JPH093077A - New silicon compound containing tricarbonyl group and metallic surface treating agent containing the same as active component - Google Patents

Abstract

PURPOSE: To obtain a new silicon compound which is a silane compound containing a specific tricarbonyl group, excellent in adhesion to a metallic surface and rust preventing properties and useful as a metallic surface treating agent, etc., in order to carry out an improvement, etc., in rust prevention of a metal and adhesion of the metal to a resin. CONSTITUTION: A silicon compound containing a new tricarbonyl group of formula I [R<1> is a 1-5C alkyl; R<2> is a 2-10C alkylene; R<3> is a 1-5C alkyl; R<4> is a 2-10C alkylene; (x), (y) and (z) are each 0 or 1]. The compound is excellent in adhesion and rust preventing properties to a metallic surface and useful as a metallic surface treating agent, etc., in order to carry out an improvement, etc., in rust prevention of a metal and adhesion of the metal to a resin. The compound is obtained by reacting an unsaturated dicarbonyl compound of formula II (e.g. allyl acetoacetate) and an unsaturated chlorocarbonyl compound of formula III (e.g. 10-undecenoyl chloride), to provide a compound of formula IV and then reacting the resultant compound of formula IV with a silane compound of the formula HSi(OR<3> )3 (e.g. trimethoxysilane) in the presence of a platinum catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a surface treatment agent for rust-preventing metal mainly composed of copper, steel and aluminum products and improving adhesion between metal and resin, and to the surface treatment agent. It relates to suitable novel compounds.

[0002]

BACKGROUND OF THE INVENTION There are various requirements for various metals. For example, a copper foil for a printed circuit is heated and pressed on a paper-phenol resin-impregnated base material or a glass-epoxy resin-impregnated base material to form a copper-clad laminate, which is etched to form a circuit network. A board for an electronic device is made by forming and mounting an element such as a semiconductor device thereon. In these processes, adhesion with a substrate, heating, dipping in an acid or alkaline solution, application of resist ink, soldering, etc. are performed, so that various performances are required for the copper foil. It is also required that the surface of the copper foil does not undergo oxidative discoloration during storage. In order to meet these requirements, a brass layer forming treatment (Japanese Patent Publication No.
35711 and 54-6701), chromate treatment, zinc-chromium group mixture coating treatment comprising zinc or zinc oxide and chromium oxide (Japanese Patent Publication No. 58-707).
No. 7) is carried out. However, since the printed circuit has been densified recently, the characteristics required for the copper foil for the printed circuit used have become more and more severe.

Steel products are used for buildings, automobiles, ships,
It is used in various places such as cans, but it has the serious drawback of rusting. As a rust preventive agent for iron products, various conventional rust preventive agents such as a water-soluble rust preventive agent, a vaporizable rust preventive agent, and an oil rust preventive agent are used. Generally, a water-soluble rust inhibitor is intended for temporary short-time rust prevention and is not used for long-term rust prevention. Further, the vaporizable rust preventive exerts its original rust preventive power in a sealed state. Oil-based rust preventives have a relatively strong rust preventive power and can withstand long-term rust prevention.Liquid rust preventive oil, rust preventive additives, film forming agents, etc. dissolved in a volatile organic solvent There is rust preventive grease etc. In this way, various rust preventive agents have been developed and used properly according to each environment.
At present, there is still a demand for further enhancement of rust preventive agents. Further, since aluminum or aluminum alloy is lightweight, it is beginning to be noticed in the field of automobiles from the viewpoint of improving fuel efficiency. When an aluminum alloy is used as a panel material, it is usually coated after being subjected to processing such as press molding, and especially for automobile outer panel materials, cation-type electrodeposition coating is required due to the requirement for corrosion resistance. It has been subjected. However, there are disadvantages that the adhesion of the coating to the aluminum alloy is not sufficiently obtained and the corrosion resistance after coating is not sufficient.

[0004]

The present invention is capable of meeting such demands, that is, it strongly adsorbs on metals, particularly copper, steel and aluminum products, on metal surfaces, and has a rust preventive action even in a thin film, and It is an object of the present invention to provide a novel silane compound having excellent adhesiveness with a resin and a novel metal surface treating agent using the same.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors, a silicon compound containing a tricarbonyl group represented by the following general formula (1) has an excellent rust preventive action on a metal surface. It was also found that the adhesion between metal and resin is improved. The present invention has been made based on such findings, and the gist thereof is a novel tricarbonyl group-containing silicon compound represented by the following general formula (1).

[0006]

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[However, the tricarbonyl group-containing silicon compound also includes an enol form which is a tautomer of the general formula (1). Further, in the general formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 5 and R ⁴ is 2 to 10 The alkylene group and x, y, and z each represent 0 or 1, respectively.] (2) A metal surface treating agent containing the novel tricarbonyl group-containing silicon compound represented by the general formula (1) as an active ingredient. Hereinafter, the present invention will be described in more detail. R ¹ and R ³ in the above general formula (1) are alkyl groups having 1 to 5 carbon atoms, but in particular, in view of easiness of synthesis and hydrolysis of silane (in the case of R ³ ), methyl is used. Groups or ethyl groups are preferred. R ² and R ⁴ are alkylene groups having 2 to 10 carbon atoms. Among the compounds represented by the above general formula (1) of the present invention, particularly preferable compounds are, for example,

[0008]

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[0009]

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[0010] However, although the above compound only describes the keto form, it exists as a tautomer of the keto form and the enol form as shown by the following formula, and the enol form is also included in the scope of claims of the present invention (hereinafter , Only the keto form is listed, but the enol form is also included).

[0011]

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The tricarbonyl group-containing silane compound (1) of the present invention is synthesized by the reactions represented by the general formulas (2) and (3). That is, the following compound A, preferably allyl acetoacetate, and the following compound B are reacted in the presence of magnesium chloride and an amine to synthesize a tricarbonyl compound having two double bonds [see reaction formula (2)], It can be produced by reacting with trialkoxysilane (compound C) in the presence of platinum [hydrosilylation reaction, see reaction formula (3)].

[0013]

[Chemical 6]

(In the above formula, R ¹ is an alkyl group having 1 to 5 carbon atoms, R ⁵ and R ⁶ are a bond or an alkylene group having 1 to 8 carbon atoms, and x, y, z are 0 or 1)

[0015]

[Chemical 7]

(Note that in the above equation

[0017]

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Are R ² in the general formula (1),
It is synonymous with R ³ and R ⁴ . ) Acrylic acid chloride and 10-undecenoyl chloride are preferred as the compound B represented by the above reaction formula (2). Further, a carboxylic acid having a double bond, such as vinyl acetoacetic acid or 4-pentanoic acid, may be converted to an acid chloride with thionyl chloride, phosphorus trichloride, phosphorus pentachloride or the like. Further, as the trialkoxysilane (compound C) represented by the above reaction formula (3), trimethoxysilane and triethoxysilane are preferable. The reaction of the compound B of the above reaction formula (2) with a preferred compound A, allyl acetoacetate, is described in the literature [M. W. Rathke, P.M. J. Cowan, J .;
Org. Chem. 50,2622 (1988) or J. Skarzewski, Tetrahedro
n, 45 , 4593 (1989)]. That is, allyl acetoacetate and magnesium chloride are mixed in a reaction solvent to obtain a mixed solution, and the amine and the compound B are sequentially added dropwise to this mixed solution. After dropping these, it is preferable to reflux them in order to sufficiently carry out the reaction. A reaction time of about 5 minutes to 24 hours is sufficient. As the reaction solvent, methylene chloride, acetonitrile or the like is suitable. Further, since this reaction does not like water, it is preferable to carry out the reaction in an atmosphere of a gas containing no water such as dry nitrogen or argon so that the water is not mixed from the gas phase.

