JP2022094214A - Rust-prevention film and rust-prevention package - Google Patents

Abstract

To provide a rust-prevention film capable of preventing rust from generating to a content being packaged by a simple layer constitution without using a volatile rust-prevention agent.SOLUTION: A rust-prevention film includes a first layer and a second layer laminated on one side of the first layer. The first layer is composed of an olefin resin having heat sealability. The first layer includes, as additive, an antioxidizing agent, a neutralizer, an antiblocking agent and a slip agent. A content of the antioxidizing agent in the first layer is 50 to 100 ppm, a content of the neutralizer is 50 to 100 ppm, a content of the antiblocking agent is 50 to 100 ppm, and a content of the slip agent is 50 to 100 ppm.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a rust-preventive film that suppresses the generation of rust on the packaged contents, and a rust-preventive package having the rust-preventive film.

Packaging materials for the purpose of transporting and long-term storage of metal articles, for example, metal articles and metal articles made of metal parts, are being developed, and the functions and properties of the metal articles as contents can be maintained. As described above, there is a demand for a packaging material that has higher and more stable rust resistance and can be manufactured by a simple manufacturing process with a simple layer structure.
For example, Patent Documents 1 to 3 describe packaging laminates containing a highly vaporizable rust preventive, which volatilizes at room temperature and exhibits a rust preventive effect, in a resin for the purpose of preventing rust on metal articles. There is.
However, in a rust-preventive film using a volatile rust-preventive agent, if the airtightness of the package produced from this rust-preventive film is insufficient, the rust-preventive effect on the contents is almost the same. There is a problem that it is not exhibited. In addition, volatile rust inhibitors may contain substances that are harmful to the human body (for example, carcinogenicity), and care must be taken when handling them. Therefore, a rust-preventive film that does not use a volatile rust-preventive agent is desired.

Japanese Unexamined Patent Publication No. 2010-254350 JP-A-2007-308726 Japanese Unexamined Patent Publication No. 2010-052751

The present disclosure has been made in view of the above circumstances, and a rust-preventive film capable of suppressing the generation of rust on the contents to be packaged with a simple layer structure without using a volatile rust-preventive agent is provided. The main purpose is to provide.

The rust-preventive film of the present disclosure has a first layer and a second layer laminated on one surface of the first layer, and the first layer is composed of an olefin resin having a heat-sealing property. The first layer has an antioxidant, a neutralizing agent, an anti-blocking agent, and a slip agent as additives, and the content of the antioxidant in the first layer is 50 ppm or more and 100 ppm or less. The content of the neutralizing agent in the first layer is 50 ppm or more and 100 ppm or less, the content of the antiblocking agent in the first layer is 50 ppm or more and 100 ppm or less, and the content of the slip agent in the first layer. Is 50 ppm or more and 100 ppm or less.

In the rust-preventive film of the present disclosure, the second layer is composed of an olefin resin, and the total content of the additives contained in the second layer is the content of the additives contained in the first layer. May be greater than the sum of.

The rust-preventive film of the present disclosure may have a base material layer laminated on the second layer.

In the rust-preventive film of the present disclosure, the base material layer may be a barrier base material layer.

In the rust preventive film of the present disclosure, the antioxidant may contain a phenolic antioxidant.

In the rust preventive film of the present disclosure, the neutralizing agent may contain calcium oxide.

In the rust preventive film of the present disclosure, the antiblocking agent may contain sodium aluminosilicate.

In the rust preventive film of the present disclosure, the slip agent may contain stearic acid.

The rust-preventive package of the present disclosure is composed of the rust-preventive film and has the first layer inside.

The rust-preventive package of the present disclosure may be sealed at a pressure lower than the atmospheric pressure inside the package.

According to the present disclosure, it is possible to provide a rust-preventive film capable of suppressing the generation of rust on the contents to be packaged with a simple layer structure without using a volatile rust-preventive agent.

Schematic cross-sectional view showing an example of the layer structure of the rust-preventive film of the present disclosure. Schematic cross-sectional view showing another example of the layer structure of the rust-preventive film of the present disclosure.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In each figure, the size and ratio of the members may be changed or exaggerated for the sake of clarity. In addition, for the sake of readability, unnecessary parts for explanation and repeated codes may be omitted.
Further, although omitted in each figure, a functional layer such as an adhesive layer may be provided between the layers.
Furthermore, if necessary, in order to strengthen the adhesive strength (adhesion strength) between the layers, the laminated surface of each layer is subjected to physical treatment such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblast treatment, etc. It is also possible to perform a chemical surface treatment such as a specific surface treatment or an oxidation treatment using a chemical in advance.

(Rustproof film)
FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the rust-preventive film of the present disclosure. The rust-preventive film 1 shown in FIG. 1 has a first layer 11 and a second layer 12 laminated on one surface of the first layer 11.
In the rust-preventive film 1 shown in FIG. 1, the form in which the first layer 11 is a single layer is exemplified, but the first layer of the rust-preventive film of the present disclosure is composed of a plurality of layers. You may. Similarly, in the rust-preventive film 1 shown in FIG. 1, the form in which the second layer 12 is a single layer is exemplified, but the second layer of the rust-preventive film of the present disclosure is composed of a plurality of layers. May be.

FIG. 2 is a schematic cross-sectional view showing another example of the layer structure of the rust-preventive film of the present disclosure. The rust-preventive film of the present disclosure may have a structure having a base material layer laminated on the second layer.
For example, the rust-preventive film 2 shown in FIG. 2 has a second layer 12 laminated on the first layer 11, and further has a base material layer 13 laminated on the second layer 12. is doing.
Although the rust-preventive film 2 shown in FIG. 2 illustrates a form in which the base material layer 13 is a single layer, the base material layer of the rust-preventive film of the present disclosure is composed of a plurality of layers. You may.

Further, an adhesive layer may be provided between the layers of the rust-preventive film 1 shown in FIG. 1 and the rust-preventive film 2 shown in FIG.

The thickness of the rust-preventive film of the present disclosure is not particularly limited, but is preferably 25 μm or more and 200 μm or less. If the thickness of the rust-preventive film is thinner than the above range, there is a problem that the rigidity of the rust-preventive film is too low or the rust-preventive film is easily torn. In addition, it tends to be difficult for the rust-preventive film to exhibit sufficient supportability, rust-preventive effect, heat-sealing property, etc. in a well-balanced manner. On the other hand, when the thickness of the rust-preventive film is thicker than the above range, the rigidity of the rust-preventive film is too strong, and the usability as a packaging material tends to deteriorate.

