JP5901449B2 - Ink composition for oil-based ballpoint pen and oil-based ballpoint pen using the same - Google Patents
Ink composition for oil-based ballpoint pen and oil-based ballpoint pen using the same Download PDFInfo
- Publication number
- JP5901449B2 JP5901449B2 JP2012147194A JP2012147194A JP5901449B2 JP 5901449 B2 JP5901449 B2 JP 5901449B2 JP 2012147194 A JP2012147194 A JP 2012147194A JP 2012147194 A JP2012147194 A JP 2012147194A JP 5901449 B2 JP5901449 B2 JP 5901449B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- based ballpoint
- ink composition
- thiadiazole
- ballpoint pen
- 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
- 239000000203 mixture Substances 0.000 title claims description 48
- 239000000976 ink Substances 0.000 claims description 79
- -1 thiadiazole compound Chemical class 0.000 claims description 45
- 239000000049 pigment Substances 0.000 claims description 32
- 239000000975 dye Substances 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000981 basic dye Substances 0.000 claims description 10
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 claims description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- HMPUHXCGUHDVBI-UHFFFAOYSA-N 5-methyl-1,3,4-thiadiazol-2-amine Chemical compound CC1=NN=C(N)S1 HMPUHXCGUHDVBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 150000004867 thiadiazoles Chemical class 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- NBNQOWVYEXFQJC-UHFFFAOYSA-N 2-sulfanyl-3h-thiadiazole Chemical compound SN1NC=CS1 NBNQOWVYEXFQJC-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 description 31
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000010419 fine particle Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000006229 carbon black Substances 0.000 description 8
- 230000001050 lubricating effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- FPVUWZFFEGYCGB-UHFFFAOYSA-N 5-methyl-3h-1,3,4-thiadiazole-2-thione Chemical compound CC1=NN=C(S)S1 FPVUWZFFEGYCGB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- XURABDHWIADCPO-UHFFFAOYSA-N 4-prop-2-enylhepta-1,6-diene Chemical compound C=CCC(CC=C)CC=C XURABDHWIADCPO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- FROQWJSIUIGXQA-UHFFFAOYSA-N S[S+]1N=NC=C1 Chemical compound S[S+]1N=NC=C1 FROQWJSIUIGXQA-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 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
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は油性ボールペン用インキ組成物に関し、さらに詳細としてはインキ組成物中に、チアジアゾール化合物を含有する油性ボールペン用インキ組成物に関するものである。 The present invention relates to an ink composition for oil-based ballpoint pens, and more particularly to an ink composition for oil-based ballpoint pens containing a thiadiazole compound in the ink composition.
従来より、ボールペンは他の種類の筆記具と異なり、先端にステンレス鋼などからなる金属チップと、該金属チップのボール受け座に抱持される超鋼などの金属からなる転写ボールと、からなるボールペンチップをインキ収容筒に装着した構成を有するが、筆記時にボールの回転によって、ボール座に摩耗が発生し、筆跡に線飛び、カスレなどが生じたり、書き味が悪くなるという問題があった。 Conventionally, unlike other types of writing instruments, a ballpoint pen is composed of a metal tip made of stainless steel or the like at the tip and a transfer ball made of metal such as super steel held in a ball receiving seat of the metal tip. Although it has a configuration in which the chip is mounted on the ink storage cylinder, there is a problem that wear of the ball seat occurs due to rotation of the ball during writing, lines are scattered on the handwriting, blurring, etc., and writing quality is deteriorated.
こうした問題を解決するため、ボールペンチップのボールとボール座との潤滑性向上を目的として、様々な潤滑剤を用いた油性ボールペン用インキ組成物が多数提案されている。 In order to solve these problems, a large number of oil-based ballpoint pen ink compositions using various lubricants have been proposed for the purpose of improving the lubricity between the ball of the ballpoint pen tip and the ball seat.
このような潤滑剤を用いた油性ボールペン用インキ組成物としては、アルキルβ−Ｄ−グルコシドを用いたものとしては、特開平５−３３１４０３号公報「油性ボールペンインキ」、平均分子量が２００〜４００００００であるポリエチレングリコールを用いたものとしては、特開平７−１９６９７１号公報「油性ボールペン用インキ組成物」、Ｎ−アシルアミノ酸、Ｎ−アシルメチルタウリン酸、Ｎ−アシルメチルアラニンを用いたものとしては、特開２００７−１７６９９５号公報「油性ボールペン用インキ」等に、開示されている。 As the ink composition for oil-based ballpoint pens using such a lubricant, as the one using alkyl β-D-glucoside, JP-A-5-331403 “Oil-based ballpoint pen ink” has an average molecular weight of 200 to 4000000. As what uses a certain polyethylene glycol, as what uses Unexamined-Japanese-Patent No. 7-196971 "Ink composition for oil-based ball-point pens", N-acylamino acid, N-acylmethyltauric acid, N-acylmethylalanine, Japanese Patent Application Laid-Open No. 2007-17695 “Oil-based ballpoint pen ink” and the like.
しかし、特許文献１〜３のような各種潤滑剤を用いた場合、ある程度書き味を向上しつつ、ボール座の摩耗を抑制することはできるが、高筆圧筆記（５００g）では、潤滑性が満足できるものではなく、筆跡に線飛び、かすれ等が発生してしまう問題を抱えていた。 However, when various lubricants such as Patent Documents 1 to 3 are used, the wear of the ball seat can be suppressed while improving the writing quality to some extent, but with high writing pressure writing (500 g), the lubricity is low. It was not satisfactory, and had a problem that a line jumped on the handwriting and blurring occurred.
本発明の目的は、高筆圧筆記（５００g）においても潤滑性を保ち、書き味が良好で、ボール座の摩耗を抑制し、筆跡が良好である油性ボールペン用インキ組成物を提供することである。 An object of the present invention is to provide an ink composition for an oil-based ballpoint pen that maintains lubricity even in high writing pressure writing (500 g), has good writing quality, suppresses wear of a ball seat, and has good handwriting. is there.
本発明は、上記課題を解決するために
「１．少なくとも着色剤、有機溶剤、チアジアゾール化合物からなる油性ボールペン用インキ組成物であって、前記チアジアゾール化合物が、２−アミノ−５−メルカプト−１,３,４−チアジアゾール、５−メチル−１,３,４−チアジアゾール−２−チオール、２−アミノ−５−メチル−１,３,４−チアジアゾールの中からいずれか１種以上のチアジアゾール化合物を選択し、含有することを特徴とする油性ボールペン用インキ組成物。
２．前記チアジアゾール化合物が、２−アミノ−５−メルカプト−１,３,４−チアジアゾールであることを特徴とする第１項に記載の油性ボールペン用インキ組成物。
３．前記チアジアゾール化合物の含有量が、０．１〜１０．０質量％であることを特徴とする第１項または第２項に記載の油性ボールペン用インキ組成物。
４．前記着色剤が、顔料であることを特徴とする第１項ないし第３項のいずれか１項に記載の油性ボールペン用インキ組成物。
５．前記着色剤が、顔料と染料を併用し、前記染料がアルキルベンゼンスルホン酸と塩基性染料の造塩染料であることを特徴とする第１項ないし第４項のいずれか１項に記載の油性ボールペン用インキ組成物。
６．前記有機溶剤が、芳香族アルコール系溶剤を含有することを特徴とする第１項ないし第５項のいずれか１項に記載の油性ボールペン用インキ組成物。
７．２０℃、剪断速度５００ｓｅｃ−１におけるインキ粘度が、１０〜５０００ｍＰａ・ｓであることを特徴とする第１項ないし第６項の何れか１項に記載の油性ボールペン用インキ組成物。
８．インキ収容筒の先端部に、ステンレス綱材からなる チップ本体のボール抱持室にボールを回転自在に抱持したボールペンチップを直接又はチップホルダーを介して具備し、前記インキ収容筒内に、第１項ないし第７項のいずれか１項に記載の油性ボールペン用インキ組成物を直に収容していることを特徴とする油性ボールペン。」とする。
In order to solve the above problems, the present invention
“1. An oil-based ballpoint pen ink composition comprising at least a colorant, an organic solvent, and a thiadiazole compound, wherein the thiadiazole compound is 2-amino-5-mercapto-1,3,4-thiadiazole, 5-methyl-1 Oil-based ballpoint pen characterized by selecting and containing one or more thiadiazole compounds from 2,3,4-thiadiazole-2-thiol and 2-amino-5-methyl-1,3,4-thiadiazole Ink composition.
2. 2. The oil-based ballpoint pen ink composition according to item 1, wherein the thiadiazole compound is 2-amino-5-mercapto-1,3,4-thiadiazole.
3. The content of the thiadiazole compound is 0.1 to 10.0% by mass, The ink composition for oil-based ballpoint pens according to item 1 or 2.
4). 4. The ink composition for oil-based ballpoint pens according to any one of items 1 to 3, wherein the colorant is a pigment.
5. The oil-based ballpoint pen according to any one of claims 1 to 4, wherein the colorant is a combination of a pigment and a dye, and the dye is a salt-forming dye of an alkylbenzenesulfonic acid and a basic dye. Ink composition.
6). The ink composition for oil-based ballpoint pens according to any one of claims 1 to 5, wherein the organic solvent contains an aromatic alcohol solvent.
7. The ink composition for oil-based ballpoint pens according to any one of Items 1 to 6, wherein the ink viscosity at 20 ° C. and a shear rate of 500 sec-1 is 10 to 5000 mPa · s.
8). A ball-point pen tip having a ball rotatably held in a ball holding chamber of a chip body made of a stainless steel material is provided directly or via a chip holder at the tip of the ink storage cylinder, An oil-based ballpoint pen comprising the oil-based ballpoint pen ink composition according to any one of items 1 to 7 directly contained therein. "
本発明は、高筆圧筆記（５００g）においてもボールの潤滑性を保ち、書き味が良好で、ボール座の摩耗を抑制し、筆跡に線飛び、かすれがなく筆跡が良好である油性ボールペン用インキ組成物を提供することができた。 The present invention is for oil-based ballpoint pens that maintain the lubricity of the ball even in high writing pressure writing (500 g), have good writing quality, suppress wear of the ball seat, and have good handwriting with no lines flying and blurring. An ink composition could be provided.
本発明の第一の特徴は、油性ボールペン用インキ組成物中に特定のチアジアゾール化合物を含有することである。 The first feature of the present invention is that a specific thiadiazole compound is contained in the oil-based ballpoint pen ink composition.
本発明に用いるチアジアゾール化合物は、複素環式化合物の１種で、５員環の１位に硫黄、３位と４位に窒素原子を有する化合物であり、前記チアジアゾール化合物として、２−アミノ−５−メルカプト−１,３,４−チアジアゾール、５−メチル−１,３,４−チアジアゾール−２−チオール、２−アミノ−５−メチル−１,３
,４−チアジアゾールの中からいずれか１種以上のチアジアゾール化合物を選択し、含有することで、高筆圧筆記（５００g）においてもボールの潤滑性を保ち、書き味が良好で、かつ、ボール座の摩耗を抑制することが可能となることが解った。ここで、２−アミノ−５−メルカプト−１,３,４−チアジアゾールは一般式（化１）で、５−メチル−１,３,４−チアジアゾール−２−チオールは一般式（化２）で、２−アミノ−５−メチル−１,３,４−チアジアゾール一般式（化３）で表される。これらは、単独または２種以上混合して使用してもよい。
By selecting and containing any one or more thiadiazole compounds from 1,4-thiadiazole, the ball lubricity is maintained even in high writing pressure writing (500 g), the writing quality is good, and the ball seat It has been found that it is possible to suppress wear of the steel. Here, 2-amino-5-mercapto-1,3,4-thiadiazole is represented by the general formula (Formula 1), and 5-methyl-1,3,4-thiadiazole-2-thiol is represented by the general formula (Formula 2). 2-amino-5-methyl-1,3,4-thiadiazole is represented by the general formula (Formula 3). You may use these individually or in mixture of 2 or more types.
これは、前記チアジアゾール化合物が二重結合を有する複素環式構造であることで、立体構造をとることで、クッション作用が働き、ボールとチップ本体間の金属接触を抑制する効果があり、潤滑性を向上することで、書き味が良好で、かつ、ボール座の摩耗を抑制するものと推測する。特に、チアジアゾール化合物の−S−が金属に強固に吸着することで、ボールの剪断力でも剥がれにくいため、高筆圧筆記（５００g）において、潤滑性を保つことが可能になるものと推測する。 This is because the thiadiazole compound is a heterocyclic structure having a double bond, and by taking a three-dimensional structure, it acts as a cushion and has the effect of suppressing metal contact between the ball and the chip body, and lubricity It is presumed that the writing quality is good and the wear of the ball seat is suppressed. In particular, since the thiadiazole compound -S- is strongly adsorbed to the metal, it is difficult to peel off even with the shearing force of the ball, so that it is assumed that the lubricity can be maintained in high writing pressure writing (500 g).
また、前記チアジアゾール化合物の中でも、より高筆圧筆記における潤滑性を考慮すれば、メルカプト基（−SH）を有する、２−アミノ−５−メルカプト−１,３,４−チアジアゾール（化１）、５−メチル−１,３,４−チアジアゾール−２−チオール（化２）を用いる方が好ましい。これは、メルカプト基（−SH）が金属吸着しやすく、より強固に吸着しやすくなり、ボールの剪断力でもより剥がれにくくなるため効果的である。また、有機溶剤への溶解安定することで、インキの経時安定性を考慮すれば、アミノ基を有するチアジアゾール化合物として、２−アミノ−５−メルカプト−１,３,４−チアジアゾール（化１）が最も好ましい。 In addition, among the thiadiazole compounds, 2-amino-5-mercapto-1,3,4-thiadiazole (Chemical Formula 1) having a mercapto group (—SH), considering the lubricity in higher writing pressure writing, It is preferable to use 5-methyl-1,3,4-thiadiazole-2-thiol (Chemical Formula 2). This is effective because the mercapto group (—SH) is easily adsorbed to the metal, more easily adsorbs more strongly, and is less likely to be peeled off even by the shearing force of the ball. In addition, considering the stability of the ink over time by being stable in dissolution in an organic solvent, 2-amino-5-mercapto-1,3,4-thiadiazole (Chemical Formula 1) is used as a thiadiazole compound having an amino group. Most preferred.
また、前記チアジアゾール化合物の含有量は、インキ組成物全量に対し、０．１質量％より少ないと、潤滑効果が得られないおそれがあり、１０．０質量％を越えると、インキ経時安定性に影響するおそれがあるため、インキ組成物全量に対し、０．１〜１０．０質量％が好ましく、より潤滑性を考慮すれば、１．０〜１０．０質量％が好ましく、さらに、インキ経時安定性などを考慮すれば、１．０〜５．０質量％が最も好ましい。 Further, if the content of the thiadiazole compound is less than 0.1% by mass with respect to the total amount of the ink composition, there is a concern that a lubricating effect may not be obtained. Since there is a possibility of influence, 0.1 to 10.0% by mass is preferable with respect to the total amount of the ink composition, and 1.0 to 10.0% by mass is preferable in consideration of lubricity. Considering stability and the like, 1.0 to 5.0% by mass is most preferable.
本発明の第二の特徴は、着色剤として、少なくとも顔料を含有することである。顔料を用いることで、ボールとチップ本体の隙間に顔料粒子が入り込むことで、ベアリングのような作用が働き、金属接触を抑制することで、潤滑性を向上することが可能である。さらに、上述のように、前記チアジアゾール化合物を含有することで、
クッション作用が働くことで潤滑性を向上するが、前記チアジアゾール化合物によるクッション作用と顔料粒子とのベアリング作用による相乗効果で、より金属接触を抑制することで、より高筆圧筆記においても潤滑性を向上し、書き味とチップ本体の摩耗を抑制することが可能となる。
The second feature of the present invention is that it contains at least a pigment as a colorant. By using the pigment, the pigment particles enter the gap between the ball and the chip body, thereby acting like a bearing and suppressing the metal contact, thereby improving the lubricity. Furthermore, as described above, by containing the thiadiazole compound,
The cushioning action improves lubricity, but the synergistic effect of the cushioning action of the thiadiazole compound and the bearing action of the pigment particles further suppresses metal contact, thereby improving lubricity even in higher writing pressure writing. It is possible to improve the writing quality and the wear of the chip body.
また、顔料については、無機、有機、加工顔料などが挙げられるが、具体的にはカーボンブラック、アニリンブラック、群青、黄鉛、酸化チタン、酸化鉄、フタロシアニン系、アゾ系、キナクリドン系、DPP系、キノフタロン系、スレン系、トリフェニルメタン系、ペリノン系、ペリレン系、ギオキサジン系、メタリック顔料、パール顔料、蛍光顔料、蓄光顔料等が挙げられる。これら顔料は、チップ本体の隙間に入り込むことで、金属接触を抑制し、潤滑性を向上しやすい。特に、潤滑性の向上を考慮すれば、カーボンブラックを用いる方が好ましい。また、チップ内部の隙間関係を考慮し、平均粒子径は、３００nm以下が好ましい。より好ましくは、１５０nm以下である。ここで、平均粒子径とは、粒度分布計による平均粒子径ｄ50のことである。これらの顔料は、単独又は２種以上組み合わせて使用してもかまわない。顔料の含有量は、インキ組成物全量に対し、０．５〜１５．０質量％が好ましい。これは０．５質量％未満だと、潤滑効果が得られにくい傾向があり、１５．０質量％を越えると、インキ中で凝集しやすい傾向があるためであり、よりその傾向を考慮すれば、２．０〜１０．０質量％が好ましく、最も好ましくは、３．０〜７．０質量％である。 Examples of pigments include inorganic, organic, and processed pigments. Specifically, carbon black, aniline black, ultramarine, yellow lead, titanium oxide, iron oxide, phthalocyanine, azo, quinacridone, and DPP Quinophthalone, selenium, triphenylmethane, perinone, perylene, goxazine, metallic pigment, pearl pigment, fluorescent pigment, phosphorescent pigment and the like. These pigments tend to suppress metal contact and improve lubricity by entering the gaps in the chip body. In particular, in consideration of improvement in lubricity, it is preferable to use carbon black. Further, in consideration of the gap relationship inside the chip, the average particle size is preferably 300 nm or less. More preferably, it is 150 nm or less. Here, the average particle diameter is an average particle diameter d50 measured by a particle size distribution meter. These pigments may be used alone or in combination of two or more. The content of the pigment is preferably 0.5 to 15.0% by mass with respect to the total amount of the ink composition. This is because if it is less than 0.5% by mass, the lubricating effect tends to be difficult to obtain, and if it exceeds 15.0% by mass, it tends to aggregate in the ink. 2.0-10.0 mass% is preferable, Most preferably, it is 3.0-7.0 mass%.
また、染料としては、油溶性染料、酸性染料、塩基性染料、含金染料などや、それらの各種造塩タイプの染料等が採用するが、潤滑性の向上とインキ経時安定性を考慮すれば、有機酸と塩基性染料との造塩染料を用いる方が好ましく、その中でも、アルキルベンゼンスルホン酸と塩基性染料との造塩染料を用いる方が好ましい。これは、芳香環を有し、スルホ基(-SO３H)を有することで、フェニルスルホン基が、金属に吸着し易い潤滑膜を形成することで、より潤滑性を向上する効果が得られるためである。また、塩基性染料は、アルキルベンゼンスルホン酸と塩基性染料間のイオン結合力が強い造塩染料とすることで、油性インキ中において、様々な環境下や長期間インキ経時安定性が保つことが可能であるため好ましい。 In addition, as dyes, oil-soluble dyes, acid dyes, basic dyes, metal-containing dyes and the like, and various salt-forming dyes thereof are adopted, but considering improvement in lubricity and stability with time of ink It is preferable to use a salt-forming dye of an organic acid and a basic dye. Among them, it is preferable to use a salt-forming dye of an alkylbenzene sulfonic acid and a basic dye. This is because it has an aromatic ring and has a sulfo group (—SO 3 H), so that a phenyl sulfone group forms a lubricating film that is easily adsorbed to a metal, so that an effect of improving lubricity can be obtained. Because. In addition, the basic dye is a salt-forming dye that has a strong ionic bond between the alkylbenzene sulfonic acid and the basic dye, so that the ink aging stability can be maintained in various environments and for a long period of time in oil-based inks. Therefore, it is preferable.
また、アルキルベンゼンスルホン酸としては、ドデシルジフェニルオキシドジスルホン酸、ドデシルベンゼンスルホン酸などが挙げられるが、潤滑性を向上することを考慮すれば、スルホ基(-SO３H)が多いドデシルジフェニルオキシドジスルホン酸が好ましい。 Further, examples of the alkylbenzene sulfonic acid include dodecyl diphenyl oxide disulfonic acid, dodecyl benzene sulfonic acid, etc. In consideration of improving lubricity, dodecyl diphenyl oxide disulfonic acid having a large sulfo group (—SO 3 H). Is preferred.
また、前記染料の含有量は、インキ組成物全量に対し、０．１質量％より少ないと、所望の潤滑性が得られづらく、４０．０質量％を越えると、インキ経時が不安定性になりやすいため、インキ組成物全量に対し、０．１〜４０．０質量％が好ましい。より好ましくは、インキ組成物全量に対し、３．０〜３０．０質量％であり、最も好ましくは、１０．０〜３０．０質量％である。 Further, if the content of the dye is less than 0.1% by mass relative to the total amount of the ink composition, it is difficult to obtain desired lubricity, and if it exceeds 40.0% by mass, the ink aging becomes unstable. Since it is easy, 0.1-40.0 mass% is preferable with respect to the ink composition whole quantity. More preferably, it is 3.0-30.0 mass% with respect to the ink composition whole quantity, Most preferably, it is 10.0-30.0 mass%.
また、顔料分散剤については、ポリビニルブチラール樹脂、ポリアセタール樹脂、ポリビニルアルコール樹脂、セルロース樹脂、ポリビニルピロリドン等が例示でき、これらを１種又は２種以上用いることができる。その中でも、ポリビニルブチラール樹脂が好ましいが、これは、有機溶剤中に速やかに微細に分散しやすく、さらにポリビニルブチラール樹脂が、顔料に吸着することで、長期間の顔料の分散を維持しやすいためである。特に、顔料の中でも、ポリビニルブチラール樹脂との顔料分散性を考慮すれば、塩基性カーボンブラックが好ましい。ここで、塩基性カーボンブラックとは、カーボンブラック粒子をｐＨ７のイオン交換水に分散し、ｐＨメーターにて２５℃のｐＨを測定したｐＨ値が７以上を塩基性カーボンブラックと定義する。より顔料分散性を考慮すれば、ｐＨ値が７〜１０の塩基性カーボンブラックが最も好ましい。 Examples of the pigment dispersant include polyvinyl butyral resin, polyacetal resin, polyvinyl alcohol resin, cellulose resin, polyvinyl pyrrolidone, and the like, and one or more of these can be used. Among them, polyvinyl butyral resin is preferable, because it is easy to disperse quickly and finely in an organic solvent, and the polyvinyl butyral resin is easily adsorbed to the pigment, so that it is easy to maintain long-term dispersion of the pigment. is there. In particular, among the pigments, basic carbon black is preferable in consideration of pigment dispersibility with the polyvinyl butyral resin. Here, the basic carbon black is defined as a basic carbon black having a pH value of 7 or more obtained by dispersing carbon black particles in ion exchange water having a pH of 7 and measuring the pH at 25 ° C. with a pH meter. In consideration of pigment dispersibility, basic carbon black having a pH value of 7 to 10 is most preferable.
