JP2012214645A - Oil-based ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-based ink composition, with which handwriting is not extended and handwriting is not thickened even if used for a marking pen or the like with a pen point by a fiber converged body, a synthetic resin molding or the like, and written in a non-absorbing surface with high hydrophilic properties such as glass and metal.SOLUTION: The oil-based ink composition at least comprises: a colorant composed of pigment and/or dye; a solvent; modified silicone oil having an alcoholic hydroxyl group in the structure; and dibasic acid ester.

Description

  The present invention is used for a marking pen having a nib made of a fiber converging body, a synthetic resin molded article, etc., and a handwriting without blurring is obtained on a non-absorbing surface, and the fixability of a coating film after drying is also good. The present invention relates to an oil-based ink composition.

Oil-based inks can be written not only on ink-absorbing surfaces such as paper and cloth, but also on non-ink-absorbing surfaces such as glass, metal, and plastic, compared to water-based inks containing water-soluble dyes and water as components.
As solvents for oil-based inks, aromatic hydrocarbons such as toluene and xylene having high solubility in oil-soluble dyes and glycol ethers such as ethylene glycol monomethyl ale and ethylene glycol monoethyl ether have been used. However, in recent years, from the viewpoint of safety to the human body, aliphatic alcohols having 4 or less carbon atoms, which have low odor and toxicity, are often used as the main solvent for oil-based inks.
However, oil-based inks containing a lower aliphatic alcohol having 4 or less carbon atoms as a solvent as a solvent have a low ink viscosity and a low surface tension of the ink, so that writing on a non-absorbing surface is possible. There is a problem that a phenomenon occurs in which the width gradually increases and widens as time passes immediately after writing. In particular, when writing on hydrophilic glass surfaces, metal surfaces, etc., aliphatic alcohols having 4 or less carbon atoms tend to have a good affinity with oxygen present on glass surfaces and metal surfaces, so the handwriting gradually spreads. The phenomenon of becoming thicker is remarkable.
In order to suppress the spread of such handwriting, Patent Document 1 discloses one obtained by adding polyether-modified silicone oil to ink, and Patent Document 2 discloses one obtained by adding polyalkylalkoxysiloxane to ink. ing.

Japanese Patent Laid-Open No. 06-271803 JP 2002-356636 A

  However, with the addition of polyether-modified silicone oil or polyalkylalkoxysiloxane, wetting and spreading gradually progressed over time, and in particular, the handwriting on the hydrophilic glass and metal surfaces became thick. .

  That is, the gist of the present invention is an oil-based ink containing at least a colorant, a solvent, a modified silicone oil having an alcoholic hydroxyl group in the structure, and a dibasic acid ester.

The modified silicone oil and dibasic acid ester having an alcoholic hydroxyl group in the structure interacts with the modified silicone oil having an alcoholic hydroxyl group in the structure at two positions due to two ester bonds of the dibasic acid ester. Will do. When the ink is applied to the writing surface, the alkyl chain of the dibasic acid ester is aligned in parallel with the writing surface to form a dense nonpolar surface, and the ink containing the polar solvent forms a surface that is difficult to wet. Thus, wetting and spreading of ink can be suppressed.
Since polyether-modified silicone oil and polyalkylalkoxysiloxane cannot form such a writing surface modified with ink repellency, the handwriting gradually increases over time. Since the surface is modified to positively suppress the extended wetting of the ink, it is assumed that a high effect can be obtained.

