BR102012004960A2 - anti-corrosion composition - Google Patents

Abstract

ANTICORROSIVE COMPOSITION. The present invention relates to an anti-corrosion composition comprising 100 parts by weight of a polyolefin resin having a density of 0.880 to 0.95 g / cm3 and a mfr of 0.1 to 30.00g / 10min, and 0.1 to 10 parts by weight of one, two or more volatile anticorrosive agents selected from amine / ammonium / ammonium / inorganic acid metal salt or an organoic acid, a urea compound, and a heterocyclic compound, wherein 0.2 to 30.0 parts by weight of one, two or more porous adsorbents having an average particle size of 0.1 to 20 µm and a specific surface area of 100 to 800 m 2 / g selected from porous silica, and zeolite They are dispersed with respect to 1 part by weight of the anti-corrosive agent to then maintain evaporation and release the amount of volatile antechamber for a long time. packaging material which can not only perform an anti-corrosion function during transport provided by conventional anti-corrosion packaging materials but also stably maintain the same function for a long time in the environment of the place where metal products are used. Furthermore, the present invention relates to a packaging material formed from said anti-roadway composition.

Description

Descriptive Report of the Invention Patent for "ANTICORROSIVE COMPOSITION".

Technical Field

The present invention relates to an anti-corrosion composition and a packaging material for packaging and preserving various types of metal products which require protection against oxidation.

Description of Related Art

To transport metallic products in the anti-corrosion packaging, the method of transporting the products moistened in anti-corrosion oil has been adopted, thus eliminating contact with air or the method of transporting them wrapped in an anti-corrosion paper (paper with corrosion inhibiting agent application). ). But 30 or 40 years ago, when exporting auto parts and other metal products abroad, there was a tendency to look for low-cost packaging materials that were easy to handle and did not require as much work to use. As a result, plastic packaging materials that show an anti-corrosion function during transportation have been developed by some companies and individuals.

But at the present time when users require not only the availability of the limited corrosion protection function only during the transport process, but also a guarantee of storage in the metal products warehouse as the responsibility of the manufacturer of the same products, there is a tendency The demand for packaging material manufacturers to provide materials capable of preserving the anti-corrosion function also during the storage period in the warehouse prevents the deterioration of the function of metal products.

Above all, if the shelf life of the product is guaranteed for a long period of 10 years, some measures are required to prevent the formation of oxidation on the surface of metal products for a very long period of time, but it is It is very difficult to store such products so as not to allow oxidation to form during the storage period.

A volatile corrosion inhibiting agent is divided into two types, immediate effect corrosion inhibiting agent and slow effect corrosion inhibiting agent, according to the characteristic perspiration of this substance. By adding only one corrosion inhibiting agent with immediate effect, it emits a large amount of the anti-corrosion component in a short time, but is not suitable for a long time anti-corrosion effect. Furthermore, the use of only slow-acting corrosion inhibiting agent is not sufficient for the initial anti-corrosion effect.

For this reason, the combination of the immediate effect corrosion inhibiting agent and the slow effect corrosion inhibiting agent is used as a technique to develop a stable anti-corrosion prevention effect.

On the other hand, to obtain a long time effect of the volatile corrosion inhibiting agent, there is a technique for dispersing and supporting it in the resin. As the resin in this case, a non-polar polyolefin resin is often selected, with its typical example being low density polyethylene because it is easy to treat, but in general this type of resin is hardly compatible with the corrosion inhibiting agent. whereby the volatile behavior of the corrosion inhibiting agent is still unstable for a long period of time.

An addition of a large amount of the inhibitor of

Corrosion to compensate for it mentioned above causes a so-called bleed-out or bloom-out phenomenon by depositing the corrosion inhibiting agent on the surface of the packaging product within a relatively short period of time after its manufacture. This phenomenon not only noticeably deteriorates the appearance of the goods, severely reducing the commercial value, but also leads to a possibility of generating foreign body contamination by the direct adhesion of this deposit to metal products or other grievance problems, hence the addition thereof. cannot be recognized as a sufficient prevention method.

