JP5123052B2 - Surface chemical conversion solution, chemical conversion metal plate and method for producing the same, and upper-layer metal plate and method for producing the same - Google Patents

Description

  The present invention relates to a surface chemical conversion treatment liquid, a chemical conversion treatment metal plate and a production method thereof, and an upper layer coated metal plate and a production method thereof.

Almost all metal materials as well as galvanized steel sheets, when left in the atmosphere, corrode SO ₂ , NO ₂ , flying sea salt particles, etc. in the presence of moisture physically adsorbed from the atmosphere. Corrosion occurs on the surface due to the action of the accelerated adhesion substance. In order to prevent this corrosion, as a conventional corrosion prevention method for metallic materials such as galvanized steel sheets, the chromate film is deposited or applied by bringing the surface of the metallic material into contact with a treatment liquid containing chromium such as chromate chromate. Then, there is a method of forming a chromate film on the surface of the metal material by drying and the like.

  Typical examples of depositing a chromate film by bringing the surface of a metal material into contact with a treatment liquid include chromic acid chromate conversion treatment and phosphoric acid chromate chemical conversion treatment. The former chromate chromate conversion treatment was put into practical use around 1950 and is still widely used for galvanized steel sheets. The treatment liquid used for this chromate chromate conversion treatment contains chromic acid (CrO3) and hydrofluoric acid (HF) as main components, and further contains an accelerator, and is a deposited film containing hexavalent chromium. Can be formed.

Patent Document 1 describes the latter phosphoric acid chromate chemical conversion treatment method. This chemical conversion treatment solution contains chromic acid (CrO ₃ ), phosphoric acid (H ₃ PO ₄ ), and hydrofluoric acid (HF), and the formed deposited film is hydrated chromium phosphate (CrPO ₄ .4H _2). O) as a main component. However, since these chromate type surface treatment solutions contain harmful hexavalent chromium, the use of not only hexavalent chromium, which is problematic from the environmental and safety aspects, but also trivalent chromium is restricted. With the trend of the times, it is desired to switch to a non-chromate type surface treatment method that does not contain chromium at all.

  Non-chromate type surface treatment methods include a precipitation type and a coating type, and the precipitation type has already been proven as a surface treatment method for aluminum-containing metal materials. The reason why the non-chromate type treatment liquid has been applied to aluminum-containing metal materials from a relatively early stage is that this metal material has been widely used as a material in contact with food such as aluminum cans.

  Patent Document 2 describes a non-chromate type chemical precipitation type surface treatment solution for an aluminum-containing metal material. This treatment liquid is an acidic aqueous surface treatment liquid containing zirconium or titanium, or a mixture thereof, phosphate and fluoride, and having a pH of about 1.0 to 4.0. When treatment is performed using this chemical conversion treatment solution, a deposited film containing a phosphorus compound of zirconium or titanium as a main component is formed on the surface of the aluminum-containing metal material. Compared to such a chemical precipitation type surface treatment liquid for aluminum-containing metal materials, there are almost no existing technologies or achievements for a non-chromate type chemical precipitation type surface treatment liquid for galvanized steel sheets.

  In addition, in the sheet coil manufacturers of galvanized steel sheets, the coating type surface treatment is now becoming the mainstream rather than the precipitation type surface treatment. However, depending on the sheet coil manufacturer's line, the introduction of coating-type surface treatment may not be possible due to equipment costs and locational reasons, and the existing chromate treatment is replaced with a non-chromate treatment by the precipitation-type equipment. The desire to want is strong.

  In addition, the precipitation-type surface treatment is capable of treating both surfaces of a metal plate such as a zinc-based plated steel sheet at the same time, and because it can remove soluble components in the subsequent washing process, it can be expected to improve the corrosion resistance, etc. It has many attractive merits, such as the very small amount of pretreatment liquid brought into the processing liquid in the process.

  Patent Document 3 discloses an aqueous composition for coating aluminum, iron or magnesium alloys, including titanium, zirconium and the like, magnesium and calcium, dissolved fluorine ions, and a pH of 2.0 to 5 An aqueous composition is described that forms a film so that there is little or no etching. However, application of this aqueous composition to a galvanized steel sheet is not described.

  Patent Documents 4 to 12 contain metals such as zirconium, titanium, and hafnium, fluorine, accelerators, etc., and by adjusting the concentration and molar ratio thereof, do not contain chromium, exhibit high corrosion resistance, and Further, a chemical conversion treatment agent, a chemical conversion treatment method, and a chemical conversion treatment material technique that are excellent in stability are described. However, in these treatments, it takes a long time to deposit the film, and it cannot be applied to the sheet coil.

  On the other hand, Patent Document 13 discloses a chemical conversion treatment agent composed of zirconium, fluorine, an amino group-containing silane coupling agent, a hydrolyzate thereof, a polymer thereof, and an amino group-containing aqueous phenol compound, A chemical conversion treatment agent is described in which the content of the chemical conversion treatment agent is 25 to 2000 ppm in terms of metal, and the molar ratio of the fluorine and zirconium content is 3 ≦ F / Zr ≦ 6. However, this technology uses an amino group-containing silane coupling agent or an amino group-containing phenolic compound as a stabilizer for the treatment liquid, and has no special effect on the film performance. Since it is comparable, it cannot be applied to the sheet coil as described above.

  Patent Document 14 and Patent Document 15 are chemical conversion treatment agents composed of at least one selected from the group consisting of zirconium, titanium, and hafnium, fluorine, and a water-soluble resin, and have a low environmental impact. A chemical conversion treatment agent capable of performing a good chemical conversion treatment on all metals such as iron, zinc, and aluminum, and a technique related to a surface-treated metal obtained using the chemical conversion treatment agent are described. However, even in this technique, the processing time cannot be shortened and cannot be applied to a sheet coil.

  Patent Document 16 includes at least one compound (a) which is a chemical conversion treated metal plate and contains at least one element selected from the group consisting of Zr, Ti, Hf and Si, and is subjected to self-deposition or electroanalysis. The technique regarding the chemical conversion treatment metal plate which has the surface chemical conversion treatment layer which came out on the surface of a metal plate is described.

  Patent Document 17 discloses that “an organic compound having a resonance structure in the molecule and an electrophilic reactive functional group (a1), and a phosphoric acid group, a phosphonic acid group, a silanol group, an alkoxysilyl group, Describes a metal surface chemical conversion treatment solution containing an organic compound (A) having at least one functional group (a) selected from at least one functional group (a2) selected from mercapto groups and sulfonium groups " .

  In addition, a multilayer coated metal material in which about 1 to 3 layers of resin-based film is formed as an upper layer on the chromate film formed by the precipitation-type surface treatment to provide high functionality such as corrosion resistance and fingerprint resistance. Are known.

US Pat. No. 2,438,877 JP 52-131937 A Japanese National Patent Publication No. 9-503823 JP 2004-043913 A Japanese Patent Application Laid-Open No. 2004-218070 JP 2004-218072 A JP 2004-218073 A JP 2004-218074 A JP 2005008982 A JP 2006-124751 A JP 2006-161115 A JP 2007-314888 A JP 2007-262577 A JP 2004-218075 A JP 2004-292874 A International Publication No. 2006-323358 Pamphlet JP 2001-329379 A

  The surface chemical conversion treatment method described in Patent Document 16 can be applied to a sheet coil in that it has corrosion resistance in a short time and has a very high industrial value. However, the performance of the chemical conversion film, particularly the corrosion resistance of the processed part is further increased. There is room for improvement.

  Moreover, since the organic compound (A) does not have an amino group, the metal surface chemical conversion solution described in Patent Document 17 has a problem of poor stability.

  Therefore, the present invention is for solving the above-mentioned problems of the prior art, and specifically, the same corrosion resistance as that of the chromate film (particularly the corrosion resistance of the Erichsen machined part, the bent part and the collar part) and the coating. Surface chemical conversion treatment liquid capable of forming in a short time a surface chemical conversion treatment layer having film adhesion and not containing chromium, a method for producing a chemical conversion treatment metal plate using the same, and production of an upper layer coated metal material It is an object of the present invention to provide a method, and a chemical conversion treated metal plate and an upper layer coated metal material.

  In the present invention, the “short time” is a short time that can be applied to a production line such as a sheet coil, for example, preferably 20 seconds or less, more preferably 10 seconds or less, and 5 seconds or less. Even more preferred.

In order to achieve the above object, the present invention provides a surface chemical conversion liquid for metal plate surface treatment, comprising an alkoxysilyl group, an aromatic ring, a hydroxy group directly bonded to the aromatic ring, a first A water-soluble compound (A) having at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium group, and Zr, Ti and Hf A fluoride (B) containing at least one metal element selected from the group consisting of: at least one acid component (C) selected from the group consisting of hydrofluoric acid, nitric acid, sulfuric acid and salts thereof; and Mn A compound (D) containing at least one metal element selected from the group consisting of Co, Mg, Al and Zn, and an aqueous medium (E), wherein the compound (A) is a polymer, Compound (A) The fluoride (B), the acid component (C), and the compound (D) are dissolved in the aqueous medium (E), and the surface chemical conversion treatment layer is self-deposited by contacting the surface of the metal plate. Alternatively, there is provided a surface chemical conversion treatment solution for electrolytically depositing a surface chemical conversion treatment layer by contacting the surface of the metal plate as a cathode.

  Here, the alkoxysilyl group is preferably bonded to the nitrogen atom of the amino group directly or via an alkylene group.

  The free fluorine ion concentration is 1 to 30 mg / L, and the total mass concentration of the metal elements contained in the compound (D) with respect to the total mass concentration (b) of the metal elements contained in the fluoride (B). It is preferable that (d) / (b), which is the ratio of mass concentration (d), is 1 to 200.

Moreover, it is preferable that pH is 2.0-X. (However, said X is represented by the following formula. In the following formula, (d) is the total mass concentration (d) of said metal elements contained in said compound (D), and (b) is said fluoride. (This is the total mass concentration (b) of the metal elements contained in (B).)
X = −0.02 × [(d) / (b)] + 6.0

  Moreover, the oxide equivalent mass of Si derived from the compound (A) including the precipitate of the compound (A) and the metal element contained in the fluoride (B) on at least one surface of the metal plate. The mass ratio [(a) / (b ′)] of a) and the total precipitation mass (b ′) of the metal elements contained in the fluoride (B) is preferably 0.03 to 0.3. .

Moreover, it is preferable that the surface chemical conversion treatment layer whose total precipitation mass (b ') of the said metal element contained in the said fluoride (B) is 5-50 mg / m < ² > can be formed.

  The metal plate is preferably a zinc-based plated steel plate.

  In order to achieve the above object, the present invention provides a method for producing a chemical conversion treated metal plate, wherein a surface chemical conversion treatment layer of the present invention is used to form a non-coating surface chemical conversion treatment layer on at least one surface of the metal plate. provide.

  Here, the surface chemical conversion treatment liquid is brought into contact with the surface of the metal plate to form a surface chemical conversion treatment layer by self-deposition on the surface of the metal plate, and the metal plate on which the surface chemical conversion treatment layer has been formed is washed with water. It is preferable to do this.