A silicone oil modified with a substituent having an alcoholic hydroxyl group is used together with a dibasic acid ester to prevent blotting of the handwriting on the non-absorbing surface and to improve the fixability of the handwriting.
Specific examples of silicone oils modified with a substituent having an alcoholic hydroxyl group include KF-6001, KF-6002, KF-6003, X-22-601AS (both ends carbinol-modified silicone oil), X-22-4015, X-22-4039 (above, side chain carbinol-modified silicone oil), X-22-170BX, X-22-170DX (above, one-end carbinol-modified silicone oil), X-22 -1821 (phenol-modified silicone oil) (manufactured by Shin-Etsu Silicone Co., Ltd.), BY16-201, BY16-004, SF8427 (both ends carbinol-modified silicone oil), SF8428 (side chain carbinol-modified silicone oil) ), BY16-752, BY16-799 (above, Lumpur modified silicone oil) (manufactured by Toray-Dow Corning Co., Ltd.), XF42-B0970 (both end carbinol-modified silicone oil, Momentive Performance Materials Japan Co. LLC), and the like.
The amount used is preferably 0.1% by weight or more and 5% by weight or less based on the total amount of the ink composition. If it is less than 0.1% by weight, the effect of improving the fixability of the handwriting may be small, and even if it is added in excess of 5% by weight, the effect of suppressing the spread of the handwriting does not change.

A dibasic acid ester is an ester produced by an esterification reaction of a dicarboxylic acid and an alcohol, and with silicone oil modified with a substituent having an alcoholic hydroxyl group, prevents blurring of the handwriting on the non-absorbing surface. It is used for improving the fixing property.
Specific examples of dibasic acid esters include DMA (dimethyl adipate), DBA (dibutyl adipate), DIBA (isobutyl adipate), DOA (di-2-ethylhexyl adipate), DINA (diisononyl adipate), DIDA (diisodecyl adipate), DOZ (di-2-ethylhexyl azelate), DMS (dimethyl sebacate), DBS (dibutyl sebacate), DOS (di-2-ethylhexyl sebacate), BXA (dibutyl diglycol adipate), BXA-R (dibutyl diglycol adipate) (manufactured by Daihachi Chemical Industry Co., Ltd.), NIKKOL DES-SP (diethyl sebacate), DID (diisopropyl adipate), DIS (diisopropyl sebacate), DISM (Diisostearate Malate Ril), (manufactured by Nikko Chemicals Co., Ltd.), DS-1220 (dibutyl 2-ethylhexyl sebacate, manufactured by Toyokuni Seiyaku Co., Ltd.), and the like.
The amount used is preferably 0.5% by weight or more and 5% by weight or less based on the total amount of the ink composition. If the amount is less than 0.5% by weight, the effect of suppressing the spread of the handwriting may be small. If the amount exceeds 5% by weight, the effect of improving the fixability of the handwriting may be small.

