JP2001039927A - New tricarbonyl compound and metal surface treating agent using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the new compound strongly adsorbing on the surface of a metal material such as aluminum, iron and steel product, etc., having an excellent rustproofing action even in a thin film, useful as a metal surface treating agent. SOLUTION: This compound containing tricarbonyl groups is shown by formula I (R1 is H or methyl; R2 and R3 are each a 2-10C alkenyl containing a double bond at a 2-10C end or a 1-10C alkyl; (1) is a 1-3C alkylene; (x), (y) and (z) are each 0 or 1) such as a compound of formula II. The compound of formula I is obtained, for example, by reacting a dicarbonyl compound of formula III with a compound of formula IV in the presence of magnesium chloride and an amine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treating agent for improving rust prevention on a metal surface or a substrate treated with the same, and is used for a machine industry, an electric equipment industry, a building material, It can be widely used in various industrial fields that use aluminum products such as the automobile industry.

[0002]

2. Description of the Related Art It has been known to perform various treatments for the purpose of improving the corrosion resistance of various metals. Chromate treatment, which is a surface treatment using a compound containing chromic acid, is generally used because it has good corrosion resistance of metal and shows good characteristics in adhesion to paint. However, due to recent environmental problems, regulations on chromium have been greatly strengthened, and materials that do not use chromium have been proposed. In this regard, surface technology 49 (3), 221 (1998)
Tannic acid, organophosphorus compounds, as described in
There are silane-based films and surfactants. Further, for example, copolymers of unsaturated carboxylic acids (JP-A-5-2223)
No. 24), a glycidyl group-containing unsaturated monomer-acrylate copolymer (JP-A-3-192166), and the like. Each of these materials uses an acrylic resin, but it is necessary to thicken the film in order to exhibit sufficient rust prevention. However, the adhesion between these materials and various metals such as iron and aluminum is not always sufficient, and in a wet environment, the adhesion is significantly reduced and the film is peeled off. On the other hand, as a material for improving the adhesion to the base material, there is an epoxy resin-based material as disclosed in Japanese Patent No. 2682168. However, although these materials have high adhesion, it is necessary to increase the film thickness in order to enhance rust prevention.

[0003]

SUMMARY OF THE INVENTION The present invention can respond to such a demand, that is, it strongly adheres to the surface of metals, particularly metal materials such as aluminum and steel products, and has an excellent rust preventive action even in a thin film. It is an object of the present invention to provide a novel tricarbonyl compound, a novel tricarbonyl group-containing acrylic (co) polymer, and a metal surface treating agent using the same.

[0004]

As a result of intensive studies, the present inventors have found that a novel tricarbonyl compound represented by the following general formula (1) has an excellent rust-preventive action on metal surfaces. . The present invention has been made based on such findings, and the gist of the present invention is to provide (1) a compound having three carbonyl groups represented by the following general formula (1),

[0005]

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However, the compound also includes an enol type which is a tautomer. The general formula R ¹ is H or a methyl group,
R ² and R ³ are an alkenyl group having a double bond at the terminal having 2 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms, 1 is an alkylene having 1 to 3 carbon atoms, x, y, z is 0 or 1
Is shown.

(2) A polymer of a tricarbonyl compound represented by the general formula (1) or a copolymer of the compound represented by the general formula (1) and one or more polymerizable unsaturated monomers And (3) the copolymer according to (2), wherein the polymerizable unsaturated monomer has an alkoxysilyl group; and (4) the tricarbonyl compound according to (1) to (3) as an active ingredient. (5) the polymer or copolymer described in (2), an organosilicon compound having an imidazole group and an alkoxysilyl group, and an epoxy resin having two or more epoxy groups in one molecule. A metal surface treatment agent as an active ingredient;
Or, a metal material treated with the metal surface treatment agent according to the above (5).

Hereinafter, the present invention will be described in more detail. The acryloyl group in the above general formula (1) can be polymerized and polymerized on the surface by heat or ultraviolet treatment after being applied to the metal surface. The tricarbonyl group contained in the molecule has a very high reactivity such as a chelate reaction with a metal ion or a reaction with an aldehyde, an amine or the like at room temperature. However, although the above compound describes only the keto form, it exists in an enol form which is a tautomer as shown below, and the enol form is also included in the present invention (hereinafter, only the keto form is referred to) To be described,
Enol type is also included).

