TW438747B - Novel polyoxyethylene alkylphenyl ether derivatives, process for preparing the same, and surface treating agent for metals containing the same - Google Patents

Abstract

A novel polyoxyethylene alkylphenol ether derivative represented by the following general formula (1): (wherein m and n are each 1 to 20). The ether derivatives are prepared by reacting a specific polyoxyethylene alkylphenol ether with a specific phenyl isocyanate and provides a surface treating agent for metals which can form a film on a metallic material with excellent adhesion to thereby impart rustproofness to the material.

Description

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[Background of the invention; 1 of the invention, the present invention relates to a surface treatment agent for rust prevention of metal materials. In particular, the invention relates to a novel polyethylene oxide alkyl phenyl ether derivative, which can be used as a rust preventer for copper, nickel, iron, aluminum, zinc, or an alloy thereof, and a method for preparing the derivative, and Its use. , Λ epoxy phenyl ether derivatives can be used as non-ionic surfactants, f is widely used in industry as cleaners, emulsifiers, antistatic agents, wetting agents, and edge penetration agents. When considering this series of compounds from the surface treatment of metals, each compound consists of a hydrophilic group part (polyethylene oxide group part) that can be adsorbed and adsorbed, and the metal surface can be made hydrophobic to impart It is composed of water-repellent and other functions of the hydrophobic group part (alkyl main oxy part). Further, a patent application has been filed for a rust inhibitor for silver containing the compound as an active ingredient (Japanese Patent Gazette No. 61-55596). At the same time, I have also applied for a patent application for a surface treatment agent for high-durability metals. The surface treatment agent includes a compound obtained by introducing the oxyhydroxyl group into a polyethylene oxide fired benzene puzzle (Japanese patent (Japanese Laid-Open Patent Publication No. 9-4594) ^ When using this series of compounds together with long-chain thiol as a rust inhibitor for silver etc. 'It is believed that the compounds appear to accelerate the adsorption of long-chain alkyl thiols on metals Both active and emulsifying activity. However, the above-mentioned polyethylene oxide alkyl stupid ether has the following characteristics: when Jin Guang is surface-treated with an aqueous surface treatment agent containing any ether as an active ingredient, and then washed with water, the active ingredient has a high solubility in water.

C: \ Progmm Files \ Patent \ 310618.ptd Page 5 Λ38747 V. Description of the invention (2) The problem of unsatisfactory adsorption on genus. On the other hand, oxysilyl derivatives + 榀 *, hard, and on the other hand, although the MU organisms are superior in initial characteristics, but the alkane = rrx will be water-soluble ... : = 表; 々, capable of excellent rust resistance ^ At least the inventors have devoted themselves to research and have found that it can be used as an active ingredient by using a poly (ethylene oxide) alkylbenzene derivative containing thallium. Surface treatment agent to solve the above problems. The present invention has been completed based on this finding. That is, the gist of the present invention is: U) — a new type of polyethylene oxide alkyl phenyl ether derivative, expressed by the following general formula :

C, where m and η are each 1 to 20), (2) a method of preparing a polyethylene oxide alkyl phenyl ether derivative as shown in the above item (丨), includes using the following general formula (2 Polyethylene oxide alkyl phenyl ether represented by) is reacted with phenyl isocyanate represented by the following general formula (3): c η

OCH2 OH (2) (where m and n are each 1 to 20)

C: \ Program Files \ Patent \ 310618.ptd Page 6 438747 V. Description of the Invention (3)

(3) (3) — a metal surface treatment agent containing at least — (4) a metal surface treatment agent shown in the item of a polyethylene oxide alkylbenzene derivative represented by general formula (1), Contains at least ~ alkyl thiols shown in the polyethylene oxide alkyl phenyl ether derivative represented by the general formula (1), and a solvent, and at least 1) 5) a metal surface treatment agent containing at least- A kind of polyethylene oxide alkylene benzene derivative represented by general formula (η), to a small extent, a kind of thiol, at least one polycycloalkylene surfactant, and a solvent. [Schematic diagram Brief description] FIG. 1 is a H-NMR chart of the polyethylene oxide alkyl phenyl ether derivative (B1) prepared in Example 1. FIG. 2 is a polyethylene oxide alkyl prepared in Example 1. I-C-NMR chart of the phenylene ether derivative (B1). Figure 3 is the FT-IR circle of the polyethylene oxide alkyl phenyl ether derivative (B1) prepared in Example 1. Figure 4 is an example. 1Η-NM diagram of the polyethylene oxide alkyl phenyl ether derivative (Bu 2) prepared in 2. FIG. 5 shows the polyethylene oxide alkyl phenyl ether derivative (Bu 2) prepared in Example 2. 13C-NMR chart Figure 6 It is the FT-IR chart of the polyethylene oxide alkyl phenyl ether derivative (B2) prepared in Example 2.

