JP2009280889A - Aquaous surface-treatment agent, pretreatment method for precoating metallic material, manufacturing method for precoating metallic material, and precoating metallic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a precoating metallic material, in which the precoating metallic material having excellent paint adhesion, chemical resistance, corrosion resistance, and coin scratch resistance, and cold bending adhesion is obtained, and a pretreatment method of the precoating metallic material, and a pretreatment method of the precoating metallic material, and an aqueous surface-treatment agent excellent in storage stability used for the same. <P>SOLUTION: In the pretreatment method of the precoating metallic material, the aqueous surface-treatment agent containing a water-soluble compound (A) having an alkoxysilyl group, an aromatic ring, a hydroxyl group directly bonded to the aromatic ring, and at least one amino group selected from a group consisting of a primary amino group, a secondary amino group, a ternary amino group, and a quaternary amino group, and a compound (B) containing at least one element selected from a group consisting of boron, titanium, zirconium, and silicon, is applied on the surface of the metallic material, then dried without cleaning the surface with water, for forming a pretreatment layer of 0.01 to 1 g/m<SP>2</SP>. The method for manufacturing a precoating metallic material is provided with a coating step for forming a resin layer on the pretreatment layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a water-based surface treatment agent used as a pretreatment metal material pretreatment metal material, a precoat metal material pretreatment method, a precoat metal material production method, and a precoat metal material.

  Conventional post-painted products that have been painted after processing on parts for home appliances, building materials, automobiles, etc. have been subjected to many pretreatments such as phosphates. Instead of pretreatment, precoated steel sheets coated with colored organic films have been used. This pre-coated steel sheet is obtained by coating an organic film on a steel sheet that has been subjected to a base treatment, and has good workability and good corrosion resistance while having an aesthetic appearance.

  Examples of the processing of the pre-coated steel sheet include bending and drawing. When the coating film cannot follow the steel plate, there arises a problem of destruction of the coating film such as cracking and peeling. Therefore, the first characteristic required for the surface treatment to withstand such processing is coating adhesion (processing adhesion), and both the two interfaces with the base metal as the lower layer and the primer as the upper layer are good. It is required to adhere to. This coating adhesion may be evaluated after being immersed in boiling water for a predetermined time. This is particularly called secondary coating adhesion, and is distinguished from coating primary adhesion which is coating adhesion before being immersed in boiling water. Both the primary and secondary adhesion properties are extremely important characteristics that are essential for pre-coated steel sheets that are premised on being processed into complicated shapes by post-processing. The bending test is an extremely strict test and is used for evaluating the adhesion of precoated steel sheets. A more severe test is a cold bending test. This is a characteristic required for processing performed in a cold region, and the film becomes harder than normal temperature, and the processing adhesion deteriorates. Therefore, it is used as a stricter test than the bending test at room temperature. These processes not only impair the appearance but also reduce the corrosion resistance.

  The second characteristic required for the pretreatment of the precoated steel sheet is coin scratch resistance. This is a characteristic that is influenced not only by the adhesion but also by the film hardness of the ground treatment.

  Next, as a third characteristic required for the pretreatment of the precoated steel sheet, corrosion resistance can be mentioned. In the case of a pre-coated steel plate, usually, a base treatment, a primer coating treatment, and a top coat coating treatment are sequentially performed on the steel plate. In the case of a precoated steel sheet subjected to conventional chromate treatment, chromate is contained not only in the base treatment layer but also in the primer layer. In particular, the primer layer used as thick as 3 to 10 μm contains many chromium components as anti-corrosion pigments, as compared to the base treatment that is usually not used exceeding 0.5 μm, and plays a major role in imparting corrosion resistance to precoated steel sheets. Is responsible. However, the actual condition is that the primer in the precoated steel sheet not containing chromium can only provide corrosion resistance that does not reach the primer containing the chromium-based rust preventive pigment. Therefore, in the chromium-free pre-coated steel sheet, it is desired that the ground treatment portion plays a role of imparting corrosion resistance more than the conventional chromate system.

  Patent Document 1 discloses a technique for improving white rust resistance and work adhesion by surface-treating zinc and a zinc alloy with an aqueous solution containing tannic acid and a silane coupling agent. Therefore, it is not possible to secure the various performances required for pre-coated steel sheets that are currently required.

  Patent Document 2 includes a metal ion such as manganese, a fluoride such as titanium and zirconium, a silane coupling agent having a functional group such as an amino group and an epoxy group containing active hydrogen, and a polymer having a phenol skeleton. This surface treatment agent is a simple mixture of a polymer having a phenol skeleton and a silane coupling agent, and a strong bonding state in which the phenol moiety and the silane coupling agent are covalently bonded. Is not. Therefore, various performances such as work adhesion, chemical resistance and corrosion resistance required for the precoated steel sheet cannot be satisfied.

  Patent Document 3 describes a surface treatment agent comprising a polymer of a compound having a benzene ring such as phenol. This surface treatment agent is classified into a reactive surface treatment agent in which a film is deposited by contact with a steel material. When this surface treatment agent is used as a coating type surface treatment agent, since there is no water washing step after the application step, etc., the treatment method and usage are greatly different, so the chemical resistance and corrosion resistance, etc. required for the pre-coated steel sheet are particularly I can't get it.

  Patent Document 4 describes a surface treatment agent containing a silane coupling agent and a phenolic polymer. Even in this surface treatment agent, sufficient performance required for a precoated steel sheet cannot be obtained for the same reason as in Patent Document 3.

  Further, Patent Document 5 discloses a metal surface treatment agent comprising a silane coupling agent, water-dispersible silica, and an aqueous resin. However, even with this surface treatment agent, the work adhesion and corrosion resistance required for a pre-coated steel sheet are as follows. It's not enough.

  Patent Document 6 describes an aqueous liquid composition for metal surface treatment comprising a fluorometalate anion, a divalent or tetravalent cation component, a phosphorus-containing inorganic oxyanion, and a water-soluble organic polymer. However, although the paint adhesion achieved using this method is relatively good, the corrosion resistance and chemical resistance are not as good as those achieved with chromate treatment.

  Patent Document 7 describes a chemical conversion film composed of a titanium compound, a zirconium compound, and a phenol resin. However, this chemical conversion film cannot satisfy the processing adhesion and chemical resistance required for precoated steel sheets.

  Patent Document 8 discloses an organic compound having a resonance structure in a molecule and having an electrophilic reactive functional group and an organic functional group such as a phosphate group, a silanol group, and an alkoxysilyl group, and vanadium. And surface treatment agents formed from an etching agent. This surface treatment agent is not sufficiently stable for industrial use. In addition, the processing adhesion, chemical resistance, etc. have not reached the level required for precoated steel sheets.

  Patent Document 9 discloses a silane coupling agent component comprising at least one silane coupling agent having at least one reactive functional group selected from an amino group, an epoxy group, a vinyl group, a mercapto group, and a methacryloxy group, and A surface treatment agent for a metal material containing a phenol resin, further silica, and a metal compound is described. However, the phenol resin used in this technique cannot satisfy the work adhesion required for the precoated steel sheet.

  Patent Document 10 describes a surface treatment agent containing a specific metal ion, fluoro acid, silane coupling agent, and cationic urethane resin. However, while this surface treatment agent is excellent in temporary rust prevention, it cannot be said that the chemical resistance and corrosion resistance required for the precoated steel sheet are sufficient.

