JP5466677B2 - Rust prevention composition - Google Patents

Description

  The present invention is a rust preventive composition and packaging material for packing and storing various metal products that require rust prevention.

  For rust-proof packaging and transportation of metal products, a method of transporting the product by immersing it in rust-preventing oil and blocking it from the atmosphere, or a method of transporting it by a prescription wrapped in a rust-proof paper (paper coated with a rust preventive agent) has been taken. However, in order to export metal products typified by automobile parts from 30 to 40 years ago, there has been a demand for packaging materials that are inexpensive, easy to handle, and have little trouble in use. As a result, several companies and individuals have developed plastic packaging materials that have a rust prevention function during transportation.

However, not only does it have a rust prevention function only at the time of transportation, but also as a metal product manufacturer's responsibility, the product inventory guarantee is required by users, and the rust prevention function is maintained even during the inventory storage period. The packaging material manufacturers have been asked for packaging materials that do not cause functional deterioration.
In particular, when the product inventory guarantee period is as long as 10 years, it is required to prevent the surface of metal products from generating rust for a very long time, but it is recommended not to generate rust during the storage period. It is extremely difficult to store in

  Vaporizable rust preventives are classified into two types, immediate-acting rust preventives and delayed-acting rust-preventing agents, depending on the transpiration of the substance. When only an immediate effect rust preventive agent is added, a large amount of rust preventive components are released in the short term, but not suitable for long term rust prevention. Moreover, the initial rust preventive effect is insufficient only with the slow-acting rust preventive.

  Therefore, a combination of an immediate-acting rust inhibitor and a slow-acting rust inhibitor is used as a technique for expressing a stable rust-preventing effect.

On the other hand, as a method for obtaining the long-term effect of the vaporizable rust preventive agent, there is a method of dispersing and supporting in a resin. As the resin, a non-polar polyolefin resin represented by low density polyethylene is often selected for convenience of processing. However, since the resin and the rust preventive agent are generally difficult to be compatible, the rust preventive agent is still used. The vaporization behavior is not stable in the long term.
When a large amount of rust preventive agent is added to make up for it, the product appearance is significantly reduced after the product is manufactured, causing rust preventive agent to deposit on the product surface in a relatively short period of time, so-called bleed out or bloom out phenomenon occurs. In addition to greatly detracting from the commercial value, this deposit is directly attached to the metal product, which may lead to complaints such as contamination with foreign matter, and is not a sufficient avoidance technique.
In addition, simply adding a rust inhibitor to non-polar polyolefins may cause rust when stored for several years, and the rust preventive effect is maintained throughout the product inventory warranty period over the last several years. It was difficult.
Some examples of molded articles obtained by blending a resin with a rust preventive agent are shown as Patent Documents 1 to 3 below, but Patent Document 1 discloses a heat-fusible polyolefin, a vaporizable rust preventive agent, and an oxidized substance. A composition containing a conductive metal powder and a zeolite is disclosed in Patent Document 2 as a composition containing a vaporizable rust preventive agent such as an alkyldicarboxylic acid ammonium salt in a thermoplastic resin such as LDPE. It is only described as a rust-preventing molded body containing a filler such as calcium carbonate, a rust preventive agent which is an inorganic acid or organic acid salt of an organic amine, and has a specific specific surface area. It is not an invention intended to add the above filler to try to exhibit rust prevention over a long period of time.

JP 2010-254350 A JP 2007-308726 A Japanese Patent Laid-Open No. 11-181143

  The present invention is capable of stably maintaining the antirust function for a long period of time in the environment where metal products are stored as well as the antirust function during transportation of conventional antirust packaging materials. It is an object of the present invention to provide a rust preventive composition used for various packing materials and a packing material formed from the rust preventive composition.

The present invention, as a method for more stably maintaining the rust prevention effect of the conventional rust preventive composition for a long period of time, by dispersing a porous adsorbent in a base composed of a resin and a vaporizable rust inhibitor, The present invention provides a rust-preventing composition that gradually evaporates and releases a rust-preventing agent over a long period of time in each environment, and the following means are employed for this purpose.
1. An amine / ammonium / metal of an inorganic acid or an organic acid with respect to 100 parts by weight of a polyolefin-based resin having a density of 0.880 to 0.950 g / cm ³ and an MFR (melt flow rate) of 0.1 to 30.0 g / 10 min. Contains 0.1 to 10 parts by weight of one or more vaporizable rust inhibitors selected from salts, urea compounds and heterocyclic compounds, and has an average particle size of 0.1 to 20 μm and a specific surface area of 100 to 800 m. Disperse 0.2 to 30.0 parts by weight of one or more porous adsorbents selected from ² / g porous silica, porous alumina, and zeolite with respect to 1 part of the rust inhibitor. A rust preventive composition characterized by maintaining the vaporized release amount of the vaporizable rust preventive agent for a long period of time.
A packaging material formed from the rust preventive composition described in 2.1.

