JP2013007072A - Rust prevention film - Google Patents
Rust prevention film Download PDFInfo
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- JP2013007072A JP2013007072A JP2011138948A JP2011138948A JP2013007072A JP 2013007072 A JP2013007072 A JP 2013007072A JP 2011138948 A JP2011138948 A JP 2011138948A JP 2011138948 A JP2011138948 A JP 2011138948A JP 2013007072 A JP2013007072 A JP 2013007072A
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- dicarboxylic acid
- rust
- film
- salt
- rust prevention
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000002265 prevention Effects 0.000 title claims abstract description 11
- -1 dicarboxylic acid amine salt Chemical class 0.000 claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003449 preventive effect Effects 0.000 description 11
- 239000003814 drug Substances 0.000 description 7
- 229940079593 drug Drugs 0.000 description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000008034 disappearance Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000001729 Ammonium fumarate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000723347 Cinnamomum Species 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019297 ammonium fumarate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CKKXWJDFFQPBQL-SEPHDYHBSA-N azane;(e)-but-2-enedioic acid Chemical compound N.N.OC(=O)\C=C\C(O)=O CKKXWJDFFQPBQL-SEPHDYHBSA-N 0.000 description 1
- SATJMZAWJRWBRX-UHFFFAOYSA-N azane;decanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCCC([O-])=O SATJMZAWJRWBRX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、金属を包装するための防錆フィルムに関する。 The present invention relates to a rust-proof film for packaging metal.
鉄、アルミニウム等の金属製品を包装し、当該金属製品の酸化（錆の発生）を防ぐために用いられるフィルムとして、気化性防錆剤をフィルム中に含有させたフィルムが多数提案されている（例えば、特許文献１）。気化性防錆剤としては、分子中にアンモニウムカチオン又はその前駆体（以下、『アンモニウム部位』と称する場合がある。）を含むアミン系の防錆剤が知られている。アミン系防錆剤は、分子そのものの気化に加え、分子中のアンモニウム部位が、該分子から遊離して気化することにより防錆効果を発現すると考えられている。 As a film used for packaging metal products such as iron and aluminum and preventing oxidation (generation of rust) of the metal products, many films containing a vaporizable rust preventive agent in the film have been proposed (for example, Patent Document 1). As the vaporizable rust inhibitor, an amine-based rust inhibitor containing an ammonium cation or a precursor thereof (hereinafter sometimes referred to as “ammonium moiety”) in the molecule is known. In addition to vaporization of the molecule itself, the amine-based rust preventive agent is considered to exhibit a rust-preventing effect when the ammonium moiety in the molecule is released from the molecule and vaporizes.
しかしながら、アミン系の防錆剤は、フィルムに多量に含有させるとフィルムの諸特性の低下を引き起こし、含有量が少ないと十分な防錆効果が得られない。フィルムの諸特性を維持しつつ、十分な防錆効果を発現する防錆フィルムが望まれていた。 However, if the amine-based rust preventive agent is contained in a large amount in the film, the various characteristics of the film are deteriorated. There has been a demand for a rust preventive film that exhibits a sufficient rust preventive effect while maintaining various characteristics of the film.
本発明者等は鋭意検討した結果、特定のアミン系防錆剤と、２種以上のカルボン酸金属塩とを組み合わせてフィルムに含有させることにより、上記課題を解決しうることを見いだし本発明を完成した。 As a result of intensive studies, the present inventors have found that the above problems can be solved by including a specific amine-based rust inhibitor and two or more kinds of carboxylic acid metal salts in combination in the film. completed.
すなわち本発明は、熱可塑性樹脂と、下記式（１）で表されるジカルボン酸アミン塩と、鎖状または環状の脂肪族ジカルボン酸金属塩および芳香族モノカルボン酸金属塩を含む、防錆フィルムを提供する。 That is, the present invention relates to a rust-preventing film comprising a thermoplastic resin, a dicarboxylic acid amine salt represented by the following formula (1), a chain or cyclic aliphatic dicarboxylic acid metal salt and an aromatic monocarboxylic acid metal salt. I will provide a.
