JP5563359B2 - Metal surface treatment agent - Google Patents

Description

  The present invention relates to a metal surface treatment agent that is excellent in storage stability, low-temperature short-time drying properties, fingerprint resistance, corrosion resistance, and adhesion to a top coat film.

  In the field of surface treatment agents for metal materials used for home appliances and the like, chromate treatment agents have been the mainstream in the past, but the hexavalent chromium compounds used therein are substances harmful to the human body. Development of a surface treatment agent that does not contain a hexavalent chromium compound is underway. As a surface treatment agent not containing chromium, there is a phosphate treatment agent such as a zinc phosphate treatment agent, but there is a problem that sludge is generated.

  Development of organic surface treatment agents has been actively conducted as an alternative to chromate treatment. By using an organic resin, it is possible to obtain a treated film having excellent processability and adhesion with the top coat film, and by combining a rust preventive agent therewith, a certain degree of corrosion resistance can be ensured.

  The polyurethane resin composition of Patent Document 1 discloses a carbonyl group-containing polyurethane obtained by a reaction between a terminal isocyanate group-containing prepolymer and a carbonyl group-containing Michael (Michael) addition reaction product.

  In the Michael addition reaction, an amine compound having a plurality of primary amino groups is used, so that the equivalent ratio of the primary amino group contained in the amine compound to the carbonyl group-containing unsaturated monomer is 2 or more. In this case, a Michael addition reaction product containing the primary amino group unreacted is obtained. Therefore, the carbonyl group-containing polyurethane obtained by reacting the reaction product with the terminal isocyanate group-containing prepolymer has a urea bond formed by the reaction of the primary amino group and the isocyanate group, and is included in the urea bond. Each of the two nitrogen atoms has one hydrogen atom. Since hydrogen bonds caused by these hydrogen atoms act between polyurethane molecules, the viscosity of the polyurethane resin may increase, and the surface treatment agent using the aqueous dispersion of polyurethane has a problem in stability. It was.

Patent Document 2 discloses an aqueous resin composition for treating an aluminum-zinc alloy-plated steel sheet comprising an anionic polyurethane aqueous dispersion (a), a silane coupling agent (b) and a water-soluble zirconium compound (c). Has been.
Further, Patent Document 3 discloses (A) an aqueous dispersion of a polyurethane resin (I) having a cationic group and a polyoxyalkylene chain in the side chain, and (B) a phosphoric acid compound, a nickel compound, a silane coupling agent, and silica. A metal surface treatment composition characterized by containing at least one selected from particles is disclosed.
However, the film obtained by applying the aqueous resin composition of Patent Document 2 or the surface treatment composition of Patent Document 3 is insufficient in any of fingerprint resistance, corrosion resistance, and adhesion to the top coat film. .

JP 2006-28343 A JP 2004-204333 A JP 2009-127057 A

  An object of the present invention is to provide a metal treating agent that is excellent in storage stability, low-temperature short-time drying properties, fingerprint resistance, corrosion resistance, and adhesion to a top coat film.

  As a result of intensive studies to achieve the above object, the present inventors have found that an aqueous dispersion of a specific carbonyl group-containing urethane urea resin (A), a functional group capable of reacting with the carbonyl group in the resin (A). A metal surface characterized by containing at least one metal compound (D) selected from Ti, Zr and V, a curing agent (B) containing 2 or more per molecule, silica particles (C) The present inventors have found that the above problems can be solved by the treatment agent, and have completed the present invention.

That is, the present invention
1. An aqueous dispersion of a carbonyl group-containing urethane urea resin (A) having the following characteristics, a curing agent (B) containing two or more functional groups capable of reacting with the carbonyl group in the resin (A), and silica particles A metal surface treating agent comprising (C) and at least one metal compound (D) selected from Ti, Zr and V.
Aqueous dispersion of carbonyl group-containing urethane urea resin (A): amine compound containing one primary amino group in the molecule, amine compound containing one primary amino group and one secondary amino group, and secondary compound at least one amine compound, Ru obtained allowed Michael addition reaction against diacetone acrylamide, secondary amino group and carbonyl group in the molecular selected from the group consisting of an amine compound containing amino groups or two 1. An aqueous dispersion obtained by dispersing a resin (A) obtained by reacting a compound (a1), a polyol compound (a2) and a polyisocyanate compound (a3) in water or a medium containing water. The metal surface treatment agent according to 1, wherein the functional group of the curing agent (B) is a hydrazide group and / or a semicarbazide group,
3. The metal surface treatment agent according to 1 or 2, wherein the metal compound (D) is at least one selected from titanium hydrofluoride, zirconium hydrofluoride, ammonium zirconium carbonate, metavanadate, and vanadyl sulfate. ,
4).
It is related with the surface treatment steel plate obtained by apply | coating the metal surface treating agent of any one of 1-3 to a metal base material, and heat-drying.

  The metal surface treating agent of the present invention is an aqueous dispersion of a specific carbonyl group-containing urethane urea resin (A) and a curing containing two or more functional groups capable of reacting with the carbonyl group of the resin (A) in one molecule. By containing the agent (B), the material maximum achieved temperature (PMT) is excellent in curability in drying at a low temperature and short time of several tens of seconds at a low temperature of about 80 ° C. A coating film having excellent adhesion can be formed. Furthermore, by containing the silica particles (C) and the metal compound (D), it is possible to prevent penetration of coating deterioration factors such as water and acidic components from the outside, and to obtain a coating having excellent corrosion resistance.

  The present invention relates to an aqueous dispersion of a carbonyl group-containing urethane urea resin (A), a curing agent (B) containing at least two functional groups capable of reacting with the carbonyl group in the resin (A), silica, A metal surface treatment agent comprising particles (C) and at least one metal compound (D) selected from Ti, Zr and V. Details will be described below.

Aqueous dispersion of carbonyl group-containing urethane urea resin (A) An aqueous dispersion of carbonyl group-containing urethane urea resin (A) is an amine compound containing one primary amino group in the molecule, a primary amino group and a secondary amino group. Obtained by Michael addition reaction of diacetone acrylamide with at least one amine compound selected from the group consisting of amine compounds each containing one amino group and amine compounds containing two or more secondary amino groups. In a medium containing water or water, the resin (A) obtained by reacting the compound (a1), polyol compound (a2) and polyisocyanate compound (a3) containing a secondary amino group and carbonyl group in the molecule is reacted. An aqueous dispersion dispersed in

Compound (a1) containing secondary amino group and carbonyl group
The compound (a1) containing a secondary amino group and a carbonyl group (hereinafter sometimes abbreviated as “compound (a1)”) contains one primary amino group in the molecule relative to diacetone acrylamide. Michael addition of at least one amine compound selected from the group consisting of an amine compound, an amine compound containing one primary amino group and one secondary amino group, and an amine compound containing two or more secondary amino groups It is a compound obtained by reacting.

  Specific examples of an amine compound containing one primary amino group in the molecule, an amine compound containing one primary amino group and one secondary amino group, and an amine compound containing two or more secondary amino groups Are methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, t-butylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-methylthiopropylamine, N- Methyl ethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-isopropylethylenediamine, N- (2-hydroxyethyl) ethylenediamine, N-butylethylenediamine, N, N-dimethylethylenediamine, 2-aminoethanol 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 2- (2 -Aminoethoxy) Aliphatic compounds having C1 to C16 carbon atoms which may contain nitrogen, oxygen and sulfur atoms such as ethanol and allylamine; cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, amino C1-C16 carbon number which may contain nitrogen atom, oxygen atom, sulfur atom such as methylcyclohexane, 4-methylcyclohexylamine, 1-cyclohexylethylamine, 3,3,5-trimethylcyclohexylamine, N-cyclohexylethylenediamine, etc. An alicyclic compound having benzene; Nitrogen atom, oxygen atom, sulfur atom such as amine, phenethylamine, 4-methylbenzylamine, N-aminopropylaniline, 2-amino-1,2-diphenylethanol, 9-aminofluorene, benzhydrylamine, N-benzylethylenediamine C1-C16 aromatic compounds which may contain; piperazine, N-aminopropylpiperazine, N-aminoethylpiperidine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, furfurylamine, tetrahydrofurfurylamine 3-aminopyrrolidine, 3- (methylamino) pyrrolidine, 5-methylfurfurylamine, 2- (furfurylthio) ethylamine, 2-picolylamine, 3-picolylamine, 4-picolylamine, N-aminopropylpiperidine, etc. The heterocyclic compound etc. which have C1-C16 carbon number which may contain these nitrogen atoms, oxygen atoms, and sulfur atoms, etc. can be mentioned.

Among the above-described compounds, amine compounds containing one primary amino group and one secondary amino group, such as N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-isopropylethylenediamine, N- (2 -Hydroxyethyl) ethylenediamine, N-cyclohexylethylenediamine, N-benzylethylenediamine, and N-aminopropylpiperidine can increase the carbonyl group concentration of the carbonyl group-containing urethane urea resin or increase the molecular weight of the resin (A). This is preferable from the viewpoint of improving the corrosion resistance of the resulting film.

Here, when N-ethylethylenediamine, which is an aliphatic compound, is selected as the amine compound, the reaction for generating the compound (a1) by the Michael addition reaction to diacetone acrylamide is represented by the following formula (1). The compound (a1) in the formula (1) contains two secondary amino groups and one carbonyl group in the molecule.

  The Michael addition reaction in the present invention is usually carried out in the range of 0 to 200 ° C., preferably in the range of 50 to 120 ° C., so that a desired reaction product can be obtained in a short time and an unintended side reaction. It is preferable from the point which can suppress.

