WO2008065696A1

WO2008065696A1 - Surface-treating agent, metallic material treated with the same, and novel compound and process for producing the same

Info

Publication number: WO2008065696A1
Application number: PCT/JP2006/323545
Authority: WO
Inventors: Tomohiro Iko; Ryosuke Sako; Kazuya Tanaka
Original assignee: Nihon Parkerizing Co., Ltd.
Priority date: 2006-11-27
Filing date: 2006-11-27
Publication date: 2008-06-05
Also published as: CN101622377B; KR101152564B1; CN101622377A; JP4934677B2; KR20090087000A; JPWO2008065696A1

Abstract

A surface-treating agent which is of the chromium-free type and, despite this, can give a coating film excellent in adhesion, corrosion resistance, and chemical resistance. The surface-treating agent comprises a water-soluble compound (A) comprising an alkoxysilyl group, an aromatic ring, and a hydroxy group directly bonded to the aromatic ring.

Description

Specification

Surface treatment agent, metal material using the same, novel compound and method for producing the same

Technical field

The present invention relates to a surface treatment agent, a metal material using the same, a novel compound, and a method for producing the same.

Background art

[0002] Conventionally, aromatic compounds having a hydroxy group (hereinafter also referred to as “phenolic hydroxy group”) directly bonded to an aromatic ring are among thermosetting materials. However, since it has relatively good processability, adhesiveness, mechanical properties, electrical insulation, heat resistance and chemical resistance, it has been put into practical use for a long time and has a wide range of uses.

However, in recent years, in order to further expand applications, it has been required to further improve processability, adhesion, chemical resistance, and the like.

[0003] In order to meet such demands, various methods for modifying aromatic compounds having a water-soluble phenolic hydroxy group have been studied.

For example, substitution is made at the ortho-position or para-position of the hydroxy group of the aromatic ring of the aromatic compound by the Mannheim reaction of an aromatic compound having a phenolic hydroxy group with formaldehyde and a primary amine or secondary amine. There is known a method for synthesizing an aromatic compound having a secondary or tertiary amino group and a phenolic hydroxy group by introducing a group (see, for example, Patent Document 1).

[0004] On the other hand, in the field of metal surface treatment, a non-chromate treatment that does not use chromium is demanded, and an aqueous surface containing an aromatic compound having a phenolic hydroxy group as described above. Treatment agents are used.

[0005] In addition, Patent Document 2 states that “at least partly has a metal surface, and the metal surface is at least 90% zinc, aluminum and Z or magnesium and Z or strong metal based on the metal surface. A vehicle body or home appliance made of an alloy of or an alloy of brilliant metal and other alloy elements, the vehicle being cleaned, passivated and coated A body or home appliance anti-bacterial treatment method, wherein the body or home appliance has a ρ 製 1-12 for the passivation, and is a complex fluoride of Ti, Zr, Hf, Si and Z or B An aqueous solution containing Ti, Zr, Hf, Si and Z or B in an amount of 20 to 500 mg ZL and an organic polymer of 50 to 20 OO mg / L, the composition of which is crystalline zinc-containing phosphorus The antifungal treatment method comprising contacting with the aqueous solution set so that an acid salt layer is not formed on the metal surface. Is described.

[0006] Patent Document 3 discloses that "an organic polymer compound having at least one nitrogen atom or a salt thereof having a water-soluble, water-dispersible or emulsion form; 0.01-: LOgZ Metal surface treatment agent characterized by containing 1. J is described.

[0007] In addition, Patent Document 4 describes an aqueous antifungal agent characterized by containing a modified bisphenol A epoxy resin having a specific structure or a derivative thereof.

Further, Patent Document 5 discloses that “at least one (A) selected from the group consisting of zirconium, fluorine, an amino group-containing silane coupling agent, a hydrolyzate thereof, and a polymer thereof, and an amino group-containing aqueous solution. A chemical conversion treatment agent comprising a phenol compound (B), wherein the content of the above-mentioned zirconum in the chemical conversion treatment agent is 25 to 2000 ppm in terms of metal, and the molar ratio of the fluorine and zirconium content is Chemical conversion treatment agent characterized by 3≤FZZr≤6. "

Patent Document 1: Japanese Patent Laid-Open No. 49 10888

Patent Document 2: Special Table 2003-526013

Patent Document 3: Japanese Patent Laid-Open No. 10-1782

Patent Document 4: Japanese Patent Laid-Open No. 10-60233

Patent Document 5: Japanese Unexamined Patent Application Publication No. 2006-241579

Disclosure of the invention

Problems to be solved by the invention

[0010] However, the surface treatment method using the surface treatment agent described in Patent Documents 1 to 5 has a lower performance than the conventional chromate treatment, and in particular, adhesion (work adhesion, etc.) Corrosion resistance (temporary corrosion resistance, corrosion resistance of processed parts, corrosion resistance under the coating film, etc.) and chemical resistance become a problem There is.

Accordingly, an object of the present invention is to provide a surface treatment agent that can obtain a coating film excellent in adhesion, corrosion resistance, and chemical resistance while being non-chromic. Another object of the present invention is to provide a metal material using the surface treating agent of the present invention. Another object of the present invention is to provide a compound that can be used in the surface treating agent of the present invention. Another object of the present invention is to provide a method for producing the compound of the present invention.

Means for solving the problem

As a result of diligent investigation, the present inventor has found that when the water-soluble compound (A) having an alkoxysilyl group, an aromatic ring, and a hydroxy group directly bonded to the aromatic ring is contained, It has been found that it becomes a surface treatment agent capable of obtaining a coating film excellent in adhesion, corrosion resistance and chemical resistance despite being chromium-based. In addition, the present inventors have synthesized a novel compound that can be used in the surface treatment agent of the present invention. The present inventor has completed the present invention based on these findings.

That is, the present invention provides the following (1) to (20).

(1) A surface treatment agent comprising a water-soluble compound (A) having an alkoxysilyl group, an aromatic ring, and a hydroxy group directly bonded to the aromatic ring.

(2) The compound (A) has at least one amino group selected from the group power consisting of a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. The surface treating agent according to (1) above.

(3) The surface treating agent according to the above (2), wherein the alkoxysilyl group is bonded to the nitrogen atom of the amino group directly or via an alkylene group.

(4) The compound (A) is a polymer, and has 0.01 to 4 alkoxysilyl groups per repeating unit of the compound (A), according to any one of (1) to (3) above Surface treatment agent.

(5) The surface treating agent according to any one of (1) to (4), wherein the compound (A) is directly bonded to the aromatic ring and has a hydroxy group.

(6) The compound (A) is a polymer and has 0.01 to 4 hydroxy groups not directly bonded to the aromatic ring per repeating unit of the compound (A). Table of Surface treatment agent.

(7) The above compound (A) is a compound obtained by reacting an aromatic compound (al) having at least one hydroxy group directly bonded to an aromatic ring, aminosilane (a2), and formaldehyde ( The surface treating agent according to any one of 1) to (6).

(8) The compound (A) comprises an aromatic compound (al) in which at least one hydroxy group is directly bonded to an aromatic ring, an aminosilane (a2), an amine compound (a3), and formaldehyde. The surface treating agent according to any one of (1) to (6) above, which is a compound obtained by a reaction

(9) The surface treatment agent according to (8), wherein the amine compound (a3) is a compound represented by the following formula (1).

[0014] [Chemical 1]

R ²

I 0)

\

[In the formula, R ¹ and R ² are each a hydrogen atom, an alkyl group, an alkyl group, an alkyl group, a benzyl group, an aryl group, a hydroxyalkyl group, a dihydroxyalkyl group, or a trihydroxyalkyl group. A group, an aminoalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a dialkoxysilylalkyl group, a trialkoxysilylalkyl group, an acetyl group or an alkylcarbonyl group, and R ¹ and R ² are bonded to each other. To form a morpholino group.)