The rust-preventive film is preferably transparent, and more preferably has high transparency. This is because the contents of the rust-preventive package manufactured from the highly transparent rust-preventive film can be easily visually recognized.
The rust-preventive film is usually used in combination with other packing materials in steel packaging, and it is often required to distinguish it from a transparent general-purpose olefin film (polyethylene, polypropylene). Therefore, colorants such as blue, orange, yellow, and green are added and supplied as a light-colored film, but the content (steel material) is manufactured with a transparency that can be confirmed.
Such a colored film is light in color by itself and has a small difference in color from that without a colorant added, but it can be clearly distinguished from other packaging materials in the wound state.

In addition, "transparent" means having transparency to the extent that one side of the rust preventive film can be seen through the other side through the rust preventive film, for example, 90. It is desirable to have a visible light transmittance of% or more. The visible light transmittance is the transmittance at each wavelength when measured using a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation, JIS K 0115 compliant product) within the measurement wavelength range of 380 nm to 780 nm. Specified as the average value of.
Therefore, the haze of the rust-preventive film is also set to be less than 20%. The haze value is measured according to JIS K7136, for example, using a haze meter HM-150 manufactured by Murakami Color Technology Research Institute Co., Ltd.

In the rust-preventive film of the present disclosure, in order to avoid the influence on the rust-preventive effect of the first layer 11, no colorant is added to the first layer 11, and the second layer formed on the first layer 11 is formed. It is manufactured by adding a colorant to 12 and the base material layer 13.
In particular, like the rust-preventive film 2 shown in FIG. 2, it has a second layer 12 laminated on the first layer 11, and a base material layer 13 laminated on the second layer 12. In the case of the configuration having the above, by adding the colorant only to the second layer 12, even if the base material layer 13 comes into contact with the first layer 11 when the rust preventive film 2 is wound up, it can be further improved. Specifically, even if the outer surface of the base material layer 13 touches the inner surface of the first layer 11 (that is, the surface on the side of the first layer 11 that comes into contact with the contents as a package), the base material layer 13 still has a surface. Since no colorant is added, it is possible to prevent the colorant from affecting the rust preventive property of the first layer 11.

(1st layer)
The first layer 11 of the rust-preventive film of the present disclosure is composed of an olefin resin having a heat-sealing property, and has a predetermined amount of an antioxidant, a neutralizing agent, an anti-blocking agent, and a slip agent as additives. is doing.
Specifically, the content of the antioxidant in the first layer 11 is 50 ppm or more and 100 ppm or less. The content of the neutralizing agent in the first layer 11 is 50 ppm or more and 100 ppm or less. The content of the anti-blocking agent in the first layer 11 is 50 ppm or more and 100 ppm or less. The content of the slip agent in the first layer 11 is 50 ppm or more and 100 ppm or less.

The first layer 11 of the rust-preventive film of the present disclosure has a second layer 12 on one surface thereof, and the surface on the side opposite to the surface having the second layer 12 is at least a part thereof. Will come into contact with an article having metal, which is the content packaged by the rust-preventive film of the present disclosure. For example, when the rust-preventive film 1 shown in FIG. 1 is used as a package, the side of the first layer 11 is the inner layer (that is, the inner layer) of the package, and the side of the second layer 12 is the package. Becomes the outer layer (ie, the outer layer) of. Further, when the rust-preventive film 2 shown in FIG. 2 is used as a package, the side of the first layer 11 becomes the inner layer (that is, the inner layer) of the package, and the side of the base material layer 13 becomes the package. Becomes the outer layer (ie, the outer layer) of.

Since each of the above-mentioned additives contained in the first layer 11 of the rust-preventive film of the present disclosure has the above-mentioned predetermined content, stable film-forming property is obtained during the production of the rust-preventive film of the present disclosure. While ensuring, it exerts a rust preventive effect on the contents packaged in the rust preventive film of the present disclosure.

The thickness of the first layer 11 of the rust-preventive film of the present disclosure can be appropriately set within the range of the thickness of the rust-preventive film, but is preferably 5 μm or more and 150 μm or less, and more preferably 10 μm or more and 100 μm or less. More preferably, it is 10 μm or more and 50 μm or less.
When the thickness of the first layer 11 is within the above range, a sufficient rust preventive effect can be exhibited, and the rigidity of the entire rust preventive film can be made appropriate.
On the other hand, if the thickness of the first layer 11 is thinner than the above range, a sufficient rust preventive effect may not be exhibited. Further, when the thickness of the first layer 11 is thicker than the above range, the rust preventive effect is not improved so much, and the rigidity of the entire rust preventive film becomes too strong, which may deteriorate the usability as a packaging material. ..

<Olefin resin>
The olefin resin constituting the first layer 11 of the rust-preventive film of the present disclosure is preferably a resin having an affinity suitable for dispersing the rust-preventive agent and having excellent film-forming property, and a resin having heat-sealing property is preferable. More preferred. As the olefin resin, one or more selected from a polyolefin-based polymer, that is, a homopolymer of an olefin and / or a copolymer using an olefin as a monomer can be selected and used.

Examples of the olefin (olefin monomer) constituting the polyolefin-based polymer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, and 4-methyl-1. -Pentene, 1-hexene, 1-octene and the like can be mentioned.
Therefore, examples of the polyolefin-based polymer include an ethylene-based polymer, a propylene-based polymer, a 1-butene-based polymer, a 1-hexene-based polymer, and a 4-methyl-1-pentene-based polymer. These polymers may be used alone or in combination of two or more. That is, the polyolefin-based polymer may be a mixture of various polymers.

Among the above, examples of the ethylene-based polymer include an ethylene homopolymer (polyethylene) and a copolymer of ethylene and another monomer (ethylene copolymer).

Examples of the ethylene homopolymer include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).

The ethylene copolymer includes ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1-hexene copolymer, and ethylene / 1-octene. Examples thereof include polymers, ethylene / 4-methyl-1-pentene copolymers and the like.
Of these, linear low-density polyethylene with a density of 0.89 g / cm ³ or more and 0.93 g / cm ³ or less polymerized by a metallocene catalyst is excellent in heat sealability, strength, tactile sensation, and flexibility. (LLDPE) is preferably used.
The ethylene unit (constituent unit derived from ethylene) contained in the ethylene copolymer may be larger than 50% of the total number of constituent units (usually 99.999% or less), but for example, the total number of constituent units. Of these, 80% or more and 99.999% or less can be used, 90% or more and 99.995% or less can be used, and 99.0% or more and 99.990% or less can be used.

