JP5060796B2 - Method for forming surface treatment film - Google Patents

Description

 The present invention relates to a method for forming a surface-treated film excellent in anticorrosion and finishing properties of a coating film and uniform precipitation of the film, and a film structure formed by the method for forming the surface-treated film and a coated article.

  Conventionally, an industrial metal substrate has been subjected to zinc phosphate treatment as a ground treatment for the purpose of improving corrosion resistance and adhesion. However, the chemical conversion treatment with a zinc phosphate treatment agent contains a large amount of phosphorus and nitrogen in the treatment agent, and contains a large amount of heavy metals such as nickel and manganese in order to improve the performance of the formed chemical conversion film. Therefore, there is a problem in the treatment of industrial waste, etc. due to environmental impact and a large amount of sludge such as zinc phosphate and iron phosphate after treatment.

In addition, in order to improve the corrosion resistance of industrial metal substrates, a lot of space and time are required for processing steps such as “degreasing—surface conditioning—chemical conversion treatment—electrodeposition coating” in the coating line.
Patent Document 1 proposes a chemical conversion treatment agent for iron and / or zinc-based substrates that contains substantially no phosphate ions and contains zirconium ions and / or titanium ions and fluorine ions. However, after the treatment using the chemical conversion treatment agent for iron and / or zinc-based substrate described in Patent Document 1, sufficient anticorrosion and finish cannot be ensured unless a coating film is applied by a coating process. There's a problem.

  Patent Document 2 describes (A) a compound containing at least one metal element selected from Ti, Zr, Hf, and Si, and (B) a surface treatment of a metal containing a fluorine-containing compound as a supply source of fluorine ions. By using the composition, a surface treatment film having excellent corrosion resistance can be deposited on the surface of a metal containing at least one of iron and zinc, and the surface adjustment (surface tone) step is not required, so that the treatment step is shortened. It is disclosed to save space. However, after the treatment using the surface treatment composition described in Patent Document 2, there is a problem that sufficient anticorrosion and finish cannot be ensured unless a coating film is applied by a coating process.

Patent Document 3 and Patent Document 4 include at least one compound selected from (A) amine-modified acrylic resin, (B) phosphoric acid compound, hydrofluoric acid, metal hydrofluoric acid, and metal hydrofluoride. , (C) coating a zinc-plated steel sheet used for automobile bodies, home appliances, etc., with a surface treatment composition for lubricating steel sheets containing at least one compound selected from molybdenum compounds, tungsten compounds and vanadium compounds Discloses a surface treatment composition for a lubricating steel sheet capable of obtaining a lubricating steel sheet having excellent press formability and corrosion resistance. However, steel sheets using the surface treatment composition for lubricating steel sheets described in Patent Document 3 and Patent Document 4 have sufficient anticorrosion properties and finish properties unless a coating film subjected to a chemical conversion treatment and a coating process is applied. Since it cannot be secured, it is not possible to shorten the process and save space.

  Patent Document 5 discloses a polymer composition for a metal surface treatment agent comprising a specific copolymer having a salicylideneamino group and an amino group. However, the steel sheet using the polymer composition for metal surface treatment agent described in Patent Document 5 also has a coating process in the painting process, so that sufficient corrosion resistance and finish cannot be ensured. And space saving cannot be achieved.

  Patent Document 6 discloses that a coating film having a gap of 500 μm or less is formed in a gap portion of a coating object having a complicated structure such as an automobile body by cation electrodeposition coating of a multistage energization method. A method is disclosed that can do this. The multi-stage energization method described in Patent Document 6 is effective in improving the anticorrosion property by covering the gap portion of the object to be coated having a gap of 500 μm or less. Not reached.

  Furthermore, Patent Document 7 discloses a method of forming a multilayer electrodeposition coating film by applying a cationic electrodeposition coating containing a plurality of emulsions with a constant difference in the amount of electricity required for the start of deposition by a multi-stage energization method. Although disclosed, this method has not yet achieved sufficient corrosion resistance.

JP 2003-155578 A International Publication No. 02/05860 Pamphlet JP 2003-166073 A JP 2003-226882 A JP 2003-293161 A JP-A-2-282499 JP 2003-328192 A

 An object of the present invention is to provide a method for forming a surface-treated film excellent in the anticorrosion and finishing properties of the surface-treated film and the uniform precipitation of the film.

 As a result of intensive studies, the present inventor has found that the above object can be achieved by immersing a specific film forming agent in a metal base material and applying an electric current under specific conditions, The present invention has been completed.

Thus, the present invention is a method of forming a film on a metal substrate by coating the film forming agent (I) in at least two stages of multi-stage methods,
Film forming agent (I) is a zirconium compound and a metal selected from titanium, cobalt, vanadium, tungsten, molybdenum, copper, indium, zinc, aluminum, bismuth, yttrium, lanthanoid metal, alkali metal and alkaline earth metal (a ) And at least one compound (A) selected from the compounds of 30 to 5,000 ppm in terms of the total metal amount (in terms of mass), and 1 to 40% by mass of the resin component (B),
(1) a step of immersing a metal material in a tank of the film forming agent (I) for 1 to 600 seconds without energizing; and (2) after the step (1), in the tank of the film forming agent (I), The present invention provides a method for forming a surface treatment film, comprising a step of energizing an immersed metal material at 50 to 400 V for 60 to 240 seconds.

  The film formed by the method for forming a surface-treated film of the present invention is excellent in anticorrosion and finishing properties and uniform precipitation of the film.

The reason why the film structure obtained by the method for forming a surface-treated film of the present invention is excellent in corrosion resistance and finish is that the film (F1) deposited on the coated side contributes to the suppression of corrosion under the film. Moreover, it is considered that the function sharing that the coating (F2) blocks the finish and the corrosion promoting substances (for example, O ₂ , Cl ⁻ , Na ⁺ ) can be imparted in the coating structure.

  Furthermore, the method for forming a surface treatment film according to the present invention can be easily deposited inside an article to be coated having a bag structure or a gap, and in particular, a uniform zirconium compound that has an effect on corrosion resistance by the first stage coating. Since it is excellent in precipitation, it is useful for improving the anticorrosive property of the article having a bag structure or a gap. The reason for this is that the present forming method forms a film by dipping the first stage. For example, in the formation of a film by energization coating, the current density differs depending on the complicated part of the object to be coated, and the film composition becomes non-uniform.

  In addition, in a coating line that performs continuous production, electrodes are usually fixed, and a metal base material to be coated moves on a conveyor. In this case, since the distance between the metal substrate and the electrode varies with the movement of the metal substrate, the current density of the metal substrate also changes, so the obtained film composition and film thickness are uneven. It becomes. However, the method for forming the surface-treated film according to the present invention does not cause such a problem because the first coating is automatically deposited by the dipping method.

  Hereinafter, the method for forming the surface treatment film of the present invention will be described in more detail.

  The present invention uses a specific “film-forming agent (I)” on a metal substrate to form a surface-treated film under specific conditions (a multistage method in which an object is immersed and energized). Is.

Metal substrate:
Examples of the metal substrate to which the film forming agent of the present invention can be applied include iron, zinc, zinc alloy; a sheet plated with these metals; a sheet laminated with the metal, and the like.

Film forming agent (I):
The film-forming agent (I) used in the present invention comprises a zirconium compound and, if necessary, titanium, cobalt, vanadium, tungsten, molybdenum, copper, indium, zinc, aluminum, bismuth, yttrium, lanthanoid metal, alkali metal and Compound (A) with at least one metal (a) compound selected from alkaline earth metals is 30 to 5,000 ppm in terms of total metal amount (mass conversion), and resin component (B) is 1 to 40% by mass. Is included.

  In the first-stage coating according to the present invention, the film (F1) is formed by uniformly depositing metal ions from the compound (A) on the surface of the metal substrate by immersing the metal substrate.

  The zirconium compound in the film forming agent (I) is, for example, zirconyl nitrate, zirconyl acetate, zirconyl sulfate, or the like as a compound that generates zirconium oxymetal ions; Examples thereof include hydrofluoric acid and zirconium hydrofluoride (for example, sodium salt, potassium salt, lithium salt, ammonium salt and the like).

  Among these, zirconyl nitrate, zirconium hydrofluoric acid, zirconium ammonium fluoride, and the like promote film deposition in the step of immersing the metal material without energization in the film forming agent (I) bath.