(10) Aromatic compound (a 1) Strength Phenols, bisphenol A, p-Buhlphenol, naphthol, novolac resin, polybisphenol A, poly p-Buhlphenol and phenol-naphthalene polycondensate The surface treatment agent according to any one of the above (7) to (9), which is at least one selected from group power.

(11) The surface treating agent according to any one of (7) to (10) above, wherein the aminosilane (a2) is a compound represented by the following formula (2).

[0016] [Chemical 2]

^{_{R 3 - N-- (CH 2)}} n -. SiR 4 3 m (OR 5) m (2) [In the formula, R ³ is a hydrogen atom, an alkyl group, an alkyl group, an alkyl group, a benzyl group, an aryl group, a hydroxyalkyl group, a dihydroxyalkyl group, a trihydroxyalkyl group, an aminoalkyl group, An alkylaminoalkyl group, a dialkylaminoalkyl group, a acetyl group or an alkylcarbo group, R ⁴ and R ⁵ are each an alkyl group, n is an integer of 1 to 3, and m is 1 to 3 )

[0018] (12) The surface treatment agent according to the above (3), wherein the compound (A) is a polymer containing a repeating unit represented by the following formula (3).

[0019]

[Wherein R ⁶ represents a hydrogen atom, an alkyl group, an alkyl group, an alkyl group, a benzyl group, an aryl group, a hydroxyalkyl group, a dihydroxyalkyl group, a trihydroxyalkyl group, an aminoalkyl group, An alkylaminoalkyl group, a dialkylaminoalkyl group, a dialkoxysilylalkyl group, a trialkoxysilylalkyl group, a acetyl group or an alkylcarbonyl group, R ⁷ is a single bond or an alkylene group, R ⁸ and R ⁹ are R ^1Q and R ¹¹ are each a hydrogen atom, alkyl group, alkyl group, alkyl group, benzyl group, aryl group, hydroxyalkyl group, dihydroxyalkyl group, and trihydroxy group. Alkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, di An alkoxysilylalkyl group, a trialkoxysilylalkyl group, a acetyl group or an alkylcarbonyl group, and R ^1Q and R ¹¹ may be bonded to each other to form a morpholino group.p is an integer of 1 to 3. )

(13) The surface treatment agent according to any one of (1) to (12) above, wherein the compound (A) has a weight average molecular weight of 1,000 to 500,000.

(14) The surface treatment agent according to any one of (1) to (13), further containing water. (15) having a metal substrate and a surface-treated coating layer formed by performing a surface treatment on the surface of the metal substrate using the surface treatment agent according to any one of (1) to (14) above Metal material.

(16) A compound having a polymer strength containing a repeating unit represented by the following formula (4).

[Chemical 4]

(17) The compound according to (16) above, wherein the weight average molecular weight is 1, 1, ′ ′ 500,000.

(18) Poly p-Burfenol,

γ-phenolaminopropyl Η γ-aminopropyltriethoxysilane,

2-methylaminoethanol, monoethanolamine, diethanolamine, methylamino 1,2 propanediol, Ν-methyl-1,3 propanediamine, Ν methylaniline, ethylamine, jetylamine, arylamine, benzylamine, 2-ethylaminoethanol and morpholine Power A compound obtained by reacting at least one selected amine compound with formaldehyde in an organic solvent.

(19) 100 parts by mass of the poly ρ burfenol,

1 to 1200 parts by mass of the aminosilane,

0.2 to 360 parts by mass of the amine compound,

The compound according to the above (18) obtained by reacting 1.6 to 140 parts by mass of the formaldehyde in an organic solvent.

(20) A method for producing a compound to obtain the compound according to the above (18) or (19), A method for producing a compound, wherein the compound is obtained by reacting the poly (P-vinylphenol), the aminosilane, the amine compound, and the formaldehyde in an organic solvent. The invention's effect

[0022] Although the surface treatment agent of the present invention is non-chromic, it can provide a coating film excellent in adhesion, corrosion resistance and chemical resistance.

In addition, the metal material of the present invention is excellent in adhesion to a metal substrate or a coating film, and excellent in corrosion resistance and chemical resistance.

Moreover, the compound of this invention can be used for the surface treating agent of this invention. Moreover, the manufacturing method of the compound of this invention can manufacture the compound of this invention. Brief Description of Drawings

FIG. 1 shows the ¹ H-nuclear magnetic resonance spectrum of the compound of Synthesis Example 1.

FIG. 2 shows an infrared absorption spectrum of the compound of Synthesis Example 1.

BEST MODE FOR CARRYING OUT THE INVENTION

[0024] Hereinafter, the present invention will be described in more detail.

First, the surface treatment agent of the present invention will be described.

The surface treatment agent of the present invention is a surface treatment agent containing a water-soluble compound (A) having an alkoxysilyl group, an aromatic ring, and a hydroxy group directly bonded to the aromatic ring.

[0025] The compound (A) used in the surface treatment agent of the present invention includes at least an alkoxysilyl group, an aromatic ring, and a hydroxy group (phenolic hydroxy group) directly bonded to the aromatic ring. One water-soluble compound. Compound (A) may be a monomer or a polymer.

It is considered that the introduction of an alkoxysilyl group into a compound having an aromatic ring and a phenolic hydroxy group increases the crosslinking point, and as a result, the adhesion, corrosion resistance and chemical resistance of the surface treatment agent of the present invention are greatly improved. It is done.

[0026] The alkoxysilyl group is a group having a key atom and an alkoxy group directly bonded to the key atom, as long as the alkoxy group is directly bonded to the key atom and the key atom. And a group having at least two alkoxy groups bonded directly to the silicon atom and more preferably having three alkoxy groups. As the alkoxy group, a methoxy group or an ethoxy group is more preferable, and an alkoxy group having 1 to 10 carbon atoms is more preferable.

The group that the alkoxysilyl group other than the alkoxy group has is not particularly limited. For example, a hydrogen atom, a C1-CLO alkyl group, and the like are preferable.

Specific examples of the alkoxysilyl group include a dimethylmethoxysilyl group, a methyldimethoxysilyl group, a trimethoxysilyl group, a jetylethoxysilyl group, an ethyldiethoxysilyl group, and a triethoxysilyl group.

[0027] 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) in such an embodiment is obtained by reacting, for example, an aromatic compound (al) in which at least one hydroxy group is directly bonded to an aromatic ring, aminosilane (a2), and formaldehyde, as described later. (Hereinafter referred to as “first method”), or an aromatic compound (al) in which at least one hydroxy group is directly bonded to an aromatic ring, an aminosilane (a2), and an amine compound. (A3) can be obtained by a method of reacting formaldehyde (hereinafter referred to as “second method”).

[0028] When the compound (A) is a polymer (when it has a repeating unit in the main chain), the compound

(A) is a force having 0.01 to 4 alkoxysilyl groups per repeating unit of the compound (A) S, preferably 0.05 to 2 and more preferably 0.1 to 1 It is even more preferable to have five. When the compound (A) has an alkoxysilyl group within this range, the adhesion, corrosion resistance and chemical resistance are excellent.

[0029] The compound (A) preferably has 1 to 4 alkoxysilyl groups in one molecule, more preferably 1 to 3 more preferably 1 to 2 more preferably 1 to 2 molecules. When compound (A) has an alkoxysilyl group within this range, it has excellent adhesion, corrosion resistance and chemical resistance.

[0030] The aromatic ring of the compound (A) is not particularly limited !, but examples include a benzene ring, a naphthalene ring, an anthracene ring, and the like, and a benzene ring is preferable.

The phenolic hydroxy group is a hydroxy group directly bonded to the aromatic ring of the compound (A).