In addition, simply mixing the corrosion inhibiting agent into the

Non-polar polyolefin can cause oxidation to form after a few years of preservation, which ultimately made it difficult to maintain the anti-corrosion effect for the period of a few years for the shelf-life of the metal products. Some examples of a molded body consisting of mixing the corrosion inhibiting agent in the resin are shown in the aforementioned patent documents 1 to 3, but these examples are limited to the composition containing thermally bondable polyolefin, volatile corrosion inhibiting agent, powder. oxidizable metal and zeolite in document 1; the thermoplastic resin composition, for example LDPE, containing volatile corrosion inhibiting agent, for example alkyldicarboxylic acid ammonium salt, in document 2; and to the anti-corrosive molded body 10 consisting of a mixture of polyolefin, etc., of the filler such as calcium carbonate, etc., and the corrosion inhibiting agent which is an inorganic acid salt or organic amine organic acid, in the document. 3; and do not correspond to an invention which attempts to develop anti-corrosion characteristics over a long period of time by adding a porous filler with a specified specific surface.

Patent Document 1 is Japanese Patent Publication No. 2010-254350

Patent Document 2 is Japanese Patent Publication No. 2007-308726

Patent Document 3 is Japanese Patent Publication No. Hei 11-181143

An object of the present invention is to provide an anti-corrosion composition to be used in a packaging material which not only has an anti-corrosion function at the time of transport provided by conventional anti-corrosion packaging materials, but which can keep the anti-corrosion function stable for a long time. period of time in an environment of the place where a metal product is stored, and provide a packaging material formed from the anticorrosive composition.

SUMMARY OF THE INVENTION

The present invention provides an anti-corrosion composition wherein a corrosion inhibiting agent is gradually evaporated and released over a long period of time in each environment by dispersing porous adsorbent on a base comprising resin and a volatile corrosion inhibiting agent, as well as a A method for improving the viability of the anti-corrosion effect provided by conventional anti-corrosion compositions 5 for greater stability over a long period of time by the following means:

1. An anti-corrosion composition comprising 100 parts by weight of a polyolefin resin having a density of 0.880 to 0.950 g / cm3 and an MFR of 0.1 to 30.0 g / 10 min, and 0.1 to 10 parts by weight. on one,

two or more volatile anti-corrosive agents selected from amine / ammonium salt / inorganic acid metal or an organic acid, a urea compound, and a heterocyclic compound, wherein 0.2 to 30.0 parts by weight of one, Two or more porous adsorbents having an average particle size of 0.1 to 20 pm and a specific surface area of 100 to 15 800 m2 / g selected from porous silica, porous alumina, and zeolite are dispersed relative to 1 part. by weight of the anti-corrosion agent to then maintain evaporation and release the amount of volatile anti-corrosion agent for a long time.

packaging material which can not only develop an anti-corrosion function during transport provided by conventional anti-corrosion packaging materials, but also stably maintain the same function for a long time in the environment where metal products are used.

2. packaging material comprising an anti-corrosion composition according to item 1.

As described above, an anti-corrosion packaging material comprising an anti-corrosion composition containing a volatile anti-corrosion agent and a porous adsorbent dispersed in a polyolefin resin is thereby formed to control evaporation and the amount of anti-corrosion agent to ensure the effect. anti-corrosion on a metal part over a long period of time thus avoiding reducing the quality value of the metal product due to the generation of rust. At the same time, it is possible to provide an anti-corrosion packaging material that is easily handled by an operator, as the smell and bleeding phenomenon of an anti-corrosion agent is reduced by controlling the free amount of the anti-corrosion agent.

Brief Description of the Drawings

Figure 1 shows the residual rate of a corrosion inhibiting agent for each porous adsorbent;

Figure 2 shows the residual rate of a corrosion inhibiting agent on each specific surface area of silica; and Figure 3 shows the residual rate of a color inhibiting agent.

roson in each added quantity of silica.