On the other hand, in the compound of the metal (a), examples of the compound that generates titanium metal ions include titanium chloride and titanium sulfate; examples of the compound that generates fluoro metal ions of titanium include titanium hydrofluoric acid and titanium hydrofluoric acid. Salts (for example, sodium salt, potassium salt, lithium salt, ammonium salt, etc.);
Examples of compounds that generate cobalt ions include cobalt chloride, cobalt bromide, cobalt iodide, cobalt nitrate, cobalt sulfate, cobalt acetate, and cobalt ammonium sulfate;
Examples of compounds that generate vanadium metal ions include lithium orthovanadate, sodium orthovanadate, lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, sodium pyrovanadate, vanadyl chloride, and vanadyl sulfate. Being;
Examples of compounds that generate metal ions of tungsten include lithium tungstate, sodium tungstate, potassium tungstate, sodium metatungstate, sodium paratungstate, ammonium pentatungstate, ammonium heptungstate, sodium phosphotungstate, boron. Examples of compounds that generate metal ions of molybdenum include lithium molybdate, sodium molybdate, potassium molybdate, ammonium heptamolybdate, calcium molybdate, magnesium molybdate, strontium molybdate, and molybdenum. Barium acid, phosphomolybdic acid, sodium phosphomolybdate, zinc phosphomolybdate and the like; Examples of compounds that generate metal ions include copper sulfate, copper hydroxide nitrate, copper nitrate ammonia, cupric oxide, and copper phosphide; examples of compounds that generate indium metal ions include indium sulfate. Examples of the compound that generates zinc metal ions include zinc acetate, zinc lactate, and zinc oxide. Examples of the compounds that generate aluminum metal ions include aluminum phosphate and trialuminate. Calcium, sodium aluminate and the like;
Examples of compounds that generate bismuth metal ions include inorganic bismuth such as bismuth chloride, bismuth oxychloride, bismuth bromide, bismuth silicate, bismuth hydroxide, bismuth trioxide, bismuth nitrate, bismuth nitrite, and bismuth oxycarbonate. Containing compounds; bismuth lactate, triphenyl bismuth, bismuth gallate, bismuth benzoate, bismuth citrate, bismuth methoxyacetate, bismuth acetate, bismuth formate, bismuth 2,2-dimethylolpropionate, etc .; metal ion of yttrium Examples of the compound that generates yttrium nitrate, yttrium acetate, yttrium chloride, yttrium sulfamate, yttrium lactate, yttrium formate, and the like. Ojimu, such as neodymium oxide, and the like.

  In the lanthanoid metal compounds, examples of compounds that generate cerium metal ions include cerium (III) nitrate, cerium (III) chloride, cerium acetate (III), cerium oxalate (III), ammonium cerium nitrate (III), and nitric acid. Diammonium cerium (IV) and the like; Examples of the compound that generates a lanthanum metal ion include, for example, lanthanum nitrate, lanthanum fluoride, lanthanum acetate, lanthanum boride, lanthanum phosphate, and lanthanum carbonate; Examples thereof include praseodymium nitrate, praseodymium sulfate, and praseodymium oxalate.

Examples of the compound that generates an alkali metal ion include potassium sulfate, potassium nitrate, lithium sulfate, lithium nitrate, sodium sulfate, and sodium nitrate. Examples of compounds that generate alkaline earth metal ions include calcium carbonate, magnesium nitrate, magnesium oxide, magnesium trioxide, magnesium orthosilicate, and magnesium pyrophosphate.
These metal compounds can be used alone or in combination of two or more.

[Resin component (B)]
The resin component (B) used in the film treatment agent of the present invention is preferably a cationic resin composition from the standpoint of improving corrosion resistance. Examples of the cationic resin composition include those comprising a base resin having a group that can be cationized in an aqueous medium such as amino group, ammonium base, sulfonium base, phosphonium base and a crosslinking agent in the molecule. The resin type of the base resin includes, for example, an epoxy resin type, an acrylic resin type, a polybutadiene resin type, an alkyd resin type, a polyester resin type, and the like. (B1) is preferable, and from the viewpoint of weather resistance, an amino group-containing acrylic resin (B2) is preferable.

Amino group-containing epoxy resin (B1):
The amino group-containing epoxy resin (B1) includes an epoxy resin obtained by reacting an amine compound with an epoxy resin, and the epoxy resin used as a starting material is particularly a polyphenol compound and an epihalohydrin from the viewpoint of the corrosion resistance of the film. For example, an epoxy resin obtained by reaction with epichlorohydrin is suitable.

  As the polyphenol compound that can be used for forming the epoxy resin, those known per se can be used. Examples of such a polyphenol compound include 2,2-bis (4-hydroxyphenyl) propane ( So-called bisphenol A), 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl) methane (so-called bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy) Phenyl) isobutane, 2,2-bis (4-hydroxy-tert-butyl-phenyl) propane, bis (2-hydroxynaphthyl) methane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, 4, 4-dihydroxydiphenylsulfone (bisphenol S), phenol novola Click, such as cresol novolac and the like. Moreover, as an epoxy resin obtained by reaction of a polyphenol compound and epichlorohydrin, the following formula induced | guided | derived from bisphenol A is mentioned especially,

Formula (1)
(Where n = 0-8) are preferred.

  The epoxy resin generally has an epoxy equivalent of 200 to 2,000, preferably 400 to 1,500, and a number average molecular weight (Note 1) of generally 400 to 4,000, preferably 800 to 2,500. Those within range are suitable.

  Examples of such commercially available epoxy resins include those sold by Japan Epoxy Resins Co., Ltd. under the trade names such as Epicoat 828EL, 1002 on the left, 1004 on the left, and 1007 on the left.

  (Note 1) Number average molecular weight: according to JIS K 0124-83, 4 separation columns “TSK GEL4000HXL”, “TSK G3000HXL”, “TSK G2500HXL”, “TSK G2000HXL” (above, manufactured by Tosoh Corporation) Using a book, using tetrahydrofuran for GPC as an eluent at 40 ° C. and a flow rate of 1.0 ml / min, a chromatogram obtained with an RI refractometer and a standard polystyrene calibration curve are used.

  The amine compound that can be reacted with the epoxy resin is not particularly limited as long as it contains at least one active hydrogen that reacts with an epoxy group and can cationize the epoxy resin. It is preferable to use a primary amine compound capable of introducing a primary amino group.

  Examples of the primary amine compound capable of introducing the primary amino group include ethanolamine, propanolamine, 2- (2-aminoethylethanol), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylene. Hexamines and their ketimines are mentioned.

The primary amine compound can be used in combination with other amine compounds, and as such amine compounds, those usually used for cationization of epoxy resins can be used as well. Are preferable, and examples include diethylamine, diisopropylamine, diethanolamine, di (2-hydroxypropyl) amine, monomethylaminoethanol, monoethylaminoethanol, and the like. An amino group-containing epoxy resin can be obtained by reacting the epoxy resin with an amine compound by a method known per se.

  Such an amino group-containing epoxy resin (B1) can generally have an amine value in the range of 30 to 70 mg KOH / g resin solids, and in particular has an amine value in the range of 40 to 60 mg KOH / g resin solids. It is preferable from the viewpoint of securing water dispersibility and anticorrosiveness of the film.

  Furthermore, in order to increase the water dispersibility of the amino group-containing epoxy resin (B1), it is preferable to achieve molecular polarization with a hydrophobic modifier, and as such a modifier, the reactivity with the epoxy group can be improved. The caprolactone polyol compound, xylene formaldehyde resin, etc. which have can be used.

  The caprolactone polyol compound can be obtained, for example, by adding caprolactone to a compound containing a plurality of active hydrogen groups in one molecule. Here, the active hydrogen group means an atomic group containing at least one active hydrogen, and includes, for example, an alcoholic hydroxyl group, a primary amino group, a secondary amino group, and the like.

  The compound containing a plurality of active hydrogen groups in one molecule can generally have a number average molecular weight in the range of 62 to 5,000, preferably 62 to 4,000, more preferably 62 to 1,500. . In addition, the active hydrogen-containing compound preferably contains an average of at least 2 to less than 30, particularly 2 to 10 active hydrogen groups per molecule.

  Specific examples of the compound containing a plurality of active hydrogen groups in one molecule include (1) a polyol compound, (2) a primary amino group and / or a secondary amino group, or a hydroxyl group and a primary amino group. An amine compound having a group and / or a secondary amino group, (3) a linear or branched polyether polyol, (4) a linear or branched polyester polyol, and the like.

