JPH093127A - Polymer having tricarbonyl group and metal surface treating agent using the same - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a metal surface treating agent excellent in rust prevention and adhesion of a metal surface and a polymer composition therefor. [Structure] A polymer obtained by polymerizing a compound having three carbonyl groups represented by the following general formula (2) and one or more double bonds. Embedded image [However, the compound also includes an enol type. Further, in the general formula (2), R ¹ , R ² , and R ⁴ are alkenyl groups having 2 to 10 carbon atoms and having a double bond at the terminal or 1 to 1 carbon atoms.
An alkyl group of 0, and at least one of R ¹ , R ² and R ⁴ is an alkenyl group having a terminal double bond, x,
y and z represent 0 or 1]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent for preventing corrosion of metals mainly of copper, steel and aluminum products and improving adhesion between metal and resin, and a novel polymer suitable therefor. .

[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, 54-6701), chromate treatment, zinc-chromium group mixture coating treatment comprising zinc or zinc oxide and chromium oxide, etc. (Japanese Patent Publication No. 58-70).
77). 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.

Further, steel products are used in various places such as buildings, automobiles, ships and cans, but they have a serious drawback of rusting. Conventionally, various rust preventive agents such as water-soluble rust preventive agents, vapor rust preventive agents and oil rust preventive agents have been used as rust preventive agents for iron products. 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. As described above, a large number of various rust preventive agents have been developed and used properly according to their respective environments, but at present, it is still desired to further enhance the 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 can meet such demands, that is, it strongly adsorbs on metals, particularly copper, steel and aluminum products, on the metal surface, and has a rust preventive action even in a thin film, Another object of the present invention is to provide a novel polymer having a tricarbonyl group, which has excellent adhesiveness to a resin, and a novel metal surface treating agent using the polymer.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventor, a polymer having a tricarbonyl group represented by the following general formula (1) has an excellent antirust effect on a metal surface. It has been found that the surface-treated metal has excellent adhesion to the resin. The present invention has been made based on such findings, and the gist thereof is (1) a tricarbonyl group-containing polymer having a repeating unit represented by the following general formula (1).

[0006]

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[However, the tricarbonyl group-containing polymer also includes an enol form which is a tautomer of the general formula (1). Further, in the general formula (1), R ¹ and R ² have 1 to 1 carbon atoms.
0 is an alkyl group, R ³ is a bond or an alkylene group having 1 to 8 carbon atoms, and x, y, and z are 0 or 1] (2) Three carbonyl groups represented by the following general formula (2) And a polymer obtained by polymerizing a compound having one or more double bonds.

[0008]

Embedded image

[However, the tricarbonyl group-containing polymer also includes an enol form which is a tautomer of the general formula (2). Further, in the general formula (2), R ¹ , R ² and R ⁴ are alkenyl groups having 2 to 10 carbon atoms and having a double bond at the terminal or alkyl groups having 1 to 10 carbon atoms, and R ¹ , At least one of R ² and R ⁴ is an alkenyl group having a double bond at the terminal, and x, y, and z are 0 or 1.] (3) The polymer described in (1) above or the polymer described in (2) above. A metal surface treatment agent containing a combined composition as an active ingredient. Hereinafter, the present invention will be described in more detail. As long as R ¹ and R ² in the general formula (1) are hydrocarbon groups having 1 to 10 carbon atoms, the effects of the present invention can be sufficiently exhibited.
When the hydrocarbon group is long, it exhibits water repellency because the hydrocarbon group is oriented outward when the metal is surface-treated. When the hydrocarbon group is short, steric hindrance is reduced, so that the adsorptivity of the tricarbonyl group to metal is increased. That is, it is desirable that the number of carbon atoms in the hydrocarbon group varies depending on the type of metal used and its application. R ³ is a bond or has 1 to 8 carbon atoms
If it is an alkylene group, the effect of the present invention can be sufficiently exhibited, but if the alkylene group is short, the degree of freedom of the side chain tricarbonyl group becomes small, and it becomes difficult to adsorb on the metal surface, so that the alkylene group is preferably long. . Further, x, y, z are 0 or 1, and n is 5 to 100,000. Particularly preferable examples of the polymer represented by the above general formula (1) of the present invention include:

[0010]

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[0011]

[Chemical 6]

And the like. However, although the above compound describes only 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 will be described, but the enol form is also included).

