KR101278311B1 - Surface treating agent for metallic materials - Google Patents

Abstract

According to the present invention, in the coating formed by the surface treatment of a coating type, the coating film has all the performances of corrosion resistance and paintability, and in particular, the formed coating is excellent in adhesion to the surface of the metal material and acts as a corrosion inhibitor of the metal material. An object of the present invention is to provide a surface treating agent for a metal material which can be immobilized in a coating film. The metal material surface treatment agent of this invention is a silicic acid compound (A), organoalkoxysilane (B), Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Metal compound (C) comprising at least one metal element selected from the group consisting of Nb, Cr, and Zn, at least one compound (D) and water (E) selected from the group consisting of phosphoric acid compounds and fluorine compounds And a alcohol (F) generated from hydrolysis of the organoalkoxysilane (B), and a molar concentration (mol / L) in the treatment agent of the alcohol (F) is a treatment agent adjusted to a predetermined range. .

Description

Surface treating agent for metallic materials

The present invention relates to a surface treatment agent for metal materials, a surface treatment method using the surface treatment agent for metal materials, and a surface treatment metal material having a coating.

In order to obtain anticorrosiveness or paintability, the metallic material is subjected to surface treatment. That is, it is important to obtain the effect of suppressing the corrosion of the metal by the surface treatment, or preventing the coating film from peeling off when the coating is applied, or preventing corrosion from the portion even if the coating film is peeled off. Conventionally, as the surface treatment of a metallic material, the phosphate treatment which precipitates the crystal | crystallization of the metal salt of phosphoric acid, and the chromate treatment which forms the film containing hexavalent chromium have been performed.

In the phosphate treatment, first, the metal material is brought into contact with an aqueous solution containing phosphoric acid and metal ions. At this time, the metal is dissolved with an acid, and the pH rises because hydrogen is consumed at the interface of the metal material by the dissolution reaction. By this increase in pH, the metal salt of phosphoric acid, which cannot be dissolved, is precipitated on the surface of the metal material to form a phosphate film. Since the phosphate film is precipitated by dissolution on the surface of the metal material, the adhesion with the metal material is very excellent. Moreover, since a film is formed by aggregation of fine crystal | crystallization, adhesiveness with the coating film coated by the anchor effect by fine unevenness | corrugation is also excellent. Therefore, it is the outstanding surface treatment currently widely used as a base treatment of painting.

However, since it is a so-called reactive surface treatment which originates in contacting an acidic aqueous solution containing phosphoric acid and causing a dissolution reaction, there exists a problem that the component of the processing liquid containing phosphoric acid changes according to the kind of metal material. In addition, since the phosphate which did not precipitate on the surface of the metal material was suspended in the treatment liquid as sludge, it was necessary to remove it. In addition, it was necessary to appropriately change the contact conditions (temperature, time, etc.) between the aqueous solution and the metal material, and also had a problem that a washing process (generation of drainage) was required after the surface treatment. In addition, it could not be applied to a material such as stainless steel that lacked reactivity.

The chromate treatment also has a reaction type similar to phosphate, and a coated chromate treatment which is only applied by drying an aqueous solution is well known. The coating type chromate treatment is a simple method of simply applying an aqueous solution containing hexavalent chromium to the metal material surface and drying it. Therefore, since the washing process is unnecessary after the surface treatment and it becomes a closed system which is not drained, it is employ | adopted very much in the surface treatment of a sheet coil. In addition, the coated chromate coating has a form in which a soluble hexavalent chromium (chromic acid) is retained and maintained in the coating skeleton based on the polymerization of trivalent chromium. Excellent corrosion resistance is imparted to the metal material from the oxidation action (passivation action, self-healing action) by hexavalent chromium. In addition, when applying as a base treatment of coating, it is known that a coating film becomes difficult to peel off by carrying out a trace displacement plating of Ni as the pretreatment. One of the reasons is that the substitution plating improves the adhesion between the chromate coating and the metal surface.

The ideal surface treatment of the metal material is excellent in adhesion to the surface of the metal material, the coating component is polymerized, and a soluble corrosion inhibitor is present in the coating, which forms a coating that can be held and maintained for a long time. It is. In the coating type chromate treatment, a film having the above characteristics is formed.

However, the coating film formed by the coated chromate treatment contains hexavalent chromium, and since the hexavalent chromium is eluted by contact with water, it tends to be light from the viewpoint of the environment and safety. Therefore, various research and development which suppressed elution of hexavalent chromium from the chromate coating was performed.

However, in recent years, the presence of hexavalent chromium itself is reluctant, and a lot of development of the non-chromate process which does not contain hexavalent chromium is performed.

As the non-chromate treatment, Patent Document 1 discloses a steel sheet having a film formed of a P compound, a Si compound, and a tetravalent vanadium compound. However, with this technique, adhesion to the surface of the metal material could not be sufficiently secured and sufficient corrosion resistance could not be obtained.

In patent document 2, the processing liquid containing a silane coupling agent, specific resin, the metal complex in which F is four or more, and a metal compound (Mn, Co, Zn, Mg, Ni, Ti, V, Zr) is disclosed. However, with this technique, adhesion to the surface of the metal material could not be sufficiently secured and sufficient corrosion resistance could not be obtained.

In patent document 3, the water dispersion of the core / cell-shaped composite particle obtained by the reaction operation which superposes colloidal silica, organoalkoxysilane, and the vinyl monomer which has ethylenically unsaturated group is disclosed. . However, at least 80% of these particles are colloidal silica. As a technique for stably mixing this particle | grain with resin, even if it used as it is, a film could not be formed and corrosion resistance was not obtained either.

In patent document 4, the technique using the composition containing a silane and a metal chelate is disclosed. Metal chelates play a role of dissolving metal ions (especially in cationic state) and at the same time bonding to metal surface. However, this technique chelates the metal ions to form a form in which the metal ions are easy to dissolve. As a result, their elution cannot be sufficiently suppressed and long-term corrosion resistance cannot be obtained.

In patent document 5, 0.01-100 g / L of a silane coupling agent, 0.05-100 g / L of silica, 0.01-50 g / L of Zr, and / or 0.01-50 g / L of Ti, 0.01-100 g / of thiocarbonyl group containing compounds The processing liquid containing L and 0.1-100 g / L of acrylic resin is disclosed. Since this technique is excellent in adhesiveness, paintability is good, but corrosion resistance at the time of unpainting is inadequate. Furthermore, because the treatment liquid gelled with time, it could not be used industrially.

In patent document 6, the technique using a carboxyl group-containing polyurethane resin, a silane coupling agent, a silica, and flaky silica is disclosed.

In patent document 7, the technique using a polyurethane resin, a silane coupling agent, and silica is disclosed. The technique disclosed in patent documents 6 and 7 was not able to ensure the adhesiveness with the metal material surface enough. In addition, since the silica could not be sufficiently immobilized in the film, sufficient corrosion resistance could not be obtained.

In patent document 8, the film containing organic resin and a silane coupling agent is formed in the lower layer, and the organic resin film which contains a thiocarbonyl group in the upper layer is disclosed. This technology relates to the lower layer in the two-layer process, and the object can be achieved only by combining with the upper layer. Therefore, as a single film, adhesiveness and corrosion resistance with a metal material cannot be acquired.

In patent document 9, the technique using a vanadium compound and Zr, Ti, Mo, W, Mn, Ce is disclosed. However, sufficient adhesion between the coating film and the metal material formed by this technique could not be obtained and the elution of the metal compound could not be suppressed.

In patent document 10, the technique using a silane coupling agent, a silica sol, and an aqueous organic resin is disclosed. In this technique, the silica component can be immobilized in order to bond the silane coupling agent to the silica surface, but elution of the metal compound could not be suppressed.

As described above, no surface-treated steel sheet has been obtained by replacing the chromate coating in any of the above methods, and it satisfies all characteristics such as corrosion resistance and paintability, and in particular, improves the adhesion between the formed coating and the metallic material, and the metallic material. There has been a strong desire to develop a surface treatment agent capable of producing a surface treated steel sheet in which corrosion is inhibited.

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-48199

Patent Document 2: Japanese Patent Application Laid-Open No. 2005-120469

Patent Document 3: Japanese Patent No. 3818689

Patent Document 4: Japanese Patent Publication No. 2006-519307

Patent Document 5: Japanese Patent Application Laid-Open No. 2001-316845

Patent Document 6: Japanese Patent Application Laid-Open No. 2005-178213

Patent Document 7: Japanese Patent Application Laid-Open No. 2005-200757

Patent Document 8: Japanese Patent No. 3722658

Patent Document 9: Japanese Patent Application Laid-Open No. 2002-30460

Patent Document 10: Japanese Patent Application Laid-Open No. 2001-98215

The present invention has all the characteristics such as corrosion resistance, overcoat, etc. in the coating formed by the surface treatment of the coating type, and in particular, the formed coating has excellent adhesion to the metal material surface and acts as a corrosion inhibitor of the metal material. An object of the present invention is to provide a surface treatment agent for a metal material which can immobilize components in a film, and a surface treatment method using the surface treatment agent for a metal material.

MEANS TO SOLVE THE PROBLEM The present inventors focused on the property of organoalkoxysilane, and as a result of earnestly examining, by using the processing agent in which the quantity of the alcohol which contains a predetermined compound and is produced | generated from the hydrolysis of organoalkoxysilane is controlled, The problem was found to be solved.

That is, this invention provides the following (1)-(9).

(1) a silicic acid compound (A)

Organoalkoxysilane (B),

Metal compound comprising at least one metal element selected from the group consisting of Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr, and Zn (C )and,

At least one compound (D) selected from the group consisting of a phosphoric acid compound and a fluorine compound,

Water (E),

As a surface treatment agent for metal materials containing alcohol (F) produced | generated from the hydrolysis of the said organoalkoxysilane (B),

And the molar concentration _{(mol / L) (C F1} ) in water treating agent of the alcohol (F), wherein the organoalkoxysilane molar concentrations in the agent of the alcohol that is generated when all the alkoxy groups are hydrolyzed contained in (B) The surface treating agent for metal materials whose ratio (C _F1 / C _F2 ) of (mol / L) (C _F2 ) is adjusted to the range of 0.05-0.9.

(2) The surface treating agent for metal materials according to (1), wherein the mass ratio (C / F) of the alcohol (F) and the metal compound (C) is in the range of 0.01 to 50.

(3) The surface treating agent for metal materials according to (1) or (2), wherein the mass ratio (D / F) of the alcohol (F) and the compound (D) is 0.01 to 25.

(4) The mass ratio (A / B) of the silicic acid compound (A) and the organoalkoxysilane (B) is 0.01 to 3.0,

The mass ratio (C / (A + B)) of the total mass (A + B) and the metal compound (C) of the silicic acid compound (A) and the organoalkoxysilane (B) is 0.01 to 2.0,

(1) to which the mass ratio (D / (A + B)) of the total mass (A + B) of the silicic acid compound (A) and the organoalkoxysilane (B) and the compound (D) is 0.01 to 1.5. The surface treating agent for metal materials in any one of (3).

(5) The surface treating agent for metal materials according to any one of (1) to (4), wherein the organoalkoxysilane (B) has an amino group and / or an epoxy group.

(6) The surface treating agent for a metal material according to any one of (1) to (5), further comprising at least one compound (G) selected from the group consisting of a water-soluble polymer and an aqueous emulsion resin.

(7) The total mass (A + B) of the silicic acid compound (A) and the organoalkoxysilane (B) and the mass ratio (G (A + B)) of the compound (G) in the treating agent are 0.01 to 0.3. , Surface treatment agent for metal materials as described in (6).

(8) The surface treatment agent for a metal material according to any one of (1) to (7) is applied on the surface of the metal material and dried by heating to form a film having a coating amount of 2 to 1000 mg / m 2 as the Si adhesion amount. The surface treatment method of a metal material formed on the surface.

(9) The surface-treated metal material which has a film on the surface obtained by the surface treatment method of the metal material as described in (8).

The present invention has all the performances such as excellent corrosion resistance, overcoat, and the like in a coating formed by a coating type surface treatment, and in particular, the formed coating has excellent adhesion to the metal material surface and acts as a corrosion inhibitor of the metal material. The surface treatment agent for metal materials which can fix | immobilize the to-be-constituted component in a film, and the surface treatment method using the surface treatment agent for metal materials are provided.

Below, the surface treatment method using the surface treating agent for metal materials of this invention, and this surface treating agent for metal materials is demonstrated.

First, the surface treating agent for metal materials is demonstrated in detail.

<Surface Treatment Agent for Metal Materials>

The surface treatment agent for metal materials of this invention is a silicic acid compound (A), organoalkoxysilane (B), Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W , A metal compound (C) comprising at least one metal element selected from the group consisting of Nb, Cr, and Zn, a compound (D) selected from the group consisting of a phosphoric acid compound and a fluorine compound, water (E), And a surface treating agent for metal materials containing an alcohol (F) generated from hydrolysis of the organoalkoxysilane (B). Further, the molar concentrations in the agent of the alcohol that is generated when all the alkoxy groups are hydrolyzed contained in a molar concentration _{(mol / L) (C F1} ) and the organoalkoxysilane (B) in water treating agent of the alcohol (F) The ratio (C _F1 / C _F2 ) of (mol / L) (C _F2 ) is adjusted in the range of 0.05 to 0.9.

First, the various components which comprise the surface treating agent for metal materials are demonstrated.

<Silic acid compound (A)>

The silicic acid compound (A) is contained in the surface treating agent for metal materials of this invention. By using a silicic acid compound, the film which is excellent in all the performances, such as corrosion resistance, overcoat, heat resistance, weldability, and continuous workability, can be formed.

The silicic acid compound is mainly composed of silicon and oxygen, and the kind thereof is not particularly limited. For example, colloidal silica, liquid silica, and silicon chloride obtained by alkali silicate such as sodium silicate, potassium silicate, lithium silicate, and sodium silicate obtained by a method such as removing sodium, potassium, or lithium by ion exchange, and solvating the silicate The dispersion which disperse | distributed the gas phase silica produced by combustion oxidation in air in water, Furthermore, the hydrolyzate of an alkoxysilane, etc. are mentioned. Especially, colloidal silica and liquid silica are preferable at the point which the performance of the obtained film is more excellent.

For example, as liquid silica, Snowtex C, Snowtex CS, Snowtex CM, Snowtex O, SnowtexOS, Snowtex OM, Snowtex NS, Snowtex N, SnowtexNM, Snowtex S, Snowtex 20, Snowtex 30, Snowtex 40, Aderaito AT-20N, Aderaito AT-20A, Aderaito AT-20Q, and also Snowtex UP, SnowtexOUP, Snowtex processed in a special chain shape PS-S, Snowtex PS-SO, Snowtex PS-M, Snowtex PS-MO, Snowtex PS-L, Snowtex PS-LO.

Moreover, as fine particle silica called gas phase silica, Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil MOX80, Aerosil MOX170 etc. are mentioned, A dispersion can also be used.

Although content of a silicic acid compound (A) in a surface treating agent for metal materials is not specifically limited, From the viewpoint of the corrosion resistance, the coating property, the heat resistance, the weldability, and the continuous workability of the coating film obtained, with respect to the total solid in a processing agent, 0.1-70 mass% is preferable, and 1-50 mass% is more preferable. In addition, the total solid in a processing agent means the solid component which comprises the film mentioned later, and a solvent etc. are not contained.

<Organoalkoxysilane (B)>

The organoalkoxysilane (B) is contained in the surface treating agent for metal materials of this invention. By using together an organoalkoxysilane (B) and the above-mentioned silicic acid compound (A), the film which has a three-dimensional structure by the siloxane bond of a silicic acid compound (A) and an organoalkoxysilane (B) is formed. Thereby, it is guessed that the corrosion resistance, the overcoat, heat resistance, weldability, continuous workability, earth resistance, adhesiveness with the surface of a metal material, etc. of the film obtained are improved.

The organoalkoxysilane used in the present invention is not particularly limited, but for example, tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Methyltrimethoxysilane, methyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-hexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , Decyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, isobutyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (amino Ethyl) γ-aminoprop Philmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercapto Propylmethyldimethoxysilane, p-styryltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ- Chloropropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-isocyanatepropyltriethoxysilane, γ-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine , N- (vinylbenzylamine) -β-aminoethyl-γ-aminopropyltrimethoxysilane, and the like.

Especially, since it is easy to adjust alcohol concentration, the trialkoxysilane which has 3 mol of active alkoxy groups is preferable.

Moreover, it is preferable that organoalkoxysilane (B) has 1 or more types of functional groups chosen from an amino group and an epoxy group. By organoalkoxysilane (B) having these functional groups, the siloxane bond of the said silicon compound (A) and said organoalkoxysilane (B) is accelerated | stimulated more, and the film | membrane which has a more dense three-dimensional bridge | crosslinking is estimated. do. As a result, the coating can be further fixed to a component acting as a corrosion inhibitor of the metal material, further improving corrosion resistance.

As one of the preferable embodiment of organoalkoxysilane, the compound represented by the following general formula (I) is mentioned.

(I)

In the formula (I), X represents any one functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, an acryloxy group, a ureido group, an isocyanate group, and a vinyl group. L represents a divalent linking group or simple coupling | bonding number. R represents an alkyl group or a hydrogen atom. and n represents an integer of 1 to 3.

In the formula (I), X represents any one functional group selected from the group consisting of an epoxy group, an amino group, a mercapto group, an acryloxy group, a ureido group, an isocyanate group, and a vinyl group. Especially, an epoxy group and an amino group are preferable. In addition, when n is two or more, X may be same or different.

In the formula (I), L represents a divalent linking group or a simple bond number.

As the linking group represented by L, for example, an alkylene group (having a carbon number of 1 to 20 is preferred), -O-, -S-, an arylene _{group, -CO-, -NH-, -SO 2 -} , -COO- , -CONH-, or a combination thereof. Especially, an alkylene group is preferable. In the case of a simple bond water, X in formula (I) refers to the direct connection with Si (silicon atoms).

In addition, when n is two or more, L may be same or different.

In general formula (I), R represents an alkyl group (preferably C1-C4) or a hydrogen atom each independently.

In general formula (I), n represents the integer of 1-3. Especially, 1 is preferable.

The organoalkoxysilane (B) may be a hydrolyzate in which a part of the alkoxy group is hydrolyzed.