The polyol compound (1) is a compound containing at least two alcoholic hydroxyl groups in one molecule, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, Diols such as 1,6-hexanediol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-dimethylol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A; triols such as glycerin, trimethylolethane, trimethylolpropane Tetrols such as pentaerythritol and α-methyl glucooxide; hexols such as sorbitol and dipentaerythritol; octols such as sucrose;

  Examples of the amine compound (2) include butylenediamine, hexamethylenediamine, ethanolamine, diethanolamine, dipropanolamine, triethanolamine, isophoronediamine, ethylenediamine, propylenediamine, diethylenetriamine, and triethylenetetramine.

  As the linear or branched polyether polyol of the above (3), an alkylene oxide having a number average molecular weight in the range of usually 62 to 10,000, preferably 62 to 2,000 (for example, ethylene oxide, For example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (oxyethylene / oxypropylene) glycol, and bisphenol A ethylene. Examples include glycol ether and bisphenol A polypropylene glycol ether.

  The linear or branched polyester polyol of the above (4) can usually have a number average molecular weight in the range of 200 to 10,000, preferably 200 to 3,000, specifically, for example, organic Examples thereof include those obtained by polycondensation reaction of dicarboxylic acid or anhydride thereof and organic diol under the condition of excess organic diol.

  Examples of the organic dicarboxylic acid used herein include fatty acid-based, alicyclic or aromatic dicarboxylic acids having 2 to 24 carbon atoms, particularly 4 to 12 carbon atoms, such as succinic acid, adipic acid, azelaic acid, sebacic acid and maleic acid. Examples include acid, fumaric acid, glutaric acid, hexachloroheptanedicarboxylic acid, cyclohexanedicarboxylic acid, o-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, and tetrachlorophthalic acid. In addition to these dicarboxylic acids, a small amount of polycarboxylic acid anhydrides or unsaturated fatty acid adducts having three or more carboxyl groups can be used in combination. Examples of the organic diol include polypropylene glycol, polyethylene glycol, and polylactone diol.

  The xylene formaldehyde resin can be produced, for example, by subjecting xylene, formaldehyde and optionally phenols to a condensation reaction in the presence of an acidic catalyst.

  As said formaldehyde, the compound etc. which generate | occur | produce formaldehyde, such as formalin, paraformaldehyde, and trioxane which are industrially easy to acquire, can be illustrated. In the present specification, when a polymer such as paraformaldehyde or trioxane is used, the blending amount is defined based on one molecule of formaldehyde.

Furthermore, the above phenols include monovalent or divalent phenolic compounds having two or three reaction sites, and specifically include, for example, phenol, cresols, para-octylphenol, nonylphenol, Bisphenol propane, bisphenol methane, resorcin, pyrocatechol, hydroquinone, para-tert-butylphenol, bisphenol sulfone, bisphenol ether, para-phenylphenol and the like can be mentioned, and these can be used alone or in combination of two or more. .
Of these, phenol and cresol are particularly preferable.

  The xylene formaldehyde resin thus obtained can generally have a viscosity in the range of 20 to 50,000 centipoise (25 ° C.), preferably 30 to 15,000 centipoise (25 ° C.), and generally 100 to It is preferred to have a hydroxyl equivalent weight in the range of 50,000, in particular 200 to 10,000.

  The reaction method of the polycaprolactone polyol compound and / or the xylene formaldehyde resin to the epoxy resin is not particularly limited, but it is generally preferable to react the amine compound and the modifier simultaneously with the epoxy group of the epoxy resin.

  The above addition reaction of the amine compound and the modifier to the epoxy resin is usually performed in a suitable solvent at a temperature of about 80 to about 170 ° C., preferably about 90 to about 150 ° C. for about 1 to 6 hours, preferably By performing the reaction for about 1 to 5 hours, an amino group-containing epoxy resin (B11) modified with a polycaprolactone polyol compound or an amino group-containing epoxy resin (B12) modified with a xyleneformaldehyde resin can be obtained.

  Examples of the organic solvent include hydrocarbons such as toluene, xylene, cyclohexane, and n-hexane; esters such as methyl acetate, ethyl acetate, and butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone. Examples include ketones; amides such as dimethylformamide and dimethylacetamide; alcohols such as methanol, ethanol, n-propanol, and iso-propanol; water or a mixture thereof.

  The use ratio of the above modifier is not strictly limited and can be appropriately changed according to the use of the film-forming agent, but 5 to 50% by mass based on the solid content mass of the epoxy resin, A range of 10 to 30% by mass is preferable. If it is less than this, the required amount of the neutralizing agent for the resin will increase, and if it is more than this, the water dispersion stability may be inferior.

  In addition, the amino group-containing epoxy resin (B1) described above is reacted with a polyol compound obtained by adding caprolactone to a phenol, an amino group-containing compound, and a compound containing a plurality of active hydrogen groups. A phenol-added type polyol-modified amino group-containing epoxy resin (B13) can be used.

  The epoxy resin used for the phenol-modified type polyol-modified amino group-containing epoxy resin (B13) is a polycaprolactone polyol compound-modified amino group-containing epoxy resin (B11) or a xylene formaldehyde resin-modified amino group-containing epoxy resin (B12). Resins similar to those described above for the production of can be used.

  Examples of the alkylphenols that can be used in the phenol addition type polyol-modified amino group-containing epoxy resin include those represented by the following formula (1).

Formula (2)
[Wherein, X is a substituent selected from the group consisting of a hydrogen atom, —OH, —OR, —NH ₂ , —NHR, C ₆ H ₆ — (CH ₂ ) —NR ¹ R ² , —SH and —SR. Represents a hydrocarbon group having 1 to 15 carbon atoms, and R, R ¹ and R ² each independently represents an alkyl group]
In the above formula (2), the hydrocarbon group having 1 to 15 carbon atoms represented by X can be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, Alkyl groups having 1 to 15 carbon atoms, particularly 1 to 12 carbon atoms such as isopropyl, n-butyl, tert-butyl and nonyl groups are preferred. These groups are optionally composed of a hydroxyl group (—OH), an alkoxy group (—OR), a mercapto group (—SH), an amino group (—NH ₂ , —NHR, —NR ¹ R ² ) and an alkylthio group (—SR). It may be substituted with a group selected from the group consisting of

  Specific examples of the phenols of the above formula (2) include phenol, cresol, ethylphenol, para-tert-butylphenol, nonylphenol and the like.

  The polyol compound includes a polyol compound in which caprolactone is added to a compound containing a plurality of active hydrogen groups, and includes a polycaprolactone polyol compound-modified amino group-containing epoxy resin (B11) or a xylene formaldehyde resin-modified amino group-containing epoxy resin. The polyol compound mentioned above regarding manufacture of (B12) can be used.

The polyol compound is a compound containing at least two alcoholic hydroxyl groups in one molecule, for example, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexane. Diols such as diol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-dimethylol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A; Triols such as glycerin, trimethylolethane, trimethylolpropane; pentaerythritol, Examples include tetrols such as α-methyl glucooxide; hexols such as sorbitol and dipentaerythritol; octols such as sucrose.

  The amino group-containing compound should be the same amino group-containing compound as described above for the production of the polycaprolactone polyol compound-modified amino group-containing epoxy resin (B11) or xylene formaldehyde resin-modified amino group-containing epoxy resin (B12). Can do.

  Examples of the amino group-containing compound include ketiminates of amines such as monoethanolamine, propanolamine, hydroxyethylaminoethylenediamine, hydroxyethylaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; , Diisopropylamine, diethanolamine, di (2-hydroxypropyl) amine, monomethylaminoethanol, monoethylaminoethanol and the like.

  As a resin component (B) used for a film forming agent, the following formula (3)

Formula (3)
An amino group-containing and / or phenol compound-containing epoxy resin (B14) obtained by reacting an epoxy resin having at least two epoxy group-containing functional groups in one molecule with an amino group-containing compound and / or a phenol compound Can also be used.

  Epoxy resins having an epoxy group-containing functional group represented by the above formula (3) are known per se, for example, JP-A-60-170620, JP-A-62-135567, Those described in JP-A-60-166675, JP-A-60-161973, JP-A-2-265975 and the like can be used.

Epoxy resins also include those in which a residue of a polymerization initiating component, that is, an active hydrogen-containing organic compound residue is bonded to the terminal. Examples of the active hydrogen-containing organic compound that is a precursor thereof include alcohols such as aliphatic monohydric alcohols, aromatic monohydric alcohols, divalent or higher aliphatic or alicyclic polyhydric alcohols; phenols; fatty acids Aliphatic, alicyclic or aromatic dibasic acid or polybasic acid; oxyacid; polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, allyl polyol resin Styrene-allyl alcohol copolymer, alkyd resin, polyester polyol resin, polycaprolactone polyol resin, and the like. These active hydrogen-containing organic compounds may have a structure in which unsaturated double bonds are epoxidized in the skeleton together with active hydrogen.

  In addition, as an epoxy resin, for example, the above active hydrogen-containing organic compound is used as an initiator, and in the presence of 4-vinylcyclohexene-1-oxide alone or in combination with another epoxy group-containing compound, Ring-opening (co) polymerization with epoxy groups contained in each of them to form a polyether resin, and then the vinyl group present in the side chain of the resin is epoxyized with an oxidizing agent such as peracids or hydroperoxides. It is also possible to use a product manufactured by making it.

  4-vinylcyclohexene-1-oxide can be obtained, for example, by partially epoxidizing vinylcyclohexene obtained by dimerization reaction of butadiene with peracetic acid.

The other epoxy group-containing compound that can be copolymerized is not particularly limited as long as it is a compound having an epoxy group, but is preferably a compound having one epoxy group in one molecule for production.
Specifically, for example, ethylene oxide, propylene oxide, butylene oxide, the following formula (4)

Formula (4)
Α-epoxy olefins represented by the formula: oxides of terminal unsaturated compounds such as styrene oxide; allyl glycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and the like.

  Other glycidyl group-containing compounds further include alicyclic oxirane group-containing vinyl monomers having an unsaturated bond, and specific examples include those exemplified below.

In the above formulas, R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ₅ is hydrocarbon divalent C1-10 Represents a hydrogen group.

In the above formula, the divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ₄ is, for example, a linear or branched alkylene group such as methylene, ethylene, propylene, tetra Examples include methylene, ethylethylene, and pentamethylene groups.

Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ₅ include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, phenylene, cyclohexylene, and xylylene. And so on.

  Further, the following formula (5)

Formula (5)
(Wherein R ₃ and R ₄ have the same meaning as above)
Compounds such as glycidyl acrylate, glycidyl methacrylate, etc .; partially formed as a by-product by partial epoxidation of vinylcyclohexene (6)

Formula (6)
A compound having an alicyclic unsaturated group as shown by the above can also be used as another epoxy group-containing compound. Furthermore, 4-vinylcycloheptene (vinyl norbornene) or the like can also be used.

  The ring-opening (co) polymerization reaction of an epoxy group carried out in the presence of 4-vinylcyclohexene-1-oxide or in combination with another epoxy group-containing compound is carried out in the presence of an active hydrogen-containing organic compound and using a catalyst. It is preferable to carry out.

Examples of the catalyst include amines such as methylamine, ethylamine, propylamine and piperazine; organic bases such as pyridines and imidazoles; organic acids such as formic acid, acetic acid and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; Alkali metal alcoholates such as sodium methylate; alkalis such as KOH and NaOH; Lewis acids such as BF ₃ SnCl ₂ , AlCl ₃ and SnCl ₄ or their complexes; organometallic compounds such as triethylaluminum and diethylzinc Can do.

  These catalysts are usually used in the range of 0.001 to 10% by mass, preferably 0.1 to 5% by mass, based on the reactants. The ring-opening (co) polymerization reaction can generally be performed at a temperature in the range of -70 to 200 ° C, preferably -30 to 100 ° C. This reaction is preferably carried out in a solvent, and a normal organic solvent having no active hydrogen can be used as the solvent.

The polyether resin (ring-opening (co) polymer) thus obtained is then epoxidized with a vinyl group (—CH═CH ₂ ) directly bonded to the carbon atom of the alicyclic structure of the side chain. And an epoxy resin having a functional group represented by the formula (3).

  Epoxidation can be performed using peracids or hydroperoxides. Examples of peracids include formic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid. Examples of hydroperoxides include hydrogen peroxide, tert-butyl peroxide, and cumene peroxide. Etc. can be used. The epoxidation reaction can be carried out in the presence of a catalyst, if necessary.

  When the vinyl group based on 4-vinylcyclohexene-1-oxide in the ring-opening (co) polymer is epoxidized, the functional group represented by the formula (3) is generated. In this epoxidation reaction, when the alicyclic oxirane group-containing compound or the like is present as another epoxy group-containing compound, the vinyl group contained in the compound may be epoxidized. It is different from the functional group represented by.

  The presence or absence of the solvent used in the epoxidation reaction and the reaction temperature can be appropriately adjusted according to the apparatus used and the physical properties of the raw materials. Depending on the conditions of the epoxidation reaction, the following formula (7) in the raw material is simultaneously formed with the epoxidation of the vinyl group in the raw material polymer.

Formula (7)
As a result of the side group reaction with the epoxidizing agent and the like, the resulting substituent group represented by formula (3) and / or the generated substituent group may be modified and mixed in the resin. is there.
As a commercial product of such a resin, EHPE-3150 (trade name, manufactured by Daicel Chemical Industries, Ltd.) in which a vinyl group in a ring-opening polymer of 4-vinylcyclohexene-1-oxide is epoxidized can also be used. .

  In addition, the epoxy group containing functional group shown by said Formula (3) should just exist at least 2 in 1 molecule of an epoxy resin, and generally an epoxy resin becomes like this. Preferably it is 140-1000, More preferably, it is 170. Epoxy equivalents in the range of ~ 300, and preferably a number average molecular weight (see note 1) in the range of 200 to 50,000, more preferably 1000 to 10,000.

  The amino group-containing compound that reacts with the epoxy resin is a cationic component for introducing an amino group into an epoxy resin substrate to make the epoxy resin cationic, and the amino group-containing epoxy resin (B11) The same amino group-containing compound as described above for the production of the amino group-containing epoxy resin (B12) and amino group-containing epoxy resin (B13) can be used.

  In addition, as an amino group-containing compound, the following formula (8) having a hydroxyl group, a secondary amino group and an amide group in one molecule.

Formula (8)
(In the formula, n is an integer of 1 to 6, R ₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ₂ may have a hydroxyl group and / or a polymerizable unsaturated bond. (Represents a carbon hydrogen group having 4 to 36 carbon atoms)
The compound shown by can be used.

  The amine compound of the above formula (8) is, for example, the following reaction formula:

(Wherein R ₁ , R ₂ and n have the same meaning as described above)
As shown in FIG. 1, it can be produced by reacting about 1 mol of N-hydroxyalkylalkylenediamine with about 1 mol of a monocarboxylic acid having 5 to 37 carbon atoms, preferably 8 to 23 carbon atoms.

  Examples of the diamine used in this reaction include 2- (2-aminoethylamino) ethanol, N-hydroxyethylethylenediamine, N-hydroxyethylpropylenediamine, N-hydroxyethylbutylenediamine, N-hydroxyethylpentylenediamine, N-hydroxyethylhexylenediamine, N- (2-hydroxy) propylethylenediamine, N- (2-hydroxy) propylpropylenediamine, N- (2-hydroxy) propylbutylenediamine, N- (2-hydroxy) propylpentylenedi Examples thereof include amines and N- (2-hydroxy) propylhexylenediamine. Among them, 2- (2-aminoethylamino) ethanol and N-hydroxyethylpropylenediamine are preferable.

  Examples of monocarboxylic acids include mixed fatty acids such as coconut oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, soybean oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, sweet potato oil fatty acid, and tung oil fatty acid. Caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, eleostearic acid, 12-hydroxystearic acid, behenic acid and the like. Of these, stearic acid, oleic acid, 12-hydroxystearic acid and mixed fatty acids containing these acids are particularly preferred.

  The reaction of N-hydroxyalkylalkylenediamine and monocarboxylic acid is, for example, mixing both components in an approximately equimolar ratio, and removing a specified amount of reaction product water using an organic solvent such as toluene or methyl isobutyl ketone. The residual organic solvent is removed by a reduced pressure method or the like.

As said phenol compound, what has at least 1 phenolic hydroxyl group in 1 molecule, Preferably 1-5 pieces can be used. Specifically, for example, 2,2-bis (p-hydroxyphenyl) propane, 4,4′-dihydroxybenzophenone, 1,1-bis (p-hydroxyphenyl) ethane, 1,1-bis (p-hydroxy) Phenyl) isobutane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane, Examples thereof include polyhydric phenol compounds such as 1,1,2,2-tetra (p-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl ether, 4,4-dihydroxydiphenyl sulfone, phenol novolac, and cresol novolac.

  Furthermore, monophenol compounds such as phenol, nonylphenol, α- or β-naphthol, p-tert-octylphenol, o- or p-phenylphenol can also be used.

  In order to form a coating film having better anticorrosion properties, the phenol compound is particularly bisphenol A [2,2-bis (p-hydroxyphenyl) propane] or bisphenol F [bis (p-hydroxyphenyl) methane]. It is preferable to use a reaction product of bisphenols and epichlorohydrin.