[0013]

[Chemical 7]

The polymer having a repeating unit having a tricarbonyl group represented by the above general formula (1) of the present invention is
First, it is obtained by synthesizing a tricarbonyl compound having a double bond by the reaction represented by the reaction formula (3), and then polymerizing it with a polymerization initiator as a monomer.
During the polymerization reaction, a copolymerizable vinyl monomer may be allowed to coexist, and in this case, a copolymer of a repeating unit having a tricarbonyl group and a vinyl monomer unit is obtained. The vinyl monomer is not particularly limited as long as it has copolymerizability.

[0015]

Embedded image

[However, in the above formula, R ¹ , R ² and R ⁴
Is an alkyl group having 1 to 10 carbon atoms or 2 to 10 carbon atoms
Is an alkenyl group having a double bond at the terminal and only one of R ¹ , R ² and R ⁴ is the alkenyl group, and x, y and z represent 0 or 1] The compound represented by the general formula (2) includes a tricarbonyl compound represented by the general formula (2 ′), and any two or more of R ¹ , R ² and R ^{4 in} the compound have a double terminal. The case where it is an alkenyl group having a bond is also included. When such a tricarbonyl compound is polymerized as a monomer, a cross-linking reaction between the polymers also occurs, and a polymer including a cross-linked portion is obtained. By applying this polymer on a metal surface, a coating film having more excellent durability can be formed. In addition, since a double bond can be left in the obtained polymer, a stronger coating can be formed by heating the polymer after coating. Compound A represented by the above reaction formula (3) is acetyl chloride, propionyl chloride, butyryl chloride, t-butyl acetyl chloride, 2-ethylbutyryl chloride, valeryl chloride, isovaleryl chloride, 2-methylvaleryl. Chloride, hexanoyl chloride, 2-ethylhexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoyl chloride, decanoyl chloride, acrylic acid chloride, 1
0-undecenoyl chloride and the like. Alternatively, the carboxylic acid may be converted to an acid chloride with thionyl chloride, phosphorus trichloride, phosphorus pentachloride or the like.

The dicarbonyl compound represented by the above reaction formula (3) is 2,4-pentanedione, 2,2,2.
6,6-tetramethyl-3,5-heptanedione, methyl acetoacetate, ethyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, ethyl propionyl acetate,
Examples include ethyl butyryl acetate, dimethyl malonate, diethyl malonate, allyl acetoacetate and the like. The reaction of the above reaction formula (3) is described in the literature [M. W. Rathke, P.M.
J. Cowan, J .; Org. Chem. , 50 , 2
622, 1988 or J. Skarzewski, T
etrahedron, 45 , 4593 (1989)]
Can be synthesized based on. That is, a dicarbonyl compound and magnesium chloride are mixed in a reaction solvent to obtain a mixed solution, and an amine and a compound A 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 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. The polymerization of the tricarbonyl compound represented by the general formulas (2) and (2 ′) having the above double bond can be obtained by a general polymerization method such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization and the like. However, a radical polymerization method using an initiator such as azobisisobutyronitrile, cumene hydroperoxide, ditertiary butyl peroxide is simple and preferable. A reaction solvent is not particularly required, but a solvent such as water, tetrahydrofuran or toluene may be used. Further, these polymers are purified by a known means such as reprecipitation. When the polymer compound having a tricarbonyl group is used as a metal surface treatment agent, the target metal is not particularly limited, but it is preferable to use it as a surface treatment agent for copper, steel, aluminum and alloys thereof. . The film thickness is different depending on the type of metal and the use, but is preferably several molecular layers to several hundreds of μm. The above-mentioned polymer having a tricarbonyl group is diluted with a solvent such as alcohols such as methanol and ethanol, a solvent such as acetone and ethyl acetate to a concentration of 0.001 to 20% by weight, and a metal is immersed in this solution. It is convenient and preferable to apply the solution by showering the liquid on the metal.