  Patent Document 11 describes a surface treatment agent for a metal material containing a compound containing a metal such as Zn, Fe, or Ni, a silicon compound, a phosphorus compound, a zirconium compound, a titanium compound, or a phenol resin. This technique also cannot satisfy the work adhesion required for the precoated steel sheet for the same reason as in Patent Document 9.

  Pre-coated steel plates are required to have paint adhesion that can withstand severe post-processing such as bending. The adhesion achieved by the treatment liquid for imparting temporary rust resistance is the Erichsen extrusion level processing adhesion, and the level of processing adhesion that passes the bending test is not achieved. The same applies to reactive surface treatment agents, anti-fingerprint surface treatment agents, and lubricating surface treatment agents applied to pretreatment of precoated steel sheets, and the level of work adhesion that passes the bending test is not achieved. . As described above, a surface treatment agent having sufficient paint adhesion required for a precoated steel sheet and sufficient chemical resistance and corrosion resistance has not been put into practical use at present, and rapid development has been desired.

JP 59-116381 A JP-A-11-106945 JP 7-278410 A JP-A-9-241576 JP 2001-164195 A Japanese National Patent Publication No. 10-505636 JP 2005-169765 A JP 2001-329379 A Japanese Patent Laid-Open No. 11-256096 JP 2005-120469 A International Publication No. 2002/061175 Pamphlet

Accordingly, the present invention provides a method for producing a precoated metal material that can provide a precoat metal material having excellent paint adhesion (process adhesion of a coating film), chemical resistance, corrosion resistance, coin scratch resistance, and cold folding adhesion. It is another object of the present invention to provide a surface treatment method for a pre-coated metal material and an aqueous surface treatment agent having excellent storage stability.
Another object of the present invention is to provide a precoated metal material that is excellent in coating adhesion (coating adhesion of coating film), chemical resistance, corrosion resistance, coin scratch resistance, and cold bending adhesion.

  In order to achieve the above object, the present invention provides an aqueous surface treatment agent used as a base treatment agent for a precoat metal material, comprising an alkoxysilyl group, an aromatic ring, and a hydroxy group directly bonded to the aromatic ring. 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, boron, titanium And an aqueous surface treating agent containing a compound (B) containing at least one element selected from the group consisting of zirconium and silicon.

Here, the alkoxysilyl group is preferably bonded to the nitrogen atom of the amino group directly or via an alkylene group.
The compound (B) is preferably at least one selected from the group consisting of tetrafluoroboric acid, titanium hydrofluoric acid, zirconium hydrofluoric acid, silicohydrofluoric acid and their metal acid salts.
Furthermore, it is preferable to contain at least one silicon compound (C) selected from the group consisting of water-dispersible silica and silane coupling agents.
Further, a compound containing at least one element selected from the group consisting of vanadium, tungsten, cobalt, aluminum, manganese, cerium, niobium, tin, magnesium, yttrium, calcium, zinc, bismuth, nickel, chromium and molybdenum ( D) is preferably contained.
Furthermore, it is preferable to contain at least one organic resin (E) selected from the group consisting of acrylic resins, urethane resins, epoxy resins, polyester resins, phenol resins and polyamide resins.

In order to achieve the above-mentioned object, the present invention applies a water-based surface treatment agent of the present invention to the surface of a metal material, and then dries without washing with water to provide a base of 0.01 to 1 g / m ² . Provided is a pretreatment metal material base treatment method for forming a treatment layer.

  In order to achieve the above object, the present invention provides a base treatment step of forming a base treatment layer on the surface of the metal material by the pretreatment method of the pre-coated metal material of the present invention, and on the base treatment layer, There is provided a method for producing a pre-coated metal material comprising a coating step for forming a resin layer.

  Moreover, in order to achieve the said objective, this invention provides the precoat metal material obtained by the manufacturing method of the precoat metal material of this invention.

The aqueous surface treatment agent of the present invention is excellent in storage stability, and according to the pre-treatment method of the precoated metal material of the present invention using the same, paint adhesion, chemical resistance, corrosion resistance, coin scratch resistance, and cold bending are used. It is possible to form a base treatment layer of a pre-coated metal material having excellent adhesion.
Moreover, according to the method for producing a precoated metal material of the present invention, a precoated metal material excellent in coating adhesion, chemical resistance, corrosion resistance, coin scratch resistance and cold bending adhesion can be obtained.
The precoated metal material of the present invention is excellent in paint adhesion, chemical resistance, corrosion resistance, coin scratch resistance, and cold bending adhesion.

The present invention is described in detail below.
The aqueous surface treatment agent of the present invention is an aqueous surface treatment agent used as a base treatment agent for a pre-coated metal material, and includes an alkoxysilyl group, an aromatic ring, a hydroxy group directly bonded to the aromatic ring, and 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, boron, titanium, zirconium, and An aqueous surface treating agent containing a compound (B) containing at least one element selected from the group consisting of silicon.

The compound (A) used in 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, and a tertiary amino group. And a water-soluble compound having at least one amino group selected from the group consisting of quaternary ammonium groups. 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 treatment solution.

  The compound (A) 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. Among these, a secondary amino group and a tertiary amino group are more preferable, and a tertiary amino group is further preferable. 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. Furthermore, as a result of the electrostatic interaction between the unshared electron pair present on the nitrogen atom of the amino group and the steel material or the upper layer coating film, the adhesion is improved. Moreover, in the case of a primary amino group and a secondary amino group, as a result of the amino group acting as a reactive functional group, adhesion is improved.

  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 other than the phenolic hydroxy group, the water solubility of the compound (A) is increased. Moreover, the coating-film adhesiveness, corrosion resistance, and chemical resistance of the surface treatment liquid obtained 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 within this range, the water solubility of the compound (A) and the coating film adhesion, corrosion resistance, and chemical resistance of the resulting surface treatment solution are excellent.

  In addition, the compound (A) preferably has 1 to 4 hydroxy groups that are not directly bonded to the aromatic ring in one molecule, more preferably 1 to 3, and more preferably 1 to 2. Further preferred. When the compound (A) has a hydroxy group that is not directly bonded to the aromatic ring within this range, the water solubility of the compound (A) and the coating film adhesion, corrosion resistance, and chemical resistance of the resulting surface treatment solution 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 an 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 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 formula (2), R ³ is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a benzyl group, an aryl group, a hydroxyalkyl group, a dihydroxyalkyl group, a trihydroxyalkyl group, an aminoalkyl group, or an 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 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 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.

  As for the usage-amount of the said aminosilane (a2) in a 1st method, 1-1000 mass parts is preferable with respect to 100 mass parts of said aromatic compounds (a1), 2-600 mass parts is more preferable, 3-300 mass parts is preferable. Is more preferable.

  As for the usage-amount of the said aminosilane (a2) in a 2nd method, 1-1000 mass parts is preferable with respect to 100 mass parts of said aromatic compounds (a1), 2-600 mass parts is more preferable, 3-300 mass parts is preferable. 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 formula (1), R ¹ and R ² are the same as R ^{3 in the} 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 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 the 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 the aminosilane (a2) and the amino group of the 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 formula (3), R ⁶ is the same as R ^{3 in the} 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} 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 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 formulas (3) to (9).

In the above formulas (5) to (9), R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and p are respectively R ⁶ , R ⁷ , R ⁸ , R in the 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 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 formula (4). The compound of the present invention is represented by the repeating unit represented by the 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 one of the formulas (4) and (10) to (14).

