JP5531187B2 - Rust-proof resin composition and rust-proof film - Google Patents
Rust-proof resin composition and rust-proof film Download PDFInfo
- Publication number
- JP5531187B2 JP5531187B2 JP2009288434A JP2009288434A JP5531187B2 JP 5531187 B2 JP5531187 B2 JP 5531187B2 JP 2009288434 A JP2009288434 A JP 2009288434A JP 2009288434 A JP2009288434 A JP 2009288434A JP 5531187 B2 JP5531187 B2 JP 5531187B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- component
- rust
- carbon atoms
- salt
- 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.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims description 34
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 203
- -1 aromatic monocarboxylic acid Chemical class 0.000 claims description 113
- 230000003449 preventive effect Effects 0.000 claims description 86
- 239000000203 mixture Substances 0.000 claims description 82
- 229910052751 metal Inorganic materials 0.000 claims description 77
- 239000002184 metal Substances 0.000 claims description 77
- 230000002265 prevention Effects 0.000 claims description 67
- 125000004432 carbon atom Chemical group C* 0.000 claims description 58
- 150000003839 salts Chemical class 0.000 claims description 52
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 47
- 125000001931 aliphatic group Chemical group 0.000 claims description 41
- 229910052783 alkali metal Inorganic materials 0.000 claims description 30
- 150000003973 alkyl amines Chemical class 0.000 claims description 27
- 150000001412 amines Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims description 20
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 19
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 19
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001530 fumaric acid Substances 0.000 claims description 11
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 9
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 8
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 claims description 3
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims description 3
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 claims description 3
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 2
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims 1
- 239000013556 antirust agent Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 37
- 230000000694 effects Effects 0.000 description 36
- 239000003112 inhibitor Substances 0.000 description 35
- 229910001018 Cast iron Inorganic materials 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000010959 steel Substances 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 23
- 229910001208 Crucible steel Inorganic materials 0.000 description 20
- 230000008016 vaporization Effects 0.000 description 20
- 238000009834 vaporization Methods 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 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 13
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229960003975 potassium Drugs 0.000 description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 8
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 150000001339 alkali metal compounds Chemical class 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 4
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010669 acid-base reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical class SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 1
- LJVQHXICFCZRJN-UHFFFAOYSA-N 1h-1,2,4-triazole-5-carboxylic acid Chemical compound OC(=O)C1=NC=NN1 LJVQHXICFCZRJN-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 description 1
- ZQEXIXXJFSQPNA-UHFFFAOYSA-N 1h-imidazole-5-carbaldehyde Chemical compound O=CC1=CNC=N1 ZQEXIXXJFSQPNA-UHFFFAOYSA-N 0.000 description 1
- NDELSWXIAJLWOU-UHFFFAOYSA-N 2,5-dimethyl-4h-pyrazol-3-one Chemical compound CN1N=C(C)CC1=O NDELSWXIAJLWOU-UHFFFAOYSA-N 0.000 description 1
- JDYGPDBLCMPADW-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid;potassium Chemical compound [K].OC(=O)CN(CC(O)=O)CC(O)=O JDYGPDBLCMPADW-UHFFFAOYSA-N 0.000 description 1
- WKVMOQXBMPYPGK-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].OC(=O)CN(CC(O)=O)CC(O)=O WKVMOQXBMPYPGK-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- MVRGLMCHDCMPKD-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid Chemical compound NC1=NNC(C(O)=O)=N1 MVRGLMCHDCMPKD-UHFFFAOYSA-N 0.000 description 1
- NHLAPJMCARJFOG-UHFFFAOYSA-N 3-methyl-1,4-dihydropyrazol-5-one Chemical compound CC1=NNC(=O)C1 NHLAPJMCARJFOG-UHFFFAOYSA-N 0.000 description 1
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical compound [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- MSJMDZAOKORVFC-SEPHDYHBSA-L disodium fumarate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C\C([O-])=O MSJMDZAOKORVFC-SEPHDYHBSA-L 0.000 description 1
- 235000019524 disodium tartrate Nutrition 0.000 description 1
- NCXUIEDQTCQZRK-UHFFFAOYSA-L disodium;decanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCCCCCC([O-])=O NCXUIEDQTCQZRK-UHFFFAOYSA-L 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019294 sodium fumarate Nutrition 0.000 description 1
- WPUMTJGUQUYPIV-UHFFFAOYSA-L sodium malate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)CC([O-])=O WPUMTJGUQUYPIV-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000019794 sodium silicate Nutrition 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
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、金属に対する防錆効果を有する防錆剤組成物、防錆用樹脂組成物、および防錆用フィルムに関するものである。 The present invention relates to a rust inhibitor composition having a rust preventive effect on a metal, a resin composition for rust prevention, and a film for rust prevention.
従来、金属製品の防錆手段として、防錆油の塗布や気化性防錆紙による梱包が行われている。また、防錆油を塗布した、あるいは気化性防錆紙で梱包した金属製品の上からフィルムで覆って外気から遮蔽したり、金属製品を内包したフィルム内に気化性防錆剤を同封もしくは噴霧する方法等も行われている。近年では、防錆効果を有する薬剤を熱可塑性樹脂に練り込んだり、塗布または印刷した防錆用フィルムが開発されている。 Conventionally, as a rust preventive means for metal products, application of rust preventive oil and packing with vaporizable rust preventive paper have been performed. In addition, a metal product coated with rust-preventive oil or packed with vaporizable rust-proof paper is covered with a film to shield it from the outside air, or a vaporizable rust inhibitor is enclosed or sprayed in the film containing the metal product. The method of doing is also performed. In recent years, a rust-preventing film has been developed in which a chemical having a rust-preventing effect is kneaded into a thermoplastic resin, or applied or printed.
例えば、特許文献１には、気化性防錆剤としてアルキルジカルボン酸アンモニウムと、防錆助剤として脂肪族モノカルボン酸塩と芳香族カルボン酸塩と炭酸塩とからなる群から選ばれる少なくとも１種を混合した防錆剤組成物や、当該防錆剤組成物と熱可塑性樹脂とを溶融および混練して得られる防錆フィルムが開示されている。しかし、特許文献１に開示される防錆剤組成物は、鋳鉄や鉄鋼等の鉄系金属に対しては気化性防錆効果を有するが、銅に対しては腐食を促進させたり変色させるおそれがあり、適用範囲が限られていた。 For example, Patent Document 1 discloses at least one selected from the group consisting of ammonium alkyldicarboxylate as a vaporizable rust inhibitor and an aliphatic monocarboxylate, aromatic carboxylate and carbonate as a rust inhibitor. And a rust preventive film obtained by melting and kneading the rust preventive composition and a thermoplastic resin. However, the rust inhibitor composition disclosed in Patent Document 1 has a vaporizing rust preventive effect for iron-based metals such as cast iron and steel, but may promote corrosion or discolor the copper. And the scope of application was limited.
本発明は前記事情に鑑みてなされたものであり、その目的は、鉄系金属に対して防錆効果を発揮して、銅等の非鉄系金属の気化性防錆効果に対し悪影響を及ぼさないとともに、熱可塑性樹脂と配合して樹脂成形品を製造するのに適した防錆剤組成物を提供することにある。また、前記防錆剤組成物を含有する防錆用樹脂組成物および防錆用フィルムを提供することにある。 This invention is made | formed in view of the said situation, The objective demonstrates a rust prevention effect with respect to a ferrous metal, and does not exert a bad influence with respect to the vaporizable rust prevention effect of nonferrous metals, such as copper. A further object is to provide a rust inhibitor composition suitable for blending with a thermoplastic resin to produce a resin molded product. Moreover, it is providing the resin composition for rust prevention and the film for rust prevention containing the said rust inhibitor composition.
前記課題を解決することができた本発明の防錆剤組成物とは、下記成分Ａを含有するところに特徴を有する。
成分Ａ：炭素数２〜８の脂肪族ジカルボン酸と炭素数６〜１４のアルキルアミンとの塩、炭素数２〜８の脂肪族ジカルボン酸と炭素数６〜１４のシクロアルキルアミンとの塩、および炭素数７〜１２の芳香族モノカルボン酸と炭素数６〜１４のアルキルアミンとの塩よりなる群から選ばれる少なくとも１種。
The rust preventive composition of the present invention capable of solving the above problems is characterized by containing the following component A.
Component A: a salt of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms and an alkylamine having 6 to 14 carbon atoms, a salt of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms and a cycloalkylamine having 6 to 14 carbon atoms, And at least one selected from the group consisting of a salt of an aromatic monocarboxylic acid having 7 to 12 carbon atoms and an alkylamine having 6 to 14 carbon atoms.
本発明の防錆剤組成物は、成分Ａを含有することにより、アルキルアミンやシクロアルキルアミンに由来するガスが発生し、このガスが金属に対する防錆効果を発揮する。本発明の防錆剤組成物は、鋳鉄や鉄鋼等の鉄系金属に対しては接触性および非接触性（気化性）の防錆効果を発揮するとともに、銅やアルミニウム等の非鉄系金属に対しては腐食を促進させる等の悪影響を及ぼさない。また、本発明の防錆剤組成物は熱可塑性樹脂と配合して樹脂成形品を製造する際、樹脂成形品のブリード現象が起こりにくく、例えば防錆用フィルム等を好適に作製できる。 When the rust preventive composition of the present invention contains component A, a gas derived from alkylamine or cycloalkylamine is generated, and this gas exhibits a rust preventive effect on metal. The rust preventive composition of the present invention exerts a contact and non-contact (vaporization) rust preventive effect on iron-based metals such as cast iron and steel, and is suitable for non-ferrous metals such as copper and aluminum. On the other hand, it does not adversely affect corrosion. Further, when the rust preventive composition of the present invention is blended with a thermoplastic resin to produce a resin molded product, the bleed phenomenon of the resin molded product hardly occurs, and for example, a rust preventive film can be suitably produced.
本発明の防錆剤組成物はさらに、成分Ｂとして、炭素数１０〜１４の脂肪族ジカルボン酸とアルカリ金属との塩を含有してもよい。防錆剤組成物が成分Ｂを含有していれば、成分Ｂに含まれるアルカリ金属の作用により、成分Ａに由来してアルキルアミンやシクロアルキルアミンが気化しやすくなり、鉄系金属に対する防錆効果を高める。また、炭素数１０〜１４の脂肪族ジカルボン酸アルカリ金属塩も、鉄系金属に対する接触性の防錆効果を高める。 The rust inhibitor composition of the present invention may further contain, as Component B, a salt of an aliphatic dicarboxylic acid having 10 to 14 carbon atoms and an alkali metal. If the rust preventive composition contains Component B, the alkali metal contained in Component B is likely to vaporize alkylamine and cycloalkylamine derived from Component A, thereby preventing rust on iron-based metals. Increase the effect. Moreover, the C10-14 aliphatic dicarboxylic acid alkali metal salt also enhances the rust-proofing effect of contact with iron-based metals.
本発明の防錆剤組成物はさらに、成分Ｃとして、トリアゾール化合物、ピラゾロン化合物、およびイミダゾール化合物よりなる群から選ばれる少なくとも１種を含有してもよい。防錆剤組成物は、成分Ｃを含有することにより、銅、亜鉛、アルミニウム等の非鉄系金属に対する接触性および非接触性（気化性）の防錆効果が高められる。 The rust inhibitor composition of the present invention may further contain at least one selected from the group consisting of a triazole compound, a pyrazolone compound, and an imidazole compound as Component C. By containing the component C, the rust preventive composition enhances the contact resistance to non-ferrous metals such as copper, zinc and aluminum and the non-contact (vaporization) rust prevention effect.
本発明の防錆剤組成物はさらに、成分Ｄとして、無機アルカリ金属塩、多塩基有機酸アルカリ金属塩（ただし、前記成分Ｂの塩は除く）、アルカリ土類金属の酸化物、およびアルカリ土類金属の水酸化物よりなる群から選ばれる少なくとも１種を含有してもよい。防錆剤組成物が成分Ｄを含有していれば、成分Ｄがアルカリとして作用して、成分Ａに由来してアルキルアミンやシクロアルキルアミンが気化しやすくなり、防錆剤組成物の防錆効果を高める。 The rust inhibitor composition of the present invention further includes, as Component D, an inorganic alkali metal salt, a polybasic organic acid alkali metal salt (except the salt of Component B), an alkaline earth metal oxide, and alkaline earth. You may contain at least 1 sort (s) chosen from the group which consists of a hydroxide of a similar metal. If the rust preventive composition contains component D, component D acts as an alkali, and the alkylamine or cycloalkylamine is easily vaporized from component A. Increase the effect.
