KR20200058224A - Desiccant with VCI for Aluminium without chlorine chemicals - Google Patents

Abstract

The present invention relates to a moisture-proof anti-rust agent for aluminum. More particularly, the present invention relates to a moisture-proof rust preventive agent having excellent hygroscopicity and further improved corrosion resistance to aluminum and a product including the same.

Description

Non-chlorinated moisture-proof anti-corrosive agent for aluminum {Desiccant with VCI for Aluminum without chlorine chemicals}

The present invention relates to a moisture-proof anti-rust agent for aluminum. More particularly, the present invention relates to a moisture-proof rust preventive agent having excellent hygroscopicity and further improved corrosion resistance to aluminum and a product including the same.

Aluminum has a passivation film, which is a kind of oxide film on the surface, similar to stainless steel. Corrosion does not proceed well, but it is vulnerable to corrosive substances such as acid, alkali, and chlorine, and is easily destroyed. do.

In the automotive industry, potassium-based additives are used in the cleaning process after casting to prevent corrosion of cylinder heads and cylinder blocks used as aluminum castings, but these methods have limitations in preventing corrosion in extreme seawater environments.

Moreover, the moisture-proof and rust-preventing agents produced are not separately manufactured for iron and non-ferrous products, and are not mixed separately, so they are insufficient to realize performance specific to aluminum.

An object of the present invention is to provide a moisture-proof rust preventive agent having a remarkable effect in effectively suppressing the whitening phenomenon by effectively preventing corrosion of aluminum.

In addition, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention is any component selected from (A) sodium carbonate, sodium phosphate, sodium hydrogen carbonate, sodium citrate, sodium oxalate, sodium sulfate and mixtures thereof, (B) sodium 2-propenate 2-propenamide A moisture-proof rust preventive agent for aluminum comprising a polymer, (C) an alkali metal-based benzoate compound, a triazole-based compound and a mixture thereof, and (D) hexamethylenetetraamine.

In the moisture-proof anti-rust agent according to an embodiment of the present invention, the moisture-proof anti-rust agent is (A) 5 to 50% by weight of the component, (B) 20 to 80% by weight of the component, (C) 10 to 40% by weight of the component and (D) It may be a component containing 2 to 20% by weight.

In the moisture-proof rust preventive agent according to an embodiment of the present invention, the alkali metal-based benzoate is at least one selected from sodium benzoate, lithium benzoate and potassium benzoate, and the triazole-based compound is benzotriazole and tolitria. It may be any one or more selected from sol.

In the moisture-proof anti-rust agent according to an embodiment of the present invention, the moisture-proof anti-rust agent may further include any one component selected from cross-linked polyacrylate, uncrosslinked polyacrylate, and mixtures thereof.

In the moisture-proof anti-rust agent according to an embodiment of the present invention, the moisture-proof anti-rust agent may further include any one component selected from ethyl cellulose, sodium carboxymethyl cellulose, cellulose acetate, and mixtures thereof.

In addition, another aspect of the present invention relates to a rust-proof moisture-proof product for aluminum containing the moisture-proof rust-preventing agent.

Anti-rust and moisture-proof products for aluminum according to an embodiment of the present invention may include a breathable packaging film selected from the group consisting of Tyvek, polypropylene nonwoven fabric, polyethylene nonwoven fabric, polyethylene terephthalate nonwoven fabric, paper and cloth.

The moisture-proof anti-rust agent according to an aspect of the present invention can not only significantly improve the moisture absorption rate, but also realizes a very excellent performance of the anti-rust function even in extreme environments with high temperature and high humidity. In particular, it has an excellent corrosion resistance to aluminum.

In addition, the moisture-proof rust-preventive product according to the present invention has an effect of effectively preventing the occurrence of contamination due to phase separation, gelation, and transition due to excellent stability of the moisture-proof rust-preventing agent contained therein.

Figure 1 shows the appearance after evaluating the stability of the moisture-proof anti-rust product according to Example 1.
Figure 2 shows the appearance after evaluation of the stability of the moisture-proof anti-rust product according to Comparative Example 3.
Figure 3 shows the results according to the corrosion resistance evaluation of the aluminum test piece using the moisture-proof anti-rust product of Example 1.
Figure 4 shows the results according to the corrosion resistance evaluation of the aluminum test piece using the moisture-proof anti-rust product of Comparative Example 3.