[0031] In order to ensure the water solubility of the compound (A), the compound (A) is bonded directly to the aromatic ring. In addition, it is preferable to have a polar group such as a hydroxy group. Since compound (A) is water-soluble, it can be used as an aqueous surface treatment agent.

[0032] The compound (A) has at least one amino group selected from the group force consisting of a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. More preferably, it has a tertiary amino group, more preferably a secondary amino group or a tertiary amino group. In the case where the compound (A) has an amino group, the polarity of the compound (A) is increased, so that the compound (A) becomes water-soluble.

[0033] The compound (A) is preferably bonded directly to the aromatic ring! /, And preferably has a hydroxy group V. When the compound (A) has a hydroxy group in addition to the phenolic hydroxy group, the water solubility of the compound (A) is increased. In addition, the adhesion, corrosion resistance, and chemical resistance of the resulting surface treatment agent can be improved.

[0034] 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) having such an embodiment can be obtained, for example, by the second method.

[0035] When the compound (A) is a polymer (when the main chain has a repeating unit), the compound (A) is directly bonded to the aromatic ring! /, A hydroxy group It is preferable to have 0.01 to 4 repeating units per unit of (A), more preferably 0.05 to 2 more preferably 0.1 to 1.5. . When the compound (A) is directly bonded to the aromatic ring within this range and has a hydroxy group, the water solubility of the compound (A) and the adhesion, corrosion resistance and chemical resistance of the resulting surface treatment agent are improved. Excellent.

[0036] 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 hydroxy groups. It is even better to have two. When compound (A) is directly bonded to the above aromatic ring within this range and has a hydroxy group, the water solubility of compound (A) and the adhesion, corrosion resistance, and chemical resistance of the resulting surface treatment agent Excellent in properties.

[0037] Compound (A) is obtained by reacting an aromatic compound (al) in which at least one hydroxy group is directly bonded to an aromatic ring, aminosilane (a2), and formaldehyde (first method). The resulting compound is preferred and is one of the embodiments. [0038] As another preferred embodiment of the compound (A), an aromatic compound (al) in which at least one hydroxy group is directly bonded to an aromatic ring, an aminosilane (a2), an amine compound ( Preferred examples include compounds obtained by the reaction of a3) with formaldehyde (second method).

[0039] The compound (A) of these embodiments is obtained by the so-called Mannich reaction, wherein the aromatic compound (al) has an amino group at the ortho or para position of the hydroxy group of the aromatic ring via a methylene group derived from formaldehyde. Is considered to be a combined 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 hydroxyl group of the aromatic ring are substituted.

[0040] The aromatic compound (al) 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-taresol, 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 (al), a phenol-cresol novolak copolymer, a burfurol-styrene copolymer, or the like can also be used.

In addition, the aromatic compound (al) described above is added to haloepoxides such as epichlorohydrin, carboxylic acids such as acetic acid, esters, amides, organic silanes such as trimethylsilyl chloride, alkyls such as alcohols and dimethyl sulfate. Those denatured with porridge can also be used.

These aromatic compounds (al) may be used alone or in combination of two or more.

[0041] The aromatic compound (al) is a group consisting of phenol, bisphenol A, p-buluphenol, naphthol, novolac coconut resin, polybisphenol A, poly p-buluphenol and phenol-naphthalene polycondensate Power is preferably at least one selected from the group power consisting of novolak coconut resin, polybisphenol A, poly p-buhlphenol and phenol-naphthalene polycondensate. More preferred is poly p-bulufenol. [0042] Here, in the present specification, the polybisphenol A means a compound represented by the following formula.

[0043] [Chemical 5]

In the above formula, s is an integer of 1 to 2000, and preferably an integer of 5 to 1000.

[0045] The poly p-bulufenol means a compound represented by the following formula.

A commercially available product may be used as the poly-P-buhlphenol, which may be a polymer obtained by polymerizing bulufenol by a known polymerization method. An example of a commercial product is Marukarinka manufactured by Maruzen Petrochemical.

[0046] [Chemical 6]

[0047] In the above formula, t is an integer of 1 to 4000, and preferably an integer of 10 to 2000.

[0048] The weight average molecular weight of the aromatic compound (al) is not particularly limited.

A force of 0,000 S preferred <, a force of 500-500,000 S preferred <, 1,000-200

More preferably, 000.

[0049] The aminosilane (a2) includes a primary amino group and a Z or secondary amino group (imino group). Although it will not specifically limit if it is a compound which has an alkoxy silyl group, For example, the compound represented by following formula (2) is mentioned suitably.

[0050] [Chemical 7]

R ³ - N one _{_{(CH 2) n -. SiR}} 3 m (OR 5) m (2)

[0051] In the above formula (2), R ³ represents a hydrogen atom, an alkyl group, an alkyl group, an alkyl group, a benzyl group, an aryl group, a hydroxyalkyl group, a dihydroxyalkyl group, or a trihydroxyalkyl group. , An aminoalkyl group, an alkylaminoalkyl group, a dialkylaminoalkyl group, a acetyl group or an alkylcarbo yl group.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an ipropyl group, or a t-butyl group.

Preferred examples of the alkenyl group include alkenyl groups having 1 to 10 carbon atoms, and more preferred are aryl groups.

As said alkynyl group, a C1-C10 alkyl group is mentioned suitably, More preferably, a propynyl group is mentioned.

The aryl group is preferably an aryl group having 1 to 10 carbon atoms, more preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group, 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 the dihydroxyalkyl group, a dihydroxyalkyl group having 1 to 10 carbon atoms is preferably exemplified, and more preferably a bis (hydroxyethyl) group.

As the above-mentioned trihydroxyalkyl group, a trihydroxyalkyl group having 1 to 10 carbon atoms is preferably exemplified, and more preferably a tris (hydroxyethyl) group.

The aminoalkyl group is preferably an aminoalkyl group having 1 to 10 carbon atoms, more preferably an aminoethyl group.

As said alkylaminoalkyl group, a C1-C10 alkylaminoalkyl group is mentioned suitably, More preferably, 2-methylaminoethylene is mentioned.

Examples of the dialkylaminoalkyl group include dialkylaminoalkyls having 1 to 10 carbon atoms. Group, and dimethylaminoethylene is more preferable.

As the above-mentioned alkyl carbo group, an alkyl carbo group having 1 to 10 carbon atoms is preferably exemplified, and more preferably an acetyl group.

In the above formula (2), R ⁴ and R ⁵ are each an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group. preferable. Multiple R ⁴ and R ⁵ may be the same or different! /.

In the above formula (2), n is an integer of 1 to 3, and an integer of 2 to 3 is preferable, and 3 is more preferable.

In the above formula (2), m is preferably an integer of 1 to 3, more preferably 2 or 3, and even more preferably 3.