前記成分Ａの炭素数２〜８の脂肪族ジカルボン酸は、シュウ酸、マレイン酸、フマル酸、マロン酸、コハク酸、グルタル酸、およびアジピン酸よりなる群から選ばれる少なくとも１種であり、前記成分Ａの炭素数７〜１２の芳香族モノカルボン酸は、安息香酸、ｍ−アミノ安息香酸、ｐ−アミノ安息香酸、ｐ−ニトロ安息香酸、サリチル酸、ｐ−ヒドロキシ安息香酸、トルイル酸、ｐ−ｔ−ブチル安息香酸、およびβ−オキシナフトエ酸よりなる群から選ばれる少なくとも１種であり、前記成分Ａの炭素数６〜１４のアルキルアミンは、モノヘキシルアミン、モノオクチルアミン、モノデカノイックアミン、モノドデカノイックアミン、およびモノ−２−エチルヘキシルアミンよりなる群から選ばれる少なくとも１種であり、前記成分Ａの炭素数６〜１４のシクロアルキルアミンは、ジシクロヘキシルアミンであることが好ましい。 The C 2-8 aliphatic dicarboxylic acid of Component A is at least one selected from the group consisting of oxalic acid, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, and adipic acid, The aromatic monocarboxylic acid having 7 to 12 carbon atoms of Component A is benzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, toluic acid, p- It is at least one selected from the group consisting of t-butylbenzoic acid and β-oxynaphthoic acid, and the alkylamine having 6 to 14 carbon atoms of Component A is monohexylamine, monooctylamine, monodecanoic And at least one selected from the group consisting of amine, monododecanoic amine, and mono-2-ethylhexylamine, Number 6-14 cycloalkyl amine is preferably dicyclohexylamine.
本発明はまた、本発明の防錆剤組成物と熱可塑性樹脂とを含有する防錆用樹脂組成物と、当該防錆用樹脂組成物から得られる防錆用フィルムも提供する。また、本発明の防錆剤組成物、防錆用樹脂組成物、または防錆用フィルムを用いて、鉄系金属および／または非鉄系金属を防錆する防錆方法も提供する。 The present invention also provides a rust preventive resin composition containing the rust preventive composition of the present invention and a thermoplastic resin, and a rust preventive film obtained from the rust preventive resin composition. Moreover, the rust prevention method which rusts an iron-type metal and / or a nonferrous metal using the rust preventive composition of this invention, the resin composition for rust prevention, or the film for rust prevention is also provided.
本発明の防錆剤組成物、防錆用樹脂組成物、および防錆用フィルムは、鉄系金属に対して防錆効果を発揮するとともに、銅等の非鉄系金属の気化性防錆効果に対し悪影響を及ぼさない。また、本発明の樹脂組成物は、熱可塑性樹脂と配合して防錆用フィルム等の樹脂成形品を製造するのに適している。 The rust preventive composition, the rust preventive resin composition, and the rust preventive film of the present invention exhibit a rust preventive effect on ferrous metals, and also have a vaporizable rust preventive effect on non-ferrous metals such as copper. Does not adversely affect. In addition, the resin composition of the present invention is suitable for blending with a thermoplastic resin to produce a resin molded product such as an anticorrosive film.
本発明の防錆剤組成物は、下記成分Ａを含有する。
成分Ａ：炭素数２〜８の脂肪族ジカルボン酸と炭素数６〜１４のアルキルアミンとの塩、炭素数２〜８の脂肪族ジカルボン酸と炭素数６〜１４のシクロアルキルアミンとの塩、および炭素数７〜１２の芳香族モノカルボン酸と炭素数６〜１４のアルキルアミンとの塩よりなる群から選ばれる少なくとも１種。
The rust preventive composition of the present invention contains the following component A.
Component A: a salt of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms and an alkylamine having 6 to 14 carbon atoms, a salt of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms and a cycloalkylamine having 6 to 14 carbon atoms, And at least one selected from the group consisting of a salt of an aromatic monocarboxylic acid having 7 to 12 carbon atoms and an alkylamine having 6 to 14 carbon atoms.
本発明の防錆剤組成物は、金属の腐食環境下に置かれると、成分Ａが分解反応を起こしてアルキルアミンやシクロアルキルアミンに由来するガスが発生し、このガスが金属に対する防錆効果を発揮する。すなわち、成分Ａからアルキルアミンやシクロアルキルアミンに由来するガスが発生すると、高温高湿の腐食環境下において金属表面に結露が生じた場合でも、金属表面に吸着したアルキルアミンやシクロヘキシルアミンにより金属表面が撥水性となり、防錆効果が発現する。本発明の防錆剤組成物は、鋳鉄、鉄鋼等の鉄系金属や、銅、アルミニウム等の非鉄系金属に対して、接触性および／または非接触性（気化性）の防錆効果を発揮する。特に、鋳鉄、鉄鋼等の鉄系金属の非接触性（気化性）および接触性の防錆効果に優れる。 When the rust preventive composition of the present invention is placed in a corrosive environment of a metal, the component A undergoes a decomposition reaction to generate a gas derived from alkylamine or cycloalkylamine, and this gas has a rust preventive effect on the metal. To demonstrate. That is, when a gas derived from alkylamine or cycloalkylamine is generated from component A, even if condensation occurs on the metal surface in a high-temperature and high-humidity corrosive environment, the metal surface is absorbed by the alkylamine or cyclohexylamine adsorbed on the metal surface. Becomes water-repellent and exhibits a rust-proofing effect. The rust preventive composition of the present invention exerts a contact and / or non-contact (vaporization) rust prevention effect on iron-based metals such as cast iron and steel, and non-ferrous metals such as copper and aluminum. To do. In particular, it is excellent in non-contact (vaporization) and contact rust-preventing effects of ferrous metals such as cast iron and steel.
本発明の防錆剤組成物はまた、熱可塑性樹脂と配合して樹脂成形品を製造する際、樹脂成形品のブリード現象が起こりにくく、例えば防錆用フィルム等を好適に作製できる。これは、成分Ａの塩と熱可塑性樹脂との相溶性が優れているためと考えられる。これに対し、例えば、炭素数７〜１２の芳香族モノカルボン酸と炭素数６〜１４のシクロアルキルアミンとの塩を用いた場合は、樹脂成形品の表面に粉が吹いたようになり、いわゆるブリード現象が起こりやすくなる。従って、炭素数７〜１２の芳香族モノカルボン酸と炭素数６〜１４のシクロアルキルアミンとの塩を用いた場合は、防錆用フィルム等の防錆用樹脂成形品を製造することが難しい。 When the rust preventive composition of the present invention is blended with a thermoplastic resin to produce a resin molded product, the resin molded product is less likely to bleed, and for example, a rust preventive film can be suitably produced. This is probably because the compatibility between the salt of component A and the thermoplastic resin is excellent. On the other hand, for example, when a salt of an aromatic monocarboxylic acid having 7 to 12 carbon atoms and a cycloalkylamine having 6 to 14 carbon atoms is used, powder appears to be blown on the surface of the resin molded product, A so-called bleeding phenomenon is likely to occur. Accordingly, when a salt of an aromatic monocarboxylic acid having 7 to 12 carbon atoms and a cycloalkylamine having 6 to 14 carbon atoms is used, it is difficult to produce a rust-proof resin molded product such as a rust-proof film. .
成分Ａの塩を構成するアルキルアミンまたはシクロアルキルアミンはいずれも炭素数が６〜１４である。このようなアミンが成分Ａに含まれることにより、防錆剤組成物が、特に鋳鉄や鉄鋼等の鉄系金属に対する防錆効果を発揮しやすくなる。 The alkylamine or cycloalkylamine constituting the salt of component A has 6 to 14 carbon atoms. When such an amine is contained in Component A, the rust preventive composition tends to exhibit a rust preventive effect particularly on iron-based metals such as cast iron and steel.
アルキルアミンおよびシクロアルキルアミンは、１級または２級アミンであることが好ましい。アルキルアミンおよびシクロアルキルアミンが１級または２級アミンであれば、カルボン酸との塩形成が容易になるとともに、アルキルアミンやシクロアルキルアミンに由来して発生したガスが、防錆効果を発揮しやすくなる。防錆効果の点からは、アルキルアミンは１級、つまりモノアルキルアミンであり、シクロアルキルアミンは２級、つまりジシクロアルキルアミンであることが好ましい。 The alkylamine and cycloalkylamine are preferably primary or secondary amines. If alkylamine and cycloalkylamine are primary or secondary amines, salt formation with carboxylic acid is facilitated, and gas generated from alkylamines and cycloalkylamines exerts a rust prevention effect. It becomes easy. From the viewpoint of the antirust effect, the alkylamine is preferably primary, that is, monoalkylamine, and the cycloalkylamine is preferably secondary, that is, dicycloalkylamine.
炭素数６〜１４のアルキルアミンとしては、モノヘキシルアミン、モノオクチルアミン、モノデカノイックアミン、モノドデカノイックアミン、およびモノ−２−エチルヘキシルアミンよりなる群から選ばれる少なくとも１種が好ましく、モノオクチルアミン、モノデカノイックアミン、およびモノドデカノイックアミンよりなる群から選ばれる少なくとも１種がより好ましい。炭素数６〜１４のシクロアルキルアミンとしては、ジシクロヘキシルアミンが好ましい。アルキルアミンまたはシクロヘキシルアミンとして、このようなアミンを用いることにより、防錆効果の高い防錆剤組成物が得やすくなる。 The alkylamine having 6 to 14 carbon atoms is preferably at least one selected from the group consisting of monohexylamine, monooctylamine, monodecanoic amine, monododecanoic amine, and mono-2-ethylhexylamine, More preferred is at least one selected from the group consisting of monooctylamine, monodecanoic amine, and monododecanoic amine. As the cycloalkylamine having 6 to 14 carbon atoms, dicyclohexylamine is preferable. By using such an amine as the alkylamine or cyclohexylamine, it becomes easy to obtain a rust inhibitor composition having a high rust prevention effect.
成分Ａを構成する炭素数２〜８の脂肪族ジカルボン酸または炭素数７〜１２の芳香族モノカルボン酸は、アルキルアミンやシクロアルキルアミンの気化性や、塩の形成容易性に影響を及ぼす。アルキルアミンやシクロアルキルアミンの対イオンであるカルボン酸として、炭素数２〜８の脂肪族ジカルボン酸または炭素数７〜１２の芳香族モノカルボン酸を用いれば、カルボン酸とアミンとの塩形成が容易になるとともに、アミンの気化性が向上する。 The aliphatic dicarboxylic acid having 2 to 8 carbon atoms or the aromatic monocarboxylic acid having 7 to 12 carbon atoms constituting Component A affects the vaporization properties of alkylamines and cycloalkylamines and the ease of salt formation. If an aliphatic dicarboxylic acid having 2 to 8 carbon atoms or an aromatic monocarboxylic acid having 7 to 12 carbon atoms is used as the carboxylic acid which is a counter ion of alkylamine or cycloalkylamine, salt formation between the carboxylic acid and the amine can be achieved. It becomes easy and the vaporization property of amine improves.
脂肪族カルボン酸としては、炭素数２〜８の脂肪族ジカルボン酸を用いる。この場合、成分Ａの塩としては、脂肪族ジカルボン酸１モルとアミン２モルとから得られるジアミン塩、または脂肪族ジカルボン酸１モルとアミン１モルとから得られるモノアミン塩となる。このとき、脂肪族ジカルボン酸の炭素数が２〜８であれば、酸強度が強くなりアミン塩の形成が容易になるとともに、防錆剤組成物を使用する際にアミンが遊離しやすくなり、アミンの気化性が向上する。一方、脂肪族ジカルボン酸の炭素数が９以上であれば、アミン塩（特にジアミン塩）を形成しにくくなり、成分Ａの塩のｐＨが低下しやすくなる。その結果、防錆剤組成物が金属材料と接触した場合、金属材料を腐食させるおそれがある。炭素数２〜８の脂肪族ジカルボン酸とアミンとの塩としては、接触性および非接触性（気化性）の防錆効果の点から、ジアミン塩を用いることが好ましい。 As the aliphatic carboxylic acid, an aliphatic dicarboxylic acid having 2 to 8 carbon atoms is used. In this case, the salt of component A is a diamine salt obtained from 1 mol of aliphatic dicarboxylic acid and 2 mol of amine, or a monoamine salt obtained from 1 mol of aliphatic dicarboxylic acid and 1 mol of amine. At this time, if the aliphatic dicarboxylic acid has 2 to 8 carbon atoms, the acid strength becomes strong and the formation of an amine salt is facilitated, and the amine is easily liberated when the rust preventive composition is used, The vaporization of amine is improved. On the other hand, if the aliphatic dicarboxylic acid has 9 or more carbon atoms, it is difficult to form an amine salt (particularly a diamine salt), and the pH of the component A salt is likely to decrease. As a result, when the rust inhibitor composition comes into contact with the metal material, the metal material may be corroded. As the salt of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms and an amine, a diamine salt is preferably used from the viewpoint of contact and non-contact (vaporization) rust prevention effects.