[0009]

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The tricarbonyl group-containing compound represented by the general formula (1) of the present invention is synthesized by a reaction represented by the following reaction formula (2). That is, it is obtained by reacting a dicarbonyl compound with compound A in the presence of magnesium chloride and an amine.

[0011]

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However, the compound also includes an enol type which is a tautomer. The general formula R ¹ is H or a methyl group,
R ² and R ³ are an alkenyl group having a double bond at the terminal having 2 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms, 1 is an alkylene having 1 to 3 carbon atoms, x, y, z is 0 or 1
Is shown.

Preferred as the compound A represented by the above reaction formula (2) are acetyl chloride, propionyl chloride, butyryl chloride, t-butylacetyl chloride, valeryl chloride, heptanoyl chloride,
Decanoyl chloride, 2-ethylhexanoyl chloride, octanoyl chloride, and 10-undecenoyl chloride.

Preferred examples of the compound represented by the general formula (1) used in the present invention and an unsaturated monomer having polymerizability include alkyl acrylates such as methyl acrylate and isopropyl acrylate, hydroxyethyl acrylate, polyethylene glycol acrylate, and dimethyl acrylate. Aminoethyl acrylate, glycidyl acrylate, 2-cyano acrylate, benzyl acrylate, phenoxyethyl acrylate, tetrahydrofuryl acrylate, dicyclopentenyloxy acrylate, fluoroacrylate, sulfopropyl acrylate, β-ethoxyethyl acrylate, γ-acryloxypropyl alkoxysilane And methacrylates of these. Also, styrenes such as 4-chlorostyrene and pentafluorostyrene. Particularly preferred are those having an alkoxysilyl group, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane and its methacryloquine,
Alternatively, 4-vinylphenyltrimethoxysilane and the like are exemplified. As for these materials, not only one kind of material may be used in combination but also a plurality of materials may be used in combination.

As the radical polymerization initiator used in the present invention, organic peroxides, organic azo compounds and persulfates can be used. Benzoyl peroxide and t-butyl peroxypivalate are preferred as organic peroxides, and 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4- Dimethylvaleronitrile).

The (co) polymer of the present invention can be obtained as a substantially linear structure as shown in the following general formula (3). When R ² and / or R ³ in the general formula (1) is an alkenyl group, it can be obtained as a curable (co) polymer having a structure in which the alkenyl group is suspended. After the (co) polymer is applied to the metal surface, it can be cross-linked and cured by heat, ultraviolet light, or a curing catalyst or a curing agent. Although the molecular weight of the linear (co) polymer of the present invention is not particularly limited, it is about 1,000 to 1,000.
It is about 1 million, preferably 5000 to 200,000.

[0017]

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Although the tricarbonyl compound of the present invention can be used alone as a metal surface treating agent, it can also be used together with this and other materials. Such materials include epoxy resin, urethane resin, polyester resin and the like.

The organosilicon compound having an imidazole group and an alkoxysilyl group used in the present invention is exemplified by imidazole silane and the like, and is preferably disclosed in JP-A-6-17753 together with its synthesis method. The following compounds have been used.

[0020]

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[0021] (wherein, R ¹ is hydrogen, a vinyl group or an alkyl group having a carbon number of 1 to 5, R ² is hydrogen or a carbon number 1
-20 alkyl groups, R ³ and R ⁴ are alkyl groups having 1 to 3 carbon atoms, and n is 1 to 3) In the method disclosed herein, the general formula (1 ′):
It is obtained as a mixture of the compounds represented by (2 ′) and (3 ′), but in the present invention, it is not necessary to separate them particularly, and the mixture can be used as it is.

On the other hand, epoxy resins having two or more epoxy groups in one molecule used in the present invention include bisphenol A and bisphenol A based on bisphenol A.
Type epoxy resin. Others include a brominated epoxy resin in which hydrogen on the benzene ring of a bisphenol A epoxy resin is partially substituted with bromine, a dimer acid glycidyl ester epoxy resin, a phenoxy resin, a glycidylamine epoxy resin, a novolak epoxy resin, Glycidyl ester type epoxy resins and the like can be mentioned.

In the present invention, it is desirable to use an organic solvent in order to uniformly apply the composition to an adherend. Examples of the organic solvent include aromatic solvents such as toluene and xylene, cell solvents such as methoxyethanol and ethoxyethanol, ketone solvents such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and alcohols such as methanol and isopropyl alcohol. Is mentioned.

