JP6984868B2 - Metallic anticorrosive agents containing sulfur-containing polymers and anticorrosive methods for metals - Google Patents

Description

The present invention relates to molecular sulfur (S ₈₎ and corrosion protection method of the metal coating the surface of the metal in the metal corrosion inhibitor and the metal corrosion inhibitor comprising a sulfur-containing polymer obtained by reacting an alkenyl compound.

Sulfur produced during recovery during petroleum refining is used in a wide range of applications such as industrial products such as sulfuric acid, additives such as rubber, and fertilizers. However, the amount of sulfur consumed in these applications is less than the amount of sulfur produced, and the storage of excess sulfur has become a problem. Therefore, new uses of sulfur have been studied, and sulfur has come to be used as a material for the positive electrode of a secondary battery. The secondary battery is sulfur-containing polymer obtained is specific monoallyl compound and S ₈ are mixed and heated with a particular diallyl compounds or alkyl group having 5 to 20 carbon atoms is used as the material of the positive electrode were studied (e.g. , Patent Document 1).

On the other hand, the amount of copper used continues to increase in applications such as electric wires and copper products (plates, pipes, rods, wires, etc.). Anticorrosion technology for metals is being researched in order to ensure the safety of plants and stabilize operations in which metal products containing copper as a component are used. Benzotriazole (BTA) derivatives are widely used as anticorrosive agents for copper, but their biodegradability is low, there is concern about adverse effects on the environment, and the amount used is decreasing. In addition to the BTA derivative, the use of a self-assembled alkanethiol film chemically adsorbed on the copper surface as a protective film for a two-dimensionally polymerized ultrathin film prepared by chemically modifying it with alkylchlorosilanes has been studied (see Non-Patent Document 1). ).

Japanese Unexamined Patent Publication No. 2015-227438

Kuniji Aramaki, Surface Technology, Vol. 47, No. 12 (1996) Pages 1002 to 1007

A copper anticorrosive agent having a higher anticorrosive effect on copper than the above two-dimensional polymerized ultrathin film has been sought, but such an anticorrosive agent has not been realized. An object to be solved by the present invention is to provide a novel metal anticorrosive agent having a high anticorrosive effect on metals such as copper, in place of the BTA derivative.

The present inventors have found that sulfur-containing polymer obtained is heated above monoallyl compounds and S ₈ are mixed, can be used a metal, including copper as anticorrosive metals containing as a component, completed the present invention I came to let you.

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［４］［１］〜［３］のいずれかに記載された金属防食剤で金属の表面を被覆する、金属の防食法に関する。 That is, the present invention
[1] The following formula (I)

(In the equation, R represents a substituted or unsubstituted linear or branched alkyl group having 2 to 20 carbon atoms. X represents a positive integer of 1 or more, and the number of x in each unit is different. A metal anticorrosive agent containing a sulfur-containing polymer having a repeating unit represented by (good).
[2] The metal anticorrosive agent according to [1], wherein R is an n-nonyl group.
[3] The metal corrosion inhibitor according to [1] or [2], wherein the metal is copper or a copper alloy.
[4] The present invention relates to a metal anticorrosive method in which a metal surface is coated with the metal anticorrosive agent according to any one of [1] to [3].

The metal anticorrosive agent of the present invention has a high anticorrosive effect on metals such as copper.

1-undecene, ¹ H NMR spectrum of the sulfur-containing polymer obtained by reaction with _{S 8} 1-undecene [SUD (1.0)] 1-undecene, SUD (1.0), FT- IR spectrum of the sulfur-containing polymer obtained by reaction with _{S 8} 1-undecene [SUD (0.5)] ^{1-Undecene and 1} H NMR spectra of SUD (0.5) XPS spectra of unmodified copper plate and copper plate coated with SUD (0.5) XPS spectra of unmodified copper plate and copper plate coated with SUD (0.5) Polarization curve obtained using an unmodified copper electrode and an electrode coated with SUD (0.5) ^{1 1 1} H NMR spectrum of sulfur-containing polymer SUDA (1.0) obtained by reacting sulfur with 10-undecenoic acid. FT-IR spectrum of sulfur-containing polymer SUDA (1.0) obtained by reacting sulfur with 10-undecenoic acid. ^{1 1 1} H NMR spectrum of sulfur-containing polymer SUDA (0.5) obtained by reacting sulfur with 10-undecenoic acid FT-IR spectrum of sulfur-containing polymer SUDA (0.5) obtained by reacting sulfur with 10-undecenoic acid

The sulfur-containing polymer contained in the metal anticorrosive agent of the present invention has the following formula (II).
H ₂ C = CHR (II)
(Wherein, R,. To represent a substituted or unsubstituted straight or branched alkyl group having 2 to 20 carbon atoms) is produced by reacting an alkenyl compound and S ₈ having a skeleton represented by.

Specific examples of the "linear or branched alkyl group having 2 to 20 carbon atoms" of the above-mentioned "substituted or unsubstituted linear or branched alkyl group having 2 to 20 carbon atoms" are ethyl group and n-propyl. Group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1, 2-dimethylpropyl group, 2,2-dimethylpropyl group, 3-pentyl group, n-hexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 1, 1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3,3- Dimethylbutan-2-yl group, 2,3-dimethylbutane-2-yl group, 3-hexyl group, 2-ethylpentyl group, 2-methylpentane-3-yl group, heptyl group, octyl group, nonyl group, A decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group and the like.

The substituent of the above-mentioned "substituted or unsubstituted linear or branched alkyl group having 2 to 20 carbon atoms" is a carboxyl group, a hydroxyl group, a fluorine atom, an aromatic group shown below, a dialkylamino group, or an alkyloxycarbonyl. Group, alkoxy group, nitrogen-containing heterocyclic group, etc. The alkyl in the dialkylamino group, alkyloxycarbonyl group and alkoxy group is a linear or branched alkyl having 1 to 4 carbon atoms, and specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. They are s-butyl, t-butyl and isobutyl. Specific examples of the nitrogen-containing heterocyclic group include pyrrolidine, pyrazolidine, imidazolidine, oxazolidine, isooxazolidine, piperidine, piperazine, morpholine, and thiomorpholine.

The aromatic group is a monovalent aromatic ring. The aromatic ring is a 5- to 7-membered monocyclic or polycyclic hetero having a monocyclic or polycyclic aryl group having 6 to 10 carbon atoms and 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms. It includes an aryl group and a heteroaryl group consisting of a fused ring in which a benzene ring and a 5- to 7-membered heterocycle having 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms as heteroatoms are condensed.

Specific examples of the aromatic ring include benzene, naphthalene, azulene, anthracene, tetracene, pentasen, phenanthrene, pyrene, pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, thiazole, triazole, oxadiazole, thiadiazole, pyridine, and pyridazine. , Pyrimidine, pyrazine, triazole, indole, isoindole, benzoxazole, benzthiazole, benzoisoxazole, benzisothiazole, benzoxaziazole, benzthiazole, pyrrolopyridine, pyrrolopyrazine, purine, quinoline, isoquinoline, sinolin, quinazoline , Kinoxalin and the like.

The method for producing the sulfur-containing polymer contained in the metal anticorrosive agent of the present invention is not limited to a specific method. Specific examples of the manufacturing method are as follows.
S _8, because the hard to insoluble or dissolved in an organic solvent, the first stage of the sulfur-containing polymer synthesis metal corrosion inhibitor of the present invention contains is a melting caused by heating in a reaction vessel of sulfur. Sulfur has many allotropes (S ₈ , S ₆ , S ₁₂ , S ₁₈ , S _20, etc.), each with a melting point. Most stable allotrope of sulfur is S ₈ in which the cyclic structure, S ₈ has three crystal forms (alpha sulfur, beta sulfur and γ sulfur), their melting points are respectively 112.8 ° C., 119.6 ° C. , 106.8 ° C. Therefore, heating at a temperature of at least 120 ° C. are required for the melting of S _8. Further, S ₈ is β sulfur with increasing temperature from α sulfur stable structure, lambda sulfur, gradually transferred to the μ sulfur proceeds radical cleavage of cyclic sulfur 159.4 ° C. or more, it is a divalent radical .. In this way, since S ₈ generates radicals at a temperature of 159.4 ° C. or higher, the melting temperature needs to be set lower than the above temperature. The melting temperature of the S ₈ is preferably 120 ° C. to 155 ° C., more preferably 135 ° C. to 155 ° C., more preferably 145 ° C. to 155 ° C., and most preferably 0.99 ° C. to 155 ° C..

Then, added to S ₈ alkenyl compound represented by the formula (II) is melted, the formula (I) in the sulfur-containing polymer metal corrosion inhibitor of the present invention contains expressed is synthesized in one step .. At that time, as the alkenyl compound represented by the formula (II) are uniformly dispersed in S ₈ which is melted during the reaction, may stirring is performed.

Temperature of the reaction is a temperature range in which S ₈ generates the radical, preferably 160 ° C. to 175 ° C..

The sulfur-containing polymer contained in the metal anticorrosion agent of the present invention is soluble in organic solvents such as chloroform, dichloromethane, tetrahydrofuran and N-methyl-2-pyrrolidone. The sulfur-containing polymer contained in the metal anticorrosive agent of the present invention synthesized by the above method usually does not need to be purified, but when a high-purity sulfur-containing polymer is required, the reaction product is dissolved in the above organic solvent. And filtered to remove sulfur insoluble in organic solvents. Further, the solution after filtration is subjected to molecular sieving such as gel filtration chromatography, and the polymer and the monomer are separated.

The sulfur content with respect to the sulfur-containing polymer contained in the metal corrosion inhibitor of the present invention is preferably 50 to 95% by mass, more preferably 55 to 95% by mass, and further preferably 60 to 95% by mass.
The number average molecular weight (Mn) of the sulfur-containing polymer contained in the metal corrosion inhibitor of the present invention is preferably 1000 to 20000, more preferably 2000 to 15000, and most preferably 5000 to 10000. Further, the number average molecular weight (Mn) of the sulfur-containing polymer contained in the metal anticorrosive agent of the present invention can be measured by GPC.

In sulfur-containing polymer containing the metal corrosion inhibitor of the present invention, the molar ratio of the compound represented by the S ₈ and the formula (II) is preferably 1: 0.01 to 1: 100, more preferably , 1: 0.25 to 1:10, more preferably 1: 0.25 to 1: 5.

Further, the sulfur-containing polymer contained in the metal anticorrosive agent of the present invention is dissolved in the above organic solvent, and if necessary, an antiaging agent, an adhesion imparting agent, a corrosion inhibitor, a thixo property imparting agent, a leveling agent, etc. A liquid sulfur-containing polymer composition to which other components such as liquid preparations, pigments, dyes, and inorganic fillers are added is applied to the metal surface, and then the organic solvent is evaporated to make the metal surface sulfur-containing. It is covered with a film of polymer. The coating has a high corrosion-preventing ability against metal corrosion.

The metal coated with the metal anticorrosive agent of the present invention is not limited to a specific metal. Specific examples of the metal include copper, aluminum, iron, titanium, alloys thereof, and materials obtained by subjecting these metals to various platings.

Hereinafter, the present invention will be described in more detail by way of examples, but the technical scope of the present invention is not limited thereto. The method for analyzing the synthesized sulfur-containing polymer is as follows.

(1) ¹ H NMR analysis A sample of about 5 mg was dissolved in 800 μL deuterated chloroform, and tetramethylsilane was used as an internal standard by a Fourier transform nuclear magnetic resonance measuring device (JNM-ECA manufactured by JEOL Ltd.). ¹ H NMR spectrum was measured.

(2) FT-IR measurement Using the diamond ATR accessory Durasamp 1 IR II [ST Japan Co., Ltd.] as an accessory, use a Fourier transform infrared spectrophotometer (IR Prestige-21, Shimadzu Corporation). It was used for measurement by total reflection absorption spectroscopy (FT-IR-ATR).

Sulfur-containing polymer production example 1
S ₈ (manufactured by Ishizu Pharmaceutical Co., Ltd.) 0.9958 parts by mass and 1-Undesen (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.6013 g ( _{molar ratio of S 8} and 1-Undesen is approximately 1: 1) is 175 ° C. Was stirred for 3 hours. Then, the reaction product was allowed to stand until it reached room temperature, tetrahydrofuran (THF) (manufactured by Nacalai Tesque, Inc.) was added to the cooled reaction product, and the THF-soluble portion was separated by filtration. THF was removed from the THF soluble part and the solidified sulfur-containing polymer SUD (1.0) was recovered. 1-Undecene and SUD (1.0) were used as samples, and ^{1 1} H NMR analysis and FT-IR analysis were performed. ^{1 1} H NMR spectrum and FT-IR spectrum are shown in FIGS. 1 and 2, respectively.

Sulfur-containing polymer production example 2
S ₈ .9958 parts by using the 0.4992 parts by weight in place of (molar ratio of _{S 8} and 1-undecene almost 1: 2) except, sulfur-containing polymers solidified in the same manner as in Preparation Example 1 SUD (0.5) was recovered. 1-Undecene and SUD (0.5) were used as samples, and ^{1 1} H NMR analysis and FT-IR analysis were performed. The FT-IR spectrum and the ¹ H NMR spectrum are shown in FIGS. 2 and 3, respectively.

From FIGS. 1 and 2, the peak attributed to the 1-Undecene double bond (the range indicated by the arrow a in FIGS. 1 and 2) disappears from the spectrum of SUD (1.0), and the CS bond disappears. It can be seen that the peak derived from (the range indicated by the arrow b in FIGS. 1 and 2) appears. Therefore, it can be seen that SUD (1.0) is a sulfur-containing polymer in which R in the above formula (I) is an n-nonyl group.

From FIGS. 2 and 3, the peak attributed to the 1-Undecene double bond (the range indicated by the arrow a in FIGS. 2 and 3) disappears from the spectrum of SUD (0.5) and becomes a CS bond. It can be seen that the derived peak (the range indicated by the arrow b in FIGS. 2 and 3) appears. Therefore, it can be seen that SUD (0.5) is a sulfur-containing polymer in which R in the above formula (I) is an n-nonyl group.

Pretreatment of copper plate The copper plate was cut into 1 cm × 1 cm, polished with abrasive paper (# 2000), and then the polished copper plate was washed with ion-exchanged water three times. Further, the polished copper plate was washed three times with methanol (manufactured by Wako Pure Chemical Industries, Ltd.) for degreasing, washed with ion-exchanged water, and then naturally dried before use.

Preparation of Copper Plate Not Covered with Sulfur-Containing Polymer The pretreated copper plate was immersed in 10 ml of THF at room temperature for 24 hours, washed 3 times with THF, and then naturally dried at room temperature to prepare an unmodified copper plate.

Preparation of copper plate coated with SUD (0.5) 1
A solution prepared by dissolving 1 mg of SUD (0.5) in 10 ml of THF was prepared, and the pretreated copper electrode was immersed in this solution for 30 minutes, and then washed 3 times with THF. It was naturally dried at room temperature to prepare a copper plate (SUD (0.5) -1-30 min).

Preparation of copper plate coated with SUD (0.5) 2
A solution prepared by dissolving 5 mg of SUD (0.5) in 10 ml of THF was prepared, and the pretreated copper electrode was immersed in this solution for 0.5 hours, and then washed 3 times with THF. Then, it was air-dried at room temperature to prepare a copper plate (SUD (0.5) -5-0.5H).

Analysis of Copper Plate Surface by X-ray Photoelectron Spectroscopy (XPS) The surface of each copper plate was examined using an X-ray photoelectron spectroscopy system (k-Alpha manufactured by Thermo Fisher Scientific). The measurement conditions are shown in Table 1. Table 2 shows the Start energy and End energy of Narrow Scan.

The measurement results are shown in FIGS. 4A and 4B. Sulfur was not present on the surface of the unmodified copper plate, but was confirmed to be present on the surfaces of SUD (0.5) -1-30 min and SUD (0.5) -5-0.5H.

Pretreatment of copper electrode A copper electrode with a diameter of 3 mm (manufactured by BAS Co., Ltd.) is polished with a diamond polishing solution having a particle diameter of 1 μm, further polished with an alumina powder of 0.5 μm, and then polished. Was washed 3 times with ion-exchanged water. Further, the polished copper electrode was washed three times with methanol (manufactured by Wako Pure Chemical Industries, Ltd.) for degreasing, washed with ion-exchanged water, and then naturally dried before use.

Preparation of Copper Electrode Not Coated with Sulfur-Containing Polymer The pretreated copper electrode was immersed in 10 ml of THF for 24 hours at room temperature, washed 3 times with THF, and then naturally dried at room temperature to prepare an unmodified copper electrode. ..

Fabrication of Copper Electrode Coated with SUD (0.5) 1
A solution prepared by dissolving 1 mg of SUD (0.5) in 10 ml of THF was prepared, and the pretreated copper electrode was immersed in this solution for 0.5 hours, 1 hour, and 24 hours, respectively. The electrodes were washed 3 times with THF and allowed to air dry at room temperature. Hereinafter, the electrodes having the respective immersion times are referred to as SUD (0.5) -1-0.5H, SUD (0.5) -1-1-1H, and SUD (0.5) -1-24H.

Fabrication of Copper Electrode Coated with SUD (0.5) 2
A solution of 5 mg of SUD (0.5) dissolved in 10 ml of THF was prepared, and the pretreated copper electrode was immersed in this solution for 10 minutes, 30 minutes, and 60 minutes, and each electrode was treated. , Washed 3 times with THF and allowed to air dry at room temperature. Hereinafter, the electrodes having the respective immersion times are referred to as SUD (0.5) -5-10 min, SUD (0.5) -5-30 min, and SUD (0.5) -5-60 min.