Although content of organoalkoxysilane (B) is not specifically limited in the surface treating agent for metal materials, Corrosion resistance, overcoat, heat resistance, weldability, continuous workability, earth resistance, and adhesiveness with the surface of a metal material are more limited. From a viewpoint of being excellent, 0.1-70 mass% is preferable with respect to the total solid in a processing agent, and 1-50 mass% is more preferable.

<Metal Compound (C)>

The surface treatment agent for a metal material of the present invention is one selected from the group consisting of Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr, and Zn. Metal compound (C) containing the above metal element is contained. A poorly soluble salt is formed in a film by using together a metal compound (C) and a phosphoric acid compound and / or a fluorine compound mentioned later. This poorly water-soluble salt promotes the crosslinking reaction of the silicon compound (A) and the organoalkoxysilane (B) to form a film having a more dense network structure, whereby a metal compound acting as a corrosion inhibitor of a metal material ( It is guessed that C) will become easy to fix in a film.

The metal compound (C) is not particularly limited as long as it contains the metal element. Examples thereof include nitrates, acetates, phosphates, sulfates, ammonium salts, and fluorides.

As a specific example of a metal compound (C), as a metal compound containing Zr, zirconium nitrate, zirconium oxynitrate, zirconyl acetate, zirconyl sulfate, zirconyl ammonium carbonate, zirconyl potassium carbonate, zirconyl carbonate Sodium, zirconia sol and the like. Moreover, the zirconic acid and its salt which are produced by ion-exchange or alkali neutralization of the aqueous solution of water-soluble zirconium salt are also mentioned.

Examples of the metal compound containing Ti include titanium sulfate, titanium nitrate, titanium nitrate, titanium chloride, titanium chloride, titanazole, titanium oxide, potassium oxalate, titanium lactate, and titanium tetraisopropoxide. , Titanium acetylacetonate, diisopropyl titanium bisacetyl acetone, and the like. Moreover, metatitanic acid obtained by thermal hydrolysis of the aqueous solution of titanyl sulfate, ortho titanic acid obtained by alkali neutralization, and these salts are also mentioned.

Examples of the metal compound containing Co include cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt phosphate, cobalt chloride, cobalt oxide, and cobalt hydroxide.

As a metal compound containing Fe, iron sulfate, iron nitrate, iron chloride, iron phosphate, iron oxide, iron hydroxide, iron powder, etc. are mentioned, for example.

As a metal compound containing V, for example, vanadium pentoxide, ammonium metavanadate, sodium metavanadate, vanadium oxychloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadiumoxyacetylacetonate, vanadium acetyl Acetonate, vanadium trichloride, invanado molybdate, vanadium sulfate and the like.

Examples of the metal compound containing Ce include cerium nitrate, cerium acetate, cerium chloride, cerium sol, and the like.

As a metal compound containing Mo, ammonium molybdate, sodium molybdate, potassium molybdate, ammonium molybdate phosphate, etc. are mentioned, for example.

Examples of the metal compound containing Mn include potassium permanganate, ammonium permanganate, sodium permanganate, permanganate, manganese sulfate, manganese nitrate, manganese oxide, manganese carbonate, manganese chloride, and manganese phosphate.

As a metal compound containing Mg, magnesium sulfate, magnesium nitrate, magnesium carbonate, magnesium phosphate, magnesium chloride, magnesium oxide, magnesium hydroxide, etc. are mentioned, for example.

As a metal compound containing Al, aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum phosphate, aluminum chloride, etc. are mentioned, for example.

As a metal compound containing Ni, nickel oxide, nickel hydroxide, nickel sulfate, nickel nitrate, nickel phosphate, nickel chloride, etc. are mentioned, for example.

Examples of the metal compound containing Ca include calcium oxide, calcium hydroxide, calcium sulfate, calcium nitrate, calcium phosphate, calcium chloride and the like.

Examples of the metal compound containing W include ammonium metatungstate, sodium metatungstate, potassium metatungstate, paratungstic acid, ammonium paratungstate, and sodium paratungstate.

As a metal compound containing Nb, niobium oxalate, niobium oxide, niobazole, etc. are mentioned, for example.

As a metal compound containing Cr, trivalent chromium is mentioned, for example, chromium sulfate, chromium nitrate, chromium chloride, chromium hydroxide, chromium oxide, chromium phosphate, etc. are mentioned.

Examples of the metal compound containing Zn include zinc oxide, zinc hydroxide, zinc sulfate, zinc nitrate, zinc chloride, zinc phosphate, acetyl zinc, and the like, and since zinc is an amphoteric metal, alkali side Sodium zincate, potassium zincate, and the like.

Among these, since the effect of improving corrosion resistance is high, it is more preferable to contain at least 1 sort (s) chosen from a metal compound containing Zr, V, Al, or Zn, and these salts.

Although content of a metal compound (C) is not specifically limited in the surface treating agent for metal materials, 0.05-50 mass% is preferable with respect to the total solid in a processing agent from the viewpoint of being more excellent in the corrosion resistance and earth resistance of the film obtained. , 0.1-30 mass% is more preferable.

<Phosphate Compounds and / or Fluorine Compounds>

The surface treating agent for metal materials of this invention contains 1 or more types of compound (D) chosen from the group which consists of a phosphoric acid compound and a fluorine compound. As described above, the phosphoric acid compound and / or the fluorine compound is used in combination with the metal compound (C) to promote the crosslinking reaction between the silicon compound (A) and the organoalkoxysilane (B). Furthermore, since a phosphate compound and / or a fluorine compound etch the metal which is a base material, and form the film combined with the surface of a base material, it is guessed that the corrosion resistance of a film and adhesiveness with the surface of a metal material are further improved.

Examples of the phosphoric acid compound include ammonium salts and metal salts of phosphoric acid (as metals, for example, alkali metals, V, Co, W, Ti, Zr, Al, Zn); Condensed phosphoric acid such as pyrophosphoric acid; The organic phosphoric acid compound which has a phytic acid, a phosphon group, a phosphine group, etc. are mentioned. For example, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, diacid, and ammonium salts, aluminum salts, magnesium salts, nitrilotris methylenephosphonic acid, nitrilotrispropylene phosphonic acid, nitrilodiethylmethylene phosphate Phonic acid, nitrilopropylbismethylenephosphonic acid methane, 1-hydroxymethane-1,1-diphosphonic acid, etc. are mentioned.

Phosphoric acid compounds are used individually or in combination of 2 or more types.