The metal surface treating agent of the present invention is applied to a metal material, but exhibits an excellent rust-preventing action particularly to aluminum and aluminum alloys. As a method for applying the metal surface treating agent according to the present invention to a metal surface, known coating methods such as spray coating, dip coating, brush coating, and roll coating can be applied.

In order to bring out the effects of the present invention, it is desirable to heat and dry after coating. Heat drying at 100-230 ° C
For 30 seconds to 60 minutes. The coating thickness after drying is desirably 0.1 to 100 μm. More preferably, it is 0.5 to 10 μm. If it is less than 0.1 μm, sufficient rust prevention cannot be imparted, and if it exceeds 100 μm, a uniform coating film cannot be obtained.

In the present invention, a resin, a silane coupling agent, a viscosity modifier, a defoamer, an ultraviolet absorber, a preservative,
A surfactant or the like may be added.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 Synthesis of New Tricarbonyl Compound 1 9.52 g (0.1 mol) of magnesium chloride, 110 ml of methylene chloride, 15.82 g (0.2 mol) of pyridine
l) was placed in a 500 ml flask, heated and stirred at an oil temperature of 60 ° C for 10 minutes, and then 21.41 g (0.1 mol) of 2-acetoacetoxyethyl methacrylate (manufactured by ACROSS) was added. Stirred. After slowly adding dropwise 20.27 g (0.1 mol) of 10-undecenoyl chloride, the mixture was stirred at an oil temperature of 60 ° C. for 8 hours. After cooling to room temperature, 80 ml of water was added and the mixture was stirred to extract an organic layer.
After the solvent was distilled off, the residue was dried under reduced pressure to obtain 36.3 g of a yellow liquid (compound represented by the following formula).

[0028]

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The compound was identified by ¹ H-NMR (FIG. 1), ¹³
C-NMR (FIG. 2) and FT-IR (FIG. 3) were performed.

Example 2 Synthesis of novel tricarbonyl compound 2 9.52 g (0.1 mol) of magnesium chloride, 110 ml of methylene chloride, 15.82 g (0.2 mol) of pyridine
l) was placed in a 500 ml flask, heated and stirred at an oil temperature of 60 ° C for 10 minutes, 20.01 g (0.1 mol) of 2-acetoacetoxyethyl acrylate was added, and the bath temperature was further adjusted to 60 °
Stirred at C for 10 minutes. 10-undecenoyl chloride 2
After slowly dropping 0.27 g (0.1 mol),
The mixture was stirred at an oil temperature of 60 ° C. for 8 hours. Cool down to room temperature and water 80m
1 was added and stirred to extract an organic layer. After distilling off the solvent,
Dry under reduced pressure and yellow liquid (compound represented by the following formula) 35.
1 g was obtained.

[0031]

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The compounds were identified by ¹ H-NMR (FIG. 4), ¹³
It performed by C-NMR (FIG. 5) and FT-IR (FIG. 6).

Example 3 Synthesis of tricarbonyl polymer 1 Novel tricarbonyl compound 1 obtained in Example 1
6 g (20 mmol), azobisisobutyronitrile 6
30.4 g of a 6 mg (0.4 mmol) toluene solution was placed in a 100 ml flask and stirred at 80 ° C. for 8 hours. A polymer was precipitated by adding 300 g of methanol, and the polymer was isolated and dried under reduced pressure to obtain a yellow solid 5.3 having a number average molecular weight of 40,000 (polystyrene equivalent) represented by the following formula.
g was obtained.

[0034]

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The compounds were identified by ¹³ C-NMR (FIG. 7), F
Performed by T-IR (FIG. 8).

Example 4 Synthesis of tricarbonyl polymer 2 Novel tricarbonyl compound 1 obtained in Example 1
8 g (10 mmol), 1.52 g (10.0 mmol) of 2-dimethylaminoethyl methacrylate, and 21.5 g of a toluene solution of 66 mg (0.40 mmol) of azobisisobutyronitrile were placed in a 100 ml flask,
Stirred at 80 ° C. for 8 hours. After the solvent was distilled off, the residue was dried under reduced pressure to obtain 5.1 g of a yellow solid represented by the following formula and having a number average molecular weight of 40,000 (in terms of polystyrene).

[0037]

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The compounds were identified by ¹³ C-NMR (FIG. 9), F
Performed by T-IR (FIG. 10).

Example 5 Preparation of solvent-based surface treatment agent 1.7 g of tricarbonyl synthesized in Example 1, 3.7 g of epoxy resin (Epicoat 1004, manufactured by Yuka Shell Epoxy Co., Ltd.), JP-A-6-177535 Example 1 of
4.7 g of imidazole silane synthesized according to the above was added, and 190 g of ethyl cellosolve was added thereto, to thereby obtain a composition A.
Similarly, the types of tricarbonyl synthesized in Examples 2, 3 and 4 were changed, and solutions of compositions B, C and D were prepared.

[0040]

[Table 1]

Example 6 Preparation of a solvent-based surface treating agent 7.6 g of the novel tricarbonyl compound obtained in Example 1
(20 mmol), 5.8 g (20 mmol) of γ-methacryloxypropyltrimethoxysilane, 0.067 g (0.4 mmol) of azobisisobutyronitrile, and 120 g of ethylcellosolve were put into a 100 ml flask,
The mixture was stirred at 85 ° C. for 4 hours under a nitrogen atmosphere. After the solvent was distilled off, the number average molecular weight was reduced to 40,000 (polystyrene conversion) by drying under reduced pressure.
13.4 g of a yellow solid were obtained.

The obtained copolymer, epoxy resin (Epicoat 1004 made from Yuka Shell Epoxy) and imidazole silane were adjusted with ethyl cellosolve so that the solid content ratio became 5: 5: 1 (total solid content was adjusted to 10%) as composition E.

Example 7 Preparation of Water-Soluble Surface Treatment Agent Novel Tricarbonyl Compound 1 Obtained in Example 1
8 g (10 mmol), 2-dimethylaminoethyl methacrylate 0.99 g (6.5 mmol), hydroxyethyl methacrylate 0.84 g (6.7 mmol),
Azobisisobutyronitrile 75 mg (0.46 mmol
22.5 g of the toluene solution of l) was placed in a 100 ml flask, and stirred at 80 ° C for 8 hours. After distilling off the solvent,
By drying under reduced pressure, 5.3 g of a yellow solid having a number average molecular weight of 40,000 (in terms of polystyrene) was obtained. 1.5 g of lactic acid was added to 5.0 g of the obtained polymer, and 43.5 g of pure water was added to obtain an aqueous solution of a tricarbonyl compound. Add 1 to pure water in advance
15.0 g of a water-soluble epoxy resin (Adeka Resin EM-0434 manufactured by Asahi Denka Kogyo KK) diluted to 0% concentration and imidazole silane diluted to 10% concentration with pure water.
The composition F was obtained by mixing 0 g.

Example 8 Preparation of Water-Soluble Surface Treatment Agent Novel Tricarbonyl Compound 1 Obtained in Example 1
8 g (10 mmol), acrylic acid 0.74 g (10 m
mol), 0.067 g of azobisisobutyronitrile
(0.4 mmol) of toluene solution (21.5 g) in 100
The mixture was placed in a ml flask and stirred at 80 ° C. for 8 hours. After the solvent was distilled off, the residue was dried under reduced pressure to obtain 4.3 g of a yellow solid having a number average molecular weight of 40,000 (in terms of polystyrene). To 3.0 g of the obtained polymer, 1.2 g of 29% aqueous ammonia (19.0 mm
ol), 25.8 g of pure water was added to obtain an aqueous solution of a tricarbonyl compound. Add 10 to this with pure water beforehand.
Imidazole silane 100 obtained by diluting 70.0 g of a water-soluble epoxy resin (Adeka Resin EM-0436 manufactured by Asahi Denka Kogyo KK) diluted to a concentration of 10% with 10% concentration with pure water.
g was mixed to obtain a composition G.

Example 9 Preparation of Water-Soluble Surface Treatment Agent Novel Tricarbonyl Compound 1 Obtained in Example 1
72 g (9.8 mmol), methyl methacrylate 0.6
g (6 mmol), isobutyl methacrylate 1.42
g (10 mmol), styrene 0.16 g (1.5 mm
ol), 0.52 g of hydroxyethyl methacrylate
(4 mmol), 0.67 g (7.8 mm) of methacrylic acid
ol), 0.067 g of azobisisobutyronitrile
(0.4 mmol), 18 g of toluene and 18 g of isopropyl alcohol in a 100 ml flask,
For 4 hours. After evaporating the solvent, 5.9 g of a yellow solid having a number average molecular weight of 40,000 (polystyrene equivalent) was obtained by drying under reduced pressure.
I got After adding 0.38 g (6.1 mmol) of 29% aqueous ammonia to 3.0 g of the obtained polymer, 26.62.
g of pure water was added to obtain an aqueous solution of tricarbonyl. To this, a water-soluble epoxy resin (Adeka Resin EM-043 manufactured by Asahi Denka Kogyo KK) previously diluted to a concentration of 10% with pure water.
The composition H was prepared by mixing 30.0 g of 4) and 12.0 g of imidazole silane diluted to 50% with methanol.

Test Piece Preparation Conditions An aluminum plate having a size of 55 × 55 × 1 was pretreated with an alkaline degreasing solution (Surf Cleaner: Nippon Paint), and then dried with a spin coater to a thickness of 1 μm. The surface treatment agent composition was applied and heat-treated at 200 ° C. for 1 minute to prepare a surface-treated aluminum plate.

Rust prevention evaluation method A salt spray test described in JIS-Z-2371 was conducted for 240 hours.

Comparative Example 1 Composition not containing a tricarbonyl compound in Composition A Comparative Example 2 Composition not containing a tricarbonyl compound in Composition C Comparative Example 3 Composition not containing a tricarbonyl compound in Composition F Comparative Example 4 Composition G Composition containing no tricarbonyl compound in Comparative Example 5 Aluminum plate

[0049]

[Table 2]

[0050]

As described above, the composition having the novel tricarbonyl compound according to the present invention is useful as a metal surface treatment agent, particularly as a surface treatment agent for aluminum, and exhibits excellent rust prevention. is there.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of a tricarbonyl compound 1 of the present invention synthesized in Example 1.

FIG. 2 is a ¹³ C-NMR chart of the above.

FIG. 3 is an FT-IR chart of the above.

FIG. 4 is a ¹ H-NMR chart of a tricarbonyl compound 2 of the present invention synthesized in Example 2.

FIG. 5 is a ¹³ C-NMR chart of the above.

FIG. 6 is an FT-IR chart of the above.

FIG. 7 is a ¹³ C-NMR chart of a polymer of tricarbonyl compound 1 of the present invention synthesized in Example 3.

FIG. 8 is an FT-IR chart of the above.

FIG. 9 is a ¹³ C-NMR chart of a copolymer of tricarbonyl compound 1 of the present invention and 2-dimethylaminoethyl methacrylate synthesized in Example 4.

FIG. 10 is an FT-IR chart of the above.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Toru Imori 187-4 Usuba, Hanakawa-cho, Kitaibaraki-shi, Ibaraki Japan Energy Isohara Plant Co., Ltd. (72) Inventor Takashi Ouchi Hachikawa-cho, Ibaraki 187, Usuba 4 Japan Energy Isohara Factory F-term (reference) 4H006 AA01 AB46 BR10 4J100 AB08Q AB10Q AL03Q AL08P AL08Q AL09Q AL10Q BA04Q BA06Q BA08Q BA10P BA12P BA20P BA31Q BA40Q BA53Q BB07Q BC28QBC04A JA01 BC09 BC12 BC13 BC19 GA08

Claims (6)

[Claims] 1. A compound having three carbonyl groups represented by the following general formula (1). Embedded image However, the compound also includes an enol type which is a tautomer.
The above general formula R ¹ is H or a methyl group, R ² and R ³ are an alkenyl group having a double bond at a terminal having 2 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms, and l is a carbon atom having 1 to 3 carbon atoms. Alkylene, x, y, and z represent 0 or 1. 2. A polymer of a tricarbonyl compound represented by the general formula (1) or a copolymer of a compound represented by the general formula (1) and one or more polymerizable unsaturated monomers. 3. The copolymer according to claim 2, wherein the polymerizable unsaturated monomer has an alkoxysilyl group. 4. A metal surface treating agent comprising the tricarbonyl compound according to claim 1 as an active ingredient. 5. A metal surface comprising the polymer or copolymer according to claim 2, an organosilicon compound having an imidazole group and an alkoxysilyl group, and an epoxy resin having two or more epoxy groups in one molecule as an active ingredient. Processing agent. 6. A metal material treated with the metal surface treating agent according to claim 4.