JPH11349550A - New polyoxyethylenealkylphenyl ether derivative and its production and metal surface-treating agent using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of forming coating films having excellent adhesiveness to metal materials and capable of imparting excellent corrosion resistance to the surfaces of the metal materials, and useful an active ingredient for metal surface-treating agents. SOLUTION: A compound of formula I [(m) and (n) are each 1-20]. For example, a compound of formula II. The compound of formula I is preferably obtained by reacting 1 mole of a polyoxyethylene alkylphenyl ether of formula III with 1-2 moles of a phenyl isocyanate compound of formula IV in an organic solvent such as ethyl acetate r preferably in the absence of a solvent preferably in the presence of a catalyst such as dibutyltin laurate at 20-100 deg.C for about 30 min to about 10 hr.

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 preventing rust of a metal material, and particularly suitable as a discoloration preventing agent for silver, gold, copper, nickel, iron, aluminum, zinc or an alloy thereof. The present invention relates to a novel polyoxyethylene alkylphenol ether derivative, a method for producing the same, and uses thereof.

[0002]

2. Description of the Related Art Polyoxyethylene alkylphenols are nonionic surfactants and are widely used industrially as detergents, emulsifiers, antistatic agents, defoamers and wetting penetrants. When this type of compound is considered as a metal surface treatment agent, a hydrophilic part (polyoxyethylene part) that is adsorbable to metal and a hydrophobic part that imparts hydrophobicity to the surface and imparts functions such as water resistance are provided. (Alkylphenol moiety), and a patent for a silver discoloration inhibitor containing the active ingredient as an active ingredient has been filed (Japanese Patent Publication No. 61-55596). We have also applied for a patent (Japanese Patent Application No. 9-4594) that a compound obtained by introducing an alkoxysilyl group into a polyoxyethylene alkylphenol ether provides a highly durable metal surface treating agent. When a compound of this system is used as a discoloration inhibitor such as silver in combination with a long-chain alkyl mercaptan, it is said that the compound exhibits two functions, that is, an action of promoting the adsorption of the long-chain alkyl mercaptan to a metal and an action of emulsifying. However, when a metal is surface-treated with an aqueous solution-based surface treating agent and the surface is washed with water, polyoxyethylene alkylphenol ether has a high water solubility, so that a sufficient amount of the active ingredient to be adsorbed cannot be obtained. In the case of, the initial properties were good, but there was a risk of gelation due to hydrolysis and condensation in an aqueous solution.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal surface treating agent capable of forming a film with excellent adhesion to a metal material and imparting excellent rust prevention to the surface. Is what you do.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a metal surface treating agent containing at least one specific polyoxyethylene alkylphenol ether derivative as an active ingredient. And found the present invention. That is, the present invention provides (1) a novel polyoxyethylene alkylphenol ether derivative represented by the following general formula (1).

[0005]

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(2) The method according to (1), wherein the polyoxyethylene alkylphenol ether represented by the following general formula (2) is reacted with a phenyl isocyanate compound represented by the following general formula (3). The method for producing the polyoxyethylene alkylphenol ether derivative according to the above.

[0007]

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(3) A metal surface treating agent comprising as an active ingredient at least one of the polyoxyethylene alkylphenol ether derivatives represented by the general formula (1) described in the above (1); A metal surface treatment agent comprising: at least one polyoxyethylene alkylphenol ether derivative represented by the general formula (1) described in (1), at least one alkyl mercaptan, and a solvent; 5) At least one polyoxyethylene alkylphenol ether derivative represented by the general formula (1) described in (1), at least one alkyl mercaptan, at least one polyoxyethylene surfactant, and a solvent And a metal surface treating agent characterized by containing

In the above formula, m is from 1 to 20, preferably from 8 to 12. In the above general formula, n is 1 to 20, but 2 to 9 is preferable from the viewpoint of rust prevention. In addition, since it is difficult to obtain a single substance having the same n value in the synthesis of a polyoxyethylene alkylphenol ether compound, n has a certain distribution, and the n value shown in the following examples is an integer value close to the average value. It is.

The novel polyoxyethylene alkylphenol ether derivative represented by the general formula (1) of the present invention is represented by the general formula (3) and the polyoxyethylene alkylphenol ether compound represented by the general formula (2). It can be easily produced by reacting with a phenyl isocyanate compound at 20 to 100 ° C.

The compound represented by the general formula (2) includes
For example

[0012]

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And the like.

In the reaction of the polyoxyethylene alkylphenol compound represented by the general formula (2) with the phenyl isocyanate compound, an organic solvent such as ethyl acetate may be used, but it is convenient to carry out the reaction without a solvent. preferable. It is preferable to react 1 to 2 moles of the phenyl isocyanate compound with respect to 1 mole of the polyoxyethylene alkylphenol ether compound of the formula (2). The reaction time is about 30 minutes to 10 hours. It is preferable to use a catalyst for this reaction, so that the reaction can be promoted. Examples of such a catalyst include dibutyltin laurate.

Particularly preferred examples of the novel polyoxyethylene alkylphenol ether derivative represented by the general formula (1) of the present invention are described below.

