JP2014109523A - Ink composition for hydrogen peroxide gas detection, and hydrogen peroxide gas detection indicator - Google Patents
Ink composition for hydrogen peroxide gas detection, and hydrogen peroxide gas detection indicator Download PDFInfo
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- JP2014109523A JP2014109523A JP2012264676A JP2012264676A JP2014109523A JP 2014109523 A JP2014109523 A JP 2014109523A JP 2012264676 A JP2012264676 A JP 2012264676A JP 2012264676 A JP2012264676 A JP 2012264676A JP 2014109523 A JP2014109523 A JP 2014109523A
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- hydrogen peroxide
- peroxide gas
- indicator
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000007789 gas Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000001514 detection method Methods 0.000 title claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 238000002845 discoloration Methods 0.000 claims abstract description 46
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 38
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 34
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000011787 zinc oxide Substances 0.000 claims abstract description 19
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 18
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 18
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 18
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 17
- 235000019359 magnesium stearate Nutrition 0.000 claims abstract description 17
- 230000001954 sterilising effect Effects 0.000 claims description 48
- 238000004659 sterilization and disinfection Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 30
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000003093 cationic surfactant Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 10
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical class C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 239000000976 ink Substances 0.000 description 51
- 239000000975 dye Substances 0.000 description 30
- 238000007639 printing Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- 239000004606 Fillers/Extenders Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BNGPVKSKKYIJCR-UHFFFAOYSA-N 2-chloro-1,3-dimethylimidazolidine;hydrochloride Chemical compound [Cl-].CN1CC[NH+](C)C1Cl BNGPVKSKKYIJCR-UHFFFAOYSA-N 0.000 description 2
- MSJLMQTXVKCUCD-UHFFFAOYSA-M 2-dodecylisoquinolin-2-ium;bromide Chemical compound [Br-].C1=CC=CC2=C[N+](CCCCCCCCCCCC)=CC=C21 MSJLMQTXVKCUCD-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004775 Tyvek Substances 0.000 description 2
- 229920000690 Tyvek Polymers 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- YSJGOMATDFSEED-UHFFFAOYSA-M behentrimonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C YSJGOMATDFSEED-UHFFFAOYSA-M 0.000 description 2
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000007644 letterpress printing Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- NDRLPYIMWROJBG-UHFFFAOYSA-M pyridin-1-ium-1-amine;iodide Chemical compound [I-].N[N+]1=CC=CC=C1 NDRLPYIMWROJBG-UHFFFAOYSA-M 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229920005792 styrene-acrylic resin Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BRVTVERRBKAUQL-UHFFFAOYSA-M 1-(3-methylhexyl)pyridin-1-ium;chloride Chemical compound [Cl-].CCCC(C)CC[N+]1=CC=CC=C1 BRVTVERRBKAUQL-UHFFFAOYSA-M 0.000 description 1
- CNQZEJATTBCPSL-UHFFFAOYSA-M 1-(3-methyloctyl)pyridin-1-ium;chloride Chemical compound [Cl-].CCCCCC(C)CC[N+]1=CC=CC=C1 CNQZEJATTBCPSL-UHFFFAOYSA-M 0.000 description 1
- AANCOISQVBSNFE-UHFFFAOYSA-M 1-(3-methylpentyl)pyridin-1-ium;chloride Chemical compound [Cl-].CCC(C)CC[N+]1=CC=CC=C1 AANCOISQVBSNFE-UHFFFAOYSA-M 0.000 description 1
- UTBPDHFBLINOEF-UHFFFAOYSA-M 1-(4-methylhexyl)pyridin-1-ium;chloride Chemical compound [Cl-].CCC(C)CCC[N+]1=CC=CC=C1 UTBPDHFBLINOEF-UHFFFAOYSA-M 0.000 description 1
- VFCHAZLGOMHZOU-GMFCBQQYSA-N 1-[2-[(z)-octadec-9-enyl]-4,5-dihydro-1h-imidazol-1-ium-1-yl]ethanol;chloride Chemical compound [Cl-].CCCCCCCC\C=C/CCCCCCCCC1=NCC[NH+]1C(C)O VFCHAZLGOMHZOU-GMFCBQQYSA-N 0.000 description 1
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- XUIICNWHMBNPKV-UHFFFAOYSA-N 1-chlorohexadecane;pyridine;hydrate Chemical compound O.C1=CC=NC=C1.CCCCCCCCCCCCCCCCCl XUIICNWHMBNPKV-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- ABFDKXBSQCTIKH-UHFFFAOYSA-M 1-ethylpyridin-1-ium;bromide Chemical compound [Br-].CC[N+]1=CC=CC=C1 ABFDKXBSQCTIKH-UHFFFAOYSA-M 0.000 description 1
- IGGJECTWQNIJLC-UHFFFAOYSA-N 1-hexadecylisoquinolin-2-ium;bromide Chemical compound [Br-].C1=CC=C2C(CCCCCCCCCCCCCCCC)=[NH+]C=CC2=C1 IGGJECTWQNIJLC-UHFFFAOYSA-N 0.000 description 1
- BTPXFUCYVMELJG-UHFFFAOYSA-N 1-hexadecylisoquinolin-2-ium;chloride Chemical compound [Cl-].C1=CC=C2C(CCCCCCCCCCCCCCCC)=[NH+]C=CC2=C1 BTPXFUCYVMELJG-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- JHYYWKUENNZTMD-UHFFFAOYSA-M 1-pyridin-1-ium-1-ylpropan-2-one;chloride Chemical compound [Cl-].CC(=O)C[N+]1=CC=CC=C1 JHYYWKUENNZTMD-UHFFFAOYSA-M 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ABFPKTQEQNICFT-UHFFFAOYSA-M 2-chloro-1-methylpyridin-1-ium;iodide Chemical compound [I-].C[N+]1=CC=CC=C1Cl ABFPKTQEQNICFT-UHFFFAOYSA-M 0.000 description 1
- WBXDKDRNXQVSGV-UHFFFAOYSA-M 2-dodecylisoquinolin-2-ium;chloride Chemical compound [Cl-].C1=CC=CC2=C[N+](CCCCCCCCCCCC)=CC=C21 WBXDKDRNXQVSGV-UHFFFAOYSA-M 0.000 description 1
- IMJBHWDMQIYCEI-UHFFFAOYSA-N 2-pyridin-1-ium-1-ylacetamide;chloride Chemical compound [Cl-].NC(=O)C[N+]1=CC=CC=C1 IMJBHWDMQIYCEI-UHFFFAOYSA-N 0.000 description 1
- HEJOROWXIWLCMS-UHFFFAOYSA-M 2-pyridin-1-ium-1-ylacetonitrile;chloride Chemical compound [Cl-].N#CC[N+]1=CC=CC=C1 HEJOROWXIWLCMS-UHFFFAOYSA-M 0.000 description 1
- NJIRSTSECXKPCO-UHFFFAOYSA-M 3-[n-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]anilino]propanenitrile;chloride Chemical compound [Cl-].C1=CC(N(CCC#N)C)=CC=C1\C=C\C1=[N+](C)C2=CC=CC=C2C1(C)C NJIRSTSECXKPCO-UHFFFAOYSA-M 0.000 description 1
- QMPUCZGGNKXEQF-UHFFFAOYSA-N 4-cyclohexyl-2-[[4-[1-[4-[(5-cyclohexyl-2-hydroxyphenyl)diazenyl]-3-methylphenyl]cyclohexyl]-2-methylphenyl]diazenyl]phenol Chemical compound C1(CCCCC1)(C1=CC(=C(C=C1)N=NC1=C(C=CC(=C1)C1CCCCC1)O)C)C1=CC(=C(C=C1)N=NC1=C(C=CC(=C1)C1CCCCC1)O)C QMPUCZGGNKXEQF-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- JMHWNJGXUIJPKG-UHFFFAOYSA-N CC(=O)O[SiH](CC=C)OC(C)=O Chemical compound CC(=O)O[SiH](CC=C)OC(C)=O JMHWNJGXUIJPKG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- LFZDEAVRTJKYAF-UHFFFAOYSA-L barium(2+) 2-[(2-hydroxynaphthalen-1-yl)diazenyl]naphthalene-1-sulfonate Chemical compound [Ba+2].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21.C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 LFZDEAVRTJKYAF-UHFFFAOYSA-L 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- JQZWHMOVSQRYRN-UHFFFAOYSA-M n-(2-chloroethyl)-n-ethyl-3-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].CC1=CC(N(CCCl)CC)=CC=C1C=CC1=[N+](C)C2=CC=CC=C2C1(C)C JQZWHMOVSQRYRN-UHFFFAOYSA-M 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000007793 ph indicator Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HAOKKJHTFUZWIM-UHFFFAOYSA-N pyridin-1-ium-2-amine;chloride Chemical compound Cl.NC1=CC=CC=N1 HAOKKJHTFUZWIM-UHFFFAOYSA-N 0.000 description 1
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- GMHCEDDZKAYPLB-UHFFFAOYSA-N pyridine-2-carboximidamide;hydrochloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=N1 GMHCEDDZKAYPLB-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Abstract
Description
本発明は、過酸化水素ガス検知用インキ組成物及び過酸化水素ガス検知インジケーターに関する。 The present invention relates to an ink composition for hydrogen peroxide gas detection and a hydrogen peroxide gas detection indicator.