Examples of the propylene-based polymer include a propylene homopolymer (polypropylene) and a copolymer of propylene and another monomer (propylene copolymer). Examples of the propylene copolymer include a propylene / ethylene copolymer, a propylene / 1-butene copolymer, a propylene / 1-pentene copolymer, a propylene / 1-octene copolymer and the like.
In general, polypropylene is a highly rigid homopolymer obtained by polymerizing only propylene (homopolypropylene), a highly transparent and flexible random polymer copolymerized with a small amount of ethylene (random polypropylene), and a rubber component (EPR) homo-random. It is classified as a block copolymer having high impact resistance uniformly and finely dispersed in a polymer. Among these, homopolypropylene has excellent odor blocking properties.
The propylene unit (constituent unit derived from propylene) contained in the propylene copolymer may be 50% or more (usually 99.999% or less) of the total number of constituent units, but for example, the total number of constituent units. Of these, 80% or more and 99.999% or less can be used, 90% or more and 99.995% or less can be used, and 99.0% or more and 99.990% or less can be used.

The density of the polyolefin resin is preferably 0.880 g / cm ³ or more and 0.950 g / cm ³ or less from the viewpoint of processability.

Further, from the viewpoint of mechanical strength and workability, the melt flow rate value (MFR) is preferably in the range of 1.0 g / 10 min or more and 10.0 g / 10 min or less. By having an appropriate viscosity during melt processing, it becomes possible to include and coat the saturated fatty acid in the form of particles in the resin, and it is possible to prevent the saturated fatty acid from falling off from the film.

<Additives>
In the rust-preventive film of the present disclosure, since the content of each of the above-mentioned additives in the first layer 11 is the above-mentioned predetermined content, stable film-forming property is obtained during the production of the rust-preventive film of the present disclosure. While ensuring, it exerts a rust preventive effect on the contents packaged in the rust preventive film of the present disclosure.
Each additive contained in the first layer 11 of the rust-preventive film of the present disclosure is uniform on the surface of the first layer 11 (more specifically, the surface opposite to the surface having the second layer 12). It is preferable that they are dispersed in. The surface of the first layer 11 is a surface in contact with the contents packaged by the rust-preventive film of the present disclosure, and the additives are uniformly dispersed on this surface, so that the contents are uniformly dispersed. This is because the rust preventive effect can be uniformly exerted.
It should be noted that each additive contained in the first layer 11 of the rust-preventive film of the present disclosure may be uniformly dispersed on the surface of the first layer 11 as described above, for example, in the first layer 11. In the thickness direction, it may be dispersed with a concentration gradient. In other words, each additive contained in the first layer 11 of the rust-preventive film of the present disclosure may be dispersed with a concentration gradient in the thickness direction of the first layer 11. It is preferable that the layers 11 are uniformly dispersed in the plane direction.

Each additive contained in the first layer 11 of the rust-preventive film of the present disclosure is preferably contained by using a masterbatch in which each additive is melt-blended with an olefin resin at a high concentration. This is because it becomes easy to contain each of the predetermined additives in the first layer 11 of the rust-preventive film of the present disclosure in a uniformly dispersed state.
Each of the additives and the olefin resin melt-blended in the masterbatch may be one kind or two or more kinds. Further, one masterbatch may contain one kind or two or more kinds of each additive.
The olefin resin used in the masterbatch may be the same as or different from the main olefin resin constituting the first layer 11 of the rust-preventive film of the present disclosure.

The content of the above-mentioned four kinds of additives (antioxidant, neutralizing agent, anti-blocking agent, and slip agent) contained in the first layer 11 of the rust-preventive film of the present disclosure is in the range of 50 ppm or more and 100 ppm or less, respectively. It is preferable to have. When the content of each additive is within this range, the rust-preventive film of the present disclosure can exhibit a sufficient rust-preventive effect while maintaining film-forming properties and quality stability during long-term storage.
On the other hand, when the content of each additive is less than 50 ppm, the film-forming property and the quality stability during long-term storage tend to be inferior, which is not preferable. Further, when the content of each additive exceeds 100 ppm, it is difficult to exhibit a sufficient rust preventive effect, which is not preferable.

Here, the reason why a sufficient rust preventive effect is difficult to be exhibited when the content of each additive exceeds 100 ppm has not been clarified in detail. However, as in the examples described later, this phenomenon has been confirmed in the evaluation test. For example, it is conceivable that the masterbatch used to uniformly disperse each additive contains a corrosive substance that causes rust. However, it is difficult to identify the presence of this corrosive substance or the like because the content is expected to be extremely small.

Therefore, in the rust-preventive film of the present disclosure, by setting each of the above additives to a predetermined content, the film-forming property and the corrosiveness to be mixed while ensuring the stability of the quality during long-term storage. By reducing substances and the like to the utmost limit, it exerts a rust preventive effect on the contents packaged in the rust preventive film of the present disclosure.

<Antioxidant>
The additive contained in the first layer 11 of the rust preventive film of the present disclosure contains an antioxidant.
As the antioxidant, it is preferable to use a primary antioxidant that captures the generated radical and a secondary antioxidant that decomposes the hydroperoxide generated from the radical in combination. Antioxidants having both functions may be used.
Examples of the primary antioxidant include phenol-based antioxidants, amine-based antioxidants and hindered amine-based antioxidants, and examples of the secondary antioxidants include phosphorus-based antioxidants and sulfur-based antioxidants. Examples of the antioxidant having both the functions of a primary antioxidant and a secondary antioxidant include a hydroxylamine-based antioxidant and the like.
The antioxidant contained in the first layer of the rust-preventive film of the present disclosure includes a phenol-based antioxidant, a phenol-based antioxidant and a phosphorus-based antioxidant, and a hydroxylamine-based antioxidant. Of these, those having a hydrophilic group and a hydrophobic group are more preferable.
In addition, phosphorus-based antioxidants and hydroxylamine-based antioxidants also function to prevent the polyethylene film from being colored.