[0016]

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The novel polyoxyethylene alkylphenol ether derivative of the present invention is suitable as a metal surface treating agent. The film of the polyoxyethylene alkylphenol ether derivative of the present invention formed on the metal surface can significantly improve the rust prevention of the metal.

The metal surface treating agent of the present invention will be described in more detail. The target metal is not particularly limited. For example, it is effective as a surface treatment agent for silver, gold, copper, iron, aluminum, zinc, and alloys thereof. However, it is more preferable to use it as a surface treatment agent for silver, gold, and copper, and particularly to a surface treatment agent for copper foil used for silver-plated, gold-plated electronic components, copper-clad laminates for printed circuits, and the like. When used as a (color-change inhibitor), the effects of the present invention can be sufficiently exhibited.

In the metal surface treating agent of the present invention, at least one of the above polyoxyethylene alkylphenyl ether derivatives is at least one of alcohols such as methanol, ethanol and i-propanol, ketones such as acetone and methyl isobutyl ketone, and water. It is simple and preferable to dilute the solution to a concentration of 0.01 to 20% and immerse the metal in the solution. The polyoxyethylene alkylphenol ether derivative may be used alone, or may be mixed with another rust inhibitor, a coupling agent, a surfactant, or the like. Another preferred rust inhibitor is an alkyl mercaptan. The alkyl of the alkyl mercaptan preferably has 14 to 20 carbon atoms. A preferred surfactant is polyoxyethylene alkylphenyl ether. The alkyl of the polyoxyethylene alkyl phenyl ether preferably has 8 to 12 carbon atoms, and the ethylene oxide of the polyoxyethylene alkyl phenyl ether preferably has an addition mole number of 5 to 12.

[0020]

Example 1 Synthesis of polyoxyethylene alkyl phenyl ether derivative (1-1) A polyoxyethylene alkyl phenol ether compound represented by the following formula (2-1) and a compound represented by the following formula (3-1) By the reaction with phenyl isocyanate, the following formula (1-
Synthesis of the compound represented by 1).

9.68 g of a polyoxyethylene alkylphenol ether compound represented by the following formula (2-1)
(0.02 mol), 1 drop of dibutyltin laurate as a reaction catalyst was added and stirred at room temperature to dissolve. To this solution was added phenyl isocyanate represented by the following formula (3-1).
38 g (0.02 mol) was added dropwise over 10 minutes and reacted at room temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 50 ° C., and the reaction was further continued for 1 hour and 30 minutes. The solution after the reaction was obtained as a transparent and viscous liquid. The polyoxyethylene alkylphenol derivative as a reaction product was identified by FT-IR and NMR.

[0022]

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Example 2 Synthesis of polyoxyethylene alkyl phenyl ether derivative (1-2) Polyoxyethylene alkyl phenol ether compound represented by the following formula (2-2) and isocyanate represented by the following formula (3-1) The following formula (1-
Synthesis of the compound represented by 2).

6.16 g of a polyoxyethylene alkylphenol ether compound represented by the following formula (2-2)
(0.02 mol), 1 drop of dibutyltin laurate as a reaction catalyst was added and stirred at room temperature to dissolve. To this solution was added phenyl isocyanate represented by the formula (3-1).
38 g (0.02 mol) was added dropwise over 10 minutes and reacted at room temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 50 ° C., and the reaction was further continued for 1 hour and 30 minutes. The solution after the reaction was obtained as a transparent and viscous liquid. The polyoxyethylene alkylphenol derivative as a reaction product was identified by FT-IR and NMR.

[0025]

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Example 3 Synthesis of polyoxyethylene alkyl phenyl ether derivative (1-3) A polyoxyethylene alkyl phenol ether compound represented by the following formula (2-3) and an isocyanate represented by the following formula (3-1) The following formula (1-
Synthesis of the compound represented by 3).

7.45 g of a polyoxyethylene alkylphenol ether compound represented by the following formula (2-3)
(0.02 mol), 1 drop of dibutyltin laurate as a reaction catalyst was added and stirred at room temperature to dissolve. To this solution was added phenyl isocyanate represented by the formula (3-1).
38 g (0.02 mol) was added dropwise over 10 minutes and reacted at room temperature for 1 hour. Thereafter, the temperature of the reaction solution was raised to 50 ° C., and the reaction was further continued for 1 hour and 30 minutes. The solution after the reaction was obtained as a transparent and viscous liquid. The polyoxyethylene alkylphenol derivative as a reaction product was identified by FT-IR and NMR.

[0028]

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Example 4 The above formulas (1-1) and (1-) were added to 5 ml of isopropanol.
2), 0.04 g of the polyoxyethylene alkylphenol ether derivative represented by (1-3) and 0.06 g of hexadecyl mercaptan were dissolved. This solution was added dropwise to 95 ml of pure water while stirring to prepare a metal surface treatment liquid. This solution was heated to 40 ° C., and a silver-plated test piece was immersed for 1 minute, then the surface was washed with pure water and dried to prepare a surface-treated sample. The rust prevention of the obtained sample was evaluated by immersing the test piece in an aqueous solution of ammonium sulfide and visually observing the degree of discoloration. The outline of the evaluation is shown below.