A conventionally well-known dye and pigment can be used individually or in mixture as a coloring agent.
As dyes, Japanol Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Fast Black Conch (51), Kayara Spragley VGN (71), Kayalas Direct Brilliant Yellow G (CI Direct Yellow 4), Direct Fast Yellow 5GL (same 26), Eisen Primula Aero GCLH (same 44), Direct Fast Yellow R (same 50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX ( 4) Direct Fast Scarlet 4BS (same as 23), Eisen Direct Rhodulin BH (same as 31), Direct Scarlet B (same as 37), Kayak Direct Scarlet 3B (same as 39), Eisen Primula Pink 2BLH (same as 75), Sumi Light Red F3B (80), Eisen Primula Red 4BH (81), Calas Spral Bin BL (83), Calas Light Red F5G (225), Calas Light Red F5B (226), Calas Light Rose FR (same as 227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (same as 15), Sumilite Splash Blue BRR Conk (same as 71), Dibogen Turquoise Blue S (same as 86) , Water Blue # 3 (86) Kayala Star Coyze Blue GL (86) Kayala Supra Blue FF2GL (106), Kayara Splatter Turquoise Blue FBL (199), Acid Blue Black 10B (CI Acid Black 1), Nigrosine (2) , Suminoll Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conch (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conque (52) ), Sumilan Black WA (52), Ranil Black BG Extra Conk (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (109), Kayanol Milling Black TLR (110) , Eisen Opal Black New Conque (119), Water Black 187-L (154), Kayaku Acid Brilliant Flavin FF (C.I.) I. Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Tarrazine (23), Kayaktor Torazin (23) , Suminol Fast Yellow R (25), Diacid Light Yellow 2GP (29), Suminoll Milling O O (38), Suminol Milling MR MR (42), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol Yellow N5G (110), Suminol Milling Yellow 4G 200% (same 141), Kayanor Yellow NG (same 135), Kayano Lumiling Yellow 5 GW (127), Kayanol Milling 6 GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Coxin (18), Eisenbonso RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayasil Rubinol 3GS (37), Eisen Erythrosin ( 51), kayak acid rhodamine FB (52), Suminol leveling rubinol 3GP (57), diacid alizarin rubinol F3G 200% (82), Eiseneosin GH (87), water pink # 2 (same) 92), Eisen Acid Phloxin PB 92), Rose Bengal (94), Cyanol Milling Scarlet FGW (111), Cyanol Milling Lubin 3BW (129), Sinoall Milling Brilliant Red 3BN Conch (131), Suminol Milling Brilliant Red BS ( 138), Eisen Opal Pink BH (186), Suminoll Milling Brilliant Red B Conch (249), Kayaku Acid Brilliant Red 3BL (254), Kayaku Acid Brilliant Red Brilliant Red BL (265), Kayanol Milling Red GW (276), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (17), Sumitomo Patent Pure Blue VX (CI Acid Blue) 1), Water Blue # 106 (same 1), Patent Blue AF (same 7), Water Blue # 9 (same 9), Daiwa Blue 1 (same 9), Spranol Blue B (same 15), Orient Solve Blue OBC (22), Suminol Leveling Blue 4GL (23), Mitsui Nylon Fast Blue G (25), Kayasil Blue AGG (40), Kayasil Blue BR (41), Mitsui Alizarin Saphirol SE (43) , Suminol Leveling Sky Blue R Extra Conk (62), Mitsui Nylon Fast Sky Blue B (78), Sumitomo Brilliant Indocyanine 6Bh / c (83), Sandlancyanine N-6B 350% (90), Water Blue # 115 (90), Orient Soluble Blue OBB The same 93), Sumitomo brilliant blue 5G (the 103), Kaya Nord milling Ultra Sky SE (the 112), Kaya Nord milling cyanine 5R (the 113), Aizen Opal Blue 2GLH (the 158), Daiwa Guinea green B (C. I. Acid Green 3), Acid Brilliant Milling Green B (same 9), Daiwa Green # 70 (same 16), Cyanol Cyanine Green G (same 25), Water-soluble dyes such as Suminol Milling Green G (same 27), Nigrosine Base EE, EEL, EX, EX, EXBP, EB, Oil Yellow 101, 107, Oil Pink 312, Oil Brown BB, GR, Oil Green BG, Oil Blue 613, BOS Oil Black HBB, 860, BS, Balifast Yellow 1101, 1105, 3108, 4120, Bali Orange 2210, 3209, 3210, Bali Red 1306, 1308, 1355, 1360, 2303, 2320, 3304, 3306, 332 0, Bali Fast Pink 2310N, Bali Fast Brown 2402, 3405, Bali Fast Green 1501, Bali Fast Blue 1603, 1605, 1607, 1631, 2606, 2610, 2620, Bali Fast Violet 1701, 1702 , Bali Fast Black 1802, 1807, 3804, 3806, 3806, 3810, 3820, 3830, Spirit Red 102, OSPY Yellow RY, ROB-B, MVB3, SP Blue 105 (above, Orient Chemical Industry) Co., Ltd.), Eisenspiron Yellow 3RH, GRLH Special, C-2GH, C-GNH, Eisenspiron Orange 2RH, GRH Conch Special, Eisenspiron Red GEH, BEH GRLH Special, C-GH, C-BH, Eisenspiron Violet RH, C-RH, Eisenspiron Brown BH Conch, RH, Eisenspiron Mahogany RH, Eisenspiron Blue GNH, 2BNH, C-RH, BPNH, Eisenspiron Green C-GH, 3GNH Special, Eisenspiron Black BNH, MH, RLH, GMH Special, BH Special, S.C. B. N. Orange 703, S.I. B. N. Violet 510, 521, S.I. P. T.A. Orange 6, S. P. T.A. Blue 111, SOT Pink 1, SOT Blue 4, SOT Black 1, 6, 10, 12, 13 Liquid, Eisen Rhodamine B Base, Eisen Methyl Violet Base, Eisen Victoria Blue B Base (above, Hodogaya Chemical Industry ( Co., Ltd.), Oil Yellow CH, Oil Pink 330, Oil Blue 8B, Oil Black S, FS Special A, 2020, 109, 215, AL Yellow 1106D, 3101, AL Red 2308, Neo Super Yellow C -131, C-132, C-134, Neo Super Orange C-233, Neo Super Red C-431, Neo Super Blue C-555, Neo Super Brown C-732, C-733 (above, central synthesis Chemical Co., Ltd.), Oreosol Fast Yellow 2G, GCN, Oreosol Fast Orange GL, Oreosol Fast Red BL, RL (above, manufactured by Taoka Chemical Co., Ltd.), Savinyl Yellow 2GLS, RLS, 2RLS, Savinyl Orange RLS, Savinyl Fire Red GLS, Savinyl Red 3BLS, Savinyl Pink 6BLS, Savinyl Blue RN, GLS, Savinyl Green 2GLS, Savinyl Brown GLS (Sand, Made in Switzerland), Magenta SP 247%, Crystal Violet 10B 250%, Malachite Green Crystal Conch, Brilliant Green Crystal H 90%, Spirit Soluble Red 64843 (above, Holiday, UK), Neptune Red Base 543, Neptune Blue Base 634, Nep -Menu emissions Violet base 604, Baso Neil Red 540, Baso Neil Violet 600 (or, BASF Corp., Germany), and the oil-soluble dyes such.

As the pigment, Special Black 6, S170, S610, 5, 4, 4A, 550, 35, 250, 100, Printex 150T, U, V, 140U, 140V, 95 90, 85, 80, 75, 55, 45, P, XE2, L6, L, 300, 30, 30, 35, 25, 200, A, G (above, Degussa Japan Co., Ltd.), # 2400B, # 2350, # 2300, # 2200B, # 1000, # 950, # 900, # 850, # MCF88, MA600, MA100, MA7, MA11 # 50, # 52, # 45, # 44, # 40, # 33, # 32, # 30, CF9, # 20B, # 4000B (Mitsubishi Chemical Industry Co., Ltd.), MONARCH1300 100, 1000, 900, 880, 800, 700, MOGUL L, REGAL 400R, 660R, 500R, 330R, 300R, 99R, ELFTEX8, 12, BLACK PEARLS2000 (above, USA) Manufactured by Cabot Corp.), Raven 7000, 5750, 5250, 5000, 3500, 2000, 1500, 1255, 1250, 1200, 1170, 1060, 1040, 1035, 1020 , 1000, 890H, 890, 850, 790, 780, 760, 500, 450, 430, 420, 410, 22, 22, 16, 14, H20, C, Conductex 975, 900, SC (above, Colombian Carbon black such as Carbon Japan Co., Ltd.), KA-10, 10P, 15, 20, 30, 35, 60, 80, 90, KR-310, 380, 460, 480 (above, manufactured by Titanium Industry Co., Ltd.), Taipure R-900, 902, 960 (above, manufactured by DuPont Co., Ltd.), Type CR-50, 58, 60, 67, 80, 90, R-580, 670, 680, 780, 820, 820, 930 (above, manufactured by Ishihara Sangyo Co., Ltd.), JR-300, 403, 600A, 800, 805 (above, Titaca Co., Ltd.), P25 (Nihon Aerosil Co., Ltd.) and other titanium oxides, BS-605, 607 (above, manufactured by Toyo Aluminum Co., Ltd.), Bronze Powder P-555, P-777 (above) Made by Nakajima Metal Foil Industry Co., Ltd. ), Metal powder pigments such as Bronze Powder 3L5 and 3L7 (Fukuda Metal Foil Industry Co., Ltd.), black iron oxide, yellow iron oxide, red iron oxide, ultramarine, bitumen, cobalt blue, chrome green, Inorganic pigments such as chromium oxide, Hansa Yellow-10G, 5G, 3G, 4, GR, A, Benzidine Yellow, Permanent Yellow NCG, Tartrazine Lake, Quinoline Yellow, Sudan 1, Permanent Orange, Indusren Brilliant Orange GN, Permanent Brown FG, Para Brown, Permanent Red 4R, Fire Red, Brilliant Carmine BS, Pyrazolone Red, Lake Red C, Quinacridone Red, Brilliant Carmine 6B, Bordeaux 5B, Thioindigo Red, Fast Violet B, Dioxazine Ioretto, alkali blue lake, phthalocyanine blue, indigo, acid green lake, and organic pigments such as phthalocyanine green and the like. In addition, inorganic fluorescent pigments such as zinc sulfide, zinc silicate, zinc cadmium sulfate, calcium sulfide, strontium sulfide, and calcium tungstate can be used. Further, a water-based ink base of a dispersed pigment in which a pigment is dispersed in an aqueous medium can also be used. Specifically, Fuji SP Black 8031, 8119, 8167, 8276, 8276, 8381, 8406, Fuji SP Red 5096, 5111, 5193, 5220, 5543, 5544, Fuji SP Bordeaux 5500, Fuji SP Blue 6062 6133, Fuji SP Green 7051, Fuji SP Yellow 4060, 4178, Fuji SP Violet 9011, Fuji SP Pink 9524, 9527, Fuji SP Orange 534, Fuji SP Brown ol, 307 FB, Emacol Green LXB, Violet BL, Brown 3101 , Carmine FB, Red BS, OrangeR, Yellow FD, Sandy Super Black K, Black C, Super Gray B, Super Brown SB, Super Blue SB, Super Blue SB, Super Blue SB. Super Pink FBL, Super Rubin FR, Super Carmine FB, Super Red FFG, Super Yellow D215, Orange FL, (from Sanyo Dye Co., Ltd.), NKW-2101, 2102, 2102 2104, 2105, 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2 02P, 2103P, 2104P, 2105P, 2105P, 2106P, 2107P, 2108P, 2108P, 2117P, 2127P, 2137P, 2167P, 3002, 3003, 3004, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3405, 3407, 3408, 3477, 3602, 3603, 3604, 3605, 3607, 3677, 3608, 3702, 3703, 3704 , 3705, 3777, 3708, 6013, 6038, 6559 (made by Nippon Fluorescence Co., Ltd.), Pollux Blue PC5T-1020, Black PC8T-135, Red IT-1030, etc. (Sumika Color Co., Ltd.) It is below.
Furthermore, processed pigments obtained by kneading and dispersing a pigment in a resin soluble in a solvent together with a plasticizer, and processed pigments whose surface is resin-coated are preferably used from the viewpoint of dispersibility, stability over time, and workability. Specific examples thereof include Fuji AS Black, AS Red 575, AS Blue 650, AS Green 737, AS Orange 200, AS Yellow 458, AS Violet (above, manufactured by Fuji Dye Co., Ltd.), Lavester, Dirac TN (manufactured by Dainippon Ink & Chemicals, Inc.), Polybride N (manufactured by Nippon Oil & Fats Co., Ltd.), High Corp (manufactured by Special Colorant Industries, Ltd.), and the like.
The above-mentioned colorants can be used alone or in combination, and the amount used is preferably 2.0% by weight or more and 25.0% by weight or less based on the total amount of the ink composition. If it is less than 2.0% by weight, the concentration may be too low to confirm the handwriting, and if it exceeds 25.0% by weight, the viscosity of the ink composition increases and ink ejection from the writing instrument nib may be insufficient. is there.