脂肪族ジカルボン酸の炭素数２〜８とは、脂肪族を構成する炭素数とカルボン酸を構成する炭素数とを含む。従って、ジカルボン酸を除く炭素数は０〜６となる。脂肪族ジカルボン酸の炭素数は、好ましくは２〜６である。脂肪族ジカルボン酸を構成する脂肪族としては、炭素数１〜６（好ましくは、炭素数１〜４）のアルキレン基、炭素数２〜６（好ましくは、炭素数２〜４）のアルケニル基が好ましい。また、炭素数２〜８の脂肪族ジカルボン酸としては、カルボキシル基の炭素が単結合で繋がったシュウ酸であってもよい。炭素数２〜８の脂肪族ジカルボン酸としては、シュウ酸、マレイン酸、フマル酸、マロン酸、コハク酸、グルタル酸、およびアジピン酸よりなる群から選ばれる少なくとも１種が好ましい。これらの中でも、入手容易性や防錆剤としての機能の点から、フマル酸およびアジピン酸が好ましく、フマル酸がより好ましい。 The aliphatic dicarboxylic acid having 2 to 8 carbon atoms includes the number of carbon atoms constituting the aliphatic group and the number of carbon atoms constituting the carboxylic acid. Therefore, the carbon number excluding the dicarboxylic acid is 0-6. The carbon number of the aliphatic dicarboxylic acid is preferably 2-6. Examples of the aliphatic constituting the aliphatic dicarboxylic acid include an alkylene group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) and an alkenyl group having 2 to 6 carbon atoms (preferably 2 to 4 carbon atoms). preferable. Moreover, as C2-C8 aliphatic dicarboxylic acid, the oxalic acid which the carbon of the carboxyl group was connected by the single bond may be sufficient. The aliphatic dicarboxylic acid having 2 to 8 carbon atoms is preferably at least one selected from the group consisting of oxalic acid, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Among these, fumaric acid and adipic acid are preferable and fumaric acid is more preferable from the viewpoint of availability and function as a rust inhibitor.
芳香族カルボン酸としては、炭素数７〜１２の芳香族モノカルボン酸を用いる。炭素数７〜１２の芳香族カルボン酸とアミンとの塩であれば、アミン塩の形成が容易になるとともに、防錆剤組成物を使用する際にアミンが遊離しやすくなり、アミンの気化性が向上する。 An aromatic monocarboxylic acid having 7 to 12 carbon atoms is used as the aromatic carboxylic acid. If it is a salt of an aromatic carboxylic acid having 7 to 12 carbon atoms and an amine, formation of the amine salt is facilitated, and when the rust preventive composition is used, the amine is easily liberated, and the vaporization property of the amine. Will improve.
芳香族モノカルボン酸の炭素数７〜１２とは、芳香族を構成する炭素数とカルボン酸を構成する炭素数とを含む。従って、モノカルボン酸を除く炭素数は６〜１１となる。芳香族モノカルボン酸に含まれる芳香環としては、製造容易性からベンゼン環またはナフタレン環が好ましく、芳香環にはメチル基、水酸基、アミノ基、ニトロ基等の置換基が結合していてもよい。炭素数７〜１２の芳香族モノカルボン酸としては、安息香酸、ｍ−アミノ安息香酸、ｐ−アミノ安息香酸、ｐ−ニトロ安息香酸、サリチル酸、ｐ−ヒドロキシ安息香酸、ｐ−トルイル酸、ｐ−ｔ−ブチル安息香酸、およびβ−オキシナフトエ酸よりなる群から選ばれる少なくとも１種が好ましい。これらの中でも、入手容易性や防錆剤としての機能の点から、安息香酸およびｐ−ヒドロキシ安息香酸がより好ましい。 The aromatic monocarboxylic acid having 7 to 12 carbon atoms includes the number of carbon atoms constituting the aromatic and the number of carbon atoms constituting the carboxylic acid. Therefore, the carbon number excluding the monocarboxylic acid is 6 to 11. As the aromatic ring contained in the aromatic monocarboxylic acid, a benzene ring or a naphthalene ring is preferable from the viewpoint of ease of production, and a substituent such as a methyl group, a hydroxyl group, an amino group, or a nitro group may be bonded to the aromatic ring. . Examples of the aromatic monocarboxylic acid having 7 to 12 carbon atoms include benzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, p-toluic acid, p- At least one selected from the group consisting of t-butylbenzoic acid and β-oxynaphthoic acid is preferred. Among these, benzoic acid and p-hydroxybenzoic acid are more preferable from the viewpoint of availability and function as a rust inhibitor.
成分Ａとしては、フマル酸、およびアジピン酸よりなる群から選ばれる少なくとも１種と、モノオクチルアミン、モノデカノイックアミン、モノドデカノイックアミン、およびジシクロヘキシルアミンよりなる群から選ばれる少なくとも１種との塩、もしくは、安息香酸、およびｐ−ヒドロキシ安息香酸よりなる群から選ばれる少なくとも１種と、モノオクチルアミン、モノデカノイックアミン、およびモノドデカノイックアミンよりなる群から選ばれる少なくとも１種との塩が好ましい。より好ましくは、フマル酸とモノオクチルアミンとの塩、アジピン酸とモノオクチルアミンとの塩、フマル酸とジシクロヘキシルアミンとの塩、アジピン酸とジシクロヘキシルアミンとの塩、およびｐ−ヒドロキシ安息香酸とモノオクチルアミンとの塩よりなる群から選ばれる少なくとも１種である。特に好ましいのは、フマル酸とモノオクチルアミンとのジアミン塩である。 Component A includes at least one selected from the group consisting of fumaric acid and adipic acid, and at least one selected from the group consisting of monooctylamine, monodecanoic amine, monododecanoic amine, and dicyclohexylamine. Or at least one selected from the group consisting of benzoic acid and p-hydroxybenzoic acid, and at least one selected from the group consisting of monooctylamine, monodecanoic amine, and monododecanoic amine A salt with a seed is preferred. More preferably, a salt of fumaric acid and monooctylamine, a salt of adipic acid and monooctylamine, a salt of fumaric acid and dicyclohexylamine, a salt of adipic acid and dicyclohexylamine, and p-hydroxybenzoic acid and mono It is at least one selected from the group consisting of salts with octylamine. Particularly preferred is a diamine salt of fumaric acid and monooctylamine.
成分Ａは、例えば、脂肪族ジカルボン酸または芳香族モノカルボン酸と、アルキルアミンまたはシクロアルキルアミンとを、酸塩基反応させることにより得られる。反応原料となるカルボン酸やアミンが液体である場合は、溶媒で希釈することなくそのままカルボン酸とアミンとを反応させて、アミン塩を生成してもよい。また、水溶液中でカルボン酸とアミンとを反応させて、アミン塩を生成してもよい。さらにまた、脂肪族ジカルボン酸のアルカリ金属塩または芳香族モノカルボン酸のアルカリ金属塩の水溶液と、アルキルアミンまたはシクロアルキルアミンの硫酸塩、リン酸塩、有機酸塩（ギ酸塩、酢酸塩等）等の水溶液とを混合し、複分解反応によってアミン塩を生成してもよい。酸塩基反応により析出したアミン塩は、ろ過等の公知の固液分離手段により分離してもよく、加熱乾燥や真空乾燥等によりアミン塩を固体として回収してもよい。 Component A can be obtained by, for example, acid-base reaction of an aliphatic dicarboxylic acid or aromatic monocarboxylic acid with an alkylamine or cycloalkylamine. When the carboxylic acid or amine used as a reaction raw material is liquid, the carboxylic acid and amine may be reacted as they are without diluting with a solvent to produce an amine salt. Alternatively, an amine salt may be produced by reacting a carboxylic acid and an amine in an aqueous solution. Furthermore, an aqueous solution of an alkali metal salt of an aliphatic dicarboxylic acid or an alkali metal salt of an aromatic monocarboxylic acid, and an alkylamine or cycloalkylamine sulfate, phosphate, organic acid salt (formate, acetate, etc.) An amine salt may be produced by mixing with an aqueous solution such as a metathesis reaction. The amine salt precipitated by the acid-base reaction may be separated by a known solid-liquid separation means such as filtration, or the amine salt may be recovered as a solid by heat drying or vacuum drying.
本発明の防錆剤組成物は、下記成分Ｂをさらに含有してもよい。
成分Ｂ：炭素数１０〜１４の脂肪族ジカルボン酸とアルカリ金属との塩。
The rust preventive composition of the present invention may further contain the following component B.
Component B: A salt of an aliphatic dicarboxylic acid having 10 to 14 carbon atoms and an alkali metal.
防錆剤組成物が成分Ｂを含有していれば、成分Ｂの脂肪族ジカルボン酸とアルカリ金属との塩からアルカリ金属が遊離して、成分Ｂがアルカリとして作用するようになる。その結果、成分Ａの分解反応が促進され、アルキルアミンやシクロアルキルアミンが気化しやすくなり、鋳鉄や鉄鋼等の鉄系金属に対する防錆効果を高める。また、炭素数１０〜１４の脂肪族ジカルボン酸のアルカリ金属塩が、鋳鉄や鉄鋼等の鉄系金属に対する接触性の防錆効果を高める。 If the rust inhibitor composition contains component B, the alkali metal is liberated from the salt of the aliphatic dicarboxylic acid of component B and the alkali metal, and component B acts as an alkali. As a result, the decomposition reaction of component A is promoted, alkylamine and cycloalkylamine are easily vaporized, and the rust prevention effect for iron-based metals such as cast iron and steel is enhanced. In addition, the alkali metal salt of an aliphatic dicarboxylic acid having 10 to 14 carbon atoms enhances the rust preventive effect of contact with iron-based metals such as cast iron and steel.
成分Ｂを構成する脂肪族ジカルボン酸としては、セバシン酸（ＨＯＯＣ（ＣＨ2）8ＣＯＯＨ）、ウンデカン２酸（ＨＯＯＣ（ＣＨ2）9ＣＯＯＨ）、ドデカン２酸（ＨＯＯＣ（ＣＨ2）10ＣＯＯＨ）、ブラシル酸（ＨＯＯＣ（ＣＨ2）11ＣＯＯＨ）、テトラデカン２酸（ＨＯＯＣ（ＣＨ2）12ＣＯＯＨ）等の飽和脂肪族ジカルボン酸；２−オクテン２酸（ＨＯＯＣＣＨ＝ＣＨ（ＣＨ2）6ＣＯＯＨ）、４−ノネン２酸（ＨＯＯＣ（ＣＨ2）2ＣＨ＝ＣＨ（ＣＨ2）3ＣＯＯＨ）等の不飽和脂肪族ジカルボン酸；４，４'−ジシクロヘキシルジカルボン等の脂環式ジカルボン酸等が挙げられる。これらの脂肪族ジカルボン酸は、単独で用いてもよく、２種以上を併用してもよい。これらの中でも、セバシン酸、ウンデカン２酸、ドデカン２酸、ブラシル酸、テトラデカン２酸等の炭素数１０〜１４の飽和脂肪族ジカルボン酸が好ましい。 Examples of the aliphatic dicarboxylic acid constituting Component B include sebacic acid (HOOC (CH 2 ) 8 COOH), undecanoic acid (HOOC (CH 2 ) 9 COOH), dodecanedioic acid (HOOC (CH 2 ) 10 COOH), Saturated aliphatic dicarboxylic acids such as brassic acid (HOOC (CH 2 ) 11 COOH), tetradecanedioic acid (HOOC (CH 2 ) 12 COOH); 2-octene diacid (HOOCCH═CH (CH 2 ) 6 COOH), 4 - nonene 2 acid (HOOC (CH 2) 2 CH = CH (CH 2) 3 COOH) unsaturated aliphatic dicarboxylic acids like; alicyclic dicarboxylic acids such as 4,4'-dicyclohexylmethane di-carboxylic and the like. These aliphatic dicarboxylic acids may be used alone or in combination of two or more. Among these, C10-14 saturated aliphatic dicarboxylic acids such as sebacic acid, undecanoic acid, dodecanedioic acid, brassic acid, and tetradecanedioic acid are preferable.
成分Ｂを構成するアルカリ金属としては、リチウム、ナトリウム、およびカリウム等が挙げられる。これらのアルカリ金属は単独で用いてもよいし、２種以上を併用してもよい。これらの中でも、ナトリウムおよびカリウムが好ましい。 Examples of the alkali metal constituting Component B include lithium, sodium, and potassium. These alkali metals may be used independently and may use 2 or more types together. Among these, sodium and potassium are preferable.
成分Ｂの脂肪族ジカルボン酸とアルカリ金属との塩は、脂肪族ジカルボン酸１モルに対しアルカリ金属が２モル結合したジアルカリ金属塩であってもよく、アルカリ金属が１モル結合したモノアルカリ金属塩であってもよい。しかし、アルカリ金属が多く含まれる塩の方が成分Ａの分解反応がより促進されることから、成分Ｂはジアルカリ金属塩を含むことが好ましい。 The salt of the aliphatic dicarboxylic acid and alkali metal of Component B may be a dialkali metal salt in which 2 moles of alkali metal are bonded to 1 mole of aliphatic dicarboxylic acid, or a monoalkali metal salt in which 1 mole of alkali metal is bonded. It may be. However, since a salt containing a large amount of alkali metal promotes the decomposition reaction of component A more, component B preferably contains a dialkali metal salt.
成分Ｂの脂肪族ジカルボン酸とアルカリ金属との塩としては、セバシン酸、ウンデカン２酸、ドデカン２酸、ブラシル酸、およびテトラデカン２酸よりなる群から選ばれる少なくとも１種のナトリウム塩またはカリウム塩が好ましい。これらの中でも、セバシン酸（２）ナトリウム、セバシン酸（２）カリウム、ドデカン２酸（２）ナトリウムがより好ましい。 Examples of the salt of the aliphatic dicarboxylic acid of component B and the alkali metal include at least one sodium salt or potassium salt selected from the group consisting of sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, and tetradecanedioic acid. preferable. Among these, sebacic acid (2) sodium, sebacic acid (2) potassium, and dodecanedioic acid (2) sodium are more preferable.
成分Ｂは、例えば、脂肪族ジカルボン酸またはその塩とアルカリ金属化合物とを、酸塩基反応させることにより得られる。アルカリ金属化合物としては、アルカリ金属の酸化物、水酸化物、または塩を用いればよい。成分Ｂの塩は、市販品を用いてもよい。 Component B can be obtained, for example, by subjecting an aliphatic dicarboxylic acid or a salt thereof and an alkali metal compound to an acid-base reaction. As the alkali metal compound, an alkali metal oxide, hydroxide, or salt may be used. A commercial item may be used for the salt of component B.
脂肪族ジカルボン酸またはその塩とアルカリ金属化合物とを反応させて成分Ｂの塩を製造する場合、脂肪族ジカルボン酸またはその塩とアルカリ金属化合物の仕込み比は、脂肪族ジカルボン酸およびその塩に対するアルカリ金属のモル比（アルカリ金属／脂肪族ジカルボン酸）として１．４以上２．０以下とすることが好ましい。前記モル比が１．４以上であれば、成分Ｂに含まれるジアルカリ金属塩の割合が高くなり、防錆剤組成物の防錆効果が向上する。前記モル比が２．０を超えると、未反応のアルカリ金属化合物が残留して、得られる防錆剤組成物が液状やペースト状になり、取り扱い性が悪くなるおそれがある。 When the salt of component B is produced by reacting an aliphatic dicarboxylic acid or a salt thereof with an alkali metal compound, the charge ratio of the aliphatic dicarboxylic acid or the salt thereof to the alkali metal compound is an alkali to the aliphatic dicarboxylic acid and the salt thereof. The metal molar ratio (alkali metal / aliphatic dicarboxylic acid) is preferably 1.4 or more and 2.0 or less. If the said molar ratio is 1.4 or more, the ratio of the dialkali metal salt contained in component B will become high, and the rust prevention effect of a rust preventive composition will improve. When the molar ratio exceeds 2.0, an unreacted alkali metal compound remains, and the resulting rust preventive composition becomes liquid or pasty, which may deteriorate the handleability.
防錆剤組成物が成分Ｂを含有する場合、成分Ｂの含有率は、２０質量％以上が好ましく、３０質量％以上がより好ましく、８５質量％以下が好ましく、８０質量％以下がより好ましい。成分Ｂの含有率が２０質量％以上であれば、鋳鉄、鉄鋼等の鉄系金属に対する接触性の防錆効果が十分高められやすくなる。成分Ｂの含有率が８５質量％以下であれば、鋳鉄、鉄鋼等の鉄系金属に対する非接触性（気化性）の防錆効果が高められやすくなり、銅、亜鉛、アルミニウム等の非鉄系金属に対する悪影響を及ぼしにくくなる。なお、成分Ｂの含有率とは、成分Ａと成分Ｂと後記する成分Ｃと成分Ｄの和に対する成分Ｂの質量比率（Ｂ／（Ａ＋Ｂ＋Ｃ＋Ｄ））を意味する。前記質量比率（Ｂ／（Ａ＋Ｂ＋Ｃ＋Ｄ））において、成分Ｃと成分Ｄは任意成分であるため、ＣとＤは０であってもよい。 When the rust inhibitor composition contains component B, the content of component B is preferably 20% by mass or more, more preferably 30% by mass or more, preferably 85% by mass or less, and more preferably 80% by mass or less. If the content rate of the component B is 20 mass% or more, the contact rust prevention effect with respect to ferrous metals, such as cast iron and steel, will become easy to be fully improved. If the content of component B is 85% by mass or less, the non-contact (vaporization) rust prevention effect for iron-based metals such as cast iron and steel is likely to be enhanced, and non-ferrous metals such as copper, zinc, and aluminum. It becomes difficult to have an adverse effect on. In addition, the content rate of the component B means the mass ratio (B / (A + B + C + D)) of the component B with respect to the sum of the component A and the component B and the component C and the component D mentioned later. In the mass ratio (B / (A + B + C + D)), since component C and component D are optional components, C and D may be zero.
防錆剤組成物に含まれる成分Ａと成分Ｂの割合は、成分Ａに対する成分Ｂの質量比（Ｂ／Ａ）として０／１００以上が好ましく、１０／９０以上がより好ましく、９０／１０以下が好ましく、８０／２０以下がより好ましい。前記質量比（Ｂ／Ａ）が０／１００〜８０／２０の範囲であれば、鋳鉄、鉄鋼等の鉄系金属に対する非接触性（気化性）の防錆効果が確保されやすくなる。 The ratio of component A and component B contained in the rust inhibitor composition is preferably 0/100 or more, more preferably 10/90 or more, and more preferably 90/10 or less as a mass ratio (B / A) of component B to component A. Is preferable, and 80/20 or less is more preferable. When the mass ratio (B / A) is in the range of 0/100 to 80/20, it becomes easy to ensure a non-contact (vaporizable) rust preventive effect for iron-based metals such as cast iron and steel.
本発明の防錆剤組成物は、下記成分Ｃをさらに含有してもよい。防錆剤組成物は、成分Ｃを含有することにより、銅、亜鉛、アルミニウム等の非鉄系金属に対する接触性および非接触性（気化性）の防錆効果が高められる。
成分Ｃ：トリアゾール化合物、ピラゾロン化合物、およびイミダゾール化合物よりなる群から選ばれる少なくとも１種。
The rust preventive composition of the present invention may further contain the following component C. By containing the component C, the rust preventive composition enhances the contact resistance to non-ferrous metals such as copper, zinc and aluminum and the non-contact (vaporization) rust prevention effect.
Component C: At least one selected from the group consisting of triazole compounds, pyrazolone compounds, and imidazole compounds.
前記トリアゾール化合物は、分子中にトリアゾール骨格を有する化合物であれば特に限定されない。トリアゾール化合物としては、１，２，３−トリアゾール、１，２，４−トリアゾール、１，２，４−トリアゾール−３−カルボン酸、３−アミノ−１，２，４−トリアゾール、１，２，３−ベンゾトリアゾール、トリルトリアゾール、ニトロベンゾトリアゾール、４−アミノ−１，２，４−トリアゾール、５−アミノ−１，２，４−トリアゾール−３−カルボン酸、３−メルカプト−１，２，４−トリアゾール、およびこれらのアルカリ金属塩等が挙げられる。これらのトリアゾール化合物は単独で用いてもよいし、２種以上を併用してもよい。これらの中でも、ベンゾトリアゾール、およびトリルトリアゾールよりなる群から選ばれる少なくとも１種、またはそのナトリウム塩が好適である。 The triazole compound is not particularly limited as long as it is a compound having a triazole skeleton in the molecule. Examples of the triazole compound include 1,2,3-triazole, 1,2,4-triazole, 1,2,4-triazole-3-carboxylic acid, 3-amino-1,2,4-triazole, 1,2, 3-benzotriazole, tolyltriazole, nitrobenzotriazole, 4-amino-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 3-mercapto-1,2,4 -Triazoles and their alkali metal salts. These triazole compounds may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of benzotriazole and tolyltriazole, or a sodium salt thereof is preferable.
前記ピラゾロン化合物は、分子中にピラゾロン骨格を有する化合物であれば特に制限されない。ピラゾロン化合物としては、３−メチル−５−ピラゾロン、１，３−ジメチル−５−ピラゾロン、１−フェニル−３−メチル−５−ピラゾロン等が挙げられる。これらのピラゾロン化合物は単独で用いてもよいし、２種以上を併用してもよい。 The pyrazolone compound is not particularly limited as long as it is a compound having a pyrazolone skeleton in the molecule. Examples of the pyrazolone compound include 3-methyl-5-pyrazolone, 1,3-dimethyl-5-pyrazolone, and 1-phenyl-3-methyl-5-pyrazolone. These pyrazolone compounds may be used alone or in combination of two or more.
前記イミダゾール化合物は、分子中にイミダゾール骨格を有する化合物であれば特に限定されない。イミダゾール化合物としては、２−メチルイミダゾール、２−フェニルイミダゾール、２−ホルミルイミダゾール、４−ホルミルイミダゾール、２−フェニル−４−メチルイミダゾール、イミダゾール−４，５−ジカルボン酸、２−メルカプトベンゾイミダゾール等が挙げられる。これらのイミダゾール化合物は単独で用いてもよいし、２種以上を併用してもよい。これらの中でも、２−メチルイミダゾール、２−フェニルイミダゾール、および２−メルカプトベンゾイミダゾールよりなる群から選ばれる少なくとも１種が好ましい。 The imidazole compound is not particularly limited as long as it is a compound having an imidazole skeleton in the molecule. Examples of the imidazole compound include 2-methylimidazole, 2-phenylimidazole, 2-formylimidazole, 4-formylimidazole, 2-phenyl-4-methylimidazole, imidazole-4,5-dicarboxylic acid, 2-mercaptobenzimidazole, and the like. Can be mentioned. These imidazole compounds may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of 2-methylimidazole, 2-phenylimidazole, and 2-mercaptobenzimidazole is preferable.
防錆剤組成物が成分Ｃを含有する場合、成分Ｃの含有率は、５質量％以上が好ましく、１０質量％以上がより好ましく、６０質量％以下が好ましく、５０質量％以下がより好ましい。成分Ｃの含有率が５質量％以上であれば、銅、亜鉛、アルミニウム等の非鉄系金属に対する接触性および非接触性（気化性）の防錆効果が十分高められやすくなる。成分Ｃの含有率が６０質量％以下であれば、鋳鉄、鉄鋼等の鉄系金属に対する防錆効果が高められる。なお、成分Ｃの含有率とは、成分Ａと成分Ｂと成分Ｃと後記する成分Ｄの和に対する成分Ｃの質量比率（Ｃ／（Ａ＋Ｂ＋Ｃ＋Ｄ））を意味する。前記質量比率（Ｃ／（Ａ＋Ｂ＋Ｃ＋Ｄ））において、成分Ｂと成分Ｄは任意成分であるため、ＢとＤは０であってもよい。 When the rust inhibitor composition contains component C, the content of component C is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 60% by mass or less, and more preferably 50% by mass or less. If the content rate of the component C is 5 mass% or more, the contact property with respect to non-ferrous metals, such as copper, zinc, and aluminum, and the non-contact property (vaporizable) rust preventive effect will become easy enough. If the content rate of the component C is 60 mass% or less, the rust prevention effect with respect to ferrous metals, such as cast iron and steel, will be improved. In addition, the content rate of the component C means the mass ratio (C / (A + B + C + D)) of the component C with respect to the sum of the component A, the component B, the component C, and the component D mentioned later. In the mass ratio (C / (A + B + C + D)), since component B and component D are optional components, B and D may be zero.
防錆剤組成物が成分Ｃを含有する場合、成分Ａ、成分Ｂおよび成分Ｃの含有割合は、成分Ａと成分Ｂとの和に対する成分Ｃの質量比（Ｃ／Ａ＋Ｂ）として、５／９５以上が好ましく、１０／９０以上がより好ましく、７０／３０以下が好ましく、６０／４０以下がより好ましい。なお、前記質量比（Ｃ／Ａ＋Ｂ）において、Ｂは０であってもよい。前記質量比（Ｃ／Ａ＋Ｂ）が５／９５以上であれば、銅、亜鉛、アルミニウム等の非鉄系金属に対する防錆効果が確保されやすくなる。前記質量比（Ｃ／Ａ＋Ｂ）が７０／３０以下であれば、鋳鉄、鉄鋼等の鉄系金属に対する防錆効果が確保されやすくなる。 When the rust preventive composition contains component C, the content ratio of component A, component B and component C is 5/95 as the mass ratio of component C to the sum of component A and component B (C / A + B). The above is preferable, 10/90 or more is more preferable, 70/30 or less is preferable, and 60/40 or less is more preferable. In the mass ratio (C / A + B), B may be 0. If the said mass ratio (C / A + B) is 5/95 or more, the antirust effect with respect to nonferrous metals, such as copper, zinc, aluminum, will become easy to be ensured. If the said mass ratio (C / A + B) is 70/30 or less, the antirust effect with respect to ferrous metals, such as cast iron and steel, will become easy to be ensured.
本発明の防錆剤組成物は、下記成分Ｄをさらに含有してもよい。防錆剤組成物が成分Ｄを含有していれば、成分Ｄがアルカリとして作用して成分Ａの分解反応を促進し、成分Ａを構成するアルキルアミンやシクロアルキルアミンが気化しやすくなる。
成分Ｄ：無機アルカリ金属塩、多塩基有機酸アルカリ金属塩（ただし、成分Ｂの塩は除く）、アルカリ土類金属の酸化物、およびアルカリ土類金属の水酸化物よりなる群から選ばれる少なくとも１種。
The rust preventive composition of the present invention may further contain the following component D. If the rust preventive composition contains component D, component D acts as an alkali to promote the decomposition reaction of component A, and the alkylamine and cycloalkylamine constituting component A are easily vaporized.
Component D: At least selected from the group consisting of inorganic alkali metal salts, polybasic organic acid alkali metal salts (excluding the salt of component B), alkaline earth metal oxides, and alkaline earth metal hydroxides One kind.
成分Ｄとしては、水に溶かした場合にアルカリ性（ｐＨ＞７．０）を呈する化合物が好ましい。そのような化合物であれば、成分Ａの分解反応が促進されやすくなる。 Component D is preferably a compound that exhibits alkalinity (pH> 7.0) when dissolved in water. With such a compound, the decomposition reaction of component A is likely to be promoted.
前記無機アルカリ金属塩としては、金属に対する接触腐食を低減する点から、リン酸アルカリ金属塩、ケイ酸アルカリ金属塩、またはアルミン酸アルカリ金属塩を用いることが好ましい。リン酸アルカリ金属塩としては、リン酸１水素２リチウム、リン酸１水素２ナトリウム、リン酸１水素２カリウム等の第２リン酸塩；リン酸３リチウム、リン酸３ナトリウム、リン酸３カリウム等の第３リン酸塩；無水ピロリン酸４ナトリウム、トリポリリン酸ナトリウム、テトラポリリン酸ナトリウム、ペンタポリリン酸ナトリウム、ヘキサメタリン酸ナトリウム等の重合リン酸塩等が挙げられる。ケイ酸アルカリ金属塩としては、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム等が挙げられる。アルミン酸アルカリ金属塩としては、アルミン酸ナトリウム、アルミン酸カリウム等が挙げられる。 As the inorganic alkali metal salt, it is preferable to use an alkali metal phosphate, an alkali metal silicate, or an alkali metal aluminate from the viewpoint of reducing contact corrosion to a metal. Examples of alkali metal phosphates include secondary phosphates such as dilithium monohydrogen phosphate, dibasic sodium hydrogen phosphate, and dibasic potassium hydrogen phosphate; trilithium phosphate, trisodium phosphate, and tripotassium phosphate. And tertiary phosphates such as anhydrous sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium pentapolyphosphate, sodium hexametaphosphate, and the like. Examples of the alkali metal silicate include sodium silicate, potassium silicate, sodium metasilicate and the like. Examples of the alkali metal aluminate include sodium aluminate and potassium aluminate.
アルカリ金属塩としては、有機酸塩を用いることもできる。ただし、成分Ｄは固体である方が防錆剤組成物の取り扱い性が向上することから、入手容易な固体の有機酸塩として、多塩基有機酸塩を用いることが好ましい。また、多塩基有機酸塩を用いれば、成分Ｄがアルカリとして効率よく作用することも期待できる。なお、成分Ｄは成分Ｂと異なり、多塩基有機酸塩による防錆効果を有さなくてもよい点から、多塩基有機酸塩には炭素数１０〜１４の脂肪族ジカルボン酸塩（成分Ｂ）は含まれない。 An organic acid salt can also be used as the alkali metal salt. However, it is preferable to use a polybasic organic acid salt as a solid organic acid salt that is easily available, since the component D is solid so that the handleability of the rust inhibitor composition is improved. Moreover, if a polybasic organic acid salt is used, it can also be expected that component D acts as an alkali efficiently. Component D differs from Component B in that it does not have to have a rust-preventing effect due to the polybasic organic acid salt. Therefore, the polybasic organic acid salt is an aliphatic dicarboxylate having 10 to 14 carbon atoms (Component B). ) Is not included.
前記多塩基有機酸アルカリ金属塩としては、リンゴ酸２ナトリウム、酒石酸２ナトリウム、コハク酸２ナトリウム、フマル酸２ナトリウム、フタル酸２ナトリウム、フタル酸２カリウム等の炭素数９以下の２塩基有機酸塩；クエン酸３ナトリウム、クエン酸３カリウム、トリメリット酸３ナトリウム、トリメリット酸３カリウム、ピロメリット酸３ナトリウム、ピロメリット酸３カリウム、ニトリロ３酢酸３ナトリウム、ニトリロ３酢酸３カリウム等の３塩基有機酸塩；ピロメリット酸４ナトリウム、ピロメリット酸４カリウム、エチレンジアミン４酢酸３ナトリウム、エチレンジアミン４酢酸３カリウム、エチレンジアミン４酢酸４ナトリウム、エチレンジアミン４酢酸４カリウム等の４塩基有機酸塩等が挙げられる。 Examples of the alkali metal salt of polybasic organic acid include dibasic organic acids having 9 or less carbon atoms such as disodium malate, disodium tartrate, disodium succinate, disodium fumarate, disodium phthalate and dipotassium phthalate. 3 salts such as 3 sodium citrate, 3 potassium citrate, 3 sodium trimellitic acid, 3 potassium trimellitic acid, 3 sodium pyromellitic acid, 3 potassium pyromellitic acid, 3 sodium nitrilotriacetic acid, 3 potassium nitrilotriacetic acid Base organic acid salts: 4-base organic acid salts such as pyromellitic acid 4 sodium, pyromellitic acid 4 potassium, ethylenediamine tetraacetic acid 3 sodium, ethylenediamine tetraacetic acid 3 potassium, ethylenediamine tetraacetic acid 4 sodium, ethylenediamine tetraacetic acid 4 potassium It is done.
前記アルカリ土類金属の酸化物または水酸化物としては、酸化カルシウム、酸化マグネシウム、水酸化カルシウム、および水酸化マグネシウム等が挙げられる。 Examples of the alkaline earth metal oxide or hydroxide include calcium oxide, magnesium oxide, calcium hydroxide, and magnesium hydroxide.
成分Ｄとして前記例示した化合物は、単独で用いてもよいし、２種以上を併用してもよい。また、成分Ｄとして前記例示した化合物は、無水化合物であっても、含水化合物であってもよい。なお、防錆剤組成物を熱可塑性樹脂と配合して樹脂成形品を製造する場合は、樹脂成形品の製造容易性の点から、成分Ｄの化合物は無水化合物であることが好ましい。成分Ｄとしては、リン酸１水素２リチウム、リン酸１水素２ナトリウム、リン酸１水素２カリウム、無水ピロリン酸４ナトリウム、トリポリリン酸ナトリウム、テトラポリリン酸ナトリウム、ペンタポリリン酸ナトリウム、ヘキサメタリン酸ナトリウム、メタケイ酸ナトリウム、アルミン酸ナトリウム、クエン酸３ナトリウム、酸化カルシウム、酸化マグネシウム、水酸化カルシウム、および水酸化マグネシウムが好ましい。より好ましくは、成分Ｄとしては、メタケイ酸ナトリウム、リン酸１水素２ナトリウム、アルミン酸ナトリウム、クエン酸３ナトリウム、水酸化カルシウム、および水酸化マグネシウムよりなる群から選ばれる少なくとも１種である。 The compounds exemplified above as Component D may be used alone or in combination of two or more. In addition, the compound exemplified above as component D may be an anhydrous compound or a hydrous compound. In addition, when manufacturing a resin molded product by mix | blending a rust preventive composition with a thermoplastic resin, it is preferable that the compound of the component D is an anhydrous compound from the point of the ease of manufacture of a resin molded product. As component D, 1 lithium 2 hydrogen phosphate, 2 sodium hydrogen phosphate, 2 potassium hydrogen phosphate, 4 sodium pyrophosphate anhydrous, sodium tripolyphosphate, sodium tetrapolyphosphate, sodium pentapolyphosphate, sodium hexametaphosphate, Sodium metasilicate, sodium aluminate, trisodium citrate, calcium oxide, magnesium oxide, calcium hydroxide, and magnesium hydroxide are preferred. More preferably, Component D is at least one selected from the group consisting of sodium metasilicate, disodium monohydrogen phosphate, sodium aluminate, trisodium citrate, calcium hydroxide, and magnesium hydroxide.
防錆剤組成物が成分Ｄを含有する場合、成分Ｄの含有率は、４０質量％以下が好ましく、３０質量％以下がより好ましい。成分Ｄの含有率が４０質量％以下であれば、防錆剤組成物中の他の成分、すなわち成分Ａと必要に応じて含まれる成分Ｂと成分Ｃの含有率が確保され、鋳鉄、鉄鋼等の鉄系金属や非鉄系金属に対する防錆効果が高められる。成分Ｄの含有率の下限は特に限定されないが、成分Ｄの含有率は、例えば０．１質量％以上が好ましく、０．２質量％以上がより好ましい。なお、成分Ｄの含有率とは、成分Ａと成分Ｂと成分Ｃと成分Ｄの和に対する成分Ｄの質量比率（Ｄ／（Ａ＋Ｂ＋Ｃ＋Ｄ））を意味する。前記質量比率（Ｄ／（Ａ＋Ｂ＋Ｃ＋Ｄ））において、成分Ｂと成分Ｃは任意成分であるため、ＢとＣは０であってもよい。 When the rust inhibitor composition contains component D, the content of component D is preferably 40% by mass or less, and more preferably 30% by mass or less. If the content rate of the component D is 40 mass% or less, the content rate of the other component in a rust preventive composition, ie, the component A and the component B and the component C contained as needed, is ensured, cast iron, steel Rust prevention effect for ferrous metals such as non-ferrous metals is enhanced. Although the minimum of the content rate of the component D is not specifically limited, For example, 0.1 mass% or more is preferable and the content rate of the component D has more preferable 0.2 mass% or more. In addition, the content rate of the component D means the mass ratio (D / (A + B + C + D)) of the component D with respect to the sum of the component A, the component B, the component C, and the component D. In the mass ratio (D / (A + B + C + D)), since component B and component C are optional components, B and C may be zero.
防錆剤組成物は、必要に応じて、ポリアクリル酸ナトリウム等の吸湿性ポリマー等を含有していてもよい。また、バインダー、増量剤、顔料、色素等を含有してもよい。 The rust preventive composition may contain a hygroscopic polymer such as sodium polyacrylate as necessary. Moreover, you may contain a binder, an extender, a pigment, a pigment | dye, etc.
以上のように、本発明の防錆剤組成物は成分Ａを必須的に含有し、必要に応じて成分Ｂ、成分Ｃ、および成分Ｄよりなる群から少なくとも１種を含有する。本発明の防錆剤組成物は、成分Ａをそのまま防錆剤として用いてもよく、成分Ａと任意成分である成分Ｂ、成分Ｃ、および／または成分Ｄとを配合して得られるものを防錆剤として用いてもよい。 As described above, the rust inhibitor composition of the present invention essentially contains component A, and contains at least one from the group consisting of component B, component C, and component D as necessary. In the rust inhibitor composition of the present invention, the component A may be used as it is as a rust inhibitor, and is obtained by blending the component A and optional components B, C, and / or D. You may use as a rust preventive.
防錆剤組成物が複数の成分を含有する場合、固体（好ましくは粉体）の各成分を混合することにより、防錆剤組成物を製造することが好ましい。つまり、前記説明した各成分は、いずれも常温常圧（２５℃、１気圧）で固体であることが好ましく、粉体であることがより好ましい。各成分の混合方法は、公知の方法を用いればよい。 When the rust inhibitor composition contains a plurality of components, it is preferable to produce a rust inhibitor composition by mixing solid (preferably powder) components. That is, each of the components described above is preferably solid at room temperature and normal pressure (25 ° C., 1 atm), and more preferably powder. A known method may be used for mixing each component.
防錆剤組成物は、常温常圧（２５℃、１気圧）で固体であることが好ましい。また、防錆剤組成物が複数の成分を含有する場合は、複数の成分を均一な混合状態で含有することが好ましい。防錆剤組成物は、粉体状であってもよく、任意の形状の塊状であってもよく、任意の方法で造粒した粒状、あるいは任意の方法で成形したペレット状等であってもよい。 The rust preventive composition is preferably solid at room temperature and normal pressure (25 ° C., 1 atm). Moreover, when a rust preventive composition contains a some component, it is preferable to contain a some component in a uniform mixed state. The rust inhibitor composition may be in the form of a powder, may be in the shape of an arbitrary shape, may be in the form of granules granulated by an arbitrary method, or pellets formed by an arbitrary method, etc. Good.
次に、本発明の防錆用樹脂組成物について説明する。本発明の防錆用樹脂組成物は、本発明の防錆剤組成物と熱可塑性樹脂とを含有する。 Next, the resin composition for rust prevention of this invention is demonstrated. The rust preventive resin composition of the present invention contains the rust preventive composition of the present invention and a thermoplastic resin.
熱可塑性樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂；ポリスチレン樹脂；アクリロニトリル樹脂；ブタジエン・スチレン樹脂；ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル系樹脂；ナイロン６、ナイロン１２、非晶質ナイロン等のポリアミド系樹脂；エチレン−酢酸ビニルやアクリル酸エステル等の共重合体樹脂；アイオノマー樹脂等が挙げられる。これらの熱可塑性樹脂は、単独で使用してもよいし、２種以上を併用してもよい。これらの中でもポリエチレン、ポリプロピレン等のポリオレフィン系樹脂が好ましく、ポリエチレンがより好ましい。 Examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene; polystyrene resins; acrylonitrile resins; butadiene / styrene resins; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 12, amorphous nylon, etc. Polyamide resins; copolymer resins such as ethylene-vinyl acetate and acrylic esters; ionomer resins and the like. These thermoplastic resins may be used alone or in combination of two or more. Among these, polyolefin resins such as polyethylene and polypropylene are preferable, and polyethylene is more preferable.