C: \ Program Files \ Patent \ 31061 B.ptd 438747 V. Description of the invention (4) --- Figure 7 shows the 1H-NMR of the polyethylene oxide alkyl phenyl ether (1-3) prepared in Example 3. Illustration. Fig. 8 is a 13C-NMR chart of the polyethylene oxide alkyl phenyl ether (Bu 3) prepared in Example 3. Figure 9 is an FT-IR chart of the polyethylene oxide alkyl phenyl ether derivative (1-3) prepared in Example 3. [Detailed description of preferred embodiments] In the above general formula, m is 1 to 20 ', preferably 8 to 12. On the other hand, although η is generally 1 to 20, n is preferably 2 to 9 from the viewpoint of rust prevention. It should be noted that it is difficult to synthesize polyethylene oxide alkyl phenyl ethers in a single substance form in which n is the same, and therefore the " η " value of such synthesized ethers generally has several distributions. In the examples given, the values of each "η" shown are expressed as integers closest to the average value ^ as the novel polyethylene oxide alkylbenzene of the present invention represented by the general formula (1) above The ether derivative can be easily prepared by reacting a polyethylene oxide alkyl phenyl ether represented by the general formula (2) with a phenyl isofluorate represented by the general formula (3) at 20 to 100 π. A preferred embodiment of the compound represented by the general formula (2) includes the following examples:

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From the viewpoint of easy and simple, the reaction of the polycyclic gas ethane alkyl phenyl ether compound represented by general formula (2) with phenyl isocyanate is preferably performed without using any solvent, although organic solvents such as : Ethyl acetate. It is also preferable to react the stearic acid isocyanate with the polyethylene oxide alkyl phenylhydrazone of the general formula (2) at a molar ratio of 1: 1 to 2: 1. The reaction time may be about 30 minutes to 10 hours. Further, it is desirable to use a catalyst in the reaction to accelerate the reaction. For example, di-n-butyltin dilaurate can be used as such a catalyst. Particularly preferred examples of the novel polyethylene oxide alkyl phenyl ether derivative of the present invention as represented by the above general formula (1) include the following compounds:

438747 V. Description of the invention (6) 〇 Η (1-1) OCH2 CHVII

Ο Η II I OCH2'CH277 ° 'C'N ^ 0 > (1-2)

OCH „ch-4- 0 · 〇 HI! (1-3) The novel polyethylene oxide alkyl phenyl ether derivative according to the present invention is suitable for use as a surface treatment agent for metals. Self-polymerizing epoxy on the surface of metal materials Films made from ethanealkylphenyl ether derivatives can significantly improve the rust prevention of metallic materials. For the surface treatment agent of the present invention, in more detail, the surface treatment agent is not particularly limited to the metal to be treated with it. Type. That is, the surface treatment agent is effective for silver, gold, copper, iron, aluminum, zinc, and alloys thereof, although it is more suitable for use with silver, gold, and copper. In particular, when the surface treatment agent is used When used as a rust preventive for silver-plated or gold-plated electronic parts or copper pavilions for the manufacture of copper-plated laminates for printed circuits, the effects of the present invention can be fully exerted. It is easy and simple to use the above-mentioned present invention. The inventive polyethylene oxide alkyl phenyl ether derivative treats metal materials, preferably by using an alcohol (such as methanol, ethanol, or isopropanol), a ketone (such as acetone or methyl isobutyl ketone, or Dilute at least one of this derivative with water to obtain a concentration of 〇_〇1 to 20% And immersing the material in the resulting solution. Although polyethylene oxide can be used alone