The reaction mixture is subjected to column chromatography,
Although it can be purified and isolated by a known means such as extraction or distillation, the method of extracting and distilling is simple and preferable. In addition, in the hydrosilylation reaction of the reaction formula (3), a tricarbonyl compound having two double bonds and a trialkoxysilane in an amount of 2 to 20 times by mole are added to the tricarbonyl compound in an amount of 10 times.
^-5 to 10 ^-7 times the molar amount of chloroplatinic acid at room temperature to 15
It is synthesized by reacting at 0 ° C for several hours. This reaction does not particularly require a reaction solvent, but a solvent such as toluene may be used. The reaction mixture can be purified and isolated by a known means such as column chromatography or distillation, but a tricarbonyl group-containing silane compound can be obtained in good purity only by removing excess trialkoxysilane by concentration.

When the above-mentioned tricarbonyl group-containing silane compound is used as a metal surface treatment agent, the target metal is not particularly limited, but is preferably used as a surface treatment agent for copper, steel, aluminum and alloys thereof. is there.
Further, the film thickness varies depending on the type and use of the metal, but is preferably several molecular layers to several hundred μm. The tricarbonyl group-containing silane compound may be directly applied to a metal, but alcohols such as methanol and ethanol,
It is convenient and preferable to apply a method of diluting with a solvent such as acetone or ethyl acetate to a concentration of 0.001 to 20% by weight and dipping the metal in this solution or a method of showering this solution on the metal. Further, if a small amount of water, an acetic acid aqueous solution, hydrochloric acid or the like is added to these diluted solutions and stirred for about 1 to 24 hours, the hydrolysis of silane will proceed sufficiently and more siloxane films will be formed. The effect can be fully exerted.

[0021]

【Example】

I. Synthesis of silane compound containing tricarbonyl group 1. Reaction of allyl acetoacetate with 10-undecenoyl chloride

[0022]

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After thoroughly replacing a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.15 mol (21.0) of allyl acetoacetate was added.
g), methylene chloride 160 ml, magnesium chloride 0.
15 mol (14.1 g) was added. After cooling to 0 ° C., 0.3 mol (23.4 g) of pyridine was added,
Stirred for minutes. 0.15 mol (30.0 g) of 10-undecenoyl chloride was added dropwise to the mixed solution, and the mixture was stirred at 0 ° C for 1 hour and then at 50 ° C for 2 hours. Reaction mixture
It was cooled to 0 ° C., and 110 ml of 6 mol / L hydrochloric acid was added dropwise. After thoroughly stirring, the organic layer was washed with water and dried over magnesium sulfate. After removing the solvent, a tricarbonyl compound having two unsaturated bonds was obtained by distillation under reduced pressure [boiling point: 1
25.0 to 137.1 ° C./0.5 mmHg, yield: 7
1.0% (yield: 32.4 g)]. The obtained compound is G
It was confirmed to be a single component by C, and ¹ H-NMR, ¹³
It was identified by C-NMR and FT-IR. The results are shown in FIGS. The following signals were recognized as shown in FIGS. From the ¹ H-NMR integration ratio, it was confirmed that this compound exists in almost enol form.

[0024]

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[FIG. 1 ¹ H-NMR (CDCl ₃ , δppm)] a: 2.3 (s, 3H) b: 17.9 (s, enol form), 3.4 (s, keto form) c: 4.7 (m, 2H) d: 6.0 to 6.1 (m, 1H) e: 5.3 to 5.4 (m, 2H) f: 1.3 to 2.7 (m, 16H) g: 5.7 to 6.0 (m, 1H) h: 4.7 to 5.0 (m, 2H) [FIG. 2 ¹³ C-NMR (CDCl ₃ , δppm)] a: 25.7 b: 108 .2 (enol form) c: 65.5 d: 131.9 e: 119.0 f: 28.8 to 37.8 g: 139.0 h: 114.1 i or k: 195.8 or 199. 1 j: 166.8 [FIG. 3 IR (cm ⁻¹ )] ν _CH : 2820 to 3030, ν _{c = o} : 1550 to 17
20 2. Hydrosilyl reaction

[0026]

