JP2024060483A - Flame retardant and rust-proof film - Google Patents
Flame retardant and rust-proof film Download PDFInfo
- Publication number
- JP2024060483A JP2024060483A JP2022167883A JP2022167883A JP2024060483A JP 2024060483 A JP2024060483 A JP 2024060483A JP 2022167883 A JP2022167883 A JP 2022167883A JP 2022167883 A JP2022167883 A JP 2022167883A JP 2024060483 A JP2024060483 A JP 2024060483A
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- JP
- Japan
- Prior art keywords
- rust
- flame
- retardant
- film
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 190
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- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 106
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- 229940045845 sodium myristate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- UFLMJULGUPSTCY-UHFFFAOYSA-M sodium;4-nitrobenzoate Chemical compound [Na+].[O-]C(=O)C1=CC=C([N+]([O-])=O)C=C1 UFLMJULGUPSTCY-UHFFFAOYSA-M 0.000 description 1
- KTTMJIJHZNYOFB-UHFFFAOYSA-M sodium;4-tert-butylbenzoate Chemical compound [Na+].CC(C)(C)C1=CC=C(C([O-])=O)C=C1 KTTMJIJHZNYOFB-UHFFFAOYSA-M 0.000 description 1
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
【課題】難燃防錆フィルムとして、十分な防錆性と十分な難燃性を共に備え、さらに光透過性と視認性に優れた難燃防錆フィルムを得ること。【解決手段】下記ポリオレフィン系樹脂層１と下記ポリオレフィン系樹脂層２を有し、全体の厚さが５０～１５０μｍであり、難燃防錆フィルム全層中にハロゲン系難燃剤を２．５重量％以上含有する、難燃防錆フィルム。（ポリオレフィン系樹脂層１）アミン系及び／又はアンモニウム系気化性防錆剤を含有するポリオレフィン系樹脂からなる層（ポリオレフィン系樹脂層２）ハロゲン系難燃剤を含有するポリオレフィン系樹脂からなる層【選択図】図１[Problem] To obtain a flame-retardant/rust-proof film that has both sufficient rust prevention and sufficient flame retardancy, and further has excellent light transmission and visibility. [Solution] A flame-retardant/rust-proof film having the following polyolefin-based resin layer 1 and the following polyolefin-based resin layer 2, having a total thickness of 50 to 150 μm, and containing 2.5% by weight or more of a halogen-based flame retardant in all layers of the flame-retardant/rust-proof film. (Polyolefin-based resin layer 1) A layer made of a polyolefin-based resin containing an amine-based and/or ammonium-based volatile rust inhibitor (Polyolefin-based resin layer 2) A layer made of a polyolefin-based resin containing a halogen-based flame retardant [Selected Figure] Figure 1
Description
本発明は難燃防錆フィルムに関する。 The present invention relates to a flame-retardant and rust-preventive film.
金属製品を包装する等の材料として使用するために、防錆剤の長期的な効果を得る方法として、加工し易い点で優れる低密度ポリエチレンに代表される無極性のポリオレフィン樹脂に、防錆剤を分散・担持させた防錆フィルムが知られている。防錆フィルムにポリオレフィン樹脂を使用すると、フィルム等に加工する際の加熱温度においても防錆剤が融解せずに粒子の状態のまま存在させることや、気化・消失させずに存在させることができる。
一般に、工場内において、高温での加工や、火の気を使用する加工を行う場所の近くに、ポリオレフィン樹脂等の組成物からなる製品を置くことは好ましくない。但し、一時的にもそのような場所の近くに樹脂組成物からなる製品を置く場合があり、このようなときに特に細心の注意を払う必要があった。
In order to obtain the long-term effect of rust inhibitors for use as materials for packaging metal products, etc., rust inhibitor films in which the rust inhibitors are dispersed and supported in non-polar polyolefin resins, such as low-density polyethylene, which is excellent in terms of ease of processing, are known. When polyolefin resins are used in rust inhibitor films, the rust inhibitors do not melt and remain in the form of particles even at the heating temperatures used for processing into films, etc., and can be maintained without vaporizing or disappearing.
In general, it is not preferable to place products made of compositions such as polyolefin resins near places in factories where high-temperature processing or processing using fire is performed. However, there are cases where products made of resin compositions are placed near such places even temporarily, and in such cases, it is necessary to pay particular attention.
例えば特許文献１に記載の防錆包装材は、防錆フィルム層を有する防錆包装材において、該防錆フィルム層が、熱融着性ポリオレフィン系樹脂層に気化性防錆剤を含有する内層と、熱融着性ポリオレフィン系樹脂層に被酸化性金属粉末と酸素吸収剤と水分吸収剤を含有する外層とからなるものであり、いずれかの層には限定されないが、難燃剤や、酸化防止剤、スリップ剤、アンチブロッキング剤等の各種添加剤を配合できるに留まる。
さらに特許文献２には、水蒸気バリア樹脂層と酸素バリア樹脂層とを有する外層と、気化性防錆剤を含有する熱融着性樹脂層からなる内層からなる防錆フィルムであって、内層に難燃剤や、酸化防止剤、スリップ剤、アンチブロッキング剤等の各種添加剤を配合できることが記載されているに留まる。
For example, the rust-preventive packaging material described in Patent Document 1 has an anti-rust film layer, and the anti-rust film layer is composed of an inner layer containing a volatile rust inhibitor in a heat-sealable polyolefin-based resin layer, and an outer layer containing an oxidizable metal powder, an oxygen absorbent, and a moisture absorbent in a heat-sealable polyolefin-based resin layer. Although not limited to any of the layers, various additives such as flame retardants, antioxidants, slip agents, and anti-blocking agents can be blended therein.
Furthermore, Patent Document 2 merely describes an anti-rust film comprising an outer layer having a water vapor barrier resin layer and an oxygen barrier resin layer, and an inner layer made of a heat-fusible resin layer containing a volatile rust inhibitor, and that various additives such as a flame retardant, an antioxidant, a slip agent, and an anti-blocking agent can be blended in the inner layer.
本発明は、難燃防錆フィルムとして、十分な防錆性と十分な難燃性を共に備え、さらに光透過性と視認性に優れた難燃防錆フィルム、又は、光透過性が小さい難燃防錆フィルム表面上に形成した印刷や筆記による文字や模様等を見やすくした難燃防錆フィルムを得ることを課題とする。 The present invention aims to obtain a flame-retardant and rust-proofing film that has both sufficient rust prevention and sufficient flame retardancy, and also has excellent light transmittance and visibility, or a flame-retardant and rust-proofing film with low light transmittance that makes it easy to see printed or written letters, patterns, etc. formed on the surface.
本発明者らは、前記課題を解決するために鋭意検討した結果、以下の手段で解決することができることを見出し、本発明をなすに至った。
１．下記ポリオレフィン系樹脂層１と下記ポリオレフィン系樹脂層２を有し、全体の厚さが５０～１５０μｍであり、難燃防錆フィルム全層中にハロゲン系難燃剤を２．５重量％以上含有する、難燃防錆フィルム。
（ポリオレフィン系樹脂層１）
アミン系及び／又はアンモニウム系気化性防錆剤を含有するポリオレフィン系樹脂からなる層
（ポリオレフィン系樹脂層２）
ハロゲン系難燃剤を含有するポリオレフィン系樹脂からなる層
２．ＦＭＶＳＳ Ｎｏ．３０２に適合する１に記載の難燃防錆フィルム。
３．酸素指数が２６以上である１又は２に記載の難燃防錆フィルム。
４．ＤＩＮ４１０２－１Ｂ２に適合する１～３のいずれかに記載の難燃防錆フィルム。
５．全光線透過率が４０％以上である１～４のいずれかに記載の難燃防錆フィルム。
６．ポリオレフィン系樹脂層２が、亜硝酸塩を含有する１～５のいずれかに記載の難燃防錆フィルム。
７．１～６のいずれかに記載の難燃防錆フィルムから形成され、ポリオレフィン系樹脂層１側の面が包装される物品側である難燃防錆用包装袋。
As a result of extensive investigations aimed at solving the above problems, the present inventors have found that the problems can be solved by the following means, and have thus completed the present invention.
1. A flame-retardant and rust-proofing film having the following polyolefin-based resin layer 1 and the following polyolefin-based resin layer 2, having a total thickness of 50 to 150 μm, and containing 2.5% by weight or more of a halogen-based flame retardant in all layers of the flame-retardant and rust-proofing film.
(Polyolefin-based resin layer 1)
Layer made of polyolefin resin containing amine-based and/or ammonium-based volatile rust inhibitor (polyolefin resin layer 2)
2. A layer made of a polyolefin resin containing a halogen-based flame retardant. 3. The flame-retardant and rust-preventive film according to 1, which complies with FMVSS No. 302.
3. The flame-retardant, rust-preventive film according to 1 or 2, having an oxygen index of 26 or more.
4. The flame-retardant, rust-preventive film according to any one of 1 to 3, which complies with DIN 4102-1B2.
5. The flame-retardant, rust-preventive film according to any one of 1 to 4, having a total light transmittance of 40% or more.
6. The flame-retardant and rust-preventive film according to any one of 1 to 5, wherein the polyolefin-based resin layer 2 contains a nitrite.
7. A flame-retardant and rust-preventive packaging bag formed from the flame-retardant and rust-preventive film according to any one of 1 to 6, wherein the surface on the polyolefin resin layer 1 side is the side on which an article is to be packaged.
本発明によれば、十分な防錆性と十分な難燃性を共に備え、さらに光透過性に優れるために包装袋等の包装用途に用いたときの被包装物の視認性に優れた難燃防錆フィルム、又は、光透過性が低いときに、難燃防錆フィルム表面上に形成した印刷や筆記による文字や模様等を見やすくした難燃防錆フィルムを得ることができた。中でも難燃性については、ＦＭＶＳＳに適合することを前提とし、さらに、場合によっては酸素指数２６以上及び／又はＤＩＮ４１０２－１Ｂ２（以下場合により「ＤＩＮ４１０２」と記載することがある）にも適合する難燃防錆フィルムを得ることができた。 According to the present invention, it has been possible to obtain a flame-retardant and rust-proof film that has both sufficient rust prevention and sufficient flame retardancy, and further has excellent light transmittance, which allows excellent visibility of the packaged item when used for packaging applications such as packaging bags, or a flame-retardant and rust-proof film that makes it easy to see printed or written characters and patterns formed on the surface of the flame-retardant and rust-proof film when the light transmittance is low. In particular, regarding flame retardancy, it has been possible to obtain a flame-retardant and rust-proof film that, assuming compliance with FMVSS, further has an oxygen index of 26 or more and/or in some cases also complies with DIN 4102-1B2 (hereinafter sometimes referred to as "DIN 4102").
本発明は、特定の防錆剤を含有するポリオレフィン系樹脂層と、特定の難燃剤を含有するポリオレフィン系樹脂層を有する難燃防錆フィルムであることを基礎とする。
そして、本発明の難燃防錆フィルムを袋状に加工して、防錆を行うべき対象の物品を包装するための難燃防錆用包装袋等とする。
以下に本発明の難燃防錆フィルム及び難燃防錆用包装袋を説明する。
なお、本明細書において、難燃防錆フィルムを単に「フィルム」と記載するときがあり、難燃防錆フィルム全層は、難燃防錆フィルムの全体の層を意味し、難燃防錆フィルム全層を単に「フィルム全層」と記載するときがある。
The present invention is based on a flame-retardant, rust-proofing film having a polyolefin-based resin layer containing a specific rust inhibitor and a polyolefin-based resin layer containing a specific flame retardant.
The flame-retardant and rust-preventive film of the present invention is processed into a bag shape to form a flame-retardant and rust-preventive packaging bag or the like for packaging an article that needs to be rust-prevented.
The flame-retardant and rust-preventive film and the flame-retardant and rust-preventive packaging bag of the present invention will be described below.
In this specification, the flame-retardant, rust-proofing film may be simply referred to as "film", and the entire flame-retardant, rust-proofing film layer may refer to all layers of the flame-retardant, rust-proofing film, and the entire flame-retardant, rust-proofing film layer may be simply referred to as "the entire film layer".
（ポリオレフィン系樹脂層１用及びポリオレフィン系樹脂層２用のポリオレフィン系樹脂）
本発明中のポリオレフィン系樹脂層１及びポリオレフィン系樹脂層２に使用されるポリオレフィン系樹脂は、容器や包装フィルム等に使用されるものを使用できる。
そしてポリオレフィン系樹脂層１及びポリオレフィン系樹脂層２は、下記の樹脂の中から、それぞれ独立して１種以上を採用することができる。そのため、ポリオレフィン系樹脂層１及びポリオレフィン系樹脂層２は、同じポリオレフィン系樹脂からなる組成物を使用しても良く、異なる組成物を使用しても良い。
ポリオレフィン系樹脂として、ポリオレフィン系重合体、つまり、オレフィンの単独重合体、及び／又は、オレフィンを単量体として用いた共重合体から選ばれた１種以上を選択して使用することができる。
(Polyolefin Resins for Polyolefin Resin Layer 1 and Polyolefin Resin Layer 2)
The polyolefin resin used in the polyolefin resin layer 1 and the polyolefin resin layer 2 in the present invention may be one used for containers, packaging films, and the like.
The polyolefin resin layer 1 and the polyolefin resin layer 2 can each independently adopt one or more of the following resins. Therefore, the polyolefin resin layer 1 and the polyolefin resin layer 2 may use a composition made of the same polyolefin resin or different compositions.
As the polyolefin-based resin, one or more types selected from polyolefin-based polymers, that is, olefin homopolymers and/or copolymers using olefins as monomers, can be selected and used.
ポリオレフィン系重合体を構成するオレフィン（オレフィン単量体）としては、エチレン、プロピレン、１－ブテン、３－メチル－１－ブテン、１－ペンテン、３－メチル－１－ペンテン、４－メチル－１－ペンテン、１－ヘキセン、１－オクテン等が挙げられる。従って、ポリオレフィン系重合体としては、エチレン系重合体、プロピレン系重合体、１－ブテン系重合体、１－ヘキセン系重合体、４－メチル－１－ペンテン系重合体等が挙げられる。これら重合体は１種のみで用いてもよく、２種以上を併用してもよい。すなわち、ポリオレフィン系重合体は各種の重合体の混合物であっても良い。
上記のうち、エチレン系重合体としては、エチレン単独重合体（ポリエチレン）、及び、エチレンと他の単量体との共重合体（エチレン共重合体）が挙げられる。エチレン単独重合体及びエチレン共重合体としては、例えば、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）が挙げられる。
また、エチレン共重合体としては、エチレン・プロピレン共重合体、エチレン・１－ブテン共重合体、エチレン・１－ペンテン共重合体、エチレン・１－へキセン共重合体、エチレン・１－オクテン共重合体、エチレン・４－メチル－１－ペンテン共重合体、エチレン-ヘキセン共重合体等のエチレンとＣ３－Ｃ８のα-オレフィンとの共重合体や、エチレンとシクロペンタジエンやノルボルネン等の環状オレフィンを共重合させたエチレン－環状オレフィン共重合体、エチレン-酢酸ビニル共重合体（ＥＶＡ）、エチレン-アクリル酸共重合体、エチレン-酢酸ビニル-メチルメタクリレート共重合体等のエチレン性不飽和結合を有するカルボン酸誘導体とエチレンとの共重合体等、及びそれらのブレンド物が挙げられる。
なお、エチレン共重合体に含まれるエチレン単位（エチレンに由来する構成単位）は、全構成単位数のうち５０％よりも大きければよいが（通常９９．９９９％以下）、例えば、全構成単位数のうち８０～９９．９９９％とすることができ、また９０～９９．９９５％とすることができ、さらには９９～９９．９９０％とすることができる。
Examples of the olefin (olefin monomer) constituting the polyolefin polymer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Thus, examples of the polyolefin polymer include ethylene polymers, propylene polymers, 1-butene polymers, 1-hexene polymers, and 4-methyl-1-pentene polymers. These polymers may be used alone or in combination of two or more. In other words, the polyolefin polymer may be a mixture of various polymers.
Among the above, the ethylene-based polymer includes ethylene homopolymer (polyethylene) and copolymer of ethylene and other monomer (ethylene copolymer). Examples of the ethylene homopolymer and ethylene copolymer include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).
Examples of the ethylene copolymer include copolymers of ethylene and C3-C8 α-olefins, such as ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, and ethylene-hexene copolymer; ethylene-cyclic olefin copolymers obtained by copolymerizing ethylene with cyclic olefins such as cyclopentadiene and norbornene; copolymers of ethylene and a carboxylic acid derivative having an ethylenically unsaturated bond, such as ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer, and ethylene-vinyl acetate-methyl methacrylate copolymer; and blends thereof.
The ethylene units (structural units derived from ethylene) contained in the ethylene copolymer may account for more than 50% of the total number of structural units (usually 99.999% or less), but can account for, for example, 80 to 99.999% of the total number of structural units, or 90 to 99.995%, or even 99 to 99.990%.
また、プロピレン系重合体としては、プロピレン単独重合体（ポリプロピレン）、及び、プロピレンと他の単量体との共重合体（プロピレン共重合体）が挙げられる。プロピレン共重合体としては、プロピレン・エチレン共重合体、プロピレン・１－ブテン共重合体、プロピレン・１－ペンテン共重合体、プロピレン・１－オクテン共重合体等が挙げられる。
なお、プロピレン共重合体に含まれるプロピレン単位（プロピレンに由来する構成単位）は、全構成単位数のうち５０％以上（通常９９．９９９％以下）であればよいが、例えば、全構成単位数のうち８０～９９．９９９％とすることができ、また９０～９９．９９５％とすることができ、さらには９９～９９．９９０％とすることができる。
Examples of the propylene polymer include propylene homopolymers (polypropylene) and copolymers of propylene and other monomers (propylene copolymers). Examples of the propylene copolymers include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-pentene copolymers, and propylene-1-octene copolymers.
The propylene units (structural units derived from propylene) contained in the propylene copolymer may account for 50% or more (usually 99.999% or less) of the total number of structural units, but can be, for example, 80 to 99.999% of the total number of structural units, or 90 to 99.995%, or even 99 to 99.990%.
また、ポリオレフィン系重合体には、本発明の目的を害しない範囲で、オレフィンを除く単量体に由来する構成単位を含んでもよい。オレフィン以外の単量体としては、不飽和カルボン酸（アクリル酸、メタクリル酸、フマル酸、マレイン酸等）、不飽和カルボン酸エステル（アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、マレイン酸ジメチル、マレイン酸ジエチル等）、ビニルエステル（酢酸ビニル、プロピオン酸ビニル、マレイン酸モノエステル等）などが挙げられる。これらは１種のみを用いてもよく２種以上を併用してもよい。
なお、ポリオレフィン系重合体に含まれるオレフィン以外の単量体に由来する構成単位は、含まれるとしても全構成単位数のうち４０％以下（通常０．００１％以上）が好ましい。例えば、全構成単位数のうち０．００１～２５％とすることができ、また０．００５～１５％とすることができ、さらには０．０１～１０％とすることができる。
ポリオレフィン系樹脂の密度としては加工性の観点から０．８８０～０．９６０ｇ／ｃｍ３が好ましく、０．８９０～０．９５０ｇ/ｃｍ３がより好ましい。また、機械強度や加工性の観点から、メルトフローレート値（ＭＦＲ）は０．１～３０．０ｇ／１０ｍｉｎが好ましく、１．０～１０．０ｇ／１０ｍｉｎがより好ましく、１．５～５．０ｇ／１０ｍｉｎが更に好ましく、ＭＦＲがこの範囲であると溶融加工時に適度な粘度を持つことにより、粒子状の防錆剤を樹脂中に包含及び被覆することが可能となり、樹脂成形体から防錆剤が脱落することを防ぐことが可能となる。
In addition, the polyolefin polymer may contain a structural unit derived from a monomer other than olefin, as long as it does not impair the object of the present invention. Examples of monomers other than olefin include unsaturated carboxylic acids (acrylic acid, methacrylic acid, fumaric acid, maleic acid, etc.), unsaturated carboxylic acid esters (methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, etc.), and vinyl esters (vinyl acetate, vinyl propionate, maleic acid monoester, etc.). These may be used alone or in combination of two or more.
In addition, the proportion of structural units derived from monomers other than olefins contained in the polyolefin polymer, if any, is preferably 40% or less (usually 0.001% or more) of the total number of structural units, for example, 0.001 to 25%, 0.005 to 15%, or even 0.01 to 10% of the total number of structural units.
The density of the polyolefin resin is preferably 0.880 to 0.960 g/cm 3 from the viewpoint of processability, and more preferably 0.890 to 0.950 g/cm 3. In addition, from the viewpoint of mechanical strength and processability, the melt flow rate value (MFR) is preferably 0.1 to 30.0 g/10 min, more preferably 1.0 to 10.0 g/10 min, and even more preferably 1.5 to 5.0 g/10 min. When the MFR is in this range, the resin has a suitable viscosity during melt processing, which makes it possible to include and coat the particulate rust inhibitor in the resin, and prevents the rust inhibitor from falling off from the resin molded body.
（ポリオレフィン系樹脂層１用のポリオレフィン系樹脂）
上記ポリオレフィン系樹脂のうち、例えば難燃防錆用包装袋の用途として用いる場合には、製品コストや、製造の簡便性からみてポリエチレンを選択することが適当であり、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等、各種のポリエチレンの特性を考慮して採用することができる。そして、これらのポリエチレンから１種を選択して使用しても良く、２種以上をブレンドしても良い。
(Polyolefin Resin for Polyolefin Resin Layer 1)
Among the above polyolefin resins, when used for, for example, flame-retardant and rust-proof packaging bags, polyethylene is appropriate to be selected in terms of product cost and ease of production, and various polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), etc. may be adopted in consideration of their properties. One of these polyethylenes may be selected for use, or two or more may be blended.
（ポリオレフィン系樹脂層２用のポリオレフィン系樹脂）
上記ポリオレフィン系樹脂のうち、例えば難燃防錆用包装袋の用途として用いる場合には、製品コストや、製造の簡便性からみてポリエチレンを選択することが適当であり、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等、各種のポリエチレンの特性を考慮して採用することができる。そして、これらのポリエチレンから１種を選択して使用しても良く、２種以上をブレンドしても良い。
(Polyolefin Resin for Polyolefin Resin Layer 2)
Among the above polyolefin resins, when used for, for example, flame-retardant and rust-proof packaging bags, polyethylene is appropriate to be selected in terms of product cost and ease of production, and various polyethylenes such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), etc. may be adopted in consideration of their properties. One of these polyethylenes may be selected for use, or two or more may be blended.
（ポリオレフィン系樹脂層１（内層））
ポリオレフィン系樹脂層１は上記のポリオレフィン系樹脂に対してアミン系及び／又はアンモニウム系気化性防錆剤を含有してなる層である。本発明の難燃防錆フィルムを用いて袋状に加工し、難燃防錆用包装袋としたときには、ポリオレフィン系樹脂層１は内層側になり、被包装物の物品側に向く内層となる。
このアミン系及び／又はアンモニウム系気化性防錆剤としては、公知の防錆剤でよく、脂肪族カルボン酸アンモニウム塩、脂肪族カルボン酸アミン塩、芳香族カルボン酸アンモニウム塩、芳香族カルボン酸アミン塩のいずれでも良い。
アンモニウム系気化性防錆剤としては、例えば、酪酸、イソ酪酸、メタクリル酸、吉草酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、トリデシル酸、ミリスチン酸、パルミチン酸、ステアリン酸、ソルビン酸、オレイン酸、オレイル酸、イソヘキサン酸、２－メチルペンタン酸、２－エチルブタン酸、イソヘプタン酸、イソオクタン酸、２－エチルヘキサン酸、イソノナン酸、イソデカン酸、２－プロピルヘプタン酸、イソウンデカン酸、イソドデカン酸、２－ブチルオクタン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、コルク酸、アゼライン酸、セバシン酸、ウンデカン二カルボン酸、ドデカン二酸等の脂肪族カルボン酸のアンモニウム塩や、安息香酸、アミノ安息香酸、サリチル酸、p-tert-ブチル安息香酸、o-スルホ安息香酸、1-ナフトエ酸、2-ナフトエ酸、フタル酸、イソフタル酸、テレフタル酸、ケイ皮酸等の芳香族カルボン酸のアンモニウム塩、上記の酸のシクロヘキシルアミン塩や、ジシクロヘキシルアミン塩から、１種以上を採用できる。
また、アミン系気化性防錆剤としては、モノ-、ジ-、トリ-エタノールアミン、n-、ジ-、tert-ブチルアミン、ヘキサメチレンジアミン、ヘキサメチレンテトラミン、モノ-、ジ-シクロヘキシルアミン、イソプロピルアミン、オレイルアミン、ナフチルアミン、ジ-フェニルアミンの燐酸、亜硝酸、炭酸、カルボン酸塩より選ばれた有機アミン塩から、１種以上を採用できる。
(Polyolefin-based resin layer 1 (inner layer))
The polyolefin resin layer 1 is a layer containing an amine-based and/or ammonium-based volatile rust inhibitor in the above-mentioned polyolefin resin. When the flame-retardant and rust-preventive film of the present invention is processed into a bag shape to form a flame-retardant and rust-preventive packaging bag, the polyolefin resin layer 1 becomes the inner layer side, and becomes the inner layer facing the article side of the packaged item.
The amine and/or ammonium volatile rust inhibitor may be any known rust inhibitor, such as an aliphatic carboxylic acid ammonium salt, an aliphatic carboxylic acid amine salt, an aromatic carboxylic acid ammonium salt, or an aromatic carboxylic acid amine salt.
Examples of ammonium-based volatile rust inhibitors include butyric acid, isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, isoundecanoic acid, isododecanoic acid, 2-butyloctanoic acid, oxalic acid, maloic acid, and the like. One or more of the ammonium salts of aliphatic carboxylic acids, such as benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, and the like, and the cyclohexylamine salts and dicyclohexylamine salts of the above-mentioned acids can be used.
As the amine-based volatile rust inhibitor, one or more organic amine salts selected from phosphoric acid, nitrous acid, carbonic acid, and carboxylate salts of mono-, di-, and tri-ethanolamine, n-, di-, and tert-butylamine, hexamethylenediamine, hexamethylenetetramine, mono- and di-cyclohexylamine, isopropylamine, oleylamine, naphthylamine, and diphenylamine can be used.
ポリオレフィン系樹脂層１中のアミン系及び／又はアンモニア系気化性防錆剤の含有量としては、ポリオレフィン系樹脂層１中０．１重量％以上が好ましく、０．３重量％以上がより好ましく、０．５重量％以上が更に好ましい。また５．０重量％以下が好ましく、３．０重量％以下がより好ましく、２．０重量％以下が更に好ましい。本発明の場合、０．１重量％未満であると場合によっては十分な防錆性を発揮させることが困難になる可能性があり、５．０重量%を超えると成形加工が困難になる場合がある。 The content of the amine-based and/or ammonia-based volatile rust inhibitor in the polyolefin-based resin layer 1 is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and even more preferably 0.5% by weight or more in the polyolefin-based resin layer 1. Also, it is preferably 5.0% by weight or less, more preferably 3.0% by weight or less, and even more preferably 2.0% by weight or less. In the case of the present invention, if it is less than 0.1% by weight, it may be difficult to achieve sufficient rust prevention in some cases, and if it exceeds 5.0% by weight, molding processing may be difficult.
アミン系及び／又はアンモニア系気化性防錆剤は粒子状の形状で、又は樹脂層中に相溶した状態でポリオレフィン系樹脂層１に含有されている。粒子状であっても、又は相溶していても良い。
この範囲の平均粒径及び／又は最大粒径であると、ポリオレフィン系樹脂層１の表面にアミン系及び／又はアンモニア系気化性防錆剤の粒子が、樹脂に覆われた状態での凸部が形成される。このような凸部の存在によって、防錆のためのガスをより多く発生させることができ、防錆性の向上に寄与できることになる。また、このようなフィルム表面の凸部により防錆対象の物品等に対する密着防止の効果があり、かつ防錆対象の物品にアミン系及び／又はアンモニア系気化性防錆剤の粒子が直に接触して、防錆対象の物品の表面を汚染することを防止できる。
また、アミン系及び／又はアンモニア系気化性防錆剤を樹脂層中に相溶した状態で含有したとき、及び／又は上記のように粒子状で樹脂層中に含有したときには、その気化性防錆剤の種類毎の揮発性等の特性により、気化性を調整できる。
The amine-based and/or ammonia-based volatile rust inhibitor is contained in the polyolefin-based resin layer 1 in a particulate form or in a state where it is compatible with the resin layer. It may be in a particulate form or may be compatible with the resin layer.
When the average particle size and/or maximum particle size are within this range, the particles of the amine-based and/or ammonia-based volatile rust inhibitor are covered with resin to form convex portions on the surface of the polyolefin resin layer 1. The presence of such convex portions allows more gas for rust prevention to be generated, which contributes to improving rust prevention. In addition, such convex portions on the film surface have the effect of preventing adhesion to the object to be rust-inhibited, and can prevent the particles of the amine-based and/or ammonia-based volatile rust inhibitor from directly contacting the object to be rust-inhibited and contaminating the surface of the object to be rust-inhibited.
In addition, when an amine-based and/or ammonia-based volatile rust inhibitor is contained in the resin layer in a compatible state and/or when it is contained in the resin layer in particulate form as described above, the volatility and other characteristics of each type of volatile rust inhibitor can be adjusted.
但し、ポリオレフィン系樹脂層を構成する樹脂にアミン系及び／又はアンモニア系気化性防錆剤の粒子を配合し、樹脂を溶融・混練し、例えばシート状等に成形する一連の工程を経ることによって、配合前のアミン系及び／又はアンモニア系気化性防錆剤の粒子は、粉砕されて平均粒径が小さくなることがある。
このため、本発明における上記平均粒径は、ポリオレフィン系樹脂層１を形成した後に、ポリオレフィン系樹脂層１に含有されるアミン系及び／又はアンモニア系気化性防錆剤の粒子に関する値である。
この特定の粒子径を持つ又は樹脂中に相溶したアミン系及び／又はアンモニア系気化性防錆剤を含有することにより、発生する防錆ガスの量を制御することができ、防錆効果を長期にわたって安定的に維持できる。
また、詳細なメカニズムは定かではないが、アミン系及び／又はアンモニア系気化性防錆剤の粒径を特定の範囲にすることで、フィルム表面に凸部が形成され、それにより長期的な防錆効果を発現していると考えられる。
ポリオレフィン系樹脂層１には、防錆剤として、更にベンゾトリアゾール系、トリルトリアゾール系、無機酸の金属塩、カルボン酸、カルボン酸金属塩を含有しても良い。
However, by going through a series of steps in which amine-based and/or ammonia-based volatile rust inhibitor particles are blended with the resin constituting the polyolefin-based resin layer, the resin is melted and kneaded, and then molded into, for example, a sheet, the amine-based and/or ammonia-based volatile rust inhibitor particles before blending may be pulverized to reduce the average particle size.
Therefore, the above average particle size in the present invention is a value relating to particles of the amine-based and/or ammonia-based volatile rust inhibitor contained in the polyolefin-based resin layer 1 after the polyolefin-based resin layer 1 is formed.
By containing an amine-based and/or ammonia-based volatile rust inhibitor having this specific particle size or compatible with the resin, the amount of rust-preventing gas generated can be controlled, and the rust-preventing effect can be stably maintained for a long period of time.
Although the detailed mechanism is unclear, it is believed that by setting the particle size of the amine-based and/or ammonia-based volatile rust inhibitor within a specific range, convex portions are formed on the film surface, thereby providing a long-term rust prevention effect.
The polyolefin resin layer 1 may further contain, as a rust inhibitor, a benzotriazole-based agent, a tolyltriazole-based agent, a metal salt of an inorganic acid, a carboxylic acid, or a metal salt of a carboxylate.
（ポリオレフィン系樹脂層２（外層））
ポリオレフィン系樹脂層２は上記のポリオレフィン系樹脂に対してハロゲン系難燃剤を含有してなる層である。本発明の難燃防錆フィルムを用いて包装材としたときに、このような難燃剤を含有するポリオレフィン系樹脂層２を外層、つまり、包装される物品側の内側ではない外側の層にすることが好ましい。それにより、その外側の層に着火等があっても、内側の層や包装される物品に影響を与えることがなく難燃効果を発揮することが期待できる。
ハロゲン系難燃剤としては、ハロゲン元素として例えば公知の塩素系難燃剤や臭素系難燃剤から選ばれた１種以上を使用できる。プラスチックの中でも特に燃えやすいオレフィン系樹脂への難燃効果の付与には、難燃効果が高い臭素系難燃剤を選定することがより好ましい。
塩素系難燃剤として、塩素化ポリエチレン、塩素化パラフィン等を使用でき、臭素系難燃剤として、ヘキサブロモシクロドデカン（ＨＢＣＤ）、ヘキサブロモベンゼン、デカブロモジフェニルエーテル、オクタブロモジフェニルエーテル、テトラブロモビスフェノールＡ（ＴＢＢＡ）、テトラブロモビスフェノ－ルS、ビス（トリブロモフェノキシ）エタン、ビス（ペンタブロモフェノキシ）エタン（ＢＰＢＰＥ）、テトラブロモビスフェノールＡエポキシ樹脂（ＴＢＢＡエポキシ）、テトラブロモビスフェノールＡカーボネート（ＴＢＢＡ－ＰＣ）、エチレン（ビステトラブロモフタル）イミド（ＥＢＴＢＰＩ）、エチレンビスペンタブロモジフェニル、トリス（トリブロモフェノキシ）トリアジン（ＴＴＢＰＴＡ）、ビス（ジブロモプロピル）テトラブロモビスフェノールＡ（ＤＢＰ－ＴＢＢＡ）、ビス（ジブロモプロピル）テトラブロモビスフェノールＳ（ＤＢＰ－ＴＢＢＳ）、臭素化ポリフェニレンエーテル（ポリ（ジ）ブロモフェニレンエーテルなどを含む）（ＢｒＰＰＥ）、臭素化ポリスチレン（ポリジブロモスチレン、ポリトリブロモスチレン、架橋臭素化ポリスチレン等）（ＢｒＰＳ）、臭素化架橋芳香族重合体、臭素化エポキシ樹脂、臭素化フェノキシ樹脂、臭素化スチレン－無水マレイン酸重合体、ペンタブロモベンジルアクリレートポリマー、テトラブロモビスフェノールＳ（ＴＢＢＳ）、トリス（トリブロモネオペンチル）ホスフェート（ＴＴＢＮＰＰ）、ポリブロモトリメチルフェニルインダン（ＰＢＰＩ）、及びトリス（ジブロモプロピル）－イソシアヌレート（ＴＤＢＰＩＣ）等を使用できる。
本発明は、難燃防錆フィルムの全層中にハロゲン系難燃剤を２．５重量％以上含有する。２．５重量％未満であると難燃防錆フィルムは十分な難燃性を発揮できない可能性がある。
本発明の難燃防錆フィルム全体が視認性を有し、難燃防錆フィルムで包装した被包装物を目視により確認できることや、難燃防錆フィルムを通した先の文字や模様等を確認できることを求める場合には、その難燃防錆フィルムの全光線透過率を４０％以上にすることが好ましく、５０％以上がより好ましく、６０％以上が更に好ましく、７０％以上が最も好ましい。
このような全光線透過率の範囲にするには、難燃防錆フィルムの全層中のハロゲン系難燃剤の含有量を２．５～３０．０重量％にすることが好ましい。中でも、全光線透過率をより高くするには、２５．０重量%以下がより好ましく、２０．０重量％以下が更に好ましく、１７．０重量％以下が最も好ましい。なお難燃防錆フィルムの全層中のハロゲン系難燃剤の含有量を２．５～３０．０重量％にする場合には、難燃防錆フィルムの全層の厚さを１２５μm以下にすることが好ましい。
また、その全光線透過率を高くはせず、全光線透過率が低下しても、その低下に代えて、難燃防錆用包装袋に加工をして、内部に被包装物を入れたときには、外部から物品を隠蔽することができる効果や、着色料等を添加せずに白色化できる。そして、得られた全光線透過率が小さい難燃防錆フィルムには、模様形成やバーコード等印刷や筆記等をして、何らかの表示等をしたときの、その表示の識別性を向上させたり、難燃防錆フィルムの表裏を区別しやすくできる効果を得ることができる。
このような表示の識別性の向上や難燃防錆フィルムの表裏を区別しやすくできる効果を得るには、難燃防錆フィルムの全層中のハロゲン系難燃剤の含有量は、３０．０重量％以上が好ましく、３３．０重量％以上がより好ましく、３５．０重量％以上が更に好ましく、３７重量％以上が最も好ましい。なお、ハロゲン系難燃剤の含有量が３０．０重量％のときには、難燃防錆フィルムの全層の厚さが１３０μｍ以上であることが好ましい。ポリオレフィン系樹脂層２中の難燃剤の濃度が高くなり白色化をし、難燃防錆フィルム全体としての全光線透過率が低下する。
(Polyolefin-based resin layer 2 (outer layer))
The polyolefin resin layer 2 is a layer containing a halogen-based flame retardant in the above-mentioned polyolefin resin. When the flame-retardant and rust-proof film of the present invention is used to make a packaging material, it is preferable that the polyolefin resin layer 2 containing such a flame retardant is made the outer layer, that is, the outer layer that is not on the inside side of the packaged article. In this way, even if the outer layer is ignited, it is expected that the flame retardant effect will be exerted without affecting the inner layer or the packaged article.