The solvent used in the present invention provides, for example, conventionally known methyl alcohol, ethyl alcohol, normal-propyl alcohol, isopropyl alcohol, normal-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl in order to impart handwriting drying properties. One or two or more kinds of lower alcohols having 4 or less carbon atoms such as alcohol are used in combination, and 50% by weight or more of the solvent is used as the main solvent. The amount used is determined in various mixing ratios in consideration of miscibility with other components used, but is preferably 30 to 90% by weight based on the total amount of ink.
Also, aromatic hydrocarbons such as xylene and toluene, lower aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, lower alcohol esters of lower fatty acids such as ethyl acetate and butyl acetate, and aliphatic hydrocarbons such as hexane and heptane Organic solvents such as cycloaliphatic hydrocarbons such as cyclohexane and ethylcyclohexane, glycol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and esters thereof, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mononormal butyl ether, propylene glycol mononormal propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Glycol ether solvents such as monoethyl ether, dipropylene glycol mononormal propyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, ethylene Glycol solvents such as recall, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, glycerin, polyethylene glycol, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, acetic acid isobutyl, acetic acid-n- Ester solvents such as amyl, 2-ethylhexyl acetate, isobutyl isobutyrate, ethyl lactate, n-butyl lactate, alcohols and their ethylene oxide and / or propylene oxide addition derivatives, β-phenylethyl alcohol, α-methyl Alcohol solvents such as benzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, isotridecyl alcohol, ethylene glycol monophenyl ether, propylene glycol The glycol ether solvents or the like having an aromatic ring such as monophenyl ether and ethylene oxide and / or propylene oxide adduct derivative alone or a mixture of a plurality of to be used.