Specific examples of the aminosilane (a2) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Ν-phenyl-1-propyltrimethoxysilane, and Ν- 1 propyltriethoxysilane, Ν— (2 aminoethyl) aminopropyltrimethoxysilane, Ν— (2-aminoethyl) aminopropylmethyldimethoxysilane, Ν— (2-aminoethyl) aminopropyltriethoxy Silane, Ν— (2-Aminoethyl) aminopropylmethyl jetoxysilane, Ν— (2-Aminoethyl) aminopropylmethyl dimethyloxysilane, Ν—β— (ΝBulbendylaminoethyl) 3-Amino Propyltrimethoxysilane, Ν-β- (ΝBulbendylaminoethyl) 3-aminominomethyldimethoxysilane Ν- β- (Ν Bulle base down Jill aminoethyl) 3 § amino propyl triethoxysilane, Ν- β- (Ν Bulle base down Jill aminoethyl) 3 § amino propyl methylate Rougier butoxy _silane, Ί - Anirino Propyltrimethoxysilane, γ-anilinopropylmethylenoresimethoxysilane, γ-anilinopropyltriethoxysilane, γ-anilinopropylmethyljetoxysilane, bis (trimethoxysilyl) aminovinyltrimethoxysilane, Ν — (3-Acryoxyl-2-hydroxypropyl) 3 Aminopropyltriethoxysilane, Ν— (3-Methacryloxy-2-hydroxypropinole) 3 Aminopropyltriethoxysilane, (Aminoethylaminomethyl) phenethyltri Methoxysilane, (aminoethylamino) 3-isobutyldimethylmethoxysila , Η-Butylaminopropyltrimethoxysilane, Νethylamino Allylamino) propyltrimethoxysilane, N cyclohexylaminopropyltrimethoxysilane, N phenylaminomethyltriethoxysilane, N-methylaminopropylmethyldimethoxysilane, bis (trimethoxysilyl) amine, bis [( 3-trimethoxysilyl) propyl] ethylenediamine, bis [3- (triethoxysilyl) propyl] urea, bis (methyljetoxysilylpropyl) amine, ureidopropyltriethoxysilane, ureidopropyltrimethoxysilane, N, N dioctyl-N '--Triethoxysilylpropylurea, N- (3-Triethoxysilylpropyl) darconamide, (3-triethoxysilylpropyl) t-butylcarbamate, triethoxysilylpropyl strength rubamate, 1,3 dibutyltetramethyldi Razan, trimethoxysilylpropyl (polyethylene I Min), 3- (2, 4 Jinitorofue - Le Amino) propyl triethoxysilane, 3- (triethoxysilylpropyl) -p - Torobenza Min, and the like. These may be used alone or in combination of two or more. Among these, γ-phenolaminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, Ν-2- (aminoethyl) 3 aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, Ν-methyl There is at least one aminosilane selected from the group power of aminopropyltrimethoxysilane, Ν-cyclohexylaminopropyltrimethoxysilane, bis (trimethoxysilyl) amine, and 3- (ァ amilamino) propyltrimethoxysilane. I like it!

[0054] The amount of the aminosilane (a2) used in the first method is preferably 1 to 1200 parts by mass, more preferably 2 to 600 parts by mass with respect to 100 parts by mass of the aromatic compound (al). More preferably 3 to 300 parts by mass.

[0055] The amount of the aminosilane (a2) used in the second method is preferably 1 to 1200 parts by mass, more preferably 2 to 600 parts by mass with respect to 100 parts by mass of the aromatic compound (al). More preferably 3 to 300 parts by mass.

The amine compound (a3) is not particularly limited as long as it is a compound having a primary amino group and Z or a secondary amino group (imino group). For example, the amine compound (a3) is represented by the following formula (1): Preferred examples of the compound are:

The amine compound (a3) may be the same as the aminosilane (a2).

[0057] [Chemical 8] R ²

I 0)

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

Specific examples of the amine compound (a3) include alkylamines such as methylamine, ethylamine, isopropylamine, dimethylamine, jetylamine, diisopropylamine, monoethanolamine, diethanolamine, 2 —Alkanolamines such as methylethanolamine, 2-ethylethanolamine, arrine, p-methylamine, aromatic amines such as N-methylamine, unsaturated amines such as buramine and allylamine, Examples include heterocyclic amines such as pyrrole, pyrrolidine, imidazole, indole and morpholine. These may be used alone or in combination of two or more.

Among these, 2-methylaminoethanol, monoethanolamine, diethanolamine, methylamino-1,2 propanediol, N-methyl-1,3 propanediamine, N-methylaniline, ethylamine, jetylamine, arylamine, benzylamine, 2-ethylamine At least one amine compound selected from the group power also comprising minoethanol and morpholinker is preferred.

[0060] The amount of the amine compound (a3) used in the second method is such that the aromatic compound (al) 1

0.2 to 360 parts by mass is preferable to 00 parts by mass 0.4 to 270 parts by mass is more preferable

More preferably, 6 to 180 parts by mass.

[0061] As the formaldehyde used in the above reaction, one diluted with a solvent is 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 ketone solvents such as

[0062] The amount of formaldehyde used in the first method is preferably such that the molar ratio of formaldehyde to amino groups (formaldehyde Z amino groups) of aminosilane (a2) is 1 to LOO. More preferred is 50. [0063] The amount of formaldehyde used in the second method is such that the molar ratio of formaldehyde to the total of the amino group of aminosilane (a2) and the amino group of amine compound (a3) (formaldehyde Z amino group) ~ 100 is preferred. 2-50 is more preferred.

[0064] As the compound (A), a polymer containing a repeating unit represented by the following formula (3) is one preferred embodiment.

[0065]

In the above formula (3), R ° is the same as R ^{3 in the} above formula (2).

R ⁷ is a single bond or an alkylene group, more preferably a trimethylene group (— (CH 2) 2 —), preferably an alkylene group having 1 to 10 carbon atoms. When R ⁷ is a single bond

twenty three

Means that R ⁷ does not exist and the nitrogen atom and the key atom are directly bonded.

R ⁸ and R ⁹ are each an alkyl group, more preferably a methyl group or an ethyl group, preferably an alkyl group having 1 to 10 carbon atoms. Multiple R ⁸ and R ⁹ may be the same or different! /.

R ^1Q and R ¹¹ are the same as R ^{3 in the} above formula (2), respectively. R ^1Q and R ¹¹ may be bonded to each other to form a morpholino group.

p is an integer of 1 to 3, 2 or 3 is preferred, and 3 is more preferred.

[0067] The polymer may contain a repeating unit other than the repeating unit represented by the above formula (3). The polymer is represented by the repeating unit represented by the above formula (3), the repeating unit represented by the following formula (5), the repeating unit represented by the following formula (6), and the following formula (7). A group consisting of a repeating unit represented by the following formula (8) and a repeating unit represented by the following formula (9): a polymer comprising at least one selected repeating unit. One of the aspects is preferred.

The polymer may further contain a repeating unit other than the repeating unit represented by the deviation in formulas (3) to (9).

[0068] [Chemical 10]

[0069] In the above formulas (5) to (9), R ⁶ ,

R ^1Q , R ¹¹ and p are each represented by the above formula (3)

The same as R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and p.

[0070] The method for producing the polymer is not particularly limited, but the polymer is reacted with poly p-bulufenol, the aminosilane (a2), the amine compound (a3), and formaldehyde. The method to obtain is mentioned suitably.

[0071] Specific examples of the polymer include, for example, a polymer containing a repeating unit represented by the following formula (4) (hereinafter referred to as "the compound of the first embodiment of the present invention"). It is done.

[Chemical 11]

[0072] The compound of the first aspect of the present invention may contain a repeating unit other than the repeating unit represented by the above formula (4). The compound of the present invention is represented by the repeating unit represented by the above formula (4), the repeating unit represented by the following formula (10), the repeating unit represented by the following formula (11), and the following formula (12). A repeating unit represented by the following formula (13) and a repeating unit force represented by the following formula (14): a group force consisting of at least one selected repeating unit and a polymer having a force. This is one of the preferred embodiments.

The compound of the first aspect of the present invention may further contain a repeating unit other than the repeating unit represented by any of the formulas (4) and (10) to (14).

[0073] [Chemical 12]

[0074] The method for producing the compound of the first aspect of the present invention is not particularly limited, but poly-p-butanol, γ-phenolaminopropyltrimethoxysilane, 2-methylaminoethanol, and formaldehyde. A method of obtaining the above polymer by reacting is preferable. More specifically, the method of the synthesis example 1 mentioned later is mentioned, for example.

[0075] As other preferred embodiments of the compound (Α), for example, poly ρ buluphenol, y-phenylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Ν-2- (aminoethyl) ) 3-Aminopropyltrimethoxysilane, γ-Aminopropylmethyl dimethoxysilane, Ν-Methylaminopropyltrimethoxysilane, ΝCyclohexylaminopropyltrimethoxysilane, bis (trimethoxysilyl) amine and 3- ( Νarylamino) propyltrimethoxysilane force at least one selected aminosilane, 2 methylaminoethanol, monoethanolamine, diethanolamine, methylamino-1,2 propanediol, Ν-methyl-1,3 propanediamine, Ν—Methylaniline, ethylamine, A group obtained by reacting at least one amine compound selected from ethylamine, arylamine, benzylamine, 2-ethylaminoethanol and morpholinker in an organic solvent (hereinafter referred to as “this”). A compound of the second aspect of the invention ”).

[0076] The method for producing the compound of the second aspect of the present invention is not particularly limited, but the present invention comprises reacting the poly-ρ vinylphenol, the aminosilane, the amine compound, and the formaldehyde in an organic solvent. The method for obtaining the compound of the second aspect is preferably mentioned.

The compound according to the second aspect of the present invention has a structure in which an amino group is bonded to the ortho position of the hydroxy group of the aromatic ring of poly (rho-bufenol) via a methylene group derived from formaldehyde by a so-called Mannig reaction. It is thought that.

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. It is preferable that the ortho position of the phenolic hydroxy group is substituted.

[0077] Preferable combinations of aminosilane and amine compounds used in the above reaction include combinations of Synthesis Examples 1 to 21 described later.

[0078] The amount of aminosilane used in the reaction is as follows: 1 to 1200 parts by mass is preferable with respect to 0 parts by mass, 2 to 600 parts by mass is more preferable, and 3 to 300 parts by mass is more preferable.

The amount of the amine compound used in the above reaction 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 poly (P-vinylphenol). ~ 180 parts by weight is even more preferred.

The amount of formaldehyde used in the above reaction is preferably 0.3 to 300 parts by mass, more preferably 0.6 to 200 parts by mass, with respect to 100 parts by mass of poly p-buhlphenol. Part is more preferred.

[0079] The organic solvent is not particularly limited as long as it does not participate in the reaction. Examples thereof include water; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and 1,4-dioxane; dichloromethane and chloroform. And halogen solvents such as acetone; ketone solvents such as acetone.

[0080] The amount of the organic solvent used is 0 to 10 parts per 100 parts by mass of poly p-vinylphenol.

1,000 to 5,000 parts by mass is preferred. 10 to 5,000 parts by mass is more preferred.

[0081] In the method for producing a 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 hydrochloric acid, hydrogen chloride gas, sulfuric acid, and fuming sulfuric acid.

Inorganic acids such as nitric acid, concentrated nitric acid and phosphoric acid; organic acids such as P-toluenesulfonic acid, trifluoromethanesulfonic acid, formic acid and acetic acid.

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, for example, aluminum chloride, titanium chloride, lanthanum trifonolite methanemethanerenolate, scandium trifonolone methanemethanesulfonate, ittribium trifluoromethanesulfonate, and the like.

[0082] The amount of the catalyst to be added is not particularly limited, but is preferably 1 to 300 parts by mass, more preferably 2 to 150 parts by mass with respect to 100 parts by mass of poly p-buhlphenol. [0083] The reaction temperature in the method for producing the compound of the second aspect of the present invention is not particularly limited, but is preferably 0 to 150 ° C, more preferably 20 to 100 ° C.

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 low reaction temperature requires a relatively long reaction time, and a high reaction temperature enables production in a relatively short time. However, if the reaction temperature is too high, the target product may be adversely affected or reactions other than the target reaction may be promoted.

[0084] 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.

[0085] 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 above 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. The mixture is heated to 80 ° C. and stirred for 24 hours to obtain the compound of the present invention.

Here, the order in which the aminosilane, the amine compound, formaldehyde and the catalyst are added is not particularly limited, but it is preferable to formaldehyde after caloring the aminosilane and amine compound. . The catalyst is preferably added after formaldehyde is added.

[0086] 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 under normal or reduced pressure, or use of chromatography.

[0087] The weight average molecular weight of the above-mentioned compound (A) is preferably 1,000 to 500,000 <, more preferably 1,500 to 250,000 than force S <, 2,000 A force of ~ 200,000 S is more preferred. When the molecular weight is within this range, a coating film having excellent adhesion, corrosion resistance and chemical resistance can be obtained.

[0088] The production method of the compound (A) is not particularly limited, and for example, the second aspect of the present invention described above. A method for producing the compound is preferably mentioned.

[0089] The surface treating agent of the present invention preferably further contains water.

The water content is not particularly limited, but in the treatment agent of the present invention, the content of the compound (A) is preferably 1 to 70% by mass, more preferably 2 to 60% by mass. More preferably, it is 3 to 50% by mass. Within this range, the handleability is excellent.

[0090] The surface treating agent of the present invention preferably contains a quaternizing agent in addition to the compound (A) and water. The quaternizing agent, when the compound (A) has a primary amino group, a secondary amino group or a tertiary amino group, can convert these groups into a quaternary ammonium group, Thereby, the water solubility of the compound (A) can be improved.

Examples of the quaternizing agent include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as formic acid, acetic acid, and propionic acid; low acidity, alcohols; and dialkyl sulfates such as dimethyl sulfate and jetyl sulfate. And halogenoalkyl such as methyl chloride, methyl bromide, methyl iodide, and benzylbutamide. Two or more of these may be used alone.

[0091] The surface treatment agent of the present invention includes an antifoaming agent, a metal compound, an organic substance, a silane coupling agent, an organic crosslinking agent, in addition to the compound (A), and optionally contained water and a quaternizing agent. Inorganic cross-linking agent, water-soluble resin, water-dispersible resin, water-dispersible silica, gas phase silica, metal oxide, conductive compound, color pigment, surfactant, thickener, etc. Also good.

[0092] The antifoaming agent can suppress or defoam foaming when the line is used.

The metal compound and the organic compound can impart antifungal properties.

The silane coupling agent, the organic crosslinking agent, and the inorganic crosslinking agent can improve adhesiveness.

The water-soluble rosin and the water-dispersible rosin can impart flexibility or improve barrier properties.

The water-dispersible silica, the gas phase silica, and the metal oxide can be used as binders.

The conductive compound can improve weldability.

The color pigment can improve the design. The above thickener can adjust the coating amount by changing the viscosity of the liquid.

[0093] The method for producing the surface treating agent of the present invention is not particularly limited. For example, the compound (A), water, and if necessary, a quaternizing agent and other components are placed in a reaction vessel, and a mixing mixer is used. A method of sufficiently mixing using a stirrer or the like can be used.

[0094] The surface treatment agent of the present invention described above reacts with the surface of a metal material to form a film having good adhesion, and the compound (A) forms a film, and exhibits excellent corrosion resistance and chemical resistance. Conceivable. In particular, the surface treatment agent of the present invention can provide a coating film excellent in coating adhesion, temporary anti-molding property, processed part corrosion resistance, and under-coating corrosion resistance. Further, the surface treatment agent of the present invention is excellent in storage stability even when an aqueous surface treatment agent is used.

Therefore, the surface treatment agent of the present invention is useful as a metal surface treatment agent.

[0095] Next, the metal material of the present invention will be described.

The metal material of the present invention is a metal material having a metal substrate and a surface-treated coating layer formed by surface treatment using the surface treatment agent of the present invention on the surface of the metal substrate.

[0096] The metal substrate is not particularly limited, and a known metal material and an adhesive plate can be applied. Specifically, for example, 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 , Aluminum plate, copper plate, titanium plate, magnesium plate and the like.

[0097] The metal base material is preferably such that the surface to be treated is cleaned using a cleaning agent such as warm water, a solvent, an alkaline degreasing agent or an acidic degreasing agent.