また、ポリブチラール樹脂は、ポリビニルアルコール(PVA) をブチルアルデヒド(BA)と反応させたものであり、ポリビニルブチラール樹脂は、分子中の 水酸基が、２０〜４０ｍｏｌ％が好ましい。これは、２０ｍｏｌ％未満だと、アルコール系の有機溶剤に溶解しづらい傾向があり、４０ｍｏｌ％を越えると耐水性が劣りやすい傾向があるためであり、さらに、より好ましくは、３０〜４０ｍｏｌ％が好ましい。また、有機溶剤に溶解性を考慮すれば、分子量が１０００００以下である方が好ましく、より考慮すれば、３００００以下である方がより好ましい。 The polybutyral resin is obtained by reacting polyvinyl alcohol (PVA) with butyraldehyde (BA), and the polyvinyl butyral resin preferably has 20 to 40 mol% of hydroxyl groups in the molecule. This is because if it is less than 20 mol%, it tends to be difficult to dissolve in an alcohol-based organic solvent, and if it exceeds 40 mol%, the water resistance tends to be inferior, and more preferably 30-40 mol%. preferable. In consideration of solubility in an organic solvent, the molecular weight is preferably 100,000 or less, and more preferably 30000 or less.
前記顔料分散剤の含有量は、０．１質量％より少ないと、顔料分散性が劣りやすく、２０．０質量％を越えると、インキ中で溶解性が劣りやすく、インキ粘度も高くなりやすいため、インキ組成物全量に対し、１．０〜２０．０質量％が好ましく、より考慮すれば、３．０〜１０．０質量％が好ましい。 If the content of the pigment dispersant is less than 0.1% by mass, the pigment dispersibility tends to be inferior, and if it exceeds 20.0% by mass, the solubility in the ink tends to be inferior and the ink viscosity tends to increase. The total amount of the ink composition is preferably 1.0 to 20.0% by mass, and more preferably 3.0 to 10.0% by mass in consideration.
本発明に用いる有機溶剤としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、３―メトキシブタノール、３―メトキシー３―メチルブタノール等のグリコールエーテル系、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ブチレングリコール、エチレングリコール等のグリコール系、ベンジルアルコール、メタノール、エタノール、１−プロパノール、２−プロパノール、イソプロパノール、イソブタノール、ｔ−ブタノール、プロパギルアルコール、アリルアルコール、３−メチル−１−ブチン−３−オール、エチレングリコールモノメチルエーテルアセタートやその他の高級アルコール等のアルコール系など、油性ボールペン用インキとして一般的に用いられる溶剤が例示できる。これらの中でも、前記チアジアゾール化合物、アルキルベンゼンスルホン酸と塩基性染料との造塩染料との溶解安定性や、顔料とのインキ経時安定性を考慮すれば、少なくともアルコール系溶剤を用いる方が好ましい。さらに、ベンジルアルコールなどの芳香族アルコ−ルは、潤滑性を向上する効果もあるため、少なくとも用いる方が最も好ましい。これらの有機溶剤は、を１種又は２種以上用いることができる。溶剤の含有量は、チアジアゾール化合物、着色剤の溶解性、筆跡乾燥性、にじみ等を考慮すると、インキ組成物全量に対し、１０．０〜７０．０質量％が好ましく、よりその傾向を考慮すれば、３０．０〜６５．０質量％が好ましく、最も好ましくは、４５．０〜６５．０質量％である。 Examples of the organic solvent used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, 3 -Glycol ethers such as methoxybutanol, 3-methoxy-3-methylbutanol, glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, ethylene glycol, benzyl alcohol, methanol, ethanol, 1-propanol, 2-pro For oil-based ballpoint pens such as alcohols such as diol, isopropanol, isobutanol, t-butanol, propargyl alcohol, allyl alcohol, 3-methyl-1-butyn-3-ol, ethylene glycol monomethyl ether acetate and other higher alcohols The solvent generally used as ink can be illustrated. Among these, it is preferable to use at least an alcohol solvent in view of dissolution stability of the thiadiazole compound, a salt-forming dye of alkylbenzene sulfonic acid and a basic dye, and ink aging stability with a pigment. Furthermore, aromatic alcohol such as benzyl alcohol is most preferably used because it has an effect of improving lubricity. These organic solvents can use 1 type (s) or 2 or more types. The content of the solvent is preferably 10.0 to 70.0% by mass with respect to the total amount of the ink composition in consideration of the thiadiazole compound, the solubility of the colorant, the handwriting drying property, the bleeding, etc. 30.0 to 65.0 mass% is preferable, and 45.0 to 65.0 mass% is most preferable.
さらに、高筆圧筆記（筆記荷重５００ｇｆ）においても潤滑性を保ち、ボール座の摩耗を抑制するには、リン酸エステル系界面活性剤を用いる方が好ましい。リン酸基によって、より強固な潤滑層を形成しやすく、前記チアジアゾール化合物との相互作用で、より金属接触を抑制することで、高筆圧下（筆記荷重５００ｇｆ）においても潤滑性を保ちやすくなる。 Furthermore, in order to maintain lubricity even in high writing pressure writing (writing load 500 gf) and suppress wear of the ball seat, it is preferable to use a phosphate ester surfactant. It is easy to form a stronger lubricating layer by the phosphoric acid group, and it is easy to maintain lubricity even under high writing pressure (writing load of 500 gf) by further suppressing metal contact by interaction with the thiadiazole compound.