C: \ Program Files \ Patent \ 310618.ptd Page 10 438747 V. Description of the invention (7) Burning alkyl phenyl ether derivative, but it can also be mixed with other rust inhibitors, coupling agents, surfactants, etc. use. Preferred examples of such rust inhibitors include alkyl mercaptans, wherein the desired alkyl group has 14 to 20 carbon atoms. Preferred examples of surfactants include polyethylene oxide alkyl phenyl ether Among them, the desired alkyl group has 8 to 12 carbon atoms, and the desired number of addition ethylene oxide molecules is 5 to 12. Example 1 Synthesis of polyethylene oxide alkyl phenyl ether derivative (1-1) _ · The following formula (2-1) The reaction of phenyl isocyanate represented by) is synthesized to compound represented by the following formula ui) Add a drop of di-n-butyltin dilaurate as a catalyst to 9 68 g (0.02 mol) of the following formula (2-1) Polyethylene oxide alkyl phenyl ether. The obtained mixture was dissolved by stirring at room temperature, and then added dropwise to 2.38 g (0.02 mol) of isocyanate phenyl ester represented by the following formula (3-1) over 10 minutes. The mixture thus obtained was kept at room temperature for one hour to perform the reaction. The reaction mixture was heated to 5 Q ° C and further reacted for 1.5 hours to obtain a transparent viscous liquid. The polyethylene oxide alkyl phenyl ether derivative obtained as a reaction product was identified by FT-IR and NMR.

C: \ Program Files \ Patent \ 3106l8.ptd Page 11 438747 V. Description of the invention (8)

〇 K

(1-1)

Synthesis of polyethylene oxide alkyl phenyl ether derivative (1-2) The polyethylene oxide alkyl phenyl ether represented by the following formula (2-2) and the following formula (3-1) Reaction of phenyl isocyanate to synthesize a compound represented by the following formula (丨 -2) Add a drop of di-n-butyltin dilaurate as a catalyst to 6. i6g (0. 02 mole) as shown in the following formula (2-2) The polyethylene oxide alkyl phenyl ether shown. The obtained mixture was dissolved by stirring at room temperature, and then added dropwise to 2.38 g (0.02 mol) of isocyanate phenyl ester represented by the following formula (3-1) over 10 minutes. The mixture thus obtained was kept at room temperature for one hour to perform the reaction. The reaction mixture was heated to 50 t and further reacted for 1.5 hours to obtain a transparent viscous liquid. The polyethylene oxide alkyl phenyl ether derivative obtained as a reaction product was identified by FT-IR and NMR.

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fExample 3 Synthesis of polyethylene oxide alkylene phenyl ether derivative (1-3), the polyethylene oxide alkyl phenyl ether represented by the following formula (2-3) and the following formula (3-1) The reaction of the phenyl isocyanate shown below synthesizes the compound represented by the following formula π_3). Add a drop of di-n-butyltin dilaurate as a catalyst to 7.45 g (0.02 mol) of the polycyclic ring represented by the following formula (2-3). Oxyethane alkyl phenyl ether. The obtained mixture was dissolved by stirring at room temperature, and then was added dropwise to 2.38 g (0.02 mol) of isocyanate phenyl ester represented by the following formula (3-1) within 0 minutes. The mixture thus obtained was kept at room temperature for one hour to perform the reaction. The reaction mixture was heated to 50 t and further reacted for 5 hours to obtain a transparent viscous liquid. The polyethylene oxide alkyl phenyl ether derivative obtained as a reaction product was identified by FT-r and 肫 ^. "

438747 V. Description of the Invention (ίο)

Example 4: 0.04 g of each polyethylene oxide alkyl stupid ether derivative represented by formulae (1-1), (1-2), and (1-3) and 0.06 g of hexadecyl sulfur The alcohol was dissolved in isopropanol. The obtained solution was dropped into 95 ml of pure water with stirring to prepare a surface treatment liquid for metal. This liquid was heated to 40 ° C, and the silver-plated test piece was immersed in this liquid for one minute ', washed with pure water, and dried by immersing the surface-treated sample thus obtained in an aqueous sulfur bond solution, and The rust resistance was evaluated, and the degree of matting of the obtained samples was determined by visual observation. The evaluation summary is as follows: Test solution: 0.2% ammonium sulfide aqueous solution Soaking time: 30 minutes The evaluation results are shown in Table 1. Table 1 Test results of silver gloss samples being tarnished by vulcanization