  Further, the surface chemical conversion treatment liquid is brought into contact with the surface of the metal plate serving as a cathode, and a surface chemical conversion treatment layer is formed by electrolytic deposition on the surface of the metal plate, thereby forming the surface chemical conversion treatment layer. The metal plate is preferably washed with water.

Further, the surface chemical conversion treatment liquid at a temperature of 30 to 70 ° C. is brought into contact with the surface of the metal plate for 0.5 to 20 seconds, and the metal element contained in the fluoride (B) on the surface of the metal plate It is preferable to form a surface chemical conversion treatment layer containing 5 to 50 mg / m ^{2 in} total.

  Moreover, in order to achieve the said objective, this invention is a manufacturing method of the chemical conversion treatment metal plate of this invention, and also comprises the process of forming a resin layer on the upper surface of the said surface chemical conversion treatment layer. A manufacturing method is provided.

In order to achieve the above object, the present invention provides an alkoxysilyl group, an aromatic ring, a hydroxy group directly bonded to the aromatic ring, a primary amino group, a second A water-soluble compound (A) having at least one amino group selected from the group consisting of a primary amino group, a tertiary amino group and a quaternary ammonium group, and at least selected from the group consisting of Zr, Ti and Hf Provided is a chemical conversion treated metal plate having a surface chemical conversion treatment layer containing one metal element, wherein the compound (A) is a polymer, and is autodeposited or electrolytically deposited.

  Here, it is preferable to obtain by the manufacturing method of the chemical conversion treatment metal plate of this invention.

  Moreover, in order to achieve the said objective, this invention is obtained by the manufacturing method of the upper coating metal plate of this invention, and provides the upper coating metal plate in which the said resin layer has fingerprint resistance.

  In order to achieve the above object, the present invention is obtained by the method for producing an upper coated metal sheet of the present invention, wherein the resin layer is at least two layers of a layer made of a non-chromate primer paint and a layer made of a top coat paint. An upper coated metal sheet is provided.

The surface chemical conversion treatment liquid of the present invention has a surface chemical conversion treatment layer that has the same degree of corrosion resistance as that of the chromate film (particularly the corrosion resistance of the elixir processed part, the bent part, and the collar part) and the coating film adhesion, and does not contain chromium. It can be formed in a short time.
Moreover, according to the manufacturing method of the chemical conversion treatment metal plate of this invention, it has corrosion resistance comparable to a chromate film (especially the corrosion resistance of an elixir processed part, a bending part, and a collar part), and coating-film adhesiveness, and chromium is used. Since the surface chemical conversion treatment layer not included can be formed on the metal plate in a short time, it can be applied to a production line such as a sheet coil.
Moreover, the chemical conversion treatment metal plate of the present invention has the same degree of corrosion resistance as that of the chromate film (particularly the corrosion resistance of the Erichsen processed part, the bent part and the collar part) and the coating film adhesion, and does not contain chromium. The layer can be formed in a short time.
Moreover, according to the manufacturing method of the upper coating metal plate of this invention, it is excellent in corrosion resistance and coating-film adhesiveness, and can manufacture the upper coating metal material which does not contain chromium.
Further, the upper coated metal sheet of the present invention is excellent in corrosion resistance and coating film adhesion, and does not contain chromium.

Hereinafter, the present invention will be described in more detail.
The surface chemical conversion treatment liquid of the present invention (hereinafter also referred to as “treatment liquid of the present invention”) is a surface chemical conversion liquid for surface treatment of a metal plate, and is directly applied to an alkoxysilyl group, an aromatic ring, and the aromatic ring. A water-soluble compound having a bonded hydroxy group and at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium group ( A), a fluoride (B) containing at least one metal element selected from the group consisting of Zr, Ti and Hf, and at least one selected from the group consisting of hydrofluoric acid, nitric acid, sulfuric acid and salts thereof Containing the acid component (C) of the seed, the compound (D) containing at least one metal element selected from the group consisting of Mn, Co, Mg, Al and Zn, and the aqueous medium (E), (A) The chemical compound (B), the acid component (C), and the compound (D) are dissolved in the aqueous medium (E) and contact the surface of the metal plate to self-deposit the surface chemical conversion treatment layer, or A surface chemical conversion treatment solution for electrolytically depositing a surface chemical conversion treatment layer by contacting the surface of the metal plate as a cathode.

Hereinafter, the compound (A) will be described.
The compound (A) used in the treatment liquid of the present invention comprises an alkoxysilyl group, an aromatic ring, a hydroxy group directly bonded to the aromatic ring, a primary amino group, a secondary amino group, a third A water-soluble compound having at least one amino group selected from the group consisting of a quaternary amino group and a quaternary ammonium group. The compound (A) may be a monomer or a polymer.
By introducing an alkoxysilyl group into a compound having an aromatic ring and a phenolic hydroxy group, the coating film adhesion, corrosion resistance and chemical resistance of the treatment liquid of the present invention are greatly improved.
Moreover, when a compound (A) has an amino group, water solubility becomes high, stability of the processing liquid of this invention becomes high, and also corrosion resistance and coating-film adhesiveness become higher.

The alkoxysilyl group may be a group having a silicon atom and an alkoxy group directly bonded to the silicon atom, and is a group having at least two alkoxy groups bonded directly to the silicon atom and the silicon atom. Are preferable, and a group having three silicon groups and three alkoxy groups directly bonded to the silicon atoms is more preferable.
As said alkoxy group, a C1-C10 alkoxy group is preferable and a methoxy group or an ethoxy group is more preferable.
Although the group which the said alkoxy silyl group other than the said alkoxy group has is not specifically limited, For example, a hydrogen atom, a C1-C10 alkyl group, etc. are mentioned suitably.
Specific examples of the alkoxysilyl group include a dimethylmethoxysilyl group, a methyldimethoxysilyl group, a trimethoxysilyl group, a diethylethoxysilyl group, an ethyldiethoxysilyl group, and a triethoxysilyl group.

  In one preferred embodiment, the alkoxysilyl group of the compound (A) is bonded to the nitrogen atom of the amino group directly or via an alkylene group. The compound (A) of such an embodiment is prepared by, for example, reacting an aromatic compound (a1) in which at least one hydroxy group is directly bonded to an aromatic ring, aminosilane (a2), and formaldehyde, as described later. An aromatic compound (a1) in which at least one hydroxy group is directly bonded to an aromatic ring, an aminosilane (a2), an amine compound (a3), , And a method of reacting with formaldehyde (hereinafter referred to as “second method”).

  When the compound (A) is a polymer (when the main chain has a repeating unit), the compound (A) has 0.01 to 4 alkoxysilyl groups per repeating unit of the compound (A). Preferably, it has 0.05-2, more preferably 0.1-1.5. When the compound (A) has an alkoxysilyl group in this range, it is excellent in coating film adhesion, corrosion resistance and chemical resistance.

  Moreover, it is preferable that a compound (A) has 1-4 alkoxysilyl groups in 1 molecule, It is more preferable to have 1-3, It is still more preferable to have 1-2. When the compound (A) has an alkoxysilyl group in this range, it is excellent in coating film adhesion, corrosion resistance and chemical resistance.

Although the aromatic ring which the said compound (A) has is not specifically limited, For example, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned, It is preferable that it is a benzene ring.
The phenolic hydroxy group is a hydroxy group directly bonded to the aromatic ring of the compound (A).

  In order to ensure the water solubility of the compound (A), the compound (A) preferably has a polar group such as an amino group or a hydroxy group that is not directly bonded to an aromatic ring. Since compound (A) is water-soluble, it can be used in an aqueous surface chemical conversion treatment solution.

  The compound (A) preferably has at least one amino group selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group and a quaternary ammonium group. It is more preferable to have an amino group or a tertiary amino group, and it is more preferable to have a tertiary amino group. In the case where the compound (A) has an amino group, the polarity of the compound (A) is increased, so that the compound (A) is easily water-soluble.

  The compound (A) preferably has a hydroxy group that is not directly bonded to the aromatic ring. When the compound (A) has a hydroxy group in addition to the phenolic hydroxy group, the water solubility of the compound (A) is increased. Moreover, the coating film adhesion, corrosion resistance, and chemical resistance of the obtained surface chemical conversion treatment liquid can be improved.

  In one preferred embodiment, the hydroxy group that is not directly bonded to the aromatic ring is bonded to the nitrogen atom of the amino group via an alkylene group. The compound (A) of such an embodiment can be obtained, for example, by the second method.

  When the compound (A) is a polymer (when it has a repeating unit in the main chain), the compound (A) has a hydroxy group that is not directly bonded to the aromatic ring per repeating unit of the compound (A). It is preferable to have 0.01-4, more preferably 0.05-2, and still more preferably 0.1-1.5. When the compound (A) has a hydroxy group that is not directly bonded to the aromatic ring in this range, the water solubility of the compound (A) and the coating film adhesion, corrosion resistance, and chemical resistance of the resulting surface chemical conversion liquid are excellent. .

  Moreover, it is preferable that a compound (A) has 1-4 hydroxy groups which are not directly couple | bonded with the said aromatic ring in 1 molecule, It is more preferable to have 1-3, It is having 1-2. Further preferred. When the compound (A) has a hydroxy group that is not directly bonded to the aromatic ring in this range, the water solubility of the compound (A) and the coating film adhesion, corrosion resistance, and chemical resistance of the resulting surface chemical conversion liquid are excellent. .

  Compound (A) is a compound obtained by a reaction (first method) of an aromatic compound (a1) in which at least one hydroxy group is directly bonded to an aromatic ring, aminosilane (a2), and formaldehyde. Is one of the preferred embodiments.

  As another preferred embodiment of the compound (A), an aromatic compound (a1) in which at least one hydroxy group is directly bonded to an aromatic ring, an aminosilane (a2), an amine compound (a3), and formaldehyde A compound obtained by the reaction with (second method) is preferably mentioned.

In the compound (A) of these embodiments, an amino group is bonded to the ortho-position or para-position of the hydroxy group of the aromatic ring of the aromatic compound (a1) through a methylene group derived from formaldehyde by a so-called Mannich reaction. It is considered to be a structure.
In the compound (A), the position at which the aromatic ring has a substituent is not particularly limited, but it is preferable that the ortho position and / or the para position of the hydroxy group of the aromatic ring are substituted.

The aromatic compound (a1) is an aromatic compound in which at least one hydroxy group is directly bonded to the aromatic ring. Specific examples include phenol, bisphenol A, p-vinylphenol, naphthol, o-cresol, m-cresol, p-cresol, and the like. Moreover, these polymers can also be used. The polymerization method is not particularly limited, and known polymerization methods such as radical polymerization, cationic polymerization, and condensation polymerization can be employed.
In addition to these, as the aromatic compound (a1), a phenol-cresol novolac copolymer, a vinylphenol-styrene copolymer, or the like can also be used.
Further, the above-described aromatic compound (a1) is modified with haloepoxides such as epichlorohydrin, carboxylic acids such as acetic acid, organic silanes such as esters, amides, and trimethylsilyl chloride, alcohols, alkylated products such as dimethyl sulfate, and the like. It is also possible to use what has been done.
These aromatic compounds (a1) may be used alone or in combination of two or more.

  The aromatic compound (a1) is at least one selected from the group consisting of phenol, bisphenol A, p-vinylphenol, naphthol, novolac resin, polybisphenol A, poly p-vinylphenol, and phenol-naphthalene polycondensate. It is preferably at least one selected from the group consisting of novolak resin, polybisphenol A, poly p-vinylphenol and phenol-naphthalene polycondensate, and is poly p-vinylphenol. Is more preferable.

  Here, in the present specification, the polybisphenol A means a compound represented by the following formula.

  In said formula, s is an integer of 1-2000, and it is preferable that it is an integer of 5-1000.

Moreover, the said poly p-vinylphenol means the compound represented by a following formula.
As said poly p-vinylphenol, what superposed | polymerized vinylphenol by the well-known polymerization method may be used, and a commercial item may be used. As a commercial item, the Maruka linker made from Maruzen Petrochemical Co., Ltd. is mentioned.

  In said formula, t is an integer of 1-4000 and it is preferable that it is an integer of 10-2000.

  The weight average molecular weight of the aromatic compound (a1) is not particularly limited, but is preferably 200 to 1,000,000, more preferably 500 to 500,000, and 1,000 to 200,000. More preferably.

  The aminosilane (a2) is not particularly limited as long as it is a compound having a primary amino group and / or a secondary amino group (imino group) and an alkoxysilyl group. For example, the aminosilane (a2) is represented by the following formula (2). Preferred examples thereof include:

In the above formula (2), R ³ is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, benzyl group, aryl group, hydroxyalkyl group, dihydroxyalkyl group, trihydroxyalkyl group, aminoalkyl group, alkylaminoalkyl group. A dialkylaminoalkyl group, an acetyl group or an alkylcarbonyl group.
As said alkyl group, a C1-C10 alkyl group is mentioned suitably, More preferably, a methyl group, an ethyl group, i-propyl group, and t-butyl group are mentioned.
As said alkenyl group, a C1-C10 alkenyl group is mentioned suitably, More preferably, an allyl group is mentioned.
As said alkynyl group, a C1-C10 alkynyl group is mentioned suitably, More preferably, a propynyl group is mentioned.
As said aryl group, a C1-C10 aryl group is mentioned suitably, More preferably, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group are mentioned suitably, More preferably, a phenyl group is mentioned.
As said hydroxyalkyl group, a C1-C10 hydroxyalkyl group is mentioned suitably, More preferably, a 2-hydroxyethyl group is mentioned.
As said dihydroxyalkyl group, a C1-C10 dihydroxyalkyl group is mentioned suitably, More preferably, a bis (hydroxyethyl) group is mentioned.
As said trihydroxyalkyl group, a C1-C10 trihydroxyalkyl group is mentioned suitably, More preferably, a tris (hydroxyethyl) group is mentioned.
As said aminoalkyl group, a C1-C10 aminoalkyl group is mentioned suitably, More preferably, an aminoethyl group is mentioned.
As said alkylaminoalkyl group, a C1-C10 alkylaminoalkyl group is mentioned suitably, More preferably, 2-methylaminoethylene is mentioned.
As said dialkylaminoalkyl group, a C1-C10 dialkylaminoalkyl group is mentioned suitably, More preferably, dimethylaminoethylene is mentioned.
As said alkylcarbonyl group, a C1-C10 alkylcarbonyl group is mentioned suitably, More preferably, an acetyl group is mentioned.

In the above formula (2), R ⁴ and R ⁵ are each an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group or an ethyl group. A plurality of R ⁴ and R ⁵ may be the same or different.
In said formula (2), n is an integer of 1-3, it is preferable that it is an integer of 2-3, and it is more preferable that it is 3.
In the above formula (2), m is preferably an integer of 1 to 3, more preferably 2 or 3, and still more preferably 3.

Specific examples of the aminosilane (a2) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3-propyltrimethoxysilane, and N-phenyl-3-propyltrimethyl. Ethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, N- (2-aminoethyl) aminopropyltriethoxysilane, N- (2- Aminoethyl) aminopropylmethyldiethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane, N-β- ( N-vinylbenzylaminoethyl) -3-aminopropyl Tildimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropylmethyldiethoxysilane, γ-ani Linopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilane, bis (trimethoxysilyl) aminovinyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, Aminoethylamino -3-isobutyldimethylmethoxysilane, n-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, N-cyclohexyl Aminopropyltrimethoxysilane, N-phenylaminomethyltriethoxysilane, N-methylaminopropylmethyldimethoxysilane, bis (trimethoxysilyl) amine, bis [(3-trimethoxysilyl) propyl] ethylenediamine, bis [3- ( Triethoxysilyl) propyl] urea, bis (methyldiethoxysilylpropyl) amine, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, N, N-dioctyl-N'-trie Xylylpropylurea, N- (3-triethoxysilylpropyl) gluconamide, (3-triethoxysilylpropyl) -t-butylcarbamate, triethoxysilylpropylcarbamate, 1,3-divinyltetramethyldisilazane, trimethoxysilyl Examples include propyl (polyethyleneimine), 3- (2,4-dinitrophenylamino) propyltriethoxysilane, and 3- (triethoxysilylpropyl) -p-nitrobenzamine. These may be used alone or in combination of two or more.
Among these, γ-phenylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-methylamino Preference is given to at least one aminosilane selected from the group consisting of propyltrimethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, bis (trimethoxysilyl) amine and 3- (N-allylamino) propyltrimethoxysilane.

  The amount of aminosilane (a2) used in the first method is preferably 1 to 1200 parts by weight, more preferably 2 to 600 parts by weight, and more preferably 3 to 300 parts by weight with respect to 100 parts by weight of the aromatic compound (a1). Is more preferable.

  The amount of the aminosilane (a2) used in the second method is preferably 1 to 1200 parts by weight, more preferably 2 to 600 parts by weight, and more preferably 3 to 300 parts by weight with respect to 100 parts by weight of the aromatic compound (a1). Is more preferable.

The amine compound (a3) is not particularly limited as long as it is a compound having a primary amino group and / or a secondary amino group (imino group). For example, a compound represented by the following formula (1) is preferable. It is mentioned in.
The amine compound (a3) may be the same as the aminosilane (a2).

In the above formula (1), R ¹ and R ² are the same as R ^{3 in the} above formula (2), respectively, but R ¹ and R ² may be bonded to each other to form a morpholino group.

Specific examples of the amine compound (a3) include alkylamines such as methylamine, ethylamine, i-propylamine, dimethylamine, diethylamine, and dii-propylamine, monoethanolamine, diethanolamine, and 2-methyl. Alkanolamines such as ethanolamine, 2-ethylethanolamine, N-methylamino1,2-propanediol and N-methylglucamine, aromatic amines such as aniline, p-methylaniline and N-methylaniline, vinylamine and allylamine Unsaturated amines such as pyrrole, pyrrolidine, imidazole, indole, morpholine, piperazine, etc., ethylenediamine, N, N-dimethylethylenediamine, ethylenediamine, sym-dimethylethylenediamine, 1,6 Hexamethylenediamine, 1,3-propanediamine, etc. can be used. These may be used alone or in combination of two or more.
Among these, 2-methylaminoethanol, monoethanolamine, diethanolamine, methylamino-1,2-propanediol, N-methylglucamine, N-methyl-1,3-propanediamine, N-methylaniline, ethylamine, diethylamine And at least one amine compound selected from the group consisting of allylamine, benzylamine, 2-ethylaminoethanol, ethylenediamine, sym-dimethylethylamine and morpholine.

  The amount of the amine compound (a3) used in the second method is preferably 0.2 to 360 parts by mass, more preferably 0.4 to 270 parts by mass with respect to 100 parts by mass of the aromatic compound (a1). 0.6-180 mass parts is still more preferable.

As the formaldehyde used in the above reaction, those diluted with a solvent can be used.
The solvent is not particularly limited as long as it does not participate in the reaction. For example, water; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and 1,4-dioxane; halogen solvents such as dichloromethane and chloroform; acetone and the like And ketone solvents.

  The amount of formaldehyde used in the first method is preferably such that the molar ratio of formaldehyde to amino groups of the aminosilane (a2) (formaldehyde / amino group) is 1 to 100, more preferably 2 to 50. .

  The amount of formaldehyde used in the second method is such that the molar ratio of formaldehyde (formaldehyde / amino group) to the total of the amino group of aminosilane (a2) and the amino group of amine compound (a3) is 1 to 100. Is preferable, and it is more preferable that it is 2-50.

  As said compound (A), the polymer containing the repeating unit represented by following formula (3) is one of the preferable aspects.

In the above formula (3), R ⁶ is the same as R ^{3 in the} above formula (2).
R ⁷ is a single bond or an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably a trimethylene group (— (CH ₂ ) ₃ —). When R ⁷ is a single bond, R ⁷ does not exist and a nitrogen atom and a silicon atom are directly bonded.
R ⁸ and R ⁹ are each an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group or an ethyl group. A plurality of R ⁸ and R ⁹ may be the same or different.
R ¹⁰ and R ¹¹ are the same as R ^{3 in the} above formula (2), respectively, but R ¹⁰ and R ¹¹ may be bonded to each other to form a morpholino group.
p is an integer of 1 to 3, preferably 2 or 3, and more preferably 3.

The polymer may contain a repeating unit other than the repeating unit represented by the formula (3). The polymer is represented by the repeating unit represented by the above formula (3), the repeating unit represented by the following formula (5), the repeating unit represented by the following formula (6), and the following formula (7). And a polymer comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (8) and a repeating unit represented by the following formula (9): This is one aspect.
The polymer may further contain a repeating unit other than the repeating unit represented by any one of the above formulas (3) to (9).

In said formula (5)-(9), R < ⁶ >, R < ⁷ >, R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R < ¹¹ > and p are respectively R < ⁶ >, R < ⁷ >, R < ⁸ >, R of said formula (3). ^{The same as 9} , R ¹⁰ , R ¹¹ and p.

  The method for producing the polymer is not particularly limited, but a method of obtaining the polymer by reacting poly p-vinylphenol, the aminosilane (a2), the amine compound (a3), and formaldehyde is preferable. Can be mentioned.

Specific examples of the polymer include, for example, a polymer containing a repeating unit represented by the following formula (4) (hereinafter referred to as “the compound of the first aspect of the present invention”).

The compound of the first aspect of the present invention may contain a repeating unit other than the repeating unit represented by the above formula (4). The compound of the present invention is represented by the repeating unit represented by the above formula (4), the repeating unit represented by the following formula (10), the repeating unit represented by the following formula (11), and the following formula (12). And a polymer comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (13) and a repeating unit represented by the following formula (14): This is one of the preferred embodiments.
The compound of the first aspect of the present invention may further contain a repeating unit other than the repeating unit represented by any of the above formulas (4) and (10) to (14).

  The method for producing the compound of the first aspect of the present invention is not particularly limited, but the above heavy compound is obtained by reacting poly p-vinylphenol, γ-phenylaminopropyltrimethoxysilane, 2-methylaminoethanol, and formaldehyde. A preferred method is to obtain a coalescence.