Test solution: 0.2% aqueous solution of ammonium sulfide Immersion time: 30 minutes The evaluation results obtained are shown in Table 1.

[0031]

[Table 1]

Example 4-1: When the compound represented by the formula (1-1) is used as the polyoxyethylene alkylphenol ether derivative Example 4-2: The compound represented by the formula (1- When the compound represented by 2) is used Example 4-3: When the compound represented by the formula (1-3) is used as the polyoxyethylene alkylphenol ether derivative Comparative Example 1: Polyoxyethylene alkylphenol ether derivative In the case where the polyoxyethylene alkylphenol ether compound represented by the formula (2-1) is used in place of the above Comparative Example 2: Polyoxyethylene represented by the formula (2-2) instead of the polyoxyethylene alkylphenol ether derivative Using ethylene alkyl phenol ether compound Comparative Example 3: When a polyoxyethylene alkylphenol ether compound represented by the above formula (2-3) was used instead of the polyoxyethylene alkylphenol ether derivative Comparative Example 4: Untreated Example 5 Example 4-1 Using the metal surface treatment solution prepared in the above section, the evaluation of the discoloration prevention property for copper was performed. The copper foil used for the evaluation is an electrolytic copper foil.

Evaluation was made by leaving the surface-treated copper foil in a constant temperature / humidity bath at 80 ° C. and a relative humidity of 95% for 24 hours, and visually evaluating the degree of discoloration. The evaluation results are shown below.

[0034]

[Table 2]

Example 5: Using the metal surface treating agent described in Example 4-1 Comparative Example 5: Untreated Example 6 Using the metal surface treating solution prepared in Example 4, the following base materials were used. The anti-discoloration property was evaluated.

(Substrate) After nickel plating on a brass substrate, (1) gold, (2) gold-copper, (3)
Test piece plated with tin-zinc-nickel (Evaluation method) Artificial sweat immersion test The test piece was immersed in an artificial sweat solution and stored in a 50 ° C constant temperature bath for 16 hours.

Artificial sweat solution: 9.9 g of sodium chloride, 0.8 g of sodium sulfide, 1.7 g of urea, 0.067 ml of aqueous ammonia, 1.1 ml of lactic acid, 0.2 g of sucrose, 990 ml of pure water Table 3 shows the evaluation results. Show.

[0038]

[Table 3]

Example 6: Using the metal surface treating agent described in Example 4-1 Comparative Example 6: Untreated

[0040]

From the above results, it has been found that the novel polyoxyethylene alkylphenol ether derivative according to the present invention is effective as a metal surface treatment agent for improving rust resistance.

[Brief description of the drawings]

¹ H-NMR of [1] alkylphenol ethoxylate derivative obtained in Example 1 (1-1)
chart.

FIG. 2 is a ¹³ C-NMR of the polyoxyethylene alkylphenol ether derivative (1-1) obtained in Example 1.
chart.

FIG. 3 is an FT-IR chart of the polyoxyethylene alkylphenol ether derivative (1-1) obtained in Example 1.

FIG. 4 is a ¹ H-NMR chart of a polyoxyethylene alkylphenol derivative (1-2) obtained in Example 2.

FIG. 5 is a ¹³ C-NMR of the polyoxyethylene alkylphenol ether derivative (1-2) obtained in Example 2.
chart.

FIG. 6 is an FT-IR chart of the polyoxyethylene alkylphenol ether derivative (1-2) obtained in Example 2.

FIG. 7 is a ¹ H-NMR of the polyoxyethylene alkylphenol ether derivative (1-3) obtained in Example 3.
chart.

FIG. 8 is a ¹³ C-NMR of the polyoxyethylene alkylphenol ether derivative (1-3) obtained in Example 3.
chart.

FIG. 9 is an FT-IR chart of the polyoxyethylene alkyl ether derivative (1-3) obtained in Example 3.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hisashi Nakamura 2-10-1, Toranomon, Minato-ku, Tokyo Inside Japan Energy Corporation

Claims (5)

[Claims] 1. A novel polyoxyethylene alkylphenol ether derivative represented by the following general formula (1). Embedded image 2. The method according to claim 1, wherein a polyoxyethylene alkylphenol ether represented by the following general formula (2) is reacted with a phenyl isocyanate compound represented by the following general formula (3). A method for producing a polyoxyethylene alkylphenol ether derivative. Embedded image 3. A metal surface treating agent comprising as an active ingredient at least one of the polyoxyethylene alkylphenol ether derivatives represented by the general formula (1) according to claim 1. 4. A metal comprising at least one polyoxyethylene alkylphenol ether derivative represented by the general formula (1) according to claim 1, at least one alkyl mercaptan, and a solvent. Surface treatment agent. 5. A polyoxyethylene alkylphenol ether derivative represented by the general formula (1) according to claim 1, at least one alkyl mercaptan, at least one polyoxyethylene surfactant, And a solvent.