[0019]

【Example】

I. Synthesis Example 1 of Polymer Having Tricarbonyl Group (Reaction of Methyl Acetoacetate with 10-Undecenoyl Chloride)

[0020]

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After fully replacing a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel with argon, 0.15 mol of methyl acetoacetate (17.2 mol.
g), methylene chloride 200 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 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. The reaction mixture 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 a double bond was obtained by distillation under reduced pressure [boiling point: 123.5 to 13].
0.0 ° C / 0.4mmHg, Yield: 81% (Yield: 3
3.8 g)]. It was confirmed by GC that the obtained compound was a single component, and ¹ H-NMR, ¹³ C-NMR, FT-
It was identified by IR. The results are shown in FIGS.
As shown in FIGS. 1 to 3, the following signals were observed. From the ¹ H-NMR integration ratio, it was confirmed that this compound exists in almost enol form.

[0022]

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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: 3.8 (s, 3H) d: 2.6 to 2.7 (t, 2H) e: 1.6 (m, 2H) f: 1.3 (m, 10H) g: 1.9 to 2.0 (m, 2H) h: 5.7 to 5.9 (m, 1H) i: 4.8 to 5.0 (m, 2H) [Fig. 2. ¹³ C-NMR (CDCl ₃ , δppm)] a: 25.7 b: 108.1 (enol form), 48.0 (keto form) c: 51.4 d: 37.8 e: 25.7 f: 28.9 to 29.8 g: 33.7 h: 138.9 i: 114.0 j or l: 195.6 or 199.0 k: 167.4 [Fig. 3. IR (cm ^-1 )] ν _CH : 2820 to 3030, ν _{C = O} : 1550 to 172
0 (Polymerization reaction) A 100 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel was sufficiently replaced with argon, and then 5.5 g of the tricarbonyl compound having the above double bond and di-t-butyl were added. 0.55 g of peroxide was added. After carrying out the polymerization reaction by stirring at 150 ° C. for 5.5 hours, the reaction mixture was dissolved in 5 ml of tetrahydrofuran,
The solution was added to 300 ml of methanol. The precipitated polymer was washed with methanol and then dried under reduced pressure to obtain a polymer A having a tricarbonyl group (yield 3.65).
g). This polymer is a pale yellow transparent viscous liquid,
Weight average molecular weight (M
It was confirmed that w) was 9000. Also, ¹ H−
The results of identification by NMR, ¹³ C-NMR, and FT-IR are shown in FIGS. As shown in FIGS. 4 to 6, the following signals were observed, and the results confirmed that polymer A had the following repeating units.

[0024]

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[FIG. 4. ¹ H-NMR (CDCl ₃ , δppm)] a: 2.3 (3H) b: 3.5, 5.4 (1H, keto form) c: 3.8 (3H) d: 1.2 to 1. 6 (16H) e: 1.2 to 1.6 (1H) f: 1.2 to 1.6 (2H) [Fig. ¹³ C-NMR (CDCl ₃ , δppm)] a, d, e, f: 23.0 to 46.0 b: 108.2 c: 51.8 g, h, i: 167.8 to 203.0 [ Figure 6. IR (cm ^-1 )] ν _CH : 2820 to 3030, ν _{C = O} : 1550 to 172
0 II. Synthesis Example 2 of Polymer Having Tricarbonyl Group (Reaction of Allyl Acetoacetate with Octanoyl Chloride)

[0026]

[Chemical 12]