  Among the reaction products, in particular, the number average molecular weight is at least 200, preferably in the range of about 800 to about 3,000 and an average of 2 or less per molecule, preferably 0.8 to 1. Those typically represented by the following formula containing two phenolic hydroxyl groups are suitable.

(In the formula, n is an average number of 0 to 7, and R ₆ represents a residue of an active hydrogen compound)
Examples of the active hydrogen-containing compound which is a precursor of R _{6 in} the above formula include amines such as secondary amines; phenols such as nonylphenol; organic acids such as fatty acids; thiols; alkyl alcohols, ethylene Examples include alcohols such as glycol monobutyl ether and carbitol; and compounds such as inorganic acids. Of these, dialkanolamine, which is a secondary amine having a primary hydroxyl group, and monophenols such as nonylphenol, phenylphenol, and phenol are particularly preferable. In particular, when a primary hydroxyl group-containing amine is used, curability is improved, and when monophenol is used, stability is improved.

  Further, as a phenol compound, for example, 1 mol of a bisphenol A diglycidyl ether type polyepoxide having a molecular weight of 200 or more, preferably 380 to 2000, and 1 mol of a bisphenol A polyphenol having a molecular weight of 200 or more, preferably 200 to 2000, are used. And 1 mol of a compound having active hydrogen can be used at a temperature of 30 to 300 ° C., preferably 70 to 180 ° C., in the presence of a catalyst or a solvent, if necessary. These reaction molar ratios are merely examples, and are not limited to these, and can be arbitrarily selected.

In addition, as phenolic compounds, polyols such as dimer diol, ethylene glycol, propylene glycol, and butylene glycol; polyether glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyester polyols such as polycaprolactone; polycarboxylic acids Polyisocyanates; monoisocyanates; oxides of unsaturated compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide; allyl glycidyl ether, polypropylene glycol diglycidyl ether, 2-ethylhexyl glycidyl ether, methyl glycidyl ether, butyl Compounds having hydroxyl groups such as glycidyl ether and phenyl glycidyl ether Glycidyl esters of organic acids such as fatty acids; glycidyl ethers of cycloaliphatic oxirane containing compounds and the like may also be used those obtained by reacting bisphenol A. Furthermore, what carried out graft polymerization of (epsilon) -caprolactone, an acrylic monomer, etc. to this compound can also be used.

  The amino group-containing and / or phenol compound-containing epoxy resin (B1-4) is obtained by reacting the above-described epoxy resin with an amino compound and / or a phenol compound.

  Such an amino group-containing and / or phenol compound-containing epoxy resin (B14) has the advantage of superior corrosion resistance and stability compared to those obtained by reaction with conventional bisphenol A type epoxy resins. Yes.

The reaction ratio of the epoxy resin, the amino group-containing compound and the phenol compound is not particularly limited and can be appropriately selected according to the use of the resulting coating resin. However, in general, the epoxy group-containing functional group of the epoxy resin is used. Per mole of group, the amino compound has a primary or secondary amino group in the range of 0.1 to 1 mole, especially 0.4 to 0.9 mole, and the phenolic compound has a phenolic hydroxyl group therein. Is preferably used in such a proportion that it is in the range of 0.02 to 0.4 mol, particularly 0.1 to 0.3 mol. Moreover, the total number of moles of the primary or secondary amino group of the amino compound and the phenolic hydroxyl group of the phenol compound is based on 1 mol of the epoxy group-containing functional group in the amino group-containing and / or phenol compound-containing epoxy resin (B14). 0.75 to 1.5 mol, particularly 0.8 to 1.2 mol.

  The reaction between the epoxy resin and the amino group-containing compound or the epoxy resin and the phenol compound can be performed, for example, at a temperature in the range of 50 to 300 ° C, particularly 70 to 200 ° C. The reaction order is not particularly limited, and all components may be charged at the same time and reacted, or other components may be added to the epoxy resin in an arbitrary order and reacted sequentially.

  The amino group-containing epoxy resin (B14) generally has an amine value in the range of 20 to 150 mgKOH / g, particularly 30 to 125 mgKOH / g, a hydroxyl value in the range of 300 to 1,000 mgKOH / g, particularly 325 to 850 mgKOH / g. And a number average molecular weight (Note 1) in the range of 800 to 15,000, especially 900 to 10,000.

  The amino group-containing epoxy resin (B14) is particularly excellent in water dispersibility because the hydrophobic part and the hydrophilic part are co-polarized. For this reason, the film forming agent using the amino group-containing epoxy resin (B14) as the resin component (B) is particularly zirconium and optionally titanium, cobalt, vanadium, tungsten, molybdenum, zinc, aluminum, bismuth, yttrium, Even when at least one metal ion of metal (a) selected from lanthanoid metals, alkali metals and alkaline earth metals is present, the stability of the film-forming agent is excellent.

Amino group-containing acrylic resin (B2):
As the resin component (B), an amino group-containing acrylic resin (B2) can also be used. The acrylic resin used as a starting material can be obtained by radical copolymerization of a hydroxyl group-containing acrylic monomer, an amino group-containing acrylic monomer, and other monomers as monomer components constituting the acrylic resin.

  Examples of hydroxyl group-containing acrylic monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and addition of 2-hydroxyethyl (meth) acrylate and caprolactone. (For example, Plaxel FA-2 and FM-3 as trade names manufactured by Daicel Corporation) and the like. These can be used alone or in combination of two or more.

  Examples of the amino group-containing acrylic monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-di. -T-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, etc. are mentioned.

  Examples of other monomers include aromatic vinyl monomers such as styrene, vinyl toluene, and α-methyl styrene; for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) Examples include alkyl esters of (meth) acrylic acid such as acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. It is done.

  In addition, a resin obtained by adding an amine compound containing active hydrogen to a glycidyl group of a copolymer of a radically polymerizable unsaturated monomer containing glycidyl (meth) acrylate can be suitably used to improve coating stability. Can contribute.

  The amino group compound that can be reacted with the acrylic resin is not particularly limited as long as it can cationize the acrylic resin. For example, ethanolamine, propanolamine, 2- (2-aminoethylamino) Ketiminates of amines such as ethanol, hydroxyethylaminopropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; diethylamine, diisopropylamine, diethanolamine, di (2-hydroxypropyl) amine, monomethylaminoethanol, mono Examples include ethylaminoethanol.

  An amino group-containing acrylic resin (B2) can be obtained by reacting the above acrylic resin with an amino group compound by a method known per se. The amino group-containing acrylic resin (B2) generally has a hydroxyl value in the range of 10 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, generally 30 to 70 mgKOH / g resin solids, preferably 40 to 60 mgKOH / g resin solids. It can have an amine number in the range of minutes and a number average molecular weight in the range of generally 2,000 to 100,000, preferably 3,000 to 50,000.

Blocked polyisocyanate compound (B3):
The resin component (B) can contain a blocked polyisocyanate compound (B3) as a crosslinking agent. Examples of the blocked polyisocyanate compound (B3) include those obtained by blocking an aromatic, alicyclic or aliphatic polyisocyanate compound with a blocking agent, and these may be used alone or in combination of two or more. Can do.

  Specific examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, crude TDI, and 2,4′-diphenylmethane diisocyanate. 4,4′-diphenylmethane diisocyanate, crude MDI [mixture of 2,4′-diphenylmethane diisocyanate and 4,4′-diphenylmethane diisocyanate], 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4, 4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- Or p-isocyanatopheny And rusulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, p -Xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), and cyclohexylene diisocyanate.

  Of these polyisocyanate compounds, aliphatic polyisocyanates and alicyclic polyisocyanates are preferred from the viewpoints of weather resistance and corrosion resistance.

  The blocking agent is to block by adding to the isocyanate group of the polyisocyanate compound, and the blocked polyisocyanate compound produced by the addition of the blocking agent is stable at ordinary temperature and at a general electrodeposition coating baking temperature. It is desirable that the isocyanate group can be regenerated by dissociating the blocking agent when heated to a temperature of about 100 ° C. to about 200 ° C.

Examples of the blocking agent satisfying such requirements include lactam compounds such as ε-caprolactam and γ-butyrolactam; oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol. Aliphatic alcohols such as n-butanol and 2-ethylhexanol; aromatic alkyl alcohols such as phenyl carbinol and methyl phenyl carbinol; ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; propylene glycol; Dipropylene glycol, 1,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol 1,4-pentanediol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,5-hexane Examples thereof include hydroxyl group-containing compounds such as diol, 1,4-hexanediol, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, dimethylolvaleric acid and glyceric acid. As the block polyisocyanate compound, isophorone diisocyanate blocked with methyl ethyl ketoxime is particularly preferable.

  The resin component (B) comprising the base resin and the crosslinking agent described above can be used for the preparation of a film forming agent as a resin emulsion by being dispersed in water with a neutralizing agent such as carboxylic acid and deionized water. it can.

  The mixing ratio of the base resin and the crosslinking agent in the resin component (B) is usually 50 to 90% by mass, preferably 70 to 85% by mass, based on the total solid mass of the base resin and the crosslinking agent. The crosslinking agent can be in the range of 10 to 50% by mass, preferably 15 to 30% by mass.

  The film forming agent of the present invention is at least one selected from zirconium compounds, titanium, cobalt, vanadium, tungsten, molybdenum, copper, indium, zinc, aluminum, bismuth, yttrium, lanthanoid metals, alkali metals, and alkaline earth metals. The compound (A) with the compound of the metal (a) is contained in a total metal amount (in terms of mass) of 30 to 5,000 ppm, preferably 50 to 3,000 ppm, and more preferably 100 to 2,500 ppm.

For example, as the compound (A), a zirconium compound can be used alone. Or a zirconium compound and at least one metal (a) selected from titanium, cobalt, vanadium, tungsten, molybdenum, copper, indium, zinc, aluminum, bismuth, yttrium, lanthanoid metal, alkali metal, and alkaline earth metal A compound can be used in combination.
When the zirconium compound and the metal (a) compound are used in combination, the zirconium compound is 24 to 4,000 ppm, preferably 40 to 2,400 ppm, and the metal (a) compound is 6 to 1,000 ppm, preferably 10 to 10 ppm. The range of 600 ppm is also preferable for the precipitation of the film.

  Further, the resin component (B) can be contained in an amount of 1 to 40% by mass, preferably 5 to 35% by mass, and more preferably 10 to 30% by mass, thereby providing a film structure excellent in corrosion resistance and finish. Can be formed.

[Oxidizing agent (C)]
The film-forming agent (I) used in the method for forming a surface-treated film of the present invention comprises an oxidizing agent (C) for the purpose of promoting film precipitation, particularly promoting the precipitation of a zirconium compound and improving the stability of the film-forming agent (I). Can also be contained.

  Examples of the oxidizing agent (C) include hydrofluoric acid and its salt, silicofluoric acid and its salt, titanium hydrofluoric acid and its salt, ferric ion, acetic acid, phosphoric acid, sulfuric acid, nitric acid, hydrogen peroxide, It is selected from the group consisting of peroxyacid, citric acid and its salts, and tartaric acid and its salts. More preferably, hydrogen peroxide is preferable from the aspect of promoting precipitation.

  The content of the oxidizing agent (C) is 0.01 to 5% by mass, preferably 0.05 to 1% by mass, based on the total mass of the film forming agent, thereby stabilizing the film forming agent. Thus, a deposited film with few defects can be formed uniformly.

  The film-forming agent (I) is further used in a compounding amount in which color pigments, extender pigments, rust preventive pigments, organic solvents, pigment dispersants, surface conditioners, surfactants, catalysts, etc. are usually used as necessary. Can be contained. Examples of the pigments and catalysts include coloring pigments such as titanium white and carbon black; extender pigments such as clay, talc and barita; rust preventive pigments such as aluminum dihydrogen phosphate and aluminum phosphomolybdate; dibutyl tin Organic tin compounds such as oxide and dioctyltin oxide; aliphatic dialkyltin such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin benzoateoxy, dibutyltin benzoateoxy, dioctyltin dibenzoate, dibutyltin dibenzoate Or tin compounds, such as aromatic carboxylate, are mentioned.

  The film forming agent can be prepared, for example, by the methods (1) to (3) described below.

  (1) Resin component (B) and optionally other additives are mixed together and mixed thoroughly to prepare a dissolved varnish, and then formic acid, acetic acid, lactic acid, propionic acid, citric acid, malic acid in an aqueous medium A method of adding the compound (A) to an emulsion obtained by adding a neutralizing agent selected from sulfamic acid or a mixture of one or more thereof, and then dispersing in water.

  (2) A method of adding a pigment, a catalyst, other additives and water to the compound (A) to disperse the pigment to prepare a pigment dispersion paste in advance, and adding the pigment dispersion paste to the emulsion of the resin component (B) .

  (3) A pigment, paste, catalyst, other additives, and water are added to disperse the pigment to prepare a pigment dispersion paste in advance. The pigment dispersion paste is added to the emulsion of the resin component (B) and then diluted with water. And bathing and compounding compound (A).

  The film-forming agent is diluted with deionized water or the like, and the bath solid content concentration is usually 1 to 40% by mass, preferably 5 to 25% by mass, pH 1 to 9, preferably pH 3 to 6. It can be adjusted and used to be inside.

Multi-stage painting:
The coating of the film-forming agent according to the present invention can be performed by a multi-stage method in which a metal base material to be coated is immersed in a bath without energization, and then energized and coated, specifically, as described above. By using the film forming agent as a bath, the metal substrate as the object to be coated can be immersed, and the film thickness can be increased according to the immersion time and the energization coating time.

  Specifically, as the dipping time, the metal substrate is dipped for 1 to 600 seconds, preferably 30 to 480 seconds, more preferably 60 to 300 seconds, and then the energization coating is set to 50 to 400V, preferably 150 to 350V. It can be carried out by applying a voltage for 60 to 180 seconds, preferably 90 to 150 seconds.

The bath temperature of the film-forming agent is usually 5 to 45 ° C., preferably 10 to 40 ° C., more preferably 20 to 35 ° C. The baking temperature of the film is 100 to 200 ° C., preferably 120 to 180 ° C. on the surface of the metal substrate, and the baking time is 5 to 90 minutes, preferably about 10 to 50 minutes. Can do.
By this film formation method, a film structure having a film (F1) formed on the side of the metal base material to be coated and having a film (F2) having a thickness of 0.1 to 30 μm can be obtained.

  It is also possible to immerse the metal base material, then remove the metal base material from the tank, and then apply the metal base material again with electrical conduction, thereby obtaining a film structure with further excellent anticorrosion properties. The reason is considered to form a dense oxide film.

About the precipitation mechanism:
As a film deposition mechanism, by immersing a metal substrate in a film forming agent, the pH in the vicinity of the object to be coated is increased by the etching action of acidic components contained in the film forming agent. , Hexafluorozirconium ion) undergoes a hydrolysis reaction, and a hardly soluble film (F1) (mainly zirconium oxide) is deposited on the metal substrate.
Next, when the pH in the vicinity of the metal substrate is increased by energization after the dipping step, the aqueous dispersion of the resin component (B) that is stabilized by ionization becomes unstable, and the resin Component (B) aggregates to form a film (F2).

  Specifically, on the basis of the total mass solid content of the film, at least one compound (A) selected from a zirconium compound and a metal (a) compound is 25 to 99 in terms of total metal amount (mass conversion). At least 1 selected from a zirconium compound and a compound of metal (a) on the basis of the coating (F1) containing 30% by mass, particularly 30 to 60% by mass, and the total mass solid content of the coating on the coating (F1). A film containing the seed compound (A) in a total metal amount (in terms of mass) of less than 25% by mass, particularly 1 to 10% by mass and containing the resin component (B) in an amount of 50 to 95% by mass, particularly 70 to 90% by mass. A film structure comprising (F2) can be formed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited only to these Examples. “Parts” and “%” are “parts by mass” and “% by mass”.

Production Example 1 Amino group-containing epoxy resin No. 1 Production of 1 solution 300 parts of ε-caprolactone was added to 400 parts of PP-400 (manufactured by Sanyo Chemical Industries, trade name, polypropylene glycol molecular weight 400), and the temperature was raised to 130 ° C. Thereafter, 0.01 part of tetrabutoxy titanium was added and the temperature was raised to 170 ° C. Sampling was performed over time while maintaining this temperature, and when it was confirmed that the unreacted ε-caprolactone substantially disappeared, the modifier 1 was obtained.
To another flask, 1000 parts of Epicoat 828EL (trade name, epoxy resin, epoxy equivalent 190, molecular weight 350, manufactured by Japan Epoxy Resin Co., Ltd.), 400 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added, and the epoxy equivalent was 750 at 130 ° C. The reaction was continued until Next, 200 parts of modifier 1, 140 parts of diethanolamine and 65 parts of diethylenetriamine ketiminate were added and reacted at 120 ° C. for 4 hours. The solid content was adjusted with ethylene glycol monobutyl ether, and the resin solid content was 80%. Polyol-modified amino group-containing epoxy resin no. One solution was obtained. The amino group-containing epoxy resin no. 1 had a resin amine value of 56 mgKOH / g and a number average molecular weight of 2,000.