本発明の防錆用樹脂組成物は、例えば、前記防錆剤組成物と熱可塑性樹脂とを配合して、混合することにより得られる。防錆剤組成物と熱可塑性樹脂とを混合する方法は特に限定されず、公知の方法を採用すればよい。例えば、粉末状の防錆剤組成物を熱可塑性樹脂のペレットまたは粉末に添加し、バンバリーミキサー、ミキシングロールニーダー、二軸混練押出機等の混合装置を用いて混合すればよい。この際、防錆用樹脂組成物は粉砕機等で粉砕し、任意の粒度に調整してもよい。防錆剤組成物と熱可塑性樹脂との混合物を、加熱して任意の形状に成形して、成形品を得てもよい。 The rust preventive resin composition of the present invention can be obtained, for example, by blending and mixing the rust inhibitor composition and the thermoplastic resin. The method for mixing the rust inhibitor composition and the thermoplastic resin is not particularly limited, and a known method may be employed. For example, a powdery rust inhibitor composition may be added to a pellet or powder of a thermoplastic resin and mixed using a mixing device such as a Banbury mixer, a mixing roll kneader, or a twin-screw kneading extruder. At this time, the resin composition for rust prevention may be pulverized with a pulverizer or the like and adjusted to an arbitrary particle size. A mixture of the rust inhibitor composition and the thermoplastic resin may be heated and molded into an arbitrary shape to obtain a molded product.
防錆用樹脂組成物中の防錆剤組成物の含有率は、防錆剤組成物と熱可塑性樹脂との合計１００質量％中、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１０質量％以下が好ましく、５質量％以下がより好ましい。前記防錆剤組成物の含有率が０．１質量％以上であれば、金属に対する防錆効果が発揮されやすくなる。前記防錆剤組成物の含有率が１０質量％以下であれば、防錆用樹脂組成物から得られる成形品の強度が確保されやすくなる。また、成形品（特にフィルム状の成形品）の水蒸気透過性およびガス透過性が大きくなりすぎず、防錆効果が発揮されやすくなる。 The content of the rust preventive composition in the rust preventive resin composition is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, in a total of 100% by weight of the rust preventive composition and the thermoplastic resin. Is more preferable, 10 mass% or less is preferable, and 5 mass% or less is more preferable. If the content rate of the said rust preventive composition is 0.1 mass% or more, the rust preventive effect with respect to a metal will become easy to be exhibited. If the content rate of the said rust preventive composition is 10 mass% or less, it will become easy to ensure the intensity | strength of the molded article obtained from the resin composition for rust prevention. Moreover, the water vapor permeability and gas permeability of the molded product (particularly a film-shaped molded product) do not become too large, and the rust prevention effect is easily exhibited.
防錆用樹脂組成物は、防錆剤組成物と熱可塑性樹脂とに加え、必要に応じて、可塑剤、老化防止剤、酸化防止剤、帯電防止剤、着色剤、補強剤等を含有してもよい。防錆用樹脂組成物は、溶融して成形することにより、防錆効果を有する任意の樹脂成形品を得ることができる。 In addition to the rust preventive composition and the thermoplastic resin, the rust preventive resin composition contains a plasticizer, an anti-aging agent, an antioxidant, an antistatic agent, a colorant, a reinforcing agent, and the like as necessary. May be. The resin composition for rust prevention can obtain an arbitrary resin molded product having a rust prevention effect by melting and molding.
本発明の防錆用フィルムについて説明する。本発明の防錆用フィルムは、本発明の防錆用樹脂組成物から得られるものである。 The antirust film of the present invention will be described. The antirust film of the present invention is obtained from the antirust resin composition of the present invention.
防錆用樹脂組成物から防錆用フィルムを作製する方法としては、公知のフィルム作製方法を採用することができ、例えば、インフレーション法、Ｔ−ダイキャスト法等を挙げることができる。防錆用フィルムを成形する際の温度は、防錆剤組成物に含まれる成分の蒸発や昇華を極力抑えるために、防錆剤組成物に含まれる成分の分解温度以下の温度とすることが好ましい。そのため、フィルム成形温度は１８０℃以下が好ましく、１６０℃以下がより好ましく、１４０℃以下がさらに好ましい。 As a method for producing a rust-proof film from a rust-proof resin composition, a known film production method can be employed, and examples thereof include an inflation method and a T-die cast method. The temperature at which the film for rust prevention is formed may be set to a temperature equal to or lower than the decomposition temperature of the component contained in the rust preventive composition in order to suppress evaporation and sublimation of the component contained in the rust preventive composition as much as possible. preferable. Therefore, the film forming temperature is preferably 180 ° C. or lower, more preferably 160 ° C. or lower, and further preferably 140 ° C. or lower.
本発明の防錆用フィルムは、本発明の防錆剤組成物を含有するため、フィルムに成形してもブリード現象が起こりにくい。従って、例えば、防錆用フィルムで金属材料を包んで、金属材料の発錆を好適に抑制することができる。 Since the rust preventive film of the present invention contains the rust preventive composition of the present invention, the bleed phenomenon hardly occurs even if the film is formed into a film. Therefore, for example, the metal material can be wrapped with a rust-preventing film to suitably suppress rusting of the metal material.
防錆用フィルムの厚みは、３０μｍ以上が好ましく、５０μｍ以上がより好ましく、５００μｍ以下が好ましく、２００μｍ以下がより好ましい。防錆用フィルムの厚みが３０μｍ〜５００μｍの範囲にあれば、フィルムの強度と防錆効果とが確保されやすくなる。 The thickness of the anticorrosive film is preferably 30 μm or more, more preferably 50 μm or more, preferably 500 μm or less, and more preferably 200 μm or less. If the thickness of the film for rust prevention is in the range of 30 μm to 500 μm, the strength of the film and the rust prevention effect are easily secured.
次に、本発明の防錆方法について説明する。本発明の防錆剤組成物、防錆用樹脂組成物、および防錆用フィルムはいずれも、鉄系金属および／または非鉄系金属の防錆のために、使用することができる。すなわち、本発明の防錆方法は、前記防錆剤組成物、前記防錆用樹脂組成物、または前記防錆用フィルムを用いて、鉄系金属および／または非鉄系金属を防錆するところに特徴を有する。 Next, the rust prevention method of this invention is demonstrated. Any of the rust inhibitor composition, the rust preventive resin composition, and the rust preventive film of the present invention can be used for rust prevention of ferrous metals and / or non-ferrous metals. That is, the rust-preventing method of the present invention is a method for rusting ferrous metals and / or non-ferrous metals using the rust inhibitor composition, the rust preventive resin composition, or the rust preventive film. Has characteristics.
防錆の対象となる金属としては、鋳鉄、鉄鋼等の鉄系金属、および／または、銅、亜鉛、アルミニウム等の非鉄系金属である。本発明の防錆方法は、前記示した少なくとも１種の金属の防錆に効果を発揮すればよい。 As a metal subject to rust prevention, iron-based metals such as cast iron and steel and / or non-ferrous metals such as copper, zinc and aluminum are used. The rust prevention method of the present invention may be effective for the rust prevention of the at least one metal shown above.
防錆剤組成物を用いて金属を防錆する方法としては、防錆剤組成物を粉末状にして金属製品と同封する方法；防錆剤組成物を紙に塗布し、防錆紙として金属製品を包装する方法等が挙げられる。防錆剤組成物を粉末状にして金属製品と同封する場合は、取り扱い性を高めるため、通気性の不織布、あるいは孔開きフィルムや連続気泡タイプの発泡フィルムのような通気性フィルムからなる袋などに適量包装して用いることが好ましい。ここで使用される不織布や通気性フィルムの種類は特に制限されない。防錆剤組成物の漏出を防止しつつ、防錆効果を有するガスの通過を許すものであれば、通常の植物性繊維、動物性繊維、再生繊維、合成繊維等の不織布、あるいは各種樹脂の連続発泡シート、孔開きフィルム等が使用可能である。 As a method of rust-preventing metal using a rust-preventive agent composition, a method in which a rust-preventive composition is powdered and enclosed with a metal product; Examples include a method of packaging a product. When encapsulating a metal product with a rust preventive composition in a powder form, a bag made of a breathable non-woven fabric or a breathable film such as a perforated film or an open-celled foam film is used to improve handling. It is preferable to use an appropriate amount after packaging. The kind of non-woven fabric or breathable film used here is not particularly limited. As long as it allows the passage of gas having a rust-preventing effect while preventing leakage of the rust-preventing agent composition, it is possible to use ordinary non-woven fabrics such as plant fibers, animal fibers, regenerated fibers, synthetic fibers, or various resins. A continuous foam sheet, a perforated film, or the like can be used.
防錆用樹脂組成物を用いて金属を防錆する方法としては、防錆用樹脂組成物を溶剤等で希釈または溶解して、塗工、スプレー、浸漬等の手段によって、防錆用樹脂組成物を金属製品に塗布する方法等が挙げられる。防錆用フィルムを用いて金属を防錆する方法としては、防錆用フィルムにより金属製品を被覆または包装する方法等が挙げられる。これらの中でも、より省力化を図れることから、防錆用フィルムにより金属製品を被覆または包装する方法が好ましい。 As a method of rust-proofing a metal using a rust-proof resin composition, the rust-proof resin composition is diluted or dissolved with a solvent or the like, and applied by means such as coating, spraying or dipping, etc. The method etc. which apply | coat a thing to a metal product are mentioned. Examples of a method for rust-proofing a metal using a rust-proof film include a method for coating or packaging a metal product with a rust-proof film. Among these, a method of coating or packaging a metal product with a rust-preventing film is preferable because it can save more labor.
本発明の防錆剤組成物を用いた防錆方法は、特に鋳鉄や鉄鋼等の鉄系金属の防錆に対し有効である。また、銅、亜鉛、アルミニウム等の非鉄系金属の非接触性（気化性）防錆効果に対して悪影響を及ぼさず、防錆剤組成物の組成によっては、非鉄系金属に対する防錆効果も発揮する。 The rust prevention method using the rust inhibitor composition of the present invention is particularly effective for rust prevention of ferrous metals such as cast iron and steel. In addition, it does not adversely affect the non-contact (vaporization) rust prevention effect of non-ferrous metals such as copper, zinc and aluminum, and depending on the composition of the rust inhibitor composition, it also exhibits rust prevention effect against non-ferrous metals. To do.
以下に、実施例を示すことにより本発明を更に詳細に説明するが、本発明の範囲はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited thereto.
（１）成分Ａの塩の合成
（１−１）フマル酸とオクチルアミンとのジアミン塩（化合物Ａ−１）の合成
フマル酸（関東化学株式会社製、試薬）１１６ｇ（１モル）とオクチルアミン（花王株式会社製、製品名「ファーミン（登録商標）０８Ｄ」）２６０ｇ（２モル）とを脱イオン水８００ｇに加え、８０℃に加温して溶解後、２０℃まで冷却して結晶を析出させた。得られた結晶を、ろ別後、乾燥させて、化合物Ａ−１を得た。化合物Ａ−１の１質量％濃度のｐＨは、６．２であった。
(1) Synthesis of component A salt (1-1) Synthesis of diamine salt of fumaric acid and octylamine (compound A-1) 116 g (1 mol) of fumaric acid (manufactured by Kanto Chemical Co., Ltd., reagent) and octylamine (Product name “Farmin (registered trademark) 08D” manufactured by Kao Corporation) 260 g (2 mol) was added to 800 g of deionized water, heated to 80 ° C., dissolved, and then cooled to 20 ° C. to precipitate crystals. I let you. The obtained crystal was filtered off and dried to obtain compound A-1. The pH of 1% by mass concentration of Compound A-1 was 6.2.
（１−２）アジピン酸とジシクロヘキシルアミンとのジアミン塩（化合物Ａ−２）の合成
アジピン酸（関東化学株式会社製、試薬）７３ｇ（０．５モル）とジシクロヘキシルアミン（関東電化工業株式会社製、Ｄ−ＣＨＡ−Ｔ）１８１ｇ（１モル）とを脱イオン水７００ｇに加え、８０℃に加温して溶解後、２０℃まで冷却して結晶を析出させた。得られた結晶を、ろ別後、乾燥させて、化合物Ａ−２を得た。化合物Ａ−２の１質量％濃度のｐＨは、７．０であった。
(1-2) Synthesis of Diamine Salt of Adipic Acid and Dicyclohexylamine (Compound A-2) 73 g (0.5 mol) of adipic acid (manufactured by Kanto Chemical Co., Ltd., reagent) and dicyclohexylamine (manufactured by Kanto Denka Kogyo Co., Ltd.) , D-CHA-T) 181 g (1 mol) was added to 700 g of deionized water, heated to 80 ° C. and dissolved, and then cooled to 20 ° C. to precipitate crystals. The obtained crystals were filtered off and dried to obtain compound A-2. The 1 mass% pH of Compound A-2 was 7.0.