A 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel was sufficiently replaced with argon, and then 0.06 mol (8.5) of allyl acetoacetate was added.
g), methylene chloride 70 ml, magnesium chloride 0.0
6 mol (5.7 g) was added. After cooling to 0 ° C., 0.12 mol (9.5 g) of pyridine was added, and the mixture was stirred for 15 minutes. Octanoyl chloride 0.06mo in the mixture
1 (9.8 g) was added dropwise, and the mixture was stirred at 0 ° C for 1 hour and then at 50 ° C for 2 hours. The reaction mixture is cooled to 0 ° C., 6
40 ml of mol / L hydrochloric acid was added dropwise. After stirring thoroughly,
The organic layer was washed with water and dried over magnesium sulfate. After removing the solvent, a tricarbonyl compound having a double bond was obtained by distillation under reduced pressure [boiling point: 102.2-104.1 ° C /
0.55 mmHg, Yield: 67% (Yield: 10.8
g)]. The obtained compound was confirmed to be a single component by GC, and identified by ¹ H-NMR, ¹³ C-NMR, and FT-IR. These results are shown in FIGS. FIG.
As shown in 9, the following signals were observed. This compound exists in keto form and enol form, and its abundance ratio is ¹ H.
From the NMR integration ratio, it was confirmed to be about 10:90 (keto type: enol type).

[0028]

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[FIG. 7. 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: 5.9 to 6.0 (m, 1H) e: 5.2 to 5.4 (m, 2H) f: 2.6 to 2.7 (m, 2H) g: 1.5 to 1.7 (m, 2H) h: 1.3 (m, 8H) i: 0.9 (m, 3H) [FIG. ¹³ C-NMR (CDCl ₃ , δppm)] a: 25.6 b: 108.1 (enol form), 48.0 (keto form) c: 65.5 d: 131.8 e: 118.9 f: 37.8 g: 25.8 h: 29.0 to 37.8 i: 14.0 j or 1: 198.9 or 195.7 k: 166.7 [Fig. 9. IR (cm ^-1 )] ν _CH : 2820 to 3030, ν _{C = O} : 1550 to 172
0 (Polymerization reaction) A 100 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel was sufficiently replaced with argon, and then 5.0 g of the tricarbonyl compound having the above double bond and di-t-butyl were added. 0.5 g of peroxide was added. After stirring at 150 ° C. for 24 hours to carry out a polymerization reaction,
The reaction mixture was dissolved in 1 g of acetone and the solution was added to 300 ml of methanol. The precipitated polymer was washed with methanol and then dried under reduced pressure to obtain a polymer B having a tricarbonyl group (yield 1.8 g). This polymer was a pale yellow transparent viscous liquid, and it was confirmed by GPC (in terms of polystyrene) that the weight average molecular weight (Mw) was 3,500. In addition, ¹ H-NMR, ¹³ C-NMR,
The results identified by FT-IR are shown in FIGS.
The side chain tricarbonyl group of the present polymer B is present in the keto form and the enol form according to the ¹ H-NMR integration ratio, and the abundance ratio is 40:60 (keto form: enol form). confirmed. As shown in FIGS. 10 to 12, the following signals were observed, and the results confirmed that polymer B had the following repeating units. Further, the side chain tricarbonyl group of the present polymer B exists in the keto form and the enol form based on the ¹ H-NMR integration ratio, and the abundance ratio is 4
It was confirmed to be 0:60 (keto type: enol type).

[0030]

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[FIG. 10. ¹ H-NMR (CDCl ₃ , δppm)] a: 2.3 (3H) b: 17.8 (enol form), 3.4 (keto form) c: 4.2 (2H) d, e, g, h, i: 0.8 to 2.6 (16H) f: 2.6 (2H) [Fig. 11. ¹³ C-NMR (CDCl ₃ , δppm)] a: 26.7 b: 108.3 (enol form), 49.1 (keto form) c: 64.0-68.0 d, e: 22.7- 43.3 f: 38.0 g: 26.7 h: 22.7, 30.1, 32.2 i: 14.2 j or l: 195.5 or 199.1 k: 167.2 [Fig. 12] ． IR (cm ^-1 )] ν _CH : 2820 to 3030, ν _{C = O} : 1550 to 172
0 III. Synthesis Example 3 of Polymer Having Tricarbonyl Group (Reaction of Allyl Acetoacetate with Acetyl Chloride)

[0032]

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A 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel was sufficiently replaced with argon, and then allyl acetoacetate (0.15 mol, 21.3 mol) was added.
g), methylene chloride 160 ml, magnesium chloride 0.
15 mol (14.3 g) was added. After cooling to 0 ° C., 0.3 mol (23.7 g) of pyridine was added,
Stirred for minutes. 0.15 m of acetyl chloride in the mixture
ol (11.8 g) was added dropwise, and the mixture was stirred at 0 ° C for 1 hr, and then 2
Stir at 50 ° C. for hours. The reaction mixture was cooled to 0 ° C,
100 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 a double bond was obtained by distillation under reduced pressure [boiling point: 55.3-57.5 ° C. /
1.1 mmHg, Yield: 56% (Yield: 15.5
g)]. The obtained compound was confirmed to be a single component by GC, and identified by ¹ H-NMR, ¹³ C-NMR, and FT-IR. These results are shown in FIGS. As shown in FIGS. 13 to 15, the following signals were observed. From the ¹ H-NMR integration ratio, it was confirmed that this compound exists in almost enol form.

[0034]

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[FIG. 13. ¹ H-NMR (CDCl ₃ , δppm)] a: 2.4 (s, 3H) b: 18.0 (s, enol form), 3.4 (s, keto form) c: 4.7 (m, 2H) d: 5.9 to 6.0 (m, 1H) e: 5.3 to 5.4 (m, 2H) f: 2.4 (s, 3H) [Fig. 14. ¹³ C-NMR (CDCl ₃ , δppm)] a: 26.0 b: 108.4 (enol form), 49.0 (keto form) c: 65.3 d: 131.8 e: 118.8 f: 26.0 g: 196.5 h: 166.5 i: 196.5 [Fig. 15. IR (cm ^-1 )] ν _CH : 2890-3100, ν _{C = O} : 1550-172
0 (Polymerization reaction) A 100 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel was sufficiently replaced with argon, and then 5.0 g of the tricarbonyl compound having the above double bond and di-t-butyl were added. 0.5 g of peroxide was added. After carrying out a polymerization reaction by stirring at 150 ° C. for 6 hours, the reaction mixture was dissolved in 5 ml of tetrahydrofuran, and the solution was added to 300 ml of methanol. The precipitated polymer was washed with methanol and then dried under reduced pressure to obtain a polymer C having a tricarbonyl group (yield 1.3 g). This polymer was a pale yellow transparent viscous liquid and had a weight average molecular weight (Mw) of 1800 according to GPC (polystyrene conversion).
Was confirmed. In addition, ¹ H-NMR, ¹³ C-
The results identified by NMR and FT-IR are shown in FIGS.
Shown in As shown in FIGS. 16 to 18, the following signals were confirmed, and from this result, it was confirmed that the polymer C had the following repeating unit. This polymer C is ¹ H-NMR
From the integral ratio of, it was confirmed that they exist in a keto form and an enol system, and the existence ratio is 50:50 (keto form: enol form).

[0036]

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[FIG. 16. ¹ H-NMR (CDCl ₃ , δppm)] a: 2.4 (3H) b: 17.9 (enol form), 3.5 (keto form) c: 4.2 (2H) d, e: 0. 8 to 2.8 f: 2.4 (3H) [FIG. 17. ¹³ C-NMR (CDCl ₃ , δppm)] a: 26.7 b: 108.3 (enol form), 50.0 (keto form) c: 64.6-67.0 d, e: 26.2 44.0 f: 26.7 g, i: 196.6 h: 167.0 [FIG. IR (cm ^-1 )] ν _CH : 2820 to 3030, ν _{C = O} : 1550 to 172
0 IV. Synthesis Example 4 of Polymer Having Tricarbonyl Group (Reaction of Allyl Acetoacetate with 10-Undecenoyl Chloride)

[0038]

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A 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel was sufficiently replaced with argon, and then allyl acetoacetate (0.15 mol, 21.0) was used.
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, ¹ H-NMR, ¹³
The results of identification by C-NMR and FT-IR are shown in FIG.
21. As shown in FIGS. 19 to 21, the following signals were observed. From the ¹ H-NMR integration ratio, it was confirmed that this compound exists in almost enol form.

[0040]

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[FIG. 19. 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. 20. ¹³ C-NMR (CDCl ₃ , δppm)] a: 25.7 b: 108.2 (enol form) c: 65.5 d: 131.9 e: 119.0 f: 28.8-37.8 g 139.0 h: 114.1 i or k: 195.8 or 199.1 j: 166.8 [FIG. 21. IR (cm ^-1 )] ν _CH : 2820 to 3030, ν _{C = O} : 1550 to 172
0 (Polymerization reaction) A 100 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel was sufficiently replaced with argon, and then 5.0 g of the tricarbonyl compound having the above double bond and di-t-butyl were added. 0.5 g of peroxide was added. After stirring at 150 ° C. for 50 minutes to carry out a polymerization reaction,
The reaction mixture was dissolved in 5 ml of tetrahydrofuran and the solution was added to 300 ml of methanol. The precipitated polymer was washed with methanol and dried under reduced pressure to obtain a polymer D having a tricarbonyl group (yield: 2.3 g). This polymer was a pale yellow transparent viscous liquid and was confirmed to be a polymer having a molecular weight distribution of several thousand to several million by GPC (polystyrene conversion). Also, ¹ H-NM
22 to 24 show the results of identification by R, ¹³ C-NMR and FT-IR. As shown in FIGS. 22 to 24, the following signals were observed, and the results confirmed that polymer D had the following repeating units.

[0042]

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[FIG. 22. ¹ H-NMR (CDCl ₃ , δppm)] a: 2.3 (3H) b: 13-14 (enol form), 3.4 (keto form) c: 4.0-4.7 (2H) d, e: 0.7 to 2.3 f: 1.3, 1.6, 2.0, 2.6 (16H) g, h: 0.7 to 2.3 d ': 6.0 to 6.1 e ′: 5.3 to 5.4 g ′: 5.8 to 6.0 h ′: 4.9 to 5.0 [FIG. 23. ¹³ C-NMR (CDCl ₃ , δppm)] a: 26.6 b: 108.3 (enol type), 48.0 (keto type) c: 65.7 d, e, g, h: 24.0 40.0 f: 29.5, 33.9, 38.0 i, k: 195.8, 199.1 j: 167.0 d ': 131.8 e': 119.2 g ': 139.1 h ′: 114.2 [FIG. 24. IR (cm ^-1 )] ν _CH : 2820 to 3030, ν _{C = O} : 1550 to 172
0 III. Anticorrosion test for copper Electrolytic copper foil (made by Nikko Gould Foil, JTC foil, thickness 75 μm, 4.5 × 4.5 cm) is degreased with acetone,
It was washed with a 3% aqueous sulfuric acid solution. A 6% methanol solution of the above-mentioned polymers A to D having a tricarbonyl group was applied to this copper foil with a spin coater and dried at 150 ° C. for 30 minutes to give a polymer A having a tricarbonyl group of 0.3 μm.
A thin film of D was prepared and used as a test piece. 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. In addition, heat treatment was performed at 180 ° C. for 30 minutes, and 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.

[0044]

[Table 1]

VI. 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. Polymer A having the above-mentioned tricarbonyl group on the surface of this carbon steel
After applying a predetermined concentration of methanol solution of ~ D (see Table 2 for concentration) with a spin coater (500 rotations, 60 seconds), 150
It was dried at 30 ° C. for 30 minutes to prepare thin films of polymers A to D having a tricarbonyl group, which were used as test pieces. 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. Further, the sample was dipped in a 3% sodium chloride aqueous solution for 24 hours, and the salt water resistance was evaluated by the degree of discoloration. The results are shown in Table 2. For comparison, the carbon steel to which nothing was applied was also evaluated in the same manner. The results are shown in Table 2.