Resin can also be added in order to impart further fixability to the writing surface of the handwriting. Specific examples of the resin include, for example, resins for water-based ink compositions such as resin emulsions such as styrene-acrylic, acrylic, and styrene-butadiene, alkali-soluble resins, and betaine acrylic resins, phenol resins, and ketones. Examples thereof include resins for oil-based ink compositions such as resins, rosin resins, and butyral resins.
Specific examples of resins for water-based ink compositions include Primal AC-22, AC-33, AC-55, AC-64, AC-261, AC-382, AC-388, and AC- 417, AC-490, AC-507, AC-630, AC-707, AC-3444, EC-1685, EC-1791, EC-1895, EC-2218, MV- 1, MV-9, MV-17), MV-23, E-32, E-358, HA-8, HA-12, HA-24, K-24, K-3, K -87, TR-520, TR-934HS, Experimental Emulsion E-1345 (above, manufactured by Rohm & Haas Japan Co., Ltd.), etc., Ceviane-A 146, 150 (above) , Daise ), Polyzol PS-19, PS-3HA (above, Showa Polymer Co., Ltd.) and other vinyl acetate resin emulsions, Polysol PS-120, 747L (above, Showa Polymer Co., Ltd.) Styrene / acrylic copolymer such as Polyacetate AP-2678, AP-2679, AP-2694, AP-2697 (above, Showa Polymer Co., Ltd.) Examples thereof include an ethylene / vinyl acetate resin emulsion such as a coalesced resin emulsion, Polysol EVA P-3, and P-10 (above, Showa Polymer Co., Ltd.).
When the resin emulsion is added to give fixability to the writing surface, the amount used is preferably 0.5 wt% or more and 15.0 wt% or less based on the total amount of the ink composition in terms of solid content.
Specific examples of resins for oil-based ink compositions include phenolic resins such as Tamanol 100S, 510 (above, manufactured by Arakawa Chemical Co., Ltd.), Hitanol 1501, 2501 (above, manufactured by Hitachi Chemical Co., Ltd.), YP-90, YP-90L, YS Polyster S145, # 2100, # 2115, # 2130, T80, T100, T115, T130, T145, Mighty Ace G125, 150 (above, Yashara Chemical ( Co., Ltd.) as ketone resins, such as ketone resin K-90 (Arakawa Chemical Industries, Ltd.), Halon 80, 110H (above, Honshu Chemical Co., Ltd.), synthetic resin AP, SK, 1201 (Above, manufactured by Huls, Germany), etc., as rosin resins, Hercorin D, Pentalin 255, 261 (above, Chemical Hercules Co., Ltd.), Harrier Star NL, Neotor C, Gum Rosin X (above, Harima Chemical Co., Ltd.), Gum Rosin WW (Chinese), Ester Gum H (Arakawa Chemical Co., Ltd.), etc. As a butyral resin, Denka Butyral # 2000-L, # 3000-1, # 3000-2, # 3000-4, # 3000-K (above, manufactured by Denki Kagaku Kogyo Co., Ltd.), ESREC BL-1 4BL-3, BL-S, and BX-10 (manufactured by Sekisui Chemical Co., Ltd.).
These resins can be used singly or as a mixture of two or more, and when added to give fixability to the writing surface, the amount used is 0.5 to 15.0% by weight or less based on the total amount of the ink composition. preferable. If the amount is less than 0.5% by weight, the fixability of the handwriting on the writing surface may be insufficient. If the amount exceeds 15.0% by weight, the viscosity of the ink increases and the ink discharge from the pen tip becomes poor. there is a possibility.

