JPH10195081A - New polyethylene glycol phenyl ether derivative, its production and metallic surface treatment agent, using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a metallic surface treatment agent for rust prevention of metallic materials. SOLUTION: This mew compound is expressed by formula I (R1 and R2 are each a lower alkyl; Cm H2m+1 is an alkyl which may be branched; (m) is 1-20; (n) is 1-20; (p) is 1-20; (1) is 0-3), for example, a compound of formula II. The compound of formula I is obtained by reacting 1-2mols of an isocyanate silane compound of formula IV with 1mol of polyethylene glycol phenyl ether of formula III, preferably, in the absence of any solvent, in the presence of a catalyst (e.g., dibutyltin laurate) at 20-100 deg.C for 30min to 1hr. A metallic surface treatment agent that contains the subject compound either singly or, in combination with other corrosion inhibitor, coupler, surfactant and the like, as needed, is suitable as a discoloration inhibitor, through forming a film with excellent adhesion to silver, gold, copper nickel or other metals or alloys of these metals and the like.

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 as a discoloration preventing agent for silver, gold, copper, nickel, iron, aluminum, zinc or an alloy thereof. The present invention relates to suitable novel polyethylene glycol phenyl ether derivatives, a method for producing the same, and uses thereof.

[0002]

2. Description of the Related Art Polyethylene glycol phenyl ether is a nonionic surfactant, and has a detergent, an emulsifier,
It is widely used industrially as an antistatic agent, an antifoaming agent, and a wet penetrant. When considering the application as a metal surface treatment agent, this group of compounds imparts hydrophilicity (polyethylene glycol portion) with metal and hydrophobicity to the surface and imparts functions such as water resistance. It is considered that it has the potential to become an excellent metal surface treatment agent if the adsorptivity and the durability of the treated film are sufficient if it is composed of a hydrophobic portion (alkylphenol portion). In general, there are two methods for improving the durability of the organic film, a method using a polymer that has been polymerized in advance, and a method that uses a polymer on a substrate. The former is polymerized in advance,
Although the durability of the film itself is high, it has drawbacks such as the limitation of the diluent solvent and the above-mentioned lack of orientation of the molecular chains. On the other hand, in the latter method, it is necessary to introduce a site to be polymerized, but introduction of an alkoxylyl group is expected to improve both the durability of the polymer film and the adsorptivity to the substrate. In other words, by introducing an alkoxysilyl group into polyethylene glycol phenyl ether to form a polymer by a siloxane bond on the base material and at the same time forming some chemical bond with the base material by a silanol group, an excellent metal It was thought that a surface treatment agent could be obtained.

[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]

As a result of intensive studies, the present inventor has found that the above problem can be solved by a metal treating agent comprising at least one specific polyethylene glycol phenyl ether derivative as an active ingredient. Heading, and led to the present invention. The gist is (1) a novel polyethylene glycol phenyl ether derivative represented by the following general formula (1),

[0005]

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(Wherein R ₁ and R ₂ are lower alkyl groups, C _m H _{2m + 1} is an optionally branched alkyl group, m is 1 to 20, n is 1 to 20, and p is (1 to 20, l represents 0 to 3) (2) The reaction is performed by reacting a polyethylene glycol phenyl ether represented by the following general formula (2) with an isocyanate silane compound represented by the following general formula (3). A method for producing a polyethylene glycol phenyl ether derivative according to claim 1,

[0007]

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(Wherein, R ₁ and R ₂ are lower alkyl groups, C _m H _{2m + 1} is an optionally branched alkyl group, m is 1 to 20, n is 1 to 20, and p is (1) a metal surface comprising at least one of the polyethylene glycol phenyl ether derivatives represented by the general formula (1) according to claim 1 as an active ingredient. Treatment agent.

In the above formula, m is 1 to 20, preferably 7 to 10. If it exceeds 10, the solubility in the solvent is not sufficient, and if it is less than 7, the rust-preventive properties decrease. In the above general formula, n is 1 to 20, and particularly preferably 6 to 10 from the viewpoint of rust prevention. In the above formula, l is 0
To 3, but 3 is particularly preferable from the viewpoint of rust prevention. In the above formula, p is from 1 to 20, preferably from 1 to 5.
When the molecular weight is 6 or more, the orientation of the molecules is not sufficient, and is not suitable as a metal surface treatment agent. In the above formula, R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, that is, methyl, ethyl, n-propyl,
i-propyl, n-butyl, isobutyl and t-butyl are shown.

The novel polyethylene glycol phenyl ether derivative represented by the general formula (1) of the present invention comprises a polyethylene glycol phenyl ether compound represented by the general formula (2) and an isocyanate represented by the general formula (3) It can be easily produced by reacting with a silane 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 isocyanate silane compound represented by the general formula (3), R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, ie, methyl, ethyl, n-propyl,
i-propyl, n-butyl, isobutyl and t-butyl are shown. p is 1-20, preferably 1-5.
Particularly preferred as the isocyanate silane compound,

[0015]

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## EQU1 ## In the reaction between the polyethylene glycol phenyl ether compound represented by the general formula (2) and the isocyanate silane compound, an organic solvent such as ethyl acetate may be used, but it is convenient and preferable to carry out the reaction without a solvent. It is preferable to react 1 to 2 mol of an isocyanate silane compound with respect to 1 mol of the polyethylene glycol phenyl 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 promoted. Examples of such a catalyst include dibutyltin laurate.