As the halogen-based flame retardant, one or more selected from known chlorine-based flame retardants and bromine-based flame retardants can be used as the halogen element. For imparting flame retardancy to olefin-based resins, which are particularly flammable among plastics, it is more preferable to select a bromine-based flame retardant with a high flame retardancy effect.
Examples of chlorine-based flame retardants that can be used include chlorinated polyethylene and chlorinated paraffin. Examples of bromine-based flame retardants that can be used include hexabromocyclododecane (HBCD), hexabromobenzene, decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A (TBBA), tetrabromobisphenol S, bis(tribromophenoxy)ethane, bis(pentabromophenoxy)ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene (bistetrabromophthalic)imide (EBTBPI), ethylene bispentabromodiphenyl, tris(tribromophenoxy)triazine (TTBPTA), bis(dibromopropyl)tetrabromobisphenol A, and bis(dibromopropyl)tetrabromobisphenol A. Bisphenol A (DBP-TBBA), bis(dibromopropyl)tetrabromobisphenol S (DBP-TBBS), brominated polyphenylene ether (including poly(di)bromophenylene ether, etc.) (BrPPE), brominated polystyrene (polydibromostyrene, polytribromostyrene, crosslinked brominated polystyrene, etc.) (BrPS), brominated crosslinked aromatic polymers, brominated epoxy resins, brominated phenoxy resins, brominated styrene-maleic anhydride polymers, pentabromobenzyl acrylate polymers, tetrabromobisphenol S (TBBS), tris(tribromoneopentyl)phosphate (TTBNPP), polybromotrimethylphenylindane (PBPI), and tris(dibromopropyl)-isocyanurate (TDBPIC) can be used.
The present invention contains 2.5% by weight or more of a halogen-based flame retardant in all layers of the flame-retardant and rust-proofing film. If the content is less than 2.5% by weight, the flame-retardant and rust-proofing film may not exhibit sufficient flame retardancy.
In cases where it is required that the entire flame-retardant and rust-proofing film of the present invention has visibility, that the packaged item packaged with the flame-retardant and rust-proofing film can be visually confirmed, and that letters, patterns, etc. can be confirmed through the flame-retardant and rust-proofing film, the total light transmittance of the flame-retardant and rust-proofing film is preferably 40% or more, more preferably 50% or more, even more preferably 60% or more, and most preferably 70% or more.
In order to achieve such a range of total light transmittance, the content of the halogen-based flame retardant in all layers of the flame-retardant/rust-proof film is preferably 2.5 to 30.0% by weight. In particular, in order to achieve a higher total light transmittance, the content is more preferably 25.0% by weight or less, even more preferably 20.0% by weight or less, and most preferably 17.0% by weight or less. When the content of the halogen-based flame retardant in all layers of the flame-retardant/rust-proof film is 2.5 to 30.0% by weight, the thickness of all layers of the flame-retardant/rust-proof film is preferably 125 μm or less.
Even if the total light transmittance is not increased and is reduced, when the film is processed into a flame-retardant and rust-preventive packaging bag and an article is placed inside, the film can have the effect of concealing the article from the outside and can be whitened without adding coloring agents, etc. The flame-retardant and rust-preventive film obtained with a low total light transmittance can have the effect of improving the identifiability of a mark when a pattern is formed or a barcode or other mark is printed or written on the mark, and of making it easy to distinguish the front and back of the flame-retardant and rust-preventive film.
In order to obtain the effect of improving the distinguishability of such indication and making it easy to distinguish the front and back of the flame-retardant and rust-proofing film, the content of the halogen-based flame retardant in the entire layer of the flame-retardant and rust-proofing film is preferably 30.0% by weight or more, more preferably 33.0% by weight or more, even more preferably 35.0% by weight or more, and most preferably 37% by weight or more. When the content of the halogen-based flame retardant is 30.0% by weight, the thickness of the entire layer of the flame-retardant and rust-proofing film is preferably 130 μm or more. The concentration of the flame retardant in the polyolefin-based resin layer 2 increases, causing whitening, and the total light transmittance of the entire flame-retardant and rust-proofing film decreases.
ポリオレフィン系樹脂層２には、本発明による効果を毀損しない範囲に限り、上記のハロゲン系難燃剤ではない下記の他の難燃剤を含有しても良いが、含有しなくても良い。
他の難燃剤としては、低級リン酸塩、メラミン系リン化合物、ポリリン酸塩、赤リン、縮合リン酸エステル、含ハロゲンリン酸エステル、含ハロゲン縮合型リン酸エステル等のリン化合物、水酸化アルミニウム、水酸化マグネシウムなどの水和金属化合物、ホウ酸亜鉛、酸化亜鉛、錫酸亜鉛、メタ錫酸、酸化錫、三酸化モリブデン等のモリブデン化合物、三酸化アンチモン、五酸化アンチモン、アンチモン酸ナトリウム等のアンチモン化合物等、シアヌール酸またはイソシアヌール酸とトリアジン系化合物との塩等が挙げられる。
The polyolefin resin layer 2 may contain the following other flame retardants other than the above halogen-based flame retardants, but is not required to contain them, as long as the effect of the present invention is not impaired.
Other flame retardants include phosphorus compounds such as lower phosphates, melamine-based phosphorus compounds, polyphosphates, red phosphorus, condensed phosphates, halogen-containing phosphates, and halogen-containing condensed phosphates; hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide; molybdenum compounds such as zinc borate, zinc oxide, zinc stannate, metastannic acid, tin oxide, and molybdenum trioxide; antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate; and salts of cyanuric acid or isocyanuric acid with triazine-based compounds.
ポリオレフィン系樹脂層２には、防錆剤を含有させなくても、防錆難燃フィルム全体としては十分な防錆性を発揮できるが、ポリオレフィン系樹脂層２にも防錆剤を含有させてもよい。
このとき、ポリオレフィン系樹脂層２には、防錆剤として、亜硝酸金属塩等の亜硝酸塩や炭酸の金属塩、カルボン酸やカルボン酸の金属塩から選ばれた１種以上を含有することができる。
これらの防錆剤は気化性防錆剤ではないので、気化することにより、難燃防錆フィルムで包装された空間内に気化した防錆剤を存在させるものではない。亜硝酸金属塩を含有したポリオレフィン系樹脂層２を外層にして包装袋等としたときには、外気の湿気が包装内に取り込まれることにより、外層内の亜硝酸金属塩と内層内のアミン及び／又はアンモニア系気化性防錆剤が反応し、包装内にアミン及び／又はアンモニア系気化性防錆剤が気化することを促進し、防錆効果を発揮させることができる。さらに、包装内に亜硝酸を発生させることにより、防錆効果を向上させることができる。
亜硝酸金属塩としては、亜硝酸のナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等から選ばれた１種以上を採用することができ、炭酸の金属塩としてはカリウム塩やその水和物が挙げられる。
Although the rust-preventive and flame-retardant film as a whole can exhibit sufficient rust prevention properties even if the polyolefin-based resin layer 2 does not contain a rust inhibitor, the polyolefin-based resin layer 2 may also contain a rust inhibitor.
In this case, the polyolefin resin layer 2 may contain, as a rust inhibitor, one or more selected from nitrites such as metal nitrites, metal salts of carbonates, carboxylic acids and metal salts of carboxylic acids.
These rust inhibitors are not volatile rust inhibitors, so they do not vaporize and cause the vaporized rust inhibitor to exist in the space packaged with the flame-retardant rust-preventive film. When the polyolefin-based resin layer 2 containing the metal nitrite is used as the outer layer to form a packaging bag or the like, the metal nitrite in the outer layer reacts with the amine and/or ammonia-based volatile rust inhibitor in the inner layer as moisture from the outside air is taken into the packaging, accelerating the vaporization of the amine and/or ammonia-based volatile rust inhibitor in the packaging, thereby achieving the rust-preventive effect. Furthermore, the rust-preventive effect can be improved by generating nitrous acid in the packaging.
As the metal nitrite, one or more selected from sodium, potassium, calcium and magnesium salts of nitrite can be used, and as the metal carbonate, potassium salt and its hydrate can be used.
カルボン酸としては、脂肪族カルボン酸及び／又は芳香族カルボン酸を使用できる。
カルボン酸としては、イソ酪酸、メタクリル酸、吉草酸、カプロン酸、カプリル酸、カプリン酸、ラウリン酸、トリデシル酸、ミリスチン酸、パルミチン酸、ステアリン酸、ソルビン酸、オレイン酸、オレイル酸、イソヘキサン酸、２－メチルペンタン酸、２－エチルブタン酸、イソヘプタン酸、イソオクタン酸、２－エチルヘキサン酸、イソノナン酸、イソデカン酸、２－プロピルヘプタン酸、イソウンデカン酸、イソドデカン酸、２－ブチルオクタン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、コルク酸、アゼライン酸、セバシン酸、ウンデカン二カルボン酸、ドデカン二酸等の脂肪族カルボン酸や、安息香酸、アミノ安息香酸、サリチル酸、p-tert-ブチル安息香酸、o-スルホ安息香酸、1-ナフトエ酸、2-ナフトエ酸、フタル酸、イソフタル酸、テレフタル酸、ケイ皮酸等の芳香族カルボン酸から、１種以上を採用できる。
カルボン酸金属塩としては、脂肪族カルボン酸アルカリ金属塩及び／又は芳香族のカルボン酸アルカリ金属塩を使用できる。
カルボン酸アルカリ金属塩としては、フタル酸、安息香酸、ラウリン酸、デカン酸、ノナン酸、オクタン酸、ヘプタン酸、ヘキサン酸、セバシン酸、アジピン酸等のアルカリ金属塩を採用できる。
これらのカルボン酸金属塩のなかでも、ラウリン酸ナトリウム、ラウリン酸カリウム、カプリル酸ナトリウム、カプリル酸カリウム、セバシン酸ナトリウム、セバシン酸カリウム、オレイン酸ナトリウム、オレイン酸カリウム、ｐ－ｔｅｒｔブチル安息香酸ナトリウム、ｐ－ニトロ安息香酸ナトリウム、ミリスチン酸ナトリウム、ミリスチン酸カリウム、パルミチン酸ナトリウム、パルミチン酸カリウム、コハク酸ナトリウム、コハク酸カリウム、クエン酸ナトリウム、クエン酸カリウム、アジピン酸ナトリウム、アジピン酸カリウム、酒石酸ナトリウムを採用することが好ましい。又、これらの中でも炭素数１２以下の飽和モノカルボン酸のナトリウム塩を採用することができる。
As the carboxylic acid, an aliphatic carboxylic acid and/or an aromatic carboxylic acid can be used.
Examples of carboxylic acids include isobutyric acid, methacrylic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, sorbic acid, oleic acid, oleic acid, isohexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, 2-propylheptanoic acid, isoundecanoic acid, isodo ... and 2-propylheptanoic acid. One or more of the following can be used: aliphatic carboxylic acids such as butyloctanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedioic acid; and aromatic carboxylic acids such as benzoic acid, aminobenzoic acid, salicylic acid, p-tert-butylbenzoic acid, o-sulfobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, and cinnamic acid.
As the metal carboxylate, an alkali metal aliphatic carboxylate and/or an alkali metal aromatic carboxylate can be used.
As the alkali metal carboxylate, alkali metal salts of phthalic acid, benzoic acid, lauric acid, decanoic acid, nonanoic acid, octanoic acid, heptanoic acid, hexanoic acid, sebacic acid, adipic acid, and the like can be used.