Examples of the phenolic antioxidant include the following.
Examples of the monophenolic antioxidant include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisol, 2,6-di-tert-butyl-4-ethylphenol, and octadecyl-3-. (3,5-Di-tert-butyl-4-hydroxyphenyl) propionate and the like can be mentioned.
Examples of the bisphenol antioxidant include 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), and the like. 4,4'-thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 3,9-bis [{1,1 -Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl} 2,4,9,10-tetraoxaspiro] 5,5-undecane and the like. Can be done.
Examples of the high molecular weight phenolic antioxidant include 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6. -Tris (3,5-di-tert-butyl-4-vidroxybenzyl) benzene, tetrakis- {methylene-3- (3', 5'-di-tert-butyl-4'-hydrokisphenyl) propionate} Methyl, bis {(3,3'-bis-4'-hydroxy-3'-tert-butylphenyl) butyric acid} glucol ester, 1,3,5-tris (3', 5'-di-tert) -Butyl-4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, tocopherol (vitamin E) and the like can be mentioned.
Among the above, as the phenolic antioxidant, tetrakis- {methylene-3- (3', 5'-di-tert-butyl-4'-hydrokisphenyl) propionate} methane is particularly preferable.

Further, examples of the phosphorus-based antioxidant (also referred to as a phosphite-based antioxidant) include the following.
For example, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetra. Ilvis (octadecylphosphite), tris (mono and / or dinonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro- 9-Oxa-10-phosphaphenaslen-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenance Len-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, cyclic neopentanetetraylbis (2,4-di-tert-butylphenyl) phosphite, Cyclic Neopentantetraylbis (2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-tert-butylphenyl) octylphosphite, 2,4,8,10-tetra Tert-Butyl-6- (3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy) dibenzo (d, f) (1,3,2) dioxaphosfepine and the like can be mentioned. can.
Among the above, tris (2,4-di-tert-butylphenyl) phosphite is particularly preferable.

The content of the antioxidant in the first layer 11 of the rust preventive film of the present disclosure is preferably in the range of 50 ppm or more and 100 ppm or less. When the content of the antioxidant is within this range, the rust-preventive film of the present disclosure can exhibit a sufficient rust-preventive effect while maintaining film-forming properties and quality stability during long-term storage.
On the other hand, when the content of the antioxidant is less than 50 ppm, the film-forming property and the quality stability during long-term storage tend to be inferior, which is not preferable. Further, when the content of the antioxidant is larger than 100 ppm, it is difficult to exhibit a sufficient rust preventive effect, which is not preferable.
When two or more kinds of antioxidants are added, the total amount thereof shall be the amount of the antioxidant added. In other words, the content of the antioxidant contained in the first layer 11 of the rust-preventive film of the present disclosure is, when two or more kinds of antioxidants are contained, the total amount thereof is taken as the content of the antioxidant.

<Neutralizer>
The additive contained in the first layer 11 of the rust preventive film of the present disclosure also contains a neutralizing agent. The neutralizing agent is added for the purpose of taking in chlorine ions contained in polyethylene polymerized by a Cheegler catalyst, and hydrotalcites, silicates, metal oxides, metal hydroxides, fatty acid metal salts and the like are selected. To.

The hydrotalcites do not contain water-containing basic carbonates such as magnesium, calcium, zinc, aluminum and bismuth, or water of crystallization, and natural products and synthetic products can be used. Examples of natural products include those having a structure of Mg ₆ Al ₂ (OH) ₁₆ CO _{3.4H 2} O. As synthetic products, Mg _0.7 Al _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃・ 3.5H ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃ , Zn ₆ Al ₂ (OH) ₁₆ CO _{3.4H 2} O, Ca ₆ Al ₂ (OH) ₁₆ CO _{3.4H 2} O, Mg ₁₄ Bi ₂ (OH) _29.6 , 4.2H ₂ O, etc. Can be mentioned.

Examples of the silicate include aluminum silicate and calcium silicate. Examples of the metal in the metal oxide and the metal hydroxide include metals of Group II of the periodic table, zinc, aluminum, tin, lead and the like. Among such metal oxides and metal hydroxides, magnesium oxide, calcium oxide, zinc oxide, aluminum oxide, calcium hydroxide, aluminum hydroxide, magnesium hydroxide and the like are often used.

The content of the neutralizing agent in the first layer 11 of the rust-preventive film of the present disclosure is preferably in the range of 50 ppm or more and 100 ppm or less. When the content of the neutralizing agent is within this range, the rust-preventive film of the present disclosure can exhibit a sufficient rust-preventive effect while maintaining film-forming properties and quality stability during long-term storage.
On the other hand, when the content of the neutralizing agent is less than 50 ppm, the film-forming property and the quality stability during long-term storage tend to be inferior, which is not preferable. Further, when the content of the neutralizing agent is larger than 100 ppm, it is difficult to exhibit a sufficient rust preventive effect, which is not preferable.
When two or more kinds of neutralizing agents are added, the total amount thereof is taken as the addition amount of the neutralizing agent. In other words, the content of the neutralizing agent contained in the first layer 11 of the rust-preventive film of the present disclosure is the total amount of the neutralizing agents when two or more kinds of the neutralizing agents are contained.

<Anti-blocking agent>
The additive contained in the first layer 11 of the rust preventive film of the present disclosure also includes an anti-blocking agent. The anti-blocking agent is added for the purpose of preventing the films from adhering to each other. The anti-blocking agent has the effect of roughening the surface condition of the film by adding inorganic fine particles. Silica, clay, talc, diatomaceous earth, feldspar, kaolin, zeolite, kaolinite, wollastonite, sericite, aluminosilicate. Various natural or artificial inorganic minerals such as silicate and calcium aluminosilicate are used. Among these, aluminosilicates such as sodium aluminosilicate (sodium aluminosilicate) are often used.

The content of the anti-blocking agent in the first layer 11 of the rust-preventive film of the present disclosure is preferably in the range of 50 ppm or more and 100 ppm or less. When the content of the anti-blocking agent is within this range, the rust-preventive film of the present disclosure can exhibit a sufficient rust-preventive effect while maintaining film-forming properties and quality stability during long-term storage.
On the other hand, when the content of the anti-blocking agent is less than 50 ppm, the film-forming property and the quality stability during long-term storage tend to be inferior, which is not preferable. Further, when the content of the anti-blocking agent is larger than 100 ppm, it is difficult to exhibit a sufficient rust preventive effect, which is not preferable.
When two or more kinds of anti-blocking agents are added, the total amount thereof is taken as the addition amount of the anti-blocking agent. In other words, the content of the anti-blocking agent contained in the first layer 11 of the rust-preventive film of the present disclosure is, when two or more kinds of anti-blocking agents are contained, the total amount thereof is taken as the content of the anti-blocking agent.

