JP3382852B2 - Novel polyoxyethylene alkylphenol ether derivative, method for producing the same, and metal surface treating agent using the same - Google Patents

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 rust prevention of metallic materials, and is particularly suitable as a discoloration inhibitor for silver, gold, copper, nickel, iron, aluminum, zinc or alloys 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 alkylphenol is a nonionic surfactant, which is widely used industrially as a detergent, an emulsifier, an antistatic agent, an antifoaming agent, and a wet penetrant. When this type of compound is considered as a metal surface treatment agent, a hydrophilic part (polyoxyethylene part) that adsorbs metal and a hydrophobic part that imparts hydrophobicity to the surface and imparts functions such as water resistance It is composed of an (alkylphenol part), and a patent for a silver discoloration inhibitor containing the same as an active ingredient has been filed (Japanese Patent Publication No. 61-55596). We also applied for a patent that a compound obtained by introducing an alkoxysilyl group into polyoxyethylene alkylphenol ether provides a highly durable metal surface treatment agent (Japanese Patent Application No. 9-4594). When this type of compound is combined with a long-chain alkyl mercaptan to form a discoloration preventing agent such as silver, it is said to exhibit two functions of promoting the adsorption of the long-chain alkyl mercaptan to a metal and emulsifying it. However, when a metal is surface-treated with an aqueous surface-treating agent and the surface is washed with water, polyoxyethylene alkylphenol ether has a high water solubility, so that a sufficient adsorption amount of the active ingredient cannot be obtained, and the alkoxysilyl derivative is not obtained. In the case of, the initial properties were good, but there was a risk of gelation due to hydrolysis condensation in an aqueous solution.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a metal surface treating agent capable of forming a film with excellent adhesion to a metal material and imparting excellent rust preventive property to the surface. To do.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventor can solve the above problems by using a metal surface treating agent containing at least one specific polyoxyethylene alkylphenol ether derivative as an active ingredient. The present invention has been completed and the present invention has been achieved. The present invention provides: (1) lower
Novel polyoxyethylene al represented by general formula (1)
Effective with at least one of the killphenol ether derivatives
A metal surface treatment agent characterized by being a component,

[0005]

[Chemical 3]

[0006]

[0007]

(2) A metal containing at least one polyoxyethylene alkylphenol ether derivative represented by the general formula (1) described in (1 ) above, at least one alkyl mercaptan, and a solvent. Surface treatment agent, (3) at least one polyoxyethylene alkylphenol ether derivative represented by the general formula (1) described in (1 ) above, at least one alkyl mercaptan, at least one polyoxyethylene-based surfactant, And a solvent, which is a metal surface treatment agent.

In the above general formula, m is 1 to 20, preferably 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. Further, 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 etc. is an integer value close to the average value. Is.

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

[Chemical 4]

As the compound represented by the general formula (2),
For example

[0012]

[Chemical 5]

Etc. are preferred.

The reaction of the polyoxyethylene alkylphenol compound represented by the general formula (2) with the phenyl isocyanate compound may use an organic solvent such as ethyl acetate, but it is simple to carry out the reaction without a solvent. preferable. It is preferable to react 1 to 2 mol of the phenyl isocyanate compound with 1 mol of the polyoxyethylene alkylphenol ether compound of the general 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 accelerated. Examples of such a catalyst include dibutyltin laurate.

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

[0016]

[Chemical 6]

The novel polyoxyethylene alkylphenol ether derivative of the present invention is suitable as a surface treatment agent for metals. The film of the polyoxyethylene alkylphenol ether derivative of the present invention formed on the surface of a metal can remarkably improve the rust preventive property of the metal.

The metal surface treating agent of the present invention will be described in more detail. There are no particular restrictions on the target metal. 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 in particular, a surface treatment agent for copper foil used for silver-plated and gold-plated electronic components and copper-clad laminates for printed circuits. When used as a (discoloration preventing agent), 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 polyoxyethylene alkylphenyl ether derivatives is an alcohol such as methanol, ethanol or i-propanol, a ketone such as acetone or methyl isobutyl ketone, or water. It is simple and preferable to perform surface treatment by diluting the solution to 0.01 to 20% and immersing the metal in this solution. The polyoxyethylene alkylphenol ether derivative may be used alone, or may be mixed with another rust preventive agent, a coupling agent, a surfactant or the like. Alkyl mercaptans are preferred as other rust inhibitors. The alkyl of the alkyl mercaptan preferably has 14 to 20 carbon atoms. A preferable surfactant is polyoxyethylene alkylphenyl ether. The alkyl of the polyoxyethylene alkylphenyl ether preferably has 8 to 12 carbon atoms, and the ethylene oxide of the polyoxyethylene alkylphenyl ether preferably has 5 to 12 added moles.

