent 190) Eprkotel 001 (Bispheno-7L/A
type, average molecular weight approximately 900, epoxy equivalent 475) // 1002 (bisphenol A type, average molecular weight approximately 1300, epoxy equivalent 650) u 1004 (bisphenol A type, average molecular weight approximately 1400, epoxy equivalent 950) η 1007 ( Examples include bisphenol A type, average molecular weight of about 2900, epoxy equivalent of 1900), etc.

The blending ratio of the above-mentioned amino resin and/or epoxy resin (Peng and composite resin (2) is 40/60 to 40/60 in weight percentage ratio.
5/95, preferably 30/70 to 10/90.

If the amount of the amino resin and/or epoxy resin used exceeds the above range, the inherent performance of the composite resin cannot be exhibited, and if it is less than the above range, the effect as a crosslinking agent will not be sufficient.

In addition to the above-mentioned essential ingredients, the following substances may be used in combination with Zero-Hatsu #j as needed to further improve hardenability, anti-corrosion properties, lubricity of the test material,
A power-on condition can be assigned. In other words, the special public official
- Chelate compounds such as titanium, zirconium, and aluminum described in Publication No. 41711,
-30867 publication and JP-A-1 [55-629718j
By using together oxyacid salts, metal salts, etc. as described in the publication, low temperature curing becomes possible.

In addition, commonly known antirust pigments (for example, zinc chromate,
stronticum chromate, calcium chromate, red lead, lead zincide, lead cyanamide, calcium leadate, basic lead sulfate, zinc phosphate, zinc molybdate, potassium molybdate, metaphosic acid, p < IJ cum, etc.) anti-rust(
It is possible to improve anticorrosion properties by adding phenolic carboxylic acids, organic phosphoric acids, phytic acid, urea derivatives, imidazole derivatives, nitrites, etc.) with the following composition. It is also possible to use a combination of molybdenum disulfide, polyethylene resin powder, two-component resin powder, etc. to increase the lubricity of the test material and improve workability.

! The biggest problem with so-called pre-coated steel sheets, which are coated with ordinary organic resins or inorganic oxides, is that electric welding or electrophoretic painting during the forming process is not practical enough. The composition of the present invention is adjusted to a dry film thickness of 2μ or less, and the subsequently treated board exhibits electrical weldability and electrophoretic paintability equivalent to that of an untreated board, but when a conductive substance is further mixed into the composition. The composition can also be made into a composition that forms an electrically conductive Fffi film, and can provide better electric weldability and il electrophoretic paintability. Such substances include, for example, zinc, aluminum, iron, cobalt, nickel, manganese, chromium, molybdenum, tungsten, copper,
Metal powders such as lead and tin and their alloy powders, conductive carbon, graphite powder, iron phosphide powder, aluminum doped zinc oxide powder, tin oxide-titanium oxide, tin oxide-paricum sulfate, nickel oxide-alumina, etc. Examples include any semiconductor oxide.

Also, by dispersing chromatic pigments, extender pigments, dyes, etc. that are commonly used for decoration, it is also possible to create a composition that forms a film with chromatic transparent reflection or optical staining properties. .

When the resin acid value of the composite resin is 40 or more, it is also possible to make it water-soluble or water-dispersible by neutralizing it with an alkali (ammonia, amine, metal hydroxide, etc.).

Furthermore, if necessary, the properties of the film can be adjusted by mixing a resin compatible with the composite resin among conventionally known solvent-based organic resins.

The object to be coated with the composition of the present invention may be any ordinary metal (raw material or molded article), such as iron,
Aluminum, zinc, tin, copper and alloys of these metals (as alloy gold ingots, such as zinc, aluminum, chromium, silicon, cobalt, zirconium, tin, titanium,
(consisting of one or more of iron, lead, nickel, magnesium, manganese, molybdenum, phosphorus, etc.), multilayer metal plates (multilayers of two or more) of these metals, and metal rust prevention for these metals. , Metals that have been subjected to generally known metal surface treatments for the purpose of imparting base properties for painting, such as phosphate treatments such as iron phosphate, zinc phosphate, iron zinc phosphate, and chromic acid, and chromic acid. Examples include surface-treated metals subjected to chromate treatment such as chromate chromate, chromium phosphate, and electrolytic chromate, anodization treatment, and boehmite treatment.