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After sufficiently replacing a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.097 mol of trimethoxysilane (11.
9 g) and 8.1% 10 ⁻⁷ mol (0.42 ml) of chloroplatinic acid were added as a 0.2% ethanol solution. 0.0162 mol (5.0 g) of the above-synthesized tricarbonyl compound having two double bonds was added dropwise to the mixed solution at room temperature. After the dropping, the mixture was heated at 90 ° C. for 2 hours and concentrated with a vacuum pump for 1 hour to obtain a tricarbonyl group-containing silane compound (yield: 96.5%). The obtained compound was identified by ¹ H-NMR, ¹³ C-NMR and FT-IR. These results are shown in FIGS. As shown in FIGS. 4 to 6, the following signals were observed. This compound is ¹ H
-From the NMR integration ratio, it was confirmed that the compound was almost in the enol form.

[0028]

[Chemical 12]

[FIG. 4 ¹ H-NMR (CDCl ₃ , δppm)] a: 2.3 (s, 3H) b: 17.8 (s, enol form), 3.4 (keto form) c: 4. 2 (m, 2H) d: 1.3 to 1.8 (m, 2H) e: 0.6 to 0.7 (m, 2H) f: 3.6 (s, 9H) g: 1.3 to 1.8 (m, 2H) h: 1.3~1.8 (m, 2H) i: 0.6~0.7 (m, 2H) j: 3.6 (s, 9H) [5 ¹³ C-NMR (CDCl ₃ , δppm)] a: 25.6 b: 108.5 (enol form) c: 66.8 d: 22.5 e: 5.6 f: 50.3 g: 29.2 37.8 h: 22.0 i: 9.1 j: 50.3 k or m: 195.5 or 198.9 l: 167.2 [Fig. 6 IR (cm ^-1 )] ν _CH : 2820 to 3030 , Ν _{c = o} : 1550-17
20 ν _SiOCH3 : 1080, 820 II. Anti-rust test for copper Electrolytic copper foil (manufactured by Nikko Gould Foil, JTC foil: thickness 75 μm, 4.5 × 4.5 cm) was degreased with acetone, and washed with 3% sulfuric acid aqueous solution. A 6% methanol solution of the above-mentioned tricarbonyl group-containing silane compound was applied to this copper foil with a spin coater and dried at 150 ° C. for 30 minutes to form a 0.3 μm tricarbonyl group-containing silane compound thin film. The test piece was used. This test piece was placed in a thermo-hygrostat having a temperature of 80 ° C. and a humidity of 95% for 24 hours,
Moisture resistance was evaluated by the degree of discoloration. Further, heat treatment was performed at 180 ° C. for 30 minutes, and the heat resistance was evaluated by the degree of discoloration. The results are shown in Table 1. For comparison, a copper foil on which nothing was applied was also evaluated in the same manner. The results are shown in Table 1.

[0030]

[Table 1]

III. Anticorrosion test for carbon steel Carbon steel (S.45C, made by Nippon Test Panel, thickness 2.0
(5.5 mm x 5.5 cm) was sanded with No. 1000 sandpaper, and then ultrasonically washed with acetone for 5 minutes. This carbon steel surface was coated with a 6% methanol solution of the above-mentioned tricarbonyl group-containing silane compound (concentration, see Table 2 for additives) with a spin coater (500 rotations, 60 seconds),
It was dried at 30 ° C. for 30 minutes to form a thin film of a tricarbonyl group-containing silane compound, which was used as a test piece. This test piece was placed in a thermo-hygrostat at a temperature of 80 ° C. and a humidity of 95% for 24 hours, and the humidity resistance was evaluated by the degree of discoloration. The results are shown in Table 2. Further, it was immersed in a 3% aqueous sodium chloride solution for 24 hours, and the salt water resistance was evaluated by the degree of discoloration. The results are shown in Table 2.
It was shown to. Further, as a comparison, the carbon steel to which nothing was applied was similarly evaluated. The results are shown in Table 2.