<Slip agent>
The additive contained in the first layer 11 of the rust preventive film of the present disclosure also includes a slip agent. When a thermoplastic resin is heat-molded, a slip agent (also called a lubricant) is used as a material for processing, such as preventing adhesion to the metal surface of the processing equipment, reducing friction with the metal surface, and improving the fluidity of the material. It is added for the purpose of maintaining physical stability.
As the slip agent, fatty acids are used, and examples thereof include fatty acids, metal fatty acids, and fatty acid esters. Specific examples of the fatty acid include caproic acid, heptanic acid, nonadecylic acid, octanoic acid, decanoic acid, undecylic acid, lauric acid, stearic acid, nonadecylic acid, arachidic acid and the like.

Examples of the metal fatty acid include alkali metal salts such as the above-mentioned fatty acids and alkaline earth metal salts, and specific examples thereof include calcium stearate, zinc stearate, magnesium stearate and the like. These are also known to function as the neutralizers described above. In the first layer of the rust-preventive film of the present disclosure of the present disclosure, when a metal fatty acid is used as a slip agent, the metal fatty acid is not used as a neutralizing agent.

Examples of the fatty acid ester include alcohol esters such as the above fatty acids and glycerin fatty acid esters. As the glycerin fatty acid ester, glycerin trifatty acid ester is preferable, glycerin fatty acid ester is preferable, and glycerin tricaprylic acid ester is more preferable.

The content of the slip agent in the first layer 11 of the rust preventive film of the present disclosure is preferably in the range of 50 ppm or more and 100 ppm or less. When the content of the slip agent is within this range, the rust-preventive film of the present disclosure can exhibit a sufficient rust-preventive effect while maintaining film-forming properties and quality stability during long-term storage.
On the other hand, when the content of the slip agent is less than 50 ppm, the film-forming property and the quality stability during long-term storage tend to be inferior, which is not preferable. Further, when the content of the slip agent is larger than 100 ppm, it is difficult to exhibit a sufficient rust preventive effect, which is not preferable.
When two or more kinds of slip agents are added, the total amount thereof shall be the amount of the slip agent added. In other words, the content of the slip agent contained in the first layer 11 of the rust-preventive film of the present disclosure is the total amount of the slip agents when two or more kinds of the slip agents are contained.

<Other additives>
The rust-proof film of the present disclosure includes, for example, processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, releasability, flame retardancy, antifungal properties, electrical properties, and strength. It is also possible to contain various plastic compounding agents and additives other than the above-mentioned antioxidants, neutralizing agents, anti-blocking agents, and slip agents in a very small amount for the purpose of improving and modifying the above. Is. However, the content thereof is limited to a range in which the rust preventive effect of the first layer of the rust preventive film of the present disclosure is not deteriorated.
In the above, as the general compounding agent, for example, a cross-linking agent, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, a resin for modification and the like can be contained.

(2nd layer)
As described above, when the rust-preventive film of the present disclosure is used as a package, the side of the first layer 11 becomes the inner layer (that is, the inner layer) of the package, and the side of the second layer 12 becomes the second layer. It becomes the outer layer (that is, the outer layer) of the package than the 1st layer 11.
More specifically, for example, when the rust-preventive film 1 shown in FIG. 1 is used as a package, the side of the first layer 11 becomes the inner layer (that is, the inner layer) of the package, and the second layer 12 Side is the outer layer of the package (ie, the outer layer). Further, when the rust-preventive film 2 shown in FIG. 2 is used as a package, the side of the first layer 11 becomes the inner layer (that is, the inner layer) of the package, and the side of the base material layer 13 becomes the package. Becomes the outer layer (ie, the outer layer) of.
The second layer 12 of the rust-preventive film of the present disclosure may be a single layer or may be composed of a plurality of layers.

In the rust-preventive film of the present disclosure, the second layer 12 is composed of an olefin resin, and the total content of the additives contained in the second layer 12 is the total content of the additives contained in the first layer 11. More than.
Therefore, the content of the above four kinds of additives (antioxidant, neutralizing agent, antiblocking agent, and slipping agent) contained in the first layer 11 of the rust preventive film of the present disclosure is 50 ppm or more and 100 ppm or less, respectively. The rust-preventive film of the present disclosure has a laminated structure of the first layer 11 and the second layer 12, even if the amount is smaller than that of a normal film, and the content of the additive contained in the second layer 12 is contained. By setting the amount of the film to a value close to that of a normal film, the film-forming property of the rust-preventive film of the present disclosure and the stability of quality during long-term storage can be further improved.
Further, in the rust-preventive film 1 shown in FIG. 1, by optimizing the content of the slip agent contained in the second layer 12, it is possible to suppress the generation of pinholes due to rubbing during transportation. ..

Further, as described above, in the case of a configuration in which the base material layer 13 is provided on the second layer 12 as in the rust preventive film 2 shown in FIG. 2, a colorant is added only to the second layer 12. By doing so, even if the base material layer 13 comes into contact with the first layer 11 when the rust preventive film 2 is wound up, more specifically, the outer surface of the base material layer 13 is inside the first layer 11. Even if it comes into contact with a surface (that is, a surface on the side of the first layer 11 that comes into contact with the contents as a package), since no colorant is added to the base material layer 13, the rust prevention property of the first layer 11 is improved. It is possible to avoid the influence of the colorant.

The olefin resin constituting the second layer 12 of the rust-preventive film of the present disclosure includes a polyolefin-based polymer, that is, a homopolymer of an olefin, and a homopolymer of an olefin, similarly to the olefin resin contained in the first layer 11 described above. / Alternatively, one or more selected from copolymers using an olefin as a monomer can be selected and used. The olefin resin used for the second layer 12 may be the same as or different from the olefin resin constituting the first layer 11.

The thickness of the second layer 12 of the rust-preventive film of the present disclosure can be appropriately set within the range of the thickness of the rust-preventive film, but is preferably 10 μm or more and 100 μm or less. When the thickness of the second layer 12 is within the above range, there is little possibility that the heat-sealing property and the film-forming property of the entire rust-preventive film are significantly adversely affected.