The metal substrate may be surface-adjusted with an acid, an alkali, or the like as necessary after washing.

In cleaning the metal substrate surface, it is preferable to wash with water after cleaning with a cleaning agent so that the cleaning agent does not remain on the metal substrate surface as much as possible.

[0098] The treatment method using the surface treatment agent of the present invention is not particularly limited, and examples thereof include a coating-type surface treatment method and a reactive surface treatment method.

[0099] The coating-type surface treatment method is performed after the surface treatment agent of the present invention is applied to the metal material.

This is done by drying. The application method is not particularly limited, and for example, a normal application method such as roll coating, curtain flow coating, air spray, airless spray, dipping, bar coating, brush coating or the like can be employed.

The temperature of the surface treatment agent is not particularly limited, but is preferably 0 to 60 ° C. 5 to 40

More preferably, it is ° C.

[0100] As the drying method, for example, a method of leaving it to stand at room temperature and a method of drying using an air blow can be adopted. However, it is possible to accelerate the curing of the compound (A). Heat drying is preferable. The preferred temperature when heating is 50 to 250 ° C 60

~ 220 ° C is more preferred.

[0101] Examples of the reactive surface treatment method include a method in which the surface treatment agent of the present invention is brought into contact with the surface of a metal substrate, and the surface treatment film layer is self-deposited on the surface of the metal substrate. The dipping method is preferably exemplified by the spray method.

The contact time between the surface treatment agent of the present invention and the metal substrate is not particularly limited, but is preferably 0.2 to 10 seconds, and more preferably 0.5 to 5 seconds. When the contact time is within this range, the surface treatment agent can sufficiently react with the surface of the metal substrate, a surface treatment coating layer having excellent corrosion resistance can be obtained, and the productivity in the line is also good.

Here, the contact time between the surface treatment agent of the present invention and the metal substrate means the time during which the metal substrate is immersed in the surface treatment agent of the present invention in the dipping method, and the present invention in the spray method. Is the time during which the surface treatment agent is sprayed on the metal substrate.

[0102] In the above spray method, it is preferable to perform intermittent spraying twice or more at intervals of 0.2 to 5 seconds from the viewpoint of improving the formation efficiency (deposition efficiency) of the surface treatment coating layer.

When performing the surface treatment by the spray method, it is preferable to add an antifoaming agent to the surface treatment agent of the present invention. The antifoaming agent is not particularly limited as long as it does not impair the coating adhesion, and a known one can be used.

[0103] The thickness of the surface treatment coating layer is not particularly limited, but is excellent in corrosion resistance and chemical resistance ^; force, 0.001-100 / ζ πι force S, preferably 0.01-10111 More preferably, 0.02 to 5 / zm is more preferable.

[0104] The metal material of the present invention further has a coating film on the surface of the surface treatment coating layer. One of the aspects is preferred.

Examples of the method for forming the coating film include a coating method generally used for pre-coated steel sheets. For example, a method in which a non-chromate primer is applied to the surface of the surface treatment coating layer and dried, and then a top coat is applied to the primer application surface to form a coating film; a primer is used on the surface of the surface treatment coating layer A method of directly applying a top coat without forming a coating film; and a method of attaching a laminate film to the surface of the surface treatment coating layer.

[0105] The metal material of the present invention described above is excellent in adhesion to a metal substrate or a coating film, and excellent in corrosion resistance and chemical resistance.

Example

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

[0107] 1-1. Synthesis of Compound (A) (Synthesis Examples 1 to 102)

In a reactor equipped with a stirrer (1 L separable flask), 100 parts by mass of the aromatic compound shown in Table 1 below and an organic solvent in the amount (parts by mass) shown in Table 1 below are placed. It was dissolved in. Amine compound, aminosilane, 36 mass% formaldehyde solution and catalyst shown in Table 1 below were added dropwise to this mixture at the room temperature shown in Table 1 below (part by mass) at room temperature, and then 80 ° The mixture was stirred at C for 24 hours. After stirring for 24 hours, sodium sulfite was added and the unreacted formaldehyde present in the system was titrated to determine the reaction rate, confirming that the reaction was proceeding almost quantitatively.

[0108] Thereafter, water was added and only the polymer component was precipitated and filtered for purification, and each compound of Synthesis Examples 1 to 102 corresponding to the compound (A) was obtained.

[0109] The compound of Synthesis Example 1 was subjected to nuclear magnetic resonance spectrum measurement, infrared absorption spectrum measurement, and gel permeation chromatography (GPC).

FIG. 1 shows the ¹ H-nuclear magnetic resonance spectrum of the compound of Synthesis Example 1, and FIG. 2 shows the infrared absorption spectrum of the compound of Synthesis Example 1.

[0110] Each measurement data performed on the compound of Synthesis Example 1 is shown below.

Mononuclear magnetic resonance spectrum [D 0, δ (ppm)]: 0. 2-0. 6 (br, 0. 3H), 0.7.1 .9 (br, 2.2H), 2.2—2.8 (br, 4.6H), 2.8—3.45 (br, 3.4H), 3.6—3.9 5 (br, 3.1H), 4.1—4.4 (br, 0.7H), 6.2—7.2 (br, 2.7H), 7.2—7.5 (br, 1.OH)

Infrared absorption spectrum [v (cm ^-1 )]: 3419, 3049, 2956, 2881, 2841, 1601, 14 98, 1468, 1367, 1254, 1115, 1076, 1028, 879, 823, 750, 694, 663, 60 6, 453

GPC [Used column Shodex GPC KF—802 + 802.5 (Showa Denko KK), temperature 40 ° C, mobile phase THF, flow rate 1. Oml / min, sample injection 50 μ1]: weight average molecular weight (Mw) 3262, Number average molecular weight (Mn) 832, molecular weight distribution (MwZMn) 3.9184

[0111] 1-2. Reference Example 1 3

In a reactor equipped with a stirrer (1 L separable flask), 100 parts by mass of the aromatic compound shown in Table 1 below and an organic solvent in the amount (parts by mass) shown in Table 1 below are placed. It was dissolved in. To this mixture, the amine compound shown in Table 1 below and 36% by mass formaldehyde solution shown in Table 1 below (in parts by mass) were added dropwise at room temperature sequentially, followed by stirring at 50 ° C for 3 hours. The mixture was stirred and further stirred at 80 ° C for 2 hours.

Thereafter, water was added and only the polymer component was precipitated and filtered for purification, and each compound of Reference Example 13 was obtained.

[0112] [Table 1]

[0113] [Table 2]

[0114] [Table 3]

[0115] [Table 4]

[0116] [Table 5]

[Table 6]

Table 1 (Part 6)

The components in Table 1 are as follows.

'Aromatic compounds (al-l): Poly p-Buhluenol, Marker Linker, manufactured by Maruzen Petrochemical Co., Ltd.

'Aromatic compound (al-2): Novolak rosin, Sumilite resin PR, manufactured by Sumitomo Bakelite Co., Ltd.' Aromatic compound (al-3): Polybisphenol A, bisphenol FM, manufactured by Mitsui Chemicals, Inc. 'Aromatic compound (Al-4): phenol-naphthalene polycondensate, Esquid A011SV, manufactured by Shinsaku Chemical Co., Ltd.