As a fluorine compound, hydrofluoric acid, its ammonium salt, its alkali metal salt; Metal fluorides such as tin fluoride, manganese fluoride, ferrous fluoride, ferric fluoride, aluminum fluoride, zinc fluoride and vanadium fluoride; Acid fluorides, such as fluorine oxide, acetyl fluoride, and benzoyl fluoride, are mentioned.

More preferably, those having at least one element selected from the group consisting of Ti, Zr, Hf, Si, Al and B are preferably used. Specifically, for ^{_{example, (TiF 6) 2-, (}} ZrF 6) 2-, (HfF 6) 2-, (SiF 6) 2-, (AlF 6) 3-, (BF 4 OH) - , etc. Complexes having 1 to 3 atoms of hydrogen atoms added to an anion thereof, ammonium salts of these anions, metal salts of these anions, and the like. More specifically, titanium hydrofluoric acid, zircon hydrofluoric acid, hydrofluoric acid, etc. are mentioned.

A fluorine compound is used individually or in combination of 2 or more types.

Although the total content of a compound (D) in the surface treating agent for metal materials is not specifically limited, 0.01-40 mass% is preferable with respect to the total solid in a processing agent from the viewpoint of being more excellent in the corrosion resistance of the film obtained, and 0.1- 30 mass% is more preferable.

<Water (E)>

Water (E) is contained in the surface treating agent for metal materials of this invention.

Although content of water in a surface treating agent for metal materials is not specifically limited, 30-99 mass% is preferable with respect to a processing agent whole quantity, and 40-95 mass% is more preferable from a viewpoint that handling of a processing agent is easier.

<Alcohol (F)>

The surface treatment agent for metal materials of this invention contains alcohol (F) produced | generated from the hydrolysis of the organoalkoxysilane (B) mentioned above. Alcohol is produced | generated by the hydrolysis reaction of the organoalkoxysilane (B) which has an alkoxy group.

As a kind of alcohol, depending on the kind of alkoxy group of organoalkoxysilane used, methanol, ethanol, propanol, etc. are mentioned, for example.

The molar concentration (mol / L) (C _F1 ) of the alcohol (F) contained in the surface treating agent for metal materials of the present invention is the mole of alcohol in the treating agent obtained when all the alkoxy groups contained in the organoalkoxysilane are hydrolyzed. In the relationship with the concentration (mol / L) (C _F2 ), it is adjusted to satisfy C _F1 / C _F2 = 0.05 to 0.9, and preferably 0.1 to 0.8.

When the molar concentration ratio (C _F1 / C _F2 ) is less than 0.05, the effect of the reactive functional group required for the silicic acid compound (A) and the organoalkoxysilane (B) to form a siloxane bond is organoalkoxysilane (B). Since it loses from the film, corrosion resistance of a film, coating property, and the adhesiveness of the formed film and the surface of a metal material fall. In addition, when the molar concentration ratio (C _F1 / C _F2 ) exceeds 0.9, since the effect of the reactive functional group is high, the organoalkoxysilanes (B) form siloxane bonds with each other, and a component that acts as a corrosion inhibitor of the metal material is used. It becomes impossible to fix | immobilize in a film.

The method for adjusting the molarity (mol / L) (C _F1 ) of the alcohol derived from the alkoxy group of the organoalkoxysilane (B) is not particularly limited, and for example, a silanol condensation catalyst and water in the organoalkoxysilane. In the solution which mixed the above, the method of adjusting the density | concentration by controlling the amount of alcohol byproduced, the method of adjusting the density | concentration by removing the by-produced alcohol and water, etc. are mentioned.

In addition, the measuring method of alcohol concentration is not specifically limited, The chromatograph method, such as gas chromatography and ion chromatography, and nuclear magnetic resonance spectroscopy, etc. are mentioned.

Moreover, in the surface treating agent for metal materials of this invention, it is preferable that the mass ratio (C / F) of the metal compound (C) and alcohol (F) mentioned above satisfy | fills 0.01-50, and satisfy | fills 0.1-40. It is more preferable. If it is in the said range, since the component which acts as a corrosion inhibitor of a metal material becomes easy to be immobilized in a film, it is preferable at the point which is excellent in the corrosion resistance of a film obtained, an overcoat, and adhesiveness with the surface of a metal material.

Moreover, in the surface treating agent for metal materials of this invention, it is preferable that mass ratio (D / F) of a compound (D) and alcohol (F) satisfies 0.01-25, and it is more preferable to satisfy 0.1-20. It is more preferable to satisfy 0.1-15. If it is in the said range, since the component which acts as a corrosion inhibitor of a metal material becomes easy to be immobilized in a film, it is preferable at the point which is more excellent in the corrosion resistance of a film obtained, an overcoat, and adhesiveness with the metal material surface.

In the surface treating agent for metal materials of this invention, it is preferable that the mass ratio (A / B) of a silicic acid compound (A) and organoalkoxysilane (B) is 0.01-3.0, and 0.05-2.5 are more preferable. When it is less than 0.01, continuous workability may fall, and when it exceeds 3.0, adhesiveness of the film formed and the surface of a metal material may fall.

In the surface treating agent for metal materials of the present invention, the total mass (A + B) of the silicic acid compound (A) and the organoalkoxysilane (B) and the mass ratio (C / (A + B)) of the metal compound (C) are It is preferable that it is 0.01-2.0, and it is more preferable that it is 0.05-1.5. When it is less than 0.01, the corrosion resistance of a film may fall, and when it exceeds 2.0, the corrosion resistance of a film may fall and the adhesiveness of a film and a metal material surface may fall.

In the surface treatment agent for metal materials of this invention, the total mass (A + B) of a silicic acid compound (A) and organoalkoxysilane (B), and the mass ratio (D / (A + B)) of a compound (D), It is preferable that it is 0.01-1.5, and it is more preferable that it is 0.05-1.0. If it is less than 0.01, the corrosion resistance of the film may decrease, and if it exceeds 1.5, the corrosion resistance of the film, the earth resistance, the adhesion between the film and the surface of the metal material are deteriorated, and the components acting as corrosion inhibitors in the metal material. It may become difficult to fix | immobilize in a film.

<Other additives>

The surface treatment agent for metal materials of this invention may contain various additives as needed. Below, the additive contained is demonstrated.

Water-soluble polymers and / or aqueous emulsion resins

The surface treating agent for metal materials of the present invention may contain at least one compound (G) selected from the group consisting of a water-soluble polymer and an aqueous emulsion resin. By addition of this compound (G), the fingerprint-finding property and lubricity of a film improve.

Although it does not specifically limit as a kind of water-soluble polymer and / or aqueous emulsion resin, For example, Water-soluble polymers, such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol, acrylic resin of the form disperse | distributed to water, Urethane resin, epoxy resin, polyester resin, polyamide resin, polyolefin resin, ethylene-acrylic resin, polybutyral resin, polyacetal resin, fluorine resin and the like.

Content of the compound (G) in the surface treating agent for metal materials is not specifically limited.

Especially, the mass ratio (G / (A + B)) of the total mass (A + B) of a silicic acid compound (A) and organoalkoxysilane (B) and a compound (G) in a processing agent is 0.01-0.3 It is preferable and it is more preferable that it is 0.05-0.25. In the case of less than 0.01, the anti-fingerprint property and lubricity of the coating may not be observed, and in the case of more than 0.3, the corrosion resistance and heat resistance of the coating may decrease.

The silanol condensation catalyst may be contained in the surface treating agent for metal materials of this invention. Although it does not specifically limit as a silanol condensation catalyst, For example, formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, L-ascorbic acid, tartaric acid, citric acid, DL-malic acid, malonic acid, maleic acid, phthalic acid, nitrilo Trismethylenephosphonic acid, nitrilotrispropylene phosphonic acid, nitrilodiethylmethylenephosphonic acid, nitrilopropylbismethylenephosphonic acid methane, methane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy- 1,1-diphosphonic acid, propane-1-hydroxy-1,1-diphosphonic acid, sulfonic acid, benzenesulfonic acid, ketimine compound, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxy Silane and the like.

The anti-rust additive containing N may be contained in the surface treating agent for metal materials of this invention. Examples of these include ethylenediamine, triethylamine, urea, guanidine and the like.

The surface treatment agent for metal materials of this invention may contain the additive (lubricant) for improving lubricity as needed. By improving the lubricity of the coating, it is possible to prevent scratches on the coating and to effectively reduce damage to the coating during processing.

Examples of the additive include solid lubricants such as polyethylene wax, polyethylene oxide wax, polypropylene oxide, carnauba wax, paraffin wax, montan wax, rice wax, Teflon (registered trademark) wax, carbonic acid disulfide and graphite. Among these solid lubricants, it is possible to use one kind or two or more kinds.

You may add alcohol, a ketone, a cellosolve type water-soluble solvent, surfactant, an antifoamer, a leveling agent, an antibacterial mold, a coloring agent, etc. to the surface treating agent for metal materials of this invention as needed. These can improve the drying property, coating appearance, workability, shelf life, and design of the treatment agent. However, it is important to add these so that it may not impair the quality obtained by this invention, and they are several mass% in a process liquid at most.

PH of the surface treating agent for metal materials of this invention may be acidic or alkaline, as long as it can produce a process liquid stably. However, when pH is less than 0.5, reactivity with a metal material may become high, and external appearance may fall, and when it exceeds 14, the stability of a metal compound will fall and the stability of a processing agent itself will not be desired.

The surface treatment agent for metal materials of this invention may contain solvents (for example, alcohol etc.) other than the said water as needed.

The preparation method of the surface treating agent for metal materials of this invention is not specifically limited. For example, a silicic acid compound (A), an organoalkoxysilane (B), a metal compound (C), a phosphoric acid compound and / or a fluorine compound (D), and water (E) are mixed using a stirrer such as a mixing mixer. It can manufacture by mixing sufficiently.

<Surface Treatment Method>

Although the surface treatment method using the surface treating agent for metal materials of this invention is not specifically limited, The said surface treating agent for metal materials is apply | coated on the metal material surface, and it heat-drys, and the film amount is 2-1000 mg / m <2> by Si adhesion amount. The surface treatment method of forming a phosphorus film on the metal material surface is preferable.

This surface treatment method will be described below.

Before application, the metal material may be pretreated as necessary for the purpose of removing oil or dirt on the metal material surface. In metal materials, rust preventive oil is often oiled for the purpose of rust prevention. Moreover, even if it is not oiled with rust preventive oil, there exist oils, contamination, etc. which adhered during operation. By pretreatment, the surface of the metal material is cleaned, and the surface of the metal material is easily wetted by the surface treatment agent for metal materials of the present invention. In addition, when there is no oil, a contamination, etc., and a material surface wets uniformly with the surface treating agent for metal materials of this invention, a pretreatment process is not necessary in particular.

Moreover, it does not specifically limit as a method of pretreatment, The methods, such as hot water washing | cleaning, solvent washing | cleaning, and alkali degreasing washing | cleaning, are mentioned.

Although it does not restrict | limit especially as a metal material used, Hot-dip galvanized steel plate (GI), Alloyed hot dip galvanized steel plate (GA) which alloyed this, Further hot-dip zinc Zn-5% Al alloy plated steel plate (GF), Hot-dip A zinc-55% aluminum alloy plated steel plate (GL), an electrogalvanized steel plate (EG), an electro zinc-Ni alloy plated steel plate (Zn-Ni), aluminum plating, and an aluminum sheet are mentioned. Moreover, it is applicable also to the iron plate which is not plated.

As a coating method of the surface treatment agent for metal materials to a metal material, the optimal method suitably is selected according to the shape of the metal material to be processed, etc., and a roll coating method, an immersion method, a spray coating method, etc. are mentioned.

More specifically, for example, in the case of a sheet form, the coating amount is adjusted by spraying a roll coating method or a processing liquid onto a metal material and spraying a roll or a gas at a high pressure. In the case of a molded article, it is immersed in a process liquid, and it raises, and in some cases, blows an excess process liquid with compressed air, and adjusts an application amount.

As heating temperature at the time of drying the coating film formed on the metal material surface, 40-250 degreeC is preferable, 60-200 degreeC is more preferable, 60-180 degreeC is especially preferable. If it is less than 40 degreeC, the water | moisture content which is a main solvent of the processing agent of this invention remains, and a metal compound cannot be fixed, or the corrosion resistance of a film falls. When it exceeds 250 degreeC, a crack may occur easily in a film and corrosion resistance may fall. The heat drying method is not particularly limited and may be heated by hot air, an induction heater, infrared rays, near infrared rays, or the like to dry the treatment agent.