Detailed Description of Preferred Modalities

The inventors of the present invention have for the first time come to an anti-corrosion composition with a sustained anti-corrosion effect over a long period of time by adding and combining a specific porous adsorbent which is a third component to an anti-corrosion resin composition containing specific resin and a specific anti-corrosion agent.

As the base resin to be used in the present invention, polyolefin resins useful in the treatment, safety and the environment, for example, alpha olefin homopolymers such as polyethylene, polypropylene, can be cited from experiments to date. ; ethylene copolymers with C3 -C8 alpha olefins, such as ethylene propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methyl-1- pentene copolymer, ethylene-hexene copolymer; or copolymers of ethylene organic carboxylic acid derivatives having ethylenically unsaturated bond, such as ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, ethylene vinyl acetate methylmethacrylate copolymer, etc.

For example, if you use it as a packaging material,

Polyethylene should be selected from the abovementioned resins taking into account its product cost and manufacturing convenience, and can be adopted considering the characteristics of various types of polyethylene; from low density polyethylene to high density polyethylene.

Nevertheless, it is desirable to select from experiments to date a polyethylene having a density of from 0.880 to 0.950 g / cm3, preferably from 0.910 to 0.930 g / cm3.

With respect to the molding measures of said resin, there are no specifically established limitations and thus the well-known resin molding measures can be adopted.

In the present invention, the volatile corrosion inhibiting agent refers to one or two or more types of volatile corrosion inhibiting agents selected from amine / ammonium / inorganic acid or organic acid metal salts, urea compounds or heterocyclic compounds. As examples, organic amine salts selected from salts of phosphoric acid, nitrous acid, carbonic acid or carboxylic acid 15 of mono-, di-, tri-ethanoloamine, n-, di-, tert. butylamine, hexamethylenediamine, hexamethylenetetramine, mono-, di-cyclohexylamine, isopropylamine, oleylamine, naphthylamine or di-phenylamine; carboxylic acid ammonium salts selected from ammonium phthalate, ammonium benzonate, ammonium stearate, dodecanoic acid ammonium, decanoic acid ammonium, ammonium sebacate and ammonium adipate; urea compounds selected from urea, methylurea, ethylurea, propylurea, thiourea and urotropin; heterocyclic compounds selected from benzotriazole, tolyltriazole, carboxybenzotriazole, 5-hydroxybenzotriazole, 3-methyl-5-hydroxypyrazole, 5-amino-1H-tetrazole, imidazole, 2-methylimidazole, 5-methylimidazole, benzoimidazole and mercaptobenzothiazole.

It is also possible to further improve the added anticorrosive effect.

as required, alkali metal salts or alkaline earth metal salts of inorganic acid, for example nitrous acid, carbonic acid, phosphoric acid, boric acid, silicon acid, etc., which have no volatility.

With respect to the amount of addition of volatile inhibitor

suitable amount varies depending on the object metals and the required anti-corrosive effect, and furthermore on the vapor pressure characteristics of the above mentioned volatile corrosion inhibiting agents, and generally, if the same amount turns out to be too small, A sufficient anti-corrosion effect can be obtained because the anti-corrosion components do not disperse to a great extent, and on the contrary, if it turns out to be too large, the bleed-out phenomenon is caused. Therefore, to obtain a stable effect, it is effective to add 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight from the point of view of manufacture, of the volatile corrosion inhibiting agent based on 100 parts by weight. weight of MFR polyolefin resin from 0.1 to 30.0 g / 10 10 min.

But, the upper limit value of this amount of volatile corrosion inhibiting agent addition is applicable in this invention when using a porous adsorbent mentioned below, and when the porous adsorbent is not added, the maximum amount added without causing the bleed-out of the Volatile corrosion inhibiting agent is at much lower level.