C: \ Program Files \ Patent \ 310618-ptd Page 14 438747 V. Explanation of the invention (ιυ Example 4-1 A few examples 4-2 A few examples 4-3 A few comparative examples 1 Obvious comparative example 2 Obvious comparative example 3 Obvious comparative example 4-Inside .. Example 4_1: Using a compound represented by the above formula (1-1), an oxyethylenyl benzene bond derivative. Example 4-2: Using a compound represented by the above formula (1-2), oxygen Ethane alkyl phenyl ether derivatives. Example 4-3: Using a compound represented by the above formula (1-3), oxyacetonyl benzene bond derivatives. Comparative Example 1: Using the above formula (2-1) Instead of using a polyethylene oxide alkyl stupid ether derivative. Comparative Example 2: Instead of using a polyethylene oxide phenylene oxide represented by the above formula (2-2) Alkyl phenyl ether derivative. Comparative Example 3: Polyepoxyphenyl ether 'represented by the above formula (2-3) was used instead of polyethylene oxide alkyl phenyl ether derivative. Comparative Example 4: Untreated Example 5 The surface treatment liquid prepared in Example 4-1 was evaluated on copper 6. In this evaluation, electrolytic copper foil β was used as the poly ring as the poly ring as Ring B hospital burn ethane ethane alkyl group having 1 rust effect

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V. Explanation of the invention (12) By placing the surface-treated copper foil at 800 ° C and 吒%: up to 24 hours in a thermo-humidity constant, and then by visual observation, the copper foil is delustered. Degree while evaluating. The results are shown below. 、, 去 Table 2 Tests for delustering copper foil under high humidity conditions ^-~ delustering process grinding Example 5 Less _ Comparative Example 5__ by Example 5: Use the surface treatment agent described in Example 4-1. Comparative Example 5: Untreated. Example 6 The antirust effect of the surface treatment prepared in Example 4 was evaluated on the following metallic materials. < (Metallic material) By plating a brass substrate with nickel and then separately coating the obtained bonded substrate chain with (1) gold, (2) gold-copper, and (3) tin-dictionary. [Evaluation method] Soak test wheel with artificial sweat Soak the above test piece in an artificial sweat solution and then store the resulting system in a constant temperature room at 50 ° C for 16 hours. Artificial sweat solution ... includes 9.9 g of sodium chloride, 0.8 g of sodium sulfide, urea, 0% of 0,67 ml of 1% ammonia water, i.imi lactic acid, 0.2 g of strict sugar, and 990 ml of pure water. The evaluation results are not shown in Table 3.

438747 Five 'invention description (13) Table 3 Test Examples of Various Matte Coating Test Sheets by Artificial Sweat_Mineral Gold Sheet_Key Gold-Copper Plates Tin-Zinc-Ni Sheet Example 6 Comparative Matting Example 6 Significant Matte Significant Matte Significant Matte Significant Matte Example 6 · The surface treating agent described in Examples 4 to 1 was used. Comparative Example 6: Untreated. _ From the above results, it can be understood that the novel polyethylene oxide alkyl phenyl ether derivative according to the present invention can be used as a surface treatment agent for metal materials and effectively improve the recording resistance of materials.

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Claims (1)

43874 7 食 i! 81Q 8148 年 # t suspected i added 1. ι —- = ~ ^^ τπ TAt-represented poly C Η OCKq CK 2 I correction Benzene mystery derivative 0 Η li I 0 — C — ιΜ (1) (wherein and n are each 1 to 20). 2. A method for preparing a polyethylene oxide alkyl phenyl ether derivative according to item 1 of the scope of the patent application, which comprises combining a polyethylene oxide alkyl phenyl ether represented by formula (2) with a compound represented by formula (3) Isocyanate reaction: Ca H2a + I T " ◦ C% C — 〇 Η (2) (which makes in and n each be 1 to 20) 〇 Ν ′-c = 〇 (3) 3. As for the polyethylene oxide alkylene in the first scope of the patent application Derivatives are used to treat metal surfaces. A: \ 310618.ptc Page 1 2000.11.06.018