The metal surface treatment composition obtained by the present invention forms a film that exhibits excellent corrosion resistance as well as water resistance, moisture resistance, and alkali resistance, especially when applied on a chromate-based surface treatment. When performing chromate-based surface treatment for the purpose of labor saving, rationalization, and low pollution, or for the purpose of single-sided rust prevention treatment for automobile rust prevention steel plates, the trap is described in Japanese Patent Publication No. 45-38891. A waterless wash-applying type chromate treatment agent such as that described in 2009 is suitable, and in the case of single-sided treatment, an electrolytic chromate method is also effective.

The metal plate whose surface has been treated with the treatment agent of the present invention has excellent surface treatment properties for painting and exhibits good friendliness.

That is, it is characterized in that it provides top coat adhesion and corrosion resistance that are equivalent to or better than conventionally known phosphate and chromate treatments, and is also non-polluting. Paints used as top coats include known solvent-based, water-based, solvent-free, and
Any type of powder coating can be applied, and depending on the purpose of use, it can be applied in a single layer or in multiple layers such as two or three layers. In addition, painting methods include spraying, dipping,
All coating methods such as roll, electrophoresis, and electrostatic coating are possible.
Baking varies from room temperature curing to heat curing (
Any method such as infrared curing, ultraviolet curing, or electron beam curing is possible.

As a coating system for top coat paint, for example, for automobiles,
Electrodeposition coating - Intermediate coating and top coating system; Primer coating for pre-recorded metal - Totsubu Cordon Stem;
Single cordon stems for electrical appliances and steel products; heavy-duty anti-corrosion coating systems for ships, bridges, pipes, etc.; resin liners and resin laminate systems other than paints; etc. are possible.

A metal surface treatment composition consisting of a composite of final FIAK and an amino resin and/or an epoxy resin (8) is prepared in a solution with a solid content concentration of 5 to 60% by weight or 15 to 30% by weight. A metal surface treatment is performed by coating a metal object by a conventionally known method.

The coating thickness in this case is not particularly limited, but it is usually preferable to set the dry coating thickness to 1 to 30 microns.

As the coating method, for example, brush coating, spray coating, roll coating, dip coating, etc. can be used, so it can be applied to a wide range of applications such as coil coating, complex shapes, outdoor structures, etc.

In order to cure the composition of the present invention, depending on the type and properties of the monomers constituting the organic polymer used for producing the composite resin (6), for example, the composition may be cured at a temperature of from room temperature to 300°C for 2 seconds to 30 minutes. It may be hardened by natural drying or heating for about a minute.

In addition, if an organic polymer with unsaturated double bonds is used, it can be cured using an ordinary electron beam irradiation device (100 to 300 KeV,
30-100mA) or ultraviolet irradiation device (30-12
It can also be cured using a 0W/cIn high pressure mercury lamp).

The composition of the present invention has a composite resin that is a component thereof)
contains a suitable proportion of parent wood groups and hydrophobic groups in the molecule.
It can also be applied to inorganic materials such as concrete, asbestos, plastics, paint-coated objects, wood, paper, etc. The coating function of the composite resin includes metal corrosion inhibiting function and high surface hardness. Wear-resistant, scratch-resistant features,
It is possible to impart heat resistance and flammability functions based on the silica component produced by hydrolysis of the silica component, and stain resistance functions based on the silane compound, and to modify the surface of the material and use decoration 41) K. I can do it.

Examples and comparative examples are shown below. These examples are intended to explain the present invention in more detail, and are not intended to limit the scope of the present invention. Parts and percentages are parts and percentages by weight.
shows.

Synthesis Example of Organic Polymers 180 parts of isopropyl alcohol is placed in a 1 ton four-eye flask equipped with a slurry, stirrer, cooler, and dropping funnel, and after purging with nitrogen, the temperature inside the flask is adjusted to approximately 85°C. A monomer mixture consisting of 140 parts of ethyl acrylate, 68s methyl methacrylate, 15 parts of styrene, 15 parts of N-n-butoxymethylacrylamide, 38 parts of 2-hydroxyethyl acrylate, and 24 parts of acrylic acid was mixed with 2
．． 2'-azobis(2,4-dimethylvaleronitrile)
It is added dropwise with 6 parts of catalyst over a period of approximately 2 hours.

After the dropwise addition, the reaction was continued for another 5 hours at the same temperature to obtain a colorless and transparent resin solution with a polymerization rate of approximately 100%, a solid content of approximately 63%, an acid value of 67, and a hydroxyl equivalent of approximately 300.