In addition, optimal heating conditions are selected suitably according to the kind etc. of the compound in the surface treating agent for metal materials used. Especially, 0.1-60 second is preferable from a viewpoint of productivity etc., and 1-30 second is more preferable.

The film amount of the film formed on the metal material surface is adjusted so that it may become 2-1000 mg / m <2> by Si adhesion amount, Preferably it is 10-800 mg / m <2>, More preferably, it is 20-500 mg / m <2>. In the case of less than 2 mg / m 2, the effect of the present invention may not be sufficiently obtained. In the case of more than 1000 mg / m 2, the effect is saturated and economically disadvantageous. May cause deterioration of corrosion resistance.

On the film formed by the above-mentioned surface treatment method, an organic polymer film is formed so that the film thickness after drying may be 0.1-3.0 micrometers, and it can further give a high corrosion resistance, fingerprint resistance, and lubricity. As such an organic polymer film, what is known is resin emulsion, such as acryl, urethane, and epoxy, and what added silica, a rust preventive agent, a lubricating agent, a ultraviolet absorber, a pigment, etc. to this.

The surface treatment of the metal material is carried out using the surface treatment agent for the metal material, thereby providing corrosion resistance, coating paintability, heat resistance, weldability, continuous processability, earth resistance and fingerprint resistance, and in particular, the formed film has good adhesion to the surface of the metal material. It is possible to form a surface treatment film which is excellent and can fix a component which acts as a corrosion inhibitor of a metal material in the film.

The surface treatment metal material obtained using the surface treating agent for metal materials of this invention is applicable to various uses. For example, the material etc. which are used in various fields, such as a building, an electricity, and an automobile, are mentioned.

Example

Next, effects of the present invention will be described with reference to examples and comparative examples, but the present examples are merely illustrative of the present invention and are not intended to limit the present invention.

1. How to Write a Trial

(1) Test materials (materials)

The following commercially available materials were used as test materials.

(i) Electrogalvanized steel sheet (EG): plate thickness 0.8 mm, plating amount = 20/20 (g / ㎡)

(ii) Hot-dip galvanized steel sheet (GI): plate thickness 0.8 mm, plating amount = 60/60 (g / ㎡)

(iii) alloyed hot dip galvanized steel sheet (GA): plate thickness 0.8 mm, plating amount = 40/40 (g / ㎡)

The plating amount represents the plating amount on the main surface of each steel sheet. For example, in the case of an electrogalvanized steel sheet, it means 20/20 (g / m <2>), and means having 20 g / m <2> plating in each of both surfaces of a steel plate.

(2) pretreatment (washing)

As a production method of the test piece, the surface of the said test material was first processed using Nippon Parkarizing-made Perclin N364S, and the oil and contamination on the surface were removed. Next, after confirming that the surface of the metal material was 100% wet with water by washing with tap water, pure water was further flowed and water was removed from the oven at 100 ° C. atmosphere as a test plate.

(3) Adjustment of the treatment liquid of the present invention

Each component was mixed in water with the composition (solid content mass ratio) shown in Table 1, and the process liquid was obtained.

In addition, in Table 1, the compounding quantity of component (A), (B), (C), (D), and (G) shows the quantity (g) mix | blended in 1 kg of surface treatment liquids for metal materials. In addition, content of alcohol component (F) is measured using gas chromatography, Computes C _F2 from content of organoalkoxysilane, and shows it as the following molar concentration ratio (C _F1 ) / (C _F2 ).

Below, the compound used in Table 1 is demonstrated.

<Silicon Compound (A)>

A1: Snowtex C (manufactured by Nissan Chemical Industries, Ltd.)

A2: Snowtex O (manufactured by Nissan Chemical Industries, Ltd.)

<Organoalkoxysilane (B)>

B1: γ-glycidoxycitriethoxysilane

B2: aminopropyltriethoxysilane

B3: vinyltriethoxysilane

B4: tetraethoxysilane

<Metal Compound (C)>

C1: zirconium ammonium carbonate

C2: vanadium acetylacetonate

C3: magnesium nitrate

C4: aluminum nitrate

C5: zinc oxide

<Compound (D)>

D1: phosphoric acid

D2: 1-hydroxymethane-1,1-diphosphonic acid

D3: Titanium Hydrofluoric Acid

D4: Zirconic Hydrofluoric Acid

<Alcohol concentration (molar concentration ratio) (C _F1 ) / (C _F2 )>

 <Compound (G)>

G1: acrylic resin (Showa Polymer Co., Ltd. make, polysol AM-2386)

(4) Treatment method

Using the above-mentioned surface treatment liquid for metal materials, it is coated on each test plate by the following coating method, and then it is put into an oven as it is without washing with water, dried at the drying temperature shown in Table 2, The film | membrane of the film amount shown is formed.

The drying temperature was adjusted by the atmosphere temperature in oven, and the time put into oven. In addition, the drying temperature represents the temperature attained on the test plate surface. The specific method of bar coat coating and roll coat coating is as follows.

Bar coat coating: The process liquid was dripped at the test board, and it coated by the # 3-5 bar coater. The number of coatings used and the concentration of the treatment liquid were adjusted to a predetermined coating amount.

Roll coat coating: The test plate was immersed in the processing liquid at room temperature for about 1 second, and after taking out, the excess liquid was removed with a roll and the coating amount was adjusted. The amount of water drained off the roll and the concentration of the treatment liquid were adjusted to a predetermined coating amount.

(5) Method of evaluation test

(5-1) Corrosion Resistance Evaluation

The surface-treated test plate was cut out to 70 * 150 mm, the back surface and the edge part were sealed with vinyl tape, and the following test was done. Evaluation evaluated the rust generation area ratio visually.

Salt spray test (SST: according to JIS-Z-2371):

The area ratio of white rust generation after 120 hours of SST was visually evaluated according to the following criteria.

Cycle test (CCT (JASO): M609-91 (Vehicle corrosion test method for automobiles): The area ratio of white rust generated after 30 cycles of CCT was visually evaluated based on the following criteria.