リン酸エステル系界面活性剤としては、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸モノエステル、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸ジエステル、ポリオキシエチレンアルキルエーテル又はポリオキシエチレンアルキルアリールエーテルのリン酸トリエステル、アルキルリン酸エステル、アルキルエーテルリン酸エステル或いはその誘導体等が挙げられ、これらのリン酸エステル系界面活性剤は、単独又は２種以上混合して使用してもよい。その中でも、炭素数が５〜１８であるアルキル基を少なくとも有する方が好ましく、炭素数が５未満であると、高筆圧下（筆記荷重５００ｇｆ）においての潤滑性が不足しやすい傾向があり、炭素数が１８を超えると、インキ経時安定性に影響が出やすい傾向があるためであり、よりその傾向を考慮すれば、炭素数が８〜１５が最も好ましい。 Phosphate ester surfactants include polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate diester, polyoxyethylene alkyl ether Or polyoxyethylene alkylaryl ether phosphate triesters, alkyl phosphate esters, alkyl ether phosphate esters or derivatives thereof. These phosphate ester surfactants may be used alone or in combination of two or more. May be used. Among them, it is preferable to have at least an alkyl group having 5 to 18 carbon atoms, and if the carbon number is less than 5, the lubricity tends to be insufficient under high writing pressure (writing load 500 gf). This is because if the number exceeds 18, the ink aging stability tends to be affected, and in view of the tendency, the carbon number of 8 to 15 is most preferable.
また、リン酸エステル系界面活性剤の含有量は、インキ組成物全量に対し、０．１質量％より少ないと、所望の潤滑性が得られにくい傾向があり、５．０質量％を越えると、インキ経時が不安定性になりやすい傾向があるため、インキ組成物全量に対し、０．１〜５．０質量％がより好ましい。最も好ましくは、インキ組成物全量に対し、０．５〜３．０質量％である。 Further, if the content of the phosphate ester-based surfactant is less than 0.1% by mass relative to the total amount of the ink composition, the desired lubricity tends to be difficult to obtain, and if it exceeds 5.0% by mass. In addition, since ink aging tends to be unstable, 0.1 to 5.0% by mass is more preferable with respect to the total amount of the ink composition. Most preferably, it is 0.5 to 3.0 mass% with respect to the total amount of the ink composition.
本発明の油性ボールペン用インキ組成物のインキ粘度は、特に限定されるものではないが、２０℃、剪断速度５００ｓｅｃ−１におけるインキ粘度が１０ｍＰａ・ｓ未満の場合には、筆跡に滲みやインキ垂れ下がりの影響が出やすいため、また、２０℃、剪断速度５００ｓｅｃ−１におけるインキ粘度が３００００ｍＰａ・ｓを超えると、筆記時のボール回転抵抗が大きくなり、書き味が重くなる傾向がある。そのため、２０℃、剪断速度５００ｓｅｃ−１におけるインキ粘度は、１０〜３００００ｍＰａ・ｓが好ましい。より書き味の向上を考慮すれば、１０〜５０００ｍＰａ・ｓが好ましく、最も好ましくは、よりインキ垂れ下がりや書き味を考慮すれば、１００〜３０００ｍＰａ・ｓである。 The ink viscosity of the oil-based ballpoint pen ink composition of the present invention is not particularly limited. However, when the ink viscosity at 20 ° C. and a shear rate of 500 sec −1 is less than 10 mPa · s, bleeding or ink sag occurs in the handwriting. In addition, if the ink viscosity at 20 ° C. and a shear rate of 500 sec −1 exceeds 30000 mPa · s, the ball rotation resistance during writing tends to increase and the writing taste tends to be heavy. Therefore, the ink viscosity at 20 ° C. and a shear rate of 500 sec −1 is preferably 10 to 30000 mPa · s. Considering improvement in writing quality, 10 to 5000 mPa · s is preferable, and most preferable is 100 to 3000 mPa · s in consideration of ink sag and writing quality.
また、本発明のように、潤滑性をより向上させるために、微粒子を用いてもよい。これは、微粒子は、顔料と同様に、チップ本体の隙間に微粒子が入り込むことで、金属接触を抑制することで、潤滑性を向上することが可能であるためである。微粒子は具体的には、アクリル系、シリコーン系、ポリエチレン系等の樹脂微粒子やアルミナ微粒子、シリカ微粒子などが挙げられる。その中でも、球状のシリカ微粒子が好ましい。また、微粒子は、潤滑性を考慮すれば、平均粒子径が５〜１００ｎｍの微粒子が好ましく、平均粒子径はメジアン径であり、遠心沈降式やレーザー回折式、ＢＥＴ法等によって求めるこができる。 Further, as in the present invention, fine particles may be used in order to further improve the lubricity. This is because the fine particles can improve the lubricity by suppressing the metal contact by entering the fine particles into the gaps of the chip body, like the pigment. Specific examples of the fine particles include resin fine particles such as acrylic, silicone, and polyethylene, alumina fine particles, and silica fine particles. Among these, spherical silica fine particles are preferable. The fine particles are preferably fine particles having an average particle diameter of 5 to 100 nm in consideration of lubricity, and the average particle diameter is a median diameter, and can be determined by a centrifugal sedimentation method, a laser diffraction method, a BET method, or the like.
また、その他として、潤滑性やインキ経時安定性を向上させるために、界面活性剤として、フッ素系界面活性剤、シリコーン系界面活性剤、脂肪酸アルカノールアミド、陰イオン性界面活性剤、陽イオン性界面活性剤、両性界面活性剤、オキシエチレンアルキルアミン、ポリオキシエチレンアルキルアミンや、陰イオン性界面活性剤および／または陽イオン性界面活性剤の造塩体を、粘度調整剤として、ケトン樹脂、テルペン樹脂、アルキッド樹脂、フェノキシ樹脂、ポリ酢酸ビニル等の樹脂や脂肪酸アマイド、水添ヒマシ油などの擬塑性付与剤を、また、着色剤安定剤、可塑剤、キレート剤、水などを適宜用いても良い。これらは、単独又は２種以上組み合わせて使用してもかまわない。 In addition, as surfactants, fluorine surfactants, silicone surfactants, fatty acid alkanolamides, anionic surfactants, cationic interfaces are used to improve lubricity and ink aging stability. Activators, amphoteric surfactants, oxyethylene alkylamines, polyoxyethylene alkylamines and anionic surfactants and / or cationic surfactant salt formations as viscosity modifiers, ketone resins, terpenes Resins such as resins, alkyd resins, phenoxy resins, and polyvinyl acetate, and pseudoplasticity imparting agents such as fatty acid amides and hydrogenated castor oil, and colorant stabilizers, plasticizers, chelating agents, water, etc. good. These may be used alone or in combination of two or more.