  As described above, by forming a rust-proof packaging material composed of a rust-proof composition in which a vaporizable rust-proof agent and a porous adsorbent are dispersed in a polyolefin resin, the amount of vaporization and release of the rust-proof agent is controlled. Maintains the rust prevention effect on metal parts for a long time, and does not impair the quality value of metal products due to the occurrence of rust. At the same time, since the odor of the rust inhibitor and the bleed-out phenomenon are weakened by controlling the release amount of the rust inhibitor, it is possible to provide a rust preventive packaging material that is easy for the operator to handle.

Porous adsorbent and rust inhibitor residual rate Silica specific surface area and rust inhibitor residual rate Silica addition amount and rust inhibitor residual rate

  The inventors of the present invention are the first to prevent rust by adding and combining a specific porous adsorbent as the third component to a rust preventive resin composition containing a specific resin and a specific rust inhibitor. The present inventors have found a rust preventive composition for maintaining the effect over a long period of time.

  As the base resin used in the present invention, polyolefin resins useful for workability, safety and environmental aspects from the knowledge so far, for example, homopolymers of α-olefins such as polyethylene and polypropylene, ethylene-propylene copolymers, ethylene Copolymers of ethylene and C3-C8 α-olefins such as ethylene-butene-1 copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-hexene copolymer, and ethylene-vinyl acetate copolymer And a copolymer of an organic carboxylic acid derivative having an ethylenically unsaturated bond such as a polymer, an ethylene-acrylic acid copolymer, an ethylene-vinyl acetate-methyl methacrylate copolymer, and the like.

Among the above polyolefin resins, for example, when used as a packaging material, it is appropriate to select polyethylene from the viewpoint of product cost and ease of production, and various types of polyethylene from low density polyethylene to high density polyethylene. Can be adopted in consideration of the characteristics.
However, density of 0.880~0.950g / cm ^3, preferably polyethylene as a 0.910~0.930g / cm ³ is preferred from previous findings.

  Further, the resin molding means is not particularly limited, and known resin molding means can be employed.

  In the present invention, the vaporizable rust inhibitor is one or two or more vaporizable rust inhibitors selected from amine / ammonium / metal salts of inorganic or organic acids, urea compounds, and heterocyclic compounds, Specifically, mono-, di-, tri-ethanolamine, n-, di-, tert-butylamine, hexamethylenediamine, hexamethylenetetramine, mono-, di-cyclohexylamine, isopropyl, which show vaporization in the usage environment Organic amine salt selected from amine, oleylamine, naphthylamine, di-phenylamine phosphoric acid, nitrous acid, carbonic acid, carboxylate, ammonium phthalate, ammonium benzoate, ammonium stearate, ammonium dodecanoate, ammonium decanoate, sebacine Ammonium acid, ammonium adipate, more selected carboxylic acid ammonium salt, urine Urea compounds selected from silicon, methylurea, ethylurea, propylurea, thiourea, urotropine, benzotriazole, tolyltriazole, carboxybenzotriazole, 5-hydroxybenzotriazole, 3-methyl-5-hydroxypyrazole, 5- Examples include heterocyclic compounds selected from amino-1H tetrazole, imidazole, 2-methylimidazole, 5-methylimidazole, benzimidazole, mercaptobenzothiazole, and the like.

  Moreover, rust prevention effect is further improved by adding alkali metal or alkaline earth metal salts of inorganic acids such as nitrous acid, carbonic acid, phosphoric acid, boric acid, silicic acid, etc., which do not have vaporization as required It is also possible to plan.

As for the amount added, the appropriate amount varies depending on the target metal and the required rust preventive effect, and also the vapor pressure characteristics of the vaporizable rust preventive agent described above. In order to obtain a stable effect, a sufficient rust prevention effect cannot be obtained. On the contrary, if the amount is too large, 100 parts by weight of a polyolefin resin having an MFR of 0.1 to 30.0 g / 10 min. On the other hand, it is effective to add 0.1 to 10 parts by weight, and 0.5 to 5 parts by weight is desirable from the viewpoint of production.
However, the upper limit value of this addition amount is applied in the present invention using the porous adsorbent described below, and when the porous adsorbent is not added, the vaporizable rust preventive is so high that it does not bleed out. When an agent is added, the maximum amount that can be added without causing bleed-out is much lower.