病院、研究所等において使用される各種の器材、器具等は、消毒・殺菌のために滅菌処理が施される。その代表的な滅菌処理方法として過酸化水素ガスによる滅菌処理がある。
この滅菌処理では、滅菌処理が完了したかどうかを確認するためのインジケーターの設置が必要となる。具体的には、処理系内の雰囲気ガス濃度及び曝露時間に応じて変色するインジケーターを滅菌装置内に設置することが必要である。
Various equipment and instruments used in hospitals, laboratories and the like are sterilized for disinfection and sterilization. A typical sterilization method is sterilization with hydrogen peroxide gas.
In this sterilization process, it is necessary to install an indicator for confirming whether the sterilization process is completed. Specifically, it is necessary to install in the sterilizer an indicator that changes color according to the atmospheric gas concentration in the processing system and the exposure time.
上記インジケーターに関する従来技術としては、例えば主成分として過酢酸及び酢酸を含むガスを用いる低温ガスプラズマ滅菌において滅菌工程をモニタリングするに際し、ｐＨ指示薬の１種であるブロムフェノールブルーを用いてなるインジケーターが過酢酸又は酢酸ガスの作用によって晴青色から淡黄色に変色することにより滅菌処理を検知する方法（特許文献１）等が知られている。 As a conventional technique related to the above indicator, for example, when monitoring a sterilization process in low-temperature gas plasma sterilization using a gas containing peracetic acid and acetic acid as main components, an indicator using bromophenol blue, which is a kind of pH indicator, is excessive. A method of detecting sterilization by changing the color from bright blue to light yellow by the action of acetic acid or acetic acid gas (Patent Document 1) is known.
また、色素と変色助剤とバインダーとからなることを特徴とし、プラズマ滅菌法および過酸化水素ガス滅菌法により色調の変化を生じることを特徴とするインジケーターが知られている（特許文献２、特許文献３）。第一アミノ基及び第二アミノ基の少なくとも１種のアミノ基を有するアントラキノン系染料を含有するプラズマ滅菌検知用インキ組成物が知られている（特許文献２）。 Also known is an indicator characterized by comprising a dye, a color change aid and a binder, and causing a change in color tone by a plasma sterilization method and a hydrogen peroxide gas sterilization method (Patent Document 2, Patent). Reference 3). An ink composition for detection of plasma sterilization containing an anthraquinone dye having at least one amino group of a primary amino group and a secondary amino group is known (Patent Document 2).
さらに、特定の樹脂、色素からなることを特徴とし、過酸化水素ガス滅菌法により、過酸化水素ガス濃度に応じた変色をより確実に視認できるインジケーターが知られている（特許文献３）。
しかしながら、上記特許文献１のインジケーターは、滅菌による変色後にそのまま放置しておくと、変色後の色がもとの色に戻ることがあり、変色後の安定性という点では問題がある。インジケーターの変色がもとの色に戻ると、装置内に置かれた器材等が滅菌工程を経たか否かが不明になる。 However, if the indicator of Patent Document 1 is left as it is after discoloration due to sterilization, the color after discoloration may return to the original color, which is problematic in terms of stability after discoloration. When the discoloration of the indicator returns to the original color, it is unclear whether or not the equipment placed in the apparatus has undergone a sterilization process.
また、特許文献２〜３では、過酸化水素ガス曝露初期の変色の進行が比較的遅いため、過酸化水素濃度と時間の積算値であるCT値に応じた変色が起きるため、被処理物の滅菌状態を個々について知るためには非常に有用である。一方で、滅菌工程を通過したかどうかを表すプロセスインジケーターとしては、もっと低い過酸化水素暴露条件でもきっちり変色させることが必要となる。
実際には滅菌が完了していても、変色不良がおきてしまうことがある。
Moreover, in patent documents 2-3, since the progress of the discoloration at the initial stage of hydrogen peroxide gas exposure is relatively slow, discoloration occurs according to the CT value, which is an integrated value of the hydrogen peroxide concentration and time. It is very useful to know the sterilization status for each individual. On the other hand, as a process indicator indicating whether or not the sterilization process has passed, it is necessary to change the color precisely even under lower hydrogen peroxide exposure conditions.
In fact, even if sterilization is completed, discoloration defects may occur.
従って、本発明の主な目的は、低い過酸化水素ガスの濃度でも変色がより確実に視認できる過酸化水素ガス検知インジケーターを提供することにある。 Therefore, a main object of the present invention is to provide a hydrogen peroxide gas detection indicator that can be more reliably visually recognized even at a low hydrogen peroxide gas concentration.
本発明者は、従来技術の問題点を解決するために鋭意研究を重ねた結果、特定組成のインキ組成物を採用することによって、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the problems of the prior art, the present inventor has found that the above object can be achieved by employing an ink composition having a specific composition, and has completed the present invention. .
すなわち、本発明は、下記の過酸化水素ガス検知用インキ組成物及び過酸化水素ガス検知インジケーターに係る。
１． １）アルキルフェノール樹脂及びロジン系樹脂の少なくとも１種、２）メチン系染料及び３）酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種を含有する過酸化水素ガス検知用インキ組成物。
２． カチオン系界面活性剤をさらに含む、前記項１に記載の過酸化水素ガス検知用インキ組成物。
３． カチオン系界面活性剤が、アルキルトリメチルアンモニウム塩、イソキノリニウム塩、イミダゾリニウム塩及びピリジニウム塩から選ばれる少なくとも１種である、前記項２に記載の過酸化水素ガス検知用インキ組成物。
４． 樹脂バインダー（但し、アルキルフェノール樹脂及びロジン系樹脂を除く。）をさらに含む、前記項１〜３のいずれかに記載の過酸化水素ガス検知用インキ組成物。
５． 過酸化水素ガス雰囲気下で変色しない色素成分の少なくとも１種をさらに含む、前記項１〜４のいずれかに記載の過酸化水素ガス検知用インキ組成物。
６． 前記項１〜５のいずれかに記載のインキ組成物からなる変色層を含む、過酸化水素ガス検知インジケーター。
７． １）アルキルフェノール樹脂及びロジン系樹脂の少なくとも１種及び２）メチン系染料を含む変色インキと、酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種を予め塗布した基材からなる過酸化水素ガス検知インジケーター。
８． 変色インキ中に、カチオン系界面活性剤をさらに含む、前記項７に記載の過酸化水素ガス検知インジケーター。
９． カチオン系界面活性剤が、アルキルトリメチルアンモニウム塩、イソキノリニウム塩、イミダゾリニウム塩及びピリジニウム塩から選ばれる少なくとも１種である、前記項８に記載の過酸化水素ガス検知インジケーター。
１０．さらに過酸化水素ガス雰囲気下で変色しない非変色層を含む、前記項６〜９に記載のインジケーター。
１１． 前記変色層において、 50℃の温度で過酸化水素ガス15mg/Lに5分曝露したときにおける曝露前との色差ΔE*abが50以上である、前記項６〜１０に記載のインジケーター。
１２． 気体透過性包装体の内面に前記項６〜１１のいずれかに記載のインジケーターが設けられている過酸化水素ガス滅菌用包装体。
１３． インジケーターを外部から確認できるように、包装体の一部に透明窓部が設けられている、前記項１２に記載の包装体。
１４． 気体透過性包装体の外面に前記項６〜１１のいずれかに記載のインジケーター部が直接印刷されている過酸化水素ガス滅菌用包装体。
１５． 気体透過性包装体が、ポリエチレン系繊維により形成されている、前記項１２〜１４に記載の包装体。
１６． 前記項１２〜１５のいずれかに記載の包装体に被処理物を装填する工程、被処理物が装填された包装体を密封する工程、及び当該包装体を過酸化水素プラズマ滅菌雰囲気下に置く工程を有する過酸化水素ガス滅菌処理方法。
１７． 当該インジケーターの変色層が変色するまで過酸化水素ガス滅菌雰囲気下に包装体を置く、前記項１６に記載の方法。
That is, the present invention relates to the following hydrogen peroxide gas detection ink composition and hydrogen peroxide gas detection indicator.
1. 1) An ink composition for detecting hydrogen peroxide gas, comprising at least one of an alkylphenol resin and a rosin resin, 2) a methine dye, and 3) at least one of zinc oxide, magnesium stearate, and calcium carbonate.
2. Item 2. The ink composition for detecting hydrogen peroxide gas according to Item 1, further comprising a cationic surfactant.
3. Item 3. The ink composition for detecting hydrogen peroxide gas according to Item 2, wherein the cationic surfactant is at least one selected from alkyltrimethylammonium salts, isoquinolinium salts, imidazolinium salts, and pyridinium salts.
4). Item 4. The ink composition for detecting hydrogen peroxide gas according to any one of Items 1 to 3, further comprising a resin binder (excluding an alkylphenol resin and a rosin resin).
5. Item 5. The ink composition for detecting hydrogen peroxide gas according to any one of Items 1 to 4, further comprising at least one dye component that does not change color in a hydrogen peroxide gas atmosphere.
6). A hydrogen peroxide gas detection indicator comprising a discoloration layer comprising the ink composition according to any one of Items 1 to 5.
7). 1) Hydrogen peroxide gas detection comprising a discoloration ink containing at least one of an alkylphenol resin and a rosin resin and 2) a discoloration ink containing a methine dye and at least one of zinc oxide, magnesium stearate, and calcium carbonate. indicator.
8). Item 8. The hydrogen peroxide gas detection indicator according to Item 7, further comprising a cationic surfactant in the discoloration ink.
9. Item 9. The hydrogen peroxide gas detection indicator according to Item 8, wherein the cationic surfactant is at least one selected from alkyltrimethylammonium salts, isoquinolinium salts, imidazolinium salts, and pyridinium salts.
10. Item 10. The indicator according to Items 6 to 9, further comprising a non-color-changing layer that does not change color in a hydrogen peroxide gas atmosphere.
11. Item 10. The indicator according to Items 6 to 10, wherein the color-change layer has a color difference ΔE * ab of 50 or more when exposed to hydrogen peroxide gas 15 mg / L for 5 minutes at a temperature of 50 ° C. for 5 minutes.
12 A package for hydrogen peroxide gas sterilization, wherein the indicator according to any one of Items 6 to 11 is provided on the inner surface of the gas permeable package.
13. Item 13. The package according to Item 12, wherein a transparent window is provided in a part of the package so that the indicator can be confirmed from the outside.
14 12. A package for sterilization of hydrogen peroxide gas, wherein the indicator part according to any one of Items 6 to 11 is directly printed on the outer surface of the gas permeable package.
15. Item 15. The package according to any one of Items 12 to 14, wherein the gas permeable package is formed of polyethylene fiber.
16. The step of loading a workpiece into the package according to any one of Items 12 to 15, the step of sealing the package loaded with the workpiece, and placing the package in a hydrogen peroxide plasma sterilization atmosphere A hydrogen peroxide gas sterilization method having a step.
17. Item 17. The method according to Item 16, wherein the package is placed in a hydrogen peroxide gas sterilization atmosphere until the color change layer of the indicator changes color.
本発明インキ組成物及びそれによるインジケーターは、１）アルキルフェノール樹脂及びロジン系樹脂の少なくとも１種、２）メチン系染料及び３）酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種との組み合わせを採用しているので、それを用いて変色層を形成した場合、過酸化水素ガス濃度等に応じた変色が視認できるという効果が得られる。すなわち、従来技術では、過酸化水素が低い段階では変色しきっておらず、プロセスインジケーターとしては使用することができなかったのに対し、本発明の変色層では、低い過酸化水素濃度でも十分に変色することができるため、プロセスインジケーターとして使用することができる。 The ink composition of the present invention and the indicator thereby employ a combination of 1) at least one of alkylphenol resin and rosin resin, 2) methine dye, and 3) at least one of zinc oxide, magnesium stearate and calcium carbonate. Therefore, when a discoloration layer is formed using it, the effect that the discoloration according to the hydrogen peroxide gas density | concentration etc. can be visually recognized is acquired. That is, in the prior art, the color change was not complete at the low hydrogen peroxide stage and could not be used as a process indicator, whereas the color change layer of the present invention was sufficiently discolored even at a low hydrogen peroxide concentration. Can be used as a process indicator.
１．過酸化水素ガス検知用インキ組成物
本発明の過酸化水素ガス検知用インキ組成物は、１）アルキルフェノール樹脂及びロジン系樹脂の少なくとも１種、２）メチン系染料及び３）酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種を含有することを特徴とする。酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種は、予め基材に塗布してもよい。
1. Ink composition for detecting hydrogen peroxide gas The ink composition for detecting hydrogen peroxide gas of the present invention includes 1) at least one of alkylphenol resin and rosin resin, 2) methine dye, and 3) zinc oxide. And at least one of magnesium stearate and calcium carbonate. At least one of zinc oxide, magnesium stearate, and calcium carbonate may be applied to the substrate in advance.
メチン系染料
本発明組成物では、着色剤（変色色素）として少なくともメチン系染料を用いる。メチン系染料としては、メチン基を有する染料であれば良い。従って、本発明において、ポリメチン系染料、シアニン系染料等もメチン系染料に包含される。これらは、公知又は市販のメチン系染料から適宜採用することができる。具体的には、C.I.Basic Red 12、C.I.Basic Red 13、C.I.Basic Red 14、C.I.Basic Red 15、C.I.Basic Red 27、C.I.Basic Red 35、C.I.Basic Red 36、C.I.Basic Red 37、C.I.Basic Red 45、C.I.Basic Red 48、C.I.Basic Yellow 11、C.I.Basic Yellow 12、C.I.Basic Yellow 13、C.I.Basic Yellow 14、C.I.Basic Yellow 21、C.I.Basic Yellow 22、C.I.Basic Yellow 23、C.I.Basic Yellow 24、C.I.Basic Violet 7、C.I.Basic Violet 15、C.I.Basic Violet 16、C.I.Basic Violet 20、C.I.Basic Violet 21、C.I.Basic Violet 39、C.I.Basic Blue 62、C.I.Basic Blue 63等を挙げることができる。これらは、１種又は２種以上で用いることができる。
Methine dye In the composition of the present invention, at least a methine dye is used as a colorant (discoloration pigment). The methine dye may be a dye having a methine group. Therefore, in the present invention, polymethine dyes, cyanine dyes and the like are also included in the methine dyes. These can be appropriately selected from known or commercially available methine dyes. Specifically, CIBasic Red 12, CIBasic Red 13, CIBasic Red 14, CIBasic Red 15, CIBasic Red 27, CIBasic Red 35, CIBasic Red 36, CIBasic Red 37, CIBasic Red 45, CIBasic Red 48, CIBasic Yellow 11, CIBasic Yellow 12, CIBasic Yellow 13, CIBasic Yellow 14, CIBasic Yellow 21, CIBasic Yellow 22, CIBasic Yellow 23, CIBasic Yellow 24, CIBasic Violet 7, CIBasic Violet 15, CIBasic Violet 16, CIBasic Violet 20, CIBasic Violet 21, CIBasic Violet 39 CIBasic Blue 62, CIBasic Blue 63, and the like. These can be used alone or in combination of two or more.