  The method for producing the compound according to the first aspect of the present invention is not particularly limited, but poly (p-vinylphenol), γ-phenylaminopropyltrimethoxysilane, 2-methylaminoethanol, and formaldehyde are reacted to form the heavy compound. 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-methylglucamine, N-methyl-1,3- Propandia N-methylaniline, ethylamine, diethylamine, allylamine, benzylamine, 2-ethylaminoethanol, ethylenediamine, sym-dimethylethylamine and morpholine and at least one amine compound and formaldehyde as an organic solvent And a compound obtained by reaction in the following (hereinafter referred to as “compound of the second aspect 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 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, 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, lanthanium 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 adding the aminosilane and the amine compound. 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) is not particularly limited, but is preferably 200 to 1,000,000, more preferably 500 to 500,000, and 1,000 to 200. More preferably, it is 1,000. When the molecular weight of the compound (A) is less than 200, not only the molecular weight is too small to form a film sufficiently, but also the work adhesion decreases due to a decrease in film strength and the like. In addition, if the molecular weight exceeds 1,000,000, the chain of one molecule becomes longer in proportion to the molecular weight, and the interaction between the molecular chains in the molecule and the interaction between the molecules work to further increase the apparent molecular weight, thereby improving the stability. Adversely affected. The molecular weight here can be measured (calculated) by a generally known GPC method, light scattering method or the like, and the GPC method was used in the present invention.

  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 compound (B) is not particularly limited as long as it is a compound containing at least one element selected from the group consisting of boron, titanium, zirconium and silicon. Since the aqueous surface treating agent of the present invention contains the compound (B), it exhibits not only an effect on corrosion resistance but also excellent chemical resistance such as alkali resistance and acid resistance, and moisture resistance.

The form of the compound (B) is not particularly limited, but carbonate, oxide, hydroxide, nitrate, sulfate, phosphate, fluoride, fluoro acid (salt), organic acid salt, An organic complex compound, an organic titanium compound, an organic zirconium compound, an organic silicon compound, or the like can be used. Among these, a fluoride and a fluoro acid (salt) described later are preferable.
Specifically, orthoboric acid, metaboric acid, tetraboric acid, pentaboric acid, tetrafluoroboric acid, basic zirconium carbonate, zirconium lactate, zirconium sulfate, zirconium oxycarbonate, zirconium carbonate ammonium, zirconium carbonate ammonium, zirconium oxide ( IV) (zirconia), titanium oxide (IV) (titania), zirconium nitrate, zirconyl nitrate, titanium nitrate, zirconium sulfate (IV), zirconyl sulfate, tetramethoxyzirconium, tetraethoxyzirconium, zirconium tetranormal propoxide, zirconium tetranormal Butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate G), zirconium dibutoxybis (ethylacetoacetate), zirconium tributoxy systemate, zirconyl acetate titanium sulfate (III), titanium sulfate (IV), titanyl sulfate, zirconium oxyphosphate, zirconium pyrophosphate, zirconyl dihydrogen phosphate, Zirconium fluoride, hexafluorozirconic acid, ammonium hexafluorozirconate, titanium oxide, titanium sulfate, titanium (III) fluoride, titanium (IV) fluoride, hexafluorotitanic acid (H ₂ TiF ₆ ), hexafluorotitanic acid Ammonium, tetraisopropyl titanate, tetra n-butyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium lactate ethyl ester, titanium trie Tanol aminate, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra-2-ethylhexoxide, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxybis (octylene) Glycolate), titanium diisopropoxy (ethyl acetoacetate), titanium diisopropoxy bis (triethanolamate), titanium laurate, titanium lactate ammonium salt, diisopropoxy titanium bisacetone, titanium acetylacetonate, silicon dioxide ( Water-dispersible silica), hexafluorosilicic acid, ammonium hexafluorosilicate, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-3- Propyltrimethoxysilane, N-phenyl-3-propyltriethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacrylic Roxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltrimethoxysilane, N-β- (N-vinyl ben Ruaminoethyl) -3-aminopropylmethyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -3-aminopropylmethyl Diethoxysilane, N-methylaminopropyltrimethoxysilane, N-butylaminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxy Silane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysila , Methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltriethoxysilane, γ -Chloropropylmethyldiethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyldiethoxysilane, Isocyanatopropyltrimethoxysilane, isocyanatepropyltriethoxysilane, ureidopropyltriethoxysilane, bis (trimethoxysilyl) aminovinyltrimethoxysilane, vinyl Rudimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (Triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- (methyldiethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, And trimethylchlorosilane. These may be anhydrides or hydrates. These compounds may be used alone or in combination of two or more.

  The compound (B) is preferably a fluoride. Fluoride releases free fluorine ions or complex fluorine ions into the liquid and serves as an etchant for the substrate. As a result, adhesion and corrosion resistance to the metal material are imparted or improved. As the compound (B) which is the fluoride, tetrafluoroboric acid, titanium hydrofluoric acid, zirconium hydrofluoric acid, silicohydrofluoric acid and their metal acid salts are particularly effective for improving the performance. The said compound may be used individually and may be used in combination of 2 or more type.

  The aqueous surface treating agent of the present invention may further contain a compound that releases free fluorine ions or complex fluorine ions. For example, hydrofluoric acid, ammonium fluoride and the like can be mentioned as those that release free fluorine ions. Moreover, tetrafluoroboric acid, hexafluorosilicic acid, zirconium hydrofluoric acid, zirconium ammonium fluoride, titanium hydrofluoric acid, ammonium titanate, hydrosilicofluoric acid, and hafnium hydrogen fluoride are released as complex fluorine ions. Examples include acids, zinc hexafluorosilicate, manganese hexafluorosilicate, magnesium hexafluorosilicate, nickel hexafluorosilicate, and the like. These may be used alone or in combination of two or more.

  The compounding amount of the compound (B) is preferably such that the solid content mass ratio ((B) / (A)) between the compound (B) and the compound (A) is 1/100 to 2/1. / 100 to 1/1 is more preferable, and 4/100 to 90/100 is still more preferable. When the solid content mass ratio of the compound (B) and the compound (A) is 1/100 or more, sufficient corrosion resistance and chemical resistance are obtained, and when it is 2/1 or less, the storage stability is improved.

The aqueous surface treating agent of the present invention preferably further contains at least one silicon compound (C) selected from the group consisting of water-dispersible silica and a silane coupling agent.
When water-dispersible silica is contained, fine irregularities are formed by the orientation of the silica particles on the surface of the steel material, and the hardness of the ground treatment layer is increased and contributes to the improvement of adhesion. Scratch properties are improved.
The water-dispersible silica is present as particles in water, and the size is preferably 1 nm to 1 μm as the primary particle diameter. Such an aqueous dispersion may become secondary particles or tertiary particles by aggregation, but any dispersion in water is acceptable. Furthermore, even if it is a slurry form in which vapor phase silica is forcibly dispersed in water, the primary particle diameter may be in the range of 1 nm to 1 μm. Although it does not specifically limit as water-dispersible silica, For example, water-dispersible silica, silica sol, lithium silicate, 1 silicate Na, 2 silicate Na, 3 silicate Na, 4 silicate Na, silicate Water glass such as K can be mentioned.

Moreover, when a silane coupling agent is contained, the interaction with other molecules or a strong bond is formed on the steel material surface or in the bulk, thereby improving the adhesion.
The silane coupling agent preferably has a polar functional group that can be dissolved in water in its structure, and has water solubility by the action of these functional groups. The water-soluble functional group can have any functional group such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group and a salt thereof, a hydroxyl group, and an ether group. The silane coupling agent is hydrolyzed in water to produce silanol, and then the silanol group forms a siloxane bond (—O—Si—O—) after contact drying on the steel surface, resulting in adhesion, corrosion resistance, chemical resistance, etc. Various performances required for precoated steel sheets are improved.