  Next, the central function of the present invention is the sustainability of the rust prevention effect. Therefore, the vaporization release amount of the vaporizable rust preventive can be controlled by the addition amount of the porous adsorbent as the third component. Further, by dispersing the porous adsorbent in the resin, it is possible to contribute to reducing the bleedout of the vaporizable rust preventive and reducing the rust preventive odor.

The porous adsorbent used in the present invention is selected from porous silica, porous alumina, and zeolite. As a porosity standard, the specific surface area is at least 100 m ² / g or more, preferably 300 m ² / g or more. Further, in view of dispersibility for dispersing in a wide range in the base resin, 800 m ² / g or less is desirable.

  The addition amount of the porous adsorbent needs to be linked to the addition amount of the vaporizable rust inhibitor, and if the addition amount is low, the rust inhibitor may bleed out from the base resin. In addition to deteriorating the surface properties, the vaporizable rust preventive agent is held too strongly, and the expression of the rust preventive effect may be hindered. The porous adsorbent is preferably 0.2 to 30 parts by weight, preferably 1.0 to 15 parts by weight, and the vaporizable rust preventive agent has a long-term rust preventive effect on the target metal part within this range. It is necessary to select the composition and the amount added.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples as a matter of course, and appropriate modifications are made within a range that can be adapted to the above-described purpose. Of course, it is possible to implement them, and both are included in the technical scope of the present invention.

1.0 part by weight of cyclohexylamine benzoate with respect to 100 parts by weight of low-density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikacene F218-1 density = 0.919 MFR = 1.0), and an average particle size of 3 Porous silica powder having an average particle diameter of 10 μm and a specific surface area of 200 m ² / g, porous silica powder and an alumina mixture (mixing ratio of 1 to 1.5), .9 μm and specific surface area of 300 m ² / g After blending zeolite having an average particle size of 2.5 μm and a specific surface area of 100 m ² / g to 1.0 parts by weight and kneading with a twin-screw extruder, compound pellets are produced through a pelletizer. A film having a thickness of 100 μm was molded at a molding temperature of 150 ° C. by an inflation molding method. The time-dependent decay behavior of the rust preventive agent kneaded in this film is shown in FIG.

In FIG. 1, according to the rust preventive composition of the present invention, the residual ratio of the rust preventive agent decreases with time, and is about 40% for silica, alumina, silica + alumina, and 30% for zeolite. According to Comparative Example 1 in which no porous adsorbent was added, the accelerated test period was 10 days and the remaining rate was about 10%. This result has shown that vaporization of a rust preventive agent is suppressed by adding a porous adsorbent.
Table 1 also shows the results of confirming the rust prevention effect for each composition of Example 1 and the composition of Comparative Example 1, except that the accelerated test period is 10 days. As shown, after Comparative Example 1 was Δ (less than 10% rust generation relative to the area of the test piece) on the second day, further rust was generated, whereas Example 1 was 100 m ² of zeolite. In this case, there is no rust except for ◯ (less than 1 mm, less than 30 rust generation), and it can be understood that the present invention has a remarkable effect by having a porous adsorbent having a specific specific surface area. .

1. 100 parts by weight of cyclohexylamine benzoate and an average particle size of 2.100 parts by weight of low density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikasen F218-1 density = 0.919 MFR = 1.0) Four types of porous silica powders of 7-14.1 μm and specific surface areas of 50, 100, 300, 500, and 700 m ² / g were blended so as to be 1.0 parts by weight, respectively, and kneaded by a twin screw extruder. Thereafter, compound pellets were produced through a pelletizer, and a film having a thickness of 100 μm was formed from the pellets at a molding temperature of 150 ° C. by an inflation molding method. The time-dependent decay behavior of the rust inhibitor kneaded into this film is shown in FIG. 2, and the rust test results are shown in Table 2.

According to FIG. 2, in the case where the specific surface area of the added silica is 300 m ² to 700 m ² , the remaining ratio of the rust inhibitor is approximately 40 to 50% even if the accelerated test period passes 10 days. When the specific surface area is 100 m ² , it is about 30%, and when the specific surface area is 50 m ² , it is lowered to 20%. Of course, when silica is not added, it is further lowered to about 10%. This example of 50 m ^{2 is} an example corresponding to a comparative example.
Reflecting such a property, as shown in Table 2, when the specific surface area of silica 300 meters ² ～700M ^2, rust did not occur at all periods up to 10 days. When the specific surface area of silica is 100 m ² , it becomes ◯ (less than 1 mm, less than 30 rust is generated) after 8 days, and △ (less than 10% rust is generated with respect to the area of the test piece) after 10 days. However, it can be seen that the antirust performance can be exhibited over a long period of time.

1.0 part by weight of cyclohexylamine benzoate and a specific surface area of 300 m ^{2 with} respect to 100 parts by weight of low-density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikasen F218-1 density = 0.919 MFR = 1.0) After blending so that the silica component is 0.1, 0.5, 1.0, 10.0, 50.0 parts by weight and kneading with a twin screw extruder, compound pellets are produced through a pelletizer. The pellet was formed into a film having a thickness of 100 μm at a molding temperature of 150 ° C. by an inflation molding method. The time-dependent decay behavior of the rust inhibitor kneaded into this film is shown in FIG. 3, and the results of the rust test are shown in Table 3.

According to FIG. 3, as the amount of silica added increases, the residual ratio of the rust inhibitor tends to increase, and with the addition of 50.0 parts by weight, the residual ratio exceeds 70% after 10 days. Further, when the addition amount is 0.1 parts by weight, the residual ratio of the rust inhibitor is lowered and is only about 20% in 10 days. This 0.1 part by weight is an example corresponding to a comparative example.
According to Table 3, when the amount of added silica is 1.0 and 10.0 parts by weight with respect to 100 parts by weight of the low density polyethylene resin, rust is generated throughout the entire period up to 10 days. When the added amount is 0.5 parts by weight, rust is not generated until 6 days, and then deteriorates to △ (less than 10% rust is generated with respect to the area of the test piece) on 10 days. . In addition, when the addition amount is 0.1 parts by weight and 50.0 parts by weight, both remain ◯ (1 mm or less, less than 30 rust is generated) until 4 days, but then further rust is generated. .
This tendency of rust generation is considered to be due to a decrease in the amount of vaporizing the rust preventive agent because the period of time elapses while the rust preventive agent is adsorbed to the silica when the amount of silica added increases. .

Low-density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikasen F218-1 density = 0.919 MFR = 1.0) to 100 parts by weight, tolyltriazole 0.3 parts by weight, silica component 0.05, 0 .2, 0.8, 3.2, 12.8 parts by weight, kneaded with a twin screw extruder, compound pellets were made through a pelletizer, and the pellets were blown at 150 ° C. by inflation molding. A film having a thickness of 40 μm was formed at the forming temperature. Table 4 shows the results of the rust prevention test of this film.
This Example 4 is an example in which 0.3 parts by weight of tolyltriazole was added instead of adding 1.0 part by weight of cyclohexylamine benzoate in Example 3. The result was almost the same as the result of Example 3. In the example in which 0.05 part by weight of silica was added, the addition amount of silica was small with respect to 0.3 part by weight of tolyltriazole, which is a vaporizable rust preventive agent, and the result of Δ was 10 days later. The example in which 0.05 part by weight is added is an example corresponding to a comparative example.

Low-density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikacene F218-1 density = 0.919 MFR = 1.0) 100 parts by weight 0.5 parts by weight of cyclohexylamine benzoate and 0 parts of cyclohexylamine carbamate 0.5 parts by weight, benzotriazole 0.3 parts by weight, silica component 0.1, 0.5, 1.0, 10.0 50.0 parts by weight After kneading, compound pellets were produced through a pelletizer, and a film having a thickness of 100 μm was molded from the pellets at a molding temperature of 150 ° C. by an inflation molding method. Table 5 shows the results of the rust prevention test of this film.
In this Example 5, instead of adding 1.0 part by weight of cyclohexylamine benzoate in Example 3, 0.5 part by weight of cyclohexylamine benzoate, 0.5 part by weight of cyclohexylamine carbamate, benzotriazole In Example 5, when the addition amount of silica is 1.0 to 10.0 parts by weight, both the steel plate and the copper plate are rusted throughout the entire period up to 10 days. In the case of 0.5 parts by weight, rust is generated in any metal after 6 days with a steel plate and after 8 days with a copper plate, and the rust inhibitor is inorganic porous at 50.0 parts by weight. It is considered that rust is generated because the period of time elapses while adsorbed on the body silica. Moreover, when the addition amount of silica was 0.1 parts by weight, rust was generated as the period passed as in the case of 50.0 parts by weight. The examples of 0.1 parts by weight and 50.0 parts by weight are examples corresponding to comparative examples.

[Comparative Example 1]
To 100 parts by weight of low-density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikacene F218-1 density = 0.919 MFR = 1.0), cyclohexylamine benzoate was blended to be 1.0 part by weight. After kneading by a twin screw extruder, compound pellets were produced through a pelletizer, and a film having a thickness of 100 μm was formed from the pellets at a molding temperature of 150 ° C. by an inflation molding method. FIGS. 1, 2 and 3 show the time-dependent decay behavior of the rust inhibitor kneaded in this film, and Tables 1, 2 and 3 show the results of the rust prevention test.

[Comparative Example 2]
Low-density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikasen F218-1 density = 0.919 MFR = 1.0) to 100 parts by weight, tolyltriazole was blended to 0.3 parts by weight, After kneading with an extruder, compound pellets were produced through a pelletizer, and a film having a thickness of 40 μm was molded from the pellets at a molding temperature of 150 ° C. by an inflation molding method. Table 4 shows the results of the rust prevention test of this film.

[Comparative Example 3]
Low-density polyethylene resin (Sumitomo Chemical Co., Ltd. Sumikacene F218-1 density = 0.919 MFR = 1.0) 100 parts by weight 0.5 parts by weight of cyclohexylamine benzoate and 0 parts by weight of cyclohexylamine carbamate After blending to 0.5 parts by weight and 0.3 parts by weight of benzotriazole and kneading with a twin screw extruder, compound pellets are produced through a pelletizer, and the pellets are formed at a molding temperature of 150 ° C. by an inflation molding method. A film having a thickness of 100 μm was formed. Table 5 shows the results of the rust prevention test of this film.

A Confirmation of the rate of reduction of the rust preventive agent Finely cut the rust preventive film after the rust prevention evaluation for a predetermined period, water and a stir bar are put in a conical flask with rubbing, a reflux tube is attached to the flask mouth, and a 90 ° C water bath At 1 hour to extract the rust inhibitor component. The extract is adjusted and the adjusted solution is passed through high performance liquid chromatography to measure the concentration of the rust inhibitor.

B Anti-corrosion test A test piece of [C] below suspended by a nylon fishing line on a frame of 100 mm vertical x 100 mm wide x 150 mm high is put into a gusset-processed tube-shaped film and heat-sealed. . After this test configuration was placed in the test environment [D] below, the rusting condition on the metal surface was evaluated based on the evaluation method [E] below.

C Specimen

D Test environment Low temperature: 25 ° C 70% RH (4 hours), High temperature: 50 ° C 95% RH (4 hours), 2 hours for temperature and humidity fluctuations, 12 hours / cycle total Test machine: ESPEC PR4KP manufactured by KK

E Evaluation Criteria ◎: No rust ○: Less than 30 mm of rust generated 1 mm or less △: Less than 10% rust generated with respect to the test piece area ×: Less than 50% rust generated with respect to the test piece area XX: Test Rust generation of 50% or more relative to the area of the piece

From FIG. 1 and Table 1, it can be seen that by adding silica, alumina, and zeolite having a specific surface area of 100 m ² or more, long-term retention characteristics of the rust preventive agent are imparted, and at the same time, long-term sustainability of the rust preventive effect is obtained. .

As shown in FIG. 2 and Table 2, as the specific surface area of the porous adsorbent decreases, the long-term retention characteristics of the rust preventive agent and the long-term sustainability of the rust preventive effect are impaired, and when the specific surface area is less than 100 m ² / g, It is judged that there is an obstacle to rust prevention storage.

  From FIG. 3 and Tables 3, 4, and 5, as the amount of the porous adsorbent increases, the long-term retention characteristics of the rust preventive agent and the long-term sustainability of the rust preventive effect increase, but the silica component has 30 parts by weight. On the contrary, it can be seen that, on the contrary, the retention of the rust inhibitor becomes too strong and the initial release property is weakened.

Claims (2)

Density 0.880~0.950g / cm ^3, per 100 parts by weight of the polyolefin resin having a MFR0.1~30.0g / 10min.,
As vaporizable rust preventives, di-cyclohexylamine, isopropylamine, diphenylamine nitrous acid, carbonic acid, carboxylate, ammonium benzoate, ammonium dodecanoate, ammonium decanoate, benzotriazole, tolyltriazole, 3-methyl wherein 0.1 to 10 parts by weight of one or more selected from 5-hydroxypyrazole <br/>, and an average particle diameter of 0.1 to 20 [mu] m, a specific surface area of 200 ~800m ² / g of the porous silica , volatile corrosion by one or more porous adsorbent selected from porous alumina, is from 0.2 to 30.0 parts by weight dispersion with respect rustproof agent 1 part by weight A rust preventive composition characterized by maintaining the amount of the agent released by vaporization over a long period of time. A packaging material formed from the rust preventive composition according to claim 1.