'Aminosilane (a2-1): γ-phenolaminopropyltrimethoxysilane

'Aminosilane (a2-2): y-Aminopropyltriethoxysilane

• Aminosilane (a2-3): 2 aminoethyl 3 aminopropyltrimethoxysilane

'Aminosilane (a2-4): y-Aminopropylmethyldimethoxysilane Aminosilane (a2-5): N-methylaminopropyltrimethoxysilane, manufactured by AZMAX Aminosilane (a2-6): N Cyclohexinorea

Made by Su

Aminosilane (a2-7) · Π "^ K ^^ iI made by AZMAX

Aminosilane (a2-8): 3— (N arnenorea ^, 11 1: 3 ^, no, manufactured by Nozza Max

Amine compound (a3-1) 2-Methylaminoethanol, manufactured by BASF

Amamine compound (a3-2) Monoethanolamine, manufactured by BASF

Amamine compound (a3-3) Diethanolamine, manufactured by BASF

Amamine compound (a3-4) Methylamino-1,2-propanediol, Kanto Chemical Co., Ltd. Amamine compound (a3-5) N-Methyl-1,3 propanediamine, Wako Pure Chemical Industries, Ltd. Amine compound (a3-6) N-Methylamine -Phosphorus, Pure Chemical

Amine compound (a3-7) Ethylamine, manufactured by Junsei Chemical Co., Ltd.

Amine compound (a3-8) Jetylamine, manufactured by Kanto Chemical Co., Inc.

Amamine compound (a3-9) Arylamine, manufactured by Tokyo Chemical Industry Co., Ltd.

Amine compound (a3-10): Nziramine, manufactured by Junsei Chemical Co., Ltd.

Amine compound (a3- 11): 2-Ethylaminoethanol, manufactured by Kanto Chemical Co., Inc.

Amine compound (a3-12): Morpholine, manufactured by Junsei Chemical Co., Ltd.

'Catalyst 1: p Toluenesulfonic acid

'Catalyst 2: ytterbium trifluoromethanesulfonate

'Organic solvent 1: 1, 4 Dioxane

'Organic solvent 2: ethanol

• Organic solvent 3: 2 Butoxyethanol

2. Preparation of surface treatment agent (Examples 1 to 102 and Comparative Examples 1 to 4)

Into 100 parts by mass of the compounds of Synthesis Examples 1 to 102 shown in Table 1 or the compounds of Reference Examples 1 to 3, 900 parts by mass of water and 40 parts by mass of a 75% by mass phosphoric acid aqueous solution were mixed and mixed thoroughly. The surface treatment agents of Examples 1 to 102 and Comparative Examples 1 to 3 were obtained. All of the compounds of Synthesis Examples 1 to 102 and the compounds of Reference Examples 1 to 3 could be dissolved in water. Further, 900 parts by mass of water and 40 parts by mass of a 75% by mass phosphoric acid aqueous solution were added to 100 parts by mass of orthoaminophenol and mixed thoroughly to obtain the surface treating agent of Comparative Example 4.

[0122] 3. Preparation of Specimens (Experimental Examples 1-90 and Comparative Experimental Examples 1-4)

3-1. Substrate type

The following three types of steel plates were used.

• Electrogalvanized steel sheet (hereinafter referred to as “EG material” or “EG”): Plate thickness 0.6mm, plating weight 20gZm ² per side (double-sided)

'Hot-dip galvanized steel sheet (hereinafter referred to as “GI material” or “GI”): plate thickness 0.6 mm, zinc adhesion 50 gZm ² per side (double-sided)

'Aluminum-zinc alloy plated steel sheet (hereinafter referred to as “GL” or “GL”): Plate thickness 0.6 mm, adhesion amount 50 gZm ² per side (double-sided)

[0123] 3-2. Preprocessing

Alkaline degreasing agent (CL-N364S, manufactured by Nihon Parkerizing Co., Ltd.) is used as an aqueous solution with a concentration of 20 gZL and a temperature of 60 ° C. Dried.

[0124] 3-3. Surface treatment (Non-chromate aqueous surface treatment)

Each surface treatment agent is applied to the surface (one side) of each steel plate after pre-treatment using a roll coater for pre-coated steel plates (PCM) so that the dry film amount is 100 mg / m ^2, and is temporarily prevented. For application, a roll coater was used to apply a dry film weight of 500 mg / m ² , followed by drying at 80 ° C for 30 seconds in a hot air drying oven.

[0125] 3 -4. Application of base coat and top coat

Primers and topcoats (F1 or F2) shown in Table 2 below were applied to the treated surfaces of the respective surface-treated steel sheets obtained above to obtain test specimens.

[0126] Fl and F2 in Table 2 mean that the following treatment was performed.

F1: After applying primer (V knit # 200, manufactured by Dainippon Paint Co., Ltd.) on the treated surface of each surface-treated plate obtained above (film thickness 5. δ μ ηι) and baking at 200 ° C Further, a top coat (V knit # 500, manufactured by Dainippon Paint Co., Ltd.) was applied (film thickness: 17 m) and baked at 220 ° C. F2: A primer (Flexcoat 600, manufactured by Nippon Paint Co., Ltd.) was applied to the treated surface of each surface-treated plate obtained above (film thickness 5.5 111), baked at 200, and then topped. Pukot (Flexcoat 5030, Nippon Paint Co., Ltd.) was applied (film thickness 7 μm) and baked at 220 ° C.

[0127] 4. Evaluation test

The test specimen obtained! The corrosion resistance, adhesion and chemical resistance were evaluated by the following methods.

The results are shown in Table 2 below.

[0128] 4—1. Corrosion resistance

A cross-cut was made with a cutter so that the coating film of each test specimen (PCM) reached the metal substrate, and the salt spray test specified in JIS Z2371-2000 was conducted for 480 hours. The film swelling width (maximum value on one side) and the film swelling width (maximum value) of the end face force were measured.

The evaluation criteria are as follows.

: Less than 2mm

○: 2mm or more and less than 5mm

Δ: 5 mm or more and less than 10 mm

X: 10mm or more

○: 4 mm or more and less than 8 mm

△: 8mm or more and less than 12mm

X: 12mm or more

[0129] 4- 2. Bending adhesion

4- 2- 1. Primary bending adhesion

In accordance with the test method of JIS G3312-2005, each specimen (PCM) was subjected to a 2T bending test of two bent inner spacing plates at 20 ° C, and the peeled state after tape peeling was observed. did.

4- 2- 2. Secondary bending adhesion

The test was carried out in the same manner as the above-mentioned primary bending adhesion except that each test body (PCM) was immersed in boiling water for 2 hours and then left for 1 day as a test body.

The evaluation criteria are as follows.

◎: No peeling

○: Peeling area less than 10%

Mouth: peeling area 10% or more, less than 50%

Δ: peeling area 50% or more and less than 80%

X: peeling area 80% or more

[0130] 4- 3. Temporary protection

4- 3- 1. Corrosion resistance of flat surface

The test piece (for temporary flaw prevention) was cut with a cutter so that it reached the metal substrate, and the salt spray test specified in JIS Z2371-2000 was conducted for 72 hours. The generation area was determined.

The evaluation criteria are as follows.

◎ ： Bird generation area less than 5%

○: White birch occurrence area 5% or more, less than 10%

Δ: White birch occurrence area 10% or more, less than 30%

X: White birch occurrence area 30% or more, less than 50%

X X: White birch occurrence area 50% or more

[0131] 4- 3- 2. Corrosion resistance of machined parts

Each test specimen obtained (for temporary fouling) was subjected to an Erichsen 7 mm extrusion test and subjected to a salt spray test as defined in JIS Z2371-2000 for 72 hours, and the occurrence of white glaze was visually observed.

The evaluation criteria are as follows. <Evaluation criteria>

◎: almost no wrinkles

◯: There are many white spots in the processing part!

△: All of the processing parts are white, but there is no flow

X: Flow defects occur from the processing part

[0132] 4-4. Chemical resistance

4—4—1. Alkali resistance

An aqueous solution of alkaline degreasing agent (Palclean 364S, manufactured by Nihon Parkerizing Co., Ltd.) with a concentration of 20gZL and a temperature of 65 ° C is sprayed on the resulting specimen (for temporary fenders) for 5 minutes, then washed with water and at 80 ° C. Dried. The test specimen was evaluated for corrosion resistance by the same method as described above (4-3-1. Planar section corrosion resistance).