[0020]

Example 1 Synthesis of polyoxyethylene alkylphenyl ether derivative (1-1) Polyoxyethylene alkylphenol ether compound represented by the following formula (2-1) and 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)
One drop of a reaction catalyst, dibutyltin laurate, was added to (0.02 mol) and stirred at room temperature to dissolve. 1. Phenyl isocyanate represented by the following formula (3-1) was added to this solution.2.
38 g (0.02 mol) was added dropwise over 10 minutes, and the mixture was reacted at room temperature for 1 hour. Then, 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 viscous liquid. Identification of the polyoxyethylene alkylphenol derivative which is a reaction product was performed by FT-IR and NMR.

[0022]

[Chemical 7]

Example 2 Synthesis of polyoxyethylene alkylphenyl ether derivative (1-2) Polyoxyethylene alkylphenol ether compound represented by the following formula (2-2) and isocyan represented by the following formula (3-1) The following formula (1-
Synthesis of the compound represented by 2).

6.16 g of polyoxyethylene alkylphenol ether compound represented by the following formula (2-2)
One drop of a reaction catalyst, dibutyltin laurate, was added to (0.02 mol) and stirred at room temperature to dissolve. To this solution, phenyl isocyanate represented by the above formula (3-1) 2.
38 g (0.02 mol) was added dropwise over 10 minutes, and the mixture was reacted at room temperature for 1 hour. Then, 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 viscous liquid. Identification of the polyoxyethylene alkylphenol derivative which is a reaction product was performed by FT-IR and NMR.

[0025]

[Chemical 8]

Example 3 Synthesis of polyoxyethylene alkylphenyl ether derivative (1-3) Polyoxyethylene alkylphenol ether compound represented by the following formula (2-3) and isocyan 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)
One drop of a reaction catalyst, dibutyltin laurate, was added to (0.02 mol) and stirred at room temperature to dissolve. To this solution, phenyl isocyanate represented by the above formula (3-1) 2.
38 g (0.02 mol) was added dropwise over 10 minutes, and the mixture was reacted at room temperature for 1 hour. Then, 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 viscous liquid. Identification of the polyoxyethylene alkylphenol derivative which is a reaction product was performed by FT-IR and NMR.

[0028]

[Chemical 9]

Example 4 In 5 ml of isopropanol, the above formulas (1-1) and (1-
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. The solution was heated to 40 ° C., the test piece plated with silver was immersed for 1 minute, the surface was washed with pure water, and then dried to prepare a surface-treated sample. For the evaluation of the rustproof property of the obtained sample, the test piece was immersed in an aqueous solution of ammonium sulfide and the degree of discoloration was visually observed. The outline of the evaluation is shown below.

[0030] Test solution: 0.2% ammonium sulfide solution Immersion time: 30 minutes Table 1 shows the obtained evaluation results.

[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-) as the polyoxyethylene alkylphenol ether derivative is used. When using the compound represented by 2) Example 4-3: When using the compound represented by the formula (1-3) as the polyoxyethylene alkylphenol ether derivative Comparative Example 1: Polyoxyethylene alkylphenol ether derivative When a polyoxyethylene alkylphenol ether compound represented by the above formula (2-1) is used in place of Comparative Example 2: Polyoxy compound represented by the above formula (2-2) in place of the polyoxyethylene alkylphenol ether derivative Using an ethylene alkylphenol ether compound Comparative Example 3: When using a polyoxyethylene alkylphenol ether compound represented by the above formula (2-3) instead of the polyoxyethylene alkylphenol ether derivative Comparative Example 4: Untreated Example 5 In Example 4-1 Using the prepared metal surface treatment liquid, the discoloration preventive property for copper was evaluated. The copper foil used for evaluation is an electrolytic copper foil.

For the evaluation, the surface-treated copper foil was left to stand in a thermo-hygrostat at 80 ° C. and a relative humidity of 95% for 24 hours, and the degree of discoloration was visually evaluated. 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 liquid prepared in Example 4, the following base materials were used. The discoloration preventing property was evaluated.

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

Artificial sweat solution: sodium chloride 9.9 g, sodium sulfide 0.8 g, urea 1.7 g,% ammonia water 0.067 ml, lactic acid 1.1 ml, sucrose 0.2 g, pure water 990 ml 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 was revealed that the novel polyoxyethylene alkylphenol ether derivative according to the present invention is effective as a metal surface treating agent for improving the rust preventive property.

[Brief description of drawings]

FIG. 1 ¹ H-NMR of polyoxyethylene alkylphenol ether derivative (1-1) obtained in Example 1.
chart.

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

FIG. 3 is an FT-IR chart for 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 ¹³ C-NMR of the polyoxyethylene alkylphenol ether derivative (1-2) obtained in Example 2.
chart.

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

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

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

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

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hisashi Nakamura Hisashi Nakamura 2-10-1 Toranomon, Minato-ku, Tokyo Within Japan Energy Co., Ltd. (56) Reference JP-A-4-214564 (JP, A) US Patent 6294502 ( (US, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C23F 11/00 C23C 22/00 C07C 269/02 C07C 271/28 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A metal surface treating agent comprising at least one of novel polyoxyethylene alkylphenol ether derivatives represented by the following general formula (1) as an active ingredient. [Chemical 1] 2. A metal surface treatment 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. Agent. 3. At least one 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. A metal surface-treating agent comprising: