JP6370653B2 - Corrosion inhibitor composition and cleaning liquid composition - Google Patents

Description

The present invention, aluminum or an alloy or zinc or corrosion inhibitor composition of the alloy, about including wash solution compositions the corrosion inhibitor.

  Aluminum and its alloys are easy to use because they are lightweight, soft and malleable, and easy to process, and because they have corrosion resistance due to the oxide film on the surface, Aluminum foil, cans (aluminum cans), pans, window frames (aluminum sashes), exteriors, exterior walls of buildings, road signs, parts of railway vehicles and automobiles and some gasoline engines, bicycle rims, personal computers, It is used for various applications in systems where cooling water circulates in heat exchangers such as housings for home appliances, aluminum fin-type radiators, radiators, and bearing cooling water.

  Zinc and its alloys are easy to achieve dimensional accuracy, have a strong impact resistance, absorb vibrations, and have excellent damping ability, so zinc alloys include parts for precision equipment and portable equipment, It is used for various purposes such as casings, “toys” with superalloys, car malls, watch cases, plated parts such as door levers, and painted parts.

  Zinc is also used for galvanizing to protect the surface of ferrous metals, making use of its sacrificial anticorrosive effect. It is used for roads (guardrails, lighting, signposts, noise barriers, bridges), railways ( Station buildings, garages, overhead poles), electric power (transmission towers, overhead wire fittings), civil engineering (sewers, rockfall protection walls, snow fences), construction (housing, fences, factory plants, temporary equipment, parking lots), etc. It is used for various purposes.

  However, these metals have been used for many years or are mainly composed of metal oxides attached to the surface, and due to the generation and contamination of scales containing other hardness components, the thermal efficiency of the plant is reduced or the heating tubes are heated abnormally. There is a danger to cause. In addition, when processing these metals, oily components such as lubricating oil and cutting oil, and metal powder such as cutting scraps and polishing scraps adhere to them. There is a risk of inviting.

  In order to remove these scales, oily components and metal powders, methods such as acid and alkali cleaning have been taken, but aluminum or its alloys are easily corroded by acids and alkalis, and zinc or its alloys are Since it is easy to corrode, the compound which has an effective corrosion inhibitory effect was desired.

  Therefore, an anticorrosive agent for an acidic solution composed of alkyl monophosphonic acid (Patent Document 1), an aluminum corrosion inhibitor composed of aminotrimethylenephosphonic acid and 3-amino-5-alkyl-1,2,4-triazole, etc. (Patent Document 2), cleaning of metal workpieces made of orthophosphoric acid and / or pyrophosphoric acid (iron-based, copper, aluminum, zinc, magnesium (alloy)) (Patent Document 3), hexamethylenetetramine and polyvinyl alcohol An additive for pickling (Patent Document 4) has been proposed.

  Moreover, as an alkali, an aluminum cleaning liquid (Patent Document 5) made of an alkali metal hydroxide and a vanadium compound, and a metal cleaning liquid made of an alkali agent and a carbonate (Patent Document 6) have been proposed.

JP 55-44599 A JP 61-37985 A JP-A-1-219171 JP-A-1-215991 JP 2002-173785 A JP 2013-241495 A

  However, alkylmonophosphonic acid, phosphoric acid compounds such as orthophosphoric acid and / or pyrophosphoric acid, and hexamethylenetetramine as corrosion inhibitors and anticorrosives have recently been affected by environmental pollution, and have a negative impact on human health and the environment. The load is large, which is not preferable.

  Alkali metal hydroxides are not preferred because they are highly corrosive to aluminum, and there is a problem that the effect is small even when a vanadium compound or carbonate is used in combination, and there are restrictions due to legal regulations.

An object of the present invention, added at the time of aluminum or acid or alkaline cleaning of alloys or zinc or an alloy thereof, corrosion inhibitor composition having an excellent corrosion inhibiting effect on metals matrix, acid cleaning liquid composition and the alkaline cleaning liquid It is to provide a composition.

The present invention relates to a corrosion inhibitor composition to be added to a cleaning solution of aluminum or an alloy thereof or zinc or an alloy thereof, and a 1- (phenylmethyl) pyridinium-3-carboxylate compound represented by the following formula (1) and its A corrosion inhibitor composition comprising an aqueous solution containing at least one of salts.

The invention also comprises a aluminum or its alloys or zinc or an alloy thereof washings, 1 at least one hand of (phenylmethyl) pyridinium-3-carboxylate compound and its salt represented by the following formula (1) a wash solution composition you characterized in that an aqueous solution you.

The present invention, before Kiarai solution purification, characterized in that an acid cleaning solution or an alkaline cleaning solution.

The present invention, before Kiarai solution purification, characterized in that an acid cleaning solution comprising at least one of inorganic and organic acids.

  The present invention is characterized in that the inorganic acid is at least one of hydrochloric acid and sulfuric acid, and the organic acid is at least one of glycolic acid, formic acid and citric acid.

The present invention further before Kiarai solution purification is to pH3 following acids wash at least one of said formula (1) represented by 1- and (phenylmethyl) pyridinium-3-carboxylate compound a salt thereof , 100 to 5,000 mg / L.

The present invention, before Kiarai solution purification, characterized in that an alkali cleaning solution comprising an alkali metal hydroxide.

  The present invention is characterized in that the alkali metal hydroxide is at least one of sodium hydroxide and potassium hydroxide.

The present invention, before Kiarai solution purification is to pH12 or more alkaline washing liquid, at least one of the formula (1) shown by 1- (phenylmethyl) pyridinium-3-carboxylate compound and a salt thereof 7 , 30,000 to 30,000 mg / L is added.

Corrosion inhibitor compositions of the invention, aluminum or an alloy thereof, or zinc or an alloy thereof (hereinafter, these were called non-ferrous metals collectively) when the acid-or alkali washing, to significantly suppress the corrosion of metals matrix Can do.

Although the reason for the above effect is not clear, it can be estimated as follows.
First, corrosion of aluminum and its alloy in the acid solution can be expressed by electrochemical reaction formulas (A) and (B). When viewed microscopically, the surface of aluminum and its alloy is formed of an aggregate of local cells composed of an anode portion and a cathode portion, and serves as a driving force for corrosion.

At the anode portion, Al ³⁺ is eluted, and the electrons e ⁻ move through aluminum and its alloy and move to the cathode portion. For this reason, the cathode portion has a high electron density and a negative charge, and conversely, the anode portion has a low electron density and a positive charge.
Anode reaction 2Al → 2Al ³⁺ + 6e ⁻ (A)
Cathode reaction 6H ⁺ + 6e ⁻ → 3H ₂ (B)

  The corrosion of zinc alloy and galvanized steel in an acid solution can be expressed by electrochemical reaction formulas (C) and (D). When viewed microscopically, the surface of the zinc alloy and galvanized steel is formed by an aggregate of local cells composed of an anode portion and a cathode portion, and serves as a driving force for corrosion.

In the anode part, Zn ²⁺ is eluted and electrons e ⁻ move through the zinc alloy and the galvanized steel and move to the cathode part. For this reason, the cathode portion has a high electron density and a negative charge, and conversely, the anode portion has a low electron density and a positive charge.
Anodic reaction Zn → Zn ²⁺ + 2e ⁻ (C)
Cathode reaction 2H ⁺ + 2e ⁻ → H ₂ (D)

  Since the 1- (phenylmethyl) pyridinium-3-carboxylate compound represented by the formula (1) contains a carbonyl group that is an adsorbing group for non-ferrous metals, electrostatic adsorption to non-ferrous metals is strongly corrosive. Excellent suppression. Therefore, the non-ferrous metal cleaning liquid composition of the present invention in which the corrosion inhibitor composition is contained in the non-ferrous metal cleaning liquid also has an excellent anti-corrosion action.

  The corrosion inhibitor composition of the present invention is a corrosion inhibitor composition added to a non-ferrous metal cleaning solution, and is a 1- (phenylmethyl) pyridinium-3-carboxylate compound represented by the following formula (1) and a salt thereof. It is a corrosion inhibitor composition characterized by containing at least any one of these and water, and remarkably suppressing corrosion of a nonferrous metal substrate.

  In the present invention, the compound represented by the formula (1) and a salt thereof may be each alone, or may be a mixture of a free compound and a salt thereof.

  In this invention, the said aluminum alloy is an alloy which has aluminum as a main component, and is an alloy which added copper, manganese, silicon, magnesium, zinc, nickel etc. by the use.

  In the present invention, the zinc alloy is an alloy containing zinc as a main component, and is an alloy to which aluminum, copper, magnesium or the like is added depending on the application.

  The corrosion inhibitor composition of the present invention can be produced by mixing the compound represented by the formula (1) or a salt thereof with water at room temperature to warming and mixing.

  The mixing of the compound represented by the formula (1) or a salt thereof with water is not particularly limited. For example, the compound represented by the formula (1) is once or Dividing into several degrees, it can be performed by adding and stirring to a predetermined amount.

  The concentration of the mixture at this time is about 5 to 100 parts by weight of the compound represented by the formula (1) or a salt thereof (the total amount in the case where the free compound and the salt thereof are mixed) with respect to 100 parts by weight of water. In the actual processing, this concentration can be further diluted to a desired concentration and used.

The corrosion inhibitor composition of the present invention thus obtained remarkably suppresses the corrosion of the nonferrous metal substrate.
Moreover, the corrosion inhibitor composition of this invention may contain an acid or an alkali other than the compound shown by said Formula (1).
Any acid or alkali may be used as long as it has a non-ferrous metal cleaning effect and does not adversely affect the compound represented by the formula (1) during production or storage. Specifically, the acid or alkali exemplified in the description of the non-ferrous metal cleaning liquid composition described below is preferable.

  The non-ferrous metal cleaning liquid composition of the present invention contains a non-ferrous metal cleaning liquid, 1- (phenylmethyl) pyridinium-3-carboxylate compound represented by the formula (1), and a salt thereof. To do.

  In the present invention, the non-ferrous metal cleaning liquid is not particularly limited as long as it is a cleaning liquid used for non-ferrous metal cleaning.

  Moreover, the compounding quantity of the compound shown by Formula (1) in the cleaning liquid composition for nonferrous metals of this invention is suitably nonferrous based on the density | concentration of the compound shown by said Formula (1) in the said corrosion inhibitor composition. It can be adjusted by diluting while observing the corrosion inhibiting effect on the metal. If the example is shown, the compound shown by Formula (1) will be added so that it may become 100-30,000 mg / L in the cleaning liquid composition for nonferrous metals, Preferably it is 125-30,000 mg / L. Is.

  However, from the viewpoint of maximizing the corrosion inhibition effect of the compound represented by the formula (1), the non-ferrous metal cleaning liquid composition of the present invention can be combined with an acid or alkaline cleaning liquid having a stronger erosive action against non-ferrous metals. preferable.

  Examples of the acid cleaning liquid include an inorganic acid cleaning liquid and an organic acid cleaning liquid. The pH of the cleaning liquid is 3 or less.

  The inorganic acid cleaning solution may be any solution in which hydrochloric acid or sulfuric acid suitable for cleaning nonferrous metals is dissolved in water, and the pH of the cleaning solution is 2 or less. The organic acid cleaning solution may be any solution in which glycolic acid, formic acid or citric acid suitable for cleaning nonferrous metals is dissolved in water, and the pH of the cleaning solution is 3 or less.

  In the non-ferrous metal cleaning liquid composition of the present invention, in addition to the pH of the cleaning liquid, the acid concentration in the cleaning liquid may be used as an index when the corrosion inhibitor or the compound represented by the formula (1) is combined with the cleaning liquid. As such an acid cleaning liquid, for example, in the case of an inorganic acid, an inorganic acid cleaning liquid containing 1 to 5%, preferably 3 to 5% acid in the cleaning liquid can be used.

  The alkali cleaning solution may be any solution in which an alkali metal hydroxide is dissolved in water. The alkali metal hydroxide may be sodium hydroxide or potassium hydroxide, and the pH of the cleaning solution is 12 or more. Things.

  In the non-ferrous metal cleaning liquid composition, in addition to the pH of the cleaning liquid, the alkali concentration in the cleaning liquid may be used as an index when blending the corrosion inhibitor or the compound represented by the formula (1) and the cleaning liquid. Examples of the alkaline cleaning liquid include an alkaline cleaning liquid containing 1 to 3% of an alkali metal hydroxide in the cleaning liquid.

  Further, when the cleaning liquid in the cleaning liquid composition for non-ferrous metals of the present invention is the acid cleaning liquid or the alkaline cleaning liquid, the concentration of the compound represented by the formula (1) and the salt thereof may be in the above concentration range. Is an acid cleaning solution, the pH of the acid cleaning solution is 3 or less, and the concentration of the compound represented by the formula (1) and its salt is 100 to 5,000 mg / L, preferably 125 to 5,000 mg / L. It is added to become.

  When the cleaning liquid is alkaline cleaning, the pH of the alkaline cleaning liquid is 12 or more, and the concentration of the compound represented by the formula (1) and its salt is 7,000 to 30,000 mg / L, preferably 7,000. It is added so as to be ˜30,000 mg / L.

  The cleaning composition for nonferrous metals of the present invention can be produced by adding the compound represented by formula (1) to the cleaning solution for nonferrous metals at room temperature to warming and mixing them.

  Moreover, it can replace with the compound shown by Formula (1), and its salt, the corrosion inhibitor composition of the said this invention can also be added to the washing | cleaning liquid for nonferrous metals, In that case, the formula contained in a corrosion inhibitor composition What is necessary is just to calculate a required amount on the basis of the compound amount shown by (1).

  The mixing into the non-ferrous metal cleaning solution is not particularly limited. For example, the compound represented by the formula (1) is divided into the non-ferrous metal cleaning solution with stirring at room temperature once or several times. It can carry out by adding and stirring so that it may become fixed_quantity | quantitative_assay.

  Similarly, the compound represented by the formula (1) or the corrosion inhibitor composition is mixed with the acid or alkali cleaning liquid at room temperature to warming, and the compound represented by the formula (1) or the corrosion inhibitor composition is mixed. It can be produced by adding the product to an acid or alkali washing solution and mixing.

  The cleaning liquid composition for non-ferrous metals of the present invention may be added to an acid or alkaline aqueous solution at the time of use, or added in advance to an acid or alkaline aqueous solution to form a cleaning liquid composition, which is left as it is or diluted with water. It can also be used.

  The non-ferrous metal cleaning method of the present invention can be carried out by washing the non-ferrous metal with an acid or alkali with the acid or alkali cleaning liquid composition, and then washing the non-ferrous metal with water.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the following examples do not limit the present invention.
The evaluation was performed as follows.

<Evaluation of corrosion inhibition effect>
After measuring the pH of 1 L (liter) of an inorganic acid aqueous solution containing 3% or 5% concentration of hydrochloric acid, the compound represented by the formula (1) is added to the inorganic acid aqueous solution, and the cleaning liquid compositions having different compound concentrations are added. I adjusted things.
The pH was measured using a pH meter (pH meter F-22II, manufactured by Horiba, Ltd.). (same as below)

After this cleaning liquid composition was heated to 30 ° C., the aluminum plate was immersed for 60 minutes, and the amount of corrosion was measured. The corrosion inhibition effect was evaluated as follows, with the corrosion amount when the aluminum plate was immersed in an acid cleaning solution containing no corrosion inhibitor under the same conditions as the above as the reference corrosion amount in the inorganic acid aqueous solution of the concentration. .
○: Inhibition effect of 80% or more with respect to the reference corrosion amount △: Inhibition effect of 70 to less than 80% with respect to the reference corrosion amount ×: Inhibition effect with respect to the reference corrosion amount of less than 70% Inhibition effect (%) = (1− (target corrosion Amount / reference corrosion amount)) × 100

  The effects of inhibiting corrosion of aluminum by the inorganic acid cleaning liquid of the present invention were evaluated by Examples 1 to 6 and Comparative Examples 1 to 3 shown below. The evaluation results are as shown in Table 1.

Example 1
The effect of the present invention was evaluated by adding and adjusting the compound represented by the formula (1) to a hydrochloric acid aqueous solution adjusted to 3% so as to be 100 mg / L.

Example 2
The same procedure as in Example 1 was performed except that the amount of the compound represented by formula (1) was changed to 125 mg / L.

Example 3
The same operation as in Example 1 was carried out except that the amount of the compound represented by the formula (1) was changed to 1,000 mg / L.

Example 4
The same operation as in Example 1 was conducted except that the amount of the compound represented by the formula (1) was changed to 2,000 mg / L.

Example 5
The same procedure as in Example 1 was performed except that the amount of the compound represented by formula (1) was changed to 5,000 mg / L.

Comparative Example 1
It carried out like Example 1 except not containing the compound shown by a formula (1).

Comparative Example 2
The same procedure as in Example 1 was performed except that the amount of the compound represented by formula (1) was changed to 75 mg / L.

Example 6
The same operation as in Example 4 was carried out except that the aqueous hydrochloric acid solution was adjusted to 5%.

Comparative Example 3
It implemented like Example 6 except not containing the compound shown by Formula (1).

The results are as shown in Table 1.

<Evaluation of corrosion inhibition effect>
A compound represented by the formula (1) is added to 1 L (liter) of an inorganic acid aqueous solution containing 1%, 3% or 5% concentration hydrochloric acid and 3% sulfuric acid, and the acid concentration, the kind of acid, and the compound Cleaning liquid compositions having different concentrations were prepared.

After this cleaning liquid composition was heated to 30 ° C., the zinc plate was immersed for 30 minutes, and the corrosion amount of the zinc plate was measured. Assessing the corrosion inhibition effect as follows, with the corrosion amount when the zinc plate is immersed in each of the acid cleaning solutions not containing the corrosion inhibitor under the same conditions as above as the reference corrosion amount in each inorganic acid aqueous solution. went.
○: Inhibition effect of 80% or more with respect to the reference corrosion amount △: Inhibition effect of 70 to less than 80% with respect to the reference corrosion amount ×: Inhibition effect with respect to the reference corrosion amount of less than 70% Inhibition effect (%) = (1− (target corrosion Amount / reference corrosion amount)) × 100

  By the following Examples 7-14 and Comparative Examples 4-8, the corrosion inhibitory effect of zinc by the inorganic acid cleaning liquid of this invention was evaluated. The evaluation results are as shown in Table 2.

Example 7
The effect of the present invention was evaluated by adding and adjusting the compound represented by the formula (1) to a hydrochloric acid aqueous solution adjusted to 3% so as to be 100 mg / L.

Example 8
The same procedure as in Example 7 was performed, except that the amount of the compound represented by formula (1) was changed to 125 mg / L.

Example 9
The same operation as in Example 7 was carried out except that the amount of the compound represented by the formula (1) was changed to 1,000 mg / L.

Example 10
The same operation as in Example 7 was carried out except that the amount of the compound represented by the formula (1) was changed to 2,000 mg / L.

Example 11
The same operation as in Example 7 was carried out except that the amount of the compound represented by the formula (1) was changed to 5,000 mg / L.

Comparative Example 4
It implemented like Example 7 except not containing the compound shown by Formula (1).

Comparative Example 5
The same procedure as in Example 7 was performed, except that the amount of the compound represented by formula (1) was changed to 75 mg / L.

Example 12
The same procedure as in Example 10 was performed except that the acid adjusted to 3% was replaced with an aqueous sulfuric acid solution and the acid cleaning solution was heated to 50 ° C.

Comparative Example 6
It implemented like Example 12 except not containing the compound shown by Formula (1).

Example 13
The same operation as in Example 10 was carried out except that the aqueous hydrochloric acid solution was adjusted to 1%.

Comparative Example 7
The same operation as in Example 13 was carried out except that the compound represented by the formula (1) was not contained.

Example 14
The same operation as in Example 10 was carried out except that the aqueous hydrochloric acid solution was adjusted to 5%.

Comparative Example 8
The same operation as in Example 14 was carried out except that the compound represented by formula (1) was not contained.

The results are as shown in Table 2.

<Evaluation of corrosion inhibition effect>
The compound represented by the formula (1) is added to 1 L (liter) of an organic acid aqueous solution containing 3% or 5% concentration of glycolic acid and 3% formic acid or citric acid, and the acid concentration, the kind of acid, and the above-mentioned Cleaning liquid compositions having different compound concentrations were prepared.

After this cleaning liquid composition was heated to 50 ° C., the zinc plate was immersed for 30 minutes, and the corrosion amount of the zinc plate was measured. Assessing the corrosion inhibition effect as follows, with the corrosion amount when the zinc plate is immersed in each of the acid cleaning solutions not containing the corrosion inhibitor under the same conditions as above as the reference corrosion amount in each inorganic acid aqueous solution. went.
○: Inhibition effect of 80% or more with respect to the reference corrosion amount △: Inhibition effect of 70 to less than 80% with respect to the reference corrosion amount ×: Inhibition effect with respect to the reference corrosion amount of less than 70% Inhibition effect (%) = (1− (target corrosion Amount / reference corrosion amount)) × 100

  According to Examples 15 to 22 and Comparative Examples 9 to 13 shown below, the corrosion inhibition effect of zinc by the organic acid cleaning liquid of the present invention was evaluated. The evaluation results are as shown in Table 3.

Example 15
The effect of the present invention was evaluated by adding and adjusting the compound represented by the formula (1) to a glycolic acid aqueous solution adjusted to 3% so as to be 100 mg / L.

Example 16
The same procedure as in Example 15 was performed, except that the amount of the compound represented by formula (1) was changed to 125 mg / L.

Example 17
The same operation as in Example 15 was carried out except that the amount of the compound represented by the formula (1) was changed to 1,000 mg / L.

Example 18
The same procedure as in Example 15 was performed, except that the amount of the compound represented by formula (1) was changed to 2,000 mg / L.

Example 19
The same procedure as in Example 15 was performed, except that the amount of the compound represented by formula (1) was changed to 5,000 mg / L.

Comparative Example 9
The same operation as in Example 15 was carried out except that the compound represented by the formula (1) was not contained.

Comparative Example 10
The same procedure as in Example 15 was performed, except that the amount of the compound represented by formula (1) was changed to 75 mg / L.

Example 20
The same procedure as in Example 18 was performed except that the acid adjusted to 3% was replaced with a formic acid aqueous solution.

Comparative Example 11
The same operation as in Example 20 was performed except that the compound represented by the formula (1) was not contained.
The effect of was evaluated.

Example 21
The same procedure as in Example 18 was performed, except that the acid adjusted to 3% was replaced with an aqueous citric acid solution.

Comparative Example 12
The same operation as in Example 21 was performed except that the compound represented by the formula (1) was not contained.
The effect of was evaluated.

Example 22
The same operation as in Example 18 was carried out except that the aqueous glycolic acid solution was adjusted to 5%.

Comparative Example 13
The reaction was performed in the same manner as in Example 22 except that the compound represented by the formula (1) was not contained.

The results are as shown in Table 3.

<Evaluation of corrosion inhibition effect>
The compound represented by the formula (1) is added to 1 L (liter) of an alkaline aqueous solution containing 1% or 3% concentration of sodium hydroxide and 1% concentration of potassium hydroxide. Different cleaning liquid compositions were prepared.

After this cleaning liquid composition was heated to 30 ° C., the aluminum plate was immersed for 60 minutes, and the corrosion amount of the aluminum plate was measured. The corrosion inhibitory effect was evaluated as follows, with the corrosion amount when the aluminum plate was immersed in an alkaline cleaning solution containing no corrosion inhibitor under the same conditions as the above as the reference corrosion amount in the alkaline aqueous solution of the concentration.
○: Inhibition effect of 80% or more with respect to the reference corrosion amount △: Inhibition effect of 70 to less than 80% with respect to the reference corrosion amount ×: Inhibition effect with respect to the reference corrosion amount of less than 70% Inhibition effect (%) = (1− (target corrosion Amount / reference corrosion amount)) × 100

  According to Examples 23 to 29 and Comparative Examples 14 to 17 shown below, the corrosion inhibition effect of aluminum by the alkaline cleaning liquid of the present invention was evaluated. The evaluation results are as shown in Table 4.

Example 23
The effect of the present invention was evaluated by adding and adjusting the compound represented by the formula (1) to 7000 mg / L in an aqueous sodium hydroxide solution adjusted to 3%.

Example 24
The same procedure as in Example 23 was performed, except that the amount of the compound represented by formula (1) was changed to 8,000 mg / L.

Example 25
The same operation as in Example 23 was performed except that the amount of the compound represented by the formula (1) was changed to 10,000 mg / L.