[0046]

[Table 2]

VII. 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% or 0.1% methanol solution of the above-mentioned polymers A to D having a tricarbonyl group was applied to the surface of this aluminum plate with a spin coater (500 rotations, 60 seconds), followed by drying at 150 ° C for 30 minutes. Thin films of polymers A to D having carbonyl groups were prepared and used as test pieces. The test piece treated with 2% 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.
A 0.1% treated test piece was coated with a methanol solution of an epoxy resin (Epicoat 828: 100 parts, LX2S: 60 parts, methanol: 100 parts) by a spin coater,
Heat treatment was performed at 70 ° C. for 3 hours to form an epoxy resin film having a thickness of 20 μm. The test piece was dipped in 5% saline for 2 days and then a cross-cut test was conducted to evaluate the adhesiveness with the resin. The results are shown in Table 3. Further, as a comparison, the aluminum to which nothing was applied was similarly evaluated. The results are also shown in Table 3.

[0048]

[Table 3]

[0049]

INDUSTRIAL APPLICABILITY As described above, the novel polymer having a tricarbonyl group of the present invention is useful as a surface treatment agent for metal surfaces, especially for copper, steel and aluminum, and has an excellent rust preventive action. And has the effect of improving the adhesiveness with the resin.

[Brief description of drawings]

FIG. 1 ¹ H-NMR of the monomer obtained in Synthesis Example 1,

FIG. 2 is the same ¹³ C-NMR,

FIG. 3 is the same IR,

FIG. 4 ¹ H-NMR of polymer A obtained in Synthesis Example 1,

FIG. 5 shows the same ¹³ C-NMR,

FIG. 6 shows the same IR,

FIG. 7 ¹ H-NMR of the monomer obtained in Synthesis Example 2,

FIG. 8 is the same ¹³ C-NMR,

FIG. 9 is the same IR,

FIG. 10 ¹ H-NM of polymer B obtained in Synthesis Example 2
R,

FIG. 11 shows the same ¹³ C-NMR,

FIG. 12 is the same IR

FIG. 13 ¹ H-NMR of the monomer obtained in Synthesis Example 3,

FIG. 14 is the same ¹³ C-NMR,

FIG. 15 is the same IR

16: ¹ H-NM of polymer C obtained in Synthesis Example 3 FIG.
R,

FIG. 17 is the same ¹³ C-NMR,

FIG. 18 is the same IR

FIG. 19 is a ¹ H-NMR spectrum of the monomer obtained in Synthesis Example 4,

FIG. 20 shows the same ¹³ C-NMR,

FIG. 21 is the same IR,

FIG. 22 is ¹ H-NM of polymer D obtained in Synthesis Example 4.
R,

FIG. 23 shows the same ¹³ C-NMR,

FIG. 24 shows the same IR.

Claims (3)

[Claims] 1. A tricarbonyl group-containing polymer having a repeating unit represented by the following general formula (1). Embedded image [However, the tricarbonyl group-containing polymer also includes an enol form which is a tautomer of the general formula (1). Also,
In the general formula (1), R ¹ and R ² are alkyl groups having 1 to 10 carbon atoms, R ³ is a bond or an alkylene group having 1 to 8 carbon atoms, and x, y, and z are 0 or 1. ] 2. A polymer obtained by polymerizing a compound having three carbonyl groups represented by the following general formula (2) and one or more double bonds. Embedded image [However, the tricarbonyl group-containing polymer also includes an enol form which is a tautomer of the general formula (2). Also,
In the general formula (2), R ¹ , R ² and R ⁴ have 2 to 1 carbon atoms.
An alkenyl group having a double bond at the terminal of 0 or an alkyl group having 1 to 10 carbon atoms, and at least one of R ¹ , R ² and R ⁴ is an alkenyl group having a double bond at the terminal, x, y and z represent 0 or 1] 3. A metal surface treating agent comprising the polymer according to claim 1 or the polymer composition according to claim 2 as an active ingredient.