（１−３）ｐ−ヒドロキシ安息香酸とオクチルアミンとのモノアミン塩（化合物Ａ−３）の合成
ｐ−ヒドロキシ安息香酸（関東化学株式会社製、試薬）１３８ｇ（１モル）とオクチルアミン（花王株式会社製、製品名「ファーミン０８Ｄ」）１３０ｇ（１モル）とを脱イオン水８００ｇに加え、８０℃に加温して溶解後、２０℃まで冷却して結晶を析出させた。得られた結晶を、ろ別後、乾燥させて、化合物Ａ−３を得た。化合物Ａ−３の１質量％濃度のｐＨは、７．２であった。
(1-3) Synthesis of monoamine salt of p-hydroxybenzoic acid and octylamine (Compound A-3) 138 g (1 mol) of p-hydroxybenzoic acid (manufactured by Kanto Chemical Co., Inc.) and octylamine (Kao stock) 130 g (1 mol) manufactured by the company, product name “Pharmin 08D”) was added to 800 g of deionized water, heated to 80 ° C. and dissolved, and then cooled to 20 ° C. to precipitate crystals. The obtained crystals were collected by filtration and dried to give compound A-3. The pH of the 1% by mass concentration of Compound A-3 was 7.2.
（２）防錆用フィルムの作製
（２−１）フィルム１の作製
化合物Ａ−１（防錆剤組成物）を、粉砕機で１００μｍ以下に粉砕した後、濃度１．０質量％となるように低密度ポリエチレン（東ソー株式会社製、製品名「ペトロセン（登録商標）１８０」、密度０．９２２ｇ／ｃｍ3、メルトフローレート２．０ｇ／１０ｍｉｎ）と混合し、防錆用樹脂組成物を得た。得られた防錆用樹脂組成物から、インフレーション法（成形温度１６０℃）により、厚さ１００μｍのフィルム１を得た。得られたフィルム１には、ブリード現象は見られなかった。
(2) Production of film for rust prevention (2-1) Production of film 1 After pulverizing Compound A-1 (antirust composition) to 100 μm or less with a pulverizer, the concentration becomes 1.0 mass%. Are mixed with low density polyethylene (product name “Petrocene (registered trademark) 180” manufactured by Tosoh Corporation, density 0.922 g / cm 3 , melt flow rate 2.0 g / 10 min) to obtain a resin composition for rust prevention. It was. A film 1 having a thickness of 100 μm was obtained from the obtained resin composition for rust prevention by an inflation method (molding temperature 160 ° C.). In the obtained film 1, no bleed phenomenon was observed.
（２−２）フィルム２〜１７の作製
表１に示す配合割合に従い各化合物を配合し混合することにより調製した防錆剤組成物を、粉砕機で１００μｍ以下に粉砕した後、濃度１．０質量％となるように低密度ポリエチレン（東ソー株式会社製、製品名「ペトロセン１８０」、密度０．９２２ｇ／ｃｍ3、メルトフローレート２．０ｇ／１０ｍｉｎ）と混合し、防錆用樹脂組成物を得た。得られた防錆用樹脂組成物から、インフレーション法（成形温度１６０℃）により、厚さ１００μｍのフィルム２〜１７を得た。得られたフィルム１２〜１７には、ブリード現象は見られなかった。
(2-2) Production of Films 2 to 17 After the rust inhibitor composition prepared by blending and mixing the respective compounds according to the blending ratio shown in Table 1 was pulverized to 100 μm or less with a pulverizer, the concentration was 1.0. The resin composition for rust prevention is mixed with low density polyethylene (product name “Petrocene 180”, density 0.922 g / cm 3 , melt flow rate 2.0 g / 10 min, manufactured by Tosoh Corporation) so as to be mass%. Obtained. From the obtained resin composition for rust prevention, films 2 to 17 having a thickness of 100 μm were obtained by an inflation method (molding temperature 160 ° C.). In the obtained films 12 to 17, no bleed phenomenon was observed.
表１に示す各化合物について、セバシン酸２ナトリウムは豊国製油株式会社製の製品名「ＳＡ−ＮＡ」を用い、２−メルカプトベンゾイミダゾールは精工化学株式会社製の製品名「ノンフレックス（登録商標）ＭＢ」を用い、ベンゾトリアゾールはキレスト株式会社製の製品名「Ｃ．Ｖ．Ｉ．」を用い、リン酸１水素２ナトリウム（無水）とメタケイ酸ナトリウム（無水）と酸化マグネシウムとアルミン酸ナトリウムとクエン酸３ナトリウムは関東化学株式会社製の試薬を用いた。 About each compound shown in Table 1, disodium sebacate uses the product name "SA-NA" by Toyokuni Oil Co., Ltd., 2-mercaptobenzimidazole uses the product name "Nonflex (registered trademark)" by Seiko Chemical Co., Ltd. "MB", and benzotriazole using the product name "C.V.I" manufactured by Kyrest Co., Ltd., sodium monohydrogen phosphate (anhydrous), sodium metasilicate (anhydrous), magnesium oxide and sodium aluminate For trisodium citrate, a reagent manufactured by Kanto Chemical Co., Ltd. was used.
ドデカン２酸ナトリウムは、ドデカン２酸（デュポン株式会社製、製品名「コーフリーＭ−２」）１モルに対して２モルのＮａＯＨを水存在下で混合して反応させた後、スプレードライにより水分を蒸発させて得られた結晶を用いた。なお、ドデカン２酸ナトリウムの結晶の含水率は０．５質量％以下であった。 Sodium dodecanoate is mixed with 2 mol of NaOH in the presence of water with 1 mol of dodecanoic acid (product name “Corfrey M-2” manufactured by DuPont Co., Ltd.), and then dried by spray drying. Crystals obtained by evaporating were used. The water content of the crystals of sodium dodecanoate was 0.5% by mass or less.
（２−３）フィルム１８の作製
低密度ポリエチレン（東ソー株式会社製、製品名「ペトロセン１８０」、密度０．９２２ｇ／ｃｍ3、メルトフローレート２．０ｇ／１０ｍｉｎ）から、インフレーション法（成形温度１６０℃）により、厚さ１００μｍのフィルム１８を得た。
(2-3) Production of Film 18 From low density polyethylene (manufactured by Tosoh Corporation, product name “Petrocene 180”, density 0.922 g / cm 3 , melt flow rate 2.0 g / 10 min), inflation method (molding temperature 160) C.), a film 18 having a thickness of 100 μm was obtained.
（３）試験方法
（３−１）試験に用いた試験片
防錆試験（接触防錆試験、気化性防錆試験）には、下記の試験片を用いた。
鋳鉄板：ＪＩＳ Ｇ ５５０１（１９９５）に規定されるＦＣ−２００を用いた。大きさは、接触防錆試験用が５０ｍｍ×５０ｍｍ×２．０ｍｍであり、気化性防錆試験用が５０ｍｍ×５０ｍｍ×５．０ｍｍであった。
鉄鋼板：ＪＩＳ Ｇ ３１４１（２００５）に規定されるＳＰＣＣ−ＳＢを用いた。大きさは、接触防錆試験用が６０ｍｍ×８０ｍｍ×１．２ｍｍであり、気化性防錆試験用が４０ｍｍ×６０ｍｍ×３．０ｍｍであった。
銅板：ＪＩＳ Ｈ ３１００（２００６）に規定されるＣ１１００を用いた。大きさは、接触防錆試験用が４０ｍｍ×６０ｍｍ×１．５ｍｍであり、気化性防錆試験用が４０ｍｍ×６０ｍｍ×３．２ｍｍであった。
亜鉛板：ＪＩＳ Ｈ ４３２１（１９５３）に規定される第２種を用いた。大きさは、４０ｍｍ×６０ｍｍ×１．５ｍｍであった。
アルミニウム板：ＪＩＳ Ｈ ４０００（２００６）に規定されるＡ１０５０Ｐを用いた。大きさは、４０ｍｍ×６０ｍｍ×１．５ｍｍであった。
(3) Test method (3-1) Test piece used for test The following test piece was used for the rust prevention test (contact rust prevention test, vaporizable rust prevention test).
Cast iron plate: FC-200 defined in JIS G 5501 (1995) was used. The size was 50 mm × 50 mm × 2.0 mm for the contact rust test, and 50 mm × 50 mm × 5.0 mm for the vaporizable rust test.
Steel sheet: SPCC-SB defined in JIS G 3141 (2005) was used. The size was 60 mm × 80 mm × 1.2 mm for the contact rust test, and 40 mm × 60 mm × 3.0 mm for the vaporizable rust test.
Copper plate: C1100 defined in JIS H 3100 (2006) was used. The size was 40 mm × 60 mm × 1.5 mm for the contact rust test, and 40 mm × 60 mm × 3.2 mm for the vaporizable rust test.
Zinc plate: The second type specified in JIS H 4321 (1953) was used. The size was 40 mm × 60 mm × 1.5 mm.
Aluminum plate: A1050P defined in JIS H 4000 (2006) was used. The size was 40 mm × 60 mm × 1.5 mm.
鋳鉄板および鉄鋼板は、＃２４０の研磨布で乾式研磨後、メタノールおよびアセトンで脱脂および洗浄した後、乾燥したものを用いた。亜鉛板、銅板およびアルミニウム板は、＃３２０の耐水研磨紙を用いて脱イオン水中で研磨した後、メタノールおよびアセトンで脱脂および洗浄した後、乾燥したものを用いた。 The cast iron plate and the steel plate were used after dry polishing with a # 240 polishing cloth, degreased and washed with methanol and acetone, and then dried. The zinc plate, copper plate, and aluminum plate were polished in deionized water using # 320 water-resistant abrasive paper, degreased and washed with methanol and acetone, and then dried.
（３−２）接触防錆試験
フィルム１〜１８について、それぞれ、２種類の大きさ（１００ｍｍ×１５０ｍｍ、６０ｍｍ×１１０ｍｍ）の防錆用フィルム袋を作製した。鉄鋼板試験片は１００ｍｍ×１５０ｍｍの防錆用フィルム袋に、鋳鉄板、銅板、亜鉛板、およびアルミニウム板試験片は６０ｍｍ×１１０ｍｍの防錆用フィルム袋に入れ、防錆用フィルム袋内の空気を抜気した後、ヒートシールで密封包装した。防錆用フィルム袋で密封包装した試験片を２５℃で１６時間保持した後、環境試験機（ＫＡＴＯ社製、型式「シルバリーエンペラー」）を用いて、接触防錆試験を行った。防錆試験における環境試験機の温湿度条件は、（１）５℃，ＲＨ９５％で２時間、（２）５０℃，ＲＨ９５％で２時間、（３）５℃，ＲＨ９５％で２時間、（４）５０℃，ＲＨ９５％で１２時間、の順番で設定し、５℃から５０℃の昇温は３０分かけて行い、５０℃から５℃の降温は２時間３０分かけて行い、（１）から（４）までを１サイクルとして２４時間かけて行った。これを３０サイクル繰り返した後の試験片表面の錆、腐食、および変色状態を評価した。
(3-2) Contact rust prevention test About the films 1-18, the film bag for rust prevention of 2 types (100 mm x 150 mm, 60 mm x 110 mm) was produced, respectively. The steel plate test piece is put in a 100 mm × 150 mm rust prevention film bag, and the cast iron plate, copper plate, zinc plate, and aluminum plate test piece is put in a 60 mm × 110 mm rust prevention film bag, and the air in the rust prevention film bag. After evacuating, it was hermetically packaged by heat sealing. After holding the test piece hermetically packaged with a rust-proof film bag at 25 ° C. for 16 hours, a contact rust-proof test was performed using an environmental tester (type “Silverly Emperor” manufactured by KATO). The temperature and humidity conditions of the environmental testing machine in the rust prevention test are (1) 5 ° C, RH95% for 2 hours, (2) 50 ° C, RH95% for 2 hours, (3) 5 ° C, RH95% for 2 hours, ( 4) Set in the order of 12 hours at 50 ° C. and RH 95%, raise the temperature from 5 ° C. to 50 ° C. over 30 minutes, lower the temperature from 50 ° C. to 5 ° C. over 2 hours 30 minutes, (1 ) To (4) was carried out over 24 hours as one cycle. This was repeated 30 cycles, and the rust, corrosion, and discoloration state of the test piece surface was evaluated.
（３−３）気化性防錆試験
ポリプロピレン製試験管バスケット（株式会社サンプラテック社、コードＮｏ．９０４９，呼称Ｓ、外寸法１２７ｍｍ×１０２ｍｍ×１０２ｍｍ）を枠組に使用して、枠組の内部に高さ４０ｍｍ、厚み２ｍｍのポリプロピレン製間仕切りボードで井桁を組んで、そこに各試験片を固定した。試験片を固定した試験管バスケットを、フィルム１〜１８のいずれかにより包んで密封し（ガゼットシール）、２５℃で１６時間保持した後、環境試験機（ＫＡＴＯ社製、型式「シルバリーエンペラー」）を用いて、気化性防錆試験を行った。気化性防錆試験における環境試験機の温湿度条件は、接触防錆試験と同じ条件で２４時間で１サイクル行った。気化性防錆試験では、これを５サイクル繰り返した後の試験片表面の錆、腐食、および変色状態を評価した。
(3-3) Vaporization rust prevention test Polypropylene test tube basket (Sampra Tech Co., Ltd., code No. 9049, designation S, outer dimensions 127 mm x 102 mm x 102 mm) is used for the frame, and the height is set inside the frame. A cross girder was assembled with a polypropylene partition board having a thickness of 40 mm and a thickness of 2 mm, and each test piece was fixed thereto. The test tube basket to which the test piece is fixed is wrapped and sealed with any of the films 1 to 18 (gazette seal), held at 25 ° C. for 16 hours, and then an environmental tester (type “Silbury Emperor” manufactured by KATO). ) Was used to conduct a vaporizable rust prevention test. The temperature and humidity conditions of the environmental tester in the vaporizable rust prevention test were the same as those in the contact rust prevention test, and one cycle was performed for 24 hours. In the vaporizable rust prevention test, the rust, corrosion, and discoloration state of the test piece surface after repeating this for 5 cycles were evaluated.