4-4- 2.Acid resistance

The obtained specimen (for temporary fenders) was immersed in an aqueous solution of sulfuric acid at 1. Og / temperature 25 ° C for 10 seconds, washed with water, and dried at 80 ° C. The test specimen was evaluated for corrosion resistance by the same method as described above (4-3-1. Planar section corrosion resistance).

◎ ： Bird generation area less than 5%

○: White birch occurrence area 5% or more, less than 10%

Δ: White birch occurrence area 10% or more, less than 30%

X: White birch occurrence area 30% or more, less than 50%

X X: White birch occurrence area 50% or more

[0133] [Table 7]

[0134] [Table 8]

[0135] [Table 9]

[0136] [Table 10]

[0137] [Table 11]

[0138] [Table 12]

[0139] [Table 13] Table 2 (Part 7)

As can be seen from the results shown in Table 2, Comparative Experimental Examples 1 to 4 using a compound having no alkoxysilyl group were insufficient in corrosion resistance and acid resistance in the processed part. On the other hand, in Experimental Examples 1-116, regardless of the type of base material, corrosion resistance (edge) and corrosion resistance (cross cut part), primary bending adhesion and secondary bending adhesion, flat surface corrosion resistance, alkali resistance In addition, the acid resistance and the strength corrosion resistance were excellent.

Claims

The scope of the claims

[1] A surface treatment agent comprising a water-soluble compound (A) having an alkoxysilyl group, an aromatic ring, and a hydroxy group directly bonded to the aromatic ring.

[2] The compound (A) has at least one amino group selected from a primary force, a secondary amino group, a tertiary amino group and a quaternary ammonium group. The surface treatment agent according to claim 1.

[3] The surface treatment agent according to claim 2, wherein the alkoxysilyl group is bonded to a nitrogen atom of the amino group directly or via an alkylene group.

[4] The surface according to any one of claims 1 to 3, wherein the compound (A) is a polymer and has 0.01 to 4 alkoxysilyl groups per repeating unit of the compound (A). Processing agent.

[5] The surface treatment agent according to any one of [1] to [4], wherein the compound (A) is directly bonded to the aromatic ring and has! /, NA! /, A hydroxy group.

6. The surface according to claim 5, wherein the compound (A) is a polymer and has 0.01 to 4 hydroxy groups not directly bonded to the aromatic ring per repeating unit of the compound (A). Processing agent.

[7] The compound (A) is a compound obtained by reacting an aromatic compound (al) having at least one hydroxy group directly bonded to an aromatic ring, an aminosilane (a2), and formaldehyde. Item 7. The surface treating agent according to any one of Items 1 to 6.

[8] The compound (A) is a reaction between an aromatic compound (al) having at least one hydroxy group directly bonded to an aromatic ring, an aminosilane (a2), an aminic compound (a3), and formaldehyde. The surface treatment agent according to claim 1, which is a compound obtained by reaction.

[9] The surface treatment agent according to claim 8, wherein the amine compound (a3) is a compound represented by the following formula (1).

[Chemical 13]

R ²

I 0)

\

(In the formula, R ¹ and R ² are respectively a hydrogen atom, an alkyl group, an alkyl group, an alkyl group; Group, benzyl group, aryl group, hydroxyalkyl group, dihydroxyalkyl group, trihydroxyalkyl group, aminoalkyl group, alkylaminoalkyl group, dialkylaminoalkyl group, dialkoxysilylalkyl group, trialkoxysilylalkyl group, R ¹ and R ² may be bonded to each other to form a morpholino group. )

[10] Aromatic compound (al) 1S phenol, bisphenol A, p-buluphenol, naphthol, novolac coconut resin, polybisphenol A, poly p-buluphenol and phenol-naphthalene polycondensate power group power selection Claims that are at least one of

The surface treating agent according to any one of 7 to 9.

[11] The surface treatment agent according to any one of [7] to [LO], wherein the aminosilane (a2) is a compound represented by the following formula (2).

[Chemical 14]

^{_{R 3 - N-- (CH 2)}} n -. SiR 4 3 m (OR 5) m (2)

(Wherein R ³ is a hydrogen atom, an alkyl group, an alkyl group, an alkyl group, a benzyl group, an aryl group, a hydroxyalkyl group, a dihydroxyalkyl group, a trihydroxyalkyl group, an aminoalkyl group, an alkylaminoalkyl group) A group, a dialkylaminoalkyl group, a acetyl group or an alkyl carbo group, R ⁴ and R ⁵ are each an alkyl group, n is an integer of 1 to 3, and m is an integer of 1 to 3. is there. )

12. The surface treatment agent according to claim 3, wherein the compound (A) is a polymer containing a repeating unit represented by the following formula (3).

[Chemical 15]

(In the formula, R ⁶ represents a hydrogen atom, an alkyl group, an alkyl group, an alkyl group, a benzyl group, an alkyl group, Reel group, hydroxyalkyl group, dihydroxyalkyl group, trihydroxyalkyl group, aminoalkyl group, alkylaminoalkyl group, dialkylaminoalkyl group, dialkoxysilylalkyl group, trialkoxysilylalkyl group, acetyl group or alkylcarbonyl group R ⁷ is a single bond or an alkylene group, R ⁸ and R ⁹ are each an alkyl group, and R ^1Q and R ¹¹ are a hydrogen atom, an alkyl group, an alkyl group, an alkyl group, respectively. Group, benzyl group, aryl group, hydroxyalkyl group, dihydroxyalkyl group, trihydroxyalkyl group, aminoalkyl group, alkylaminoalkyl group, dialkylaminoalkyl group, dialkoxysilylalkyl group, trialkoxysilylalkyl group A acetyl group or Rukirukarubo - a le radical, R ^1Q and R ¹¹ Yogu p is an integer from 1 to 3 also form a morpholino group bonded to each other. )

[13] The surface treatment agent according to any one of [1] to [12], wherein the compound (A) has a weight average molecular weight of 1,000 to 500,000.

[14] The surface treatment agent according to any one of claims 1 to 13, further comprising water.

[15] A metal material having a metal substrate and a surface-treated coating layer formed on the surface of the metal substrate by surface treatment using the surface treatment agent according to any one of claims 1 to 14.

[16] A polymer-strength compound containing a repeating unit represented by the following formula (4).

[Chemical 16]

[17] The compound according to claim 16, which has a weight average molecular weight of 1,000 to 500,000.

[18] with poly-p-vinylphenol,

γ-phenylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 2-2 (aminoethynole) 3 aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, Ν-methylaminopropyl Trimethoxysilane, Ν cyclohexyla Minopropyltrimethoxysilane, bis (trimethoxysilyl) amine and 3- (N-arylamino) propyltrimethoxysilane force at least one selected aminosilane and

2-methylaminoethanol, monoethanolamine, diethanolamine, methylamino 1,2 propanediol, N-methyl-1,3 propanediamine, N methylaniline, ethylamine, jetylamine, arrylamine, benzylamine, 2-ethylaminoethanol and morpholinca Power A compound obtained by reacting at least one selected amine compound with formaldehyde in an organic solvent.

[19] 100 parts by mass of the poly p bulufenol,

1 to 1200 parts by mass of the aminosilane,

0.2 to 360 parts by mass of the amine compound,

19. The compound according to claim 18, obtained by reacting 1.6 to 140 parts by mass of formaldehyde in an organic solvent.

[20] A method for producing a compound, wherein the compound according to claim 18 or 19 is obtained,

A method for producing a compound, comprising: reacting the poly (P-vinylphenol), the aminosilane, the amine compound, and the formaldehyde in an organic solvent to obtain the compound.