Example 26
The same operation as in Example 23 was performed except that the amount of the compound represented by the formula (1) was changed to 20,000 mg / L.

Example 27
The same procedure as in Example 23 was performed, except that the amount of the compound represented by formula (1) was changed to 30,000 mg / L.

Comparative Example 14
The reaction was performed in the same manner as in Example 23 except that the compound represented by the formula (1) was not contained.

Comparative Example 15
The same procedure as in Example 23 was performed, except that the amount of the compound represented by formula (1) was changed to 5,000 mg / L.

Example 28
The same procedure as in Example 24 was performed except that the alkali adjusted to 3% was replaced with an aqueous potassium hydroxide solution.

Comparative Example 16
The reaction was performed in the same manner as in Example 27 except that the compound represented by the formula (1) was not contained.

Example 29
The same operation as in Example 23 was carried out except that the sodium hydroxide aqueous solution was adjusted to 1%.

Comparative Example 17
The reaction was performed in the same manner as in Example 28 except that the compound represented by the formula (1) was not contained.

The results are as shown in Table 4.

  As is apparent from the evaluation results of Examples 1 to 6 and Comparative Examples 1 to 3 described above, the corrosion inhibitor of the present invention is excellent in the corrosion inhibition effect during the inorganic acid cleaning of aluminum or an alloy thereof.

  Moreover, as is clear from the evaluation results of Examples 7 to 14 and Comparative Examples 4 to 8, the corrosion inhibitor of the present invention is excellent in the corrosion inhibition effect during the inorganic acid cleaning of zinc or an alloy thereof.

  As is clear from the evaluation results of Examples 15 to 22 and Comparative Examples 9 to 13 described above, the corrosion inhibitor of the present invention is excellent in the corrosion inhibition effect during the organic acid cleaning of zinc or an alloy thereof.

  Further, as is clear from the evaluation results of Examples 23 to 29 and Comparative Examples 14 to 17, the corrosion inhibitor of the present invention is excellent in the corrosion inhibitory effect at the time of alkali cleaning of zinc or an alloy thereof.

  As described above, the corrosion of the non-ferrous metal substrate in the acid or alkali cleaning is remarkably suppressed. Further, it is a corrosion inhibitor composition that does not use a phosphorus compound or the like and can reduce the influence on the environment, and its industrial effect is very large.

Claims (9)

A corrosion inhibitor composition added to a cleaning solution of aluminum or an alloy thereof or zinc or an alloy thereof,
A corrosion inhibitor composition comprising an aqueous solution containing at least one of a 1- (phenylmethyl) pyridinium-3-carboxylate compound represented by the following formula (1) and a salt thereof.

And the cleaning liquid of aluminum or its alloys or zinc or an alloy thereof, is an aqueous solution you containing at least one hand of the indicated are 1- (phenylmethyl) pyridinium-3-carboxylate compounds and their salts by the following formula (1) wash solution compositions you characterized by.

Before Kiarai solution purification is, wash solution composition according to claim 2, characterized in that an acid or an alkali cleaning solution. Before Kiarai solution purification is, wash solution composition according to claim 3, characterized in that the acid cleaning solution comprising at least one of inorganic and organic acids. Wherein the inorganic acid is at least one of hydrochloric acid and sulfuric acid, wash solution composition according to claim 4, wherein the organic acid is glycolic acid is formic acid and at least one or more of citric acid. Before Kiarai washing liquid composition, to pH3 following acids wash at least one of the formula (1) shown by 1- (phenylmethyl) pyridinium-3-carboxylate compound and a salt thereof, 100-5 , so as to be 000mg / L, wash solution composition according to any one of claims 2 to 5, characterized in that formed by the addition. Before Kiarai washing liquid composition, wash solution composition according to claim 3, characterized in that the alkaline cleaning solution comprising an alkali metal hydroxide. Wherein the alkali metal hydroxide is claim 7 wash solution composition, wherein at least at one of sodium hydroxide and potassium hydroxide. Before Kiarai solution purification is to pH12 or more alkaline washing liquid, at least one of the formula (1) shown by 1- (phenylmethyl) pyridinium-3-carboxylate compound and a salt thereof, 7,000～30 , wash solution composition according to claim 7 or 8, characterized by being added so as to be 000mg / L.