（式中、Ａは炭化水素から誘導される２価の基を示し、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、およびＲ６は同一又は異なって、水素原子又は炭化水素基
を示す。さらにＲａおよびＲｂは脂肪族炭化水素基を示す。）
(In the formula, A represents a divalent group derived from a hydrocarbon, and R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group. Furthermore, R a and R b represent an aliphatic hydrocarbon group.)
式（１）中、ＲａおよびＲｂは炭素数３〜１２の鎖状または環状の脂肪族炭化水素基である。 In the formula (1), R a and R b are a linear or cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms.
２種のカルボン酸金属塩の配合量の総和は、ジカルボン酸アミン塩に対して０．５〜５当量の範囲から選択される。 The sum total of the compounding quantity of 2 types of carboxylic acid metal salt is selected from the range of 0.5-5 equivalent with respect to dicarboxylic acid amine salt.
本発明の防錆フィルムは、熱可塑性樹脂と、下記式（１）で表されるジカルボン酸アミン塩と、カルボン酸金属塩とを含む。ただし、本発明の防錆フィルムは、ジカルボン酸アミン塩および／又はそのアミン部位が経時的に遊離気化して防錆フィルムから失われる。本明細書においては、このような防錆フィルムの一部が消失した状態のフィルムも本発明の防錆フィルムに含まれるものとする。 The rust preventive film of the present invention contains a thermoplastic resin, a dicarboxylic acid amine salt represented by the following formula (1), and a carboxylic acid metal salt. However, in the rust-preventing film of the present invention, the dicarboxylic acid amine salt and / or its amine moiety is free-vaporized over time and lost from the rust-preventing film. In the present specification, a film in which a part of such a rust-proof film has disappeared is also included in the rust-proof film of the present invention.
（熱可塑性樹脂）
本発明において用いられる熱可塑性樹脂としては、加熱により溶融し、フィルム状に形成可能な公知慣用の樹脂をいずれも用いることができ特に制限されない。例えば、ポリエチレン（低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン）、ポリプロピレン等のオレフィン系の樹脂を例示することができる。これらのなかで、成形性、ジカルボン酸アミン塩（下記詳述）との相溶性等の観点から低密度ポリエチレンを好適に使用することができる。
(Thermoplastic resin)
The thermoplastic resin used in the present invention is not particularly limited, and any known conventional resin that can be melted by heating and formed into a film can be used. For example, olefinic resins such as polyethylene (low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene) and polypropylene can be exemplified. Among these, low density polyethylene can be suitably used from the viewpoints of moldability, compatibility with dicarboxylic acid amine salts (detailed below), and the like.
（ジカルボン酸アミン塩）
本発明で用いられるジカルボン酸アミン塩は、下記式（１）で表される化合物である。該ジカルボン酸アミン塩は、常温で固体であり、かつ、フィルムを形成する際の加熱溶融温度（約１４０℃）において安定であることが好ましい。
(Dicarboxylic acid amine salt)
The dicarboxylic acid amine salt used in the present invention is a compound represented by the following formula (1). The dicarboxylic acid amine salt is preferably solid at room temperature and stable at the heating and melting temperature (about 140 ° C.) when forming a film.
（式中、Ａは炭化水素から誘導される２価の基を示し、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、およびＲ６は同一又は異なって、水素原子又は炭化水素基を示す。さらにＲａおよびＲｂは脂肪族炭化水素基を示す。）
(In the formula, A represents a divalent group derived from a hydrocarbon, and R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group. Furthermore, R a and R b represent an aliphatic hydrocarbon group.)
Ａを誘導する炭化水素は、脂肪族炭化水素であっても芳香族炭化水素であってもよいが、好ましくは脂肪族炭化水素である。該脂肪族炭化水素としては、直鎖状、環状のいずれもが用いられ、飽和であっても不飽和であってもよい。 The hydrocarbon from which A is derived may be an aliphatic hydrocarbon or an aromatic hydrocarbon, but is preferably an aliphatic hydrocarbon. As the aliphatic hydrocarbon, either a linear or cyclic hydrocarbon may be used, which may be saturated or unsaturated.
Ａを含有するジカルボン酸、すなわち、ジカルボン酸アミン塩を構成するジカルボン酸種としては、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、スベリン酸、アゼライン酸、セバシン酸などの飽和脂肪族ジカルボン酸、フマル酸、マレイン酸などの不飽和脂肪族ジカルボン酸を例示できる。 Examples of the dicarboxylic acid containing A, that is, the dicarboxylic acid species constituting the dicarboxylic acid amine salt include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. Examples thereof include unsaturated aliphatic dicarboxylic acids such as saturated aliphatic dicarboxylic acid, fumaric acid and maleic acid.
Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、およびＲ６は、同一又は異なって、水素原子または炭化水素基を示し、さらにＲａ、Ｒｂは、脂肪族炭化水素基である必要がある。ジカルボン酸アミン塩を構成するアンモニウムカチオンが少なくとも１つの炭化水素基を置換基として有すると、置換基を有しない場合に比して、防錆フィルムに添加した際のアンモニウム部位の遊離気化速度が適度に抑制される。これにより、防錆効果が長期間に渡り安定して発現される。また、防錆フィルム成形時および成形直後における急激なアンモニウム部位の遊離気化が顕著に抑制され、製造時の環境汚染が防止される、防錆フィルムの防錆効果発現期間（防錆フィルムの寿命）を長くすることができる、等の有利な効果が得られる。 R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and each represents a hydrogen atom or a hydrocarbon group, and R a and R b must be an aliphatic hydrocarbon group. There is. When the ammonium cation constituting the dicarboxylic acid amine salt has at least one hydrocarbon group as a substituent, the rate of free vaporization of the ammonium moiety when added to the rust-preventing film is moderate compared to when it has no substituent. To be suppressed. Thereby, the rust prevention effect is stably expressed over a long period of time. In addition, the rapid evaporation of ammonium sites immediately after molding of the rust-preventing film is remarkably suppressed, and environmental pollution during production is prevented. It is possible to obtain an advantageous effect that the length can be increased.
該炭化水素基は、アリル基、アリール基、アルキル基のいずれであってもよいが、好ましくは炭素数３〜１２の鎖状または環状の脂肪族炭化水素基である。 The hydrocarbon group may be an allyl group, an aryl group, or an alkyl group, but is preferably a chain or cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms.
該ジカルボン酸アミン塩を構成するアミン種としては、イソプロピルアミン、シクロへキシルアミン等の鎖状または環状の脂肪族第１級アミン、ベンジルアミン等の芳香族第１級アミン、ジイソプロピルアミン、ジシクロへキシルアミン等の鎖状または環状の脂肪族第２級アミン、ジベンジルアミン等の芳香族第２級アミンが例示される。 Examples of the amine species constituting the dicarboxylic acid amine salt include chain primary or cyclic aliphatic primary amines such as isopropylamine and cyclohexylamine, aromatic primary amines such as benzylamine, diisopropylamine, and dicyclohexylamine. Examples thereof include an aromatic secondary amine such as a linear or cyclic aliphatic secondary amine such as dibenzylamine.
（カルボン酸金属塩）
カルボン酸金属塩としては、鎖状または環状の脂肪族ジカルボン酸金属塩および芳香族モノカルボン酸金属塩の両方を用いる必要がある。
(Carboxylic acid metal salt)
As the carboxylic acid metal salt, it is necessary to use both a linear or cyclic aliphatic dicarboxylic acid metal salt and an aromatic monocarboxylic acid metal salt.
脂肪族ジカルボン酸種としては、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、スベリン酸、アゼライン酸、セバシン酸等が、芳香族モノカルボン酸種としては、安息香酸、桂皮酸等が例示される。 Aliphatic dicarboxylic acid species include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc., and aromatic monocarboxylic acid species include benzoic acid, cinnamon An acid etc. are illustrated.
カルボン酸金属塩を構成する金属種は、金属イオンを生成し、カルボン酸と塩を形成可能な限りとくに制限されないが、ナトリウム、カリウム等のアルカリ金属を好適に用いることができる。 The metal species constituting the carboxylic acid metal salt is not particularly limited as long as it can form a metal ion and form a salt with the carboxylic acid, but an alkali metal such as sodium or potassium can be preferably used.
熱可塑性樹脂に、ジカルボン酸アンモニウム塩および鎖状または環状の脂肪族ジカルボン酸金属塩および芳香族モノカルボン酸金属塩を添加混合して樹脂組成物を調製し、該樹脂組成物を公知乃至慣用の方法によりフィルム状に成形することにより、本発明の防錆フィルムを製造することができる。 A resin composition is prepared by adding and mixing a dicarboxylic acid ammonium salt, a chain or cyclic aliphatic dicarboxylic acid metal salt and an aromatic monocarboxylic acid metal salt to a thermoplastic resin. The rust-proof film of this invention can be manufactured by shape | molding into a film form by the method.
ジカルボン酸アミン塩および２種のカルボン酸金属塩、つまり鎖状または環状の脂肪族ジカルボン酸金属塩と芳香族モノカルボン酸金属塩の添加量は、熱可塑性樹脂１００重量部に対して、ジカルボン酸アミン塩および２種のカルボン酸金属塩の総量が１〜４重量部となる範囲から選択することができる。該添加量が１重量部より少ないと十分な防錆効果が得られず、４重量部より多いと成膜性や強度物性等、フィルムとしての諸特性を低下させることがあり、好ましくない。 The addition amount of the dicarboxylic acid amine salt and two kinds of carboxylic acid metal salt, that is, the chain or cyclic aliphatic dicarboxylic acid metal salt and the aromatic monocarboxylic acid metal salt, is dicarboxylic acid with respect to 100 parts by weight of the thermoplastic resin. It can be selected from a range in which the total amount of the amine salt and the two kinds of carboxylic acid metal salts is 1 to 4 parts by weight. If the amount added is less than 1 part by weight, a sufficient rust preventive effect cannot be obtained, and if it exceeds 4 parts by weight, various film properties such as film-forming properties and strength properties may be deteriorated.
２種のカルボン酸金属塩は、ジカルボン酸アミン塩に対して通常０．５〜５当量、好ましくは０．８〜２当量となるように配合される。カルボン酸金属塩の配合量が上記範囲外であると、防錆フィルムの防錆効果が劣ることがあり、好ましくない。 The two kinds of carboxylic acid metal salts are usually blended in an amount of 0.5 to 5 equivalents, preferably 0.8 to 2 equivalents with respect to the dicarboxylic acid amine salt. When the compounding amount of the carboxylic acid metal salt is out of the above range, the rust preventive effect of the rust preventive film may be deteriorated, which is not preferable.
上述の本発明の防錆フィルムを製造するための樹脂組成物は、フィルムの改質等を目的とする適宜な添加剤を含んでいてもよい。 The above-described resin composition for producing the rust-proof film of the present invention may contain an appropriate additive for the purpose of modifying the film.
本発明の防錆フィルムは単層でもよく、同一組成の層を複数層積層した積層体であってもよい。また、機能性を付与するために他の層を積層してもよい。 The anticorrosive film of the present invention may be a single layer or a laminate in which a plurality of layers having the same composition are laminated. Further, other layers may be stacked in order to impart functionality.
本発明の防錆フィルムは、鋼材、電気電子部品等の金属製品の酸化（錆の発生）を防止するための包装材として広範に使用することができる。 The rust preventive film of the present invention can be widely used as a packaging material for preventing oxidation (generation of rust) of metal products such as steel materials and electric / electronic parts.
以下、実施例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.
（実施例１）
熱可塑性樹脂（低密度ポリエチレン）１００重量部に対し、上記式（１）で表されるジカルボン酸アミン塩としてフマル酸ビスオクチルアンモニウム１重量部と、カルボン酸金属塩としてセバシン酸ジナトリウム１．５重量部、および安息香酸ナトリウム１．５重量部を添加して、加熱混練して樹脂組成物を得た。該樹脂組成物をインフレーション成膜法（ダイス直後の温度：１４０℃）で厚み８０μmのチューブ状フィルムに成形し、防錆フィルムを得た。
Example 1
1 part by weight of bisoctyl ammonium fumarate as a dicarboxylic acid amine salt represented by the above formula (1) and 1.5 parts of disodium sebacate as a carboxylic acid metal salt with respect to 100 parts by weight of a thermoplastic resin (low density polyethylene) Part by weight and 1.5 parts by weight of sodium benzoate were added and heated and kneaded to obtain a resin composition. The resin composition was molded into a tubular film having a thickness of 80 μm by an inflation film formation method (temperature immediately after dicing: 140 ° C.) to obtain a rust-proof film.
（比較例１〜比較例４）
ジカルボン酸アミン塩およびカルボン酸金属塩の種類、およびその配合量を表１に示す様に変更した以外は、実施例１と同様の操作を行い、防塵フィルムを得た。
(Comparative Examples 1 to 4)
A dustproof film was obtained in the same manner as in Example 1 except that the types of dicarboxylic acid amine salt and carboxylic acid metal salt and the blending amounts thereof were changed as shown in Table 1.
（イ）フマル酸ビスオクチルアンモニウム
（ロ）セバシン酸ジアンモニウム
（ハ）セバシン酸ジナトリウム
（ニ）安息香酸ナトリウム
(B) Bisoctylammonium fumarate (b) Diammonium sebacate (c) Disodium sebacate (d) Sodium benzoate
［試験評価］
実施例および比較例で作製したチューブ状防錆フィルムを裁断し、一端を熱シールにより封止して、袋（２００ｍｍ×１００ｍｍ；シール幅１０ｍｍ）を作製した。各袋内に、金属試験片密封し、保存試験に付した。金属試験片としては、大きさ５０ｍｍ×５０ｍｍ×１００ｍｍの鉄片（ＳＳ４００）およびアルミニウム（＃６０６３）を用いた。保存試験の諸条件を表２に示す。
[Test evaluation]
The tubular anticorrosive films prepared in Examples and Comparative Examples were cut and sealed at one end by heat sealing to prepare a bag (200 mm × 100 mm; seal width 10 mm). In each bag, a metal specimen was sealed and subjected to a storage test. As the metal test piece, an iron piece (SS400) and aluminum (# 6063) having a size of 50 mm × 50 mm × 100 mm were used. Table 2 shows various conditions of the storage test.
（防錆性）
保存試験終了後、金属試験片の錆の有無、およびその面積を目視で観察し、実施例および比較例で製造したフィルムの防錆効果を評価した。１試験片中に錆が１０点以上発生しているものまたは錆面積が試験片の表面積の１０％以上である試験片を、錆の発生があったものと評価した。評価結果を表３に示す。
(Rust prevention)
After completion of the storage test, the presence or absence of rust on the metal test piece and its area were visually observed to evaluate the rust prevention effect of the films produced in the examples and comparative examples. A test piece having 10 or more points of rust in one test piece or a test piece having a rust area of 10% or more of the surface area of the test piece was evaluated as having generated rust. The evaluation results are shown in Table 3.
（薬剤消失率）
前述のサイクル試験および長期保存試験において、試験前および試験後における各実施例および比較例の防錆フィルムに含まれるジカルボン酸アミン塩および／又はカルボン酸金属塩（以下、『薬剤』と総称する。）の重量を測定し、薬剤消失率を算出した。薬剤の重量測定は、以下の手順により行った。試料約１ｇを１０ｍＬのキシレンに加熱・溶解（１５０℃・３０ｍｉｎ）させ、メタノール２００ｍＬを加える。濾紙で溶媒不溶分と可溶分に分離し、可溶分を加熱・乾固（８０℃・１ｈｒ）させた後、得られた固体を電子天秤にて秤量する。薬剤消失率の算出は、下記式（１）により行った。
(Drug disappearance rate)
In the aforementioned cycle test and long-term storage test, dicarboxylic acid amine salts and / or carboxylic acid metal salts (hereinafter collectively referred to as “drugs”) contained in the rust preventive films of the examples and comparative examples before and after the test. ) Was measured, and the drug disappearance rate was calculated. The weight of the drug was measured according to the following procedure. About 1 g of a sample is heated and dissolved (150 ° C., 30 min) in 10 mL of xylene, and 200 mL of methanol is added. The solvent is separated into a solvent-insoluble component and a soluble component with a filter paper, and the soluble component is heated and dried (80 ° C., 1 hr), and then the obtained solid is weighed with an electronic balance. The drug disappearance rate was calculated by the following formula (1).
各防錆フィルムの薬剤消失率を表４に示す。
表３、４の結果より、いずれの試験条件においても、実施例１は薬剤消失率が他の比較例よりも大きく、防錆効果においても優れることが示された。一方、比較例１、比較例２、比較例３および比較例４では、実施例１よりも薬剤消失率が小さく、防錆効果も実施例１より劣ることが確認された。
実施例１と比較例１、比較例２および比較例３の比較より、実施例１ではジカルボン酸アミン塩と脂肪族ジカルボン酸金属塩および芳香族モノカルボン酸金属塩間の相互作用により、ジカルボン酸アミン塩のアミン成分の遊離が強く促進され、優れた防錆効果を発揮していることが示唆される。さらに実施例１は、１２ヶ月間の長期試験においても、十分な防錆性能を示すことが確認された。
From the results of Tables 3 and 4, it was shown that, under any test conditions, Example 1 had a higher drug disappearance rate than the other comparative examples and was excellent in rust prevention effect. On the other hand, in Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4, it was confirmed that the drug disappearance rate was smaller than that in Example 1, and the rust prevention effect was also inferior to that in Example 1.
From the comparison between Example 1 and Comparative Example 1, Comparative Example 2 and Comparative Example 3, in Example 1, the dicarboxylic acid amine salt, the aliphatic dicarboxylic acid metal salt, and the aromatic monocarboxylic acid metal salt interacted with each other. The liberation of the amine component of the amine salt is strongly promoted, suggesting that an excellent antirust effect is exhibited. Furthermore, it was confirmed that Example 1 showed sufficient rust prevention performance even in a long-term test for 12 months.
Claims (3)
（式中、Ａは炭化水素から誘導される２価の基を示し、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、およびＲ６は同一又は異なって、水素原子又は炭化水素基を示す。さらにＲａおよびＲｂは脂肪族炭化水素基を示す。） A rust-proof film comprising a thermoplastic resin, a dicarboxylic acid amine salt represented by the following formula (1), a chain or cyclic aliphatic dicarboxylic acid metal salt and an aromatic monocarboxylic acid metal salt.
(In the formula, A represents a divalent group derived from a hydrocarbon, and R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group. Furthermore, R a and R b represent an aliphatic hydrocarbon group.)
The rust-proof film according to claim 2, wherein R a and R b are a chain or cyclic aliphatic hydrocarbon group having 3 to 12 carbon atoms.
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