In Synthesis Example 1, the seven-mer composition was changed to 33.6 parts of styrene, n-
Example 1 A colorless and transparent resin solution with a solid content of about 60% and an acid value of 64 was obtained.

Put 100 parts of linseed oil, 70 parts of trimethylolpropane, and 0.07 part of litharge into a flask, heat to 220°C in a nitrogen stream while stirring, react at this temperature for 30 minutes, then cool to 70°C. When the temperature reached 7, 110 parts of curic anhydride and 13 parts of pheasant were added, and the mixture was heated to 220°C with stirring.
The reaction was stopped when the acid value decreased after 15 injections, and when cooled to 80°C, 38 parts of pheasant roll and 32 parts of ethylene glycol monoethyl ether were added to give a solid content of approximately 70%, an acid value of 15, and a hydroxyl equivalent of approximately 1200 alkyd resin solution was obtained.

Example 4 Synthesis of fatty acid-modified epoxy resin Bisphenol A type epoxy resin (trade name: Epicor) 1004 with an epoxy equivalent of 950, Shell Chemical ■
) 62 parts, linseed oil 19 parts, tung oil 19 parts, xylene 3
Place the sample in a flask and gradually heat it while passing nitrogen through it.
After raising the temperature to 240°C, it was heated under reflux for 2 hours at this temperature, cooled, and when the temperature had dropped to 70°C, 40 parts of ethylene glycol monoethyl ether was added to give a solid composition of about 70%, an acid value of 54, A fatty acid-modified epoxy resin solution with a hydroxyl equivalent of 520 was obtained.

30% solids content of the acrylic copolymer resin obtained in Organic Polymer Synthesis Example 1 was placed in a 500-Yoturo flask equipped with a thermometer, stirrer, condenser, zone Stark trap, and dropping funnel.
Add 200 tons of cellosolve solution, and after purging with nitrogen, add 100 f of ethyl polysilicate (manufactured by Nippon Colcoat Chemical ■, trade name: Ethyl Silicate 40, degree of polymerization 4 to 6.5 i02 min 40%) through the dropping funnel while thoroughly stirring. Drip. Then, 30 f of a 40% aqueous orthophosphoric acid solution was gradually added dropwise, and then the mixture was heated to 90°C. According to Synthesis Example 1 of Coated Coated Resin, composite resins 2 to 6 were synthesized under the formulation and conditions shown in Table 1. did.

Synthesis example of water-based composite resin (corresponding to Comparative Examples 1 to 3) In Synthesis Example 1, dimethylaminoethanol 10EI was mixed with 500 parts of the #nth acrylic copolymer resin solution, and after addition of water, the mixture was sufficiently stirred. An acrylic copolymer resin moisture teaching solution having a solid content of 20% and a pH of about 1O was obtained. This aqueous dispersion 3
75 t was placed in a flask and stirred thoroughly at room temperature.
9-10) It takes about 10 minutes to add 125 tons [7].

After dropping, r-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name [KBM503J]
, 1.5 f were added dropwise and mixed under stirring, and then heated to 85° C. and kept open at the same temperature for 2 hours to react, to obtain a milky white, water-dispersible composite resin.

Example 1 The solid content of the composite resin 1 synthesized above was applied to an electrogalvanized sill board that had been degreased with a silicate-based alkaline cleaner (manufactured by Nippon CB Chemical Co., Ltd., trade name CC561B).
A 20% solid solution prepared by adding 2 parts of methylated melamine resin (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name Cymel 303) was applied to the area to a dry film thickness of 2 microns. 6 in a hot air atmosphere where the steel plate temperature reaches 180℃.
Baked for 0 seconds. This coated plate was subjected to a salt spray test, a salt spray-dry-wet cycle test, a salt water immersion-dry-wet cycle test, a wet test, and a paint film adhesion test, and as shown in Table 4, all were excellent. It showed good performance. In addition, this coated plate was coated with cationic electrodeposition paint (manufactured by Kansai Paint ■, Nirekron 9210) "t'electrodeposition (voltage DC2)".
00V, 3 minutes current, bath temperature 08-30℃, baking 175℃
The above-mentioned salt spray test, cycle test, and coating film adhesion test were also carried out on the coated plate with a film thickness of 20 microns, which had been coated for 30 minutes (30 minutes), and as shown in Table 5, all K showed excellent performance.