（３−４）評価基準
接触防錆試験と気化性防錆試験の評価は、下記基準に基づいて行った。
◎：腐食、変色なし。
○：極僅かな腐食（点さび１〜３個または変色面積１０％未満）。
△：軽度の腐食（点さび４〜９個または変色面積１０〜３０％未満）。
×：明確な腐食（点さび１０個以上または変色面積３０〜５０％未満）。
××：激しい腐食（腐食、変色面積５０％以上）。
(3-4) Evaluation Criteria Evaluation of the contact rust test and the vaporizable rust test was performed based on the following criteria.
A: No corrosion or discoloration.
A: Very slight corrosion (1 to 3 point rust or less than 10% discoloration area).
Δ: Mild corrosion (4 to 9 point rust or discolored area of less than 10 to 30%).
X: Clear corrosion (10 or more point rust or discoloration area 30 to less than 50%).
XX: Severe corrosion (corrosion, discoloration area 50% or more).
（４）試験結果
試験結果を表２に示す。熱可塑性樹脂のみから作製されたフィルム１８では、銅とアルミニウムが「○」または「△」との評価であったのに対し、鋳鉄、鉄鋼、亜鉛では激しい腐食が起こった。成分Ａを含有するフィルム１では、フィルム１８と比較して、接触防錆試験と気化性防錆試験で鋳鉄と鉄鋼の腐食が抑えられ、銅とアルミニウムについては悪影響が見られなかった。
(4) Test results Table 2 shows the test results. In the film 18 made only from the thermoplastic resin, copper and aluminum were evaluated as “◯” or “Δ”, whereas severe corrosion occurred in cast iron, steel, and zinc. In the film 1 containing the component A, compared with the film 18, corrosion of cast iron and steel was suppressed by the contact rust prevention test and the vaporization rust prevention test, and no adverse effect was observed on copper and aluminum.
成分Ａに加え成分Ｂを含有するフィルム２では、鋳鉄と鉄鋼の鉄系金属に対する接触性と非接触性（気化性）の防錆効果がさらに改善した。なお、成分Ａを含有せず成分Ｂのみを含有するフィルム１５では、鋳鉄と鉄鋼の鉄系金属に対する非接触性（気化性）の防錆効果が見られなかった。 In the film 2 containing the component B in addition to the component A, the rust prevention effect of cast iron and steel with respect to the ferrous metal and non-contact property (vaporization) was further improved. In addition, in the film 15 which does not contain the component A but contains only the component B, the non-contact (vaporization) rust prevention effect with respect to the iron-based metal of cast iron and steel was not seen.
成分Ａに加え成分Ｃを含有するフィルム３では、銅、亜鉛、アルミニウムの非鉄系金属に対する接触性と非接触性（気化性）の防錆効果がさらに改善した。なお、成分Ａを含有せず成分Ｃのみを含有するフィルム１６では、鋳鉄と鉄鋼の鉄系金属に対する接触性と非接触性（気化性）の防錆効果がほとんど見られなかった。 In the film 3 containing the component C in addition to the component A, the contact resistance to the non-ferrous metal of copper, zinc and aluminum and the rust preventive effect of non-contact property (vaporization property) were further improved. In addition, in the film 16 which does not contain the component A but contains only the component C, the contact property with respect to the iron-type metal of cast iron and steel, and the non-contact property (vaporability) were hardly seen.
成分Ａに加え、成分Ｂと成分Ｃとを含有するフィルム４〜８では、いずれの金属に対しても、接触性と非接触性（気化性）の防錆効果が改善した。なお、成分Ａを含有せず成分Ｂと成分Ｃのみを含有するフィルム１７では、鋳鉄と鉄鋼の鉄系金属に対する非接触性（気化性）の防錆効果がほとんど見られなかった。 In the films 4 to 8 containing the component B and the component C in addition to the component A, the contact and non-contact (vaporizable) rust preventive effect was improved for any metal. In addition, in the film 17 which does not contain the component A but contains only the component B and the component C, the non-contact (vaporization) rust prevention effect with respect to the iron-type metal of cast iron and steel was hardly seen.
成分Ａに加え、成分Ｂと成分Ｃと成分Ｄとを含有するフィルム９〜１４では、いずれの金属試験に対しても、接触性と非接触性（気化性）の両方において優れた防錆効果が見られた。フィルム９〜１４では、成分Ａの含有率が低くなっても、優れた防錆効果が見られた。 In the films 9 to 14 containing the component B, the component C and the component D in addition to the component A, the antirust effect excellent in both contact property and non-contact property (vaporization property) for any metal test. It was observed. In the films 9 to 14, even when the content of component A was low, an excellent antirust effect was observed.
本発明の防錆剤組成物、防錆用樹脂組成物、および防錆用フィルムは、鉄系金属や非鉄系金属の防錆用途へ適用できる。 The rust preventive agent composition, the rust preventive resin composition, and the rust preventive film of the present invention can be applied to rust preventive uses of ferrous metals and non-ferrous metals.
Claims (7)
成分Ａ：炭素数２〜８の脂肪族ジカルボン酸と炭素数６〜１４のアルキルアミンとの塩、炭素数２〜８の脂肪族ジカルボン酸と炭素数６〜１４のシクロアルキルアミンとの塩、および炭素数７〜１２の芳香族モノカルボン酸と炭素数６〜１４のアルキルアミンとの塩よりなる群から選ばれる少なくとも１種。 Anticorrosive resin composition characterized by containing an anti-rust agent composition you contain the following component A and a thermoplastic resin.
Component A: a salt of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms and an alkylamine having 6 to 14 carbon atoms, a salt of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms and a cycloalkylamine having 6 to 14 carbon atoms, And at least one selected from the group consisting of a salt of an aromatic monocarboxylic acid having 7 to 12 carbon atoms and an alkylamine having 6 to 14 carbon atoms.
成分Ｂ：炭素数１０〜１４の脂肪族ジカルボン酸とアルカリ金属との塩。 The rust preventive resin composition according to claim 1, wherein the rust preventive composition further contains the following component B.
Component B: A salt of an aliphatic dicarboxylic acid having 10 to 14 carbon atoms and an alkali metal.
成分Ｃ：トリアゾール化合物、ピラゾロン化合物、およびイミダゾール化合物よりなる群から選ばれる少なくとも１種。 The rust preventive resin composition according to claim 1 or 2, wherein the rust preventive composition further contains the following component C.
Component C: At least one selected from the group consisting of triazole compounds, pyrazolone compounds, and imidazole compounds.
前記成分Ａの炭素数７〜１２の芳香族モノカルボン酸が、安息香酸、ｍ−アミノ安息香酸、ｐ−アミノ安息香酸、ｐ−ニトロ安息香酸、サリチル酸、ｐ−ヒドロキシ安息香酸、トルイル酸、ｐ−ｔ−ブチル安息香酸、およびβ−オキシナフトエ酸よりなる群から選ばれる少なくとも１種であり、
前記成分Ａの炭素数６〜１４のアルキルアミンが、モノヘキシルアミン、モノオクチルアミン、モノデカノイックアミン、モノドデカノイックアミン、およびモノ−２−エチルヘキシルアミンよりなる群から選ばれる少なくとも１種であり、
前記成分Ａの炭素数６〜１４のシクロアルキルアミンが、ジシクロヘキシルアミンである請求項１〜３のいずれか一項に記載の防錆用樹脂組成物。 The component C aliphatic dicarboxylic acid having 2 to 8 carbon atoms is at least one selected from the group consisting of oxalic acid, maleic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, and adipic acid,
The aromatic monocarboxylic acid having 7 to 12 carbon atoms of Component A is benzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, toluic acid, p -T-butylbenzoic acid and at least one selected from the group consisting of β-oxynaphthoic acid,
The C6-14 alkylamine of Component A is at least one selected from the group consisting of monohexylamine, monooctylamine, monodecanoic amine, monododecanoic amine, and mono-2-ethylhexylamine. And
The rust-proof resin composition according to any one of claims 1 to 3, wherein the cycloalkylamine having 6 to 14 carbon atoms of the component A is dicyclohexylamine.
成分Ｄ：無機アルカリ金属塩、多塩基有機酸アルカリ金属塩（ただし、成分Ｂの塩は除く）、アルカリ土類金属の酸化物、およびアルカリ土類金属の水酸化物よりなる群から選ばれる少なくとも１種。 The rust preventive resin composition according to any one of claims 1 to 4, wherein the rust preventive composition further contains the following component D.
Component D: At least selected from the group consisting of inorganic alkali metal salts, polybasic organic acid alkali metal salts (excluding the salt of component B), alkaline earth metal oxides, and alkaline earth metal hydroxides One kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009288434A JP5531187B2 (en) | 2009-12-18 | 2009-12-18 | Rust-proof resin composition and rust-proof film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009288434A JP5531187B2 (en) | 2009-12-18 | 2009-12-18 | Rust-proof resin composition and rust-proof film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011127202A JP2011127202A (en) | 2011-06-30 |
| JP5531187B2 true JP5531187B2 (en) | 2014-06-25 |
Family
ID=44290099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009288434A Active JP5531187B2 (en) | 2009-12-18 | 2009-12-18 | Rust-proof resin composition and rust-proof film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5531187B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5750316B2 (en) * | 2011-06-22 | 2015-07-22 | 凸版印刷株式会社 | Rust prevention film |
| JP6682593B2 (en) * | 2018-09-27 | 2020-04-15 | 株式会社Adeka | Concentrated liquid detergent composition for automatic dishwasher and method for washing dishes with automatic dishwasher |
| CN113166565B (en) * | 2018-12-18 | 2024-03-08 | 圣诺普科有限公司 | Flash rust inhibitor |
| JP7356705B2 (en) * | 2019-10-25 | 2023-10-05 | 国立大学法人神戸大学 | Rust prevention sheet and rust prevention method |
| CN114890969B (en) * | 2022-06-07 | 2024-01-30 | 中原工学院 | Furanyl carboxylate compound and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6328888A (en) * | 1986-07-21 | 1988-02-06 | Sekisui Plastics Co Ltd | Production of foamable thermoplastic resin granule having rust preventing performance |
| JPH03240981A (en) * | 1990-02-15 | 1991-10-28 | Nisshin Steel Co Ltd | Discoloration preventive agent for steel sheet |
| WO2007037045A1 (en) * | 2005-09-28 | 2007-04-05 | Chubu Chelest Co., Ltd. | Metal rust preventive compound powder, process for producing the same, composition for metal rust prevention and film for metal rust prevention |
-
2009
- 2009-12-18 JP JP2009288434A patent/JP5531187B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011127202A (en) | 2011-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5531187B2 (en) | Rust-proof resin composition and rust-proof film | |
| JP5025133B2 (en) | Vaporizable rust preventive, molding material and molded article using the same | |
| CN101457363B (en) | Vapor phase corrosion inhibitors and method for their production | |
| EP1281790B1 (en) | Volatile corrosion inhibitors and process for making them | |
| CN109071974A (en) | For inhibiting the polymerization agent and composition of corrosion | |
| JP5154767B2 (en) | Rust preventive resin composition and rust preventive molding | |
| JP5568753B2 (en) | Resin composition for metal rust prevention, film for metal rust prevention and metal rust prevention method | |
| TW565600B (en) | Aqueous dispersion composition process for preparing the same, rust preventive, rust prevention method, and rust-proofed metallic products | |
| JP6263693B2 (en) | Metal rust preventive composition | |
| CN108385111A (en) | Compound vapour phase inhibitor and its preparation method and application | |
| US20030213936A1 (en) | Corrosion inhibiting formula and corrosion inhibiting articles using same | |
| JPS648019B2 (en) | ||
| TWI418658B (en) | Metal rust-preventive compound powder and its production method, and metal rust-proof composition and metal rust-proof film | |
| US20030207974A1 (en) | Tarnish inhibiting formula and tarnish inhibiting articles using same | |
| KR101214390B1 (en) | Volatile corrosion inhibitor packing reinforced anti-moisture penetration | |
| TWI418659B (en) | Metal packaging with anti - rust materials | |
| US20200283590A1 (en) | Resin molded product | |
| CN109554712B (en) | Composition of gas phase corrosion inhibitor and its use and preparation method | |
| JP5631542B2 (en) | Rust preventive | |
| JP5736283B2 (en) | Rust-proof laminated film | |
| KR20220000005A (en) | Manufacturing method of Aluminium vacuum packing material which has volatile corrosion inhibiting and Anti-static function | |
| JP2011047028A (en) | Composition of volatile corrosion inhibitor | |
| JPS58193377A (en) | Volatile corrosion inhibitor | |
| TW201527597A (en) | Volatile rust inhibitor composition | |
| JP7325040B2 (en) | Method for producing volatile rust inhibitor and volatile rust inhibitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121112 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20121112 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140109 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140114 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140225 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140305 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5531187 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |