JP2016023296A - Oil-based ink composition for writing instruments, and writing instruments using the same - Google Patents
Oil-based ink composition for writing instruments, and writing instruments using the same Download PDFInfo
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- JP2016023296A JP2016023296A JP2014150755A JP2014150755A JP2016023296A JP 2016023296 A JP2016023296 A JP 2016023296A JP 2014150755 A JP2014150755 A JP 2014150755A JP 2014150755 A JP2014150755 A JP 2014150755A JP 2016023296 A JP2016023296 A JP 2016023296A
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000003086 colorant Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 22
- 239000002184 metal Substances 0.000 abstract description 22
- 150000003839 salts Chemical class 0.000 abstract description 13
- 239000002244 precipitate Substances 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000002123 temporal effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 40
- -1 stainless steel Chemical class 0.000 description 17
- 230000032683 aging Effects 0.000 description 11
- 239000000975 dye Substances 0.000 description 11
- 150000003512 tertiary amines Chemical class 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 150000004696 coordination complex Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000003973 alkyl amines Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000000981 basic dye Substances 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000004034 viscosity adjusting agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YIKYNHJUKRTCJL-UHFFFAOYSA-N Ethyl maltol Chemical compound CCC=1OC=CC(=O)C=1O YIKYNHJUKRTCJL-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229940093503 ethyl maltol Drugs 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- 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
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229940043353 maltol Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 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
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は筆記具用油性インキ組成物及びそれを用いた筆記具に関するものである。 The present invention relates to an oil-based ink composition for a writing instrument and a writing instrument using the same.
従来より、筆記具用油性インキ組成物において、着色剤、有機溶剤、樹脂などを含有した筆記具用油性インキ組成物が提案されている。 Conventionally, in oil-based ink compositions for writing instruments, oil-based ink compositions for writing instruments containing colorants, organic solvents, resins, and the like have been proposed.
このような筆記具用油性インキ組成物としては、特開平６−２１２１１１号「油性ボールペン用インキ組成物」、特開平８−４１４０８号「油性ボールペン用インキ組成物および油性ボールペン」、特開平８−１３４３９３「ボールペン用油性インキ」が開示されている。
しかしながら、特許文献１、２の油性ボールペン用インキ組成物を用いて筆記具にした場合、チップ材やインキ収容筒として、ステンレス、ブラス、洋白材などの金属類を用いたボ−ルペンチップ本体やインキ収容筒よりマンガンイオン、クロムイオン、銅イオン、亜鉛イオン、ニッケルイオン等の金属イオンが溶出し、インキ成分と反応して金属塩が発生してしまい、筆記不良の原因を起こす問題を抱えていた。 However, when a writing instrument is used using the oil-based ballpoint pen ink composition of Patent Documents 1 and 2, a ballpoint pen tip body or ink using a metal such as stainless steel, brass, or white material as a tip material or ink containing cylinder. Metal ions such as manganese ions, chromium ions, copper ions, zinc ions and nickel ions elute from the container, reacting with the ink components to generate metal salts, and had the problem of causing poor writing. .
さらに、特許文献３のように、Ｎ−アシルアミノ酸、Ｎ−アシルメチルタウリンなどの界面活性剤を用いて潤滑性を向上する技術が多数あるが、この場合でも、インキ中で、金属製のボールペンチップ本体やインキ収容筒などから溶出した金属イオンと反応しやすく、金属塩を発生してしまう問題が起こりやすい。 Furthermore, as in Patent Document 3, there are many techniques for improving lubricity using a surfactant such as N-acylamino acid and N-acylmethyltaurine. Even in this case, a metal ballpoint pen is used in the ink. It is easy to react with the metal ions eluted from the chip body or the ink container, and the problem of generating a metal salt is likely to occur.
特許文献１〜３のように、着色剤、有機溶剤、界面活性剤、樹脂などのインキ成分の選定によって、金属製のボ−ルペンチップ本体やインキ収容筒との相性もあり、インキ中で反応して発生した金属塩などの析出物の対処法が非常に重要となる。 As in Patent Documents 1 to 3, depending on the selection of ink components such as colorants, organic solvents, surfactants, resins, etc., there is compatibility with the metal ballpoint pen tip body and ink container, and it reacts in ink. It is very important to deal with deposits such as metal salts.
本発明の目的は、インキ成分と反応して発生する金属塩などの析出物を抑制した筆記具用油性インキ組成物を提供することである。 The objective of this invention is providing the oil-based ink composition for writing instruments which suppressed deposits, such as a metal salt which reacts with an ink component, and generate | occur | produces.
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、一般式（１）からなることを特徴とする筆記具用油性インキ組成物。（式中、Ｒ１、Ｒ２、Ｒ３は、アルキル基または水素基を表す）。
３．前記一般式（１）の含有量が、０．１〜５．０質量％であることを特徴とする第１項または第２項に記載の筆記具用油性インキ組成物。
４．前記筆記具用油性インキ組成物のpH値が５〜１２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項に記載の筆記具用油性インキ組成物。
５．前記筆記具用油性インキ組成物に界面活性剤を含有することを特徴とする第１項ないし第４項のいずれか１項に記載の筆記具用油性インキ組成物。
６．第１項ないし第５項のいずれか１項に記載の筆記具用油性インキ組成物をインキ収容筒内に直詰めしたことを特徴とする筆記具。
７．インキ収容筒の先端部に、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装着し、前記インキ収容筒内に、第１項ないし第５項のいずれか１項に記載の筆記具用油性インキ組成物を収容してなる油性ボールペンレフィルを軸筒内に配設した油性ボールペンであって、前記ボールペンチップがステンレス材からなるであ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-mentioned problems, the present invention provides “1. An oil-based ink composition for a writing instrument comprising at least a colorant, an organic solvent, and a general formula (1). (Wherein R 1 , R 2 , R 3 represents an alkyl group or a hydrogen group).
3. Content of the said General formula (1) is 0.1-5.0 mass%, The oil-based ink composition for writing instruments of Claim 1 or 2 characterized by the above-mentioned.
4). The pH value of the oil-based ink composition for writing instruments is 5 to 12, The oil-based ink composition for writing instruments according to any one of Items 1 to 3.
5). The oil-based ink composition for writing instruments according to any one of items 1 to 4, wherein the oil-based ink composition for writing instruments contains a surfactant.
6). A writing instrument comprising the oil-based ink composition for a writing instrument according to any one of items 1 to 5 directly packed in an ink containing cylinder.
7). 6. A ballpoint pen tip that rotatably holds a ball is attached to the tip of the ink storage cylinder directly or via a chip holder, and the ink storage cylinder is provided with any one of items 1 to 5. An oil-based ballpoint pen in which an oil-based ballpoint pen refill containing the oil-based ink composition for a writing instrument is disposed in a shaft tube, wherein the ballpoint pen tip is made of a stainless material. "
本発明は、インキ成分と反応して発生する金属塩などの析出物を抑制して、インキ経時安定性が良好である筆記具用油性インキ組成物及びそれを用いた油性インキ組成物を提供することができた。 The present invention provides an oil-based ink composition for writing instruments that has good ink aging stability by suppressing precipitates such as metal salts generated by reacting with ink components, and an oil-based ink composition using the same. I was able to.
本発明の特徴は、少なくとも着色剤、有機溶剤、一般式（１）を含むことを特徴とする筆記具用油性インキ組成物。（式中、Ｒ１、Ｒ２、Ｒ３は、アルキル基または水素基を表す）
本発明で用いる一般式（１）については、含有することで、筆記具部材のボールペンチップ本体、インキ収容筒などに、ステンレス、ブラス、洋白材などの金属類を用いた場合において、ボ−ルペンチップ本体、インキ収容筒よりマンガンイオン、クロムイオン、銅イオン、亜鉛イオン、ニッケルイオン等の金属イオンが溶出し、インキ成分と反応して金属塩を発生する前に、一般式（１）の隣接する＝Oと−OHによって、一般式（１）が金属イオンと適当なモル比で金属錯体を形成し、金属イオンを溶解安定させることを可能とし、金属塩析出物を抑制することが可能である。 About general formula (1) used by this invention, when it contains, when using metals, such as stainless steel, a brass, and a white material, for the ball-point pen-tip main body of a writing instrument member, an ink storage cylinder, etc., a ball-point pen tip Before metal ions such as manganese ions, chromium ions, copper ions, zinc ions, and nickel ions elute from the main body and the ink container and react with the ink components to generate a metal salt, the general formula (1) is adjacent. By = O and -OH, general formula (1) can form a metal complex with a metal ion at an appropriate molar ratio, and can dissolve and stabilize the metal ion, thereby suppressing metal salt precipitates. .