(Base layer)
The base material layer 13 is a layer capable of imparting various mechanical, physical, and chemical functions such as supportability, rigidity, flexibility, and pinhole resistance to the rust-preventive film of the present disclosure. Can be mentioned. For example, when a barrier-type base material layer having a barrier property against water vapor is used as the base material layer 13, the package manufactured from the rust-preventive film of the present disclosure effectively prevents the intrusion of moisture into the package. be able to.
The thickness of the base material layer 13 can be appropriately set within the range of the thickness of the rust-preventive film, but if the purpose is to impart appropriate strength and waist to the rust-preventive film, the thickness is 5 μm. It is preferably 100 μm or less, and more preferably 10 μm or more and 50 μm or less.

<Barrier base material layer>
The barrier base material layer has a resin layer and an inorganic oxide film provided on one surface of the resin layer.
The resin layer functions as a support layer for the inorganic oxide film in the barrier base material layer. As the resin layer, various resins having strength, heat resistance and the like can be used. Specifically, resin films such as polyester-based resin, polyamide-based resin, polyaramid-based resin, polyolefin-based resin, polycarbonate-based resin, polystyrene-based resin, polyacetal-based resin, and fluorine-based resin can be used. In particular, polyethylene terephthalate (PET) film is preferably used because of printability, vapor deposition suitability, and antistatic property of thin film deposition.
The resin layer may be an unstretched film, a stretched film stretched in a uniaxial direction or a biaxial direction, or the like.

Examples of the material for forming the inorganic oxide film include oxides such as silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, and barium oxide. However, among them, aluminum oxide, silicon oxide, and magnesium oxide are preferable from the viewpoint of barrier performance and production efficiency.

The inorganic oxide film may have a single-layer structure formed by one vapor deposition step, or may have a multilayer structure formed by repeating the vapor deposition step a plurality of times. In the case of a multi-layer structure, each layer may be made of the same material or may be made of different materials. Further, each layer may be formed by the same forming method or may be formed by a different forming method.

The film thickness of the inorganic oxide film can be set in the range of 5 nm or more and 100 nm or less as the thickness of the entire film. By setting the film thickness of the inorganic oxide film within the above range, it is possible to obtain a barrier base material layer having excellent flexibility and pinhole resistance.

On the other hand, if the film thickness of the inorganic oxide film exceeds 100 nm, the flexibility is lowered, and the inorganic oxide film may be cracked by an external force such as bending or pulling. Therefore, it becomes difficult to achieve sufficient barrier performance. In addition, the stress of the material itself becomes large, which is not preferable. In addition, it is not preferable because it significantly reduces productivity and tends to form protrusions from the growth of abnormal grains.
Further, when the film thickness of the inorganic oxide film is less than 5 nm, the film property is inferior and pinholes are likely to occur. Therefore, it becomes difficult to achieve sufficient barrier performance.

Examples of the method for forming the inorganic oxide film include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, plasma chemical vapor deposition, thermochemical vapor deposition, and photochemical vapor deposition. Chemical vapor deposition methods such as the growth method can be mentioned. In the present disclosure, the vapor deposition method in the vacuum vapor deposition method is desirable, and the resistance heating method, the induction heating method, the electron beam heating method and the like can be appropriately selected and adopted as necessary.

In particular, in the present disclosure, it is preferable to provide an inorganic oxide film by a resistance heating type vacuum vapor deposition method. The resistance heating type vacuum vapor deposition method heats the vapor deposition material with Joule heat using an electric resistor, and compared to other heating methods, a uniform vapor deposition film is used to heat the vapor deposition material as a whole. Can be formed. In addition, the line speed can be set high. Further, the resistance heating type vacuum vapor deposition method can suppress the charge on the film.
In the present disclosure, it is particularly preferable to provide an aluminum oxide vapor deposition film as the inorganic oxide film by a resistance heating type vacuum vapor deposition method from the viewpoints of barrier performance, antistatic property, cost and the like.

(Manufacturing method of rust preventive film)
Hereinafter, a method for manufacturing the rust-preventive film of the present disclosure will be described. The manufacturing method shown below is an example and does not limit the present disclosure.
Each layer constituting the rust-preventive film of the present disclosure can be produced by any method such as a T-die extrusion method, an extrusion inflation method, or the like.
In addition to the T-die co-extrusion method and co-extrusion inflation method, the layers of the multi-layered rust-preventive film can be laminated, for example, by wet lamination method, dry lamination method, solvent-free dry lamination method, extrusion lamination method, and co-extrusion method. It can be performed by any method such as a lamination method or the like. Among the above, the T-die co-extrusion method and the co-extrusion inflation method are preferable in terms of cost because the number of steps can be reduced as compared with the laminating method.

For example, a case where the rust-preventive film of the present disclosure is manufactured by the co-extrusion inflation method will be described. Here, a method for manufacturing a rust-preventive film having a two-layer structure of the first layer 11 and the second layer 12 will be described, but the three-layer structure of the first layer 11, the second layer 12, and the base material layer 13 will be described. A rust-preventive film can be manufactured in the same manner.
When the barrier base layer is provided as the base layer 13, the barrier base layer is provided on the exposed surface side of the second layer 12 laminated on the first layer 11. It can be manufactured by laminating the side of the surface having the inorganic oxide film 42.

In order to produce a rust-preventive film having a two-layer structure of the first layer 11 and the second layer 12, first, a resin composition for forming each of the first layer 11 and the second layer 12 is prepared. Then, the first layer 11 and the second layer 12 are co-extruded and laminated by inflation film formation to produce a rust-preventive film having a two-layer structure. Aging treatment may be performed if necessary. Further, the obtained rust-preventive film may be stretched in the uniaxial direction or the biaxial direction, if necessary.

The purpose of the rust-proof film is to impart chemical function, electrical function, magnetic function, mechanical function, friction / wear / lubrication function, optical function, thermal function, surface function such as biocompatibility, etc. As a result, secondary processing can be performed.
Examples of secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, etc.) Coating, etc.) and the like. Further, the rust-preventive film can be subjected to a laminating process (dry laminating or extruding laminating), a bag making process, and other post-treatment processes.