上記染料の含有量は、所望の色相等に応じて適宜決定できるが、一般的には本発明組成物中０．０５〜５重量％程度、特に０．１〜１重量％とすることが望ましい。 The content of the dye can be appropriately determined according to the desired hue and the like, but is generally about 0.05 to 5% by weight, particularly preferably 0.1 to 1% by weight in the composition of the present invention. .
本発明では、メチン系染料以外の染料又は顔料を併存させても良い。特に、過酸化水素ガス雰囲気下で変色しない色素成分（「非変色色素」という）を含有させても良い。これによって、ある色から他の色への色調の変化により視認効果をいっそう高めることができる。非変色色素としては、公知のインキ（普通色インキ）を使用することができる。この場合の非変色色素の含有量は、その非変色色素の種類等に応じて適宜設定すれば良い。 In the present invention, dyes or pigments other than methine dyes may coexist. In particular, a pigment component that does not change color in a hydrogen peroxide gas atmosphere (referred to as “non-color-change pigment”) may be included. Thereby, the visual recognition effect can be further enhanced by a change in color tone from one color to another. A known ink (ordinary color ink) can be used as the non-color-changing dye. What is necessary is just to set suitably content of the non-color-change pigment | dye in this case according to the kind etc. of the non-color-change pigment | dye.
アルキルフェノール樹脂、ロジン系樹脂
本発明組成物では、アルキルフェノール樹脂及びロジン系樹脂の少なくとも１種を用いる。これらの樹脂を用いることによって、染料の反応速度（変色速度）の調整、変色層の接着性付与等を効果的に行うことができる。
Alkylphenol resin, rosin resin In the composition of the present invention, at least one of an alkylphenol resin and a rosin resin is used. By using these resins, it is possible to effectively adjust the reaction rate (discoloration rate) of the dye, impart adhesion to the discoloration layer, and the like.
アルキルフェノール樹脂及びロジン系樹脂の種類及び性状は限定的でなく、公知又は市販のものを使用することができる。アルキルフェノール樹脂及びロジン系樹脂の含有量は、用いる着色剤の種類等に応じて適宜決定できるが、一般的には本発明インキ組成物中５０重量％以下程度、特に１〜３５重量％とすることが望ましい。 The types and properties of the alkylphenol resin and the rosin resin are not limited, and known or commercially available products can be used. The content of the alkylphenol resin and the rosin resin can be appropriately determined according to the type of the colorant to be used, but is generally about 50% by weight or less, particularly 1 to 35% by weight in the ink composition of the present invention. Is desirable.
酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウム
本発明インキ組成物では、酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種を用いる。これらの物質を用いることによって、染料の反応速度（変色速度）を促進することができる。
Zinc oxide, magnesium stearate, calcium carbonate In the ink composition of the present invention, at least one of zinc oxide, magnesium stearate, and calcium carbonate is used. By using these substances, the reaction rate (discoloration rate) of the dye can be accelerated.
酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの含有量は、用いる着色剤の種類等に応じて適宜決定できるが、一般的には本発明組成物中０．０１〜３０重量％程度、好ましくは０．０５〜１０重量％とすることが望ましい。さらに好ましくは０．１〜１
重量％が望ましい。０．０５重量％未満のときは、変色促進の効果がなく、１０重量％を超えるときも変色促進の効果がなくなる。
The content of zinc oxide, magnesium stearate, and calcium carbonate can be determined as appropriate according to the type of colorant used, but is generally about 0.01 to 30% by weight in the composition of the present invention, preferably 0.8. It is desirable to set it as 05 to 10 weight%. More preferably 0.1-1
% By weight is desirable. When the amount is less than 0.05% by weight, there is no effect of promoting discoloration.
カチオン系界面活性剤
本発明インキ組成物は、カチオン系界面活性剤を含有することが好ましい。上記カチオン系界面活性剤としては、特に制限されないが、特にアルキルアンモニウム塩、イソキノリニウム塩、イミダゾリニウム塩及びピリジニウム塩の少なくとも１種を用いることが望ましい。これらは、公知もの又は市販品も使用できる。本発明では、これらカチオン系界面活性剤を前記の着色剤と併用することによって、より優れた検知感度を得ることができる。
Cationic surfactant The ink composition of the present invention preferably contains a cationic surfactant. The cationic surfactant is not particularly limited, but at least one of alkylammonium salt, isoquinolinium salt, imidazolinium salt and pyridinium salt is preferably used. These may be known or commercially available products. In the present invention, a superior detection sensitivity can be obtained by using these cationic surfactants together with the colorant.
アルキルアンモニウム塩の中でも、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩等が好ましい。具体的には、塩化ヤシアルキルトリメチルアンモニウム、塩化牛脂アルキルトリメチルアンモニウム、塩化ベヘニルトリメチルアンモニウム、塩化ヘキサデシルトリメチルアンモニウム、塩化ラウリルトリメチルアンモニウム、塩化オクタデシルトリメチルアンモニウム、塩化ジオクチルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化アルキルベンジルジメチルアンモニウム等が挙げられる。特に、塩化ベヘニルトリメチルアンモニウム、塩化ラウリルトリメチルアンモニウム等が好ましい。イソキノリニウム塩としては、例えばラウリルイソキノリニウムブロマイド、セチルイソキノリニウムブロマイド、セチルイソキノリニウムクロライド、ラウリルイソキノリニウムクロライド等が挙げられる。この中でも、特にラウリルイソキノリニウムブロマイドが好ましい。 Of the alkylammonium salts, alkyltrimethylammonium salts and dialkyldimethylammonium salts are preferred. Specifically, palm alkyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, lauryltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, chloride Examples thereof include alkylbenzyldimethylammonium. In particular, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride and the like are preferable. Examples of the isoquinolinium salt include lauryl isoquinolinium bromide, cetyl isoquinolinium bromide, cetyl isoquinolinium chloride, lauryl isoquinolinium chloride and the like. Among these, lauryl isoquinolinium bromide is particularly preferable.
イミダゾリニウム塩としては、例えば１−ヒドロキシエチル−２−オレイルイミダゾリニウムクロライド、２−クロロ−１，３−ジメチルイミダゾリニウムクロライド等が挙げられる。この中でも、特に２−クロロ−１，３−ジメチルイミダゾリニウムクロライドが好ましい。 Examples of the imidazolinium salt include 1-hydroxyethyl-2-oleylimidazolinium chloride and 2-chloro-1,3-dimethylimidazolinium chloride. Among these, 2-chloro-1,3-dimethylimidazolinium chloride is particularly preferable.
ピリジニウム塩としては、例えばピリジニウムクロライド、１−エチルピリジニウムブロマイド、ヘキサデシルピリジニウムクロライド、セチルピリジニウムクロライド、１−ブチルピリジニウムクロライド、Ｎ−ｎ−ブチルピリジニウムクロライド、ヘキサデシルピリジニウムブロマイド、Ｎ−ヘキサデシルピリジニウムブロマイド、１−ドデシルピリジニウムクロライド、３−メチルヘキシルピリジニウムクロライド、４−メチルヘキシルピリジニウムクロライド、３−メチルオクチルピリジニウムクロライド、２−クロロ−１−メチルピリジニウムアイオダイド、３，４−ジメチルブチルピリジニウムクロリド、ピリジニウム−ｎ−ヘキサデシルクロリド−水和物、Ｎ−（シアノメチル）ピリジニウムクロリド、Ｎ−アセトニルピリジニウムブロマイド、１−（アミノホルミルメチル）ピリジニウムクロライド、２−アミジノピリジニウムクロライド、２−アミノピリジニウムクロライド、Ｎ−アミノピリジニウムアイオダイド、１−アミノピリジニウムアイオダイド、１−アセトニルピリジニウムクロリド、Ｎ−アセトニルピリジニウムブロマイド等が挙げられる。この中でも、特にヘキサデシルピリジニウムクロライドが好ましい。 Examples of the pyridinium salt include pyridinium chloride, 1-ethylpyridinium bromide, hexadecylpyridinium chloride, cetylpyridinium chloride, 1-butylpyridinium chloride, Nn-butylpyridinium chloride, hexadecylpyridinium bromide, N-hexadecylpyridinium bromide, 1-dodecylpyridinium chloride, 3-methylhexylpyridinium chloride, 4-methylhexylpyridinium chloride, 3-methyloctylpyridinium chloride, 2-chloro-1-methylpyridinium iodide, 3,4-dimethylbutylpyridinium chloride, pyridinium-n -Hexadecyl chloride-hydrate, N- (cyanomethyl) pyridinium chloride, N-acetonyl pyridi Umbromide, 1- (aminoformylmethyl) pyridinium chloride, 2-amidinopyridinium chloride, 2-aminopyridinium chloride, N-aminopyridinium iodide, 1-aminopyridinium iodide, 1-acetonylpyridinium chloride, N-acetonyl Examples include pyridinium bromide. Among these, hexadecylpyridinium chloride is particularly preferable.
カチオン系界面活性剤の含有量は、上記界面活性剤の種類、用いる着色剤の種類等に応じて適宜決定できるが、一般的には本発明組成物中０〜１５重量％程度、特に０．１〜１０重量％とすることが望ましい。 The content of the cationic surfactant can be appropriately determined according to the type of the surfactant, the type of the colorant to be used, and the like. It is desirable to be 1 to 10% by weight.
樹脂バインダー、増量剤等
本発明のインキ組成物では、必要に応じて樹脂バインダー（但し、アルキルフェノール樹脂及びロジン系樹脂を除く。）、増量剤、溶剤、レベリング剤、消泡剤、紫外線吸収剤、表面調整剤等の公知のインキに用いられている成分を適宜配合することができる。
Resin binder, extender, etc. In the ink composition of the present invention, if necessary, a resin binder (excluding alkylphenol resin and rosin resin), extender, solvent, leveling agent, antifoaming agent, Components used in known inks such as ultraviolet absorbers and surface conditioners can be appropriately blended.
樹脂バインダーとしては、基材の種類等に応じて適宜選択すれば良く、例えば筆記用、印刷用等のインキ組成物に用いられている公知の樹脂成分をそのまま採用できる。具体的には、例えばポリアミド樹脂、マレイン酸樹脂、ケトン樹脂、ポリビニルブチラール、セルロース系樹脂、ポリエステル系樹脂、スチレンマレイン酸樹脂、スチレンアクリル酸樹脂、アクリル系樹脂等を挙げることができる。 The resin binder may be appropriately selected according to the type of the base material and the like. For example, known resin components used in ink compositions for writing and printing can be employed as they are. Specific examples include polyamide resins, maleic resins, ketone resins, polyvinyl butyral, cellulose resins, polyester resins, styrene maleic resins, styrene acrylic resins, and acrylic resins.
樹脂バインダーの含有量は、樹脂バインダーの種類、用いる着色剤の種類等に応じて適宜決定できるが、一般的には本発明組成物中５０重量％程度以下、特に５〜３５重量％とすることが望ましい。 The content of the resin binder can be appropriately determined according to the type of the resin binder, the type of the colorant to be used, etc., but is generally about 50% by weight or less, particularly 5 to 35% by weight in the composition of the present invention. Is desirable.
増量剤としては、特に制限されず、例えばベントナイト、活性白土、酸化アルミニウム、シリカ、シリカゲル等の無機材料を挙げることができる。その他にも公知の体質顔料として知られている材料を用いることができる。この中でも、シリカ、シリカゲル及びアルミナの少なくもと１種が好ましい。特にシリカがより好ましい。シリカ等を使用する場合には、特に変色層表面に複数のクラックを効果的に生じさせることができる。その結果、インジケーターの検知感度をより高めることができる。 The extender is not particularly limited, and examples thereof include inorganic materials such as bentonite, activated clay, aluminum oxide, silica, and silica gel. In addition, materials known as known extender pigments can be used. Among these, at least one of silica, silica gel and alumina is preferable. In particular, silica is more preferable. When silica or the like is used, a plurality of cracks can be effectively generated particularly on the surface of the color changing layer. As a result, the detection sensitivity of the indicator can be further increased.
増量剤の含有量は、用いる増量剤の種類、用いる着色剤の種類等に応じて適宜決定できるが、一般的には本発明組成物中０．１〜３０重量％程度、特に０．５〜２０重量％とすることが望ましい。 The content of the extender can be appropriately determined according to the type of extender used, the type of colorant used, and the like, but is generally about 0.1 to 30% by weight in the composition of the present invention, particularly 0.5 to 20% by weight is desirable.
本発明で使用できる溶剤としては、通常、印刷用、筆記用等のインキ組成物に用いられる溶剤であればいずれも使用できる。例えば、アルコール又は多価アルコール系、エステル系、エーテル系、ケトン系、炭化水素系、グリコールエーテル系等の各種溶剤が使用でき、使用する染料、樹脂系バインダーの溶解性等に応じて適宜選択すれば良い。
溶剤の含有量は、用いる溶剤の種類、用いる着色剤の種類等に応じて適宜決定できるが、一般的には本発明組成物中４０〜９５重量％程度、特に６０〜９０重量％とすることが望ましい。
As the solvent that can be used in the present invention, any solvent that is usually used in ink compositions for printing, writing, etc. can be used. For example, various solvents such as alcohols or polyhydric alcohols, esters, ethers, ketones, hydrocarbons, glycol ethers, etc. can be used, and they are appropriately selected according to the dye used, the solubility of the resin binder, etc. It ’s fine.
The content of the solvent can be appropriately determined according to the type of solvent used, the type of colorant used, etc., but is generally about 40 to 95% by weight, particularly 60 to 90% by weight in the composition of the present invention. Is desirable.
これら各成分は、同時に又は順次に配合し、ホモジナイザー、デゾルバー等の公知の攪拌機を用いて均一に混合すれば良い。例えば、まず溶剤に前記着色剤、必要に応じてカチオン系界面活性剤、樹脂系バインダー、増量剤等を順に配合し、攪拌機により混合・攪拌すれば良い。 These components may be blended simultaneously or sequentially and mixed uniformly using a known stirrer such as a homogenizer or a dissolver. For example, the colorant, a cationic surfactant, a resin binder, an extender and the like may be blended in the solvent in order, and mixed and stirred with a stirrer.
２．過酸化水素ガス検知インジケーター
本発明のインジケーターは、前記の本発明インキ組成物からなる変色層を含む。一般的には、基材上に本発明インキ組成物を塗布又は印刷することによって変色層を形成することができる。もしくは、酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種を予め塗布した基材上に本発明インキ組成物を塗布又は印刷してもよい。この場合の基材としては、変色層を形成できるものであれば特に制限されない。例えば、金属又は合金、セラミックス、ガラス、コンクリート、プラスチックス（ポリエチレンテレフタレート（ＰＥＴ）、ポリプロピレン、ナイロン、ポリスチレン等）、繊維類（不織布、織布、その他の繊維シート）、これらの複合材料等を用いることができる。また、ポリプロピレン合成紙、ポリエチレン合成紙等の合成樹脂繊維紙（合成紙）も好適に用いることができる。
2. Hydrogen peroxide gas detection indicator The indicator of the present invention includes a discoloration layer comprising the above-described ink composition of the present invention. Generally, a discoloration layer can be formed by apply | coating or printing the ink composition of this invention on a base material. Alternatively, the ink composition of the present invention may be applied or printed on a substrate on which at least one of zinc oxide, magnesium stearate, and calcium carbonate has been previously applied. The substrate in this case is not particularly limited as long as it can form a discoloration layer. For example, metals or alloys, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, etc.), fibers (nonwoven fabric, woven fabric, other fiber sheets), composite materials of these, etc. are used. be able to. Moreover, synthetic resin fiber paper (synthetic paper) such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used.
本発明における変色層は、色が他の色に変化するもののほか、色が退色又は消色するものも包含される。 The color changing layer in the present invention includes not only the color changing to another color but also the color fading or erasing.
変色層の形成は、本発明インキ組成物を用い、シルクスクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷、フレキソ印刷等の公知の印刷方法に従って行うことができる。また、印刷以外の方法でも形成できる。例えば、基材をインキ組成物中に浸漬することによって変色層を形成することもできる。不織布等のようにインキが浸透する材料には特に好適である。 The discoloration layer can be formed by using the ink composition of the present invention according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing and the like. It can also be formed by methods other than printing. For example, the discoloration layer can be formed by immersing the substrate in the ink composition. It is particularly suitable for a material into which ink penetrates, such as a nonwoven fabric.
変色層は、50℃の温度で過酸化水素ガス15mg/Lに5分曝露したときにおける曝露前との色差ΔE*abが50以上であることが好ましい。
かかる変色度合が維持されることによって、より確実に変色を視認することができる。すなわち、被処理物の材質、状態、滅菌処理装置への積載量などの条件によらず、滅菌工程を通過したことを目視で判断することができる。このような変色性能は、１）アルキルフェノール樹脂及びロジン系樹脂の少なくとも１種、２）メチン系染料及び３）酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種との組み合わせによって得ることができる。酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種はインキ中にあっても良いし、予めバインダー樹脂を使って基材に塗布しても良い。
The discolored layer preferably has a color difference ΔE * ab of 50 or more when exposed to hydrogen peroxide gas 15 mg / L for 5 minutes at a temperature of 50 ° C. before exposure.
By maintaining such a degree of color change, the color change can be visually recognized more reliably. That is, it is possible to visually determine that the sterilization process has been passed regardless of conditions such as the material and state of the object to be processed and the load on the sterilization apparatus. Such discoloration performance can be obtained by a combination of 1) at least one of an alkylphenol resin and a rosin resin, 2) a methine dye, and 3) at least one of zinc oxide, magnesium stearate, and calcium carbonate. At least one of zinc oxide, magnesium stearate, and calcium carbonate may be in the ink, or may be applied to the substrate in advance using a binder resin.
本発明では、さらに過酸化水素ガス滅菌雰囲気下で変色しない非変色層が基材上及び／又は変色層上に形成されていても良い。非変色層は、通常は市販の普通色インキにより形成することができる。例えば、水性インキ、油性インキ、無溶剤型インキ等を用いることができる。非変色層の形成に用いるインキには、公知のインキに配合されている成分、例えば樹脂バインダー、増量剤、溶剤等が含まれていても良い。 In the present invention, a non-discoloring layer that does not change color in a hydrogen peroxide gas sterilization atmosphere may be formed on the substrate and / or the discoloring layer. The non-discoloring layer can be usually formed with a commercially available ordinary color ink. For example, water-based ink, oil-based ink, solventless ink, and the like can be used. The ink used for forming the non-discoloring layer may contain components blended in known inks, such as resin binders, extenders, solvents, and the like.
非変色層の形成は、変色層の場合と同様にすれば良い。例えば、普通色インキを用い、シルクスクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷、フレキソ印刷等の公知の印刷方法に従って行うことができる。なお、変色層・非変色層の印刷の順序は特に制限されず、印刷するデザイン等に応じて適宜選択すれば良い。 The non-discoloring layer may be formed in the same manner as in the discoloring layer. For example, normal color ink can be used according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, or flexographic printing. The order of printing of the color changing layer and the non-color changing layer is not particularly limited, and may be appropriately selected according to the design to be printed.
本発明インジケーターでは、変色層及び非変色層をそれぞれ１層ずつ形成しても良いし、あるいはそれぞれ複数層形成しても良い。また、変色層どうし又は非変色層どうしを積層しても良い。この場合、変色層どうしが互いに同じ組成であっても又は異なる組成であっても良い。同様に、非変色層どうしが互いに同じ組成であっても又は異なる組成であっても良い。 In the indicator of the present invention, one color changing layer and one non-color changing layer may be formed, or a plurality of layers may be formed. Further, discoloration layers or non-discoloration layers may be laminated. In this case, the discoloration layers may have the same composition or different compositions. Similarly, the non-discoloring layers may have the same composition or different compositions.
さらに、変色層及び非変色層は、基材又は各層の全面に形成しても良く、あるいは部分的に形成しても良い。これらの場合、特に変色層の変色を確保するために、少なくとも１つの変色層の一部又は全部が過酸化水素ガス雰囲気に晒されるように変色層及び非変色層を形成すれば良い。 Furthermore, the color-changing layer and the non-color-changing layer may be formed on the entire surface of the substrate or each layer, or may be partially formed. In these cases, in particular, in order to ensure the color change of the color change layer, the color change layer and the non-color change layer may be formed so that a part or all of at least one color change layer is exposed to the hydrogen peroxide gas atmosphere.
本発明では、過酸化水素ガス滅菌処理の完了が確認できる限り、変色層と非変色層とをどのように組み合わせても良い。例えば、変色層の変色によりはじめて変色層と非変色層の色差が識別できるように変色層及び非変色層を形成したり、あるいは変色によってはじめて変色層及び非変色層との色差が消滅するように形成することもできる。本発明では、特に、変色によってはじめて変色層と非変色層との色差が識別できるように変色層及び非変色層を形成することが好ましい。 In the present invention, the discoloration layer and the non-discoloration layer may be combined in any way as long as the completion of the hydrogen peroxide gas sterilization process can be confirmed. For example, a color-changing layer and a non-color-changing layer are formed so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only after the color-changing layer is changed, or a color difference between the color-changing layer and the non-color-changing layer disappears only after the color change. It can also be formed. In the present invention, it is particularly preferable to form the color-changing layer and the non-color-changing layer so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only by the color change.
色差が識別できるようにする場合には、例えば変色層の変色によりはじめて文字、図柄及び記号の少なくとも１種が現れるように変色層及び非変色層を形成すれば良い。本発明では、文字、図柄及び記号は、変色を知らせるすべての情報を包含する。これら文字等は、使用目的等に応じて適宜デザインすれば良い。 In order to identify the color difference, for example, the color-changing layer and the non-color-changing layer may be formed so that at least one of a character, a pattern, and a symbol appears only when the color-changing layer changes. In the present invention, characters, designs, and symbols include all information that informs discoloration. What is necessary is just to design these characters etc. suitably according to the purpose of use.
また、変色前における変色層と非変色層とを互いに異なる色としても良い。例えば、両者を実質的に同じ色とし、変色後にはじめて変色層と非変色層との色差（コントラスト）が識別できるようにしても良い。 Further, the color changing layer and the non-color changing layer before the color change may be different from each other. For example, they may be substantially the same color so that the color difference (contrast) between the color-change layer and the non-color-change layer can be identified only after the color change.
本発明インジケーターでは、変色層と非変色層とが重ならないように変色層及び非変色層を形成することができる。これにより、使用するインキ量を節約することが可能である。 In the indicator of the present invention, the color changing layer and the non-color changing layer can be formed so that the color changing layer and the non-color changing layer do not overlap. As a result, the amount of ink used can be saved.
さらに、本発明では、変色層及び非変色層の少なくとも一方の層上にさらに変色層又は非変色層を形成しても良い。例えば、変色層と非変色層とが重ならないように変色層及び非変色層を形成した層（「変色−非変色層」という）の上からさらに別のデザインを有する変色層を形成すれば、変色−非変色層における変色層及び非変色層の境界線が実質的に識別できない状態にすることができるので、より優れた意匠性を達成することができる。 Furthermore, in the present invention, a color changing layer or a non-color changing layer may be further formed on at least one of the color changing layer and the non-color changing layer. For example, if a color-changing layer having a different design is formed on a layer in which the color-changing layer and the non-color-changing layer are formed so as not to overlap the color-changing layer and the non-color-changing layer (referred to as “color-changing-non-color-changing layer”), Since the boundary line between the color changing layer and the non-color changing layer in the color changing-non-color changing layer can be made substantially indistinguishable, a more excellent design can be achieved.
本発明のインジケーターは、過酸化水素ガス雰囲気下で行う滅菌処理であればいずれにも適用できる。従って、過酸化水素ガス滅菌処理装置におけるインジケーターとして有用である。例えば、インジケーターの使用に際しては、市販の滅菌装置内に本発明インジケーターを置き、滅菌処理すべき器材等とともに滅菌処理雰囲気下に晒せば良い。この場合、装置内に置かれたインジケーターの変色により所定の滅菌処理が行われたことを検知することができる。 The indicator of the present invention can be applied to any sterilization treatment performed in a hydrogen peroxide gas atmosphere. Therefore, it is useful as an indicator in a hydrogen peroxide gas sterilization apparatus. For example, when using the indicator, the indicator of the present invention may be placed in a commercially available sterilization apparatus and exposed to a sterilization atmosphere together with equipment to be sterilized. In this case, it is possible to detect that a predetermined sterilization process has been performed by changing the color of an indicator placed in the apparatus.
３．包装体
本発明は、気体透過性包装体の内面に本発明のインジケーターが設けられている過酸化水素ガス滅菌用包装体を包含する。
気体透過性包装体は、その中に被処理物を封入したままで過酸化水素ガス滅菌できる包装体が好ましい。これは、例えば過酸化水素滅菌用包装体（パウチ）として使用されている公知又は市販のものを使用することができる。例えば、ポリエチレン系繊維（ポリエチレン合成紙）により形成されている包装体を好適に用いることができる。この包装体に被処理物を入れ、開口部をヒートシール等により密閉した後、包装体ごと滅菌処理装置中で滅菌処理することができる。
3. Packaging The present invention includes a packaging for hydrogen peroxide gas sterilization in which the indicator of the present invention is provided on the inner surface of a gas permeable packaging.
The gas permeable package is preferably a package that can be sterilized with hydrogen peroxide gas while the object to be processed is sealed therein. For example, a known or commercially available product used as a package (pouch) for hydrogen peroxide sterilization can be used. For example, a package formed of polyethylene fibers (polyethylene synthetic paper) can be suitably used. After putting an object to be processed into this package and sealing the opening by heat sealing or the like, the entire package can be sterilized in a sterilization apparatus.
本発明インジケーターは、上記包装体の内面に配置すればよい。配置する方法は限定的でなく、接着剤、ヒートシール等による方法のほか、本発明インキ組成物を直接に包装体の内面に塗布又は印刷することによりインジケーターを構成することもできる。また、上記塗布又は印刷による場合は、包装体の製造段階でインジケーターを形成しておくこともできる。 What is necessary is just to arrange | position this invention indicator to the inner surface of the said package. The arrangement method is not limited, and the indicator can also be constituted by applying or printing the ink composition of the present invention directly on the inner surface of the package, in addition to a method using an adhesive, heat sealing, or the like. Moreover, in the case of the application or printing, an indicator can be formed at the manufacturing stage of the package.
本発明包装体では、インジケーターを外部から確認できるように、包装体の一部に透明窓部が設けられていることが望ましい。例えば、包装体を透明シートと前記ポリエチレン合成紙で作製し、その透明シートを通して視認できるような位置に包装体内面にインジケーターを形成すれば良い。 In the package of the present invention, it is desirable that a transparent window is provided in a part of the package so that the indicator can be confirmed from the outside. For example, the package may be made of a transparent sheet and the polyethylene synthetic paper, and the indicator may be formed on the inner surface of the package at a position where it can be visually recognized through the transparent sheet.
また、上記包装体の外面に直接インジケーターを印刷してもよい。 Moreover, you may print an indicator directly on the outer surface of the said package.
本発明の包装体を用いて滅菌処理する場合、例えば包装体に被処理物を装填する工程、被処理物が装填された包装体を密封する工程、及び当該包装体を過酸化水素ガス滅菌雰囲気下に置く工程を有する方法によれば良い。より具体的には、被処理物（医療器具、食品等）を包装体に入れた後、ヒートシール等の公知の方法に従って密封する。次いで、その包装体ごと過酸化水素ガス滅菌雰囲気下に配置する。例えば、公知又は市販の滅菌装置（例えば過酸化水素低温プラズマ滅菌システム）の滅菌室に配置し、滅菌処理を行う。滅菌処理が終了した後は、包装体ごと取り出し、そのまま使用時まで包装体中で保管することができる。この場合、滅菌処理は、インジケーターの変色層が変色するまで過酸化水素ガス滅菌雰囲気下に包装体を置くことが好ましい。 When sterilizing using the package of the present invention, for example, a step of loading an object to be processed into the package, a step of sealing the package loaded with the object to be processed, and an atmosphere of sterile hydrogen peroxide gas A method having a step of placing underneath may be used. More specifically, after an object to be processed (medical instrument, food, etc.) is put in a package, it is sealed according to a known method such as heat sealing. Next, the whole package is placed in a hydrogen peroxide gas sterilization atmosphere. For example, it is placed in a sterilization chamber of a known or commercially available sterilization apparatus (for example, a hydrogen peroxide low temperature plasma sterilization system), and sterilization is performed. After the sterilization process is completed, the whole package can be taken out and stored in the package until it is used. In this case, the sterilization treatment is preferably performed by placing the package in a hydrogen peroxide gas sterilization atmosphere until the discoloration layer of the indicator changes color.
以下に実施例及び比較例を示し、本発明の特徴を一層明確にする。なお、本発明は、実施例の態様に制限されない。 Examples and comparative examples are shown below to further clarify the features of the present invention. In addition, this invention is not restrict | limited to the aspect of an Example.
実施例１〜４及び比較例１〜２表１に示す各成分を攪拌機にて均一に混合することによって、各インキ組成物を調製した。具体的には、まず溶剤、染料及びアルキルフェノール樹脂又はロジン系樹脂をデゾルバーで攪拌混合した。樹脂が溶解しにくい場合は、必要により加熱した。次いで、非変色色素及び樹脂バインダーを投入してさらに攪拌した後、常温に戻して界面活性剤及び酸化亜鉛、ステアリン酸マグネシウム、炭酸カルシウムの少なくとも１種を添加し、均一に攪拌することによって、インキ組成物を得た。 Examples 1-4 and Comparative Examples 1-2 Each ink composition was prepared by mixing each component shown in Table 1 uniformly with a stirrer. Specifically, the solvent, the dye, and the alkylphenol resin or rosin resin were first stirred and mixed with a dissolver. If the resin was difficult to dissolve, it was heated as necessary. Next, after adding a non-color-changing dye and a resin binder and further stirring, the temperature is returned to room temperature, and at least one of a surfactant, zinc oxide, magnesium stearate, and calcium carbonate is added, and the ink is stirred uniformly. A composition was obtained.
比較例１〜７インキ組成を表１のように変更したほかは、実施例１と同様にしてインキ組成物を調製した。 Comparative Examples 1 to 7 Ink compositions were prepared in the same manner as in Example 1 except that the ink compositions were changed as shown in Table 1.
表１に示す成分は具体的には下記の通りである。 The components shown in Table 1 are specifically as follows.
１）C.I.Basic Red 14：メチン系染料
２）C.I. Solvent Yellow 29：非変色色素
３）C.I. Basic Violet 7：メチン系染料
４）マイクロリスグリーンG-T：非変色色素、C.I. Pigment Green 7加工顔料、BASF製
５）ジョンクリル６９０：スチレンアクリル樹脂、ジョンソンポリマー製
６）デンカブチラール♯２０００L：ポリビニルブチラール樹脂、電気化学工業製
７）タマノール100S：アルキルフェノール樹脂、荒川化学工業製
８）KR-610：ロジン系樹脂、荒川化学工業製
９）MOWITAL PVB-B20H：ポリビニルブチラール樹脂、クラレ製１０）ＮＩＫＫＯＬＣＡ−２１５０：４級アンモニウム塩型界面活性剤、日光ケミカルズ製
１１）ブチルセロソルブ：溶剤１２）ソルミックスAP-1：エタノール、IPA混合溶剤
１３）プロピレングリコールモノメチルエーテル：溶剤
１４）酸化亜鉛：正同化学工業製
１５）ステアリン酸マグネシウム：油脂製品製
１６）炭酸カルシウム：紀州製紙製
１７）KA-30：酸化チタン、堺化学工業
１８）NANOBYK3810：酸化セリウム、ビッグケミージャパン製
１９）塩化亜鉛：和光純薬製
1) CI Basic Red 14: methine dye 2) CI Solvent Yellow 29: non-discoloring dye 3) CI Basic Violet 7: methine dye 4) Microlith Green GT: non-discoloring dye, CI Pigment Green 7 processed pigment, 5 manufactured by BASF ) Jonkrill 690: Styrene acrylic resin, manufactured by Johnson Polymer 6) Denkabutyral # 2000L: Polyvinyl butyral resin, manufactured by Electrochemical Industry 7) Tamanol 100S: Alkylphenol resin, manufactured by Arakawa Chemical Industry 8) KR-610: Rosin resin, Arakawa Chemical Industry 9) MOWITAL PVB-B20H: Polyvinyl butyral resin, Kuraray 10) NIKKOLCA-2150: Quaternary ammonium salt surfactant, Nikko Chemicals 11) Butyl cellosolve: Solvent 12) Solmix AP-1: Ethanol, IPA Mixed solvent 13) Propylene glycol monomethyl ether: Solvent 14) Zinc oxide: Zodo Chemical 15) Magnesium stearate: Oil and fat products 16) Calcium carbonate: Kishu Paper 17) KA-30: Titanium oxide, Sakai Chemical Industry 18) NANOBYK3810: Cerium oxide, manufactured by Big Chemie Japan 19) Zinc chloride: Wako Pure Chemical Made
試験例１
各実施例及び比較例のインキ組成物について変色性を調べた。インキ組成物を用いてタイベック１０７３Ｂ上（大きさ５０ｍｍ×1５０ｍｍ）に０μmドクターブレードを用いて塗膜を形成し、十分に乾燥させたものをサンプルとした。
Test example 1
The ink compositions of the examples and comparative examples were examined for discoloration. Using the ink composition, a coating film was formed on a Tyvek 1073B (size: 50 mm × 150 mm) using a 0 μm doctor blade and sufficiently dried.
変色性については、澁谷工業製除染庫80Lを使用した。過酸化水素濃度はドレーゲル・セイフティージャパン（株）のpolytron７０００でCT値（ｐｐｍ・分）を算出した。
変色テストの条件は、過酸化水素ガス保持時間5分、エアレーション時間30分で行った。チャンバー内に注入する３５％過酸化水素水量としては、1.2ｇ、5ｇを秤量した。曝露終了後、ブランク（曝露前のサンプル）との間での色差ΔE*abをそれぞれ測定した。測定は、顕微式色差計「ＣＲ−２４１（コニカミノルタ製）」を用いた。測定結果を表１に示す。
About discoloration property, 80L of decontamination warehouse made by Shibuya Industry was used. The hydrogen peroxide concentration was calculated as a CT value (ppm · min) with polytron 7000 of Dräger Safety Japan Co., Ltd.
The conditions for the discoloration test were a hydrogen peroxide gas retention time of 5 minutes and an aeration time of 30 minutes. As 35% hydrogen peroxide solution to be injected into the chamber, 1.2 g and 5 g were weighed. After the exposure, the color difference ΔE * ab between the blank (sample before exposure) was measured. A micro color difference meter “CR-241 (manufactured by Konica Minolta)” was used for the measurement. The measurement results are shown in Table 1.
表１の結果からも明らかなように、比較例１〜４では３５％過酸化水素水注入量が1.2ｇと5gで３５％過酸化水素水注入量を増やしても暴露前とのΔE*abが小さかった。また、比較例５では３５％過酸化水素水注入量1.2g暴露の変色は小さく、5gで暴露前とのΔE*ab≧５０となった。これに対して実施例１〜３では、３５％過酸化水素水注入量1.2ｇで暴露前とのE*ab≧５０となっているため、低い３５％過酸化水素水暴露条件でも初期との違いを肉眼で識別することができた。 As is clear from the results in Table 1, in Comparative Examples 1 to 4, even when the 35% hydrogen peroxide solution injection amount is 1.2 g and 5 g and the 35% hydrogen peroxide solution injection amount is increased, ΔE * ab before the exposure Was small. Further, in Comparative Example 5, the discoloration of the 35% hydrogen peroxide solution injection amount of 1.2 g exposure was small, and at 5 g, ΔE * ab ≧ 50 from before the exposure. On the other hand, in Examples 1 to 3, the injection amount of 35% hydrogen peroxide solution was 1.2 g, and E * ab ≧ 50 from before the exposure, so even in the low 35% hydrogen peroxide solution exposure condition, The difference could be identified with the naked eye.
実施例４
実施例１のうち酸化亜鉛を抜いた変色インキを作製する。
次に、酸化亜鉛０．３％、タマノール１００S１０％、ソルミックスAP-1を８９．７％配合してディゾルバーで１ｈｒ撹拌し、アンダーコートインキを作製する。タイベック１０７３Bに、０μｍドクターグレードを用いてアンダーコートインキを塗布して常温で１ｈｒ乾燥し、その上から同様に変色インキを塗布して十分に乾燥させて試験片を得た。これを澁谷工業製除染庫80Lで処理した。変色テストの条件は、過酸化水素ガス保持時間5分、エアレーション時間30分で行った。チャンバー内に注入する３５％過酸化水素水量としては、1.2ｇ、5ｇを秤量した。曝露終了後、ブランク（曝露前のサンプル）との間での色差ΔE*abをそれぞれ測定した。測定は、顕微式色差計「ＣＲ−２４１（コニカミノルタ製）」を用いた。
３５％過酸化水素水１．２ｇでは、暴露前とのΔE*abが５２、３５％過酸化水素水５ｇでは暴露前とのΔE*abが８２となり、低い３５％過酸化水素水暴露条件でも初期との違いを肉眼で識別することができた。
Example 4
A discoloration ink from which zinc oxide is removed from Example 1 is prepared.
Next, 0.3% of zinc oxide, 10% of Tamanol 100S, and 89.7% of Solmix AP-1 are blended and stirred for 1 hour with a dissolver to prepare an undercoat ink. An undercoat ink was applied to Tyvek 1073B using a doctor grade of 0 μm and dried at room temperature for 1 hour, and then a discoloration ink was similarly applied thereon and sufficiently dried to obtain a test piece. This was processed in 80L of decontamination chamber made by Sugaya Industry. The conditions for the discoloration test were a hydrogen peroxide gas retention time of 5 minutes and an aeration time of 30 minutes. As 35% hydrogen peroxide solution to be injected into the chamber, 1.2 g and 5 g were weighed. After the exposure, the color difference ΔE * ab between the blank (sample before exposure) was measured. A micro color difference meter “CR-241 (manufactured by Konica Minolta)” was used for the measurement.
With 35% hydrogen peroxide solution 1.2g, ΔE * ab before exposure was 52, and when 35% hydrogen peroxide solution 5g, ΔE * ab before exposure was 82, even under low 35% hydrogen peroxide exposure conditions. The difference from the initial stage was identified with the naked eye.
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| CN103849213A (en) | 2014-06-11 |
| CN103849213B (en) | 2016-04-13 |
| JP6143444B2 (en) | 2017-06-07 |
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