Preparation of Copper Electrode Coated with SUD (1.0) Prepare a solution in which 5 mg of SUD (1.0) was dissolved in 10 ml of THF, and pretreated the copper electrode to this solution for 10 minutes. The treatment was carried out by immersing for 20 minutes and 30 minutes, and each electrode was washed with THF three times and naturally dried at room temperature. Hereinafter, the electrodes having the respective immersion times are referred to as SUD (1.0) -5-10 min, SUD (1.0) -5-20 min, and SUD (1.0) -5-30 min.

Constant potential polarization measurement of copper electrode Using a potentiostat (HA-103 manufactured by Hokuto Denko Co., Ltd.) connected to a digital multimeter, a platinum wire (diameter 0.5 mm, length 5.7 cm) was counter electrode, Ag / AgCl ( Using 3M-NaCl) electrodes as reference electrodes, the constant potential polarization of each copper electrode was measured. As the electrolytic solution used for the measurement, a 0.5 M sodium sulfate aqueous solution in which oxygen was aerated for 30 minutes at room temperature was used. An unmodified copper electrode, a copper electrode coated with SUD (0.5), or a copper electrode coated with SUD (1.0) was used as a working electrode.
After assembling the electrochemical cell, the natural potential (rest potential) was measured using a potentiostat. Next, the potential setting dial of the podenshostat was set to a potential 10 mV lower than the natural potential. After the cathode polarization measurement was performed, the anodic polarization measurement was performed. The holding time at this potential was set to 1 minute, and the current value after holding for 1 minute was recorded as a steady value. Next, constant potential polarization was performed from the potential at which the potentiostat was initially set to a lower potential of 10 mV. Cathodic polarization was performed from the natural potential to about −400 mV. After polarization to this point, the potentiostat was returned to the natural potential measurement state, and the natural potential was measured. Next, the steady current value was obtained in the same manner as in the above-mentioned cathode polarization measurement, with the potential being 10 mV noble from the measured potential. Anodic polarization was performed up to about -150 mV. From the obtained polarization curve, the corrosion current density (i _cor ) is calculated, and the corrosion resistance P (%) is calculated according to the following formula (1) using the ^{corrosion current density (i 0} _{cor) in the unmodified copper electrode.} It was calculated and the copper corrosion protection of each modified film was compared.
P (%) = 100 × (1-i _cor / i ⁰ _cor ) (1)

The polarization curves of the unmodified copper electrode, the copper electrode coated with SUD (0.5) -1-0.5H, and the copper electrode coated with SUD (0.5) -5-30 min are shown in FIG. .. Cathode side current density when using unmodified copper electrode> SUD (0.5) -1-0.5H Cathode side current density when using a copper electrode coated with -1-0.5H> SUD (0.5) -5 It was found that the current density on the cathode side was obtained when the copper electrode coated with -30 min was used, and that the SUD (0.5) coating formed on the copper electrode suppressed the cathode reaction. Further, there was no significant difference between the anode side current density when the unmodified copper electrode was used and the anode side current density when the copper electrode coated with SUD (0.5) was used, and the SUD formed on the copper electrode was formed. It was found that the coating film (0.5) did not suppress the anodic reaction.

Table 3 shows the anticorrosion rate of each copper electrode coated with SUD. The anticorrosion rate of the copper electrode coated with SUD (0.5) -5 was higher than that of the copper electrode coated with SUD (0.5) -1. Moreover, the anticorrosion rate of the copper electrode coated with SUD (0.5) -5 was higher than the anticorrosion rate of the copper electrode coated with SUD (1.0) -5. The ratio of carbon chains to the number of sulfur atoms in SUD (0.5) is higher than the ratio of carbon chains to the number of sulfur atoms in SUD (1.0). Therefore, it was presumed that the higher the ratio of carbon chains to the number of sulfur atoms, the more dense a film was formed on the copper surface and the higher the corrosion protection rate.

Sulfur-containing polymer production example 3
S ₈ (Ishizu manufactured Pharmaceuticals Ltd.) 0.4913 parts by weight and 10-undecenoic acid (manufactured by Kanto Chemical Co.) 0.3611 parts by mass (molar ratio of _{S 8} and 10-undecenoic acid is approximately 1: 1) Was stirred at 175 ° C. for 3 hours. The reaction product was then left to room temperature, THF was added to the cooled reaction product and the THF soluble part was separated by filtration. THF was removed from the THF soluble part and the solidified sulfur-containing polymer SUDA (1.0) was recovered. 10-Undecenoic acid and SUDA (1.0) were used as samples, and ¹ H NMR analysis and FT-IR analysis were performed. ^{1 1} H NMR spectrum and FT-IR spectrum are shown in FIGS. 6 and 7, respectively.

Sulfur-containing polymer production example 4
S ₈ (Ishizu manufactured Pharmaceuticals Ltd.) 0.2500 parts by weight and 10-undecenoic acid (manufactured by Kanto Chemical Co.) 0.3611 parts by mass (molar ratio of _{S 8} and 10-undecenoic acid is approximately 1: 2) Was stirred at 175 ° C. for 3 hours. The reaction product was then left to room temperature, THF was added to the cooled reaction product and the THF soluble part was separated by filtration. THF was removed from the THF soluble part and the solidified sulfur-containing polymer SUDA (0.5) was recovered. 10-Undecenoic acid and SUDA (0.5) were used as samples, and ¹ H NMR analysis and FT-IR analysis were performed. ^{1 1} H NMR spectrum and FT-IR spectrum are shown in FIGS. 8 and 9, respectively.

Fabrication of Copper Electrode Coated with SUDA (1.0) 1
A solution prepared by dissolving 5 mg of SUDA (1.0) in 10 ml of THF was prepared, and the copper electrode subjected to the above pretreatment was immersed in this solution for 10 minutes, 20 minutes, and 30 minutes, and each electrode was treated. Was washed 3 times with THF and allowed to air dry at room temperature. Hereinafter, the electrodes having the respective immersion times are referred to as SUDA (1.0) -5-10 min, SUDA (1.0) -5-20 min, and SUDA (1.0) -5-30 min.

Fabrication of Copper Electrode Coated with SUDA (1.0) 2
A solution of 1 mg of SUDA (1.0) dissolved in 10 ml of THF was prepared, and the pretreated copper electrode was immersed in this solution for 30 minutes for 1 hour, and each electrode was treated with THF. It was washed 3 times and allowed to air dry at room temperature. Hereinafter, the electrodes having the respective immersion times are referred to as SUDA (1.0) -1-0.5H and SUDA (1.0) -1-1H.

Preparation of Copper Electrode Coated with SUDA (0.5) Prepare a solution of 5 mg of SUDA (0.5) in 10 ml of THF, and add the pretreated copper electrode to this solution for 20 minutes. After soaking for 30 minutes, each electrode was washed with THF three times and naturally dried at room temperature. Hereinafter, the electrodes having the respective immersion times are referred to as SUDA (0.5) -5-20 min and SUDA (0.5) -5-30 min.

A polarization curve was created using each copper electrode coated with SUDA, and the anticorrosion rate of each copper electrode coated with SUDA was calculated according to the above formula (1). The results are shown in Table 4.

Covering the surface of a metal with the metal anticorrosive agent of the present invention, which has a high anticorrosive effect on metals such as copper, improves the anticorrosive effect of the metal, ensuring the safety of plants in which metal products are used and stabilizing operations. Is measured.

Claims (4)

The following formula (I)

(In the formula, R is an unsubstituted linear or branched alkyl group having 2 to 20 carbon atoms, a carboxyl group, a hydroxyl group, a fluorine atom, an aromatic group, a dialkylamino group, an alkyloxycarbonyl group, an alkoxy group or Represents a linear or branched alkyl group with 2 to 20 carbon atoms substituted with only one of the nitrogen-containing heterocyclic groups. X represents a positive integer of 1 or more and the number of x in each unit. May be different.) A metal anticorrosive agent containing a sulfur-containing polymer having a repeating unit represented by. R is an unsubstituted linear or branched alkyl group having 9 to 20 carbon atoms, or a carboxyl group, a hydroxyl group, a fluorine atom, an aromatic group, a dialkylamino group, an alkyloxycarbonyl group, an alkoxy group or a nitrogen-containing heterocyclic group. The metal anticorrosion agent according to claim 1, which is a linear or branched alkyl group having 9 to 20 carbon atoms substituted with only one of the above. The metal corrosion inhibitor according to claim 1 or 2, wherein the metal is copper or a copper alloy. A metal anticorrosive method for coating a metal surface with the metal anticorrosive agent according to any one of claims 1 to 3.

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