(Rust-proof packaging)
The rust-preventive package of the present disclosure is a package used for packaging an article having metal, and has the rust-preventive film of the present disclosure. More specifically, the rust-preventive package of the present disclosure is composed of the rust-preventive film of the present disclosure, and has a first layer 11 inside.
The form of the rust-preventive package of the present disclosure is not particularly limited, and the rust-preventive film of the present disclosure can be bent, stacked to wrap the contents, or heat-sealed to form various forms. , It is also possible to add value by printing decoration.

For the pouch-shaped rust-preventive package, for example, the rust-preventive film is folded in half, or two rust-preventive films are prepared, the surfaces of the first layer thereof are overlapped with each other facing each other, and the peripheral end thereof. The portion can be heat-sealed to produce rust-preventive packages having various shapes.
For example, side sticker type, two-way sticker type, three-way sticker type, four-way sticker type, envelope sticker sticker type, gassho sticker sticker type (pillow sticker type), fold sticker sticker type, flat bottom sticker type, square bottom sticker type, gusset type. It is possible to manufacture rust-proof packages having various shapes by heat-sealing with a heat-sealing form such as.
In the above, as the heat sealing method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, or the like can be used.

When manufacturing the rust-proof package, the air inside the package may be sucked and the pressure inside the package may be sealed at a pressure lower than the atmospheric pressure. Further, when the rust-preventive package is manufactured, the content space may be sealed while being replaced with a gas having a low oxygen concentration or a low humidity.

In the rust-preventive package of the present disclosure, the first layer 11 of the rust-preventive film of the present disclosure is located on the inner layer side of the rust-preventive package, and the second layer 12 is located on the outer layer side of the first layer 11. To position. That is, in the rust-preventive package of the present disclosure, the first layer 11 is a layer that comes into contact with an article having a metal, which is the content of the package.
With such a positional relationship, the rust-preventive package of the present disclosure can suppress the generation of rust on the article having the metal as the content. Further, in the rust-preventive film of the present disclosure, since the second layer 12 on the outer layer side can contain a required amount of additives according to various purposes, the film-forming property of the rust-preventive film of the present disclosure. It is possible to further improve the stability of quality during long-term storage.
Further, in the rust-preventive film 1 shown in FIG. 1, by optimizing the content of the slip agent contained in the second layer 12, it is possible to suppress the generation of pinholes due to rubbing during transportation. ..

Further, in the rust-preventive package of the present disclosure, the base material layer 13 may be provided on the second layer (that is, on the outer layer side). Thereby, the rust-preventive package of the present disclosure can be imparted with various mechanical, physical and chemical functions such as supportability, rigidity, flexibility and pinhole resistance.

The present disclosure will be described in more detail with reference to the following examples and comparative examples, but the present disclosure is not limited to these examples. Details of the raw materials used in the examples and comparative examples are as follows.

[Additive]
Antioxidant: Phenolic antioxidant manufactured by ADEKA CORPORATION, A060.
Neutralizer: Calcium oxide HAL-J manufactured by Yoshizawa Petrochemical Industry Co., Ltd. (average particle size 1 μm or more and 2 μm or less).
Anti-blocking agent (AB agent): Sodium aluminosilicate (sodium aluminosilicate) particles manufactured by Mizusawa Industrial Chemicals Co., Ltd., AMT100S2 (pH = 7).
Slip agent: Stearic acid manufactured by Wako Pure Chemical Industries, Ltd.

[Olefin resin]
LDPE1: LDPE manufactured by Japan Polyethylene Corporation, Novatec LC520. Density 0.923 g / cm ³ , MFR 3.6 g / 10 minutes.
LLDPE1: LLDPE manufactured by Prime Polymer Co., Ltd., Evolu SP2020. Density 0.916 g / cm ³ , MFR = 2.0 g / 10 minutes.

<Preparation of masterbatch>
[Preparation of Masterbatch 1]
The antioxidant and LDPE1 were melt-blended at the following ratios to obtain Masterbatch 1 (MB1).
LDPE1 95 parts by mass Antioxidant 5 parts by mass

[Adjustment of masterbatch 2-4]
According to the following formulation, melt blending was performed in the same manner as in Masterbatch 1 to obtain Masterbatch 2 to Masterbatch 4 (MB2 to MB4).
MB2: LDPE1 95 parts by mass / neutralizer 5 parts by mass MB3: LDPE1 95 parts by mass / anti-blocking agent 5 parts by mass MB4: LDPE1 95 parts by mass / slip agent 5 parts by mass

[Preparation of Masterbatch 5]
The antioxidant and LDPE1 were melt-blended in the following proportions to obtain Masterbatch 5 (MB5).
LDPE1 90 parts by mass Antioxidant 10 parts by mass

[Adjustment of master batch 6-8]
According to the following formulation, melt blending was performed in the same manner as in Masterbatch 1 to obtain Masterbatch 6 to Masterbatch 8 (MB6 to MB8).
MB6: LDPE1 90 parts by mass / neutralizer 10 parts by mass MB7: LDPE1 90 parts by mass / anti-blocking agent 10 parts by mass MB8: LDPE1 90 parts by mass / slip agent 10 parts by mass