In the present invention, the Michael addition reaction is carried out by mixing the amine compound with diacetone acrylamide so that the molar ratio of the amine compound is within the range of 0.8 to 5.0, and further within the range of 0.9 to 2.2. Is preferred.
If the molar ratio of the amine compound to diacetone acrylamide is less than 0.8, unreacted diacetone acrylamide may be mixed with the reaction product required, and the urethane urea resin produced using the reaction product A film prepared from an aqueous dispersion may have a reduced water resistance because a part of the curing agent reacts with unreacted diacetone acrylamide to lower the crosslinking density.

  On the other hand, when the molar ratio is larger than 5.0, when the excess amine compound is removed from the reaction product mixture, the removal process takes time, and the production cost may increase. On the other hand, when a urethane urea resin is produced using the above reaction product mixture without removing excess amine compound, the viscosity of the resin may increase or water dispersibility may decrease.

The Michael addition reaction for obtaining the above compound (a1) can be carried out in the presence of water or an organic solvent, but is not particularly required. When using an organic solvent, the kind is not specifically limited, However, Well-known organic solvents, such as ester type, ether type, and alcohol type, can be used.
When the compound (a1) and the polyisocyanate compound (a3) are reacted, the organic solvent that reacts with the isocyanate group, such as water or an alcohol-based organic solvent, is removed from the solution containing the compound (a1) by a known method. It is preferable to keep. When water or an organic solvent is used, the solution concentration is 20% by mass or more, preferably 50% by mass or more. A solution concentration of less than 20% by mass is not preferable because the reaction hardly proceeds. Moreover, as reaction time, although it changes with kinds of amino compound to be used, normally 30 minutes-5 hours are suitable.

  When performing the Michael addition reaction, a catalyst can also be used. The catalyst is not particularly limited. For example, metal alkoxides such as sodium methoxide, sodium ethoxide, and magnesium ethoxide; metal phenoxides such as sodium phenoxide; metal carbochelates such as sodium benzoate and potassium benzoate; triethylamine, Triethylenediamine, N, N-diethylaniline, N, N-dimethylaniline, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, pyridine, picoline, 1,8 -Tertiary amines such as diazabicyclo (5,4,0) undecene-7; tetraethylammonium bromide, tetrabutylammonium bromide, benzyltriethylammonium chloride, trioctylmethylammonium chloride, cetyltrimethyl bromide Quaternary ammonium salts such as ruammonium iodide, tetrabutylammonium iodide, dodecyltrimethylammonium iodide, benzyldimethyltetradecylammonium acetate; quaternary phosphonium salts such as tetraphenylphosphonium chloride, triphenylmethylphosphonium chloride, tetramethylphosphonium bromide 2-methylimidazole, 2-ethylimidazole, 2-methyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Examples include basic compounds such as imidazole compounds such as imidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 1-azine-2-methylimidazole. The catalyst is not limited to one type, and a plurality of types can be used. When using a catalyst, the usage-amount is preferable 10 mol% or less with respect to the usage-amount of an amine compound, and multiple types can also be used as needed.

  The mixture containing the reaction product obtained by the Michael addition reaction may contain an unreacted amine compound or ketiminated compound in the Michael addition reaction product.

  When the unreacted amine compound is contained, the viscosity of the carbonyl group-containing urethane urea resin may be increased in the reaction between the Michael addition reaction product and the polyisocyanate compound described later, and therefore it is preferably removed. The removal can be performed by distillation or azeotropy with water and / or an organic solvent under normal or reduced pressure conditions. As the organic solvent, the organic solvent used in the Michael addition reaction can be used. After the Michael addition reaction, a known organic solvent such as an alcohol organic solvent or an ether organic solvent is further added. Also good.

Moreover, when a ketiminated compound is contained, the following problems may occur. 1) In the reaction between the Michael addition reaction product and polyisocyanate, viscosity may increase or gelation may occur. 2) In the aqueous dispersion of the carbonyl group-containing urethane urea resin, the ketiminated portion may be hydrolyzed to regenerate amino groups and cause yellowing of the coating film.
Therefore, the above problem can be solved by adding excess water to the mixture obtained by the Michael addition reaction to hydrolyze the ketiminated portion of the ketiminated compound to regenerate the carbonyl group. preferable. The amine compound produced by this hydrolysis can be removed in the same manner as the unreacted amine compound.

  The removal of the unreacted amine compound shown here and the amine compound formed by hydrolysis of the ketiminated compound may be performed simultaneously with the Michael addition reaction or after the completion of the Michael addition reaction. Also good.

Diacetone acrylamide is derived from a hydrogen atom bonded to a carbon atom forming a carbon-carbon double bond (CH ₂ ═CH) at 6.19 to 6.23 ppm in 1H-NMR measurement using a deuterated chloroform solvent. A peak is observed. In the measurement of 1H-NMR using a deuterated chloroform solvent of the reaction product, no peak is observed at 6.19 to 6.23 ppm. Therefore, in the present invention, the Michael addition reaction is managed by the NMR measurement. Can do.

The above-mentioned Michael addition reaction product preferably contains one or two secondary amino groups. From the viewpoint of acid resistance and water resistance of the coating film obtained using the carbonyl group-containing urethane urea resin (A). From the viewpoint of controlling the viscosity of the obtained carbonyl group-containing urethane urea resin (A), those not containing a primary amino group are preferable.
In the production of the carbonyl group-containing urethane urea resin (A), the secondary amino group contained in the Michael addition reaction product reacts with the isocyanate group of the polyisocyanate compound (a3) to form a urea bond. Only one of the two nitrogen atoms contained in the urea bond is bonded to one hydrogen atom.

  On the other hand, when the Michael addition reaction product contains a primary amino group, the primary amino group reacts with the isocyanate group of the polyisocyanate compound (a3) to form a urea bond, which is included in the urea bond. Each of the two nitrogen atoms has one hydrogen atom. Therefore, in the case where the Michael addition reaction product contains a large amount of primary amino groups, the viscosity of the resulting resin due to hydrogen bonds caused by the two hydrogen atoms of each of the two nitrogen atoms contained in the urea bond. Not only makes it difficult to stir in production, but also may reduce the finish of the resulting film.

  When a Michael addition reaction product containing only one secondary amino group is used in the production of a carbonyl group-containing urethane urea resin, it is possible to introduce a carbonyl group at the end of the carbonyl group-containing urethane urea resin. is there.

  The above-mentioned Michael addition reaction product containing one secondary amino group and Michael addition reaction product containing two secondary amino groups are used at the same time to produce a carbonyl group-containing urethane urea resin (A). You can also

Polyol compound (a2)
Next, the polyol compound (a2) has two or more hydroxyl groups in one molecule, and examples thereof include low molecular weight glycols, high molecular weight glycols, polyester polyols, polycarbonate polyols, and the like. Or two or more kinds may be used. For example, low molecular weight glycol can be used in combination with polyester polyol or high molecular weight glycol.

  Examples of the low molecular weight glycols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, and tetramethylene glycol. 1,6-hexamethylene glycol, dodecamethylene glycol, 1,8-octanediol, tricyclodecane dimethylol, cyclohexane dimethanol, bisphenol A, hydrogenated bisphenol A, bisphenol skeleton-containing diol compounds, and the like. Examples of the bisphenol skeleton-containing diol compound include ethylene oxide and / or propylene oxide adducts of bisphenols, and examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S. The above glycols may be used alone or in combination of two or more.

  Examples of the high molecular weight glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polycarbonate glycol.

  As said polyester polyol, what made the glycol component and the dicarboxylic acid component react is mentioned, for example, It can manufacture easily by a well-known method, can manufacture not only by esterification but also by transesterification. Moreover, the polyester diol obtained by ring-opening reaction of cyclic ester compounds, such as (epsilon) -caprolactone, and these cocondensation polyesters can also be included.

  The above polycarbonate polyols can be obtained by reacting a carbonic acid derivative such as diphenyl carbonate, dimethyl carbonate or phosgene with the above-mentioned glycol.

  The carbonyl group-containing polyurethaneurea resin (A) can have a branched structure using a compound having three or more hydroxyl groups in the molecule as the polyol compound (a2). Examples of the polyol compound (a2) having 3 or more hydroxyl groups in the molecule include trimethylolpropane, glycerin, tris (2-hydroxyethyl) isocyanurate (THEIC), and the like.

Polyisocyanate compound (a3)
Next, the polyisocyanate compound (a3) is not particularly limited as long as it has two or more isocyanate groups in the molecule. For example, the polyisocyanate compound has two or more isocyanate groups in one molecule. It is a compound which has, and what has been conventionally used for manufacture of a polyurethane can be used. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, such as lysine ester triisocyanate, 1,4,8- Triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, , And the like aliphatic triisocyanates such as 5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl octane.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (Common name: hydrogenated xylylene diisocyanate) or mixtures thereof, alicyclic diisocyanates such as norbornane diisocyanate, for example 1,3,5-triisocyanatocyclohexane, , 3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) ) Heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2 Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanate Natopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, etc. And alicyclic triisocyanate.

  Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω′-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4-bis. Aroaliphatic diisocyanates such as (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof, for example, aromatic aliphatic triisates such as 1,3,5-triisocyanatomethylbenzene An isocyanate etc. can be mentioned.

  Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate or its Mixtures, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, aromatic diisocyanates such as 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, for example triphenylmethane-4,4 ', Aromatic triisocyanates such as 4 ′ ″-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, such as 4,4′-diphenylmethane-2,2 ′, 5,5 - and the like aromatic tetracarboxylic isocyanates such as tetra isocyanates.