[0032]

[Table 2]

IV. Anti-rust test for aluminum Aluminum plate (A5052P, made by Nippon Test Panel, thickness 2.0 mm, 5.5 x 5.5 cm) is ultrasonically cleaned with acetone for 5 minutes, and immersed in 5% Na ₂ CO ₃ aqueous solution for 30 minutes. After that, it was washed with water. A 2% methanol solution of the above-mentioned tricarbonyl group-containing silane compound was applied to the surface of this aluminum plate by a spin coater (500 rotations, 60 seconds), dried at 150 ° C. for 30 minutes, and 0.2 μm of the tricarbonyl group-containing silane compound. A thin film was prepared and used as a test piece. This test piece was immersed in boiling water for 1 hour, and the moisture resistance was evaluated by the degree of discoloration. The results are shown in Table 3. Further, as a comparison, the same evaluation was made for aluminum to which nothing was applied. The results are also shown in Table 3.

[0034]

[Table 3]

Further, a 0.1% methanol solution of a tricarbonyl group-containing silane compound was surface-treated on an aluminum plate in the same manner as described above, and then an epoxy resin (Epicoat 828:
(100 parts, LX2S: 60 parts, methanol: 100 parts)
Was applied by a spin coater and heat-treated at 70 ° C. for 3 hours to form an epoxy resin film having a thickness of 20 μm. After dipping this test piece in 5% saline for 2 days, a cross-cut test was conducted to evaluate the adhesiveness with the resin. The results are shown in Table 4.
Further, as a comparison, the same evaluation was made for aluminum to which nothing was applied. The results are also shown in Table 4.

[0036]

[Table 4]

[0037]

INDUSTRIAL APPLICABILITY As described above, the novel tricarbonyl group-containing silane compound of the present invention is useful as a surface treatment agent for metal surfaces, especially for copper, steel, and aluminum. It has an effect of being excellent in adhesiveness with a resin.

[Brief description of drawings]

FIG. 1 shows an intermediate of a tricarbonyl compound for a silane compound containing a tricarbonyl group of the present invention obtained in an example.
¹ H-NMR,

FIG. 2 is the same ¹³ C-NMR,

FIG. 3 is the same FT-1R,

FIG. 4 ¹ H-NMR of the tricarbonyl group-containing silane compound of the present invention obtained in Examples,

FIG. 5 shows the same ¹³ C-NMR,

FIG. 6 shows the same FT-IR.

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[Procedure amendment]

[Submission date] September 12, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

[0013]

[Chemical 6] (In the above formula, R ¹ is an alkyl group having 1 to 5 carbon atoms, R ⁵ and R
⁶ is a bond or an alkylene group having 1 to 8 carbon atoms, x,
y and z represent 0 or 1)

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

[0015]

[Chemical 7]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction contents]

[FIG. 1 ¹ H-NMR (CDCl ₃ , δppm)] a: 2.3 (s, 3H) b: 17.9 (s, enol form), 3.4 (s, keto form) c: 4.7 (m, 2H) d: 6.0 to 6.1 (m, 1H) e: 5.3 to 5.4 (m, 2H) f: 1.3 to 2.7 (m, 16H) g: 5.7 to 6.0 (m, 1H) h: 4.7 to 5.0 (m, 2H) [FIG. 2 ¹³ C-NMR (CDCl ₃ , δppm)] a: 25.7 b: 108 .2 (enol form) c: 65.5 d: 131.9 e: 119.0 f: 28.8 to 37.8 g: 139.0 h: 114.1 i or k: 195.8 or 199. 1 j: 166.8 [FIG. 3 IR (cm ⁻¹ )] ν _CH : 2820 to 3030, ν _{c = o} : 1550 to 17
20 2. Hydrosilylation reaction

Claims (2)

[Claims] 1. A novel tricarbonyl group-containing silicon compound represented by the following general formula (1). Embedded image [However, the tricarbonyl group-containing silicon compound also includes an enol form which is a tautomer of the general formula (1).
Further, in the general formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² is an alkylene group having 2 to 10 carbon atoms, R ³ is an alkyl group having 1 to 5 and R ⁴ is 2 to 10 An alkylene group,
x, y and z each represent 0 or 1] 2. A metal surface treating agent comprising the tricarbonyl group-containing silicon compound according to claim 1 as an active ingredient.