一般式（１）の中でも、前記一般式（１）のＲ１〜Ｒ３のいずれかが、炭素数１〜５のアルキル基である方が好ましい。これは、アルキル基の炭素数が６以上であると、直鎖が長すぎるため、前記一般式（１）同士が反発し、一般式（１）が金属イオンと適当なモル比で金属錯体を形成し難く、金属イオンを溶解安定させにくくなり、効果が得られにくいためで、より考慮すれば、アルキル基の炭素数は１〜３である方が好ましい。特に、Ｒ１だけが炭素数１〜３のアルキル基であるマルトールやエチルマルトールなどは安定した金属錯体を作りやすく、その金属錯体を、さらに油性インキの溶剤に安定溶解させることが可能となるため、好ましく、最も好ましくは、その効果が得られやすいエチルマルトールが好ましい。 Among the general formula (1), it is preferable that any one of R 1 to R 3 in the general formula (1) is an alkyl group having 1 to 5 carbon atoms. This is because when the carbon number of the alkyl group is 6 or more, since the straight chain is too long, the general formulas (1) repel each other, and the general formula (1) forms a metal complex with a metal ion at an appropriate molar ratio. This is because it is difficult to form and it is difficult to dissolve and stabilize the metal ion, and it is difficult to obtain the effect. In consideration of this, the alkyl group preferably has 1 to 3 carbon atoms. In particular, maltol or ethyl maltol, in which only R 1 is an alkyl group having 1 to 3 carbon atoms, can easily form a stable metal complex, and the metal complex can be further stably dissolved in a solvent of oil-based ink. Preferably, most preferably, ethyl maltol is preferable because the effect can be easily obtained.
また、前記一般式（１）の含有量は、インキ組成物全量に対し、０．１〜５．０質量％がより好ましい。これは、０．１質量％より少ないと、所望の金属塩抑制効果が得られにくい傾向があり、５．０質量％を越えると、インキ中で溶解しづらく、インキ経時が不安定になりやすい傾向があるためであり、その傾向を考慮すれば、０．５〜３．０質量％が好ましく、より考慮すれば、１．０〜２．０質量％が、最も好ましい。 Moreover, as for content of the said General formula (1), 0.1-5.0 mass% is more preferable with respect to the ink composition whole quantity. If the amount is less than 0.1% by mass, the desired metal salt suppression effect tends to be difficult to obtain. If the amount exceeds 5.0% by mass, it is difficult to dissolve in the ink and the ink aging tends to become unstable. This is because there is a tendency, and considering the tendency, 0.5 to 3.0% by mass is preferable, and more considering 1.0 to 2.0% by mass is most preferable.
前記筆記具用油性インキ組成物のｐＨ値は５〜１２とする方が好ましい。これは、ｐＨ値が５未満だと、前記一般式（１）の−OHがO−になりづらく、一般式（１）の＝Oと−OHによって、安定した金属錯体を作りやすくなる効果が劣るためで、ｐＨ値が１２を越えると、着色剤が分離しやすくなるため、インキ経時安定性や、色調に影響が出やすいためである。さらに、より安定した金属錯体を作りやすくして、よりインキ経時安定性を考慮すれば、ｐＨ値が７．０〜１０．０が好ましい。 The pH value of the oil-based ink composition for writing instruments is preferably 5-12. This is because when it pH value is less than 5, -OH is O in the general formula (1) - a difficult becomes, by = O and -OH of the general formula (1), is easily made effective to make a stable metal complex This is because it is inferior, and when the pH value exceeds 12, it is easy for the colorant to be separated, so that the ink aging stability and the color tone are easily affected. Furthermore, if it is easy to make a more stable metal complex and the ink aging stability is taken into consideration, the pH value is preferably 7.0 to 10.0.
尚、本発明におけるｐＨ値は、筆記具用油性インキ組成物の測定方法において、油性インキを容器に採取し、イオン交換水を加えて、攪拌しながら加温し、加温後放冷し、蒸発した水分量を補充後、濾紙を用いて濾過する。その濾過したろ液の上層を用いて、東亜ディーケーケー社製IＭ−４０Ｓ型ｐＨメーターを用いて、２０℃にて測定した値を示すものである。 The pH value in the present invention is determined by collecting oil-based ink in a container, adding ion-exchanged water, heating with stirring, allowing to cool after heating, and evaporating in the method for measuring an oil-based ink composition for writing instruments. After replenishing the water content, it is filtered using filter paper. The value measured at 20 degreeC using the IM-40S type | mold pH meter by the Toa DK company is shown using the upper layer of the filtered filtrate.
また、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、リン酸エステル系界面活性剤、脂肪酸などを用いる場合には、インキ中に、リン酸基、脂肪酸基などが遊離して、金属製のボ−ルペンチップ本体、インキ収容筒の金属類と反応しやすく、金属塩を発生しやすいため、本発明のような一般式（１）を用いると効果的であり、好ましい。特に、リン酸エステル系界面活性剤、脂肪酸を用いる場合は効果的である。 Also, when using phosphate ester surfactants, fatty acids, etc. as surfactants to improve lubricity and ink aging stability, phosphate groups, fatty acid groups, etc. are liberated in the ink. Since it is easy to react with the metal ball pen tip main body and the metal of the ink containing cylinder and easily generate a metal salt, it is effective and preferable to use the general formula (1) as in the present invention. In particular, it is effective when using phosphate ester surfactants and fatty acids.