Hereinafter, a moisture-proof anti-rust agent for aluminum and a moisture-proof anti-rust product for aluminum according to the present invention will be described in detail. The present invention can be better understood by the following examples. The following examples are for illustrative purposes of the present invention and are not intended to limit the scope of protection defined by the appended claims.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description of the present invention are only for effectively describing a specific embodiment and are not intended to limit the present invention.

Also, the singular form used in the specification and the appended claims may be intended to include the plural form unless otherwise indicated in the context.

Also, in the specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

Moisture-proof anti-corrosive agent according to the present invention

(A) any one component selected from sodium carbonate, sodium phosphate, sodium hydrogen carbonate, sodium citrate, sodium oxalate, sodium sulfate and mixtures thereof,

(B) 2-propenate sodium 2-propenamide polymer,

(C) any one component selected from alkali metal-based benzoate compounds, triazole-based compounds and mixtures thereof, and

(D) Hexamethylenetetraamine.

According to an aspect of the present invention, the component (A) has advantageous properties to impart hygroscopicity in a low temperature range or low humidity environment. (A) The component is any one or more substances selected from sodium carbonate, sodium phosphate, sodium hydrogen carbonate, sodium citrate, sodium oxalate, sodium sulfate, and the like, preferably using any one or more selected from sodium carbonate and sodium phosphate. It is effective in terms of stability after improvement and moisture absorption, but is not limited thereto. Further, the component (A) may further include a non-chlorine deliquescent moisture-proof material such as an acetate-based compound selected from the group consisting of calcium acetate, magnesium acetate and calcium acetate, or magnesium sulfide, but is not limited thereto.

The component (A) may be included in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight based on the total weight of the moisture-proof rust preventive agent. It is possible to improve the moisture absorption rate in combination with other components in the above range, it is possible to prevent liquefaction due to excessive moisture absorption and is effective in securing product stability, but this is only a non-limiting example and is limited to the numerical range Do not receive.

The (B) 2-propenate sodium 2-propenoate polymer (sodium 2-propenoate 2-propenamide polymer) effectively prevents the moisture-proof rust preventive agent is liquefied due to the deliquescent after moisture absorption, excellent in high temperature and high humidity environment It is used to realize hygroscopic performance. The 2-propenate sodium 2-propenamide polymer is not particularly limited in molecular weight, but is preferably 5 × 10 ⁶ g / mol to 100 × 10 ⁶ g / mol, more preferably 10 × 10 ⁶ g It may be / mol to 50 × 10 ⁶ g / mol, but this is only a non-limiting example and is not limited to the numerical range.

The 2-propenate sodium 2-propenamide polymer may be included in an amount of 20 to 80% by weight, preferably 30 to 70% by weight, and more preferably 40 to 60% by weight based on the total weight of the moisture-proof anti-corrosive agent. In combination with other components in the above range, a synergistic effect of product stability and moisture absorption performance is realized, but this is only a non-limiting example and is not limited to the above numerical range.

The component (C) is one or more selected from alkali metal-based benzoate compounds, triazole-based compounds, and the like, and in combination with other components in a moisture-proof rust preventive agent, provides moisture absorption performance as well as improved corrosion resistance of aluminum.

The alkali metal-based benzoate may be any one or more selected from sodium benzoate, lithium benzoate, potassium benzoate, and the like, but is not limited thereto.

The triazole-based compound may be any one or more selected from benzotriazole, tolytriazole, and the like, but is not limited thereto.

The component (C) may be included in an amount of 10 to 40% by weight, preferably 15 to 35% by weight, more preferably 20 to 30% by weight based on the total weight of the moisture-proof rust preventive agent. In combination with other components in the above range, a high moisture absorption rate is realized, in particular, corrosion resistance of aluminum is significantly improved, and it is effective in preventing discoloration, contamination, and transition of aluminum, but this is only a non-limiting example. It is not limited to the above numerical range.

The (D) hexamethylenetetramine (hexamethylenetetramine) has the advantage of improving the moisture absorption performance, as well as to improve the corrosion resistance of aluminum by being included simultaneously with the component (C).

The (D) hexamethylenetetraamine may be included in an amount of 2 to 20% by weight, preferably 3 to 15% by weight, and more preferably 5 to 10% by weight based on the total weight of the moisture-proof rust preventive agent. In combination with other components in the above range, a high moisture absorption rate and at the same time realize the effect of improving corrosion resistance to aluminum, but this is only a non-limiting example and is not limited to the above numerical range.

According to an aspect of the present invention, the moisture-proof rust preventive agent may include a crosslinked or uncrosslinked polyacrylate.

The crosslinked polyacrylic acid (crosslinked poly-acrylic acid) is not limited in its kind, but 2-propenoic acid (2-propenoic acid), sodium 2-propenoate (sodium 2-proenoate) as a monomer And a polymer having a polymer, acrylic acid, and sodium acrylate as a monomer. In addition, as commercialized products, GOODRICH's CARBOPOL, etc. may be mentioned, but are not limited thereto.

In addition, the moisture-proof rust preventive agent may include any one or more cellulose (cellulose) -based compounds selected from ethyl cellulose, sodium carboxymethyl cellulose, cellulose acetate, and the like.

The content of these components can be adjusted within a range that does not impair the object of the present invention, preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by weight relative to the total weight of the moisture-proof rust inhibitor.

The moisture-proof anti-rust agent for aluminum according to an aspect of the present invention is a non-chlorine-based material, and has a significantly improved moisture absorption rate and anti-rust performance. In addition, it has excellent hygroscopicity even under low humidity or low temperature conditions, and particularly has an effect of significantly improving corrosion resistance to aluminum. In addition, it is of course not limited to aluminum, and has an effect of improving corrosion resistance in non-ferrous metals, so that the application range can be broadened.

Another aspect of the present invention is to provide an anti-rust moisture-proof product for aluminum containing the above-described moisture-proof anti-rust agent.

The anti-rust-proof product may include the moisture-proof anti-rust agent in a breathable packaging material, a breathable container, a breathable bag, and the like, but is not limited thereto.

The breathable packaging material included in the rust-preventive moisture-proof product of the present invention may be used without particular limitation on its shape or size. The packaging material may be filled with a moisture-proof anti-corrosive agent through heat-sealing, but is not limited thereto.

The breathable packaging material may be a packaging film. For example, it may include at least two packaging films, and the shape of the packaging material may be described by those skilled in the art according to Korean Patent Publication No. 10-2013-0027402, Korean Patent Publication No. 10-2012-0093059, and Japanese Patent Publication No. 2010-076826. Can be used as appropriate. As a specific example, two pieces of packaging films cut into a desired shape are opposed to each other, and a moisture-proof anti-corrosive agent may be positioned between two pieces of packaging films facing each other.

The packaging film of the breathable packaging material included in the rust-proof moisture-proof product of the present invention may be a monolayer film or a laminate structure of the breathable film.

The packaging film used as the breathable packaging material is not limited in its kind, but Tyvek, polypropylene (PP, polypropylene) nonwoven fabric, polyethylene (PE, polyethylene) nonwoven fabric, polyethylene terephthalate (PET) nonwoven fabric , It may be to include a breathable packaging film selected from the group consisting of paper and cloth.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following examples and comparative examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

(evaluation)

(1) Stability

The phase separation, gelation and fouling resistance (contamination or transfer of the outer packaging material) of the contents of the specimen were visually evaluated after exposure for 20 days in a thermo-hygrostat at 50 ° C and 95% relative humidity. At this time, ○ if there is no change with respect to the above item, and if there is some change, it is indicated with ×.

(2) moisture absorption rate

After the specimen was exposed for 20 days at 50 ± 2 ° C and 95 ± 5% relative humidity using a thermo-hygrostat, the moisture absorption rate was measured, and the moisture absorption rate was calculated by the following equation.

(3) Corrosion resistance

After polishing the aluminum test piece of 90mm × 50mm standard (product A-23.5 manufactured by Q-LAB) using sandpaper, etc., clean it with ethanol and acetone. The aluminum test piece was prepared by sealing the PE breathable film of Han Chemical (Korea) together with the moisture-proof anti-corrosive agent prepared in Examples and Comparative Examples in a packaging material applied with PET of Toray Saehan (Korea) as an inner shell.

The test pieces were exposed for 30 cycles at 25 to 55 ° C and 93 to 95% relative humidity. At this time, as shown in FIG. 3, one cycle is exposed at 25 ° C and 98% relative humidity for the initial 2 hours, and after raising the temperature to 55 ° C for 1 hour and 30 minutes, 4 at 55 ° C and 95% relative humidity. After exposing for 30 minutes, the temperature was reduced to 25 ° C for 30 minutes, and then exposed for 1 hour and 30 minutes at 25 ° C and 95% relative humidity. Subsequently, the corrosion resistance of the test piece was visually observed, and ○ if corrosion did not occur, and × if corrosion occurred.

(Example 1)

As shown in the composition ratio in Table 1, sodium carbonate (A-1) 20% by weight, 2-propenate sodium 2-propenamide polymer (B-1) (OCI-SNF, Mw 25 Mg / mol) 50% by weight, 2% by weight of benzotriazole (C-1), 23% by weight of sodium benzoate (C-2) and 5% by weight of hexamethylene tetraamine (D-1) were uniformly mixed using a mixer to prepare a moisture-proof anti-rust agent 25g Did. Subsequently, a moisture-proof anti-corrosive agent was added to a breathable packaging material having a length of 100 mm and a width of 100 mm, and then sealed at 120 ° C. using a heat sealing machine to prepare a specimen. The prepared specimens were evaluated for physical properties, moisture absorption, stability, and corrosion resistance, and the results are shown in Table 2 below.

(Example 2)

The specimens were prepared in the same manner as in Example 1, except that sodium phosphate (A-2) was used instead of sodium carbonate (A-1).

(Example 3)

Performed in the same manner as in Example 1, sodium carbonate (A-1) 20% by weight, sodium 2-propenate 2-propenamide polymer (B-1) 50% by weight, sodium benzoate (C-2) 25% by weight And it was carried out in the same manner as in Example 1, except that 5% by weight of hexamethylene tetraamine (D-1) was mixed to prepare a specimen and then evaluate the physical properties, and the results are shown in Table 2 below.

(Example 4)

The same procedure as in Example 1 was carried out, but sodium carbonate (A-1) 20% by weight, sodium 2-propenate 2-propenamide polymer (B-1) 50% by weight, benzotriazole (C-1) 10% by weight , Sodium benzoate (C-2) 10% by weight and hexamethylene tetraamine (D-1) 10% by weight, except for mixing in the same manner as in Example 1 to prepare a specimen and evaluate the physical properties The results are shown in Table 2 below.

(Example 5)

The same procedure as in Example 1, except that the content of hexamethylene tetraamine (D-1) was changed to 3% by weight, and 2% by weight of crosslinked polyacrylic acid (CARBOPOL 940) was used. After preparing a specimen by performing the same method as in Table 2, the results were evaluated by evaluating the physical properties.

(Comparative Example 1)

In Example 1, sodium carbonate (A-1) 25% by weight, 2-propenate sodium 2-propenamide polymer (B-1) (OCI-SNF, Mw 25 Mg / mol) 50% by weight, benzotriazole (C-1) 5% by weight and 20% by weight of sodium benzoate (C-2) were uniformly mixed using a mixer to prepare a specimen in the same manner as in Example 1, except that 25 g of a moisture-proof anti-rust agent was prepared. After preparing, the properties were evaluated and the results are shown in Table 2 below.

(Comparative Example 2)

In Example 1, sodium 2-propenate 2-propenamide polymer (B-1) (OCI-SNF, Mw 25 Mg / mol) 60% by weight, benzotriazole (C-1) 4% by weight, sodium 28% by weight of benjoate (C-2) and 8% by weight of hexamethylene tetraamine (D-1) were uniformly mixed using a mixer to prepare a moisture-proof anti-rust agent 25g.

(Comparative Example 3)

In Example 1, sodium carbonate (A-1) 20% by weight, 2-propenate sodium 2-propenamide polymer (B-1) (OCI-SNF, Mw 25 Mg / mol) 50% by weight, benzotriazole (C-1) 4% by weight and 26% by weight of sodium benzoate (C-2) were uniformly mixed using a mixer to prepare a moisture-proof anti-rust agent 25g.

(Comparative Example 4)

As a control, after using a moisture-proof anti-rust agent for iron (LF D-101, Rust Chemical), the physical properties were evaluated and the results are shown in Table 2 below.