Production Example 2 Amino group-containing epoxy resin No. 1 Production of 2 solutions A separable flask having an internal volume of 2 liters equipped with a thermometer, a reflux condenser and a stirrer was charged with 480 parts of 50% formalin, 110 parts of phenol, 202 parts of 98% industrial sulfuric acid and 424 parts of metaxylene, The reaction was carried out at 84 to 88 ° C. for 4 hours. After the reaction is completed, the resin phase is separated from the sulfuric acid aqueous phase by standing, then the resin phase is washed with water three times, and unreacted metaxylene is stripped for 20 minutes under the condition of 20-30 mmHg / 120-130 ° C. 480 parts of a phenol-modified xylene formaldehyde resin having a viscosity of 1050 centipoise (25 ° C.) were obtained.
To another flask, 1000 parts of Epicoat 828EL (trade name, epoxy resin, epoxy equivalent 190, molecular weight 350, manufactured by Japan Epoxy Resin Co., Ltd.), 400 parts of bisphenol A and 0.2 part of dimethylbenzylamine were added, and epoxy equivalent at 130 ° C. The reaction was continued until 750 was reached.
Next, after adding 300 parts of xylene formaldehyde resin, 137 parts of diethanolamine and 95 parts of ketimine of methyl isobutyl ketone of diethylenetriamine, the mixture was reacted at 120 ° C. for 4 hours, and then added with 403 parts of ethylene glycol monobutyl ether to give a resin solid content of 80 parts. % Of xylene formaldehyde resin-modified amino group-containing epoxy resin no. Two solutions were obtained. The amino group-containing epoxy resin no. 2 had a resin amine value of 57 mg KOH / g and a number average molecular weight of 2,000.

Production Example 3 Amino group-containing epoxy resin Production of 3 solutions In a flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 397 parts of ethylene glycol monobutyl ether, 900 parts of EHPE-3150 (epoxy equivalent 180, manufactured by Daicel Chemical Industries, Ltd.), amino group-containing 370 parts of a compound (Note 3), 315 parts of diethanolamine and 1651 parts of a phenol compound (Note 4) were added, and the temperature was raised to 150 ° C. while mixing and stirring. Furthermore, 3610 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 1596 parts of bisphenol A, 525 parts of diethanolamine, and 1433 parts of ethylene glycol monobutyl ether were added and reacted at 150 ° C. until the remaining amount of epoxy group became 0, and the resin solid Min. 80%, amine-added epoxy resin no. Three solutions were obtained. The amine-added epoxy resin No. 3 had a resin amine value of 65 mgKOH / g and a number average molecular weight of 2,000.
(Note 3) Amino group-containing compound:
A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a water separator is charged with 300 parts of 12-hydroxystearic acid, 104 parts of hydroxyethylaminoethylamine and 80 parts of toluene, and gradually heated while mixing and stirring. Then, if necessary, toluene was removed and 18 parts of the reaction water was separated and removed while raising the temperature, and then the remaining toluene was removed under reduced pressure to obtain an amino group-containing compound having an amine value of 148 mgKOH / g and a freezing point of 69 ° C.
(Note 4) Phenolic compounds:
To a flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 105 parts of diethanolamine, 760 parts of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 456 parts of bisphenol A and 330 parts of ethylene glycol monobutyl ether were added at 150 ° C. The reaction was continued until the remaining amount of epoxy group became 0, and a phenol compound having a solid content of 80% was obtained.

Production Example 4 Production of curing agent
44 parts of methyl isobutyl ketone was added to 222 parts of isophorone diisocyanate, and the temperature was raised to 70 ° C. Thereafter, 174 parts of methyl ethyl ketoxime was added dropwise over 2 hours, and sampling was performed over time while maintaining this temperature, and it was confirmed that absorption of unreacted isocyanate was substantially eliminated by infrared absorption spectrum measurement. A curing agent which was a block polyisocyanate compound having a solid content of 90% was obtained.

Production Example 5 Emulsion No. Production of amine-added epoxy resin No. 1 having a solid content of 80% obtained in Production Example 1 above. 1
87.5 parts (solid content 70 parts), and curing agent No. No. 1 33.3 parts (solid content 30 parts), acetic acid 1.6 parts and deionized water 190.1 parts were added to disperse in water. 1 was obtained.

Production Examples 6 to 10 Emulsion No. 2-No. Production of Emulsion No. 6 having the blending contents shown in Table 1 by the same operation as in Production Example 5. 2-No. 6 was obtained.

(Note 5) EA-142B: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name, polyoxyethylene octylphenyl ether.

Production Example 11 Acrylic Resin Solution for Dispersing Pigment In an ordinary acrylic resin reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 37 parts of ethylene glycol monobutyl ether was charged and stirred at a temperature of 110 ° C.
The following “mixture” was dropped therein over 3 hours. After completion of the dropwise addition, the mixture was aged at 110 ° C. for 30 minutes, and then an additional catalyst mixture composed of 20 parts of ethylene glycol monobutyl ether and 0.5 part of azobisisobutyronitrile was added dropwise over 1 hour. Next, the mixture was aged at 110 ° C. for 1 hour and then cooled to obtain an acrylic resin solution for pigment dispersion having a resin solid content of 55%.
"blend"
Styrene 10 parts Methyl methacrylate 25 parts 2-Ethylhexyl methacrylate 20 parts 2-Hydroxyethyl methacrylate 10 parts NF biisomer S20W (Note 6) 35 parts Azobisisobutyronitrile 1 part Isobutyl alcohol 5 parts.
(Note 6) NF biisomer S20W: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name, 50% water-diluted product of methoxypolyethylene glycol monomethacrylate, molecular weight of about 2,080.

Production Example 12 Pigment Dispersion Paste No. Production of No. 1 Acrylic resin solution for dispersing pigment having a solid content of 55% obtained in Production Example 11 (5.0 parts) (solid content 5.0 parts), JR-600E (Note 7) 14.0 parts, carbon MA- 7 (Note 8) 0.3 parts, Hydrite PXN (Note 9) 9.7 parts, Dioctyltin oxide 1.0 part and 20.4 parts deionized water were dispersed in a ball mill for 20 hours to obtain a solid content of 55 % Pigment dispersion paste No. 1 was obtained.

Production Example 13 Pigment Dispersion Paste No. Production Example No. 2 Pigment dispersion paste No. 2 was prepared in the same manner as in Production Example 12 except that the compounds shown in Table 2 below were used. 2 was obtained.

(Note 7) JR-600E: Made by Teica, trade name, titanium white (Note 8) Carbon MA-7: Made by Mitsubishi Kasei, trade name, carbon black (Note 9) Hydrite PXN: Made by Georgia Kaolin Name, kaolin.

Production Example 14
Emulsion No. No. 1 312.5 parts (100 parts solids), 55% pigment dispersion paste No. 1 obtained in Production Example 12. 1 is 54.5 parts (solid content 30 parts) and deionized water 633.0 parts is added to make a bath, then zirconium hydrogen fluoride ammonium 1.3 parts and titanium titanium fluoride 2.1 parts are added to form a film. No. 1 was obtained.

Production Examples 15 to 32
Except for the formulations shown in Table 3 and Table 4 below, the film forming agent No. 2-No. 19 was obtained.

Example 1
Film forming agent No. 1 bath was adjusted to 28 ° C., and a cold-rolled steel sheet (70 mm × 150 mm × 0.8 mm) as a metal base was immersed in “Step 1 for 180 seconds and then Step 2 at 60 V for 20 seconds”. When applied, the total dry film thickness of the film (F1) and film (F2) was 20 μm. The obtained film was baked with an electric dryer at 170 ° C. for 20 minutes. It was set to 1.

Examples 2-13
Except for using the coating conditions of Table 5 and Table 6 and the film forming agent, the film No. 2-No. 13 was obtained.

比較例１〜１０
表７の皮膜形成剤する以外は、実施例１と同様にして、試験板Ｎｏ．１４〜Ｎｏ．２３を得た。

Comparative Examples 1-10
Except for the film-forming agent shown in Table 7, the test plate No. 14-No. 23 was obtained.

(Note 10) Film state: The test plate was cut, and the film states of the film (F1) and the film (F2) were observed using HF-2000 (manufactured by Hitachi, Ltd., field emission type transmission electron microscope). The film state was evaluated according to the following criteria.
“◯” indicates that the boundary between the film (F1) and the film (F2) is not clear, but some layer separation is observed.
“-” Indicates no layer separation.