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

[0018]

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The novel polyethylene glycol phenyl derivative of the present invention is suitable as a metal surface treating agent. The coating of the novel polyethylene glycol phenyl ether derivative of the present invention formed on the metal surface can remarkably 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. But silver,
It is more preferably used as a surface treatment agent for gold and copper, and is particularly used as a surface treatment agent for copper foil used for silver-plated, gold-plated electronic components, copper-clad laminates for printed circuits, and the like. In such a case, 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-mentioned polyethylene glycol phenyl ether derivatives is formed from alcohol such as methanol, ethanol and i-propanol, ketones such as acetone and methyl isobutyl ketone or water. It is simple and preferable to dilute the solution so as to have a concentration of 01 to 20% and immerse the metal in this solution. The surface treating agent of the present invention hydrolyzes an alkoxysilyl group to form -Si (O
H) ₃ and a sikirose bond (Si-OS) on the substrate
It is preferable to increase the polymer to i) in order to enhance the rust prevention effect.

The polyethylene glycol phenyl ether derivative may be used alone, but may be used in combination with another rust inhibitor or other additives such as a coupling agent and a surfactant, if necessary. Good.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the following examples.

[0024]

【Example】

Example 1 Polyethylene glycol phenyl ether derivative (1-
Synthesis of 1) Polyethylene glycol phenyl ether compound represented by the following formula (2-1) and 3 represented by the following formula (3-1)
-Synthesis of the compound represented by the formula (1-1) from the reaction with isocyanatopropyltriethoxysilane

[0025]

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12.04 g of polyethylene glycol phenyl ether compound represented by the above formula (2-1) (0.
02 mol), several drops of a reaction catalyst, cibutyltin laurate, were added and stirred at room temperature to dissolve. To this solution, 4.94 g (0.02 mol) of 3-isocyanatopropyltriethoxysilane represented by the above formula (3-1) 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 polyethylene glycol phenyl ether derivative represented by the formula (1-1), which is a reaction product, was identified by FT-IR and NMR. The respective charts are shown in FIGS.

Evaluation of polyethylene glycol phenyl ether derivative as metal surface treating agent Example 2 1 g of the polyethylene glycol phenyl ether derivative represented by the above formula (1-1) was dissolved in a mixed solvent of 113 g of pure water and 113 g of acetone. Thereafter, an appropriate amount of acetic acid was added dropwise to this solution, and the pH of the solution was adjusted to 5 to complete the hydrolysis reaction of the alkoxysilyl group. Further, a solution prepared by dissolving 1 g of hexadecyl mercaptan as another rust inhibitor in 20 g of isopropanol was added to this solution to prepare a metal surface treatment solution. Gold strike plating (0.05μm) and silver plating (5μ)
After the test piece subjected to m) was immersed, a drying treatment was performed at 100 ° C. for 30 minutes to produce a surface-treated sample. The rust prevention of the obtained sample was evaluated by immersing the test piece in ammonium sulfide and visually checking the degree of discoloration. The outline of the evaluation method is shown below.

Test solution: 0.2% aqueous solution of ammonium sulfide Immersion time: 6 hours The evaluation results obtained are shown in Table 1.

[0029]

[Table 1]

Example 2-1: Using the metal surface treating agent described in Example 2 Example 2-2: The case where hexadecyl mercaptan was not added in the metal surface treating agent composition described in Example 2 Comparative Example 2-1: Untreated Comparative Example 2-2: When the polyethylene glycol phenyl ether derivative represented by the formula (1-1) is not added to the metal surface treating agent composition described in Example 2 Comparative Example 2- 3: In the metal surface treatment composition described in Example 2, instead of the polyethylene glycol phenyl ether derivative represented by the formula (1-1), the formula (2-
When the polyethylene glycol phenyl ether compound represented by 1) was used. Example 3 Using the metal surface treatment solution prepared in Example 2, the evaluation of the discoloration prevention property against copper was performed. The copper used for the evaluation is an electrolytic copper foil.

The evaluation was performed by leaving the surface-treated copper foil in a thermo-hygrostat 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.

[0032]

[Table 2]

Example 3-1: Use of the metal surface treating agent described in Example 5 Comparative Example 3-1: Untreated Example 4 Using the metal surface treating solution prepared in Example 2, the following The material was evaluated for its ability to prevent discoloration.

(Substrate) Nickel plating (5 μm) on a brass substrate
m) and then flash plating (1) gold, (2)
Gold-copper, (3) tin-zinc-nickel plating (each 0.0
(5 μm) Test piece (Evaluation method) Artificial sweat total immersion test The test piece was immersed in an artificial sweat solution and stored in a 50 ° C constant temperature bath for 16 hours.

An 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 The evaluation results are shown in Table 3. .

[0036]

[Table 3]

Example 4-1: Using the metal surface treating agent described in Example 5 Comparative Example 4-1: Untreated

[0038]

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

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of the polyethylene glycol phenyl ether derivative of the present invention obtained in Example 1.

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

FIG. 3 is a ²⁹ Si-NMR chart of the above.

FIG. 4 is an FT-IR chart of the above.

Claims (3)

[Claims] 1. A novel polyethylene glycol phenyl ether derivative represented by the following general formula (1). Embedded image (Wherein, R ₁ and R ₂ are lower alkyl groups, C _m H
_{2m + 1} is an alkyl group which may be branched, m is 1 to 20,
n represents 1 to 20, p represents 1 to 20, l represents 0 to 3) 2. The polyethylene glycol according to claim 1, wherein a polyethylene glycol phenyl ether represented by the following general formula (2) is reacted with an isocyanate silane compound represented by the following general formula (3). A method for producing a phenyl ether derivative. Embedded image (Wherein, R ₁ and R ₂ are lower alkyl groups, C _m H
_{2m + 1} is an alkyl group which may be branched, m is 1 to 20,
n represents 1 to 20, p represents 1 to 20, l represents 0 to 3) 3. A metal surface treating agent comprising, as an active ingredient, at least one of the polyethylene glycol phenyl ether derivatives represented by the general formula (1) according to claim 1.