[Example 1]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Example 1.
MB1 0.1 part by mass MB2 0.1 part by mass MB3 0.1 part by mass MB4 0.1 part by mass LLDPE1 99.6 part by mass In addition, MB5, MB6, MB7, MB8, and LLDPE1 are dry-blended in the following ratios. The resin composition of the second layer of the rust-preventive film of Example 1 was obtained.
MB5 1 part by mass MB6 1 part by mass MB7 1 part by mass MB8 1 part by mass LLDPE1 96 parts by mass The resin composition of the first layer and the resin composition of the second layer obtained above were coextruded and inflated. A film was formed and laminated at 160 ° C. to obtain a rust-preventive film (60 μm thickness) having the following two-layer structure.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Example 2]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Example 2.
MB1 0.2 parts by mass MB2 0.1 parts by mass MB3 0.1 parts by mass MB4 0.1 parts by mass LLDPE1 99.5 parts by mass In addition, the second rust-preventive film of Example 2 is the same as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Example 3]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Example 3.
MB1 0.1 part by mass MB2 0.2 part by mass MB3 0.1 part by mass MB4 0.1 part by mass LLDPE1 99.5 part by mass Further, the second of the rust-preventive film of Example 3 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Example 4]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Example 4.
MB1 0.1 part by mass MB2 0.1 part by mass MB3 0.2 part by mass MB4 0.1 part by mass LLDPE1 99.5 part by mass Further, the second of the rust-preventive film of Example 4 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Example 5]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Example 5.
MB1 0.1 part by mass MB2 0.1 part by mass MB3 0.1 part by mass MB4 0.2 part by mass LLDPE1 99.5 part by mass Further, the second of the rust-preventive film of Example 5 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Example 6]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Example 6.
MB1 0.2 parts by mass MB2 0.2 parts by mass MB3 0.2 parts by mass MB4 0.2 parts by mass LLDPE1 99.2 parts by mass Further, the second of the rust-preventive film of Example 6 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 1]
MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 1.
MB2 0.1 part by mass MB3 0.1 part by mass MB4 0.1 part by mass LLDPE1 99.7 part by mass Further, the resin composition of the second layer of the rust-preventive film of Comparative Example 1 was prepared in the same manner as in Example 1. Obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 2]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 2.
MB1 0.4 parts by mass MB2 0.1 parts by mass MB3 0.1 parts by mass MB4 0.1 parts by mass LLDPE1 99.3 parts by mass Further, the second rust-preventive film of Comparative Example 2 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 3]
MB1, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 3.
MB1 0.1 part by mass MB3 0.1 part by mass MB4 0.1 part by mass LLDPE1 99.7 part by mass Further, the resin composition of the second layer of the rust-preventive film of Comparative Example 3 was prepared in the same manner as in Example 1. Obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 4]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 4.
MB1 0.1 part by mass MB2 0.4 part by mass MB3 0.1 part by mass MB4 0.1 part by mass LLDPE1 99.3 part by mass Further, the second of the rust-preventive film of Comparative Example 4 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 5]
MB1, MB2, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 5.
MB1 0.1 part by mass MB2 0.1 part by mass MB4 0.1 part by mass LLDPE1 99.7 part by mass Further, the resin composition of the second layer of the rust-preventive film of Comparative Example 5 was prepared in the same manner as in Example 1. Obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 6]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 6.
MB1 0.1 part by mass MB2 0.1 part by mass MB3 0.4 part by mass MB4 0.1 part by mass LLDPE1 99.3 part by mass Further, the second of the rust-preventive film of Comparative Example 6 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 7]
MB1, MB2, MB3, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 7.
MB1 0.1 part by mass MB2 0.1 part by mass MB3 0.1 part by mass LLDPE1 99.7 part by mass Further, the resin composition of the second layer of the rust-preventive film of Comparative Example 7 was prepared in the same manner as in Example 1. Obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

[Comparative Example 8]
MB1, MB2, MB3, MB4, and LLDPE1 were dry-blended at the following ratios to obtain a resin composition for the first layer of the rust-preventive film of Comparative Example 8.
MB1 0.1 part by mass MB2 0.1 part by mass MB3 0.1 part by mass MB4 0.4 part by mass LLDPE1 99.3 part by mass Further, the second of the rust-preventive film of Comparative Example 8 in the same manner as in Example 1. The resin composition of the layer was obtained.
The resin composition of the first layer and the resin composition of the second layer obtained above are formed and laminated at 160 ° C. using a co-extrusion inflation method to form a rust-preventive film having the following two layers. 60 μm thickness) was obtained.
Layer structure: 1st layer / 2nd layer = 30 μm thickness / 30 μm thickness

The following evaluations were made for each of the films of Examples 1 to 6 and Comparative Examples 1 to 8. The results are shown in Tables 1 and 2. In Tables 1 and 2, the AB agent is an anti-blocking agent.

<Evaluation method>
[Film formation]
The appearance of each film was observed with the naked eye, and the presence or absence of defects was evaluated according to the following evaluation criteria.
◯: There were no wrinkles, bumps, peeling, etc. on the rust preventive film.
X: There were wrinkles, bumps, peeling, etc. on the rust preventive film.

[Rust prevention]
Each film is cut into 100 mm × 100 mm, the first layers are opposed to each other, and after overlapping, three-way sealing is performed on the other three sides except one side using an impulse sealer, and one side is open. A 100 mm × 100 mm pouch was made.
Next, the following metal pieces were put into the pouch as the contents, and the open side was sealed and sealed while sucking the air in the pouch, and the pouch was placed in a constant temperature bath adjusted to 60 ° C. and 90% RH for 14 days. It was stored and the change in appearance was evaluated according to the following evaluation criteria.
(Metal piece)
Iron plate: Cold rolled steel plate (SPCC), 50 mm x 50 mm x 1 mm, degreased.
Copper plate: Tough pitch copper plate (C1100P-1 / 4H), 50 mm x 50 mm x 1 mm, degreased.
(Evaluation criteria)
〇: No rust and discoloration, or only spot rust and slight discoloration.
X: Rust occurs in 50% or more of the area of the test piece.

1, 2 Rust-proof film 11 1st layer 12 2nd layer 13 Base material layer

Claims (10)

It has a first layer and a second layer laminated on one surface of the first layer.
The first layer is made of an olefin resin having a heat-sealing property.
The first layer has an antioxidant, a neutralizing agent, an anti-blocking agent, and a slip agent as additives.
The content of the antioxidant in the first layer is 50 ppm or more and 100 ppm or less.
The content of the neutralizing agent in the first layer is 50 ppm or more and 100 ppm or less.
The content of the anti-blocking agent in the first layer is 50 ppm or more and 100 ppm or less.
A rust-preventive film having a slip agent content of 50 ppm or more and 100 ppm or less in the first layer. The second layer is composed of an olefin resin and is composed of an olefin resin.
The total content of the additive contained in the second layer is
The rust-preventive film according to claim 1, which is larger than the total content of the additives contained in the first layer. The rust-preventive film according to claim 2, which has a base material layer laminated on the second layer. The rust-preventive film according to claim 3, wherein the base material layer is a barrier base material layer. The rust-preventive film according to any one of claims 1 to 4, wherein the antioxidant contains a phenolic antioxidant. The rust-preventive film according to any one of claims 1 to 4, wherein the neutralizing agent contains calcium oxide. The rust-preventive film according to any one of claims 1 to 4, wherein the anti-blocking agent contains sodium aluminosilicate. The rust-preventive film according to any one of claims 1 to 4, wherein the slip agent contains stearic acid. A rust-preventive package comprising the rust-preventive film according to any one of claims 1 to 8 and having the first layer inside. The rust-preventive package according to claim 9, wherein the pressure inside the package is sealed at a pressure lower than the atmospheric pressure.

Images