Of these metal carboxylates, it is preferable to employ sodium laurate, potassium laurate, sodium caprylate, potassium caprylate, sodium sebacate, potassium sebacate, sodium oleate, potassium oleate, sodium p-tert-butylbenzoate, sodium p-nitrobenzoate, sodium myristate, potassium myristate, sodium palmitate, potassium palmitate, sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium adipate, potassium adipate, and sodium tartrate. Of these, it is also possible to employ a sodium salt of a saturated monocarboxylic acid having 12 or less carbon atoms.
また、これらカルボン酸アルカリ金属塩以外に、例えば安息香酸やニトロ安息香酸などの遊離のカルボン酸、亜硝酸のアルカリ金属塩やアルカリ土類金属塩等のカルボン酸以外の酸やその塩、リン酸、ホウ酸、ケイ酸、ホウケイ酸など、無機酸のアルカリ金属、アルカリ土類金属等の塩を含有しても良いが、含有しなくても良い。 In addition to these alkali metal carboxylates, the composition may contain, but is not limited to, free carboxylic acids such as benzoic acid and nitrobenzoic acid, acids other than carboxylic acids and their salts such as alkali metal salts and alkaline earth metal salts of nitrous acid, and alkali metal and alkaline earth metal salts of inorganic acids such as phosphoric acid, boric acid, silicic acid, and borosilicate.
防錆剤の配合量としては、防錆対象の金属製品と、要求される防錆効果により適切な量は異なるが、一般的に少なすぎると防錆成分が広範囲に分散されず十分な防錆効果が得られない。逆に多すぎると難燃防錆フィルムの物理的強度に悪影響を及ぼすことで十分な防錆効果が得られない場合がある。
そのため、防錆性として安定した効果を得るためには、これらの防錆剤をポリオレフィン系樹脂層２に対して０．０５重量％以上含有させてもよく、０．１０重量％以上が好ましく、０．５０重量％以上がより好ましく、０．８０重量％以上が更に好ましい。また、２．００重量％以下が好ましく、１．５０重量％以下がより好ましく、１．３０重量％以下が更に好ましい。
The appropriate amount of rust inhibitor to be mixed depends on the metal product to be rust-proofed and the desired rust-proofing effect, but generally, if the amount is too small, the rust-proofing component will not disperse over a wide area and sufficient rust-proofing effect will not be obtained. Conversely, if the amount is too large, it may have a negative effect on the physical strength of the flame-retardant rust-proofing film, and sufficient rust-proofing effect may not be obtained.
Therefore, in order to obtain a stable rust-preventing effect, these rust inhibitors may be contained in an amount of 0.05% by weight or more, preferably 0.10% by weight or more, more preferably 0.50% by weight or more, and even more preferably 0.80% by weight or more, relative to the polyolefin resin layer 2. Also, the amount is preferably 2.00% by weight or less, more preferably 1.50% by weight or less, and even more preferably 1.30% by weight or less.
（ポリオレフィン系樹脂層１とポリオレフィン系樹脂層２に共通して添加できる物質）
ポリオレフィン系樹脂層１とポリオレフィン系樹脂層２それぞれに独立して添加できる共通する物質としては、本発明による効果を毀損しない範囲において、アンチブロッキング剤（ＡＢ剤）、滑剤、酸化防止剤、帯電防止剤、紫外線吸収剤、光安定剤、酸素吸収剤、酸吸収剤、核形成剤、衝撃強度増強剤、可塑剤、離型剤、着色剤、蛍光剤、相溶化剤、防曇剤、充填剤、助色剤、分散剤、安定剤、改質剤、及び抗菌・防かび剤、pＨ調整剤等の公知の添加剤をポリオレフィン系樹脂層１及び２に独立して添加することができる。但し、ポリオレフィン系樹脂層１やポリオレフィン系樹脂層２が含有する他の成分と反応しないこと、ブリードアウト等して、例えば被包装物を汚染等しないことが必要である。
なお、防錆剤を樹脂層中に保持させることを目的として、アイオノマー樹脂や官能基含有ポリオレフィン樹脂を樹脂層１や樹脂層２に配合しても良く、しなくても良い。本発明によれば十分に長期の防錆性を発揮できる。
(Substances that can be added to both polyolefin-based resin layer 1 and polyolefin-based resin layer 2)
Common substances that can be added independently to the polyolefin resin layer 1 and the polyolefin resin layer 2 include known additives such as antiblocking agents (AB agents), lubricants, antioxidants, antistatic agents, ultraviolet absorbers, light stabilizers, oxygen absorbers, acid absorbers, nucleating agents, impact strength enhancers, plasticizers, release agents, colorants, fluorescent agents, compatibilizers, antifogging agents, fillers, auxiliary colorants, dispersants, stabilizers, modifiers, antibacterial and antifungal agents, and pH adjusters, within the scope that does not impair the effects of the present invention. However, it is necessary that they do not react with other components contained in the polyolefin resin layer 1 or the polyolefin resin layer 2, and do not bleed out, for example, to contaminate the packaged item.
For the purpose of retaining the rust inhibitor in the resin layer, an ionomer resin or a functional group-containing polyolefin resin may or may not be blended in the resin layer 1 or the resin layer 2. According to the present invention, sufficient rust prevention can be exhibited for a long period of time.
また、本発明による効果を毀損しない範囲において、粒子状物質を含有してもよい
そのような粒子状物質としては、防錆剤ではない、水不溶性の無機粒子及び樹脂粒子のいずれでも良い。ガラスビーズ、シリカ、アルミナ、炭酸カルシウム、ポリメチルメタアクリレート（ＰＭＭＡ）粒子、（メタ）アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリウレタン樹脂、シリコーン樹脂等の公知の樹脂からなる粒子を採用でき、粒子表面は多孔質でも良いが、多孔質でないほうがより好ましく、無孔質であることが更に好ましい。ただし、例えばアルカリ金属やアルカリ土類金属の水酸化物の粒子、被酸化性金属粉末、珪酸塩、ニトロ安息香酸のように、粒子自体が遊離の酸基を有していたり、反応性や水溶性を有していたりするものを採用しなくてもよい。
粒子が多孔質であっても、その比表面積の上限は１００ｍ２／ｇである。粒子の比表面積は８０ｍ２／ｇ以下が好ましく、５０ｍ２／ｇ以下がより好ましく、３０ｍ２／ｇ以下が更に好ましく、２０ｍ２／ｇ以下が最も好ましい。粒子の比表面積が大きいほど、粒子表面に微細な孔を有することになり、その孔に防錆剤が侵入、吸着又は保持されやすくなる。その結果、難燃防錆フィルム表面に向けて移動する防錆剤の量が減少又は遅延し、防錆効果を低下又は遅延させることになる。
In addition, particulate matter may be contained within a range that does not impair the effects of the present invention. Such particulate matter may be any of water-insoluble inorganic particles and resin particles that are not rust inhibitors. Particles made of known resins such as glass beads, silica, alumina, calcium carbonate, polymethyl methacrylate (PMMA) particles, (meth)acrylic resins, polyester resins, polyamide resins, polyurethane resins, and silicone resins may be adopted, and the particle surface may be porous, but it is more preferable that it is not porous, and it is even more preferable that it is non-porous. However, it is not necessary to adopt particles that have free acid groups, are reactive, or are water-soluble, such as particles of hydroxides of alkali metals or alkaline earth metals, oxidizable metal powders, silicates, and nitrobenzoic acid.
Even if the particles are porous, the upper limit of the specific surface area is 100 m 2 /g. The specific surface area of the particles is preferably 80 m 2 /g or less, more preferably 50 m 2 /g or less, even more preferably 30 m 2 /g or less, and most preferably 20 m 2 /g or less. The larger the specific surface area of the particles, the more fine holes the particle surface has, and the more easily the rust inhibitor penetrates, is adsorbed, or is held in the holes. As a result, the amount of the rust inhibitor that moves toward the flame-retardant rust-preventive film surface is reduced or delayed, and the rust-preventive effect is reduced or delayed.
（ＦＭＶＳＳへの適合性）
本発明の難燃防錆フィルムは、ＦＭＶＳＳ Ｎｏ．３０２(米国自動車安全基準)に準じて行う燃焼性試験に適合するものである。
ＦＭＶＳＳに適合する難燃防錆フィルムとしては、難燃防錆フィルム全層中に難燃剤の濃度は２．５重量％以上であり、５．０重量％以上が好ましく、１０．０重量％以上がより好ましい。そして、３５．０重量％以下が好ましく、３０．０重量％以下がより好ましく、２５．０重量％以下が更に好ましい。
また、難燃防錆フィルムの全体の厚さは５０μｍ以上が好ましく、６０μｍ以上がより好ましく、７０μｍ以上が更に好ましい。そして１５０μｍ以下が好ましく、１２０μｍ以下がより好ましい。
本発明の難燃防錆フィルムは、このＦＭＶＳＳに適合するものである。さらに必要に応じて、下記に示す酸素指数及び／又はＤＩＮ４１０２－１Ｂ２に適合する。なお、図１及び２に示すグラフにおいて、フィルム全層厚さが５０～１５０μｍであり、フィルム全層中のハロゲン系難燃剤が２．５重量％以上である範囲内の難燃防錆フィルムは、ＦＭＶＳＳに適合する
(FMVSS Compatibility)
The flame-retardant and rust-preventive film of the present invention is compatible with the flammability test conducted in accordance with FMVSS No. 302 (US automobile safety standard).
For a flame-retardant/rust-proof film conforming to FMVSS, the concentration of the flame retardant in all layers of the flame-retardant/rust-proof film is 2.5% by weight or more, preferably 5.0% by weight or more, more preferably 10.0% by weight or more, and preferably 35.0% by weight or less, more preferably 30.0% by weight or less, and even more preferably 25.0% by weight or less.
The total thickness of the flame-retardant and rust-proofing film is preferably 50 μm or more, more preferably 60 μm or more, and even more preferably 70 μm or more, and is preferably 150 μm or less, and more preferably 120 μm or less.
The flame-retardant and rust-preventive film of the present invention conforms to this FMVSS. Furthermore, if necessary, it conforms to the oxygen index and/or DIN 4102-1B2 shown below. In the graphs shown in Figures 1 and 2, flame-retardant and rust-preventive films within the range of total film thickness of 50 to 150 μm and halogen-based flame retardant content of 2.5 wt % or more in the total film layers conform to FMVSS.
（酸素指数が２６以上）
さらに本発明の難燃防錆フィルムは、ＪＩＳ Ｋ ７２０１－２：２００７に準じて行なう難燃性試験により測定された酸素指数が２６以上であることが好ましい。本発明の難燃防錆フィルムがこの範囲の酸素指数を有する場合には、さらに高い難燃性を備える。
本発明において、難燃防錆フィルムの酸素指数が２６以上であるときには、ｘ軸のフィルム全層中の難燃剤濃度（重量％）と、ｙ軸のフィルム全層の厚さ（μｍ）との関係において、ｙが７ｘ+４７（ただしx≧５）で示される値以下であることが必要である。そして、ｙが７ｘ+４５で示される値以下であることが好ましく、ｙが７ｘ+４３で示される値以下であることがより好ましい。
また、酸素指数が２６以上である難燃防錆フィルムとしては、難燃防錆フィルム全層中に難燃剤の濃度は５．０重量％以上が好ましく、１０．０重量％以上がより好ましく、１５．０重量％以上が更に好ましい。そして、３５．０重量％以下が好ましく、３０．０重量％以下がより好ましく、２５．０重量％以下が更に好ましい。
また、難燃防錆フィルムの全体の厚さは５０μｍ以上が好ましく、６０μｍ以上がより好ましく、７０μｍ以上が更に好ましい。そして１５０μｍ以下が好ましく、１２０μｍ以下がより好ましい。
(Oxygen index is 26 or higher)
Furthermore, the flame-retardant and rust-proofing film of the present invention preferably has an oxygen index of 26 or more as measured by a flame retardancy test performed in accordance with JIS K 7201-2: 2007. When the flame-retardant and rust-proofing film of the present invention has an oxygen index in this range, it has even higher flame retardancy.
In the present invention, when the oxygen index of the flame-retardant and anti-corrosive film is 26 or more, in the relationship between the flame retardant concentration (wt%) in the entire film layer on the x-axis and the thickness (μm) of the entire film layer on the y-axis, it is necessary that y is equal to or less than 7x+47 (where x≧5). It is preferable that y is equal to or less than 7x+45, and it is more preferable that y is equal to or less than 7x+43.