  (Note 11) The amount of metal (%) of Zr and metal (a): The amount of metal (% by mass) in the film (F1) was measured using IX-3100RF (trade name, X-ray fluorescence analyzer, manufactured by Rigaku Corporation). Measured.

(Note 12) Content of resin component (B): The film (F2) before baking and drying was scraped off and obtained according to the following formula (2).
Mass after drying film (F2) at 105 ° C. for 3 hours: b1
Residual mass after baking for 5 hours in a crucible at 800 ° C b2
Content (%) of resin component (B) = [(b1-b2) / b1] Formula (2).

(Note 13) Corrosion resistance: The electrodeposition coating film was cut with a knife so as to reach the substrate of the test plate, and a salt water spray test was conducted for 480 hours according to JISZ-2371 using this. The evaluation was made according to the following criteria based on the rust and blister width from the knife scratch.
◎ indicates that the maximum width of rust and blisters is less than 2 mm (one side) from the cut part.
○ indicates that the maximum width of rust and blisters is 2 mm or more and less than 3 mm (one side) from the cut part.
△ indicates that the maximum width of rust and blisters is 3 mm or more and less than 4 mm (one side) from the cut part.
X indicates that the maximum width of rust and blisters is 4 mm or more (one side) from the cut part.
It shows that.

(Note 14) Exposure resistance:
After spraying the test plate with WP-300 (manufactured by Kansai Paint Co., Ltd., water-based intermediate coating) so as to have a cured film thickness of 25 μm, it is baked at 140 ° C. for 30 minutes with an electric hot air dryer. I did it. Furthermore, neo-amylac 6000 (manufactured by Kansai Paint Co., Ltd., top coating) is applied onto the intermediate coating film by spray coating so that the cured film thickness is 35 μm, and then baked at 140 ° C. for 30 minutes in an electric hot air dryer. A blank test plate was prepared.
The resulting paint film on the test plate is cross-cut with a knife so that it reaches the substrate, and this is exposed horizontally in Chikura Town, Chiba Prefecture for one year. Evaluation was made according to the following criteria according to the width.
◎ indicates that the maximum width of rust or swelling is less than 2 mm from the cut part (one side)
○ indicates that the maximum width of rust or blister is 2 mm or more from the cut part and less than 3 mm (one side)
△ indicates that the maximum width of rust or blisters is 3 mm or more and less than 4 mm from the cut part (one side)
X: The maximum width of rust or blisters is 4 mm or more (one side) from the cut part.
It shows that.

(Note 15) Finishability:
The surface roughness value (Ra) of the coated surface of the test plate was measured at a cutoff of 0.8 mm using a surf test 301 (manufactured by Mitutoyo Corporation, trade name, surface roughness meter).
◎ indicates that the surface roughness value (Ra) is less than 0.2 μm. ○ indicates that the surface roughness value (Ra) is 0.25 μm or more and less than 0.3 μm.
Δ is a surface roughness value (Ra) of 0.25 μm or more and less than 0.3 μm,
X indicates that the surface roughness value (Ra) is 0.3 μm or more.

(Note 16) Weather resistance:
Each test plate having a dry film thickness of 20 μm is subjected to an accelerated weather resistance test using a sunshine carbon arc lamp type as defined in JIS K-5400 9.8.1, and coated according to JIS K-5400 7.6 (1990). The time required for the 60-degree specular reflectance (%) to divide 80% was measured.
◎ indicates that the time when the 60-degree specular reflectance (%) divides 80% is 200 hours or more,
○ is the time when the 60-degree specular reflectance (%) divides 80% is 150 hours or more and less than 200 hours. △ is the time when the 60-degree specular reflectance (%) divides 80% is 50 hours or more and 150. Less than time ×: less than 50 hours when the 60-degree specular reflectance (%) divides 80%.

(Note 17) Film former stability:
Each film-forming agent was stirred at 30 ° C. with the container sealed for 30 days. Thereafter, the entire amount of the film-forming agent was filtered using a 400 mesh filter screen, and the remaining amount (mg / L) was measured.
◎ is less than 5 mg / L,
○ is 5 mg / L or more and less than 10 mg / L. Δ is 10 mg / L or more and less than 15 mg / L. X indicates 15 mg / L or more.

(Note 18) Uniform precipitation of film (F1):
Using a “four-box method throwability test jig” (see FIG. 1) with holes of 8 mm in diameter and four steel plates installed at 2 cm intervals, pulling up from the bath under the coating conditions in step 1 And dried at 170 ° C. for 20 minutes to obtain a steel sheet coated only with the film (F1).
In the “four-box uniform precipitation test jig” in FIG. 1, the left side surface of the leftmost steel plate is referred to as “A surface”, and the right side surface thereof is referred to as “B surface”. Similarly, the left and right surfaces of the second steel plate from the left are “C surface” and “D surface”, respectively, and the left and right surfaces of the third steel plate from the left are “E surface” and “F surface”, respectively. The right and left surfaces of the rightmost steel sheet are the “G plane” and the “H plane”, respectively. Among these, the A surface is an “outer plate”, and the G surface is an “inner plate”.
The uniform precipitation property of the film (F1) is determined by the amount of zirconium (mass%) on the outer plate (A surface) and the inner plate (G surface) by IX-3100RF (trade name, fluorescent X-ray analyzer, manufactured by Rigaku Corporation). ).
○ indicates that the content ratio (G / A%) of metal zirconium in the A plane and the G plane is 50% or more.
In Δ, the content ratio (G / A%) of metal zirconium in the A plane and the G plane is 25% or more and less than 50%.
In x, the content ratio (G / A%) of metal zirconium in the A plane and the G plane is less than 25%.

The film forming method of the present invention is industrially useful because it can provide a coated article excellent in corrosion resistance, finish, and uniform precipitation of the film.

FIG. 4 is a model diagram of a “four-box uniform precipitation test jig” used for a uniform deposition test of a film.

Explanation of symbols

1. Outer plate (surface A) in a jig for uniform precipitation test of 2.4-hole box method with 8 mm diameter hole
3. Inner plate (G surface) in the jig for uniform precipitation test by the 4-box method

Claims (5)

A method of forming a film by coating a metal substrate with a film forming agent (I) in a multi-stage manner of at least two stages,
A compound in which the film forming agent (I) produces an oxymetal ion or a fluorometal ion of zirconium , and titanium, cobalt, vanadium, tungsten, molybdenum, copper, indium, zinc, aluminum, bismuth, yttrium, lanthanoid metal, alkali metal and alkali At least one compound (A) selected from compounds that generate ions of metal (a) selected from earth metals is 30 to 5,000 ppm in terms of total metal amount (mass conversion), and resin component (B) 1 to 40 And 0.01% to 5% by mass of the oxidizing agent (C) with respect to the total mass of the film forming agent (I) ,
(1) a step of immersing a metal material in a tank of the film forming agent (I) for 30 to 480 seconds without energizing; and (2) after the step (1), in the tank of the film forming agent (I), A process of energizing the immersed metal material at 50 to 400 V for 60 to 240 seconds,
A method for forming a surface-treated film, comprising: A method of forming a film by coating a metal base material with a film forming agent (I) in a multi-stage manner of at least two stages,
The film forming agent (I) is a compound that produces an oxymetal ion of zirconium alone, or a compound that produces an oxymetal ion of zirconium , and titanium, cobalt, vanadium, tungsten, molybdenum, copper, indium, zinc, aluminum, bismuth, yttrium. A compound (A), which is a compound that generates ions of at least one metal (a) selected from lanthanoid metals, alkali metals, and alkaline earth metals, in a total metal amount (mass conversion) of 30 to 5,000 ppm, Comprising 1 to 40% by weight of component (B),
(1) a step of immersing a metal material in a tank of the film forming agent (I) for 30 to 480 seconds without energizing; and (2) after the step (1), in the tank of the film forming agent (I), A process of energizing the immersed metal material at 50 to 400 V for 60 to 240 seconds,
A method for forming a surface-treated film, comprising:   The method for forming a surface-treated film according to claim 1 or 2, wherein the resin component (B) contains a cationic resin composition. The surface-treated film according to any one of claims 1 to 3 , wherein the compound that generates an oxymetal ion of zirconium is at least one selected from zirconyl nitrate, zirconium hydrofluoric acid, and zirconium hydrofluoride. Forming method. The formation method of the surface treatment film | membrane of Claim 2 which contains 0.01-5 mass% of oxidizing agents (C) with respect to the total mass of film forming agent (I).

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