  Other preferred embodiments of the compound (A) include, for example, poly p-vinylphenol, γ-phenylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-amino Propyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-methylaminopropyltrimethoxysilane, N-cyclohexylaminopropyltrimethoxysilane, bis (trimethoxysilyl) amine and 3- (N-allylamino) propyltrimethoxysilane At least one aminosilane selected from the group consisting of: 2-methylaminoethanol, monoethanolamine, diethanolamine, methylamino-1,2-propanediol, N-methyl-1,3-propanediamine, N-methylanily , Ethylamine, diethylamine, allylamine, benzylamine, 2-ethylaminoethanol, and a compound obtained by reacting at least one amine compound selected from the group consisting of morpholine and formaldehyde in an organic solvent (hereinafter “the present invention”). Of the second embodiment of the present invention ”).

The method for producing the compound of the second aspect of the present invention is not particularly limited, but the poly p-vinylphenol, the aminosilane, the amine compound, and the formaldehyde are reacted in an organic solvent. A method for obtaining the compound of the second embodiment is preferable.
The compound according to the second aspect of the present invention is considered to have a structure in which an amino group is bonded to the ortho position of the hydroxy group of the aromatic ring of poly (p-vinylphenol) via a methylene group derived from formaldehyde by so-called Mannich reaction. It is done.
In the compound of the second aspect of the present invention, the position at which the aromatic ring has a substituent is not particularly limited, but it is preferable that the ortho position of the phenolic hydroxy group is substituted.

The amount of aminosilane used in the reaction is preferably 1 to 1200 parts by weight, more preferably 2 to 600 parts by weight, and still more preferably 3 to 300 parts by weight with respect to 100 parts by weight of poly p-vinylphenol.
The amount of the amine compound used in the reaction is preferably 0.2 to 360 parts by mass, more preferably 0.4 to 270 parts by mass, and 0.6 to 180 parts by mass with respect to 100 parts by mass of poly p-vinylphenol. Part is more preferred.
The amount of formaldehyde used in the above reaction is preferably 0.3 to 300 parts by mass, more preferably 0.6 to 200 parts by mass, and 0.9 to 150 parts by mass with respect to 100 parts by mass of poly p-vinylphenol. Further preferred.

  The organic solvent is not particularly limited as long as it does not participate in the reaction. For example, water; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and 1,4-dioxane; halogen solvents such as dichloromethane and chloroform; acetone And ketone solvents such as

  The amount of the organic solvent used is preferably 0 to 10,000 parts by mass and more preferably 10 to 5,000 parts by mass with respect to 100 parts by mass of poly p-vinylphenol.

In the method for producing the compound of the second aspect of the present invention, the reaction rate can be improved and the reaction time can be shortened by further adding a catalyst. Examples of the catalyst include an acid catalyst, a base catalyst, and a Lewis acid catalyst.
Specific examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrogen chloride gas, sulfuric acid, fuming sulfuric acid, nitric acid, concentrated nitric acid and phosphoric acid; p-toluenesulfonic acid, trifluoromethanesulfonic acid, formic acid and acetic acid. And organic acids such as
Specific examples of the base catalyst include sodium hydroxide, potassium hydroxide, sodium hydride, pyridine, triethylamine, lithium diisopropylamide, and the like.
Specific examples of the Lewis acid catalyst include aluminum chloride, titanium chloride, lanthanum trifluoromethanesulfonate, scandium trifluoromethanesulfonate, and yttrium trifluoromethanesulfonate.

  Although the addition amount of the said catalyst is not specifically limited, 1-300 mass parts is preferable with respect to 100 mass parts of poly p-vinylphenol, and 2-150 mass parts is more preferable.

Although the reaction temperature in the manufacturing method of the compound of the 2nd aspect of this invention is not specifically limited, 0-150 degreeC is preferable and 20-100 degreeC is more preferable.
In the method for producing the compound of the second aspect of the present invention, the catalyst affects the reaction efficiency as described above, but the reaction temperature also affects the reaction efficiency. Specifically, a relatively long reaction time is required at a low reaction temperature, and production is possible in a relatively short time at a high reaction temperature. However, if the reaction temperature is too high, the target product may be adversely affected or a reaction other than the target reaction may be promoted.

  The reaction time in the method for producing the compound of the second aspect of the present invention is not particularly limited. For example, when the reaction temperature is 80 ° C., about 24 hours is preferable. When the reaction temperature is 23 ° C., about 7 days is preferable.

The method for producing the compound of the second aspect of the present invention will be specifically described. However, the method for producing the compound of the second aspect of the present invention is not limited to this method.
First, poly p-vinylphenol and the organic solvent are mixed and sufficiently dissolved.
Next, the amine compound, the aminosilane, formaldehyde, and, if necessary, the catalyst are added dropwise to the mixture at room temperature with sequential stirring. After heating this mixed liquid to 80 degreeC and stirring for 24 hours, the compound of this invention can be obtained.
Here, the order of adding the aminosilane, the amine compound, formaldehyde and the catalyst is not particularly limited, but it is preferable to add formaldehyde after the aminosilane and the amine compound are added. The catalyst is preferably added after formaldehyde is added.

  The compound of the present invention obtained by the above method can be purified by a known method. For example, it can be purified by precipitation with an insoluble solvent, distillation at atmospheric pressure or reduced pressure, or use of chromatography.

  The weight average molecular weight of the compound (A) described above is preferably 1,000 to 500,000, more preferably 1,500 to 250,000, and 2,000 to 200,000. Further preferred. When the molecular weight is within this range, a coating film having excellent coating film adhesion, corrosion resistance, and chemical resistance can be obtained.

  The manufacturing method of a compound (A) is not specifically limited, For example, the manufacturing method of the compound of the 2nd aspect of this invention mentioned above is mentioned suitably.

  The concentration of the compound (A) in the treatment liquid of the present invention is not particularly limited, but is 0.5 to 120% by mass with respect to the total amount of the metal elements contained in the fluoride (B). Is preferable, it is more preferable that it is 2-80 mass%, and it is further more preferable that it is 10-50 mass%. When the concentration is within this range, the structure of the surface chemical conversion treatment layer becomes denser and the corrosion resistance and coating film adhesion become higher.

The fluoride (B) is a fluoride containing at least one metal element (hereinafter also referred to as “metal element (B ′)”) selected from the group consisting of Zr, Ti and Hf.
The fluoride (B) is not particularly limited, and examples thereof include zircon hydrofluoric acid, titanium hydrofluoric acid, hafnium hydrofluoric acid, and sodium salts, potassium salts, and ammonium salts thereof. Among these, at least one selected from the group consisting of zircon hydrofluoric acid, titanium hydrofluoric acid, and ammonium salts thereof is preferable, and zircon hydrofluoric acid and / or ammonium salts thereof are more preferable.
These may be used alone or in combination of two or more.

  The concentration of the fluoride (B) in the treatment liquid of the present invention is not particularly limited, but is 0.01 to 10 g in terms of mass concentration (b) in the total amount of the metal element (B ′) in the treatment liquid. / L is preferable, 0.05 to 5 g / L is more preferable, and 0.1 to 1 g / L is still more preferable. When the concentration is within this range, the formation rate of the surface chemical conversion treatment layer becomes faster, which is preferable for industrial use. Moreover, the dissolution stability of the fluoride (B) can be more easily maintained in the treatment liquid of the present invention.

The acid component (C) is at least one acid selected from the group consisting of hydrofluoric acid, nitric acid, sulfuric acid, and salts thereof. The acid component (C) is preferably hydrofluoric acid, nitric acid and salts thereof. These may be used alone or in combination of two or more.
The acid component (C) has an appropriate etching property, and can be easily removed in a cleaning step after chemical conversion treatment. Even if it remains slightly, it hardly affects the corrosion resistance.

  The concentration of the acid component (C) in the treatment liquid of the present invention is not particularly limited, but is preferably 0.05 to 200 g / L, and more preferably 0.2 to 100 g / L. . When it is 0.05 g / L or more, sufficient etching ability for the surface of the metal plate to which the treatment liquid of the present invention is applied can be expected. When it is 200 g / L or less, the etching ability becomes appropriate, and a uniform surface chemical conversion treatment layer can be deposited.

The compound (D) is a compound containing at least one metal element selected from the group consisting of Mn, Co, Mg, Al and Zn. Since these compounds easily form a complex with free fluorine ions, there is an effect of stabilizing the treatment liquid of the present invention.
The compound (D) is preferably a compound containing at least one metal element selected from the group consisting of Mg, Al and Zn, and more preferably a compound containing Mg and / or Al.

Examples of the compound (D) include permanganic acid, potassium permanganate, sodium permanganate, manganese nitrate, manganese sulfate, manganese fluoride, manganese carbonate, manganese acetate, cobalt chloride, cobalt sulfate, cobalt nitrate, fluorine Cobalt oxide, cobalt oxide, cobalt hydroxide, magnesium nitrate, magnesium oxide, magnesium hydroxide, magnesium sulfate, magnesium acetate, aluminum nitrate, aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum acetate, zinc chloride, zinc sulfate, zinc nitrate Zinc fluoride, zinc oxide, zinc hydroxide and the like.
These may be used alone or in combination of two or more.

Examples of the aqueous medium (E) include water, methanol, ethanol and the like, and water is preferable.
The content of the aqueous medium (E) in the treatment liquid of the present invention is not particularly limited, and for example, the amount may be adjusted so that the above-described components (A) to (D) are in a predetermined concentration range.

  The treatment liquid of the present invention has a free fluorine ion concentration of 1 to 30 mg / L, and is a total of at least one metal element selected from the group consisting of Zr, Ti and Hf contained in the fluoride (B). The total amount of at least one metal element selected from the group consisting of Mn, Co, Mg, Al and Zn contained in the compound (D) with respect to the total mass concentration (b) which is the concentration in the treatment liquid It is preferable that (d) / (b) which is the ratio of the total mass concentration (d) which is the concentration in the treatment liquid satisfies 1 to 200. When all these conditions are satisfied, the amount of the metal element contained in the fluoride (B) is increased and the treatment liquid stability is excellent.

  The free fluorine ion concentration in the treatment liquid of the present invention is preferably 1 to 30 mg / L, more preferably 2 to 25 mg / L, and still more preferably 5 to 22 mg / L. When the free fluorine ion concentration is 1 mg / L or more, the etching property becomes high, a sufficient surface chemical conversion treatment layer can be obtained, and the stability of the treatment liquid can be ensured. On the other hand, when it is 30 mg / L or less, the deposition efficiency increases, and a sufficient surface chemical conversion treatment layer can be obtained.

  Moreover, (d) / (b), which is the ratio of the total mass concentration (d) to the total mass concentration (b), is preferably 1 to 200, more preferably 10 to 180, and 20 More preferably, it is -150. When (d) / (b) is 1 or more, the chemical conversion reaction is promoted, and the chemical conversion treatment can be performed in a short time. On the other hand, when (d) / (b) is 200 or less, the fluoride (D) can be easily dissolved in water, and the stability of the treatment liquid is improved.

  Here, the free fluorine ion concentration can be adjusted to 1 to 30 mg / L by adjusting the addition amount of the element in the compound (D) (that is, the total mass concentration (d)).

Moreover, it is preferable that pH of the process liquid of this invention is 2.0-X. However, said X is represented by a following formula.
X = −0.02 × [(d) / (b)] + 6.0

In the above formula, (d) is the total mass concentration (d), and (b) is the total mass concentration (b).
When this range is satisfied, it is possible to obtain a surface chemical conversion treatment layer having a sufficient thickness in a much shorter time than in the past.

  In the treatment liquid of the present invention, the compound (A), the fluoride (B), the acid component (C), and the compound (D) must be water-soluble. When the compound (A) is not water-solubilized, not only the compound (A) is not sufficiently contained in the obtained surface chemical conversion treatment layer, but even if it is contained, it may be unevenly distributed. Further, when any of the fluoride (D), the acid component (E) and the compound (F) is not water-soluble, the chemical conversion reaction is not stabilized, and a sufficient surface chemical conversion treatment layer can be obtained in a short time. Can not.

  Moreover, the treatment liquid of the present invention forms a surface chemical conversion treatment layer on at least one surface of the metal plate by contacting with the metal plate, and the surface chemical conversion treatment layer comprises the precipitate of the compound (A), And at least one metal element (B ′) selected from the group consisting of Zr, Ti and Hf contained in the fluoride (B), and an oxide equivalent mass (a) of Si derived from the compound (A) The mass ratio [(a) / (b ′)] of the total precipitation mass (b ′) of the metal element (B ′) is preferably 0.03 to 0.3.

  The precipitate of the compound (A) is preferably precipitated without decomposition of the compound (A). On the other hand, the metal element (B ′) may be precipitated in any form of an oxide, a hydroxide, a fluoride, and a salt with the acid component (C).

  Further, the mass ratio [(a) / (b ′)] of the oxide-converted mass (a) of Si derived from the compound (A) and the total precipitation mass (b) of the metal element (B ′) is: It is preferably 0.03 to 0.3, more preferably 0.04 to 0.2, and even more preferably 0.05 to 0.15. When the mass ratio is 0.03 or more, the coating film adhesion becomes higher, and when the mass ratio is 0.3 or less, the continuity of the surface chemical conversion treatment layer is secured, so that the corrosion resistance and the coating film adhesion are further improved. Get higher.

Further, 'the total precipitation mass of (b the metal element (B)') is preferably 5 to 50 mg / m ^2, more preferably from ^{7~45mg / m 2, 10~40mg / m} 2 More preferably. When the total precipitation amount (b ′) is 5 mg / m ² or more, the surface of the metal plate is sufficiently covered and the corrosion resistance is enhanced. On the other hand, when it is 50 mg / m ² or less, the possibility of cracking in the surface chemical conversion treatment layer is low, and the coating film adhesion is further increased.

  Although the said metal plate which forms a surface chemical conversion treatment layer using the processing liquid of this invention is not specifically limited, For example, a zinc-type plated steel plate, an aluminum plating steel plate, a tin plating steel plate, a cold-rolled steel plate, an aluminum plate etc. are mentioned. .

  The zinc-based plated steel sheet is a steel sheet having a plated layer containing zinc. Examples include galvanized steel sheets, zinc alloy plated steel sheets, 55% aluminum galvanized steel sheets, 5% aluminum galvanized steel sheets, tin galvanized steel sheets, zinc nickel plated steel sheets, and iron galvanized steel sheets. Among these, a galvanized steel plate or a zinc alloy plated steel plate is preferable. The reason is that the surface chemical conversion treatment layer formed on the surface becomes dense and the adhesion between the metal plate and the surface chemical conversion treatment layer is improved as compared with other metal plates.

The manufacturing method of the said metal plate is not specifically limited, For example, it can manufacture by a well-known method. In the case of a galvanized steel sheet or a zinc alloy-plated steel sheet, for example, a known steel sheet can be produced by a known electrogalvanizing method or hot dip galvanizing method.
Further, the size and thickness of the metal plate are not particularly limited. For example, in the case of a zinc-based plated steel sheet treated by an electrogalvanizing method, for example, a coil-shaped one having a thickness of 0.4 to 2.3 mm and a width of 500 to 2080 mm may be mentioned.
Further, the thickness of the electrogalvanized layer is not limited. Usually, it is about 1 to 50 g / m ^{2 on} one side. Moreover, if it is a zinc-based plated steel plate processed by the hot dip galvanizing method, for example, a coil-shaped one having a thickness of 0.23 to 3.2 mm and a width of 500 to 1850 mm may be mentioned.
Further, the thickness of the hot dip galvanized layer is not limited. Usually, it is about ²⁰ to 150 g / m ^{2 on} one side.
According to the manufacturing method of the chemical conversion treatment metal plate of this invention mentioned later or the manufacturing method of the upper coating metal plate of this invention, such a coil-shaped metal plate can be processed continuously.

The treatment liquid of the present invention is a so-called precipitation type, and the surface chemical conversion treatment layer is self-deposited by contacting the surface of the metal plate, or the surface chemical conversion treatment layer is formed by contacting the surface of the metal plate as a cathode. Electrolytically deposited.
Since the treatment liquid of the present invention is a precipitation type, the surface chemical conversion treatment layer can be formed in a short time.

Here, in this specification, the self-deposition means that the surface chemical conversion treatment layer is formed only by bringing the treatment liquid of the present invention into contact with the metal plate.
Electrodeposition means that the surface chemical conversion treatment layer is formed by bringing the treatment liquid of the present invention into contact with the metal plate as a cathode.

In the present invention, the mechanism by which the surface chemical conversion treatment layer is deposited on the surface of the metal plate is considered as follows.
First, the surface of the metal plate is etched by the acid component (C) contained in the treatment liquid of the present invention. As a result, the pH at the interface between the surface of the metal plate and the treatment liquid of the present invention is locally increased, and the compound (A) and the fluoride (B) that have been dissolved in the treatment liquid of the present invention until then are derived. The metal element (B ′) and metal ions eluted from the metal plate such as a plated steel plate are dissolved in the treatment liquid of the present invention only at the interface between the metal plate surface and the treatment liquid of the present invention. There is no non-equilibrium state. The inventor believes that the insoluble complex (compound etc.) formed at this time is precipitated on the surface of the metal plate to form a surface chemical conversion treatment layer.

Next, the manufacturing method of the chemical conversion treatment metal plate of this invention is demonstrated.
The chemical conversion treatment metal plate production method of the present invention (hereinafter also referred to as “the production method of the present invention”) uses the surface chemical conversion treatment liquid of the present invention to form a non-coating surface chemical conversion treatment layer on at least one surface of the metal plate. It is a manufacturing method of the chemical conversion treatment metal plate which forms.

In the production method of the present invention, it is preferable to form a non-coating surface chemical conversion treatment layer after cleaning the surface of the metal plate.
The cleaning method is not particularly limited as long as it is a method of removing the oil and dirt adhering to the surface of the metal plate and cleaning, and a known method can be applied. For example, a method of washing with an alkaline degreasing agent or an acidic degreasing agent, hot water washing or solvent washing may be mentioned.
In addition, it is preferable to perform surface adjustment with acid, alkali or the like before and / or after cleaning the surface of the metal plate. This is because the adhesion of the surface chemical conversion treatment layer formed by contacting the treatment liquid of the present invention to the surface of the metal plate is improved. Moreover, it is because the formation (precipitation) efficiency per time of this surface chemical conversion treatment layer improves.
In addition, after performing such cleaning and / or surface adjustment of the surface of the metal plate, it is preferable to further wash with water so that a cleaning agent or the like does not remain on the surface of the metal plate.

Moreover, in the manufacturing method of this invention, after forming the said surface chemical conversion treatment layer, it is preferable to wash the said metal plate in which the said surface chemical conversion treatment layer was formed with water. The reason is that a surface chemical conversion treatment layer with better corrosion resistance can be obtained by removing the excess chemical conversion treatment component (for example, acid component (C)) remaining on the surface of the metal plate by washing with water. is there. The method described later can be used for the water washing method.
In the production method of the present invention, it is preferable that the metal plate on which the surface chemical conversion treatment layer is formed is washed with water and then dried.

One of preferred embodiments of the production method of the present invention is that the surface chemical conversion treatment liquid is brought into contact with the surface of the metal plate to form a surface chemical conversion treatment layer on the surface of the metal plate, and the surface chemical conversion treatment is formed. In this method, the metal plate on which the treatment layer is formed is washed with water (hereinafter referred to as “first method”).
In another preferred embodiment of the manufacturing method of the present invention, the surface chemical conversion treatment liquid is brought into contact with the surface of the metal plate as a cathode, and the surface chemical conversion treatment layer is electroanalyzed on the surface of the metal plate. In this method, the metal plate on which the surface chemical conversion treatment layer is formed is washed with water (hereinafter referred to as “second method”).
Hereinafter, these two methods will be described in detail.

In the first method, for example, a dipping method or a spray method, which are known methods, can be applied.
Here, the contact time between the treatment liquid of the present invention and the metal plate is not particularly limited, but is preferably 0.5 to 20 seconds, more preferably 1 to 10 seconds, and 0.5 to 5 seconds. More preferably. If the contact time is too short, the treatment liquid of the present invention and the surface of the metal plate may not sufficiently react, and a surface chemical conversion treatment layer having excellent corrosion resistance may not be obtained. Moreover, when this contact time is too long, the performance improvement of the surface chemical conversion treatment layer obtained is not seen, and it is not preferable also from the point of the operation efficiency in a line.

Here, in the case of the spray method, the formation efficiency (precipitation efficiency) of the surface chemical conversion treatment layer tends to be increased by performing the intermittent spraying twice or more at intervals of 0.2 to 5 seconds. In this case, when the treatment liquid of the present invention foams and causes a problem, it is preferable to add an antifoaming agent to the treatment liquid of the present invention.
The type of the antifoaming agent is not particularly limited, and a known one can be used as long as it does not impair the coating film adhesion.
In the present invention, the contact time between the treatment liquid of the present invention and the metal plate means, for example, the time during which the metal plate is immersed in the treatment liquid of the present invention in the case of an immersion method. . In the case of the spray method, it means the time during which the treatment liquid of the present invention is sprayed on the surface of the metal plate.

By the method as described above, the treatment liquid of the present invention is brought into contact with the surface of the metal plate, and the surface chemical conversion treatment layer can be self-deposited on the surface of the metal plate. Then, the surface chemical conversion treatment layer is self-deposited on the surface of the metal plate, and then washed with water.
Although the method of this water washing is not specifically limited, For example, it can carry out by the well-known dipping method and the spray method.
The washing temperature (the temperature of the washing water) is not particularly limited, and may be a commonly applied temperature, but is preferably 5 to 60 ° C, and more preferably 15 to 40 ° C. This is because the cleaning efficiency is high at such a temperature.

Drain water, industrial water, city water, and deionized water can be suitably used as flush water used for washing.
Also, the washing time is not particularly limited. For example, in the case of the dipping method or the spray method, it is preferably 0.1 to 10 seconds, and more preferably 1 to 5 seconds. If the water washing time is too short, the excess chemical conversion treatment component remaining on the surface of the metal plate is not sufficiently removed, and a surface chemical conversion treatment layer having excellent corrosion resistance may not be obtained. Moreover, even if the water washing time is too long, the performance improvement of the surface chemical conversion treatment layer obtained is not seen, and it is not preferable from the point of operation efficiency in the line. In addition, this washing | cleaning time means the time when the said metal plate is immersed in washing water, when it is the case of a dipping method, for example. In the case of the spray method, it means the time during which flush water is sprayed on the surface of the metal plate.

After such washing with water, the surface is preferably dried. When only the adhered water is removed, physical removal such as air drying or air blow may be used.
In order to make the formed surface chemical conversion treatment layer firmly adhere to the surface of the metal plate and to make it chemically stable, a heat drying treatment is effective. The heating conditions in that case are preferably heat drying so that the maximum temperature (PMT) of the surface of the metal plate on which the surface chemical conversion treatment layer is formed is 30 to 250 ° C. This temperature is more preferably 40 to 150 ° C.

In the second method, for example, a known electrolysis method can be applied. Specifically, for example, electrolytic deposition can be performed by using the metal plate as a cathode and applying a current of 0.05 to 50 A / dm ² for 0.2 to 10 seconds.
This current value is preferably 0.5~20A / dm ^2, more preferably 1 to 10 A / dm ^2. When this current value is too low, the formation (precipitation) rate of the surface chemical conversion treatment layer tends to be slow. In addition, when the current value is too high, the efficiency of formation (deposition) of the surface chemical conversion treatment layer with respect to the amount of electricity is lowered, which is not economical, and the thickness of the surface chemical conversion treatment layer tends not to be uniform.
Moreover, the preferable range of energization time is 0.5 to 5 seconds.
In addition, the counter electrode is not particularly limited as long as it does not dissolve in the treatment liquid of the present invention during such electrolytic treatment. For example, platinum or a platinum-coated metal, various stainless steels, or carbon can be used.

By such a method, the surface chemical conversion treatment layer can be electrolytically deposited on the surface of the metal plate by bringing the treatment liquid of the present invention into contact with the surface of the metal plate as the cathode. And after carrying out the electrolytic deposition of the surface chemical conversion treatment layer on the surface of a metal plate, it can wash with water.
As the water washing method, the method described in the first method can be applied. The same applies when drying after washing with water.

  Although the temperature of the process liquid of this invention in the manufacturing method of this invention will not be specifically limited if it is the temperature with which the said metal plate and the process liquid of this invention react, It is preferable that it is 30-70 degreeC, and 30-60. More preferably, it is 40 degreeC, and it is still more preferable that it is 40-55 degreeC. This is because at such a temperature, an appropriate reaction rate can be maintained, energy efficiency is further increased, and cost demerits are unlikely to occur.

As a preferable example of the manufacturing method of the present invention described above, the surface chemical conversion treatment liquid at a temperature of 30 to 70 ° C. is brought into contact with the surface of the metal plate for 0.5 to 20 seconds, and the surface of the metal plate is subjected to the process. The method of forming the surface chemical conversion treatment layer which contains 5-50 mg / m < ² > of the metal element contained in a fluoride (B) in total is mentioned.

Next, the chemical conversion treatment metal plate of this invention is demonstrated.
The chemical conversion treatment metal plate of the present invention contains the compound (A) and at least one metal element selected from the group consisting of Zr, Ti and Hf on the surface of the metal plate, and is self-deposited or electrolytically deposited. It is a chemical conversion treatment metal plate which has a surface chemical conversion treatment layer.

  The metal plate used for the chemical conversion treatment metal plate of the present invention is the same as described above.

It is preferable that the deposit of the compound (A) contained in the surface chemical conversion treatment layer is deposited without decomposing the compound (A).
On the other hand, the metal element contained in the surface chemical conversion treatment layer is preferably derived from the fluoride (B). The metal element only needs to be precipitated in any form of oxide, hydroxide, fluoride, and salt with the acid component (C).

  The mass ratio [(a) / (b) of the oxide conversion mass (a) of Si derived from the compound (A) and the total precipitation mass (b) of the metal element (B ′) in the surface chemical conversion treatment layer. ′)] Is preferably 0.03 to 0.3, more preferably 0.04 to 0.2, and even more preferably 0.05 to 0.15. When the mass ratio is 0.03 or more, the coating film adhesion becomes higher, and when the mass ratio is 0.3 or less, the continuity of the surface chemical conversion treatment layer is secured, so that the corrosion resistance and the coating film adhesion are further improved. Get higher.

The total precipitation mass of the metal element in the surface chemical conversion layer is preferably from 5 to 50 mg / m ^2, more preferably from 7~45mg / m ^2, is 10 to 40 mg / m ² More preferably. When the total precipitation amount is 5 mg / m ² or more, the surface of the metal plate is sufficiently covered, and the corrosion resistance is improved. On the other hand, when it is 50 mg / m ² or less, the possibility of cracking in the surface chemical conversion treatment layer is low, and the coating film adhesion is further increased.

  Although the manufacturing method of the chemical conversion treatment metal material of this invention is not specifically limited, According to the manufacturing method of this invention mentioned above, it is preferable from the point which can form the said surface chemical conversion treatment layer in the surface of the said metal plate in a short time. .

The chemical conversion treatment metal material of the present invention has a surface chemical conversion treatment layer that has the same degree of corrosion resistance as that of the chromate film (particularly the corrosion resistance of the Erichsen processed part, the bent part, and the collar part) and the coating film adhesion, and does not contain chromium. It can be formed in a short time.
The chemical conversion treatment metal material of the present invention can be used without further forming a coating film on the upper surface of the surface chemical conversion treatment layer, but an upper layer coating in which a resin layer is further formed on the upper surface of the surface chemical conversion treatment layer. It is preferable to use it as a metal plate.

Next, the upper coated metal sheet of the present invention and the manufacturing method thereof will be described.
The 1st aspect of the upper layer metal plate of this invention is obtained by the manufacturing method of the upper layer metal plate of this invention mentioned later, The said resin layer has fingerprint resistance.
The second aspect of the upper coated metal sheet of the present invention is obtained by the method for producing an upper coated metal sheet of the present invention, which will be described later, and the resin layer is composed of a non-chromate primer paint layer and a top coat paint layer. Of at least two layers. In this case, it is preferable to have a layer made of a non-chromate primer paint on the surface of the chemical conversion treatment metal material and further to have a layer made of a top coat paint.
In the second aspect of the upper-layer coated metal sheet of the present invention, the resin layer may have fingerprint resistance, and in such a case, it is included in the first aspect of the upper-layer-coated metal sheet of the present invention. become.

The manufacturing method of the upper coated metal sheet of this invention is a manufacturing method which comprises the process of forming the resin layer on the upper surface of the said surface chemical conversion treatment layer further to the manufacturing method of the chemical conversion treatment metal plate of this invention mentioned above.
The resin layer may be a single layer or may be composed of two or more resin layers.
The resin layer is preferably a resin layer having fingerprint resistance.
The resin layer preferably includes at least two layers of a non-chromate primer coating layer and a top coat coating layer.

  The material of the resin layer is not particularly limited. For example, the resin layer can be formed using a coating agent for the purpose of imparting corrosion resistance, fingerprint resistance, or lubricity, which is currently applied to the upper surface of the chromate pretreatment film. Is.

  When the resin layer is a resin layer having fingerprint resistance, the material of the resin layer is not particularly limited as long as it imparts fingerprint resistance to the resin layer. For example, it preferably contains at least one selected from the group consisting of acrylic resins, urethane resins, epoxy resins, polyester resins, polyamide resins, and polyolefin resins. This is because the fingerprint resistance of the resin layer is improved.

Moreover, it is preferable that the resin layer in which the resin layer has fingerprint resistance further contains silica sol. This is because fingerprint resistance and corrosion resistance are exhibited in a balanced manner.
Further, the resin layer comprises 20 to 97% by mass of at least one selected from the group consisting of acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin and polyolefin resin, 2 to 50% by mass of silica sol, and water-based wax. It is preferable that 1-30 mass% is included. In this case, fingerprint resistance and corrosion resistance are particularly exhibited in a well-balanced manner.

  The water-based wax is not particularly limited, and for example, a known water-based wax used for water-based paints can be used.

  The thickness of the resin layer having fingerprint resistance is preferably 0.1 to 5 μm, more preferably 0.4 to 5 μm, and 0.4 to 3 μm in terms of dry base thickness. More preferably it is. This resin layer may include a plurality of layers.

  In the method for producing an upper-layer covering metal material of the present invention, the resin layer is, for example, the acrylic resin, urethane resin, epoxy resin, or the like formed on the surface of the surface chemical conversion-treated metal plate of the present invention. An aqueous treatment agent containing at least one selected from the group consisting of polyester resin, polyamide resin and polyolefin resin is applied by a known method such as dipping method, spray method, roll coating method, air spray method, airless spray method, etc. Then, it can be formed by drying.

In the upper-coated metal sheet of the present invention, it is preferable that a layer made of an inorganic substance and / or an organic substance is further provided between the surface chemical conversion treatment layer and the resin layer having fingerprint resistance. This layer is preferably 0.01 to 0.2 μm thick. This layer preferably contains chromium-free metal cations.
As an organic substance that can be used here, for example, a water-soluble resin or an emulsion resin that can be used for the resin layer can be used.

The resin layer preferably includes at least two layers of a non-chromate primer coating layer and a top coat coating layer.
As the non-chromate primer paint, a non-chromate primer paint that does not contain a chromate rust preventive pigment can be used. The non-chromate primer contains a resin, and may contain a color pigment, a rust preventive pigment or the like as required.
This resin may be in any form such as aqueous, solvent-based, and powder-based. As the types of resins, generally known ones such as polyacrylic resins, polyolefin resins, polyurethane resins, epoxy resins, polyester resins, polybutyral resins, melamine resins, fluorine resins, or the like can be used. Can be used in combination.

Examples of the color pigment include titanium oxide (TiO ₂ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), alumina (Al ₂ O ₃ ), Known pigments such as inorganic pigments such as kaolin clay, carbon black and iron oxide (Fe ₂ O ₃ , Fe ₃ O ₄ ), and organic pigments such as Hansa Yellow, pyrazolone orange and azo pigments can be used.

  As the rust preventive pigment, generally known ones, for example, phosphoric acid rust preventive pigments such as zinc phosphate, iron phosphate, and aluminum phosphate, and molybdates such as calcium molybdate, aluminum molybdate, and barium molybdate. Defense pigments, vanadium rust preventive pigments such as vanadium oxide, finely divided silica such as water-dispersible silica and fumed silica can also be used. However, chromate anticorrosive pigments such as strontium chromate, zinc chromate, calcium chromate, potassium chromate and barium chromate are environmentally toxic and should not be used. Moreover, you may mix | blend additives, such as a defoamer, a dispersion adjuvant, and a diluent for reducing a coating-material viscosity, suitably.

  The thickness of the layer made of the non-chromate primer coating is preferably 1 to 30 μm, more preferably 2 to 20 μm after drying. When it is 1 μm or more, the corrosion resistance is high, and when it is 30 μm or less, the adhesion during processing is high.

  Further, the top coat paint is not particularly limited, and a normal top coat for painting can be used. For example, it contains a resin, and can contain a color pigment, a rust preventive pigment, and the like as required. As the resin, the coloring pigment, the rust preventive pigment, and the additive, the same materials as those described for the non-chromate primer can be used.

  The thickness of the layer made of the top coat paint is preferably 3 to 50 μm after drying, and more preferably 5 to 40 μm. Such a range is preferable because the effect of high corrosion resistance is exhibited. If this thickness is too thick, the adhesion tends to decrease.

  The upper coated metal sheet of the present invention having a resin layer including at least two layers of a non-chromate primer coating and a top coat coating is excellent in non-chromate having excellent corrosion resistance and coating adhesion. Functional coated metal plate, non-chromated pre-coated metal plate. The resin layer having these two layers usually further has alkali resistance, lubricity, and slip resistance (coin scratch resistance).

The method for forming the layer made of the non-chromate primer paint and the layer made of the top coat paint is not particularly limited, and a commonly used roll coat method, air spray method, airless spray method and the like can be used.
The baking and drying conditions of the non-chromate primer paint and the top coat paint are not limited. For example, the non-chromate primer paint and the top coat paint are formed by performing a treatment at 130 to 250 ° C. for 10 seconds to 5 minutes. A layer can be formed.

  In the chemical conversion treatment metal material and the upper coating metal material of the present invention, the surface chemical conversion treatment layer and the resin layer may be formed on at least one side of the metal plate.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

1. Test materials The following commercially available materials were used as test materials.
Hot-dip galvanized steel sheet (GI): plate thickness = 0.5 mm, basis weight = 90/90 (g / m ² )
Electrogalvanized steel sheet (EG): plate thickness = 0.5 mm, basis weight = 30/30 (g / m ² )
-5% aluminum-containing hot dip galvanized steel sheet (GF): plate thickness = 0.5 mm, basis weight = 90/90 (g / m ² )
-Molten 55% zinc alloy plated steel sheet (GL): plate thickness = 0.8 mm, basis weight = 90/90 (g / m ² )
The weight per unit area indicates the amount per unit area on one and the other main surfaces. For example, 90/90 (g / m ² ) means having 90 g / m ² of plating on each side.

2. Cleaning method of galvanized steel sheet The surfaces (both sides) of the above four specimens were treated with a medium alkaline degreasing agent (Fine Cleaner 4336 (registered trademark), manufactured by Nihon Parkerizing Co., Ltd.) and adhered to the surface. Removed dust and oil. Here, the alkaline degreasing agent was dissolved in tap water so as to have a concentration of 20 g / L, and then adjusted to 60 ° C. and used. The treatment was performed for 20 seconds using a spray. And the component of the medium alkaline degreasing agent remaining on the surface was washed with tap water to clean the surface of the test material.

3. Synthesis of Compound (A) (Examples 1 to 40 and Comparative Examples 5 to 7)
In a reactor equipped with a stirrer (1 L separable flask), 100 parts by mass of an aromatic compound shown in Table 1 below and an organic solvent in an amount (parts by mass) shown in Table 1 below are fully dissolved. I let you. The amine compound, aminosilane, 36 mass% formaldehyde solution and catalyst shown in Table 1 below were added dropwise to the mixture at the room temperature shown in Table 1 below (part by mass) at room temperature, and then added at 80 ° C. for 24 hours. Stir for hours. After stirring for 24 hours, sodium sulfite was added to titrate unreacted formaldehyde present in the system to obtain a reaction rate, and it was confirmed that the reaction was proceeding almost quantitatively.
Then, water was added and only the polymer component was precipitated and filtered for purification, and a compound corresponding to the compound (A) was obtained.

(Comparative Example 2)
The compound was synthesized in the same manner as in the above example except that aminosilane was not added.

(Comparative Example 3)
Instead of the compound (A), an organic compound A3 used in Examples of Patent Document 17 (Japanese Patent Laid-Open No. 2001-329379) was synthesized and used based on the document.

(Comparative Example 4)
Instead of the compound (A), γ-aminopropyltrimethoxysilane was simply used.

Each component in the following Table 1 is as follows.
Aromatic compound (a1-1): poly-p-vinylphenol, Marker linker, manufactured by Maruzen Petrochemical Co., Ltd. Aromatic compound (a1-2): polybisphenol A, bisphenol FM, manufactured by Mitsui Chemicals, Inc., aminosilane ( a2-1): γ-aminopropyltriethoxysilane / aminosilane (a2-2): N-phenyl-3aminopropyltrimethoxysilane / aminosilane (a2-3): N- (2-aminoethyl) aminopropyltrimethoxy Silane / aminosilane (a2-4): N- (2-aminoethyl) aminopropylmethyldimethoxysilane / amine compound (a3-1): 2-ethylethanolamine / amine compound (a3-2): N-methyl-1 , 3-Propanediamine

4). Preparation of surface chemical conversion liquid (Examples 1 to 40 and Comparative Examples 1 to 7)
Each surface-formation is carried out by adding the compound (A) shown in Table 1 and the components (B) to (D) shown in Table 2 below to the water in amounts (parts by mass) shown in Table 2 and mixing them well. A synthesis treatment solution was obtained.
Table 2 shows the free fluorine concentration of each surface chemical conversion treatment liquid, the total mass concentration of metal elements contained in compound (D) relative to the total mass concentration (b) of metal elements contained in fluoride (B) (d ) Ratio [(d) / (b)] and pH.

(Comparative Example 8)
Using a reactive chromate (Nihon Parkerizing Co., Ltd., Zinc Chrome 3367), it was bathed under the standard conditions of use according to the product instructions to obtain a surface chemical conversion treatment solution.

5). Preparation of chemical conversion treated metal plates (Examples 1 to 40 and Comparative Examples 1 to 8)
The sample material after cleaning shown in Table 3 below was processed under the processing conditions (processing type, liquid temperature, processing time) shown in Table 3 using each surface chemical conversion treatment liquid.
Then, the surface was cleaned by spraying city water at 25 ° C. for 5 seconds, drained using a roll squeezer, and dried at a reaching plate temperature of 50 ° C. on the surface of the chemical conversion treated metal plate.

The processing method is specifically as follows.
-Immersion treatment The test material was immersed in a predetermined surface chemical conversion treatment solution and held for a predetermined time.
Spray treatment A predetermined surface chemical conversion treatment solution was treated at a spray pressure of 0.5 kgf / cm ² for a predetermined time.
· The electrolysis test material as a cathode side, is immersed to a predetermined surface chemical conversion solution by passing current of 2.0A / dm ² in the test material at the same time, and held for a predetermined period of time.

5). 5. Formation of upper layer coated metal plate 5.1 Anti-fingerprint metal plate (Examples 1 to 40 and Comparative Examples 1 to 8)
A part of the obtained chemical conversion treated metal plate was cut out, and 80 parts by mass of urethane resin (HUX-320 manufactured by ADEKA Corporation) and 15 parts by mass of silica powder (Aerosil 300 manufactured by Nippon Aerosil Co., Ltd.) on the upper surface (one surface: evaluation surface). Part and water-based resin composition containing 5 parts by mass of water-based wax (Chemipearl W500, manufactured by Mitsui Chemicals, Inc.) was applied by bar coating.
Here, the film thickness was adjusted to 1 μm after drying.
Thereafter, drying was performed at a reaching plate temperature of 150 ° C. to obtain a fingerprint-resistant metal plate.

5.2 Painted metal plate (Examples 1 to 40 and Comparative Examples 1 to 8)
A part of the obtained chemical conversion metal plate was cut out, and a commercially available non-chromate epoxy primer (V knit # 200, manufactured by Dainippon Paint Co., Ltd.) was applied to the upper surface (one surface: evaluation surface) with a bar coat. It was dried at a plate temperature of 210 ° C., immersed in water, and drained and dried.
Next, a commercially available top coat paint (V knit # 500, manufactured by Dainippon Paint Co., Ltd.) was applied with a bar coat, dried at a reaching plate temperature of 220 ° C., immersed in water, and drained. Here, the film thickness of the primer was 5 μm after drying, and the film thickness of the top coat paint was 15 μm.

6). Evaluation Method 6.1 Stability Evaluation of Surface Chemical Treatment Solution The appearance of the surface chemical treatment solution was visually observed to confirm the occurrence of precipitation. The evaluation criteria are as follows. The results are shown in Table 3.
○: No precipitation, treatment possible ×: Precipitation occurs, treatment inappropriate

6.2 Evaluation of corrosion resistance and coating film adhesion of chemical conversion treated metal plate The corrosion resistance and coating film adhesion of the chemical conversion treated metal plate were evaluated by the following methods. The results are shown in Table 3.
(1) Plane part corrosion resistance test The salt spray test prescribed | regulated to JIS-Z2371 was implemented with respect to each chemical conversion treatment metal plate for 48 hours. And the white rust generation | occurence | production area rate was measured visually and evaluated. Here, the white rust generation area ratio is a percentage of the area of the white rust generation site to the area of the observation site. The evaluation criteria are as follows.
◎: White rust generation area ratio less than 5% ○: White rust generation area ratio of 5% or more and less than 10% △: White rust generation area ratio of 10% or more and less than 50% ×: White rust generation area ratio of 50% or more

(2) Processed part corrosion resistance test Each chemical-treated metal plate was extruded 5 mm with Erichsen, and the salt spray test specified in JIS-Z2371 was conducted for 48 hours. Was measured visually. The evaluation criteria are as follows.
◎: White rust generation area ratio less than 10% ○: White rust generation area ratio 10% or more, less than 30% △: White rust generation area ratio 30% or more, less than 50% ×: White rust generation area ratio 50% or more

(3) Cut part corrosion resistance test For each chemical conversion treated metal plate, a cross cut is made with an NT cutter, the salt spray test specified in JIS-Z2371 is carried out for 48 hours, and the maximum rust width on one side of the cut part is measured with a loupe. It was measured. The evaluation criteria are as follows.
◎: Less than 3 mm ○: 3 mm or more, 5 mm or less △: 5 mm or more, less than 10 mm ×: 10 mm or more

(4) Coating primary adhesion test Each chemical conversion treatment metal plate was painted using a paint (Amirac # 1000 (white paint) manufactured by Kansai Paint Co., Ltd.). The coating was performed by bar coating. After coating, baking was performed at 140 ° C. for 20 minutes, and a film having a thickness of 25 μm was formed after drying. What was obtained here is referred to as “metal plate A after painting”. Thereafter, 100 mm grids of 1 mm square are cut into each post-painted metal plate A with an NT cutter, extruded 5 mm with an Erichsen tester, and then subjected to a peeling test with an adhesive tape on the extruded convex portion. Evaluation was based on the number of coating films peeled. The evaluation criteria are shown below.
◎: No peeling ○: Number of peeling 1 or more, 10 or less △: Number of peeling 11 or more, 50 or less ×: Number of peeling 51 or more

(5) Coating secondary adhesion test The coated metal plate A obtained by painting under the same conditions as the above-described coating primary adhesion test was immersed in boiling water for 2 hours and then left in a room temperature room for 24 hours. Thereafter, 100 mm grids of 1 mm square are cut into each post-painted metal plate A with an NT cutter, extruded 5 mm with an Erichsen tester, and then subjected to a peeling test with an adhesive tape on the extruded convex portion. Evaluation was based on the number of coating films peeled. The evaluation standard of 6.2 (4) was used as the evaluation standard.

6.3 Evaluation of anti-fingerprint metal plate The corrosion resistance and coating film adhesion of the anti-fingerprint metal plate were evaluated by the following methods. The results are shown in Table 4.
(1) Flat surface corrosion resistance Each fingerprint metal plate was subjected to a salt spray test defined in JIS-Z2371 for 192 hours. The white rust generation area ratio was measured visually. The evaluation criteria are as follows.
◎: White rust generation area ratio less than 5% ○: White rust generation area ratio of 5% or more and less than 10% △: White rust generation area ratio of 10% or more and less than 50% ×: White rust generation area ratio of 50% or more

(2) Corrosion resistance of processed parts Extrusion processing of 7 mm was performed on each fingerprint-resistant metal plate with Erichsen, and a salt spray test specified in JIS-Z2371 was conducted for 192 hours. It was measured. As the evaluation standard, the evaluation standard of 6.3 (1) was used.

(3) Corrosion resistance after alkaline degreasing Using each fingerprint resistant metal plate, an alkaline degreasing agent (CL-N364S manufactured by Nihon Parkerizing Co., Ltd.) was degreased at 20 g / L, 60 ° C., 10 seconds spray, spray pressure 0.5 kg / cm ² . Then, spray water washing was performed for 10 seconds, and then a salt spray test defined in JIS-Z2371 was performed for 192 hours. As the evaluation standard, the evaluation standard of 6.3 (1) was used.

(4) Coating primary Eriksen adhesion test Each anti-fingerprint metal plate was painted using a paint (Amirac # 1000 (white paint) manufactured by Kansai Paint Co., Ltd.). The coating was performed by bar coating. After coating, baking was performed at 140 ° C. for 20 minutes, and a film having a thickness of 25 μm was formed after drying. What was obtained here is referred to as “metal plate B after painting”. After that, 100 mm grids of 1 mm square and 100 squares were cut into each post-painted metal plate B with an NT cutter, and this was extruded 7 mm with an Erichsen tester, and then the extruding convex part was subjected to a peeling test with an adhesive tape. Evaluation was based on the number of coating films peeled. The evaluation criteria are shown below.
◎: No peeling ○: Number of peeled 1 or more, less than 10 △: Number of peeled 11 or more, less than 50 ×: Number of peeled 51 or more

(5) Coated secondary Erichsen adhesion test After coating the coated metal plate B obtained by painting under the same conditions as the coating primary Erichsen adhesion test of 6.3 (4) above in boiling water for 2 hours, room temperature room For 24 hours.
Thereafter, 100 square grids of 1 mm square were cut with an NT cutter, and this was extruded 7 mm with an Eriksen tester. A peeling test using an adhesive tape was performed on the extruded convex part, and the number of coating films peeled was evaluated. Evaluation criteria were performed using the evaluation criteria of 6.3 (4).

6.4 Evaluation of coated metal plate The corrosion resistance and coating film adhesion of the coated metal plate were evaluated by the following methods. The results are shown in Table 4.
(1) Cut part corrosion resistance Each coated metal plate was cross-cut with an NT cutter, subjected to a salt spray test specified in JIS-Z2371 for 240 hours, and the maximum bulge width on one side of the cut part was measured with a loupe. . The evaluation criteria are as follows.
◎: Less than 3 mm ○: 3 mm or more, less than 5 mm △: 5 mm or more, less than 10 mm ×: 10 mm or more

(2) End face portion corrosion resistance Each coated metal plate was subjected to a salt spray test specified in JIS-Z2371 for 240 hours, and the maximum swollen width of the end face portion was measured with a loupe. The evaluation criteria are as follows.
◎: Less than 5 mm ○: 5 mm or more, less than 7 mm △: 7 mm or more, less than 10 mm ×: 10 mm or more

(3) Primary 2T adhesion In accordance with the test method of JIS-G3312, a 2T bending test of two folded inner spacing plates at 20 ° C. is performed on each coated metal plate, and the following criteria are determined in the peeled state after tape peeling. The paint adhesion was evaluated accordingly. The evaluation criteria are as follows.
A: No peeling B: Peeling area less than 20% B: Peeling area 20% or more and less than 50% X: Peeling area 50% or more

(4) Secondary 2T adhesion Each coated metal plate was immersed in boiling water for 2 hours and then allowed to stand in a room temperature room for 24 hours. Thereafter, a 2T bending test of two inner spacing plates bent at 20 ° C. is performed on each test plate in accordance with the test method of JIS-G3312, and in accordance with the criterion of 6.4 (3) in the peeled state after tape peeling. The coating film adhesion was evaluated.

From the examples and comparative examples shown above, the following results were confirmed.
-From Examples 1 to 3 and Comparative Example 18, the treatment liquid of the present invention has a sufficient amount of precipitation of the metal element (B ') contained in the fluoride (B) in a short period of time and has a performance equivalent to that of chromate. A treated film is formed. From Examples 1 and 4, the presence or absence of an amino group affects the stability. From Example 1 and Comparative Examples 1 to 7, the structure of the compound (A) of the present invention and others. The stability of the treatment liquid, the precipitation amount of the component (B ′), the corrosion resistance and the adhesiveness are greatly changed depending on the presence or absence of the component, and the compound (A) of the present invention exhibits a very excellent performance. From 5 to 8, a chemical conversion treatment film excellent in each performance is formed regardless of the material. From Examples 5 to 9, when the free fluorine concentration is within the range of the present invention, a sufficient component (B ′ ) And the performance is good. Examples 10 to 23 When the range of (d) / (b) is within the range of the present invention, a sufficient amount of the component (B ′) is deposited in a short time regardless of the treatment temperature, and it has good performance. From Examples 30 to 35, if the amount of the component (B ′) within the scope of the present invention is precipitated, it has good performance. From Examples 24 to 29 and 36 to 40, (a) / ( If b ′) is within the scope of the present invention, a film having excellent adhesion as well as corrosion resistance is formed on all of the chemical conversion treated metal plate, fingerprint resistant metal plate and painted metal plate.

Claims (16)

A surface chemical conversion treatment liquid for metal plate surface treatment,
Selected from the group consisting of an alkoxysilyl group, an aromatic ring, a hydroxy group directly bonded to the aromatic ring, a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group A water-soluble compound (A) having at least one amino group,
Fluoride (B) containing at least one metal element selected from the group consisting of Zr, Ti and Hf;
At least one acid component (C) selected from the group consisting of hydrofluoric acid, nitric acid, sulfuric acid and salts thereof;
A compound (D) containing at least one metal element selected from the group consisting of Mn, Co, Mg, Al and Zn;
An aqueous medium (E),
The compound (A) is a polymer,
The compound (A), the fluoride (B), the acid component (C) and the compound (D) are dissolved in the aqueous medium (E),
A surface chemical conversion treatment solution for self-depositing a surface chemical conversion treatment layer by contacting the surface of the metal plate, or electrolytic deposition of a surface chemical conversion treatment layer by contacting the surface of the metal plate as a cathode.   The surface chemical conversion treatment liquid according to claim 1, wherein the alkoxysilyl group is bonded to a nitrogen atom of the amino group directly or via an alkylene group. The free fluorine ion concentration is 1 to 30 mg / L,
(D) / (b) is a ratio of the total mass concentration (d) of the metal elements contained in the compound (D) to the total mass concentration (b) of the metal elements contained in the fluoride (B). ) Is the surface chemical conversion treatment liquid according to claim 1 or 2, wherein 1 to 200. The surface chemical conversion treatment solution according to any one of claims 1 to 3, wherein the pH is 2.0 to X.
(However, said X is represented by the following formula. In the following formula, (d) is the total mass concentration (d) of said metal elements contained in said compound (D), and (b) is said fluoride. (This is the total mass concentration (b) of the metal elements contained in (B).)
X = −0.02 × [(d) / (b)] + 6.0   At least one surface of the metal plate includes the compound (A) and the metal element contained in the fluoride (B), and the oxide-converted mass (a) of Si derived from the compound (A) and the fluorine Forming a surface chemical conversion treatment layer in which the mass ratio [(a) / (b ′)] to the total precipitation mass (b ′) of the metal elements contained in the chemical compound (B) is 0.03 to 0.3; The surface chemical conversion liquid in any one of Claims 1-4 obtained. The surface chemical conversion treatment liquid according to claim 5, wherein a surface chemical conversion treatment layer having a total precipitation mass (b ′) of the metal elements contained in the fluoride (B) of 5 to 50 mg / m ² can be formed.   The surface chemical conversion treatment solution according to claim 1, wherein the metal plate is a zinc-based plated steel plate.   The manufacturing method of the chemical conversion treatment metal plate which forms a non-coating-type surface chemical conversion treatment layer in the at least single side | surface of a metal plate using the surface chemical conversion treatment liquid in any one of Claims 1-7. The surface chemical conversion treatment liquid is brought into contact with the surface of the metal plate, and the surface chemical conversion treatment layer is formed by self-deposition on the surface of the metal plate,
The manufacturing method of the chemical conversion treatment metal plate of Claim 8 which water-washes the said metal plate in which the said surface chemical conversion treatment layer was formed. The surface chemical conversion treatment liquid is brought into contact with the surface of the metal plate as a cathode, and a surface chemical conversion treatment layer is formed by electrolytic deposition on the surface of the metal plate.
The manufacturing method of the chemical conversion treatment metal plate of Claim 8 which water-washes the said metal plate in which the said surface chemical conversion treatment layer was formed. The surface chemical conversion treatment liquid at a temperature of 30 to 70 ° C. is brought into contact with the surface of the metal plate for 0.5 to 20 seconds, and the metal elements contained in the fluoride (B) are added to the surface of the metal plate in total. The manufacturing method of the chemical conversion treatment metal plate in any one of Claims 8-10 which forms the surface chemical conversion treatment layer containing 5-50 mg / m < ² >.   The method for producing an upper coated metal sheet, further comprising the step of forming a resin layer on the upper surface of the surface chemical conversion treatment layer in the method for producing a chemical conversion treatment metal sheet according to any one of claims 8 to 11. On the surface of the metal plate, alkoxysilyl group, aromatic ring, hydroxy group directly bonded to the aromatic ring, primary amino group, secondary amino group, tertiary amino group and quaternary ammonium A water-soluble compound (A) having at least one amino group selected from the group consisting of a group and at least one metal element selected from the group consisting of Zr, Ti and Hf, the compound (A) Is a polymer, and has a surface chemical conversion treatment layer that is self-deposited or electrolytically deposited.   The chemical conversion treatment metal plate of Claim 13 obtained by the manufacturing method of the chemical conversion treatment metal plate in any one of Claims 8-11.   An upper coated metal sheet obtained by the method for producing an upper coated metal sheet according to claim 12, wherein the resin layer has fingerprint resistance.   An upper coated metal sheet obtained by the method for producing an upper coated metal sheet according to claim 12, wherein the resin layer includes at least two layers of a non-chromate primer paint layer and a top coat paint layer.