  Examples of the polyisocyanate derivative include dimer, trimer, biuret, allophanate, carbodiimide, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric). MDI) and crude TDI.

  The polyisocyanate compound (a3) may be used by modifying a part of the isocyanate group with a compound containing 1 to 5 active hydrogen groups such as a hydroxyl group or an amino group as necessary. Moreover, a polyisocyanate compound (a3) may be used independently and may be used together 2 or more types.

  Further, in order to ensure the dispersion stability and storage stability of the aqueous dispersion of the carbonyl group-containing urethane urea resin (A), a hydrophilic nonionic group, an anionic group, and a cation are added to the carbonyl group-containing urethane urea resin. One or more groups selected from the group consisting of sex groups may be introduced.

  When a hydrophilic nonionic group is introduced into the carbonyl group-containing urethane urea resin (A), the polyol compound (a2) is a polyethylene glycol, a copolymer of ethylene glycol and propylene glycol as at least a part of its components. It is preferable to include a polyol having a hydroxyl group at both ends of the polyoxyalkylene chain, or a polyol having a polyoxyalkylene chain in the side chain.

  The polyol having a polyoxyalkylene chain in the above side chain is a compound having two or more hydroxyl groups in one molecule and further having a polyoxyalkylene chain, and a carbonyl group-containing urethane urea resin (A As long as the polyoxyalkylene chain can be introduced into the portion that becomes a side chain when incorporated into (), various compounds can be used without particular limitation.

  Examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, and a block copolymer chain of polyoxyethylene and polyoxypropylene. The polyoxyalkylene chain preferably has a molecular weight in the range of 100 to 10,000, particularly 200 to 8,000.

  Specific examples of the polyol having a polyoxyalkylene in the side chain include, for example, a reaction product of an acrylate having a polyoxyalkylene chain and a dialkanolamine, a reaction product of glycerin carbonate and a polyoxyalkyleneamine, and the like. Further, it may be a reaction product of glycidol and polyoxyalkyleneamine. Moreover, commercial items, such as a brand name "Ymer N120" (made by Perstorp), can be mentioned.

  Examples of the acrylate having a polyoxyalkylene chain include the following formula (2):

(Wherein R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, m is an integer of 2 to 220, preferably 5 to 180, and n is an integer of 2 to 3, preferably 2. And m oxyalkylene units (CnH _2n O) may be the same or different from each other).
Specific examples thereof include polyethylene glycol acrylate, polypropylene glycol acrylate, methoxy polyethylene glycol acrylate, and ethoxy polyethylene glycol acrylate. Examples of dialkanolamines include diethanolamine and dipropanolamine.

  The acrylate having a polyoxyalkylene chain and the dialkanolamine are reacted so that the molar ratio of dialkanolamine to the acrylate is 0.8 to 1.2, preferably 0.95 to 1.05. Is desirable. This reaction is usually performed at a temperature of 25 to 250 ° C, preferably 50 to 160 ° C.

  As said polyoxyalkylene amine, the compound shown, for example to following formula (3) can be mentioned.

Wherein R ₂ represents a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, R ₃ represents a hydrogen atom or a methyl group, m is an integer of 2 to 220, preferably 5 to 180, and n is 2 An integer of ˜3, preferably 2, where the m oxyalkylene units (CnH _2n O) may be the same or different from one another).

  Glycerin carbonate and polyoxyalkyleneamine have a molar ratio of cyclic carbonate group in glycerin carbonate to amino group in polyoxyalkyleneamine of 1: 0.8 to 1: 1.2, preferably 1: 0.95. It is desirable to make it react so that it may become the range of -1: 1.05. This reaction is usually performed at a temperature of 25 to 250 ° C, preferably 50 to 160 ° C.

  As described above, in order to insert a nonionic group into the carbonyl group-containing urethane urea resin (A), a polyol having a hydroxyl group at both ends of the above polyoxyalkylene chain, or a polyol having a polyoxyalkylene chain in the side chain. When these are used, these polyol compounds (a2) have a water dispersibility and a water resistance of 1 to 25% by mass in the solid content of the carbonyl group-containing urethane urea resin (A), and further 3 to 15 It is more preferable to use within the range of mass%.

  In order to secure the dispersion stability and storage stability of the aqueous dispersion of the carbonyl group-containing urethane urea resin (A), when an anionic group is introduced into the carbonyl group-containing urethane urea resin (A), The polyol compound (a2) preferably contains a carboxyl group-containing diol as at least a part of its components.

  Examples of the carboxyl group-containing diol include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and polyester polyols obtained by condensing them. . Together with these, hydroxycarboxylic acids such as 12-hydroxystearic acid, 2,2-dimethyl-3-hydroxypropionic acid and salicylic acid can be used in combination. In this way, when an anionic group is introduced into the carbonyl group-containing urethane urea resin, the acid value of the resin is within the range of 1 to 35 mgKOH / g. It is preferable from the point of achieving both acid resistance, and more preferably in the range of 5 to 20 mgKOH / g. The acid value in this specification means a value measured by a titration method defined in JIS K 5601 (1999).

  In addition, when a cationic group is introduced into the carbonyl group-containing urethane urea resin (A) in order to ensure the dispersion stability and storage stability of the aqueous dispersion of the carbonyl group-containing urethane urea resin (A). It is preferable that the polyol compound (a2) contains a tertiary amino group-containing polyol as at least a part of its components, and the tertiary amino group is ammonium salified by a method described later to form a carbonyl group as a cationic group. It can be introduced into the urethane urethane resin.

As a compound other than the tertiary amino group-containing polyol, a diamine compound and a triamine compound containing a tertiary amino group may be used alone or in combination of two or more,
A tertiary amino group may be introduced together with the compound (a1), polyol compound (a2) and polyisocyanate compound (a3) component.

  Examples of the diol compound having a tertiary amino group include N-methyldiethanolamine, N-ethyldiethanolamine, and N-isobutyldiethanolamine. Examples of the triol compound having a tertiary amino group include triethanolamine. Can be mentioned.

Examples of the diamine compound having a tertiary amino group include methyliminobispropylamine and butyliminobispropylamine. Examples of the triamine compound having a tertiary amino group include tri (2-aminoethyl). An amine etc. are mentioned.
When a tertiary amino group is introduced into the carbonyl group-containing urethane urea resin (A), the amine value of the solid content of the carbonyl group-containing urethane urea resin (A) should be in the range of 5 to 50 mgKOH / g. It is preferable from the viewpoint of achieving both water dispersibility when ammonium salified and water resistance and acid resistance of the coating film, and more preferably within the range of 10 to 35 mgKOH / g. In addition, the amine value in this specification means the measured value by the titration method prescribed | regulated to JISK7237.

  Further, the carbonyl group-containing urethane urea resin (A) can be introduced into the carbonyl group-containing urethane urea resin as a cationic group by ammonium-chlorinating a tertiary amino group. Ammonium chloride can be carried out by neutralizing a part or all of the tertiary amino group with an acid or quaternizing with a quaternizing agent. Examples of the acid used for neutralization include formic acid, acetic acid, lactic acid, and phosphoric acid. These acids may be neutralized with tertiary amino groups in addition to the carbonyl group-containing urethane urea resin, or may be neutralized simultaneously with the dispersion by adding to water as a dispersion medium.

  Examples of the quaternizing agent include a combination of an epoxy compound such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin and a carboxylic acid group-containing compound, dimethyl sulfate, diethyl sulfate, methyl paratoluenesulfonate, etc. And alkyl halides such as methyl chloride, methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, and ethyl bromide.

In the reaction for obtaining the carbonyl group-containing urethane urea resin (A), the compounding ratios of the compound (a1), polyol compound (a2) and polyisocyanate compound (a3) having secondary amino group and carbonyl group in the molecule are various. Although it can be changed, it is determined that the carbonyl group concentration in the carbonyl group-containing urethane urea resin (A) is determined to be in the range of 0.1 to 2.0 mol / kg based on the resin solid content. It is preferable from the viewpoint of the reactivity of the aqueous dispersion of the urethane urea resin (A) and the curing agent (B) described later, and the stability of the surface treatment agent, and more preferably in the range of 0.2 to 1.0 mol / kg. Is within.
The equivalent ratio of the isocyanate group contained in the isocyanate compound (a3) to the total equivalent weight of the secondary amino group and hydroxyl group contained in the compound (a1) and the polyol compound (a2) is 0.75 to 2.50, preferably 0. It is desirable to be in the range of 85 to 2.20.

  The production of the carbonyl group-containing urethane urea resin (A) is not particularly limited, and a conventionally known method can be employed. For example, the compound (a1), the polyol compound (a2), and the polyisocyanate compound (a3) are used once. For example, after reacting the polyol compound (a2) and the polyisocyanate compound (a3), the compound (a1) may be reacted with the isocyanate group-containing product in multiple stages.

  This reaction can be carried out in the presence of an organic solvent. Although it does not specifically limit as an organic solvent, Well-known solvents, such as ester type | system | group, ether type | system | group, and a ketone type | system | group, can be used. The solution concentration is preferably in the range of 40 to 90% by mass in view of the reaction rate and the amount of solvent remaining when the obtained resin is dispersed with water, and more preferably 55. It is in the range of ˜80% by mass.

  The reaction is usually carried out at a temperature of 40 to 180 ° C, preferably 60 to 130 ° C. In order to promote this reaction, amine catalysts such as triethylamine, N-ethylmorpholine, and triethylenediamine used in ordinary urethanization reactions and tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate are used as necessary. It may be used.