Example 2 A chromate treatment agent (manufactured by Kansai Paint Co., Ltd., trade name Acorite C1 chromate chromate-based coating type treatment agent) was applied to the electrogalvanized steel plate used in Example I to coat the metal.
A coated plate was prepared in the same manner as in Example 1 above, using a metal plate that was coated so that the coating was 1 to 5Q++y/m' and then baked for 30 seconds in an atmosphere where the metal temperature reached 156°C. When a performance test was conducted, both showed excellent performance. The results are shown in Tables 4 and 5 below.

Examples 3 to 12 Metal surface treatment compositions and coated plates shown in Table 2 were prepared according to Examples 1 and 2 and performance tests were conducted, and all showed excellent performance.

The results are shown in Tables 4 and 5 below.

The surface treatment in Examples 4 and 8 was performed using zinc phosphate (Bonderite 43004 manufactured by Nippon Parr Ising), respectively.
) (chemical conversion treatment t is 12/W?) and a 10% chromic anhydride rinse treatment was used. Example 6. The chromate treatment in 10 and 12 was conducted in accordance with Example 2.

*4 Composite resin, amino resin, and epoxy resin all have a solid content weight of 5 types. (1) Methylated melamine resin (manufactured by Mitsui Toatsu ■).

Product name Cymel 303) Hata (2) Methylated melamine resin (manufactured by Mitsui Toatsu ■).

Product name Cymel 370) *(3) Butylated melamine resin (manufactured by Mitsui Toatsu ■).

Product name Kneepan 60R) Pot (4) Methylated urea resin (Mitsui Toatsu ■, product name U
FR65) Hata (5) Benzoguanamine resin (manufactured by Mitsui Toatsu ■).

Product name Cymel 1123) *(6) Epoxy resin (manufactured by Mitsui Toatsu ■, product name Evoky 834) Examples 13 to 18 Methylation of 16 parts of resin solid content of each of composite resins 1 to 6 synthesized above Melamine resin (Cymel 303
) was applied to a hot-dip galvanized steel sheet that had been degreased with the cleaner described in Example 1 to a dry thickness of 2 microns, and then the steel sheet temperature was increased. Baking treatment was performed for 60 seconds in an atmosphere where the temperature reached 180°C. An aminoalkyd paint (trade name: "Amilac", manufactured by Kansai Paint ■) was applied to this surface-treated board and heated at 120° C. for 20 minutes to produce a coated board with a total film thickness of 20 microns. The corrosion resistance of this coated plate in the salt water spray 1 test showed significantly superior performance compared to the current zinc phosphate treated zinc steel plate. The results are shown in Table 6 below.

Examples 19-24 Epoxy primer paint for pre-recorded metal (trade name: r
Apply KP Ka-8470 Primer (manufactured by Kansai Paint ■), heat at 210U for 50 seconds, dry 1111 thickness 5
A micron coated plate was created, and then a polyester top coat (product name: rKP Color, 1470, Blue) was applied.
, manufactured by Kansai Paint ■), heated at 220°C for 50 seconds, and completely dried Wi! A 25 micron coated plate was prepared.

The corrosion resistance of this coated plate in a salt spray test was found to be significantly superior to that of current galvanized steel sheets treated with zinc phosphate and galvanized steel sheets treated with chromate chromate. The results are shown in Table 7 below.

Comparative Examples 1 to 3 Surface treatment compositions were prepared in the same manner as in Examples 1 and 2, except that a water-based composite resin (obtained from the above-mentioned synthetic example of water-based composite resin) was used instead of composite resin 1. A product (listed in Table 3) and a coated plate were prepared, and compared with the coated plate of the present invention, the corrosion resistance in a salt water immersion-drying-wetting cycle test and the coating adhesion after a submersion test in electrodeposition coating were found. The method of the present invention showed good results. The results are shown in Table-4 and Table-5.

Comparative Example 4 A composition consisting of composite resin 10, an organic polymer resin as a base resin, and a melamine resin was prepared (listed in Table 3), and a coated plate was prepared and tested in the same manner as in Example 1.
Corrosion resistance was significantly inferior to that of Table 4 shows the results.
, shown in Table-5.

Comparative Example 5 A composition was prepared by simply mixing the constituent materials of the composite resin in Example 3 (no catalyst, no heating reaction), and a coated plate was prepared and tested in the same manner. Compared to Example 3, the corrosion resistance was significantly higher. It was inferior. The results are shown in Table-4 and Table-5.