Then the main function of this invention is durability of the anti-corrosion effect. For this purpose, the amount of volatilization and emission of the volatile corrosion inhibiting agent can be controlled according to the amount of addition of the third porous adsorbent component. Furthermore, the porous adsorbent, when dispersed in the resin, may also contribute to reducing the bleed-out phenomenon of the volatile corrosion inhibiting agent and to reducing the odor of the same anti-corrosion inhibiting agent.

The porous adsorbent to be used in this invention is selected from porous silica, porous alumina and zeolite. By reference to porosity, it is desirable to have a specific surface area of at least 100 m 2 / g or more, preferably 300 m 2 / g or more. And taking into account the dispersion required to disperse the volatile corrosion inhibiting agent to a large extent in the base resin, it is preferable that the specific surface be 800 m2 / g or less.

The amount of addition of the porous adsorbent must be

varied according to the amount of addition of the volatile corrosion inhibiting agent, because the addition of insufficient amount of the same adsorbent may cause the inhibitor to bleed out on the base resin surface, and the addition of too much may not only deteriorate the nature of the surface of the product, but also too much preserve the volatile corrosion inhibiting agent preventing the appearance of anti-corrosion effect. Therefore, to obtain a stable anti-corrosion effect, it is desirable to use 0.2 to 30 parts by weight, preferably 1.0 to 15 parts by weight, of the porous adsorbent based on 1 part by weight of the corrosion inhibiting agent, and Considering this amount limit, it is necessary to choose a composition and amount of addition of the volatile corrosion inhibiting agent so that the anti-corrosive effect appears on the metal object parts for a long period of time.

The following is a more specific explanation of the present invention by citing embodiments, but the present invention is undoubtedly not subject to limitations given by the following embodiments, and of course may be carried out with appropriate modifications within the limits. acceptable to the above and below descriptions. Such modifications will be included within the limits of the present invention.

Example 1

1.0 part by weight of benzoic acid salt was mixed

cyclohexylamine and 1.0 part by weight of pore silica powder with a mean grain diameter of 3,9 μητι and a specific surface area of 300 m2 / g, porous alumina with a medium grain diameter of 10 pm and a specific surface area of 200 µm m2 / g, a mixture of the same silica and alumina (mixing ratio: 25 1: 1,5) and of a zeolite with a mean grain diameter of 2,5 μιτι and a specific surface area of 100 m2 / g respectively, based on 100 parts by weight of the low density polyethylene resin (Sumikasen F218-1, manufactured by SUMITOMO CHEMICAL Co., Ltd., density = 0.919, MFR = 1.0), and after mixing this mixture with an extruder of double screw, the composite pellets were produced by treating the same mixture by means of a pelletizer. From these pellets a 100 µm thick film was molded at a molding temperature of 150 ° C using the inflation molding method. The degradation behavior as a function of the time of corrosion inhibiting agent shown in this film is shown in Figure 1 and the result of the anti-corrosion test in Table 1.

Figure 1 shows the corrosion inhibiting agent residual rate as a function of time, which decreases by reaching the end of the accelerated test period of 10 days approx. 40% in the case of silica, alumina and mixture of silica and alumina and 30% in the case of zeolite, but in the example of comparison without the addition of porous adsorbent, the same rate is reduced reaching approx. 10%. This result indicates that by the addition of the porous adsorbent the volatilization of the corrosion inhibiting agent is controlled.

Table 1 shows the result of verifying the anti-corrosion effect of each composition of Example 1 and the composition of Example 1, and seeing in detail the same result for the 10-day accelerated test period, it is noted that Example 1 shows a symbol Δ (meaning oxidation formation on less than 10% of the surface of the test sample) on the second day and increased oxidation formation on the following days, while the exemplary embodiment

1 indicates no oxidation formation except for the 100 m 2 zeolite, which is marked with the symbol O (meaning less than 30 oxidations of 1 mm or less), whereby it can be understood that the present invention develops a remarkable effect by having porous adsorbents with a specific surface area.