  Adjustment of the weight average molecular weight of the carbonyl group-containing urethane urea resin (A) used for the metal surface treating agent of the present invention varies the compounding ratio of the compound (a1), polyol compound (a2) and polyisocyanate compound (a3). This can be done. The weight average molecular weight is preferably in the range of 2,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is larger than 100,000, the viscosity becomes high and stirring in production may be difficult. Moreover, when the weight average molecular weight is less than 2000, the acid resistance and water resistance of the resulting coating film may be insufficient.

  The carbonyl group-containing urethane urea resin (A) may have a weight average molecular weight larger than the above-mentioned range by adding a chain extender and causing a chain extension reaction when adjusting the aqueous dispersion. In this case, since the carbonyl group-containing urethane urea resin (A) is in a state of being dispersed in water, the molecular weight can be increased without hindering stirring during production.

  The chain extender is preferably a polyamine compound, such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, polyoxyethylenediamine, polyoxypropylenediamine, amine-terminated polyoxyethylene-polyoxypropylene Diamines such as copolymers; polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine; hydroxyethylhydrazine, hydroxyethyldiethylenetriamine, 2-[(2- Minoechiru) amino] ethanol, the compound having an amino group and a hydroxyl group such as 3-amino-propanediol; hydrazines, acid hydrazides, and the like. These may be used singly or in combination.

  When the chain extender described above is used, for example, the compound (a1), polyol compound (a2) and polyisocyanate compound (a3) containing one or more secondary amino groups and one or more carbonyl groups in the molecule. ) In the reaction of compound (a1) and the polyol compound (a2) so that the number of moles of isocyanate groups stoichiometrically greater than the total number of moles of functional groups capable of reacting with the isocyanate groups contained in the polyol compound (a2). Then, after reacting with the polyisocyanate compound (a3) to obtain a urethane urea resin (prepolymer) having an isocyanate group terminal, the above-mentioned chain extender is dispersed or dispersed in water or a medium containing water. And the reaction between the isocyanate group and the chain extender can be carried out in a dispersed state. In addition, you may use the compound (a1) which contains 2 or more of secondary amino groups in a molecule | numerator, and contains 1 or more of carbonyl groups as a chain extender.

  In the present specification, the number average molecular weight and weight average molecular weight of resins other than those having a cationic group introduced are the same as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). It is a value obtained by converting to the molecular weight of polystyrene based on the retention time (retention capacity) of standard polystyrene with a known molecular weight measured in (1).

  Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” are used as columns. ”And“ TSKgel G-2000HXL ”(trade names, all manufactured by Tosoh Corporation), a differential refractometer is used as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: It can be measured under the condition of 1 mL / min. Specifically, the number average molecular weight and the weight average molecular weight of the resin into which the cationic group is introduced are “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) as a gel permeation chromatograph apparatus, and “ Using a total of three TSKgel Super-H3000 and two TSKgel Super-H2500 (trade names, both manufactured by Tosoh Corporation), a differential refractometer was used as a detector. , Mobile phase: tetrahydrofuran (containing 0.5% by weight of triethanolamine), measurement temperature; 25 ° C., flow rate: 0.6 mL / min.

  The carbonyl group-containing urethane urea resin (A) obtained as described above is dispersed in water or a medium containing water and used as an aqueous dispersion. Examples of the medium containing water include a mixture of water and an organic solvent such as a water-soluble organic solvent. Water dispersion can be performed by a conventionally known method without any particular limitation. For example, the carbonyl group-containing urethane urea resin (A) is finely divided in water or a medium containing water by applying a shearing force in the presence of an emulsifier. Obtaining method (1): Applying shear force to the carbonyl group-containing urethane urea resin into which hydrophilic groups such as nonionic groups, anionic groups, and cationic groups are introduced to form fine particles in water or a medium containing water. Method (2) to obtain; Method (3) obtained by applying shearing force to the carbonyl group-containing urethane urea resin (A) having the hydrophilic group introduced therein in the presence of an emulsifier to form fine particles in water or a medium containing water (3) ); In the present specification, the above water or a medium containing water may be referred to as an aqueous medium.

  The emulsifier is not particularly limited, and an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, an amphoteric emulsifier, a reactive emulsifier, and the like can be used.

  For example, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate and sodium dodecyl sulfate, fatty acid salts, rosinates, alkyl sulfates, alkyl sulfosuccinates, α-olefin sulfonates, alkyl naphthalene sulfonates, polyoxyethylenes Anionic emulsifiers such as alkyl (aryl) sulfate salts; quaternary ammonium salts such as lauryl trialkyl ammonium salts, stearyl trialkyl ammonium salts, trialkyl benzyl ammonium salts, primary to tertiary amine salts, lauryl pyridinium Salt, benzalkonium salt, benzethonium salt, or cationic surfactant such as laurylamine acetate; polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether Nonionic surfactants such as polyoxyethylene alkyl ester and polyoxyethylene sorbitan alkyl ester; amphoteric surfactants such as carboxybetaine type, sulfobetaine type, aminocarboxylic acid type, and imidazoline derivative type; Eleminol JS-2 (Sanyo Kasei) Industrial), Eleminol RS-30 (Sanyo Kasei Kogyo), Latemuru S-180A (Kao), Aqualon HS-05 (Daiichi Kogyo Seiyaku), Aqualon RN-10 (Daiichi Kogyo Seiyaku), Adekaria And reactive emulsifiers such as Soap SE-10N (Asahi Denka).

  In the present invention, the amount of the emulsifier used is 100 parts by mass of the solid content of the carbonyl group-containing urethane urea resin (A) from the viewpoint of the stability of the aqueous dispersion and the water resistance when used as a film-forming component of the surface treatment agent. The content is preferably in the range of 0 to 20 parts by mass, more preferably in the range of 0 to 15 parts by mass.

  Further, the concentration of the aqueous dispersion of the carbonyl group-containing urethane urea resin (A) is preferably in the range of 10 to 50% by mass, more preferably 20 to 45% by mass as a solid content from the viewpoint of stability and viscosity. %.

  In the present invention, as described above, an anionic group and / or a nonionic group may be introduced into the carbonyl group-containing urethane urea resin (A) and dispersed in water or a medium containing water. When an anionic group is introduced, the anionic group can be neutralized with a basic compound and dispersed in water. Considering the acid resistance and water resistance of the cured coating film, neutralization with ammonia that is easily volatilized is suitably performed. When a nonionic group is introduced, water dispersion is possible as it is, but if necessary, both an anionic group and a nonionic group are introduced into a carbonyl group-containing urethane urea resin, and the anionic group is converted into a basic compound. Can be used after neutralization.

Carbonyl Group-Containing Epoxy Resin The metal surface treatment agent of the present invention contains an aqueous dispersion of a carbonyl group-containing epoxy resin in addition to the aqueous dispersion of the urethane urea resin (A), depending on the required film performance. be able to. An aqueous dispersion of a carbonyl group-containing epoxy resin is obtained by reacting the compound (a1) with an epoxy resin.

  The epoxy resin is particularly preferably an epoxy resin obtained by a reaction between a polyphenol compound and an epihalohydrin, for example, epichlorohydrin, from the viewpoint of the corrosion resistance of the coating film. Examples of the polyphenol compound used for forming the epoxy resin include bis (4-hydroxyphenyl) -2,2-propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], bis ( 4-hydroxycyclohexyl) methane [hydrogenated bisphenol F], 2,2-bis (4-hydroxycyclohexyl) propane [hydrogenated bisphenol A], 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-2 or 3-tert-butyl-phenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, Tetra (4-hydroxyphenyl) -1,1,2,2-ethane 4,4'-dihydroxydiphenyl sulfone, phenol novolak, and the like cresol novolak.

  Moreover, as an epoxy resin obtained by reaction with a polyphenol compound and epichlorohydrin, what is shown by following formula (4) induced | guided | derived from bisphenol A and n is 0-8 is suitable.

エポキシ樹脂は、エポキシ当量が１４０〜５，０００、好ましくは１７０〜２，０００の範囲内、数平均分子量が２００〜５０，０００、好ましくは２５０〜１０，０００の範囲内のものが適している。

Epoxy resins having an epoxy equivalent of 140 to 5,000, preferably 170 to 2,000, and number average molecular weight of 200 to 50,000, preferably 250 to 10,000 are suitable. .

  Examples of such commercially available epoxy resins include those sold by Japan Epoxy Resins Co., Ltd. under the trade names jER828EL, jER1002, jER1004, and jER1007.

  The compounding ratio of the compound (a1) and the epoxy resin is such that the carbonyl group concentration in the obtained carbonyl group-containing epoxy resin is in the range of 0.1 to 3.5 mol / kg, more preferably 0, based on the resin solid content. It is preferable from the viewpoint of the stability of the metal surface treatment agent to be selected within the range of 5 to 3 mol / kg.

  In the present invention, the reaction between the compound (a1) and the epoxy resin can be performed in the presence of an organic solvent. Although it does not specifically limit as an organic solvent, Well-known solvents, such as ester type | system | group, ether type | system | group, and a ketone type | system | group, can be used. The solution concentration is preferably in the range of 40 to 90% by mass from the viewpoint that the reaction rate and the solvent remaining when the obtained resin is dispersed with water can be reduced, more preferably 55 to 55% by mass. It is in the range of 80% by mass. The reaction is usually carried out at a temperature of 40 to 180 ° C, preferably 60 to 130 ° C.

  The carbonyl group-containing epoxy resin has a weight average molecular weight of 2,000 to 50,000, preferably 5,000 to 20,000. When the weight average molecular weight is larger than 50,000, the viscosity becomes high, the production is difficult, and the finish of the obtained film may be deteriorated. Moreover, when the weight average molecular weight is smaller than 2,000, sufficient water resistance may not be obtained.