Comparative Examples 6 to 9 Similarly to Comparative Example 5, a coating plate was prepared in accordance with each example and a reliability test was conducted on a simple mixed composition of the constituent materials of the composite resin corresponding to the following Examples-Comparative Examples. As a result, all of them were inferior to the corresponding examples in terms of corrosion resistance and electrodeposition coating adhesion. The results are shown in Table-4 and Table-5.

Example 5 → Comparative example 6. Example 7 → Comparative Example 7゜Example 9 →
Comparative example 8. Example 11 → Comparative Example 9 Comparative Examples 10 to 21 In Examples 13 to 24, the constituent materials of the composite resin were simply mixed to make nine compositions (no catalyst, no heating reaction), and the mixture was prepared according to Examples 13 to 24. When we created and tested a coated plate, we found that
As shown in Tables 6 and 7, the adhesion and corrosion resistance of the top coat were significantly inferior to those of the corresponding examples.

Table 6: Results of amino alkyd coated board Table 7: Results of epoxy-polyester coated board* 7 Cut 11 orthogonal lines on each coated surface at 11III intervals, and cut straight fissures that reach the base surface with a sharp knife. After processing it so as to obtain 100 squares, it was extruded and deformed from the back side to a depth of 5 cm using an Erichsen extrusion tester K.

The center of the side part and the center of extrusion were made to coincide. Next, a medium 20-inch cellophane adhesive tape was pressed tightly by hand onto the scratched surface of the stitches, and the tape was rapidly pulled off to determine the number of stitches that remained without being removed. was displayed.

Hata 8 JIS-Z-237111CX Ru 6 Make a cross cut on the painted surface with a knife, and remove the one-sided paint from that part during 2
The evaluation was based on the time it took to reach the top.

*9 35% NaCl, 35°C salt water spray test 2 hours = 60°C dry; 2 hours -40°C, 100% RH wet test 4 hours is one cycle, coated surface condition and peeling of cross cut part after 100 cycles Evaluated inside.

Appearance of flat part/Peeling of cross cut part (-) * 10 5% NacL, 40℃ salt water immersion 7.5 minutes - 60℃ drying 1
Wet test at 5 minutes - 40° C., 100% RH One cycle was 7.5 minutes, and the condition of the coated surface and the peeling of the cross-cut portion after 2000 cycles were evaluated.

Appearance of flat part / Peeling off of cross cut part (■) * 1I JIS-Z-0228KJ:, &.

The coated plate was placed in a humidity test box at 50℃ and 100% RH for 200 minutes.
After leaving it for 0 hours, it was removed and the condition of the painted surface was observed.

Hata 12 Welding current 8KA, pressure between electrodes 200Kf, electrodes 1 and 2
IS, CF type 4.5 Welding was carried out under the conditions of energization time of 10co150H2, and evaluation was made by the number of dots that ensured the tensile strength of the welded member to be 400 Kf or more.

*13 After electrodeposition coating and immersing the next coated plate in 40℃ warm water for 240 hours,
It was left at room temperature for 24 hours, and an adhesion test was conducted according to *7.

*14 According to J I 5-Z-2371. A cross cut was made on the painted surface with a knife, and the state of the painted surface after a salt water spray test for a predetermined period of time and the peeling of the cross cut portion were evaluated.

Claims (4)

[Claims] (1) (4) An organic polymer containing at least one functional group selected from a hydroxyl group, a carboxyl group, and an amino group and a di-, tri-, or tetraalkoxy (or alkoxyalkoxy) silane compound are combined with an inorganic or organic acid. A metal surface treatment composition comprising 60 to 95% by weight of a composite resin reacted at a temperature of 10° C. or higher and lower than the boiling point in the presence of Bl amino resin and/or 5 to 40% by weight of epoxy resin. (2) (Organic polymer containing at least one functional group selected from Al hydroxyl group, carboxyl group, and amine 7 group and di- or tri-tetraalkoxy (or alkoxyalkoxy) silanization & compound with inorganic acid or 25 of a composition comprising 60 to 95% by weight of a composite resin reacted at a temperature of 10°C or higher and lower than the boiling point in the presence of an organic acid and (B) 5 to 40% by weight of an amino resin and/or an epoxy resin. A metal surface treatment method comprising applying a ~90 weight type (solid content) solution onto the surface of a metal object. (3) Surface treatment of metal according to claim 2, wherein the metal coating object is steel and alloy steel, aluminum and aluminum alloy, zinc and zinc alloy, and metals made of multiple layers of these metals. Method. (4) The metal surface treatment method according to claims 2 and 3, wherein the metal object is a surface-treated metal plate treated with phosphate or chromate.