次に、実施例を示して本発明を説明する。
実施例１の油性ボールペン用インキ組成物は、有機溶剤、顔料分散剤を５０℃にて混合攪拌機を用い顔料分散樹脂を溶解させて溶液Ａを製造した。得られた溶液Ａに顔料を添加し、三本ロールを用いて分散ベースを作成する。この分散ベースに残りの成分を、５０℃にて混合攪拌機を用いて攪拌して油性ボールペン用インキ組成物を得た。具体的な配合量は下記の通りである。尚、ティー・エイ・インスツルメント株式会社製AR-G2（ステンレス製 40mm2°ローター）を用いて２０℃の環境下で、剪断速度５００ｓｅｃ−１にてインキ粘度を測定したところ、１２００ｍＰａ・ｓであった。
Next, an Example is shown and this invention is demonstrated.
The ink composition for oil-based ballpoint pens of Example 1 was prepared by dissolving the pigment dispersion resin with an organic solvent and a pigment dispersant at 50 ° C. using a mixing stirrer to prepare Solution A. A pigment is added to the obtained solution A, and a dispersion base is prepared using three rolls. The remaining components were stirred on this dispersion base at 50 ° C. using a mixing stirrer to obtain an ink composition for oil-based ballpoint pens. Specific blending amounts are as follows. Ink viscosity was measured at 1200 mPa · s at a shear rate of 500 sec −1 under an environment of 20 ° C. using AR-G2 (stainless steel 40 mm 2 ° rotor) manufactured by TA Instruments Inc. there were.
実施例１
染料（アルキルベンゼンスルホン酸とキサンテン系塩基性染料との造塩染料）
１０．０質量％
染料（アルキルベンゼンスルホン酸とトリアリルメタン系塩基性染料との造塩染料）
１０．０質量％
顔料（塩基性カーボンブラック） ５．０質量％
顔料分散剤（ポリビニルブチラール） ２．５質量％
有機溶剤（ベンジルアルコール） ５０．１質量％
チアジアゾール化合物（２−アミノ−５−メルカプト−１,３,４−チアジアゾール）
３．０質量％
安定剤（オレイン酸） １．０質量％
樹脂（ケトン樹脂） １０．０質量％
Example 1
Dyes (Salt-forming dyes of alkylbenzenesulfonic acid and xanthene basic dyes)
10.0% by mass
Dyes (Salt-forming dyes of alkylbenzenesulfonic acid and triallylmethane basic dyes)
10.0% by mass
Pigment (basic carbon black) 5.0% by mass
Pigment dispersant (polyvinyl butyral) 2.5% by mass
Organic solvent (benzyl alcohol) 50.1% by mass
Thiadiazole compound (2-amino-5-mercapto-1,3,4-thiadiazole)
3.0% by mass
Stabilizer (oleic acid) 1.0% by mass
Resin (ketone resin) 10.0% by mass
実施例２〜８
表１、２に示すように、各成分を変更した以外は、実施例１と同様な手順で実施例２〜８の油性ボールペン用インキ組成物を得た。
実施例９
表２に示すように、各成分を変更した以外は、水以外の各成分を実施例１と同様な手順で行い、室温冷却後水を添加しディスパー攪拌にて油性ボールペン用インキ組成物を得た。
As shown in Tables 1 and 2, oil-based ballpoint pen ink compositions of Examples 2 to 8 were obtained in the same procedure as Example 1 except that each component was changed.
Example 9
As shown in Table 2, except that each component was changed, each component other than water was carried out in the same procedure as in Example 1, and after cooling at room temperature, water was added and an ink composition for an oil-based ballpoint pen was obtained by disper stirring. It was.
比較例１〜４
表３に示すように、各成分を変更した以外は、実施例１と同様の手順で、配合し、比較例１〜４の油性ボールペン用インキ組成物を得た。
As shown in Table 3, the components were mixed in the same procedure as in Example 1 except that each component was changed, and ink compositions for oil-based ballpoint pens of Comparative Examples 1 to 4 were obtained.
試験及び評価
実施例１〜９及び比較例１〜で作製した油性ボールペン用インキ組成物（０．４g）及びグリース状のインキ追従体を、インキ収容筒（ポリプロピレン）に、ボール径がφ０．７ｍｍのボールを回転自在に抱持したボールペン用チップ（ステンレス綱線）を装着したボールペン用レフィルに充填し、油性ボールペンを作製した。筆記試験用紙として筆記用紙ＪＩＳ Ｐ３２０１を用いて以下の試験及び評価を行った。
Testing and evaluation
The oil-based ballpoint pen ink composition (0.4 g) and the grease-like ink follower prepared in Examples 1 to 9 and Comparative Examples 1 to were placed in an ink containing cylinder (polypropylene) with a ball having a ball diameter of 0.7 mm. An oil-based ballpoint pen was prepared by filling a ballpoint pen refill equipped with a ballpoint pen tip (stainless steel wire) that was held in a rotatable manner. The following tests and evaluations were performed using a writing paper JIS P3201 as a writing test paper.
書き味：手書きによる官能試験を行い評価した。
非常に滑らかなもの ・・・◎
滑らかなもの ・・・○
やや重いもの ・・・△
重いもの ・・・×
Written taste: A hand-written sensory test was performed and evaluated.
Very smooth ・ ・ ・ ◎
Smooth thing ○○
Somewhat heavy ・ ・ ・ △
Heavy thing
高筆圧筆記試験：荷重５００ｇｆ、筆記角度７０°、４ｍ／ｍｉｎの走行試験機にて筆記試験後のボール座の摩耗を測定した。
ボール座の摩耗が５μｍ未満のもの ・・・◎
ボール座の摩耗が５μｍ以上、１０μｍ未満であるもの ・・・○
ボール座の摩耗が１０μｍ以上、２０μｍ未満であるが、筆記可能であるもの ・・・△
ボール座の摩耗がひどく、筆記不良になってしまうのもの ・・・×
High writing pressure writing test: The wear of the ball seat after the writing test was measured with a running tester with a load of 500 gf, a writing angle of 70 °, and 4 m / min.
Ball seat wear less than 5μm ・ ・ ・ ◎
Ball seat wear is 5 μm or more and less than 10 μm.
Ball seat wear is 10 μm or more and less than 20 μm, but can be written.
Wearing the ball seat is bad and results in poor writing ・ ・ ・ ×
実施例１〜９では、書き味、高筆圧筆記試験ともに良好な性能が得られた。 In Examples 1 to 9, good performance was obtained for both writing quality and high writing pressure writing test.
比較例１〜４では、チアジアゾール化合物を含有していないため、書き味が重く、高筆圧筆記試験ではボール座の摩耗がひどく筆跡にカスレが発生してしまった。 In Comparative Examples 1 to 4, since the thiadiazole compound was not contained, the writing was heavy, and in the high writing pressure writing test, the wear of the ball seat was severely generated, and the brush mark was damaged.
本発明では、ボールの表面及び／又は当接面の表面に潤滑被膜層（図示せず）を設けることで、潤滑被膜層と前記したインキ層による流体潤滑又は混合潤滑との相乗効果によって、ボールとチップ内壁との接触抵抗を著しく軽減しやすく、当接面の耐摩耗性及び筆感を著しく向上しやすくなるため、好ましい。 In the present invention, a lubricating coating layer (not shown) is provided on the surface of the ball and / or the abutting surface, so that the ball can be obtained by the synergistic effect of the lubricating coating layer and the fluid lubrication or mixed lubrication by the ink layer. This is preferable because the contact resistance between the contact surface and the inner wall of the chip can be remarkably reduced, and the wear resistance and writing feeling of the contact surface can be significantly improved.
尚、本発明に用いる潤滑被膜層としては、ダイヤモンドライクカーボン（ＤＬＣ）、二硫化タングステン（ＷＳ２）、二硫化モリブデン（ＭｏＳ２）やグラファイト、四フッ化エチレン（ＰＴＦＥ）等の含フッ素高分子、シリコーン樹脂等、従来から知られている固体潤滑剤などを適宜用いることができる。また、潤滑被膜層を被覆する方法は、特に制限されず、真空蒸着、イオン蒸着、物理的蒸着、化学的蒸着、真空アーク蒸着などが挙げられ、直接又は前記した潤滑剤を含有した被膜層であってもよい。特に前記した潤滑剤の中でも、耐摩耗性及び潤滑性を考慮してダイヤモンドライクカーボン（ＤＬＣ）を用いることが最も好ましい。 The lubricating coating layer used in the present invention includes diamond-like carbon (DLC), tungsten disulfide (WS2), molybdenum disulfide (MoS2), graphite, fluorine-containing polymers such as tetrafluoroethylene (PTFE), silicone, and the like. Conventionally known solid lubricants such as resins can be used as appropriate. The method for coating the lubricating coating layer is not particularly limited, and examples thereof include vacuum deposition, ion deposition, physical vapor deposition, chemical vapor deposition, and vacuum arc deposition. There may be. In particular, among the above-described lubricants, diamond-like carbon (DLC) is most preferably used in consideration of wear resistance and lubricity.
本発明のように、書き味を向上するために、２０℃、剪断速度５００ｓｅｃ−１におけるインキ粘度を、１０〜５０００ｍＰａ・ｓの範囲に設定する場合には、インキの垂れ下がりを防止するため、ボールペンチップ先端に回転自在に抱持したボールを、コイルスプリングにより直接又は押圧体を介してチップ先端縁の内壁に押圧して、筆記時の押圧力によりチップ先端縁の内壁とボールに間隙を与えインキを流出させる弁機構を具備し、チップ先端の微少な間隙も非使用時に閉鎖することが好ましい。 As in the present invention, in order to improve the writing quality, when the ink viscosity at 20 ° C. and the shear rate of 500 sec −1 is set in the range of 10 to 5000 mPa · s, a ballpoint pen is used to prevent the ink from dripping. The ball held rotatably at the tip of the tip is pressed against the inner wall of the tip end of the tip directly by a coil spring or via a pressing body, and the ink is applied to the inner wall of the tip end of the tip and the ball by the pressing force at the time of writing. It is preferable to provide a valve mechanism for allowing the chip to flow out, and to close the minute gap at the tip of the tip when not in use.
本発明は油性ボールペンとして利用でき、さらに詳細としては、該油性ボールペン用インキ組成物を充填した、キャップ式、ノック式等の水性ボールペンとして広く利用することができる。 The present invention can be used as an oil-based ballpoint pen. More specifically, the present invention can be widely used as a water-based ballpoint pen of a cap type or a knock type filled with the ink composition for oily ballpoint pens.
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| JPH09194784A (en) * | 1996-01-19 | 1997-07-29 | Mitsubishi Pencil Co Ltd | Ink composition for oil-based ball-point pen |
| JP5641698B2 (en) * | 2008-03-17 | 2014-12-17 | パイロットインキ株式会社 | Water-based ballpoint pen |
| JP5249824B2 (en) * | 2009-03-16 | 2013-07-31 | パイロットインキ株式会社 | Water-based ink composition for ballpoint pen and ballpoint pen incorporating the same |
| JP5501641B2 (en) * | 2009-03-23 | 2014-05-28 | パイロットインキ株式会社 | Oil ballpoint pen |
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