In addition, for a flame-retardant/rust-proof film having an oxygen index of 26 or more, the concentration of the flame retardant in the entire layer of the flame-retardant/rust-proof film is preferably 5.0% by weight or more, more preferably 10.0% by weight or more, and even more preferably 15.0% by weight or more, and is preferably 35.0% by weight or less, more preferably 30.0% by weight or less, and even more preferably 25.0% by weight or less.
The total thickness of the flame-retardant and rust-proofing film is preferably 50 μm or more, more preferably 60 μm or more, and even more preferably 70 μm or more, and is preferably 150 μm or less, and more preferably 120 μm or less.
（ＤＩＮ４１０２－１Ｂ２への適合性）
さらに本発明の難燃防錆フィルムは、上記酸素指数２６以上、及び／又は、ＤＩＮ４１０２－１Ｂ２に準じて行なう燃焼性試験に適合するものである。本発明の難燃防錆フィルムがこの試験に適合する場合には、さらに高い難燃性を備える。
本発明において、難燃防錆フィルムがＤＩＮ４１０２－１Ｂ２に適合するときには、ｘ軸のフィルム全層中の難燃剤濃度（重量％）と、ｙ軸のフィルム全層の厚さ（μｍ）との関係において、ｙが３．４ｘ+５２（ただしx≧５）で示される値以下であることが必要である。そして、ｙが３．４ｘ+５０で示される値以下であることが好ましく、ｙが３．４ｘ+４８で示される値以下であることがより好ましい。
また、ＤＩＮ４１０２－１Ｂ２に適合する難燃防錆フィルムとしては、難燃防錆フィルム全体のうち、難燃剤の濃度は５．０重量％以上が好ましく、１０．０重量％以上がより好ましく、１５．０重量％以上が更に好ましい。そして、３５．０重量％以下が好ましく、３０．０重量％以下がより好ましく、２５．０重量％以下が更に好ましい。
また、難燃防錆フィルムの全層厚さは５０μｍ以上が好ましく、６０μｍ以上がより好ましく、７０μｍ以上が更に好ましい。そして１５０μｍ以下が好ましく、１２０μｍ以下がより好ましい。
(Compliance with DIN 4102-1B2)
Furthermore, the flame-retardant and rust-proofing film of the present invention has an oxygen index of 26 or more and/or conforms to a flammability test carried out in accordance with DIN 4102-1B2. When the flame-retardant and rust-proofing film of the present invention conforms to this test, it has even higher flame retardancy.
In the present invention, when the flame-retardant and rust-preventive film conforms to DIN 4102-1B2, in the relationship between the flame retardant concentration (wt%) in all layers of the film on the x-axis and the thickness (μm) of all layers of the film on the y-axis, it is necessary that y is equal to or less than 3.4x+52 (where x≧5). It is preferable that y is equal to or less than 3.4x+50, and it is more preferable that y is equal to or less than 3.4x+48.
In addition, for a flame-retardant/rust-proofing film conforming to DIN 4102-1B2, the concentration of the flame retardant in the entire flame-retardant/rust-proofing film is preferably 5.0% by weight or more, more preferably 10.0% by weight or more, and even more preferably 15.0% by weight or more, and is preferably 35.0% by weight or less, more preferably 30.0% by weight or less, and even more preferably 25.0% by weight or less.
The total thickness of the flame-retardant and rust-proofing film is preferably 50 μm or more, more preferably 60 μm or more, and even more preferably 70 μm or more, and is preferably 150 μm or less, and more preferably 120 μm or less.
（難燃防錆フィルムの構造）
本発明の難燃防錆フィルムは、全層厚さと全層に占める難燃剤及び防錆剤の濃度を調整することにより、適切な難燃性と防錆性及び視認性をバランス良く発揮できる。
全層厚さが５０～１５０μｍであり、５５μｍ以上が好ましく、６０μｍ以上がより好ましい。また１２０μｍ以下が好ましく、１００μｍ以下がより好ましく、９０μｍ以下が更に好ましく、８０μｍ以下が最も好ましい。フィルム厚さが５０μm未満では包装用フィルムとしての強度を保持できないおそれがある。また、フィルム全層厚さが１５０μｍを超えると、インフレーション成形等によるフィルム製造が困難であったり、全光線透過率が低下して被包装物の視認性が低下する場合がある。ただし、このような場合には、フィルムに対して筆記等したときの筆記を目視にて確認しやすくなる。
ポリオレフィン系樹脂層１とポリオレフィン系樹脂層２のそれぞれの層の厚さの比は、ポリオレフィン系樹脂層１：ポリオレフィン系樹脂層２＝３０：７０～７０：３０であることが好ましく、４０：６０～６０：４０がより好ましく、４５：５５～５５：４５が更に好ましい。この厚さの比が３０：７０～７０：３０であると、それぞれの層に適切な量の防錆剤又は難燃剤を含有させたときに、防錆性と難燃性をバランスよく発揮しやすくなる。
本発明の難燃防錆フィルムは、例えば（ポリオレフィン系樹脂層１／中間層１／ポリオレフィン系樹脂層２）の３層からなっても良い。この中間層１は上記に説明したポリオレフィン系樹脂層１又は２に包含される層であっても良い。
さらに、（ポリオレフィン系樹脂層１／中間層２／ポリオレフィン系樹脂層２）の３層からなっても良い。この中間層２は上記に説明したポリオレフィン系樹脂層１又は２に包含されない防錆剤含有層や、防錆剤及び難燃剤含有層であっても良い。
また本発明の難燃防錆フィルムは、例えば（ポリオレフィン系樹脂層１／ポリオレフィン系樹脂層２／最外層）の３層からなっても良い。この最外層は上記に説明したポリオレフィン系樹脂層２に包含されない防錆剤と難燃剤を含有した層であっても良い。
これらの３層からなる場合には、これらの層の厚さの比が１０～４０／２０～８０／１０～４０であることが好ましい。
本発明の難燃防錆フィルムの形状は両面が平滑であってもよく、本発明による効果を毀損しない範囲において、任意の模様を形成していても良い。またポリオレフィン系樹脂層１とポリオレフィン系樹脂層２のそれぞれの、難燃防錆フィルムの表面側に向かない面は、いずれも平滑であることが好ましい。
本発明の難燃防錆フィルムは、ポリオレフィン系樹脂層１とポリオレフィン系樹脂層２のみから形成されていても良いが、ポリオレフィン系樹脂層１側の外面側、及び／又は、ポリオレフィン系樹脂層２側の外面側に、さらなる強度向上や美観等を考慮して、さらに任意の樹脂層や繊維質、さらに必要に応じて接着剤の層等を形成できる。またポリオレフィン系樹脂層１とポリオレフィン系樹脂層２の間に、さらなる強度向上や機能の付与、美観等を考慮して、他の任意の樹脂層や繊維層等を形成しても良い。
なお、この難燃防錆フィルムの構造において説明した構造のうち、ポリオレフィン系樹脂層１及びポリオレフィン系樹脂層２は、上記の説明に沿って防錆剤のみ又は難燃剤のみを含有しても良い。また上記に説明されたように、難燃剤含有ポリオレフィン系樹脂層１及び／又は防錆剤含有ポリオレフィン系樹脂層２であっても良い。
(Flame-retardant and rust-proof film structure)
The flame-retardant, rust-proofing film of the present invention can exhibit an appropriate balance of flame retardancy, rust prevention, and visibility by adjusting the total layer thickness and the concentration of the flame retardant and rust inhibitor in all layers.
The total layer thickness is 50 to 150 μm, preferably 55 μm or more, more preferably 60 μm or more. Also, it is preferably 120 μm or less, more preferably 100 μm or less, even more preferably 90 μm or less, and most preferably 80 μm or less. If the film thickness is less than 50 μm, it may not be possible to maintain the strength required for packaging. If the total layer thickness of the film exceeds 150 μm, it may be difficult to manufacture the film by inflation molding or the like, or the total light transmittance may decrease, reducing the visibility of the packaged item. However, in such a case, writing on the film may be easily visually confirmed.
The thickness ratio of the polyolefin resin layer 1 to the polyolefin resin layer 2 is preferably polyolefin resin layer 1:polyolefin resin layer 2=30:70 to 70:30, more preferably 40:60 to 60:40, and even more preferably 45:55 to 55:45. When the thickness ratio is 30:70 to 70:30, rust prevention and flame retardancy are easily exhibited in a well-balanced manner when an appropriate amount of rust inhibitor or flame retardant is contained in each layer.
The flame-retardant and rust-proofing film of the present invention may be composed of three layers, for example, (polyolefin-based resin layer 1/intermediate layer 1/polyolefin-based resin layer 2). The intermediate layer 1 may be a layer included in the polyolefin-based resin layer 1 or 2 described above.
Furthermore, it may be composed of three layers of (polyolefin resin layer 1/intermediate layer 2/polyolefin resin layer 2). This intermediate layer 2 may be a layer containing a rust inhibitor not included in the polyolefin resin layers 1 or 2 described above, or a layer containing a rust inhibitor and a flame retardant.
The flame-retardant and rust-proofing film of the present invention may be composed of three layers, for example (polyolefin-based resin layer 1/polyolefin-based resin layer 2/outermost layer). The outermost layer may be a layer containing a rust inhibitor and a flame retardant not included in the polyolefin-based resin layer 2 described above.
When the film is made up of these three layers, the ratio of the thicknesses of these layers is preferably 10-40/20-80/10-40.
The shape of the flame-retardant and rust-proofing film of the present invention may be smooth on both sides, or may have any pattern formed thereon as long as the effect of the present invention is not impaired. In addition, it is preferable that the surfaces of the polyolefin-based resin layer 1 and the polyolefin-based resin layer 2 that do not face the surface side of the flame-retardant and rust-proofing film are both smooth.
The flame-retardant and rust-proofing film of the present invention may be formed only from the polyolefin resin layer 1 and the polyolefin resin layer 2, but in consideration of further strength improvement, aesthetics, etc., any resin layer, fiber material, and if necessary, an adhesive layer, etc. may be formed on the outer surface side of the polyolefin resin layer 1 and/or the outer surface side of the polyolefin resin layer 2. In consideration of further strength improvement, functionality, aesthetics, etc., any other resin layer, fiber layer, etc. may be formed between the polyolefin resin layer 1 and the polyolefin resin layer 2.
In the structure described in the structure of this flame-retardant and rust-proofing film, the polyolefin-based resin layer 1 and the polyolefin-based resin layer 2 may contain only a rust inhibitor or only a flame retardant in accordance with the above explanation. Also, as described above, the polyolefin-based resin layer 1 may be a flame-retardant-containing polyolefin-based resin layer 1 and/or a rust-inhibitor-containing polyolefin-based resin layer 2.
（難燃防錆フィルムの製造方法）
本発明の難燃防錆フィルムの製造方法は特に限定されず、公知の２層からなる防錆フィルムの製造方法を採用できる。また２層の樹脂層からなる積層フィルムを形成させるための、２層を同時に押し出して積層する共押出、一方のポリオレフィン系樹脂層の上に他方のポリオレフィン系樹脂層を押し出す押出ラミネート、接着等公知の手段を採用できる。
さらに本発明においては、上記により得られた難燃防錆フィルムを公知の手段により袋状に加工して、難燃防錆用包装袋にすることができる。
(Method of manufacturing flame-retardant and rust-proof film)
The method for producing the flame-retardant and rust-preventive film of the present invention is not particularly limited, and any known method for producing a rust-preventive film consisting of two layers can be adopted. In addition, in order to form a laminate film consisting of two resin layers, any known method can be adopted, such as coextrusion in which two layers are extruded and laminated at the same time, extrusion lamination in which one polyolefin resin layer is extruded onto the other polyolefin resin layer, adhesion, etc.
Furthermore, in the present invention, the flame-retardant and rust-preventive film obtained as described above can be processed into a bag shape by a known means to form a flame-retardant and rust-preventive packaging bag.
以下に本発明の具体的実施例及び比較例について説明する。
なお、実施例は発明の１形態を示すものであり本発明はこれに限定されるものではない。
表１は、実施例又は比較例において使用した難燃防錆フィルムの詳細及びそれらによる効果について示す。
Specific examples and comparative examples of the present invention will be described below.
It should be noted that the examples show one embodiment of the invention and the present invention is not limited thereto.
Table 1 shows details of the flame-retardant and rust-preventive films used in the examples and comparative examples and their effects.
（ＦＭＶＳＳ適合（ＦＭＶＳＳ Ｎｏ．３０２(米国自動車安全基準)による燃焼性試験に基づく試験））
ＦＭＶＳＳ Ｎｏ．３０２（乗用車やトラック及びバス等の室内に使用される内装材に発生する火災を想定した試験）に準じて、燃焼距離と燃焼速度を測定した。
＜試験片＞
３５６ｍｍ×１０２ｍｍの難燃防錆フィルム
＜試験方法＞
・試験サンプルをU字の治具に挟んで取り付け、試験機にセットする。
・ガスバーナーを着火し、炎の高さが３８ｍｍで安定するまで待つ。
・着火したバーナーを試験サンプルの端（Ｕ字の治具のUの上端に想到する開口部に位置する試験サンプルの端）に１５秒間接炎する。
・燃焼時間と燃焼距離を測定し、燃焼速度を算出する。
＜判断基準＞
以下のうち、いずれか１つを満たせば適合すると評価した。そして、適合するものを〇、適合しないものを×とした。
・試験片に着火しない、またはＡ標線（着火点から３８ｍｍの位置）手前で自消する。
・燃焼距離５１ｍｍ以内かつ６０秒以内に自消する。
・燃焼速度が１０２ｍｍ／分以下であること。
(FMVSS compliant (based on the flammability test according to FMVSS No. 302 (US automobile safety standard))
The burning distance and burning speed were measured in accordance with FMVSS No. 302 (a test simulating a fire occurring in interior materials used in passenger cars, trucks, buses, etc.).
<Test piece>
356mm x 102mm flame retardant and rust-proof film <Test method>
· The test sample is attached to a U-shaped jig and set in the testing machine.
-Light the gas burner and wait until the flame height stabilizes at 38 mm.
- Apply the ignited burner to the end of the test sample (the end of the test sample located at the opening that corresponds to the upper end of the U of the U-shaped jig) for 15 seconds.
- Measure the burning time and distance and calculate the burning speed.
<Criteria>
If any one of the following conditions was met, it was evaluated as conforming. Conformance was marked with a circle, and non-conformance was marked with an X.
The test piece does not ignite or the flame goes out just before the A mark (38 mm from the ignition point).
- The flame will self-extinguish within 60 seconds and within a burning distance of 51 mm.
- The burning speed is 102 mm/min or less.
（酸素指数（燃焼試験酸素指数））
酸素指数の測定をＪＩＳ Ｋ ７２０１－２：２００７に準じて行なった。
酸素と窒素の混合ガス気流中で試験片が燃焼し続けるのに必要な最低酸素濃度を容積%で表したものであり、酸素指数が高ければ高いほど難燃効果が高い。
＜試験片＞
１４０ｍｍ×５２ｍｍの難燃防錆フィルム
＜試験方法＞
・燃焼円筒内に下から酸素/窒素ガスの混合ガスを供給し、試験サンプルを治具に挟んで燃焼円筒内に取り付ける。
・混合ガス気流の安定後、ガスバーナーを着火させ炎の高さが下向きに１６±４ｍｍになるようにセットする。
・燃焼円筒内の試験片の上端に接炎、上端から２０ｍｍの標線を超えるまで着火を繰り返す。
・燃焼継続時間と燃焼距離を計測する。
・着火した炎が標線を超えてから燃焼時間を計測する。
・試験片が３分以上継続して燃焼せず、かつ試験片が標線から縦方向に８０ｍｍ以上燃焼しないときの酸素濃度を測定した。
・酸素指数２６以上のものを〇、２６未満のものを×とした。
(Oxygen Index (Combustion Test Oxygen Index))
The oxygen index was measured in accordance with JIS K 7201-2:2007.
It is the minimum oxygen concentration required for a test specimen to continue burning in a mixed gas stream of oxygen and nitrogen, expressed in volume percent. The higher the oxygen index, the greater the flame retardant effect.
<Test piece>
140mm x 52mm flame retardant and rust-proof film <Test method>
- A mixture of oxygen and nitrogen gas is supplied into the combustion cylinder from below, and the test sample is clamped in a jig and installed inside the combustion cylinder.
After the mixed gas flow has stabilized, ignite the gas burner and set the flame height to 16±4 mm downward.
- The upper end of the test piece in the combustion cylinder is brought into contact with a flame, and ignition is repeated until the flame passes the marked line 20 mm from the upper end.
-Measure the duration and distance of burning.
- Measure the burning time after the ignited flame passes the marked line.
The oxygen concentration was measured when the test piece did not burn for 3 minutes or more continuously and did not burn for 80 mm or more vertically from the marked line.
- Oxygen index of 26 or more was marked as ◯, and oxygen index of less than 26 was marked as ×.
（ＤＩＮ４１０２適合（ＤＩＮ４１０２－１Ｂ２（ドイツ工業規格耐火試験（建築材料に対する耐火試験））））
ＤＩＮ４１０２－１Ｂ２に準じて、材料の燃焼挙動を試験した。
＜試験片＞
表面接炎：２３０ｍｍ×９０ｍｍの難燃防錆フィルム
端部接炎：１９０ｍｍ×９０ｍｍの難燃防錆フィルム
＜試験方法＞
・ＭＤ／ＴＤ方向それぞれｎ＝５、合計２０回燃焼させて試験を行なった。
・１５秒間接炎させて、その後１５０ｍｍ標線への到達有無を判定した。
・２０回燃焼の全てで標線に到達しないときに適合すると判断した。
・適合するものを〇、適合しないものを×とした。
(Complies with DIN 4102 (DIN 4102-1B2 (German Industrial Standard Fire Resistance Test (Fire Resistance Test for Building Materials)))
The burning behaviour of the materials was tested according to DIN 4102-1B2.
<Test piece>
Surface contact flame: 230mm x 90mm flame-retardant and rust-proof film Edge contact flame: 190mm x 90mm flame-retardant and rust-proof film <Test method>
The test was performed by burning 5 pieces in each of the MD and TD directions, a total of 20 times.
The flame was applied for 15 seconds, and then a determination was made as to whether or not the sample reached the 150 mm mark.
- It was determined to be in compliance if the marked line was not reached in all 20 burns.
・Items that fit were marked with an ◯, and items that did not fit were marked with an X.
（防錆試験）
縦１００ｍｍ×横１００ｍｍ×高さ１５０ｍｍの枠組内に下記〔A〕の試験片をナイロン製の釣糸で吊し、作製したフィルムで枠組を包み、ガゼットシールし密封した。
この試験形態を下記〔B〕の試験環境下、指定期間置いた後、表面の錆の発錆状態を下記〔C〕の評価法に基づき評価した。
〔A〕試験片
鋳鉄 （ＪＩＳ Ｇ ５５０１） サイズ：φ３０ｍｍ×８ｍｍ
〔B〕試験環境
サイクル試験条件（１２時間／１サイクル）
２５℃７０％ＲＨ維持（４時間）⇒５０℃９５％ＲＨへ移行（２時間）⇒５０℃９５％ＲＨ維持（４時間）⇒２５℃７０％ＲＨへ移行（２時間）
〔C〕評価法
期間：３日間（６サイクル）
基準： 〇 ：錆、変色なし
× ：点錆、変色発生
(Rust prevention test)
The test piece described below in [A] was hung with a nylon fishing line within a frame measuring 100 mm in length × 100 mm in width × 150 mm in height, and the frame was wrapped in the prepared film and hermetically sealed with a gusset seal.
After this test configuration was placed in the test environment described below in [B] for a specified period of time, the state of surface rust was evaluated based on the evaluation method described below in [C].
[A] Test piece: Cast iron (JIS G 5501) Size: φ30mm x 8mm
[B] Test environment
Cycle test conditions (12 hours/1 cycle)
Maintain 25°C 70% RH (4 hours) ⇒ Shift to 50°C 95% RH (2 hours) ⇒ Maintain 50°C 95% RH (4 hours) ⇒ Shift to 25°C 70% RH (2 hours)
[C] Evaluation method Duration: 3 days (6 cycles)
Criteria: 〇: No rust or discoloration
×: Rust spots and discoloration
（視認性）
ＱＲコード（株式会社デンソーウェーブの登録商標）を印刷した紙の上に難燃防錆フィルムを重ね合わせ、難燃防錆フィルムの上からスマートフォンのアプリでＱＲコードが読取り可能かどうかを確認した。
基準： ○：読み取り可能
×：読み取り不可（但し、フィルム表面に筆記時は、その筆跡を明瞭に確認できた。）
(Visibility)
A flame-retardant and rust-proof film was placed on top of paper with a QR code (a registered trademark of DENSO WAVE Inc.) printed on it, and it was confirmed whether the QR code could be read using a smartphone app through the flame-retardant and rust-proof film.
Criteria: ○: Readable
×: Unreadable (however, when writing was done on the surface of the film, the handwriting was clearly visible.)
（全光線透過率）
日本電色工業株式会社製ヘーズメーター（ＮＤＨ５０００）を用いて、ＪＩＳ Ｋ ７３６１－１に準じて測定を行った。
(Total light transmittance)
The measurement was carried out using a haze meter (NDH5000) manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS K 7361-1.
（難燃防錆フィルム用のマスターバッチの作製）
＜難燃剤マスターバッチＦＲ１＞
東京インキ株式会社製難燃剤マスターバッチＰＥＸ ＦＲ－０２３１（ハロゲン系、三酸化アンチモンフリーの難燃剤を４５～５５重量％含有、キャリアレジンはＭＦＲ＝５．０ｇ／１０分の低密度ポリエチレン）を難燃剤マスターバッチＦＲ１とした。難燃剤の濃度は平均値として５０重量％含有するとした。なお、含有するハロゲン系難燃剤は走査型電子顕微鏡ＳＥＭＥＤＸ（日本電子株式会社製ＪＳM－ＩＴ１００）により臭素系難燃剤であると同定した。
(Preparation of master batch for flame-retardant and anti-rust film)
<Flame retardant masterbatch FR1>
Flame retardant master batch PEX FR-0231 (containing 45-55% by weight of halogen-based, antimony trioxide-free flame retardant, carrier resin is low-density polyethylene with MFR = 5.0 g/10 min) manufactured by Tokyo Ink Co., Ltd. was used as flame retardant master batch FR1. The average concentration of the flame retardant was set to 50% by weight. The halogen-based flame retardant was identified as a bromine-based flame retardant by scanning electron microscope SEMEDX (JSM-IT100 manufactured by JEOL Ltd.).
＜難燃剤マスターバッチＦＲ２の調製＞
難燃剤であるキスマ５Ｊ（株式会社共和化学工業所製（水酸化マグネシウム、特殊表面処理あり））３０重量部と、低密度ポリエチレン（ＬＤＰＥ１、密度＝０．９２４ｇ／ｃｍ３、ＭＦＲ＝２．０ｇ／１０分）７０重量部とを、二軸混練機にて溶融混練して難燃剤マスターバッチＦＲ２を調製した。
<Preparation of flame retardant masterbatch FR2>
Flame retardant masterbatch FR2 was prepared by melt-kneading 30 parts by weight of Kisuma 5J (manufactured by Kyowa Chemical Industry Co., Ltd. (magnesium hydroxide, special surface treatment)) and 70 parts by weight of low-density polyethylene (LDPE1, density = 0.924 g/cm 3 , MFR = 2.0 g/10 min) in a twin-screw kneader.
＜難燃剤マスターバッチＦＲ３の調製＞
難燃剤であるＦＰ－２５００Ｓ（株式会社ＡＤＥＫＡ製（リン酸塩と酸化亜鉛の混合物））３０重量部と、低密度ポリエチレン（ＬＤＰＥ１）７０重量部とを、二軸混練機にて溶融混練して難燃剤マスターバッチＦＲ３を調製した。
<Preparation of flame retardant masterbatch FR3>
A flame retardant master batch FR3 was prepared by melt-kneading 30 parts by weight of FP-2500S (manufactured by ADEKA CORPORATION (a mixture of phosphate and zinc oxide)) and 70 parts by weight of low-density polyethylene (LDPE1) in a twin-screw kneader.
＜防錆剤マスターバッチＭＢ１の調製＞
防錆剤である安息香酸アンモニウム２０重量部と、低密度ポリエチレン（ＬＤＰＥ１）８０重量部とを、二軸混練機にて溶融混練して防錆剤マスターバッチＭＢ１を調製した。
<Preparation of Rust Inhibitor Masterbatch MB1>
20 parts by weight of ammonium benzoate, which is a rust inhibitor, and 80 parts by weight of low-density polyethylene (LDPE1) were melt-kneaded in a twin-screw kneader to prepare a rust inhibitor master batch MB1.
＜防錆剤マスターバッチＭＢ２の調製＞
防錆剤である亜硝酸ナトリウム３０重量部と、低密度ポリエチレン（ＬＤＰＥ１）７０重量部とを、二軸混練機にて溶融混練して防錆剤マスターバッチＭＢ２を調製した。
<Preparation of Rust Inhibitor Masterbatch MB2>
30 parts by weight of sodium nitrite, which is a rust inhibitor, and 70 parts by weight of low-density polyethylene (LDPE1) were melt-kneaded in a twin-screw kneader to prepare a rust inhibitor master batch MB2.
＜難燃防錆フィルムの作製＞
表１に示すフィルム類型の内層及び外層の組成になるように、各難燃剤マスターバッチと各防錆剤マスターバッチのそれぞれと低密度ポリエチレン（ＬＤＰＥ１）を混合して、各フィルム類型用の内層用及び外層用の樹脂組成物を調製した。これらの樹脂組成物を用いて、各フィルム類型になるように、２層インフレーション押出成形機により１４０℃の成形温度で難燃防錆フィルムとなるチューブ状フィルムを製造した。表１の各フィルム類型は、フィルム全体の層の厚さを限定するものではなく、各フィルム類型は、その内層と外層の層の厚さの比及び各層の組成で分けたものである。
なお、フィルム類型毎に、フィルムの全層厚さが表２で示す厚さになるように、上記の製造方法により難燃防錆フィルムを得た。
<Preparation of flame-retardant and rust-preventive film>
Each flame retardant master batch and each rust inhibitor master batch were mixed with low density polyethylene (LDPE1) to prepare resin compositions for the inner and outer layers of each film type, so as to obtain the compositions of the inner and outer layers of the film types shown in Table 1. Using these resin compositions, tubular films that become flame retardant and rust-proof films were produced at a molding temperature of 140°C using a two-layer inflation extrusion molding machine to obtain each film type. Each film type in Table 1 does not limit the layer thickness of the entire film, and each film type is divided by the layer thickness ratio of the inner layer to the outer layer and the composition of each layer.
For each film type, a flame-retardant and rust-preventive film was obtained by the above-mentioned manufacturing method so that the total layer thickness of the film was the thickness shown in Table 2.
本発明に沿った例である各実施例によれば、ＦＭＶＳＳに適合する。
さらに、フィルム全層中の難燃剤濃度が５．０重量％でフィルム全層厚さが５０～８０μｍであるとき、及び、フィルム全層中の難燃剤濃度が１０．０重量％でフィルム全層厚さが６０～１００μｍであるとき、及び、フィルム全層中の難燃剤濃度が１５．０重量％でフィルム全層厚さが１００～１５０μｍであるとき、及び、フィルム全層中の難燃剤濃度が２２．５重量％でフィルム全層厚さが１２０～１５０μｍであるとき、フィルム全層中の難燃剤濃度が３０．０重量％でフィルム全層厚さが１２０～１５０μｍであるとき、及び、フィルム全層中の難燃剤濃度が３５．０重量％でフィルム全層厚さが１２０μｍであるとき、酸素指数が２６以上であった。
この結果を図１に示す。図１では、ｙ＝７ｘ＋４７（ｙは難燃防錆フィルム全層厚さ、ｘは難燃防錆フィルム全層中の難燃剤濃度）で示される線形（境界線）上及びその右側が実施例であり、左側が対照例である。この図１によれば、上記の実施例で示されていない難燃防錆フィルムであっても、この式の線上、又は、右側に位置するフィルム全層厚さとフィルム全層中の難燃剤濃度である場合には、本発明による酸素指数上の効果を発揮できる。なお、この式は酸素指数が２６であるときを示す式である。この式は、回帰曲線（線形近似）により求めた。横軸がフィルム全層中の難燃剤濃度（重量％）、縦軸はフィルム全体の厚さ（μｍ）である。黒丸が実施例、白丸が対照例である。
Example embodiments consistent with the present invention are FMVSS compliant.
Furthermore, the oxygen index was 26 or more when the flame retardant concentration in all film layers was 5.0 wt % and the total film thickness was 50 to 80 μm, when the flame retardant concentration in all film layers was 10.0 wt % and the total film thickness was 60 to 100 μm, when the flame retardant concentration in all film layers was 15.0 wt % and the total film thickness was 100 to 150 μm, when the flame retardant concentration in all film layers was 22.5 wt % and the total film thickness was 120 to 150 μm, when the flame retardant concentration in all film layers was 30.0 wt % and the total film thickness was 120 to 150 μm, and when the flame retardant concentration in all film layers was 35.0 wt % and the total film thickness was 120 μm.
The results are shown in FIG. 1. In FIG. 1, the line (boundary line) shown by y=7x+47 (y is the total thickness of the flame-retardant/rust-proof film, and x is the concentration of the flame retardant in the total layer of the flame-retardant/rust-proof film) and the right side of it are examples, and the left side is a control example. According to FIG. 1, even if the flame-retardant/rust-proof film is not shown in the above examples, if the total thickness of the film and the concentration of the flame retardant in the total layer of the film are located on the line or on the right side of this formula, the effect on the oxygen index of the present invention can be exhibited. Note that this formula is an expression when the oxygen index is 26. This formula was obtained by a regression curve (linear approximation). The horizontal axis is the concentration of the flame retardant in the total layer of the film (wt%), and the vertical axis is the thickness (μm) of the entire film. The black circles are examples, and the white circles are control examples.
また、フィルム全層中の難燃剤濃度が５．０重量％でフィルム全層厚さが５０～６５μｍであるとき、及び、フィルム全層中の難燃剤濃度が１０．０重量％でフィルム全層厚さが６０～７０μｍであるとき、フィルム全層中の難燃剤濃度が１５．０重量％でフィルム全層厚さが１００μｍであるとき、及び、フィルム全層中の難燃剤濃度が２２．５重量％でフィルム全層厚さが１２０μｍであるとき、及び、フィルム全層中の難燃剤濃度が３０．０重量％でフィルム全層厚さが１２０～１５０μｍであるとき、及び、フィルム全層中の難燃剤濃度が３５．０重量％でフィルム全層厚さが１２０μｍであるときには、ＤＩＮ４１０２に適合した。
この結果を図２に示す。図２では、ｙ＝３．４ｘ＋５２（ｙは難燃防錆フィルム全層厚さ、ｘは難燃防錆フィルム全層中の難燃剤濃度）で示される線形（境界線）上、及び、その右側が実施例であり、左側が対照例である。この図２によれば、上記に実施例で示されていない難燃防錆フィルムであっても、この式の線上、又は、右側に位置するフィルム全層厚さとフィルム全層中の難燃剤濃度である場合には、本発明によるＤＩＮ４１０２による評価の点において効果を発揮できる。なお、この式はＤＩＮ４１０２に適合する境界を示す式である。（ｙは難燃防錆フィルム全層厚さ、ｘは難燃防錆フィルム全体中の難燃剤濃度）この式は、回帰曲線（線形近似）により求めた。横軸がフィルム全層中の難燃剤濃度（重量％）、縦軸はフィルム全層厚さ（μｍ）である。黒丸が実施例、白丸が対照例である。
実施例１～１９によると視認性が十分であり、全光線透過率が４０％以上であった。一方、実施例２０、２１についてはフィルム全層中の難燃剤濃度が３０．０重量％であって、フィルム全層厚さが１５０μｍ、又は、フィルム全層中の難燃剤濃度が３５．０重量％であって、フィルム全層厚さが１２０μｍである為、難燃効果はあるものの、視認性がなく、また全光線透過率は４０％未満であった。
In addition, when the flame retardant concentration in all film layers was 5.0% by weight and the total film thickness was 50 to 65 μm, when the flame retardant concentration in all film layers was 10.0% by weight and the total film thickness was 60 to 70 μm, when the flame retardant concentration in all film layers was 15.0% by weight and the total film thickness was 100 μm, when the flame retardant concentration in all film layers was 22.5% by weight and the total film thickness was 120 μm, when the flame retardant concentration in all film layers was 30.0% by weight and the total film thickness was 120 to 150 μm, and when the flame retardant concentration in all film layers was 35.0% by weight and the total film thickness was 120 μm, DIN 4102 was met.
The results are shown in FIG. 2. In FIG. 2, the line (boundary line) shown by y=3.4x+52 (y is the total thickness of the flame-retardant and rust-proof film, and x is the concentration of the flame retardant in the total layer of the flame-retardant and rust-proof film) is on the line, and the right side of the line is the embodiment, and the left side is the control. According to FIG. 2, even if the flame-retardant and rust-proof film is not shown in the embodiment, if the total thickness of the film and the flame retardant concentration in the total layer are on the line or on the right side of the formula, it can be effective in terms of the evaluation by DIN4102 according to the present invention. Note that this formula shows the boundary that conforms to DIN4102. (y is the total thickness of the flame-retardant and rust-proof film, and x is the concentration of the flame retardant in the entire flame-retardant and rust-proof film) This formula was obtained by a regression curve (linear approximation). The horizontal axis is the concentration of the flame retardant in the total layer of the film (wt%), and the vertical axis is the total thickness of the film (μm). The black circle is the embodiment, and the white circle is the control.
According to Examples 1 to 19, the visibility was sufficient and the total light transmittance was 40% or more. On the other hand, in Examples 20 and 21, the flame retardant concentration in all film layers was 30.0% by weight and the total film thickness was 150 μm, or the flame retardant concentration in all film layers was 35.0% by weight and the total film thickness was 120 μm, so although there was a flame retardant effect, there was no visibility and the total light transmittance was less than 40%.
Claims (7)
（ポリオレフィン系樹脂層１）
アミン系及び／又はアンモニウム系気化性防錆剤を含有するポリオレフィン系樹脂からなる層
（ポリオレフィン系樹脂層２）
ハロゲン系難燃剤を含有するポリオレフィン系樹脂からなる層 A flame-retardant and rust-proofing film having a polyolefin-based resin layer 1 and a polyolefin-based resin layer 2 described below, a total thickness of 50 to 150 μm, and containing 2.5% by weight or more of a halogen-based flame retardant in all layers of the flame-retardant and rust-proofing film.
(Polyolefin-based resin layer 1)
Layer made of polyolefin resin containing amine-based and/or ammonium-based volatile rust inhibitor (polyolefin resin layer 2)
A layer made of a polyolefin resin containing a halogen-based flame retardant
3. A flame-retardant, rust-preventive packaging bag formed from the flame-retardant, rust-preventive film according to claim 1 or 2, wherein the polyolefin resin layer 1 side faces an article to be packaged.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022167883A JP2024060483A (en) | 2022-10-19 | 2022-10-19 | Flame retardant and rust-proof film |
| PCT/JP2023/030099 WO2024084794A1 (en) | 2022-10-19 | 2023-08-22 | Flame-retardant rust-preventive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022167883A JP2024060483A (en) | 2022-10-19 | 2022-10-19 | Flame retardant and rust-proof film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2024060483A true JP2024060483A (en) | 2024-05-02 |
Family
ID=90737396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022167883A Pending JP2024060483A (en) | 2022-10-19 | 2022-10-19 | Flame retardant and rust-proof film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2024060483A (en) |
| WO (1) | WO2024084794A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01210340A (en) * | 1988-02-19 | 1989-08-23 | Aisero Kagaku Kk | Multi-layered film |
| US6420470B1 (en) * | 1999-05-28 | 2002-07-16 | Cortec Corporation | Flame retardant films |
| CN102029755A (en) * | 2010-09-27 | 2011-04-27 | 沈阳防锈包装材料有限责任公司 | Flame-retardant shrinkable anticorrosive packaging film and manufacturing method thereof |
-
2022
- 2022-10-19 JP JP2022167883A patent/JP2024060483A/en active Pending
-
2023
- 2023-08-22 WO PCT/JP2023/030099 patent/WO2024084794A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024084794A1 (en) | 2024-04-25 |
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