  The carbonyl group-containing epoxy resin obtained as described above is used as an aqueous dispersion by being dispersed in water or a medium containing water, like the carbonyl group-containing urethane urea resin (A). Examples of the medium containing water include a mixture of water and an organic solvent such as a water-soluble organic solvent.

Curing agent (B)
The metal surface treating agent of the present invention comprises a curing agent (hydrazine derivative having a hydrazino group that reacts with a carbonyl group in the carbonyl group-containing urethane urea resin (A) and a carbonyl group-containing epoxy resin that can be used as necessary. Contained as B).

  Specifically, a compound having two or more hydrazide groups and / or semicarbazide groups in one molecule can be suitably used. For example, saturated fatty acid dihydrazides having 2 to 18 carbon atoms such as succinic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, etc .; maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide Monoolefinically unsaturated dicarboxylic acid dihydrazide, phthalic acid, terephthalic acid or isophthalic acid dihydrazide, and pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotrihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide , Ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, two or more carboxylic acid lower alkyl ester groups in one molecule. A polyhydrazide compound such as polyhydrazide (see Japanese Patent Publication No. 52-22878) obtained by reacting a low polymer having hydrazine or hydrazine hydrate (hydrazine hydride); diisocyanate such as hexamethylene diisocyanate and isophorone diisocyanate; Polysemicarbazide compound obtained by reacting polyisocyanate compound derived therefrom with hydrazine or monoalkyl-substituted hydrazine, polyhydrazide obtained by reacting diisocyanate compound or polyhydrazide compound exemplified above with polyisocyanate compound containing diisocyanate Obtained from the reaction of a compound, a polyisocyanate compound and a polyether or polyol having active hydrogen such as polyethylene glycol monoalkyl ethers. Polysemicarbazide compound obtained by reacting an isocyanate group in a modified polyisocyanate compound with hydrazine or a monoalkyl-substituted hydrazine, polyhydrazide obtained by reacting the above-exemplified dihydrazide or polyhydrazide with the isocyanate group of the modified polyisocyanate compound Examples thereof include compounds, and these can be used alone or mixed together as necessary.

In general, the hydrazine derivative preferably has a total of hydrazide groups and semicarbazide groups contained in the hydrazine derivative within a range of 0.01 to 2 mol, more preferably, with respect to 1 mol of carbonyl groups of the carbonyl group-containing modified polyurethane. Is preferably in the range of 0.1 to 1.8 mol, more preferably 0.2 to 1.6 mol from the viewpoint of low temperature curability.
Moreover, in addition to the hydrazine derivative which has a hydrazino group etc. which react with a carbonyl group, as a hardening | curing agent (B), a blocked polyisocyanate compound can also be used together as needed. As the polyisocyanate compound, known compounds can be used. For example, tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,2′-diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4 , 4′-diisocyanate, crude MDI [polymethylene polyphenyl isocyanate], bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate, etc., aromatic, aliphatic or alicyclic polyisocyanate compounds A cyclized polymer or biuret of these polyisocyanate compounds; or a combination thereof.

  In particular, aromatic polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, and crude MDI are more preferable for corrosion resistance.

  On the other hand, the blocking agent is added to the isocyanate group of the polyisocyanate compound to block, and the blocked polyisocyanate compound produced by the addition is stable at room temperature, but the baking temperature of the coating film (usually about 100 to about When heated to 200 ° C., it is desirable that the blocking agent dissociates to regenerate free isocyanate groups.

  Examples of the blocking agent used in the blocked polyisocyanate compound include oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenol compounds such as phenol, para-t-butylphenol and cresol; n-butanol and 2-ethylhexanol. Aliphatic alcohol compounds such as phenyl carbinol, methyl phenyl carbinol, etc .; ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether; lactams such as ε-caprolactam and γ-butyrolactam Compounds and the like.

Silica particles (C)
The metal surface treating agent of the present invention contains silica particles (C) for improving fingerprint resistance and corrosion resistance. The silica particles (C) are preferably silica particles having an average particle diameter of 1 to 100 nm, particularly 2 to 30 nm, and may be silica particles such as gas phase method silica, pulverized silica, and water-dispersible colloidal silica.

  Specifically, SNOWTEX N, SNOWTEX C, SNOWTEX O (all manufactured by Nissan Chemical Co., Ltd., commercially available water-dispersible colloidal silica) and the like, other commercially available silica particles include, for example, AEROSIL 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, etc., especially AEROSIL200V, R972, R972V, R974, R202, R812 are preferable. AEROSIL200V, AEROSILR-811 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned. Further, silica particles having an average particle diameter of 1 to 100 nm may be used in combination with silica particles having a large particle diameter exceeding 100 nm, particularly exceeding 200 nm.

  The blending amount of the silica particles (C) described above is preferably in the range of 5 to 60 parts by mass, particularly 10 to 40 parts by mass with respect to 100 parts by mass of the solid content of the carbonyl group-containing urethane urea resin (A). . When the amount of the silica particles (C) is less than 5 parts by mass, the corrosion resistance may be inferior, and when it exceeds 60 parts by mass, the storage stability of the treatment agent may be inferior.

Metal compound (D)
The metal compound (D) used for the metal surface treating agent of the present invention is at least one metal compound selected from Ti, Zr and V.

  Examples of the titanium (Ti) compound include titanium hydrofluoric acid or a salt thereof. Examples of the salt forming salt include sodium, potassium, lithium, and ammonium. Among them, potassium, sodium and Ammonium is preferred, and specific examples include titanium potassium fluoride, titanium hydrofluoric acid, titanium sodium fluoride, titanium ammonium fluoride, and the like.

  Examples of the zirconium (Zr) compound include zirconium hydrofluoric acid and its salt, zirconium carbonate and its salt, zirconium nitrate and the like. Examples of the salt forming salt include sodium, potassium, lithium and ammonium. Among them, potassium, sodium, and ammonium are preferable, and specific examples include zirconium potassium fluoride, zirconium ammonium fluoride, zirconium ammonium carbonate, and the like.

  Examples of the vanadium (V) compound include vanadium oxide, vanadic acid, lithium orthovanadate, sodium orthovanadate, lithium metavanadate, potassium metavanadate, sodium metavanadate, ammonium metavanadate, sodium pyrovanadate, vanadyl chloride, vanadyl sulfate. Etc.

  Of these, the metal compound (D) is at least one selected from titanium hydrofluoride, zirconium hydrofluoride, ammonium zirconium carbonate, metavanadate and vanadyl sulfate, and has fingerprint resistance. From the viewpoint of corrosion resistance.

The compounding amount of the metal compound (D) is a carbonyl group-containing urethane urea resin (A).
The amount in the range of 0.1 to 20 parts by mass, particularly 1 to 10 parts by mass is preferable with respect to 100 parts by mass of the solid content. If the amount of the metal compound (D) is less than 0.1 parts by mass, the corrosion resistance may be inferior, and even if added in excess of 20 parts by mass, the corrosion resistance is little improved and the stability of the metal surface treatment agent may be impaired. is there.

Metal Surface Treatment Agent The metal surface treatment agent of the present invention is at least one selected from an aqueous dispersion of a carbonyl group-containing urethane urea resin (A), a curing agent (B), silica particles (C), Ti, Zr and V. The metal compound (D) and, if necessary, a silane coupling agent can be contained.

  Examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl). Amino group-containing silane coupling agents such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidyl group-containing silane couplings such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane γ- (2-aminoethyl) aminopropyltrimethoxysilane Agent; 3-mercaptopropylmethyldi Examples include methoxysilane 3-mercaptopropyltrimethoxysilane. Among these silane coupling agents, the metal surface treatment agent of the present invention includes N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane from the viewpoint of improving adhesion and corrosion resistance. It is preferable to mix ethoxymethoxysilane. The compounding amount of the silane coupling agent is preferably in the range of 0 to 50 parts by mass, particularly 10 to 25 parts by mass with respect to 100 parts by mass of the solid content of the carbonyl group-containing urethane urea resin (A).

  If necessary, the metal surface treatment agent of the present invention may further include a color pigment, an antirust pigment, an extender pigment, a pigment dispersant, an antisettling agent, a curing catalyst, an antifoaming agent, an antioxidant, an ultraviolet absorber, phosphorus Acid compounds, lubricity imparting agents, thickeners, anti-repellent agents, antifoaming agents, surfactants, oxidizing agents, antibacterial agents, rust preventives (tannic acid, phytic acid, benzotriazole, etc.), conductive pigments, An acrylic resin dispersion, a polyester resin dispersion, or the like may be appropriately blended and mixed and dispersed.

  The phosphoric acid compound has an effect of improving the corrosion resistance of the resulting coating film, and includes, for example, phosphorous acid, strong phosphoric acid, triphosphoric acid, hypophosphorous acid, hypophosphoric acid, trimetaphosphoric acid, dinitrous acid Monophosphoric acids such as phosphoric acid, diphosphoric acid, pyrophosphorous acid, pyrophosphoric acid, metaphosphorous acid, metaphosphoric acid, orthophosphoric acid, derivatives and salts of monophosphoric acids, condensed phosphoric acids such as tripolyphosphoric acid, tetraphosphoric acid, hexametaphosphoric acid And derivatives and salts of condensed phosphoric acids. These compounds can use 1 type (s) or 2 or more types. Moreover, as an alkaline compound which forms the salt of a phosphoric acid type compound, lithium, sodium, potassium, ammonium etc. are mentioned, for example. It is preferable to use a phosphate compound that is soluble in water. As the phosphoric acid compound, in particular, use of sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, metaphosphoric acid, orthophosphoric acid, ammonium metaphosphate, sodium hexametaphosphate, etc., the storage stability of the metal surface treatment agent, It is preferable because it exerts an excellent effect on the corrosion resistance of the film.

