JP2010052751A - Rust-proof packaging material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rust-proof packaging material which exhibits early rising of a rust-proof effect when a metal part or the like is packaged, has the rust-proof effect for a long time with adding a small amount of a rust preventive, and is excellent in sealing properties and piercing resistance. <P>SOLUTION: The rust-proof packaging material comprises a laminated film in which at least a barrier substrate layer, an adhesive resin layer, a water content absorbing film layer and a rust-proof film layer are successively piled up from the outside. The rust-proof film layer is a layer in which a vaporizable rust preventive is kneaded into a heat-fusible polyolefin resin. The water content absorbing film layer is a film with a water absorbing ability in which a drying agent is kneaded into a polyolefin resin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a packaging material for packaging machinery / equipment or parts made of metal and preventing the metal surface from being oxidized and rusted during storage, transportation and transportation, and in particular, easy to seal. The present invention relates to a rust-proof packaging material that stably maintains an excellent rust-proof effect.

  The purpose of rust-proof packaging is to use appropriate rust-proof packaging materials for metal materials and parts, considering the material, shape, degree of surface finish, and their functions, either physically or in transportation and storage. The purpose is to prevent the deterioration and damage of the article from the environment such as temperature and humidity, exhaust gas and light. Rust-proof packaging technology developed rapidly in the United States during the Second World War, with the aim of preventing long-distance transport of weapons and munitions and rusting during storage in hot and humid areas. . In 1959 (Showa 34), JIS-Z-0303 (General Rules for Rust Prevention Packaging Method) was established with reference to MIL-P-116B (US Military Standard: Rust Prevention Packaging Method), and rust prevention management was established. Widely used.

  Vaporizable rust preventives are often used for storing, transporting, and transporting machines, instruments, precision equipment and electronic components that cannot be rusted by application of rust preventive oil. Normally, when packaging an object to be rusted, a vaporizable rust inhibitor is inserted into the inner space of the package, and the volatilizing rust preventive component is chemically or physically applied to the surface of the object to be rusted. By adsorbing, oxidation (corrosion) due to atmospheric oxygen or moisture is prevented.

  Ordinary vaporizable rust preventives volatilize at room temperature and exhibit a rust preventive effect, so simply spraying or applying powder or liquid vaporizable rust preventives directly onto the object to be rusted. The rust preventive component volatilizes within a short period of time and loses the rust preventive effect. In addition, with powder and liquid vaporizable rust preventives, it takes time to spray or apply it to the object to be protected, and it is necessary to enclose the vaporizable rust preventive in a porous sachet or the like. is there. Moreover, when these carrier components of the rust preventive component adhere to the surface of the object to be rusted, it may cause a functional failure particularly in precision instruments and the like, and the trouble of removal is very complicated.

  Therefore, a rust preventive film obtained by applying or kneading the vaporizable rust preventive agent to a plastic film such as polyethylene is often used. Normally, since the rust prevention film is packaged alone, the rust prevention component escapes to the outside of the packaging, and the rust prevention effect does not last long, so in order to maintain the effect for a long period of time, a lot of rust preventive agent is kneaded. There is a need. Also, since the film base is a polyethylene single film, it is difficult to heat seal, and even if impulse seals are used, pinholes and edge breaks are likely to occur in the seal part, and rust preventives cannot be confined. There is.

  Therefore, it was necessary to wrap the outside twice with a barrier packaging material instead of the rust-proof film alone. Also, since moisture in the atmosphere is confined in the packaging material during packaging, there is no place for moisture confined in the packaging space as it is, and condensation occurs when rust-preventive components are dissipated and the temperature changes. Therefore, it is necessary to separately enclose a desiccant in a porous sachet or the like and package it at the same time, or to add a desiccant to the vaporizing rust preventive agent kneaded film and knead it. However, when the inside of the packaging space is in a low-humidity state from the beginning, it is excellent in kneading into polyethylene, and there are no volatile rust preventives such as nitrites, which are frequently used due to low persistence on the surface of metal products. Depending on the type, there is also a problem that the rise of the effect of the vaporizable rust preventive agent, that is, the vaporization of the rust preventive component from the film is delayed and rust is generated.

  The present invention has been invented in order to overcome the above problems in consideration of the above-mentioned actual situation. The purpose of the present invention is that when a metal part is packaged, the rise of the rust prevention effect is quick, the addition amount of a small rust preventive agent has a rust prevention effect for a long period of time, and the sealability and puncture resistance are excellent. It is an object to provide a rust-proof packaging material.

  The invention according to claim 1 of the present invention is characterized by comprising a laminated film laminated in the order of at least a barrier base material layer, an adhesive resin layer, a moisture absorption film layer, and a rust preventive film layer from the outside. It is a rust-proof packaging material.

  In the invention according to claim 2 of the present invention, the barrier base material layer is formed by laminating a metal foil on a stretched film that does not melt at the heat-sealing temperature of the anticorrosive film layer, or a metal on the stretched film, Or it is a water vapor | steam and oxygen barrier base material which formed the thin film of the metal oxide, It is a rust-proof packaging material described in Claim 1 characterized by the above-mentioned.

  The invention according to claim 3 of the present invention is characterized in that the rust-proof film layer is a rust-proof film in which a heat-fusible polyolefin resin is kneaded with a vaporizable rust-proofing agent. 2 is a rust-proof packaging material.

  The invention according to claim 4 of the present invention is characterized in that the vaporizable rust preventive contains nitrite or nitrite as a main component. It is a rust-proof packaging material.

  The invention according to claim 5 of the present invention is the film according to any one of claims 1 to 4, wherein the moisture-absorbing film layer is a film having a moisture-absorbing ability in which a desiccant is kneaded into a polyolefin resin. The rust-proof packaging material described in item 1.

  Since the rust-proof packaging material of the present invention is composed of a laminated film in which at least a barrier substrate layer, an adhesive resin layer, a moisture absorption film layer, and a rust-proof film layer are laminated and bonded in this order from the outside, metal parts, etc. When wrapping, while preventing moisture, oxygen or corrosive gas from entering from outside, the rust preventive component is not dissipated and the rust preventive effect can be maintained for a long time. Use a heat-resistant stretched film that does not melt at the heat-sealing temperature of the anticorrosive film layer as the base film of the barrier substrate, and laminate a metal foil such as aluminum, or consist of a metal vapor-deposited film or a metal oxide thin film Since the barrier base material made of water vapor and oxygen barrier base material with a barrier layer is used as the outer layer, it has stable heat sealability and puncture resistance that does not cause pinholes even when corners of metal parts hit. It can be set as the rust-proof packaging material which was excellent in the handleability.

  In addition, since the sealant is a rust-preventive film in which a vaporizable rust inhibitor is kneaded into a heat-sealable polyolefin resin, the sealing performance is stable and the rust-preventive components gradually enter the packaging space. By being released, it is possible to exert a rust prevention effect in the long term. Furthermore, the moisture absorption film layer containing the desiccant is sandwiched between the barrier substrate and the innermost layer has good kneading into polyolefin, is easy to form into a film, and has little contamination to the metal surface. Blocking the metal by dissolving the rust preventive component vaporized in the residual moisture adsorbed on the metal surface, with a structure in which a rust preventive film layer containing a rust inhibitor containing nitrite or nitrites is laminated. Or the residual moisture in the package reacts with the rust inhibitor and vaporizes and quickly fills the package, providing a good initial effect of rust prevention, and entering the package space from moisture and outside. By absorbing and supplementing the absorbed moisture with a moisture-absorbing film, a rust-proof packaging material having a high anti-rust effect for a long time can be obtained. In a configuration in which the moisture absorption film layer described later is used or the desiccant is kneaded with the vaporizable rust inhibitor, the initial rust preventive effect may be low or the rust preventive effect may not be exhibited.

  Hereinafter, the present invention will be described in detail based on an embodiment. FIG. 1 is a schematic view illustrating the laminated structure of the rust-proof packaging material of the present invention in cross section. Moreover, FIG. 2 is a schematic diagram explaining a state when the object to be protected such as a metal part is hermetically packaged with the antirust packaging material of the present invention.

  The rust-proof packaging material of this invention consists of the laminated | multilayer film laminated | stacked in order of the barrier base material layer 1, the adhesive resin layer 4, the moisture absorption film layer 3, and the rust prevention film layer 2 at least from the outer side. The moisture absorption film layer 3 and the rust preventive film layer 2 can be laminated using an adhesive resin or an adhesive, or can be laminated by a coextrusion method with the base resin as the same resin.

Here, the barrier base material layer 1 improves the barrier function for preventing moisture from entering the inside of the package from the outside and the evaporation of the rust-preventing component from the inside of the package to the outside, and the heat resistance during heat sealing. It bears the function of giving puncture resistance from A base material having a barrier property can be used, and a laminated film that is not melted at the heat sealing temperature of the anticorrosive film layer 2 is laminated with a metal foil such as aluminum, or a stretched film such as a metal such as aluminum or In addition, a thin film of a metal oxide such as aluminum oxide, silicon oxide, magnesium oxide formed by a vacuum deposition method, a sputtering method, a CVD (Chemical Vapor Deposition) method, or the like can be used. It is preferable to use a material having high barrier properties because the rust prevention effect is enhanced. The water vapor barrier properties to prevent the incoming water from the outside, 10g / m ² /day(40℃×90%R.H.) Or less. Further, an oxygen barrier property can be used as an index for preventing vaporized rust-preventing components from going out of the package, and the oxygen barrier property is 30 × 10 ⁻⁶ m ³ / m ² / day. / MPa (30 ° C. × 70% RH) or less is preferable. As the base film, a biaxially stretched polyethylene terephthalate (PET), polyamide (ONY), polypropylene (OPP), or other stretched film is preferable because of its high puncture strength and heat resistance.

  Next, the adhesive resin layer 4 adheres and laminates the barrier substrate 1 and the moisture-absorbing film layer 3 or a co-extruded composite film of the moisture-absorbing film layer and the rust-proof film layer. For example, the barrier substrate is anchor-coated and polyethylene is subjected to extrusion lamination, or without the anchor coat, ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer (EMAA), It is formed by extrusion lamination of an adhesive resin such as ethylene-acrylic acid copolymer (EAA) alone or by adding a tackifier to the adhesive resin. The adhesive resin layer 4 can also be formed by dry lamination with, for example, a two-component curable urethane adhesive without using the above-described molten resin.

  Next, the moisture-absorbing film layer 3 is a film having a moisture-absorbing ability obtained by kneading a desiccant with a polyolefin-based resin such as polyethylene by a known method and forming the film by a known production method such as an inflation method or an extrusion method. Here, the desiccant is at least one selected from calcium oxide, zeolite, silica gel, sulfate compounds such as magnesium sulfate and alunite, calcium chloride, zinc oxide, barium titanate, alumina, activated carbon, and clay minerals. It is also possible to use a water-absorbing polymer such as polyvinyl alcohol (PVA) or polyethylene glycol (PEG) in combination. The amount of desiccant added varies depending on the amount of internal space of the rust-proof package and the rust-prevention period. From the moisture absorption effect and the stability of film formation, the moisture absorption film layer has a content of 3% by mass to 20% by mass. It is desirable to do. The moisture-absorbing film layer exhibits the function of making a rust-proof packaging material having a high anti-rust effect for a long period of time by absorbing and capturing moisture remaining in the packaging space and moisture that has entered from the outside.

  Next, the rust prevention film layer 2 is a rust prevention film formed by kneading a vaporizable rust inhibitor into a heat-fusible polyolefin resin. The film formed by the inflation method or the extrusion casting method, or the calender alone, is laminated on the above-mentioned barrier base material layer 1 / adhesive resin layer 4 / moisture absorbing film layer 3 with an adhesive resin or an adhesive, or the moisture absorbing film It is also possible to extrusion laminate directly onto the layer. Moreover, it is also possible to produce as a film integrated with multiple layers by coextrusion with a moisture absorbing film.

The rust preventive agent kneaded into the rust preventive film layer is preferably a vaporizable rust preventive agent and is selected depending on the object to be rusted. As a material that exhibits the characteristics of the rust-proof packaging material of the present invention more effectively, it contains nitrite or nitrites that have good kneading into a polyolefin resin, are easily formed into a film, and have little contamination to the metal surface. It is desirable. Specifically, NO itself has no vaporization property, but causes hydrolysis in the presence of moisture in the atmosphere and an acid component such as carbon dioxide gas, and exhibits an excellent rust prevention effect on steel materials. ₂ ^- sodium nitrite to produce a gas, potassium nitrite, nitrite such as calcium nitrite and the like. Before the metal and hydroxide ions are combined, they combine with nitrite ions in the vaporized gas to form a rust preventive film on the metal surface. In addition, nitrites diisopropylammonium nitrite (DIPAN), dicyclohexylammonium, which are vaporizable themselves and dissolve in moisture adsorbed on the metal surface to form a film with antirust performance on the metal. Nitrolite (DICHAN), nitronaphthalene ammonium nitrite (NITAN), and mixtures thereof can also be used. In addition, the rust-proof packaging material of the present invention can be used in combination with benzotriazole or a derivative thereof having a rust-proofing effect on copper and copper alloys other than steel products, and is not particularly limited. The addition amount of the volatile corrosion inhibitor includes a packaging space volume of Hibosabi products are selected by rust period, generally a concentration of 5 g / m ³ or more anticorrosive ingredients relative packaging internal space volume It is desirable to maintain it, and it is preferable to add 2 to 15% by mass of the entire anticorrosive film layer from the viewpoints of rust preventive component dispersibility, film-forming properties, and heat sealability.

  Examples of the heat-sealable polyolefin resin used as the base of the moisture absorbing film layer and the rust-preventing film layer include low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-α olefin copolymer, polypropylene, and propylene. -Ethylene random copolymer, propylene-ethylene block copolymer, propylene-α olefin copolymer, ethylene-cyclic olefin copolymer, ethylene-vinyl acetate copolymer obtained by copolymerizing cycloolefin such as cyclopentadiene and norbornene. Polymer or part or complete saponified product thereof, ethylene- (meth) acrylic acid copolymer or esterified product thereof, ionic cross-linked product, ethylene- (meth) acrylic acid- (meth) acrylic acid ester terpolymer, etc. It is possible to select from . Also, a blend of two or more of these thermoplastic resins may be used. These polyolefin resins may further contain various additives such as antioxidants, flame retardants, slip agents, antiblocking agents, dispersants, light stabilizers and the like.

Next, the addition and blending of the desiccant and the rust preventive agent with respect to the heat-fusible polyolefin-based resin that is the base of the moisture absorption film layer and the rust preventive film layer described above are the moisture absorption function and the above required, respectively. Dry blending of materials with various specified blending amounts set by the rust prevention function using ribbon mixers, tumbler mixers, Henschel mixers, etc., extruders such as single screw extruders, twin screw extruders, kneading machines such as Banbury mixers Depending on the thermoplastic resin used as a base, it can be obtained by kneading at a melting point of 280 ° C. or less, preferably 260 ° C. or less, more preferably 240 ° C. or less. The obtained strand is cooled by air cooling, and after pelletizing, it is stored in a packaging form such as an aluminum packaging bag. Thereafter, it is possible to obtain a rust-proof packaging material using the method described above.

  Specific examples and comparative examples of the present invention will be described below.

<Example 1>
As the barrier substrate layer, a transparent vapor-deposited film of aluminum oxide (GL-AEY, manufactured by Toppan Printing Co., Ltd.) 15 μm is used, and a moisture-absorbing film 60 μm and a rust-proof film 60 μm are sequentially dry-laminated on the vapor-deposited surface. It laminated | stacked and the packaging material of Example 1 was obtained. Here, the water-absorbing film is a low density polyethylene resin (manufactured by Asahi Kasei Corporation L1850K), alum and (alum _{KAl 3 (OH) 6 (SO} 4) anhydrides _2-), polyethylene 95 wt% / alum A film formed by extruding 5% by mass was used. Further, the rust preventive film is a low-density polyethylene resin (L1850K manufactured by Asahi Kasei Co., Ltd.), a vaporizable rust preventive mainly composed of sodium nitrite previously masterbatched with 95% by mass of polyethylene / vaporizable rust preventive 5 A film formed by extruding a material having a composition of mass% was used.

<Example 2>
As the barrier substrate layer, a transparent vapor-deposited film of aluminum oxide (GL-AEY, manufactured by Toppan Printing Co., Ltd.) 15 μm was used. The vapor-deposited surface was subjected to corona discharge treatment, and the vapor-deposited surface was subjected to EMAA adhesive resin (Mitsui DuPont Chemical). Extruded “Nucleel N0908C”) with a thickness of 13 μm and sand-laminated with a moisture-absorbing film 60 μm, and then laminated with a low-density polyethylene resin (L1850K, manufactured by Asahi Kasei Co., Ltd.) with a thickness of 13 μm and sand-laminated with an anti-rust film 60 μm. Then, the packaging material of Example 2 was obtained, where the same moisture absorbing film and rust preventive film as in Example 1 were used.

<Comparative Example 1>
As the barrier substrate layer, a transparent vapor-deposited film of aluminum oxide (GL-AEY, manufactured by Toppan Printing Co., Ltd.) 15 μm was used. The vapor-deposited surface was subjected to corona discharge treatment, and the vapor-deposited surface was subjected to EMAA adhesive resin (Mitsui DuPont Chemical). "Nucleel N0908C") is extruded with a thickness of 13 µm and sand laminated with a moisture absorption film of 60 µm, and then a low density polyethylene resin (L1850K, manufactured by Asahi Kasei Co., Ltd.) is extruded with a thickness of 13 µm to produce a low density polyethylene (L1850K, manufactured by Asahi Kasei Corporation). A single film 60 μm and a sand laminate were laminated to obtain a packaging material of Comparative Example 1. Here, the same moisture absorbing film as in Example 1 was used.

<Comparative example 2>
As the barrier substrate layer, a transparent vapor-deposited film of aluminum oxide (GL-AEY, manufactured by Toppan Printing Co., Ltd.) 15 μm was used. The vapor-deposited surface was subjected to corona discharge treatment, and the vapor-deposited surface was subjected to EMAA adhesive resin (Mitsui DuPont Chemical). "Nucleel N0908C") is extruded in a thickness of 13μm and sand laminated with a single film of low density polyethylene (L1850K manufactured by Asahi Kasei Co., Ltd.) and then laminated with a low density polyethylene resin (L1850K manufactured by Asahi Kasei Co., Ltd.) in a thickness of 13μm. A film of 60 μm was sand laminated and laminated to obtain a packaging material of Comparative Example 2. Here, the same rust preventive film as that of Example 1 was used.

<Comparative Example 3>
As the barrier substrate layer, a transparent vapor deposition film of aluminum oxide (GL-AEY, manufactured by Toppan Printing Co., Ltd.) of 15 μm was used, and the vapor deposition surface was subjected to corona discharge treatment, and on the vapor deposition surface, an EMAA adhesive resin (Mitsui DuPont Chemical) was used. “Nucrel N0908C” manufactured by the company was extruded at a thickness of 25 μm, and sand laminated with a film 100 μm in which both a rust inhibitor and a desiccant were kneaded to obtain a packaging material of Comparative Example 3. Here, rust prevention and moisture were obtained. Absorbing film is a low-density polyethylene resin (L1850K, manufactured by Asahi Kasei Co., Ltd.), a vaporizable rust preventive mainly composed of sodium nitrite previously masterbatched, and baked alum. A film formed by extruding 5% by mass and 5% by mass of baked alum was used.

<Comparative example 4>
As a single rust preventive film, a vaporizable rust preventive mainly composed of sodium nitrite masterbatched in advance to a low density polyethylene resin (L1850K manufactured by Asahi Kasei Co., Ltd.), 95% by mass of polyethylene / vaporizable rust preventive 5 A material having a composition of mass% was extruded to form a film having a thickness of 100 μm to obtain a packaging material of Comparative Example 4.

  Using the packaging materials of Examples 1 and 2 and Comparative Examples 1 to 4 described above, the following rust prevention effect, sealing property, and piercing property (pinhole resistance) were evaluated. The results are shown in Table 1.

・防錆効果： 各包装材料を用いて、寸法６０ｍｍ×６０ｍｍの袋を作り、寸法５０ｍｍ
×５０ｍｍ×厚み２ｍｍの普通鋼を包み、４０℃９０％ＲＨの環境中で１ヶ月、半年間
保存し錆の発生度合いを評価。 ○:錆発生なし、△：薄く錆発生、×：錆発生
・シール性： 包装材料が完全に熱融着する温度からプラス３０度高い温度でヒートシー
ルし、シール部のピンホール発生やエッジ切れの有×、無○を確認した。
・突刺し性: 上記防錆効果評価で作製したと同じサンプルを、各１０個づつ箱に入れて
、振動試験（加速度０．７５Ｇ；５〜５０Ｈｚ×６０分）を行って、袋にピンホールが
空くかを評価した。ピンホール発生は×。

-Rust prevention effect: Each packaging material is used to make a bag with a size of 60 mm x 60 mm and a size of 50 mm
Wrapped plain steel of 50mm x 2mm thickness, stored in an environment of 40 ° C 90% RH for 1 month and half a year, and evaluated the degree of rust generation. ○: No rust generation, △: Thin rust generation, ×: Rust generation / sealability: Heat sealing is performed at a temperature that is 30 degrees higher than the temperature at which the packaging material is completely heat-sealed, and pinholes are generated and edges are broken. It was confirmed that there was no and no.
・ Puncture property: Put the same sample as the rust prevention effect evaluation into 10 boxes each and perform vibration test (acceleration 0.75G; 5-50Hz × 60min), pin hole in bag Evaluated whether is free. Pinhole generation is x.

<Comparison result>
As shown in Table 1, the packaging materials of Example 1 and Example 2 having the configuration of the rust-proof packaging material of the present invention obtained good results for both the rust-proofing effect and the packaging function. On the other hand, as a matter of course, Comparative Example 3 in which no vaporizable rust preventive was used, Comparative Example 4 in which only a rust preventive film was used and no moisture-absorbing film was used in the construction, and the desiccant was used as a rust preventive. In addition, the comparative example 5 used on the innermost layer side with kneading also resulted in an insufficient rust prevention effect. In Comparative Example 6 using a rust preventive film alone, although the initial rust preventive effect was obtained, the evaporation of the vaporizable rust preventive agent was fast, and the rust preventive effect was reduced when stored for a long period of time, and the sealing property and piercing property were reduced. Unfortunately, the handling and function as packaging materials were insufficient. From the above results, the usefulness of the rust-proof packaging material of the present invention was clarified.

Schematic explaining the laminated structure of the rust-proof packaging material of this invention in a cross section. Schematic diagram explaining the state when the object to be protected such as metal parts is hermetically packaged with the rust-proof packaging material of the present invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Barrier base material layer 2 ... Rust prevention film layer 3 ... Water absorption film layer 4 ... Adhesive resin layer 5 ... Metal component 6 ... Water vapor 7 ... Rust prevention component

Claims (5)

  A rust-proof packaging material comprising a laminated film laminated in the order of at least a barrier base material layer, an adhesive resin layer, a moisture absorption film layer, and a rust-proof film layer from the outside.   The barrier substrate layer is laminated with a metal foil on a stretched film that does not melt at the heat-sealing temperature of the anticorrosive film layer, or a thin film of metal or metal oxide is formed on the stretched film, water vapor and The rust-proof packaging material according to claim 1, which is an oxygen-barrier base material.   The rust-proof packaging material according to claim 1 or 2, wherein the rust-proof film layer is a rust-proof film obtained by kneading a vaporizable rust preventive into a heat-fusible polyolefin resin.   The rust-proof packaging material according to any one of claims 1 to 3, wherein the vaporizable rust inhibitor contains nitrite or nitrite as a main component.   The rust-proof packaging material according to any one of claims 1 to 4, wherein the moisture-absorbing film layer is a film having a moisture-absorbing ability obtained by kneading a desiccant into a polyolefin resin.

Images