  Commercially available water-dispersible silica includes liquid phase silica synthesized from the liquid phase and gas phase silica synthesized from the gas phase. Although not specifically limited, Snowtex C, Snowtex O, Snowtex N, Snowtex NXS, Snowtex OS, Snowtex OUP, Snowtex OL, Snowtex PS-MO, Snowtex PS-S, Snowtex S, Snowtex UP, Snowtex PS-M, Snowtex PS-L, Snowtex 20, Snowtex 30, Snowtex 40 (all manufactured by Nissan Chemical Industries, Ltd.), Silica Doll-20, Silica Doll-30, Silica Dole-40, Silica Doll-30S, Silica Doll-20AL, Silica Doll-20A, Silica Doll-30S, Silica Doll-20G, Silica Doll-20GA, Silica Doll-40G-80, Silica Doll-20P, Silica Doll-12S -4 (Izu Also manufactured by Nippon Chemical Industrial Co., Ltd.), AT-20, AT-30, AT-40, AT-50, AT-20A, AT-300 (all manufactured by Adeka Corporation). The gas phase silica is not particularly limited. However, Aerosil 50, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil MOX80, Aerosil MOX170 (all manufactured by Nippon Aerosil Co., Ltd.), AERODISP VP W7622, AERODISP W7520N (all made by degussa), CAB-O-SPERSE 2017A, CAB-O-SPERSE GP32 / 12, CAB-O-SIL M5 (made by CABOT CORPRATION), NIPGEL AY200, NIPGEL AY220, NIPGEL AY420, NIPGEL AY451 , NIPGEL AY460, NIPGEL AY401, NIPGEL AY601, NIPGEL AY603, NIPGEL AZ200, NIPGEL AZ201, NIPGEL AZ204, NIPGEL AZ260, NIPGEL AZ360, NIPGEL AZ400, NIPGEL AZ410, NIPGEL AZ600, NIPGEL BY200, NIPGEL BY400, NIPGEL BY400 ) And the like.

Since these vapor phase silicas are dispersed in water, the concentration can be adjusted appropriately to form a slurry.
An acid or a base may be appropriately added to these water-dispersible silicas. By adding an acid or a base, the dispersion stability of the water-dispersible silica may be improved.
Examples of the acid include hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid and the like as inorganic acids. Examples of the base include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, aluminum hydroxide and the like. Of these, only one component or a combination of a plurality of components can be used.

  The compounding amount of the silicon compound (C) is preferably such that the solid content mass ratio ((C) / (A)) between the compound (C) and the compound (A) is 1/100 to 5/1. / 100 to 4/1 is more preferable, and 5/100 to 3/1 is still more preferable. When the solid content mass ratio between the silicon compound (C) and the compound (A) is 1/100 or more, the anchor effect of the particulate matter or the adhesion improvement effect of the water-soluble substance becomes sufficient, and as a result, the processing adhesion is improved. . Further, if it is 5/1 or less, the film itself does not become brittle, the work adhesion is improved, and the storage stability is also improved.

The aqueous surface treating agent of the present invention is further at least one selected from the group consisting of vanadium, tungsten, cobalt, aluminum, manganese, cerium, niobium, tin, magnesium, yttrium, calcium, zinc, bismuth, nickel, chromium and molybdenum. It is preferable to contain the compound (D) containing a seed element. The compound (D) acts as an inhibitor (corrosion inhibiting substance) and has a function of improving the corrosion resistance at the crosscut part and the end face part.
Although the corrosion resistance improvement mechanism by the compound (D) is not clear, it seems that the point is that the compound (D) can take several valences. Even when there is no change in valence, it can take the form of a heteropolyacid depending on the pH. It is considered that this heteropolyacid is adsorbed on the surface of the material and contributes to improvement of corrosion resistance.
Examples of the compound (D) include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluorinated complex compounds, organic acid salts, and organic complex compounds of the above metals. Of these, only one component or a combination of a plurality of components can be used.

Specific examples of the compound (D) include vanadium pentoxide, metavanadate, ammonium metavanadate, vanadium oxytrichloride, vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetylacetonate, vanadium trichloride, Phosphovanadomolybdic acid, molybdenum oxide, molybdic acid, ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compounds (eg, ammonium molybdate, sodium molybdophosphate, metatungstic acid, ammonium metatungstate, metatungstic acid Sodium, paratungstic acid, ammonium paratungstate, sodium paratungstate, cobalt chloride, chloropentammine cobalt chloride, Oxaammine cobalt chloride, cobalt chromate, cobalt sulfate, cobalt sulfate ammonium, cobalt nitrate, cobalt 2 aluminum oxide, cobalt hydroxide, cobalt phosphate, nickel nitrate, nickel sulfate, nickel carbonate, nickel acetylacetonate, nickel chloride, hexa Ammine nickel chloride, nickel oxide, nickel hydroxide, aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide, zinc sulfate, Zinc carbonate, zinc chloride, zinc iodide, zinc acetylacetonate, zinc dihydrogen phosphate, permanganic acid, potassium permanganate, sodium permanganate , Manganese dihydrogen phosphate, manganese nitrate, manganese (II), (III) or (IV), manganese fluoride (II) or (III), manganese carbonate, manganese acetate (II) or (III), manganese manganese sulfate , Manganese acetylacetonate, manganese iodide, manganese oxide, manganese hydroxide, cerium oxide, cerium acetate, cerium (III) or (IV) nitrate, cerium ammonium nitrate, cerium sulfate, cerium chloride, niobium pentoxide, sodium niobate Niobium fluoride, ammonium hexafluoroniobate, tin (IV) oxide, sodium stannate, tin (II) chloride, tin (IV) chloride, tin (II) nitrate, tin (IV) nitrate, ammonium hexafluorostannate , Magnesium nitrate, magnesium sulfate, magnesium carbonate, magnesium hydroxide, fluoride Gnesium, magnesium ammonium phosphate, magnesium hydrogen phosphate, magnesium oxide, calcium hydroxide, calcium oxide, calcium chloride, calcium nitrate, yttrium oxide, zinc metal alone, zinc oxide, zinc carbonate, zinc chloride, zinc iodide, phosphoric acid Zinc dihydrogen, zinc acetylacetonate, bismuth metal alone, bismuth oxide, bismuth vanadate, limba, etc. molybdate, molybdenum oxide, molybdate, ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compounds (for example, Ammonium molybrate, sodium molybdate, nickel metal alone, nickel oxide, nickel hydroxide, nickel carbonate, nickel nitrate, nickel sulfate, nickel phosphate, nickel chloride, nickel Cetylacetonate, chromium metal alone, chromic acid, dichromic acid, chromium carbonate, chromium chloride, chromium phosphate, chromium nitrate, chromium fluoride, chromium sulfate, chromium acetylacetonate, strontium chromate, zinc chromate, etc. .
Of these, only one component or a combination of a plurality of components can be used.

  The content of the compound (D) in the aqueous surface treating agent of the present invention is such that the solid content mass ratio ((D) / (A)) between the compound (D) and the compound (A) is 1/100 to 1/1. It is preferably 2/100 to 80/100, more preferably 5/100 to 50/100. Sufficient corrosion resistance is obtained when the solid content mass ratio of the compound (D) and the compound (A) is 1/100 or more. Further, when it is 1/1 or less, the storage stability is improved, and the corrosion resistance and the work adhesion are also improved.