Table 1

Confrontation of anti-corrosion effects 1

Embodiment Example 1 Comparison Example 1 PE (parts by weight) 100 100 100 100 100 Benzoic acid-cyclo-salt 1.0 1.0 1.0 1.0 1.0 hexylamine (parts by weight) Silica 300 m2 (parts by weight) 1.0 - 0.4 - 200 m2 alumina (parts by weight) - 1.0 0.6 - 100 m2 zeolite (parts by weight) - - - 1.0 Result After 2 days @ (Q) (Q) Δ Example 1 Test Match Example 1 After 4 Days @ ® ® ® X After 6 Days ® ® © X After 8 Days ® ® ® XX After 10 Days ® ® OXX Example 2

1.0 part by weight of benzoicocyclohexylamine acid salt and 1.0 part by weight of 5 types of pore silica powder of average grain diameter from 2.7 to 14.1 pm and specific surface of 50, 100 were mixed. , 300, 500 or 700 m2 / g respectively, based on 100 parts by weight of low density polyethylene resin (Sumikasen F218-1, manufactured by SUMITOMO CHEMICAL Co., Ltd., density = 0.919, MFR = 1.0 ), and after mixing with a double screw extruder, the composite pellets were produced by treating the same mixture by means of a pelletizer. From these pellets, a 100 µm thick film was molded at a molding temperature of 150 ° C using the inflation molding method. The degradation behavior as a function of the time of corrosion inhibiting agent shown in this film is shown in Figure 2 and the result of the anti-corrosion test in Table 2.

Figure 2 shows that in each case where the surface is

If the specific silica content is 300 m 2 to 700 m 2, the residual rate of the corrosion inhibiting agent is maintained at approximately 40 to 50% even after 10 days of the accelerated testing period, while the same rate is reduced by about 30%. for the specific area of 20 100 m2 and at the lowest level of 20% for the specific area of 50 m2. Naturally in case of no addition of silica, the same rate is reduced more to approximately 10%. This example of a specific surface area of 50 m2 corresponds to the confrontation example.

Reflecting such a nature, as shown in Table 2, no oxidation formation is observed throughout the test period until 10 days should a specific silica surface of 300 to 700 m2 be adopted. If a specific silica surface of 100 m2 is adopted, the result bears an O symbol (meaning less than 30 oxidations of 1 mm or less) after 8 days and Δ (meaning oxidation). less than 10% of the surface of the test sample) after 10 days, making it clear that the anti-corrosion function can be developed in any case for a long period of time.

Table 2

Confrontation of anti-corrosion effects 2

Embodiment Example 2 Comparative Example PE (parts by weight) 100 100 100 100 100 100 Benzoic acid salt 1.0 1.0 1.0 1.0 1.0 1.0 co-cyclohexylamine (parts by weight) ) Surface 50m2 1,0 - - - - 100m2 - 1,0 - - - 300m2 - - 1,0 - - 500m2 - - - 1,0 - 700m2 - - - - 1,0 Result After 2 O (Q) ® ® Δ of the test days After 4 O (Q) ® ® X days After 6 Δ (Q) ® ® X days After 8 Δ O ® XX days After X Δ ® ® ® XX days Achievement Example 3

1.0 part by weight of benzoic acid salt was mixed

cyclohexylamine and 0.1, 0.5, 1.0, 10.0 and 50.0 parts by weight of 300 m2 / g specific surface silica component based on 100 parts by weight of the polyethylene resin of low density (Sumikasen F218-1, manufactured by SUMITOMO CHEMICAL Co., Ltd., density = 0.919, MFR = 1.0), and after mixing this mixture with a double screw extruder, composite pellets were treated by treating the same. mixing by means of a pelletizer. From these pellets a 100 µm thick film was molded at a molding temperature of 150 ° C using the inflation molding method. The degradation behavior as a function of the time of corrosion inhibiting agent shown in this film is shown in Figure 3 and the result of the anti-corrosion test in Table 3.