本発明で用いる着色剤については、染料、顔料があるが、染料の種類については、油溶性染料、酸性染料、塩基性染料、含金染料、直接染料などや、それらの各種造塩タイプの染料として、酸性染料と塩基性染料との造塩染料、有機酸と塩基性染料との造塩染料、酸性染料と有機アミンなどの造塩染料があり、インキ中で造塩染料が分離し、金属製のボールペンチップ本体やインキ収容筒などから溶出した金属イオンと反応して金属塩を発生する可能性があるため、本発明のような一般式（１）を用いると効果的であり、好ましい。 The colorant used in the present invention includes dyes and pigments. The types of dyes include oil-soluble dyes, acid dyes, basic dyes, metal-containing dyes, direct dyes, and various salt-forming dyes. There are salt-forming dyes of acid dyes and basic dyes, salt-forming dyes of organic acids and basic dyes, salt-forming dyes of acid dyes and organic amines, etc. Since there is a possibility that a metal salt is generated by reacting with a metal ion eluted from a manufactured ballpoint pen tip body or an ink containing cylinder, it is effective and preferable to use the general formula (1) as in the present invention.
染料については、具体的には、バリファーストブラック１８０２、バリファーストブラック１８０５、バリファーストブラック１８０７、バリファーストバイオレット１７０１、バリファーストバイオレット１７０４、バリファーストバイオレット１７０５、バリファーストブルー１６０１、バリファーストブルー１６０５、バリファーストブルー１６１３、バリファーストブルー１６２１、バリファーストブルー１６３１、バリファーストレッド１３２０、バリファーストレッド１３６０、バリファーストレッド１３８０、バリファーストイエロー１１０１、バリファーストイエロー１１５１、（以上、オリエント化学工業（株）製）、アイゼンスピロンブラックＧＭＨ−スペシャル、アイゼンスピロンバイオレット Ｃ−ＲＨ、アイゼンスピロンブルー ＧＮＨ、アイゼンスピロンブルー ２ＢＮＨ、アイゼンスピロンブルー Ｃ−ＲＨ、アイゼンスピロンレッド Ｃ−ＧＨ、アイゼンスピロンレッド Ｃ−ＰＨ、アイゼンスピロンレッド Ｃ−ＢＨ、アイゼンスピロンイエロー Ｃ−ＧＮＨ、アイゼンスピロンイエロー Ｃ−２ＧＨ、Ｓ．Ｐ．Ｔ．ブルー１１１、Ｓ．Ｐ．Ｔ．ブルーＧＬＳＨ−スペシヤル、Ｓ．Ｐ．Ｔ．レッド５３３、Ｓ．Ｐ．Ｔ．オレンジ６、Ｓ．Ｂ．Ｎ．バイオレット５１０、Ｓ．Ｂ．Ｎ．イエロー５１０、Ｓ．Ｂ．Ｎ．イエロー５３０、Ｓ．Ｒ．Ｃ−ＢＨ（以上、保土谷化学工業（株）製）等が挙げられる。 Regarding the dye, specifically, Bali First Black 1802, Bali First Black 1805, Bali First Black 1807, Bali First Violet 1701, Bali First Violet 1704, Bali First Violet 1705, Bali First Blue 1601, Bali First Blue 1605, Bali First Blue 1613, Bali First Blue 1621, Bali First Blue 1631, Bali First Red 1320, Bali First Red 1360, Bali First Red 1380, Bali First Yellow 1101, Bali First Yellow 1151, (above, manufactured by Orient Chemical Co., Ltd.) , Eisenspiron Black GMH-Special, Eisenspiron Violet C-RH, Eisen Pilon Blue GNH, Eisenspiron Blue 2BNH, Eisenspiron Blue C-RH, Eisenspiron Red C-GH, Eisenspiron Red C-PH, Eisenspiron Red C-BH, Eisenspiron Yellow C-GNH, Eisenspir Ron Yellow C-2GH, S. P. T. T. et al. Blue 111, S.I. P. T. T. et al. Blue GLSH-special P. T. T. et al. Red 533, S.D. P. T. T. et al. Orange 6, S. B. N. Violet 510, S.I. B. N. Yellow 510, S.I. B. N. Yellow 530, S.I. R. C-BH (above, manufactured by Hodogaya Chemical Co., Ltd.) and the like.
着色剤の含有量は、インキ組成物全量に対し、５．０〜４０．０質量％が好ましい。これは５．０質量％未満だと、濃い筆跡が得られにくい傾向があり、４０．０質量％を越えると、インキ中での溶解性に影響しやすい傾向があるためで、よりその傾向を考慮すれば、７．０〜２５．０質量％が好ましく、さらに考慮すれば、１０．０〜２０．０質量％である。 As for content of a coloring agent, 5.0-40.0 mass% is preferable with respect to the ink composition whole quantity. If the amount is less than 5.0% by mass, dark handwriting tends to be difficult to obtain. If the amount exceeds 40.0% by mass, the solubility in ink tends to be affected. Considering it, 7.0 to 25.0 mass% is preferable, and further considering it is 10.0 to 20.0 mass%.
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−３−メチルブタノール等のグリコールエーテル溶剤、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溶剤、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溶剤など、油性ボールペン用インキとして一般的に用いられる有機溶剤が例示できる。 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 ether solvents such as methoxybutanol and 3-methoxy-3-methylbutanol, glycol solvents such as diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, butylene glycol and ethylene glycol, benzyl alcohol, methanol, ethanol , 1-propanol, 2- For oil-based ballpoint pens such as lopanol, isopropanol, isobutanol, t-butanol, propargyl alcohol, allyl alcohol, 3-methyl-1-butyn-3-ol, alcohol solvents such as ethylene glycol monomethyl ether acetate and other higher alcohols The organic solvent generally used as ink can be illustrated.
また、有機溶剤の含有量は、溶解性、筆跡乾燥性、にじみ等を向上することを考慮すると、インキ組成物全量に対し、１０．０〜７０．０質量％が好ましい、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。 Further, the content of the organic solvent is preferably 10.0 to 70.0% by mass with respect to the total amount of the ink composition in consideration of improving solubility, handwriting drying property, bleeding, etc. If it does, 30.0-65.0 mass% is preferable, Most preferably, it is 45.0-65.0 mass%.
さらに、本発明の筆記具用油性インキ組成物に、有機アミンを用いるのが好ましい。これは、ｐＨ値を５〜１２の領域にしやすくすることで、一般式（１）と金属イオンとの錯体を形成しやすくするためである。有機アミンについては、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等や、ラウリルアミン、ステアリルアミン、ジステアリルアミン、ジメチルラウリルアミン、ジメチルステアリルアミン、ジメチルオクチルアミン等のアルキルアミン等や、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジメチルエタノールアミン等のアルカノールアミンが挙げられる。 それらの有機アミンの中でも、１級アミンだと反応性が強いため、着色剤の分離や、色調に影響が出やすいため、２級アミン及び／又は３級アミンを用いることが好ましい。特に、２級アミン及び／又は３級アミンの中でも、一般式（１）との安定性やｐＨ値を５〜１２にコントロールすることを考慮すれば、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が好ましい。これらは、単独又は２種以上混合して使用してもよい。 Furthermore, it is preferable to use an organic amine in the oil-based ink composition for writing instruments of the present invention. This is because it is easy to form a complex of the general formula (1) and a metal ion by making the pH value easy to be in the range of 5 to 12. For organic amines, oxyethylene alkylamines, polyoxyethylene alkylamines, etc., alkylamines such as laurylamine, stearylamine, distearylamine, dimethyllaurylamine, dimethylstearylamine, dimethyloctylamine, monoethanolamine, Examples include alkanolamines such as diethanolamine, triethanolamine, and dimethylethanolamine. Among these organic amines, primary amines are highly reactive, so that colorant separation and color tone are likely to be affected. Therefore, secondary amines and / or tertiary amines are preferably used. In particular, among secondary amines and / or tertiary amines, oxyethylene alkylamines and polyoxyethylene alkylamines are considered in consideration of stability with general formula (1) and controlling the pH value to 5-12. preferable. You may use these individually or in mixture of 2 or more types.
前記有機アミンの含有量は、インキ経時安定性、界面活性剤との中和性、ｐＨ値を考慮すると、インキ組成物全量に対し、０．１〜１０．０質量％が好ましく、より好ましくは、０．５〜５．０質量％である。 The content of the organic amine is preferably 0.1 to 10.0% by mass with respect to the total amount of the ink composition, more preferably, taking into account ink aging stability, neutralization with a surfactant, and pH value. 0.5 to 5.0 mass%.
有機アミン具体例としては、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としては、ナイミーンＬ−２０１（２級アミン）、同Ｌ−２０２（３級アミン）、同Ｌ−２０７（３級アミン）、同Ｓ−２０２（３級アミン）、同Ｓ−２０４（３級アミン）、同Ｓ−２１０（３級アミン）、同ＤＴ−２０８（３級アミン）（日本油脂（株）社製）等が挙げられる。アルキルアミンとしては、ファーミン８０（１級アミン）、ファーミンＤ８６（全２級アミン）、ファーミンＤＭ２０９８（３級アミン）、ファーミンＤＭ８６８０（３級アミン）（花王（株））等が挙げられる。これらは、単独又は２種以上混合して使用してもよい。 Specific examples of organic amines include oxyethylene alkylamine, polyoxyethylene alkylamine, Nimin L-201 (secondary amine), L-202 (tertiary amine), L-207 (tertiary amine), S-202 (tertiary amine), S-204 (tertiary amine), S-210 (tertiary amine), DT-208 (tertiary amine) (manufactured by NOF Corporation), etc. Can be mentioned. Examples of the alkylamine include Farmin 80 (primary amine), Farmin D86 (all secondary amines), Farmin DM2098 (tertiary amine), Farmin DM8680 (tertiary amine) (Kao Corporation), and the like. You may use these individually or in mixture of 2 or more types.
また、本発明によるインキ組成物には、その他の添加剤として、潤滑性やインキ経時安定性を向上させるために、（ｉ）粘度調整剤、例えば脂肪酸アマイド、水添ヒマシ油などの擬塑性付与剤、また、（ｉｉ）着色剤安定剤、（ｉｉｉ）可塑剤、（ｉｖ）キレート剤、または（ｖ）助溶剤としての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, the ink composition according to the present invention is provided with pseudoplasticity such as (i) viscosity modifier, for example, fatty acid amide, hydrogenated castor oil, etc., as other additives in order to improve lubricity and ink aging stability. An agent, (ii) a colorant stabilizer, (iii) a plasticizer, (iv) a chelating agent, or (v) water as a cosolvent may be appropriately used. These may be used alone or in combination of two or more.
また、ボ−ルペンチップ本体、インキ収容筒などの材料は、ステンレス材、洋白、ブラス（黄銅）、アルミニウム青銅、アルミニウムなどの金属材や、ポリカーボネート、ポリアセタール、 ABSなどの樹脂材が挙げられるが、ステンレス材からなるボ−ルペンチップ本体、インキ収容筒などを用いた筆記具の場合には、ステンレス材に含まれるマンガンやクロム等のマンガンイオンやクロムイオンが、インキ成分と反応することによって金属塩を生じやすいため、本発明のような一般式（１）を用いると効果的であり、好ましい。 In addition, the materials such as the ballpoint pen tip body and the ink containing cylinder include metal materials such as stainless steel, white, brass (brass), aluminum bronze, aluminum, and resin materials such as polycarbonate, polyacetal, and ABS. In the case of writing instruments using a ballpoint pen tip body made of stainless steel, an ink container, etc., manganese ions such as manganese and chromium contained in the stainless steel and chromium ions react with the ink components to produce metal salts. Since it is easy, it is effective and preferable to use the general formula (1) as in the present invention.
また、ボールペンチップのボールは、特に限定されるものではないが、タングステンカーバイドを主成分とする超硬合金ボールは、その結合材として、コバルト、ニッケル等を用いている。前記一般式（１）は、コバルト、ニッケル等の金属に対して、アミノカルボン酸のようなキレート剤よりも、ボールペンチップのボールを腐食させづらいため、腐食によるボールの回転抵抗を生じづらく、良好な書き味が得られやすく、超硬合金ボールに対して好適に用いることができる。
また、ボールの直径は、特に限定されないが、一般的には０．２ｍｍ〜２．０ｍｍ程度である。
Further, the ball-point pen tip ball is not particularly limited, but a cemented carbide ball mainly composed of tungsten carbide uses cobalt, nickel, or the like as its binder. The general formula (1) is good because it is hard to corrode the ball of the ball-point pen tip against the metal such as cobalt, nickel, etc. than the chelating agent such as amino carboxylic acid, and thus it is difficult to cause the rotation resistance of the ball due to corrosion. Can be used favorably for cemented carbide balls.
The diameter of the ball is not particularly limited, but is generally about 0.2 mm to 2.0 mm.
実施例１の筆記具用油性インキ組成物は、着色剤として染料、有機溶剤としてアルコール系溶剤、グリコールエーテル系溶剤、粘度調整剤としてケトン樹脂、界面活性剤としてリン酸エステル系界面活性剤と脂肪酸、一般式（１） （Ｒ１：Ｃ２Ｈ５、Ｒ２、Ｒ３：Ｈ） 、有機アミンとしてオキシエチレンアルキルアミン、曳糸性付与樹脂としはポリビニルピロリドン樹脂を採用し、これを所定量秤量して、６０℃に加温した後、ディスパー攪拌機を用いて完全溶解させて筆記具用油性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。また、実施例１のｐＨは、IＭ−４０Ｓ型pHメーターを用いて、２０℃にて測定したところ、ｐＨ＝７．２であった。 The oil-based ink composition for a writing instrument of Example 1 includes a dye as a colorant, an alcohol solvent as an organic solvent, a glycol ether solvent, a ketone resin as a viscosity modifier, a phosphate ester surfactant and a fatty acid as a surfactant, General formula (1) (R 1 : C 2 H 5 , R 2 , R 3 : H), oxyethylene alkylamine as organic amine, and polyvinylpyrrolidone resin as spinnability-imparting resin are weighed in a predetermined amount. And after heating at 60 degreeC, it was made to melt | dissolve completely using a disper stirrer, and the oil-based ink composition for writing instruments was obtained. Specific blending amounts are as follows. Moreover, when pH of Example 1 was measured at 20 degreeC using the IM-40S type | mold pH meter, it was pH = 7.2.
実施例１
着色剤（有機酸と塩基性染料との造塩染料） ２０．０質量％
アルコール系溶剤（ベンジルアルコール） ３１．８質量％
グリコールエーテル系溶剤（エチレングリコールモノフェニルエーテル）２１．９質量％
粘度調整剤（ケトン樹脂） １８．０質量％
界面活性剤剤（リン酸エステル系界面活性剤） ２．０質量％
界面活性剤剤（脂肪酸） ３．０質量％
一般式（１）(Ｒ１：Ｃ２Ｈ５、Ｒ２、Ｒ３：Ｈ） １．０質量％
有機アミン（オキシエチレンアルキルアミン） ２．０質量％
曳糸性付与樹脂（ポリビニルピロリドン樹脂） ０．３質量％
Example 1
Colorant (salt-forming dye of organic acid and basic dye) 20.0% by mass
Alcohol solvent (benzyl alcohol) 31.8% by mass
Glycol ether solvent (ethylene glycol monophenyl ether) 21.9% by mass
Viscosity modifier (ketone resin) 18.0% by mass
Surfactant (phosphate ester surfactant) 2.0% by mass
Surfactant (fatty acid) 3.0% by mass
Formula (1) (R 1: C 2 H 5, R 2, R 3: H) 1.0 wt%
Organic amine (oxyethylene alkylamine) 2.0% by mass
Spinnability imparting resin (polyvinylpyrrolidone resin) 0.3% by mass
実施例２〜８
表１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の筆記具用油性インキ組成物を得た。表に測定、評価結果を示す。
As shown in Table 1, oil-based ink compositions for writing instruments of Examples 2 to 8 were obtained in the same procedure as Example 1 except that each component was changed. The measurement and evaluation results are shown in the table.
比較例１〜５
表２に示すように、各成分を変更した以外は、実施例１と同様の手順で、比較例１〜５の筆記具用油性インキ組成物を得た。表に測定、評価結果を示す。
As shown in Table 2, oil-based ink compositions for writing instruments of Comparative Examples 1 to 5 were obtained in the same procedure as Example 1 except that each component was changed. The measurement and evaluation results are shown in the table.
試験及び評価
実施例１〜８及び比較例１〜５で作製した筆記具用油性インキ組成物を、インキ収容筒（ポリプロピレン製）の先端に、ボール（φ０．７ｍｍ）を回転自在に抱時したステンレス材のボールペンチップを装着するとともに、インキ収容筒内に、実施例１の油性ボールペン用インキ（０．２g）を直に収容してボールペンレフィルを（株）パイロットコーポレーション製の油性ボールペン（商品名：スーパーグリップ）に配設して、油性ボールペンを作製し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。
Test and Evaluation Stainless steel in which the oil-based ink composition for writing instruments prepared in Examples 1 to 8 and Comparative Examples 1 to 5 is held by a ball (φ0.7 mm) rotatably at the tip of an ink containing cylinder (made of polypropylene). The ballpoint pen tip of the material is mounted, and the ink for oil-based ballpoint pen of Example 1 (0.2 g) is directly accommodated in the ink-holding cylinder, so that the ballpoint refill is an oil-based ballpoint pen manufactured by Pilot Corporation (trade name: An oil-based ballpoint pen was prepared and the following tests and evaluations were performed using writing paper JIS P3201 as writing test paper.
チップ内インキ経時試験：６０℃、湿度８０％、２週間経過後に光学顕微鏡（オリンパス社製）倍率１００倍にてチップ本体内のインキを顕微鏡観察した。
析出物がなく、良好のもの ・・・◎
析出物が微少に発生したもの ・・・○
析出物が発生したが、実用上問題のないもの ・・・△
析出物が発生し、カスレや筆記不良などの原因になるもの ・・・×
In-chip ink aging test: The ink in the chip body was observed with a microscope at an optical microscope (Olympus) magnification of 100 times after 60 weeks, 80% humidity and 2 weeks.
Good without deposits ... ◎
Slightly generated precipitates ... ○
Precipitates are generated, but there are no practical problems.
Precipitates are generated, causing scumming or poor writing ・ ・ ・ ×
インキ経時試験：直径１５mmの密開閉ガラス試験管に筆記具用油性用インキ組成物を入れて、常温にて１か月放置後、適量採取し、インキを顕微鏡観察した。
析出物がなく、良好のもの ・・・◎
析出物が微少に発生したもの ・・・○
析出物が発生し、カスレや筆記不良などの原因になるもの ・・・×
Ink aging test: An oil-based ink composition for writing instruments was placed in a 15 mm diameter open / close glass test tube, allowed to stand at room temperature for 1 month, and then an appropriate amount was collected, and the ink was observed under a microscope.
Good without deposits ... ◎
Slightly generated precipitates ... ○
Precipitates are generated, causing scumming or poor writing ・ ・ ・ ×
実施例１〜８では、チップ内インキ経時試験、インキ経時試験ともに良好な性能が得られた。 In Examples 1 to 8, good performance was obtained in both the in-chip ink aging test and the ink aging test.
比較例１〜３では、一般式（１）を用いなかったため、析出物が発生し、カスレや筆記不良などが発生してしまった。 In Comparative Examples 1 to 3, since the general formula (1) was not used, precipitates were generated, causing blurring and poor writing.
比較例４、５では、アミノカルボン酸を用いたが、析出物が発生し、カスレや筆記不良などが発生してしまった。さらに、ボール表面を顕微鏡で観察したところ、腐食が見られた。 In Comparative Examples 4 and 5, aminocarboxylic acid was used, but precipitates were generated, resulting in blurring and poor writing. Furthermore, when the ball surface was observed with a microscope, corrosion was observed.
本発明は、実施例のボールペンに限らず、万年筆、マーカー、サインペン、プレートペン等に好適に使用でき、さらに詳細としては、該筆記具用油性インキ組成物を充填した、キャップ式、出没式等の筆記具として広く利用することができる。 The present invention is not limited to the ballpoint pens of the examples, and can be suitably used for fountain pens, markers, sign pens, plate pens, etc., and more specifically, cap-type, retractable type, etc. filled with the oil-based ink composition for writing instruments Can be widely used as a writing instrument.
尚、ボールペンチップ本体内にステンレス材からなるボールを押圧するコイルスプリングを配設する場合には、金属製のボールペンチップ本体やインキ収容筒と同様に、インキ成分と反応して金属塩が発生するおそれがあるため、本発明の効果は顕著である。 When a coil spring that presses a ball made of stainless steel is disposed in the ballpoint pen tip body, a metal salt is generated by reacting with the ink component, as in the case of the metal ballpoint pen tip body and the ink containing cylinder. Since there is a possibility, the effect of this invention is remarkable.
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|---|---|---|---|---|
| JPH10245518A (en) * | 1997-02-28 | 1998-09-14 | Pentel Kk | Oil-base ballpoint ink composition |
| JP2004142255A (en) * | 2002-10-24 | 2004-05-20 | Mitsubishi Pencil Co Ltd | Writing utensil |
| CN102212288A (en) * | 2010-04-07 | 2011-10-12 | 上海科迎化工科技有限公司 | Stably-complexed ink for pigment type gel-ink pen and preparation method thereof |
| US20120105553A1 (en) * | 2010-10-29 | 2012-05-03 | Sowinski Allan F | Aqueous inkjet printing fluid compositions |
| JP2012092250A (en) * | 2010-10-28 | 2012-05-17 | Pilot Corporation | Ink composition for oily ball point pen, and oily ball point pen refill using the same |
| JP2014019703A (en) * | 2012-07-12 | 2014-02-03 | Pilot Corporation | Ink composition for oily ballpoint pen and oily ballpoint pen using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10245518A (en) * | 1997-02-28 | 1998-09-14 | Pentel Kk | Oil-base ballpoint ink composition |
| JP2004142255A (en) * | 2002-10-24 | 2004-05-20 | Mitsubishi Pencil Co Ltd | Writing utensil |
| CN102212288A (en) * | 2010-04-07 | 2011-10-12 | 上海科迎化工科技有限公司 | Stably-complexed ink for pigment type gel-ink pen and preparation method thereof |
| JP2012092250A (en) * | 2010-10-28 | 2012-05-17 | Pilot Corporation | Ink composition for oily ball point pen, and oily ball point pen refill using the same |
| US20120105553A1 (en) * | 2010-10-29 | 2012-05-03 | Sowinski Allan F | Aqueous inkjet printing fluid compositions |
| JP2014019703A (en) * | 2012-07-12 | 2014-02-03 | Pilot Corporation | Ink composition for oily ballpoint pen and oily ballpoint pen using the same |
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