  The aqueous surface treating agent of the present invention preferably further contains at least one organic resin (E) selected from the group consisting of acrylic resins, urethane resins, epoxy resins, polyester resins, phenol resins and polyamide resins. However, the compound (A) is not included in the organic resin (E). By mix | blending organic resin (E), a softness | flexibility or moderate elasticity can be provided to the base-treatment layer formed. As a result, good working adhesion can be obtained even in severe processing (cold bending or the like).

  The acrylic resin is obtained by radical polymerization, cationic polymerization, or anionic polymerization of acrylic acid and acrylic acid esters. Although it does not specifically limit as a monomer used for these polymerization reaction, For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, n-hexyl Acrylate, cyclohexyl acrylate, octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, 2-hydroxylethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t -Butyl methacrylate, n-hexyl methacrylate DOO, cyclohexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, 2-hydroxyethyl methacrylate. Furthermore, it is possible to introduce an alkoxysilyl group into the structure by appropriately incorporating vinyltrimethoxysilane or the like. These may be used alone or in combination of two or more.

The urethane resin is not particularly limited in the polyol and polyisocyanate components and the polymerization method, which are constituent monomer components. For example, aliphatic, cycloaliphatic or aromatic diisocyanates such as hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), polyester polyol, polyether In some cases, polyols such as polyols and polycarbonate polyols are polymerized with a polyol having an amino group introduced into the chain by a conventionally known method, and the chain is further extended with a polyol having a tertiary amino group. A urethane resin can be obtained by partially quaternizing the amine with alkyl sulfuric acid or the like. The urethane resin thus obtained has a cationic functional group, and examples of the cationic functional group include, but are not limited to, hydrogen, alkyl, aryl, alkenyl, alkynyl, and hydroxylalkyl groups as substituents on nitrogen. It is not a thing. Urethane resins may be used alone or in combination of two or more.

  The epoxy resin is not particularly limited, and examples thereof include phenol, bisphenol A, o-, m-, p-cresol, phthalic acid, isophthalic acid, glycidyl ether obtained by reaction of terephthalic acid and epichlorohydrin, or Glycidyl ethers obtained by reaction of hydroxyl aromatic compounds such as esters, novolak phenol, poly p-vinylphenol and epichlorohydrin, aliphatics such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerol, sorbitol A glycidyl ether obtained by reacting a polyol with epichlorohydrin or the like can be further introduced with a water-soluble functional group by further reacting with an amine. Silanol groups, alkoxysilyl groups, phosphoric acid groups, and phosphoric ester groups can be introduced into these epoxy resins. Of these, only one component or a combination of a plurality of components can be used.

The polyester resin is not particularly limited as long as it is an esterified product of a polybasic acid and a polyhydric alcohol.
The polybasic acid is not particularly limited. For example, dibasic acid such as phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic anhydride, trimellitic anhydride, pyrone anhydride A tribasic or higher polybasic acid such as merit acid is used.
Although it does not specifically limit as a polyhydric alcohol, For example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 3-methylpentadiol, neopentylene glycol, 1,4- Aliphatic or alicyclic dihydric alcohols such as butanediol, 1,5-pentanediol, 1,4-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, Trivalent or higher polyvalent alkyl such as trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipentaerythritol, 1,1,2,2-tetrakis (4-hydroxylphenyl) ethane It can be used those obtained by reaction with Lumpur. Of these, only one component or a combination of a plurality of components can be used.

  The phenolic resin excluding the compound (A) is not particularly limited to a skeleton such as novolak phenolic resin, polyvinylphenol, polybisphenol A, etc., but those having no alkoxysilyl group in the structure may be used. it can.

The amide resin is not particularly limited as long as it is an esterified product of a polybasic acid and a polyvalent amine.
The polybasic acid is not particularly limited. For example, dibasic acid such as phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic anhydride, trimellitic anhydride, pyrone anhydride A tribasic or higher polybasic acid such as merit acid is used, and the polyhydric alcohol is not particularly limited. For example, ethylenediamine, propylenediamine, diethyltriamine, hexylenediamine, triethylenetetramine, tetraethylenepentamine, isophoronediamine , Piperazine, diphenylmethanediamine, hydrazine, divalent amines such as tetramethylethylenediamine, and the like can be used. Of these, only one component or a combination of a plurality of components can be used.

  The organic resin (E) is preferably cationic or nonionic, and its presence form in water is preferably a water-soluble or aqueous emulsion. These organic resins (E) may be dissolved or dispersed in water on the basis of self-solubility or self-dispersibility, and may include a cationic surfactant (such as tetraalkylammonium) and / or a nonionic interface. It may be dispersed in the presence of an activator (such as alkyl phenyl ether).

  The content of the organic resin (E) in the aqueous surface treating agent of the present invention is such that the solid content mass ratio ((E) / (A)) between the organic resin (E) and the compound (A) is 1/10 to 10. / 1, preferably 2/10 to 5/1, more preferably 4/10 to 3/1. It is preferable that the solid content mass ratio of the organic resin (E) and the compound (A) is 1/10 or more because the effects of these resins appear in the film performance. When the ratio is 10/1 or less, the balance with the effect of the compound (A) of the organic resin (E) becomes good, and the work adhesion, corrosion resistance and chemical resistance become higher.

  The surface treatment agent of the present invention further comprises a surfactant, a thickening agent, an antifoaming agent, a conductive substance for improving weldability, and a design for obtaining a uniform film on the coated surface. In order to improve the properties, a color pigment or the like may be contained within a range not impairing the liquid stability and film performance of the aqueous surface treatment agent.

  The solvent used in the aqueous surface treatment agent of the present invention is usually water, but a small amount (for example, 10% by volume or less of the entire aqueous medium) of alcohol, ketone, cellosolve water-soluble for the purpose of improving the drying property of the film. An organic solvent may be used in combination.

About pH in the aqueous surface treating agent of this invention, it is preferable that it is the range of 2.5-12, and it is more preferable that it is the range of 4-7. When the pH is 2.5 or more, the function as a base treatment agent can be sufficiently exhibited without excessive etching, and the liquid stability of the treatment agent is also improved. Moreover, when pH is 12 or less, elution of a metal material can be suppressed and the storage stability of a processing agent will also become favorable.
When pH adjustment is necessary, an alkaline component such as ammonia, dimethylamine or triethylamine, or an acidic component such as acetic acid or phosphoric acid can be added.

  The lower limit of the total solid content concentration in the aqueous surface treatment agent of the present invention is not particularly limited as long as the effect of the present invention can be achieved, but the upper limit is 40 mass from the viewpoint of the stability of the aqueous surface treatment agent of the present invention. % Or less is preferable. The total solid content concentration of the aqueous surface treatment agent of the present invention is more preferably 0.1 to 40% by mass, further preferably 1 to 30% by mass, and more preferably 5 to 25% by mass. Even more preferred.

Next, the ground treatment method for the precoated metal material of the present invention will be described.
In the ground treatment method of the present invention, the aqueous surface treatment agent of the present invention described above is applied to the surface of a metal material, and then dried without washing to form a ground treatment layer of 0.01 to 1 g / m ^2. This is a pretreatment method for a precoated metal material.

  Examples of the metal material include cold-rolled steel sheets, hot-rolled steel sheets, hot-dip galvanized steel sheets, electrogalvanized steel sheets, hot-dip galvanized steel sheets, aluminum-plated steel sheets, aluminum-zinc alloyed steel sheets, stainless steel sheets, and aluminum plates. Commonly known metal materials and plated plates such as a copper plate, a titanium plate, a magnesium plate, a nickel plated plate, and a tin plated plate can be used. Especially, the plated steel plate containing zinc is mentioned suitably.

The metal material is preferably pretreated prior to the treatment with the aqueous surface treatment agent of the present invention.
The pre-treatment method usually involves washing with an alkaline or acidic degreasing agent, hot water washing, solvent washing, etc., in order to remove oil and dirt adhering to the metal material to be treated before performing this treatment. If necessary, the surface is adjusted with acid, alkali, or the like. In cleaning the surface of the metal material, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the surface of the metal material. Furthermore, pretreatment can be performed using an acidic or alkaline surface conditioner containing at least one metal atom selected from Ni, Co, Ce, V, Mn, Zr, Ti and the like.
As a result of substitution of each metal on the steel material surface by these surface conditioners, fine irregularities are produced, and the adhesion is further improved by the anchor effect.

  The surface treatment with the aqueous surface treatment agent of the present invention is performed by applying the aqueous surface treatment agent and then drying without washing with water. In the method of the present invention, since washing with water before drying is not performed, there is an advantage that all components configured as a surface treatment agent remain. On the contrary, if the drying is performed after washing with water, the surface treating agent component does not react with the steel material, so that all the film components are washed away and hardly remain on the steel material.

The application method of the aqueous surface treatment agent of the present invention is not particularly limited, and examples thereof include a roll coating method, a curtain flow coating method, an air spray method, an airless spray method, an immersion method, a bar coating method, a brush coating method, and the like. A normal coating method can be adopted.
Although there is no restriction | limiting in particular also about the temperature of an aqueous surface treating agent, Since the solvent of the aqueous surface treating agent of this invention is mainly water, it is preferable that the process liquid temperature is 0-60 degreeC, and is 5-40 degreeC. More preferably.

About the drying process after apply | coating the aqueous surface treating agent of this invention, when it is not necessary to accelerate | stimulate hardening of a compound (A) and only removing adhesion water, it does not necessarily require heat, such as air drying or an air blow. Physical removal may be used. In order to accelerate the curing of the compound (A) or enhance the coating effect by softening, it is preferable to heat dry. In this case, the drying temperature is preferably 50 to 250 ° C, more preferably 60 to 220 ° C.

Adhesion amount of surface treatment layer formed is 0.01 to 1 g / m ² as dry coating mass, more preferably ^{0.02~0.5g / m 2, 0.03~0.25g / m} 2 Is more preferable. When the dry film mass is less than 0.01 g / m ² , sufficient corrosion resistance cannot be obtained, and when it exceeds 1 g / m ² , the coating amount is excessive, and cohesive failure is likely to occur, resulting in reduced work adhesion and cost. It becomes disadvantageous also in terms.

  In addition, although the base treatment layer formed as described above is usually used as a base treatment layer for the precoat metal material, it has excellent adhesion, and thus has been given fingerprint resistance, lubricity, etc. It can also be used as a base for a high-performance coating having a three-layer coating layer as an upper layer. It can also be used as a base for conductive steel sheets or a base for laminated steel sheets.

Next, the manufacturing method of the precoat metal material of this invention is demonstrated.
The method for producing a precoat metal material of the present invention comprises a ground treatment step of forming a ground treatment layer on the surface of the metal material by the ground treatment method of the precoat metal material of the present invention, and a resin layer on the ground treatment layer. It is a manufacturing method of the precoat metal material which comprises the coating process to form.

  The ground treatment step in the method for producing a precoated metal material of the present invention is performed in the same manner as described in the method for ground treatment of a precoated metal material of the present invention.

  The coating step is not limited as long as a resin layer can be formed on the base treatment layer. For example, after applying and drying a primer on the base treatment layer, a top coat is directly applied without using a primer. A coating method generally used for pre-coated steel sheets such as a coating method for applying a coat and a method for applying a laminate film can be used.

As the chromium-free primer, any primer can be used as long as it does not contain a chromate rust preventive pigment. The chromium-free primer usually contains a resin and, if necessary, a color pigment, a rust preventive pigment, and the like. The resin may be in any form such as water, solvent, and powder. The types of resins are generally known, for example, polyacrylic resins, polyolefin resins, polyurethane resins, epoxy resins, polyester resins, polybutyral resins, melamine resins, fluorine resins, etc. Can be used.
At the same time, a chromium primer containing a chromium pigment can also be used. In the case of a chromium primer, a color pigment can be blended as necessary. The resin may be in any form such as water, solvent, and powder. As the type of resin, generally known resins can be used, and specific examples thereof can also be the same as those of the chromium-free primer.

  Known coloring pigments include titanium white, zinc oxide, zirconium oxide, calcium carbonate, barium sulfate, alumina, kaolin clay, carbon black, iron oxide, and other inorganic pigments, and organic pigments such as Hansa Yellow, pyrazolone orange, and azo pigments. The following color pigments can be used. As rust preventive pigments, generally known rust preventive pigments, for example, phosphate phosphate rust preventive pigments such as zinc phosphate, iron phosphate, and aluminum phosphate, molybdate defense pigments such as calcium molybdate, aluminum molybdate, and barium molybdate, Vanadium-based anticorrosive pigments such as vanadium oxide, fine silica such as water-dispersible silica and fumed silica, and the like can also be used. Examples of chromate rust preventive pigments include strontium chromate, zinc chromate, calcium chromate, potassium chromate and barium chromate. Furthermore, additives such as an antifoaming agent, a dispersion aid, and a diluent for lowering the viscosity of the coating can be appropriately blended.

  The primer application method is not particularly limited, and a commonly used dipping method, spray method, roll coating method, air spray method, airless spray method, and the like can be used. The applied film thickness of the primer is preferably 1 to 30 μm, more preferably 2 to 20 μm as a dry film thickness. If it is less than 1 μm, the corrosion resistance is lowered, and if it exceeds 30 μm, the adhesion during processing tends to be lowered.

  The primer baking and drying conditions are not particularly limited, and can be, for example, 130 to 250 ° C. and 10 seconds to 5 minutes. Moreover, you may heat-dry at once after apply | coating a topcoat.

The topcoat used in the method for producing the precoat metal material of the present invention is not particularly limited, and any of ordinary coating topcoats can be used. The top coat contains a resin and, if necessary, a color pigment, a rust preventive pigment, and the like.
As the resin, the color pigment, the rust preventive pigment, and other additives, the same materials as those used for the primer can be used.
The top coat coating method and baking drying conditions may be the same as those for the primer. The coating thickness of the top coat is preferably 3 to 50 μm, more preferably 5 to 40 μm as a dry film thickness. If the thickness is less than 3 μm, it is difficult to obtain a uniform colored appearance, and the corrosion resistance is lowered when the topcoat is applied without applying a primer. On the other hand, if it exceeds 50 μm, the adhesiveness is lowered and the cost is disadvantageous.

  The pre-coated metal material of the present invention obtained by the above-described method for producing a pre-coated metal material of the present invention is excellent in paint adhesion, chemical resistance, corrosion resistance, coin scratch resistance and cold folding adhesion.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples of the present invention, but the present invention is not limited only to these examples.

1. Synthesis of Compound (A) (Synthesis Examples A1 to A13)
In a reactor equipped with a stirrer (1 L separable flask), 100 parts by weight of an aromatic compound or a polymer thereof shown in Table 1 below and an organic solvent in an amount (parts by mass) shown in Table 1 below are placed. Dissolved. The amine compound, aminosilane, 36 mass% formaldehyde solution and catalyst shown in Table 1 below were added dropwise to the mixture at room temperature, and the mixture was stirred at 80 ° C. for 48 hours. After stirring for 48 hours, sodium sulfite was added and the unreacted formaldehyde present in the system was titrated to obtain the reaction rate, and it was confirmed that the progress of the reaction was completed.
Then, water was added and only the polymer component was precipitated and filtered for purification, and each compound of the synthesis example corresponding to the compound (A) was obtained.

The meanings of the symbols in Table 1 are as follows.
a1-1: Poly p-vinylphenol (Marcalinker, Maruzen Petrochemical)
a1-2: Novolac resin (Sumilite Resin PR, Sumitomo Bakelite)
a1-3: Polybisphenol A (Mitsui Chemicals)
a1-4: Phenol-naphthalene copolymer (Nippon Steel Chemical)
a2-1: γ-phenylpropyltrimethoxysilane
a2-2: γ-aminopropyltriethoxysilane
a2-3: N-butylaminopropyltrimethoxysilane
a2-4: Tetramethoxysilane
a3-1: 2-methylaminoethanol
a3-2: Diethanolamine
a3-3: N-methylglucamine
a3-4: Dimethylethylenediamine
a3-5: Chlorosulfate
a4-1: 1,4-dioxane
a4-2: 2-butoxyethanol
a4-3: water a5-1: p-toluenesulfonic acid a5-2: benzyltriethylammonium chloride

2. Preparation of Aqueous Surface Treatment Agent Compounds (A) shown in Tables 2 to 5 and 10-11 below, Compound (B) when used, Silicon Compound (C) when used, Compound (D) when used, Add the organic resin (E) to the deionized water in this order so that the solid mass described in Tables 2 to 5 and 10 to 11 is obtained, and then stir for 10 minutes after blending each raw material to fully disperse. did. The solid concentration was adjusted with deionized water to 2%.
In Tables 2 to 5 and 10 to 11, No. 1-38 and no. Nos. 65 to 81 are surface treatment agents of the present invention. 39-62 and no. 82 to 90 are outside the scope of the present invention.

3. Preparation of pre-coated metal plate 3.1 Test material (i) Electrogalvanized steel sheet (hereinafter symbol: EG)
Plate thickness 0.6mm, plating coverage 20g / m ² per side (double-sided plating)
(Ii) Hot-dip galvanized steel sheet (hereinafter referred to as GI)
Plate thickness 0.6mm, zinc adhesion amount 50g / m ² per side (double-sided plating)
(Iii) Aluminum-zinc alloy plated steel sheet (hereinafter referred to as GL)
Plate thickness 0.6mm, plating coverage 50g / m ² per side (double-sided plating)
(Iv) Cold rolled steel sheet (hereinafter referred to as CR)
Plate thickness 0.8mm

3.2 Pretreatment The test material is CL-N364S (manufactured by Nihon Parkerizing Co., Ltd.) which is an alkaline degreasing agent, and an aqueous solution having a concentration of 20 g / L and a temperature of 60 ° C. is added to the EG material and GL material. Was dipped for 10 seconds, washed with pure water and dried. Moreover, about GI material, after degreasing similarly to the above using CL-N364S, it was immersed in the aqueous solution of the temperature of 50 degreeC bathed at 100 g / L using PL-4015 (made by Nippon Parkerizing Co., Ltd.). The surface adjustment was performed under the condition that the Ni adhesion amount was 5 mg / m ² . After the surface adjustment, it was washed with city water and dried with warm air.

3.3 Base treatment On the surface (one side) of the specimen after the pretreatment, the aqueous coating agent obtained above was used to apply a dry coat amount to 100 mg / m ² with a roll coater. Then, it did not wash with water, but it dried so that the ultimate board temperature might be 80 degreeC with a hot air drying furnace.

3.4 Coating Apply a polyester resin-based primer (V Knit # 160, manufactured by Dainippon Paint Co., Ltd.) on the treated surface of each surface-treated plate prepared in 3.3, and dry and bake at 210 ° C. A primer layer having a dry film thickness of 5 μm was applied.
Next, a top coat (V knit # 5000, manufactured by Dainippon Paint Co., Ltd.) based on a polyester resin is applied, and a top coat with a dry film thickness of 20 μm is laminated on the primer by drying and baking at 220 ° C. to obtain a pre-coated steel plate It was.

4). Evaluation test A test piece was cut out from each of the prepared precoated steel sheets, and the painted surface to be evaluated was bent outward and subjected to an adhesion test, a coin scratch test, a corrosion resistance test, a chemical resistance test, and a moisture resistance test.
The results are shown in Tables 6-9 and 12-13.
In addition, all evaluation criteria were described in (double-circle), (circle), (square), (triangle | delta), and x. Acceptance criteria were set for each evaluation item.

4.1 Corrosion resistance A scratch reaching the metal substrate was put into the coating film of each test plate produced with a cutter knife, and a salt spray test defined in JIS-Z2371 was performed for 480 hours.
The criterion for determination was the film swelling width (maximum value on one side) from the cut part. Moreover, the end surface corrosion resistance measured the coating film swelling width (maximum value) from the end surface.
<Evaluation criteria-Cut part>
◎: Less than 2 mm ○: 2 mm or more and less than 4 mm □: 4 mm or more and less than 6 mm Δ: 6 mm or more and less than 10 mm x: 10 mm or more <Evaluation Criteria—End Face>
A: Less than 3 mm B: 3 mm or more and less than 5 mm □: 5 mm or more and less than 8 mm Δ: 8 mm or more and less than 12 mm x: 12 mm or more

4.2 Coating adhesion test 4.2.1 Primary coating adhesion test (room temperature)
According to the test method of JIS-G3312, each test plate is subjected to 0T bending test without sandwiching the inner spacing plate at 20 ° C., and the state of coating film peeling after tape peeling is observed with the naked eye. Sexuality was evaluated.
<Evaluation criteria>
◎: No peeling ○: Peeling area less than 5% □: Peeling area less than 20% △: Peeling area 20% or more and less than 50% ×: Peeling area 50% or more

4.2.2 Primary paint adhesion test (cold)
In accordance with the test method of JIS-G3312, each test plate is cooled in a freezer at -20 ° C for 2 hours in advance and a 2T bending test is performed immediately after taking out from the freezer. The state was observed with the naked eye, and coating adhesion was evaluated according to the following criteria.
<Evaluation criteria>
◎: Peeling area less than 5% ○: Peeling area less than 20% □: Peeling area of 20% or more and less than 50% △: Peeling area of 50% or more and less than 80% ×: Peeling area of 80% or more It was.

4.2.3 Secondary Bending Adhesion After the test plate was immersed in boiling water for 2 hours, it was allowed to stand for 1 day and the same bending test as the primary coating adhesion test was performed. Judgment criteria are as follows.
<Evaluation criteria>
◎: No peeling ○: Peeling area less than 5% □: Peeling area less than 20% △: Peeling area 20% or more and less than 50% ×: Peeling area 50% or more

4.3 Coins scratching property A 10-yen coin is placed at an angle of 45 ° with respect to each test plate, the coating is rubbed at a constant speed of 3 kg, and the degree of damage to the coating is observed with the naked eye. The coin scratch property was evaluated as follows.
<Evaluation criteria>
A: No peeling (primer exposure only)
○: Peeling area less than 5% □: Peeling area less than 20% Δ: Peeling area of 20% or more and less than 50% ×: Peeling area of 50% or more and less than 80%

4.4 Alkali Resistance After immersing the test plate in a 5% aqueous sodium hydroxide solution at room temperature for 24 hours, the number of blisters generated and the evaluation of the density were visually observed, and the alkali resistance was evaluated according to the following criteria. It was.
<Evaluation criteria>
A: One blister is less than 0.2 mm and the generation density is F.
○: One blister is 0.2 mm or more and less than 0.6 mm, and the generation density is F.
□: The size of one blister is 0.6 mm or more and less than 1.0 mm, and the generation density is F. Alternatively, the size of one blister is 0.2 mm or more and less than 0.4 mm, and the generation density is M.
Δ: The size of one blister is 1.0 mm or more and less than 1.5 mm, and the generation density is F. Alternatively, the size of one blister is 0.4 mm or more and less than 1.0 mm, and the generation density is M. Alternatively, the size of one blister is less than 0.2 mm and the generation density is MD.
X: The size of one blister is 1.5 mm or more. Alternatively, the blister size is 0.2 mm or more and the generation density is MD. Alternatively, the generation density is D regardless of the size of the blister.
The symbols used for the generation density have the following meanings.
F: The number of blisters generated is very small.
M: The number of blisters generated is small.
MD: A large number of blisters are generated.
D: The number of blisters generated is very large.
Those with an evaluation result of □ or more were considered acceptable.

4.5 Acid resistance After the test plate was immersed in a 5% sulfuric acid aqueous solution at room temperature for 24 hours, the number of blisters generated and the generation density were evaluated. The criterion is the same as 4.4.
<Evaluation criteria>
A: One blister is 0.2 mm or less and the generation density is F.
○: One blister is 0.2 mm or more and less than 0.6 mm, and the generation density is F.
□: The size of one blister is about 0.6 mm to about 1.0 mm, and the generation density is F. Alternatively, the size of one blister is about 0.2 mm to 0.4 mm and the generation density is M.
Δ: The size of one blister is about 1.0 mm to 1.5 mm and the generation density is F. Alternatively, the size of one blister is about 0.4 mm to 1.0 mm and the generation density is M. Alternatively, the size of one blister is 0.2 mm or less and the generation density is MD.
X: The size of one blister is 1.5 mm or more. Alternatively, the blister size is 0.2 mm or more and the generation density is MD. Alternatively, the generation density is D regardless of the size of the blister.
Those with an evaluation result of □ or more were considered acceptable.

4.6 Humidity Resistance The scratches reaching the metal substrate were put into the coating film of the test plate with a cutter, and left for 1000 hours in a constant temperature and humidity machine with a humidity of 98% and a temperature of 40 ° C. The criterion for determination was the film swelling width (maximum value on one side) from the cut part.
<Evaluation criteria>
◎: Less than 1 mm ○: 1 mm or more and less than 2 mm □: 2 mm or more and less than 4 mm Δ: 4 mm or more and less than 6 mm x: 6 mm or more

4.7 Storage Stability of Aqueous Surface Treatment Agent The storage stability was evaluated according to the following criteria until gelation or precipitation was observed with the naked eye after the aqueous surface treatment agent was stored in a constant temperature apparatus at 40 ° C.
<Evaluation criteria>
○: No change for 3 months □: No change for 1 month △: Thickening in less than 1 month ×: Precipitation or gelation in less than 1 month □

Each component in Tables 2-5 and 10-11 is as follows.
B1: Tetrafluoroboric acid B2: Titanium hydrofluoric acid B3: Zirconium hydrofluoric acid B4: Silicohydrofluoric acid B5: Basic zirconium carbonate

C1: Gas phase silica (CAB-O-SIL M5, manufactured by CABOT CORPORATION)
C2: Colloidal silica (Snowtex O, manufactured by Nissan Chemical Industries)
C3: γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
C4: γ-aminopropyltriethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

D1: Nickel carbonate D2: Vanadyl acetylacetonate D3: Titanium acetylacetonate

E1: Polyester polyol urethane resin (Ichikosha, SF600, cation)
E2: Polyethylene glycol diglycidyl ether (manufactured by Nagase, Denacol EX821)
E3: Styrene acrylic resin (manufactured by Showa Polymer Co., Ltd., Polysol AP1350, cation)

5. Evaluation results Examples 1-41 in Tables 6-8 and Examples 42-58 in Table 12 are aqueous surface treatment agents of the present invention (Nos. 1-38 in Tables 2-3 and Nos. 10-11). .65 to 81) is a coated plate performance of any of the metal materials of EG, GI, GL and CR formed by coating and drying to form a coating film, which is corrosion resistance (× cut and end surface corrosion resistance), primary coating adhesion ( Normal temperature), secondary coating adhesion, coin scratch resistance, chemical resistance and moisture resistance are all good regardless of the metal material, and the storage stability of the water-based surface treatment agent is also good. 1 to 22 and Comparative Examples 23 to 31 (Nos. 39 to 62 in Tables 4 to 5 and Nos. 82 to 90 in Tables 10 to 11) showed better performance.
On the other hand, Comparative Examples 1 to 22 (Nos. 39 to 62 in Tables 4 to 5) in Tables 8 to 9 and Comparative Examples 23 to 31 in Table 13 (No. 82 in Tables 10 to 11) which are outside the scope of the present invention. ~ 90) water-based surface treatment agent is corrosion resistance (× cut portion and end surface corrosion resistance), primary coating adhesion (room temperature, cold), secondary coating adhesion and coin scratch resistance, chemical resistance, moisture resistance and aqueous surface At least two of the storage stability of the treatments were inferior and the performance was not balanced or inferior to the corresponding examples.

Claims (9)

An aqueous surface treatment agent used as a base treatment agent for a pre-coated metal material,
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,
An aqueous surface treating agent containing a compound (B) containing at least one element selected from the group consisting of boron, titanium, zirconium and silicon.   The aqueous surface treating agent according to claim 1, wherein the alkoxysilyl group is bonded to the nitrogen atom of the amino group directly or via an alkylene group.   The compound (B) is at least one selected from the group consisting of tetrafluoroboric acid, titanium hydrofluoric acid, zirconium hydrofluoric acid, silicohydrofluoric acid, and metal acid salts thereof. The aqueous surface treating agent as described.   Furthermore, the aqueous surface treating agent in any one of Claims 1-3 containing the at least 1 sort (s) of silicon compound (C) selected from the group which consists of a water dispersible silica and a silane coupling agent.   Further, a compound (D) containing at least one element selected from the group consisting of vanadium, tungsten, cobalt, aluminum, manganese, cerium, niobium, tin, magnesium, yttrium, calcium, zinc, bismuth, nickel, chromium and molybdenum The aqueous surface treating agent according to any one of claims 1 to 4, comprising:   Furthermore, the aqueous surface in any one of Claims 1-5 containing the at least 1 sort (s) of organic resin (E) chosen from the group which consists of an acrylic resin, a urethane resin, an epoxy resin, a polyester resin, a phenol resin, and a polyamide resin. Processing agent. After applying the aqueous surface treating agent according to any one of claims 1 to 6 to the surface of the metal material, it is dried without washing with water to form a ground treatment layer of 0.01 to 1 g / m ² . A pretreatment method for a pre-coated metal material. A base treatment step of forming a base treatment layer on the surface of the metal material by the precoat metal material ground treatment method according to claim 7;
The manufacturing method of the precoat metal material which comprises the coating process which forms a resin layer on the said base treatment layer.   The precoat metal material obtained by the manufacturing method of the precoat metal material of Claim 8.