According to Figure 3, the residual rate of corrosion inhibiting agent tends to be high as the amount of silica addition increases, and in case of addition of 50.0 parts by weight, the same rate exceeds 10 70%. after 10 days. And with the addition of 0.1 parts by weight, the residual rate of corrosion inhibiting agent continues to fall to just 20% or so after 10 days. This example of 0.1 parts by weight corresponds to the example of confrontation.

According to Table 3, if the silica addition amount is 1.0 and 10.0 parts by weight, based on 100 parts by weight of the low density polyethylene resin, no formation is observed. oxidation throughout the test period up to 10 days, and in case of the addition of 0.5 parts by weight, no oxidation formation is observed until after 6 days, but since then the test result 20 worsens taking □ (meaning oxidation formation on less than 10% of the sample surface) after 10 days. In case of the addition amount of 0.1 and 50.0 parts by weight, the result always takes O (which means less than 30 oxidations of 1 mm or less) until 4 days, but since then more oxidation formation.

It can be considered that this tendency of oxidation formation

is observed due to the reduction of the amount of corrosion inhibitor volatilization, which occurs because by increasing the amount of addition of silica the corrosion inhibitor becomes adsorbed on it and with this situation the corresponding test period passes.

30 Table 3

Confrontation of anti-corrosion effects 3

Embodiment Example 3 Comparative Example PE (parts by weight 100 100 100 100 100 100 100 so) Acid salt ben 1.0 1.0 1.0 1.0 1.0 1.0 zoocyclohexylamine (parts by weight ) C silica S00 m2 0,1 0,5 1,0 10,0 50,0 (parts by weight) Result After O @ ® O Δ of the test 2 days After O ® ® OX 4 days After Δ ® ® ® Δ X 6 days After Δ O ® ® Δ XX 8 days After X Δ ® ® Δ XX days Realization Example 4

0.3 parts by weight of tolyltriazole, 0.05, 0.2,

0.8, 3.2, 12.8 parts by weight of silica component, based on 100 parts by weight of low density polyethylene resin (Sumikasen F218-1, manufactured by SUMITOMO CHEMICAL Co., Ltd., density =

0.919, MFR = 1.0), and after mixing this mixture with a double screw extruder, composite pellets were produced by treating the same mixture by means of a pelletizer. From these pellets a 40 μιτι thickness film was molded at a molding temperature of 150 ° C using the inflation molding method. The result of the anti-corrosion test of this film is shown in Table 4.

This embodiment 4 is an example in which 0.3 parts by weight of tolyltriazole was added instead of 1.0 parts by weight of benzoic acid-cyclohexylamine salt used in embodiment example 3, but the result of the Anticorrosive effect of this embodiment 4 was almost equal to the result obtained in embodiment 3. In the case of addition of 0.05 parts by weight of the silica, the test result bears the symbol Δ after 10 days, due to the lower amount of addition of silica regarding

0.3 parts by weight of tolyltriazole used as volatile corrosion inhibiting agent. This example of adding 0.05 parts by weight corresponds to the comparative example.

Table 4

_Comparison of anti-corrosion effects 4 _

Example 4 Example with paractiv 2 PE (parts by weight) 100 100 100 100 100 100 Tolyltriazole (parts by 0.3 0.3 0.3 0.3 0.3 0.3 weight) 300 m2 silica 0.05 0 , 2 0.8 3.2 12.8 (parts by weight) After 2 ® ® ® ® ® days After 4 ® ® ® OO days Result After 6 O ® ® ® OO test days After 8 OO ® ® O Δ days After 10 Δ O ® ® O Δ days Example 5

0.5 part by weight of benzoic acid salt was mixed

cyclohexylamine, 0.5 parts by weight of cyclohexylamine carbamate, 0.3 parts by weight benzotriazole, 0.1, 0.5, 1.0, 10.0 and 50.0 parts by weight of 15 silica component, based on 100 parts by weight of low density polyethylene resin (Sumikasen F218-1, manufactured by SUMITOMO CHEMICAL Co., Ltd., density = 0.919, MFR = 1.0), and after mixing this mixture With a double screw extruder, composite pellets were produced by treating the same mixture by means of a pelletizer. From these pellets a 100 µm thick film was molded at a molding temperature of 150 ° C using the inflation molding method. The result of the anti-corrosion test of this film on Ta5 bela 5 is shown.

This exemplary embodiment 5 is an example in which 0.5 parts by weight of benzoic acid cyclohexylamine salt, 0.5 parts by weight of cyclohexylamine carbamate and 0.3 parts by weight of benzotriazole were added. instead of 1.0 part by weight of benzoic acid-cyclohexylamine salt used in embodiment example 3, but in this embodiment 5 no oxidation formation is observed on the steel plate or the copper plate over the entire period. 10 days after the addition of 1.0 to 10.0 parts by weight of the silica, and oxidation is observed on both metals: on the steel plate after 6 15 days and on the copper plate after 8 days, if 0.5 parts by weight of silica are added, it may be considered that the formation of oxidation upon addition of 50.0 parts by weight of silica occurs due to the state of the corrosion inhibiting agent. adsorbed on silica, which lasts during the corresponding test period. you. Also in the case of addition of 0.120 parts by weight of the silica, oxidation formation occurs over the course of the trial period, as is the case of the addition of 50.0 parts by weight. These examples of adding 0.1 parts by weight and 50.0 parts by weight correspond to the comparison example.

Table 5

Confrontation of anti-corrosion effects 5

Embodiment Example 5 Comparative Example3 PE (parts by weight) 100 100 100 100 100 100 Benzoic acid salt 0.5 0.5 0.5 0.5 0.5 0.5 cyclohexylamine (parts by weight) Carbamate 0.5 0.5 0.5 0.5 0.5 0.5 Embodiment Example 5 Comparative Example3 hexylamine (parts by weight) Benzotriazole (parts by 0.3 0.3 0.3 0.3 0 0.3 weight) 300 m2 silica (parts 0.1 0.5 1.0 10.0 50.0 weight) Result After 2 days O © © O Δ After 4 days O © © OX After 6 days Δ © © Δ X After 8 days Δ O © © Δ XX After 10 X Δ © © Δ XX days Result After 2 days © © © O After 4 days O © © OO After 6 days O © © © O Δ After 8 days O © © O O Δ After 10 Δ O © O Δ days Comparative example 1

1.0 part by weight of benzoic acid salt was mixed

cyclohexylamine, based on 100 parts by weight of low density polyethylene resin (Sumikasen F218-1, manufactured by SUMITOMO CHEM5 ICAL Co., Ltd., density = 0.919, MFR = 1.0), and after kneading In this mixture with a double screw extruder, the composite pellets were produced by treating the same mixture by means of a pelletizer. From these pellets a 100 µm thick film was molded at a molding temperature of 150 ° C using the inflation molding method.

The degradation behavior as a function of the time of corrosion inhibiting agent shown in this film is shown in Figures 1, 2, 3 and the result of the anti-corrosion test in Tables 1, 2, 3. Comparative Example 2

0.3 parts by weight of tolyltriazole based on 100 parts by weight of low density polyethylene resin (Sumikasen F218-1, manufactured by SUMITOMO CHEMICAL Co., Ltd., density 5 = 0.919, MFR = 1, 0), and after mixing this mixture with a double screw extruder, the composite pellets were produced by treating the same mixture by means of a pelletizer. From these pellets a 40 μιτι thickness film was molded at a molding temperature of 150 ° C using the inflation molding method. The result of the anti-corrosion test of this film is shown in Table 4.

Comparative Example3

0.5 parts by weight of benzoicocyclohexylamine acid salt, 0.5 parts by weight of cyclohexylamine carbamate, 0.3 parts by weight of benzotriazole, based on 100 parts by weight of polyethylene resin 15 low density (Sumikasen F218-1, manufactured by SUMITOMO CHEMICAL Co., Ltd., density = 0.919, MFR = 1.0), and after mixing this mixture with a double screw extruder, composite pellets were treated by same mixture by means of a pelletizer. From these pellets a 100 µm thick film was molded at 20 ° C at a molding temperature of 150 ° C using the inflation molding method. The result of the anti-corrosion test of this film is shown in Table 5.

A. Checking Corrosion Inhibitor Reduction Rate

An Erlenmeyer flask with a ground glass joint was fitted with the anti-corrosion film cut into very small pieces after the completion of the anti-corrosion assessment of a specified period of time, water and stir bar, and a reflux tube was then installed in the mouth of the balloon. by shaking in a 90 ° C water bath for one hour to extract the corrosion inhibiting agent components. The extracted liquid was prepared by applying the liquid prepared in high performance liquid chromatography to determine the concentration of the corrosion inhibiting agent. B. Anti-Corrosion Proof

A frame of length 100 mm x width 100 mm x height 150 mm with proof samples mentioned below in item [C] attached by a fishing line was inserted into the previously produced tubular film, treated to be raised, and then The same film was thermally sealed. After disposing of this test mode in the environment mentioned below in item [D], an evaluation of the oxidation formation on the metal surface was made according to the evaluation criterion mentioned below in item [E],

C. Proof Samples

Test Samples Metal Name Standard Size JIS Cast Iron 030 x 10 mm JIS G 5501 Steel Plate 1.0 x 30 x 50 mm JIS G 3141 Copper Plate 1.0 x 30 x 50 mm JIS H 3100 D. test

Automatic cyclic environmental proofing device for 12 hours total / cycle: low temperature: 25 ° C with 75% RH (4 hours); temperature

high: 50 ° C with 95% RH (4 hours); two hours for temperature and humidity variation.

Proofing Device: PR4KP manufactured by ESPEC CORP.

E. Criteria for evaluation @: No oxidation

O: Formation of less than 30 oxidations of 1 mm or less

Δ: Oxidation formation on less than 10% of the sample surface

x: Oxidation formation on less than 50% of sample surface

x x: Oxidation formation on 50% or more of the surface of the

proof sample

According to Figure 1 and Table 1 it is understood that by adding the silica, alumina or zeolite with the specific surface of 100 m2 or more, a corrosion inhibiting agent can be attributed a long time preservation characteristic, and At the same time, a long time durability of the anti-corrosion effect can be obtained.

According to Figure 2 and Table 2, it is believed that the charac-

long-term corrosion inhibiting agent preservation characteristics and the long-term durability of the anti-corrosion effect will be lost as the specific porous adsorbent surface is reduced, and the specific surface area of 100 m2 / g or less long-term anti-corrosion preservation becomes difficult.

According to Figures 3 and Tables 3,4 and 5, it is understood that the long-term preservation characteristic of the corrosion inhibiting agent and the long-term durability of the anti-corrosion effect increases as addition of the porous adsorbent, but if the same amount of the silica component exceeds 30 parts by weight, the conservation of the corrosion inhibiting agent becomes too strong this time, decreasing the initially recorded emission of the same inhibitor.

Claims (2)

Anticorrosive composition, characterized in that it comprises 100 parts by weight of a polyolefin resin having a density of 0.880 to 0.950 g / cm3 and an MFR of 0.1 to 30.0 g / 10 min, and 0.1 to 10 parts by weight of one, two or more volatile anticorrosive agents selected from amine / ammonium salt / inorganic acid metal or an organic acid, a urea compound, and a heterocyclic compound, wherein 0.2 to 30.0 Parts by weight of one, two or more porous adsorbents having an average particle size of 0.1 to 20 pm and a specific surface area of 100 to 800 m2 / g selected from porous silica, porous alumina, and zeolite are dispersed relative to 1 part by weight of the anti-corrosion agent to then maintain evaporation and release the amount of volatile anti-corrosion agent over a long period of time. Packaging material, characterized in that it is formed from an anti-corrosion composition as defined in claim 1.