Criteria:

◎: rust generation area rate less than 10%

○: Rust generation area rate 10% or more less than 20%

(Triangle | delta): 20% or more of rust generation area rate less than 40%

X: Rust generation area rate of 40% or more

××: front rust generation

(5-2) Evaluation of adhesion with metal materials

Method A: A round bar of stainless steel polished to a mirror surface with a diameter of 40 mm was reciprocated 10 times on a surface of a test plate surface-treated with a load of 50 kg, and the tape was peeled off to obtain a copper sulfate aqueous solution (3 % Aqueous solution, room temperature, 5 seconds immersion), and the plating was carried out to evaluate the peeling degree of the film.

Method B: The test plate surface-treated with an Ericsson extruder was extruded 7 mm, and the whole extruded part was peeled off with a cello tape (registered trademark), substituted with a copper sulfate aqueous solution (3% aqueous solution, room temperature, 5 seconds immersion), and coated. The peeling degree of was evaluated.

Criteria:

◎: no peeling

○: very slight peeling

△: slight peeling

X: There is remarkable peeling

(5-3) Evaluation of the elution of metal compounds

The test plate surface-treated was immersed in the boiling water of pure water for 2 hours, and the residual amount of the metal compound was measured with the fluorescent X-ray analyzer. The fixed ratio of metal was computed by the adhesion amount of the metal compound measured before the test.

Fixed rate (%) = residual amount (mg / m 2) / adhesion before test (mg / m 2) × 100

Criteria:

◎: more than 95% 100%

○: more than 90% less than 95%

△: 60% or more less than 90%

×: 20% or more and less than 60%

××: less than 20%

(5-4) Evaluation of paintability

A commercially available melamine alkyd paint was applied onto the surface-treated test plate, and the coating film thickness after baking at 160 ° C. was set to 20 μm. Subsequently, after immersion in boiling water for 2 hours, 100 boards of 1 mm in length and width were cut with an NT cutter, the part was extruded 6 mm with an Ericsson extruder, peeled off with a tape, and the remaining conditions of the coating film were evaluated as follows. Was carried out.

Criteria:

◎: no peeling off-less than 5%

○: 5% or more peeling less than 10%

(Triangle | delta): Peeling 10% or more and less than 20%

X: 20% or more peeling less than 60%

××: 60% or more of peeling

Corrosion Resistance Test: An incision reaching the material in an X shape with an NT cutter was placed in a test plate, and the rust occurrence after 80 cycles of the CCT (cycle test) was evaluated according to the following criteria.

Criteria:

◎: less than 1 mm from incision

○: 1 mm or more but less than 2 mm from the incision

△: 2 mm or more and less than 5 mm from the incision

X: 5 mm or more from the incision

××: coating film peeling off

The result of having evaluated said (5-1)-(5-4) about the surface-treated metal material obtained using Examples 1-51 and the surface treating agent for metal materials of Comparative Examples 52-67, It is shown in Table 3.

In addition, from a practical point of view, it is necessary that there is no "x" and "xx" in the said evaluation item.

As shown in Table 3, the treatment agent of the present invention containing a predetermined compound and in which the alcohol molar concentration ratio (C _F1 ) / (C _F2 ) is adjusted is excellent in corrosion resistance and paintability, and the formed film is It was confirmed that the adhesion to the surface of the metal material was excellent and the elution of the component acting as a corrosion inhibitor of the metal material was suppressed.

Especially, when the organoalkoxysilane which has an epoxy group or an amino group as organoalkoxysilane (B) was used from the comparison of Examples 23-26, it turned out that each characteristic is more excellent. In addition, from the comparison of Examples 16 and 17, it was found that when using two kinds of organoalkoxysilanes together, the respective properties were further improved.

On the other hand, in the comparative example, the result which satisfy | fills all the characteristics collectively was not obtained.

Claims (9)

Silicic acid compound (A)
Organoalkoxysilane (B),
Metal compound comprising at least one metal element selected from the group consisting of Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, Nb, Cr, and Zn (C )and,
At least one compound (D) selected from the group consisting of a phosphoric acid compound and a fluorine compound
Water (E),
As a surface treatment agent for metal materials containing alcohol (F) produced | generated from the hydrolysis of the said organoalkoxysilane (B),
And the molar concentration _{(mol / L) (C F1} ) in water treating agent of the alcohol (F), wherein the organoalkoxysilane molar concentrations in the agent of the alcohol that is generated when all the alkoxy groups are hydrolyzed contained in (B) The surface treating agent for metal materials whose ratio (C _F1 / C _F2 ) of (mol / L) (C _F2 ) is adjusted to the range of 0.05-0.9. The method of claim 1,
The mass ratio (C / F) of the said alcohol (F) and said metal compound (C) is 0.01-50, The surface treating agent for metal materials. The method of claim 1,
The surface treatment agent for metal materials whose mass ratio (D / F) of the said alcohol (F) and said compound (D) is the range of 0.01-25. The method of claim 1,
The mass ratio (A / B) of the silicic acid compound (A) and the organoalkoxysilane (B) is 0.01 to 3.0,
The mass ratio (C / (A + B)) of the total mass (A + B) and the metal compound (C) of the silicic acid compound (A) and the organoalkoxysilane (B) is 0.01 to 2.0,
Surface mass for metal materials whose total mass (A + B) of the said silicic acid compound (A) and the organoalkoxysilane (B) and the mass ratio (D / (A + B)) of the said compound (D) are 0.01-1.5. Treatment agent. The method of claim 1,
The organoalkoxy silane (B) has an amino group, an epoxy group, or an amino group and an epoxy group, The surface treating agent for metal materials. The method of claim 1,
Furthermore, the surface treating agent for metal materials containing 1 or more types of compound (G) chosen from the group which consists of a water-soluble polymer and an aqueous emulsion resin. The method according to claim 6,
The surface for metal materials whose total mass (A + B) of the said silicic acid compound (A) and the organoalkoxysilane (B) and the mass ratio (G / (A + B)) of the said compound (G) are 0.01-0.3. Treatment agent. The surface treatment agent for a metal material according to any one of claims 1 to 7 is applied on the surface of the metal material and dried by heating to form a film having a coating amount of 2 to 1000 mg / m 2 on the surface of the metal material. Surface treatment method of a metal material formed in the. The surface treatment metal material which has a film on the surface obtained by the surface treatment method of the metal material of Claim 8.