Content (% by weight) A-1 A-2 B-1 C-1 C-2 D-1 E-1 Example 1 20 - 50 2 23 5 - Example 2 - 20 50 2 23 5 - Example 3 22 - 50 - 25 3 - Example 4 20 50 10 10 10 - Example 5 20 - 50 2 23 3 2 Comparative Example 1 25 - 50 5 20 - - Comparative Example 2 - - 60 4 28 8 - Comparative Example 3 20 - 50 4 26 - - Comparative Example 4 Moisture-proof anti-rust products -

Water absorption rate (%) stability Corrosion resistance of aluminum Phase separation Gelation Pollution resistance Example 1 181 ○ ○ ○ ○ Example 2 138 ○ ○ ○ ○ Example 3 150 ○ ○ ○ ○ Example 4 142 ○ ○ ○ ○ Example 5 186 ○ ○ ○ ○ Comparative Example 1 62 × × × × Comparative Example 2 65 × × × × Comparative Example 3 63 × × × × Comparative Example 4 70 ○ × ○ ×

As shown in Table 2, the embodiments of the present invention implement a very high level of moisture absorption, and the stability is excellent, so that the contents do not have any contamination due to phase separation, gelation, and transition. Moreover, it was confirmed that the corrosion resistance to aluminum was excellent. 1 shows the appearance of a moisture-proof anti-rust agent after the stability evaluation according to Example 1, and was not contaminated at all. In addition, Figure 3 shows the aluminum test piece after evaluation of the corrosion resistance of aluminum, and was not discolored or contaminated at all. Particularly, in the case of Example 5 including cross-linked polyacrylic acid, the stability evaluation test conducted for 20 days was extended to 150 days, and despite the long-term, there was no change in phase separation or contamination of the contents, so long-term stability was very high. I was able to confirm the excellence. On the other hand, it was confirmed that the comparative examples were unable to secure stability due to phase separation of the contents, and the packaging material was contaminated or did not implement corrosion resistance to aluminum. 2 and 4, it was confirmed that the moisture-proof anti-rust agent was contaminated or aluminum was discolored after the stability evaluation.

Through this, the moisture-proof anti-corrosive agent according to an aspect of the present invention is expected to be more useful in various metal fields including aluminum through a high moisture absorption performance of 100% or more and a remarkable increase in corrosion resistance to aluminum.

Although the preferred embodiments of the present invention have been described above, the present invention can use various changes and equivalents, and it is clear that the above embodiments can be appropriately modified and applied in the same way. Therefore, the above description is not intended to limit the scope of the present invention as defined by the following claims.

Claims (6)

(A) any one component selected from sodium carbonate, sodium phosphate, sodium hydrogen carbonate, sodium citrate, sodium oxalate, sodium sulfate and mixtures thereof,
(B) 2-propenate sodium 2-propenamide polymer,
(C) any one component selected from alkali metal-based benzoate compounds, triazole-based compounds and mixtures thereof, and
(D) Moisture-proof anti-rust agent for aluminum containing hexamethylenetetraamine. According to claim 1,
The moisture-proof anti-rust agent for aluminum comprising (A) 5 to 50% by weight of the component, (B) 20 to 80% by weight of the component, (C) 10 to 40% by weight of the component, and (D) 2 to 20% by weight of the moisture-proof anti-rust agent for aluminum. . According to claim 1,
The alkali metal-based benzoate is at least one selected from sodium benzoate, lithium benzoate and potassium benzoate, and the triazole-based compound is a moisture-proof anti-rust agent for aluminum at least one selected from benzotriazole and tolytriazole. According to claim 1,
The moisture-proof anti-rust agent is a cross-linked or uncrosslinked polyacrylic acid salt, ethyl cellulose, sodium carboxymethyl cellulose and cellulose acetate, further comprising any one or more selected from the group consisting of moisture-proof anti-rust agent for aluminum. An anti-rust and moisture-proof product for aluminum, comprising a moisture-proof and anti-rust agent selected from claims 1 to 4. The method of claim 5,
The anti-corrosion and moisture-proof product comprises a breathable packaging film selected from the group consisting of Tyvek, polypropylene non-woven fabric, polyethylene non-woven fabric, polyethylene terephthalate non-woven fabric, paper and cloth.

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