  The compounding quantity of a phosphoric acid type compound is 0.1-50 mass parts with respect to 100 mass parts of solid content of a carbonyl group containing urethane urea resin (A) from the point of storage stability and corrosion resistance, especially 2-40 mass. Within the range of parts is preferred.

  Moreover, the lubrication function imparting agent should just be what provides lubricity to the film obtained. Specifically, for example, fluororesin fine powder (for example, tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene- Fine particles of ethylene copolymer resin, ethylene trifluoride chloride resin, vinylidene fluoride resin, etc.), polyolefin wax (eg, polyethylene wax, polypropylene wax, etc.), polyolefin and fluororesin are mixed in one particle Lubricants, graphite, boron nitride, carbon fluoride and the like.

  Moreover, you may add hydrophilic organic solvents, such as methanol, ethanol, isopropyl alcohol, ethylene glycol type, a propylene glycol type, for example to the metal surface treating agent of this invention as needed.

Film-forming method A surface-treated steel sheet can be obtained by applying a metal surface treatment agent to a metal substrate and drying by heating. The metal substrate to which the metal surface treatment agent is applied is not limited as long as it is a metal. Examples thereof include iron, copper, aluminum, tin, zinc, alloys containing these metals, and plated steel plates or vapor deposition products made of these metals. Examples of the plated steel sheet include hot dip galvanized steel sheet, electrogalvanized steel sheet, iron-zinc alloy plated steel sheet, nickel-zinc alloy plated steel sheet, aluminum-zinc alloy plated steel sheet (commercially available products such as “Galbarium”, “Galfan” Etc.), and an aluminum-plated steel sheet. Among these, zinc or zinc alloy-plated steel sheet is a metal base material with the most remarkable effect of the present invention. The coating amount of the metal surface treatment agent of the present invention, dry film weight at 0.1 to 10 g / ^{m 2,} to be within the scope especially 0.2-5 g / ^{m 2,} is suitable in terms of corrosion resistance.

The method for forming a film of the metal surface treatment agent of the present invention is performed by appropriately adjusting the viscosity of the metal surface treatment agent with a diluent such as water according to the coating amount, for example, in the range of 5 to 20 mPa · s, and then coating with a roll coater. What is necessary is just to dry normally for 5 to 60 seconds at atmospheric temperature 120-330 degreeC, after apply | coating so that it may become a predetermined | prescribed film weight by well-known methods, such as painting, dipping coating, and brush painting.
It is suitable for effective reaction that the maximum material temperature (PMT, Peak Metal Temperature) of the steel plate at this time is in the range of 70 to 150 ° C, preferably 80 to 130 ° C. Since the treatment agent is excellent in curability at a low temperature in a short time, drying conditions of PMT 80 to 100 ° C. for 5 to 20 seconds are preferable from the viewpoint of energy saving.

  An upper layer film can be further formed on the film of the metal plate formed as described above. The upper layer film-forming composition may be appropriately selected according to the purpose, and various film-forming compositions can be used. Examples of the film-forming composition include film-forming compositions used for conventionally known rust-proof steel sheet applications, fingerprint-resistant steel sheet applications, lubricating steel sheet applications, colored coating film formation applications, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.

Production Example 1 Production of Michael addition reaction product 1 Air in a 1 L flask equipped with a stirrer, thermometer, condenser, nitrogen gas inlet was replaced with nitrogen, 338.4 g of diacetone acrylamide, 180 of deionized water .2 g and 352.6 g of N-ethylethylenediamine were added and stirred, and the temperature was raised to 80 ° C. and maintained at 80 ° C. for 3 hours. Next, while reducing the pressure to about 100 mmHg, the temperature was maintained at 60 to 80 ° C. for 2 hours, and about 240 g of a mixture of water and unreacted N-ethylethylenediamine was removed azeotropically. Thereafter, 200 g of water was added and maintained at 80 ° C. for 1 hour, and then maintained at 60 to 80 ° C. for 1.5 hours while reducing the pressure to about 100 mmHg to remove azeotropically about 200 g of the mixture of water and N-ethylethylenediamine. Repeated twice. Thereafter, the pressure was reduced to about 10 mmHg and kept at 60 to 80 ° C. for 1.5 hours, and the remaining water and N-ethylethylenediamine were removed to have two secondary amino groups and further have a carbonyl group. An addition reaction product 1 ”was obtained. Since a peak of 6.19 to 6.23 ppm attributable to diacetone acrylamide was not observed in 1H-NMR measurement of the product using deuterated chloroform solvent, it was confirmed that no unreacted diacetone acrylamide remained.
0.1 g of “Michael addition reaction product 1” obtained in a 100 mL Erlenmeyer flask was weighed, 30 mL of acetic acid was added and dissolved, and then an indicator (a solution of 0.3 g of alphazulin G dissolved in 100 mL of glacial acetic acid and thymol) 0.2 mL of a solution obtained by dissolving 1.5 g of blue in methanol was added, and titrated with 0.1 N perchloric acid (acetic acid solution) until the solution changed from green to red. As a result, the amine value of Michael addition reaction product 1 was 426 mg-KOH / g.

Production Example 2 Production of Michael addition reaction product 2 Air in a 2 L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and 507.7 g of diacetone acrylamide and 270.3 g of water Then, 438.8 g of butylamine was added and stirred, and the temperature was raised to 80 ° C. and kept at 80 ° C. for 2 hours. Next, the pressure was reduced to about 100 mmHg and maintained at 60 to 80 ° C. for 1.5 hours, and about 430 g of a mixture of water and unreacted butylamine was removed azeotropically. After that, an operation for attaching a moisture determination receiver to the flask, adding 270 g of water, raising the temperature to 105 ° C., holding at 103 to 105 ° C. under normal pressure for 1 hour, and azeotropically removing about 200 g of the mixture of water and butylamine twice. Repeated. Next, while maintaining the pressure at 60 to 80 ° C. for 1.5 hours while reducing the pressure to about 10 mmHg, the remaining water and butylamine are removed to have one secondary amino group in one molecule and further have a carbonyl group. Michael addition reaction product 2 "was obtained. Since a peak of 6.19 to 6.23 ppm attributable to diacetone acrylamide was not observed in 1H-NMR measurement of the product using deuterated chloroform solvent, it was confirmed that no unreacted diacetone acrylamide remained. The amine value of the obtained “Michael addition reaction product 2” was 230 mg-KOH / g.

Production Example 3 Production of Michael addition reaction product 3 Air in a 2 L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and 507.7 g of diacetone acrylamide and 270.3 g of water Then, 366.5 g of 2-aminoethanol was added and stirred, and the temperature was raised to 80 ° C. and kept at 80 ° C. for 2 hours. Next, thin film distillation was performed using a thin film distillation apparatus at a reduced pressure of 5 mmHg and a wall surface of 100 ° C. to remove a mixture of water and unreacted 2-aminoethanol. Thereafter, air in a 2 L flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet was replaced with nitrogen, and about 720 g of reaction product was obtained by removing unreacted 2-aminoethanol by thin-film distillation. 500 g of water was added, the temperature was raised to 105 ° C., and the ketimine was hydrolyzed by maintaining at normal pressure at 103 to 105 ° C. for 1 hour. Furthermore, thin film distillation is performed on a wall at 100 ° C. under reduced pressure of 5 mmHg to remove a mixture of 2-aminoethanol formed by hydrolysis of water and ketimine, so that one secondary amino group per molecule and one hydroxyl group Thus, “Michael addition reaction product 3” having a carbonyl group was obtained. Since a peak of 6.19 to 6.23 ppm attributable to diacetone acrylamide was not observed in 1H-NMR measurement of the product using deuterated chloroform solvent, it was confirmed that no unreacted diacetone acrylamide remained. The amine value of the obtained Michael addition reaction product 3 was 255 mg-KOH / g.

Production Example 4 Production of Michael addition reaction product 4 Air in a 2 L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and 507.7 g of diacetone acrylamide and 270.3 g of water Then, 642.9 g of benzylamine was added and stirred, and the temperature was raised to 80 ° C. and kept at 80 ° C. for 2 hours. Next, thin film distillation was performed on a wall surface at a reduced pressure of 5 mmHg and 100 ° C. using a thin film distillation apparatus to remove a mixture of water and unreacted benzylamine. Thereafter, air in a 2 L flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet was replaced with nitrogen, and about 900 g of reaction product from which unreacted benzylamine was removed by thin film distillation was added to 500 g of water. Was added, and the temperature was raised to 105 ° C., and kept at 103 to 105 ° C. under normal pressure for 1 hour to hydrolyze ketimine. Furthermore, thin film distillation is performed on a wall at 100 ° C. under reduced pressure of 5 mmHg to remove a mixture of benzylamine formed by hydrolysis of water and ketimine, thereby having one secondary amino group in one molecule, and further carbonyl A Michael addition reaction product 4 having a group was obtained. Since a peak of 6.19 to 6.23 ppm attributable to diacetone acrylamide was not observed in 1H-NMR measurement of the product using deuterated chloroform solvent, it was confirmed that no unreacted diacetone acrylamide remained. The amine value of the resulting Michael addition reaction product 4 was 211 mg-KOH / g.

Production Example 5 Production of Michael addition reaction product 5 Air in a 1 L flask equipped with a stirrer, thermometer, condenser, nitrogen gas inlet was replaced with nitrogen, 331.6 g diacetone acrylamide, 210.3 g diethanolamine Is added, and the mixture is heated to 100 ° C. and held at 100 ° C. for 5 hours, so that one molecule has one tertiary amino group, two hydroxyl groups, and a carbonyl group. Product 5 "was obtained.
In the 1H-NMR measurement of the product using deuterated chloroform solvent, a peak of 6.19 to 6.23 ppm due to diacetone acrylamide was confirmed. The residual ratio of the raw material DAAm calculated from the integrated value of the peak was 3%. The amine value of the resulting Michael addition reaction product 5 was 207 mg-KOH / g.

Production Example 6 Production of Michael addition reaction product 6 Air in a 1 L flask equipped with a stirrer, thermometer, condenser, nitrogen gas inlet was replaced with nitrogen, and 72.0 g of ethylenediamine and 320.8 g of water were added. Stir. A mixture of 203.1 g of diacetone acrylamide and 320.8 g of water was dropped into this solution, and the mixture was heated to 80 ° C. and held at 80 ° C. for 3 hours to obtain an aqueous solution of Michael addition reaction product 6 having a carbonyl group. It was. In the 1H-NMR measurement of the product using heavy water as a solvent, a peak of 6.19 to 6.23 ppm due to diacetone acrylamide was not observed, and it was confirmed that no unreacted diacetone acrylamide remained. The amine value of the obtained Michael addition reaction product 6 was 490 mg-KOH / g.

Production Example 7 Aqueous dispersion No. 1 of urethane urea resin containing carbonyl group The air in a 2 L flask equipped with the production stirrer 1, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, and “Duranol T5652” (trade name, manufactured by Asahi Kasei Chemicals Corporation, polycarbonate diol) 120 0.0 g, “PEG2000” (trade name, manufactured by Sanyo Chemical Industries, polyethylene glycol) 26.9 g, “Michael addition reaction product 1” 36.8 g, dimethylolpropionic acid 9.6 g, 2-methoxy- 2.7 g of 1-propanol, 221.1 g of 2-methyl-4-pentanone and 39.0 g of N-methylpyrrolidone were added and stirred, and the mixture was heated to 80 ° C. and dissolved. Thereafter, “Desmodur I” (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate) 53.9 g, “Desmodur H” (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., hexamethylene diisocyanate) 10 0.2 g, “Neostan U-100” (trade name, manufactured by Nitto Kasei Co., Ltd., dibutyltin dilaurate) 0.10 g was added, and the mixture was held at 80 ° C. for 8 hours. Thereafter, 220 g of 2-methoxy-1-propanol was added, and then about 220 g of 2-methoxy-1-propanol and 2-methyl-4-pentanone were removed while azeotroping under reduced pressure to remove 3.1 g of 10% aqueous ammonia. And a mixture of 50.0 g of water was added. Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, and diluted with water so that the heating residue is about 30%, so that the carbonyl group concentration in the resin solid content is 0. An aqueous dispersion No. 5 of a carbonyl group-containing urethane urea resin in which a resin of .55 mol / Kg is emulsified and dispersed. 1 was obtained. The acid value of this resin was 15.4 mg-KOH / g, and the weight average molecular weight was about 15,000.

Production Example 8 Carbon dispersion-containing urethane urea resin aqueous dispersion no. The air in the 2 L flask equipped with the production stirrer, thermometer, condenser and nitrogen gas inlet was replaced with nitrogen, and “Duranol T5652” 120.0 g, “PEG2000” 26.9 g, “Michael addition reaction” 27.0 g of “Product 1”, 7.3 g of “Michael addition reaction product 2”, 9.6 g of dimethylolpropionic acid, 209.7 g of 2-methyl-4-pentanone, and 37.0 g of N-methylpyrrolidone were added. The mixture was stirred and heated to 80 ° C. for dissolution. Thereafter, 47.1 g of “Desmodur I”, 8.9 g of “Desmodur H”, and 0.10 g of “Neostan U-100” were added and held at 80 ° C. for 8 hours. Thereafter, 220 g of 2-methoxy-1-propanol was added, and about 220 g of 2-methoxy-1-propanol and 2-methyl-4-pentanone were removed azeotropically while reducing pressure, and 3.9 g of 10% aqueous ammonia was removed. And a mixture of 50.0 g of water was added. Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, and diluted with water so that the heating residue is about 30%, so that the carbonyl group concentration in the resin solid content is 0. An aqueous dispersion No. 5 of a carbonyl group-containing urethane urea resin in which a resin of .55 mol / Kg is emulsified and dispersed. 2 was obtained. The acid value of this resin was 16.3 mg-KOH / g, and the weight average molecular weight was about 14,000.

Production Example 9 Carbonyl group-containing urethane urea resin aqueous dispersion No. 9 The air in the 2 L flask equipped with the production stirrer, thermometer, condenser and nitrogen gas inlet was replaced with nitrogen, “Duranol T5652” 120.0 g, “PEG2000” 26.9 g, “Michael addition reaction” 27.0 g of “Product 1”, 8.3 g of “Michael addition reaction product 4”, 9.6 g of dimethylolpropionic acid, 210.6 g of 2-methyl-4-pentanone, and 37.2 g of N-methylpyrrolidone were added. The mixture was stirred and heated to 80 ° C. for dissolution. Thereafter, 47.1 g of “Desmodur I”, 8.9 g of “Desmodur H”, and 0.10 g of “Neostan U-100” were added and held at 80 ° C. for 8 hours. Then, after adding 220 g of 2-methoxy-1-propanol, about 220 g of 2-methoxy-1-propanol and 2-methyl-4-pentanone were removed azeotropically while reducing pressure, and 3.6 g of 10% ammonia water was removed. And a mixture of 50.0 g of water was added. Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, and diluted with water so that the heating residue is about 30%, so that the carbonyl group concentration in the resin solid content is 0. A carbonyl group-containing urethane urea resin aqueous dispersion No. 5 in which a resin of .55 mol / Kg was emulsified and dispersed. 3 was obtained. The acid value of this resin was 16.2 mg KOH / g, and the weight average molecular weight was about 14,000.

Production Example 10 Carbonyl group-containing urethane urea resin aqueous dispersion No. 10 The air in a 2 L flask equipped with a production stirrer, a thermometer, a condenser, and a nitrogen gas inlet was replaced with nitrogen, and “Duranol T5652” 120.0 g, “PEG2000” 26.9 g, “Michael addition reaction” 31.1 g of product 3 ”, 9.6 g of dimethylolpropionic acid, 2.7 g of 2-methoxy-1-propanol, 214.7 g of 2-methyl-4-pentanone and 37.9 g of N-methylpyrrolidone were added and stirred. The solution was heated to 80 ° C. and dissolved. Thereafter, 52.4 g of “Desmodur I”, 9.9 g of “Desmodur H”, and 0.10 g of “Neostan U-100” were added and held at 80 ° C. for 8 hours. Thereafter, 220 g of 2-methoxy-1-propanol was added, and about 220 g of 2-methoxy-1-propanol and 2-methyl-4-pentanone were removed azeotropically under reduced pressure to remove 4.7 g of 10% aqueous ammonia. And a mixture of 50.0 g of water was added.
Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, and diluted with water so that the heating residue is about 30%, so that the carbonyl group concentration in the resin solid content is 0. A carbonyl group-containing urethane urea resin aqueous dispersion No. 5 in which a resin having a mol. 4 was obtained. The acid value of this resin was 15.9 mgKOH / g, and the weight average molecular weight was about 15,000.

Production Example 11 Aqueous dispersion No. 4 of urethane urea resin containing carbonyl group 5 The air in a 2 L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, “Duranol T5652” 135.0 g, “Ymer N120” (trade name, manufactured by Perstorp) 13.4 g, 36.8 g of “Michael addition reaction product 1”, 9.6 g of dimethylolpropionic acid, 2.7 g of 2-methoxy-1-propanol, 223.8 g of 2-methyl-4-pentanone, N— 39.5 g of methylpyrrolidone was added and stirred, and the mixture was heated to 80 ° C. and dissolved. Thereafter, 55.2 g of “Desmodur I”, 10.4 g of “Desmodur H”, and 0.10 g of “Neostan U-100” were added and held at 80 ° C. for 8 hours. Thereafter, 220 g of 2-methoxy-1-propanol was added, and then about 220 g of 2-methoxy-1-propanol and 2-methyl-4-pentanone were removed while azeotroping under reduced pressure to remove 3.1 g of 10% aqueous ammonia. And a mixture of 50.0 g of water was added. Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, and diluted with water so that the heating residue is about 30%, so that the carbonyl group concentration in the resin solid content is 0. An aqueous dispersion of carbonyl group-containing urethane urea resin emulsified and dispersed with a resin of .54 mol / Kg No. 5 was obtained. The acid value of this resin was 15.2 mg KOH / g, and the weight average molecular weight was about 16,000.
Comparative Production Example 1 Urethane urea resin aqueous dispersion No. 6. Air in a 2 L flask equipped with a production stirrer, thermometer, condenser and nitrogen gas inlet was replaced with nitrogen, “Duranol T5652” 186.0 g, “PEG2000” 26.9 g, dimethylolpropionic acid 9.6 g, 2-methoxy-1-propanol 2.7 g, 2-methyl-4-pentanone 226.1 g, and N-methylpyrrolidone 39.9 g were added and stirred, and the mixture was heated to 80 ° C. and dissolved. Thereafter, 34.3 g of “Desmodur I”, 6.5 g of “Desmodur H”, and 0.10 g of “Neostan U-100” were added and held at 80 ° C. for 8 hours.
Then, after adding 220 g of 2-methoxy-1-propanol, about 220 g of 2-methoxy-1-propanol and 2-methyl-4-pentanone were removed azeotropically while reducing pressure, and 6.1 g of 10% ammonia water was removed. And a mixture of 50.0 g of water was added. Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, diluted with water so that the heating residue is about 30%, and does not contain carbonyl groups in the resin solids Urethane urea resin aqueous dispersion no. 6 was obtained. The acid value of this resin was 15.1 mg KOH / g, and the weight average molecular weight was about 15,000.

Comparative Production Example 2 Aqueous dispersion No. 2 of carbonyl group-containing urethane resin The air in a 2 L flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet was replaced with nitrogen, “Duranol T5652” 180.0 g, “PEG2000” 26.9 g, “Michael addition reaction” 12.3 g of product 5 ”, 2.7 g of 2-methoxy-1-propanol, and 256.5 g of 2-methyl-4-pentanone were added and stirred, and the mixture was heated to 80 ° C. and dissolved. Thereafter, 29.0 g of “Desmodur I”, 5.5 g of “Desmodur H”, and 0.10 g of “Neostan U-100” were added and held at 80 ° C. for 8 hours. Thereafter, 220 g of 2-methoxy-1-propanol was added, and about 220 g of 2-methoxy-1-propanol and 2-methyl-4-pentanone were removed while azeotroping under reduced pressure, and 2.6 g of acetic acid and 50 of water were removed. 0.0 g of the mixture was added. Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, and diluted with water so that the heating residue is about 30%, so that the carbonyl group concentration in the resin solid content is 0. An aqueous dispersion of a carbonyl group-containing urethane resin in which a resin of .18 mol / Kg was emulsified and dispersed was obtained. 7 was obtained. The weight average molecular weight of this resin was about 18,000.

Comparative Production Example 3 Aqueous dispersion No. 3 of carbonyl group-containing urethane resin The air in the 2 L flask equipped with the production stirrer, thermometer, condenser, and nitrogen gas inlet was replaced with nitrogen, “Duranol T5652” 165.0 g, “PEG2000” 26.9 g, dimethylolpropionic acid 10.1 g, 2-methyl-4-pentanone 244.7 g, and N-methylpyrrolidone 43.2 g were added and stirred, and the mixture was heated to 80 ° C. and dissolved.
Thereafter, 41.0 g of “Desmodur I”, 7.8 g of “Desmodur H”, and 0.10 g of “Neostan U-100” were added and held at 80 ° C. for 5 hours. Next, 3.8 g of triethylamine was added, and 34.4 g of an aqueous solution of “Michael addition reaction product 6” was dropped in 15 minutes. Further, after adding 1200 g of water, about 900 g is removed while azeotropically evaporating the solvent and water under reduced pressure, and diluted with water so that the heating residue is about 30%, so that the carbonyl group concentration in the resin solid content is 0. An aqueous dispersion of a carbonyl group-containing urethane resin in which a resin of .16 mol / Kg was emulsified and dispersed was obtained. 8 was obtained. The acid value of this resin was 14.6 mgKOH / g, and the weight average molecular weight could not be measured because the resin exceeded the exclusion limit molecular weight of the column used for molecular weight measurement.

Example 1 Surface treatment agent No. 1 Production of carbonyl group-containing urethane urea resin aqueous dispersion No. 1 100 parts (solid content) of 1
Mix 10% adipic acid dihydrazide aqueous solution 4.79 parts (solid content), Snowtex N (Note 2) 20 parts (solid content), titanium hydrogen fluoride 3.0 (solid content), and add deionized water. A solid content was prepared, and the surface treatment agent No. 20 having a solid content of 20% was prepared. 1 was obtained. The equivalence ratio of carbonyl group / hydrazide group = 1.0 / 1.0.

Examples 2-10
Surface treatment agent No. 1 was made in the same manner as in Example 1 except that the contents of Table 1 were used. 2
~ No. 10 was obtained.

(Note 1) Superflex 150: trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., an anionic urethane resin aqueous dispersion, solid content 30%
(Note 2) Snowtex N: trade name, manufactured by Nissan Chemical Industries, colloidal silica aqueous dispersion, average particle diameter of silica particles is about 20 nm
(Note 3) AEROSIL200V: Silica fine particles, trade name, manufactured by Nippon Aerosil Co., Ltd. (Note 4) KBM-603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, trade name, manufactured by Shin-Etsu Silicone (Note) 5) KBE-903: 3-aminopropyltriethoxymethoxysilane,
Product name, manufactured by Shin-Etsu Silicone.

Comparative Examples 1-7
Except for the blending contents in Table 2, the surface treatment agent No. 1
1-No. 17 was obtained.

Preparation of test plate and evaluation of film performance To 70 mm × 150 mm electrogalvanized steel plate (trade name: gin coat, plate thickness 0.8 mm, plating adhesion 20 g / m ² ) washed with water after alkaline degreasing, Each metal surface treating agent of Examples 1-10 and Comparative Examples 1-7 was applied using a bar coater so that the dry film weight was 1.2 g / m ^2, and the maximum temperature reached by the steel sheet was 90 ° C. Then, drying was performed for 8 seconds. Each of the obtained test plates was subjected to the following various performance tests. The results are shown in Tables 3 and 4.

Test method (Note 6) Storage stability: Each metal surface treatment agent having a solid content of 20% produced in the above examples and comparative examples was allowed to stand in a constant temperature room at 40 ° C., and the state after 30 days was evaluated according to the following criteria. did.
○: No sedimentation or gelation ×: Sedimentation or gelation is observed (Note 7) Fingerprint resistance: Vaseline was applied to half of the painted surface of the test plate and left in a constant temperature room at 20 ° C. for 24 hours. Vaseline was wiped off with gauze, and the color difference of the coated surface after wiping the petrolatum with respect to the coated surface not coated with petrolatum was measured and evaluated according to the following criteria. The color difference measurement was performed using a Minolta color difference meter “CR-100”.
○: Color difference (ΔE) is less than 2 ×: Color difference (ΔE) is 2 or more (Note 8) Corrosion resistance (no degreasing): A salt spray test specified in JISZ2371 is applied to a test plate whose end face and back face are sealed. After 120 hours, the degree of rust was evaluated according to the following criteria.
A: Occurrence of white rust is less than 5% of the coating area. O: Occurrence of white rust is 5% or more and less than 10% of the coating area. 10% or more of the area and less than 30% ×: The degree of occurrence of white rust is 30% or more of the coating film area (Note 9) Corrosion resistance (after alkaline degreasing): Alkali degreasing agent CL-N364S (trade name, Nippon Parkerizing The product was degreased for 2 minutes at 60 ° C. using an aqueous solution having a concentration of 2% in which the product was dissolved and washed with water for 10 seconds. Then, the end surface part and the back surface part of the test plate were sealed, a salt spray test prescribed in JIS Z 2371 was performed for 72 hours, and the degree of rust was evaluated according to the following criteria.
A: Occurrence of white rust is less than 5% of the coating area. O: Occurrence of white rust is 5% or more and less than 10% of the coating area. 10% or more of the area and less than 30% ×: The degree of white rust generation is 30% or more of the coating film area (Note 10) Solvent resistance: The film surface of the test plate using 4-layer gauze impregnated with ethanol After rubbing 5 times, the appearance was visually evaluated according to the following criteria.
◯: Rub marks are not noticeable Δ: Rub marks are conspicuous ×: Film is dissolved (Note 11) Adhesion to top coat film:
On the test plate, Magcron # 1000 (trade name, manufactured by Kansai Paint Co., Ltd., color white), which is a thermosetting acrylic paint, was applied to a film thickness of 25 μm and baked at 150 ° C. for 20 minutes. A painted plate was created. Then, a grid pattern (10 × 10 grid pattern at 1 mm intervals) was cut into the coated plate, and adhesion and peeling with an adhesive tape were performed. The number of coating films remaining in the grid was evaluated according to the following criteria.
◎: 100 ◯: 80 to 99 and practical range Δ: 50 to 79 ×: 49 or less

  Provided is a surface-treated steel sheet having excellent fingerprint resistance and corrosion resistance.

Claims (4)

An aqueous dispersion of a carbonyl group-containing urethane urea resin (A) having the following characteristics, a curing agent (B) containing two or more functional groups capable of reacting with the carbonyl group in the resin (A), and silica particles A metal surface treating agent comprising (C) and at least one metal compound (D) selected from Ti, Zr and V.
Aqueous dispersion of carbonyl group-containing urethane urea resin (A): amine compound containing one primary amino group in the molecule, amine compound containing one primary amino group and one secondary amino group, and secondary compound at least one amine compound, Ru obtained allowed Michael addition reaction against diacetone acrylamide, secondary amino group and carbonyl group in the molecular selected from the group consisting of an amine compound containing amino groups or two An aqueous dispersion obtained by dispersing a resin (A) obtained by reacting a compound (a1) containing a polyol, a polyol compound (a2) and a polyisocyanate compound (a3) in water or a medium containing water. The metal surface treating agent according to claim 1, wherein the functional group of the curing agent (B) is a hydrazide group and / or a semicarbazide group. The metal surface treatment agent according to claim 1 or 2, wherein the metal compound (D) is at least one selected from titanium hydrofluorate, zirconium hydrofluoride, ammonium zirconium carbonate, metavanadate, and vanadyl sulfate. . The surface-treated steel plate obtained by apply | coating the metal surface treating agent of any one of Claims 1-3 on a metal base material, and heat-drying.