  These may be used alone or in combination, and the amount used is preferably 0.5 to 20% by weight based on the total amount of oil-based ink. If it is less than 0.5% by weight, the fixability of the handwriting on the non-absorbing surface is insufficient, and if it exceeds 20% by weight, the viscosity of the ink increases and ink discharge from the pen tip becomes worse, or the pen tip dries out. Problems that make it easier to occur.

  In addition to the above components, various additives such as surfactants and rust inhibitors that are conventionally used in inks can be used as needed. Examples of surfactants include polyoxyethylene alkyl ether, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid Examples include esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl ether phosphoric acids, and the like. Examples of the rust inhibitor include benzotriazole, cyclohexylammonium chloride, 2-mercaptobenzotriazole, benzoylaminocaproic acid, and calcium nitrate.

  The oil-based ink of the present invention is obtained by a method conventionally known for the above components. When using dye for a coloring agent, it stirs and mixes using a stirrer and is obtained by melt | dissolving uniformly. When a pigment is used as a colorant, a pigment dispersed with a conventionally known dispersing machine using a dispersant or the like may be used, or a commercially available processed pigment dispersed in advance may be used. At this time, coarse pigments in the ink may be removed by filtration or centrifugation.

Example 1
Nigrosine Base EX (Oil-soluble dye, manufactured by Orient Chemical Co., Ltd.) 10.0 parts by weight Ethanol 58.5 parts by weight Normal propyl alcohol 16.5 parts by weight Benzyl alcohol 5.0 parts by weight KF-6001 (both Terminal carbinol-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.)
1.0 part by weight NIKKOL DES-SP (diethyl sebacate, manufactured by Nikko Chemicals Co., Ltd.)
1.0 part by weight YP-90L (terpene phenol copolymer resin, manufactured by Yasuhara Chemical Co., Ltd.)
8.0 parts by weight The above components were stirred with a stirrer at room temperature for 4 hours to obtain a black ink composition.

(Example 2)
In Example 1, a black oil-based ink composition for ballpoint pens was obtained in the same manner as in Example 1 except that the amount of both-end carbinol-modified silicone was increased to 6.0 parts by weight and ethanol was reduced accordingly. .

(Example 3)
In Example 1, a black oil-based ink composition for ballpoint pens was obtained in the same manner as in Example 1 except that the amount of both-end carbinol-modified silicone was reduced to 0.05 parts by weight and ethanol was increased accordingly. .

Example 4
In Example 1, a black oil-based ink composition for ballpoint pens was obtained in the same manner as in Example 1 except that diethyl sebacate was increased to 6.0 parts by weight and ethanol was reduced accordingly.

(Example 5)
A black oil-based ink composition for ballpoint pens was obtained in the same manner as in Example 1, except that the amount of diethyl sebacate was reduced to 0.1 parts by weight and the amount of ethanol was increased accordingly.

(Example 6)
VarifastBlack 3806 (dye, manufactured by Orient Chemical Co., Ltd.)
15.0 parts by weight ethanol 39.5 parts by weight propylene glycol monomethyl ether 20.0 parts by weight 3-methoxy-3-methyl-1-butanol 5.0 parts by weight X-22-170DX (both ends carbinol-modified silicone, Shin-Etsu) (Chemical Industry Co., Ltd.)
0.5 parts by weight NIKKOL DIS (diisopropyl sebacate, manufactured by Nikko Chemicals)
3.0 parts by weight Harimac T80 (rosin-modified maleic resin, manufactured by Harima Chemicals Co., Ltd.)
16.0 parts by weight DK ester F110 (sucrose fatty acid ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.0 part by weight The above components were stirred at room temperature with a stirrer for 4 hours to obtain a black ink composition. .

(Example 7)
In Example 6, except that X-22-170DX (single terminal carbinol-modified silicone) was replaced with X-22-4039 (side chain carbinol-modified silicone), the same procedure as in Example 6 was performed for a black ballpoint pen. An oil-based ink composition was obtained.

(Example 8)
In Example 6, except that X-22-170DX (one-end carbinol-modified silicone) was replaced with BY16-752 (both terminal phenol-modified silicone, manufactured by Toray Dow Corning Co., Ltd.), the same as in Example 6. Thus, a black oil-based ink composition for ballpoint pens was obtained.

(Comparative Example 1)
A black oil-based ink composition was obtained in the same manner as in Example 1 except that KF-6001 (carbinol-modified silicone) and NIKKOL DES-SP (diethyl sebacate) were replaced with the same amount of ethanol. It was.

(Comparative Example 2)
A black oil-based ink composition was obtained in the same manner as in Example 1 except that KF-6001 (carbinol-modified silicone) was replaced with the same amount of ethanol.

(Comparative Example 3)
In Example 1, KF-6001 (carbinol-modified silicone) was replaced with KP-316 (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.), and NIKKOL DES-SP (diethyl sebacate) was replaced with the same amount of ethanol. A black oil-based ink composition was obtained in the same manner as Example 1 except for the replacement.

(Comparative Example 4)
In Example 1, KF-6001 (carbinol-modified silicone) was replaced with KP-316 (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.), and NIKKOL DES-SP (diethyl sebacate) was replaced with NIKKOL BM (myristic acid). A black oil-based ink composition was obtained in the same manner as in Example 1 except that it was replaced with (butyl).

(Comparative Example 5)
In Example 1, KF-6001 (carbinol-modified silicone) was replaced with SILWET FZ-3704 (polymethylmethoxysiloxane, manufactured by Nihon Unicar Co., Ltd.), and NIKKOL DES-SP (diethyl sebacate) was replaced with the same amount of ethanol. A black oil-based ink composition was obtained in the same manner as Example 1 except for the replacement.

(Comparative Example 6)
In Example 1, KF-6001 (carbinol-modified silicone) was replaced with SILWET FZ-3704 (polymethylmethoxysiloxane, manufactured by Nippon Unicar Co., Ltd.), and NIKKOL DES-SP (diethyl sebacate) was replaced with NIKKOL BM (myristic acid). A black oil-based ink composition was obtained in the same manner as in Example 1 except that it was replaced with (butyl).

(Comparative Example 7)
In Example 1, black oiliness was obtained in the same manner as in Example 1 except that X-22-4015 (carbinol-modified silicone) was replaced with KP-316 (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.). An ink composition was obtained.

  Using the oil-based ink compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 7, the writing tool using a pen tip of a fiber core and batting (Pentel Pen <Green Label> NN60 <Round Core, Bold>, Pentel ( The oil-based writing instrument for test was obtained.

Handwriting spread test A straight line is written on a glass plate (thickness 2 mm) with a load of 100 g, and the handwriting widths at any three locations of the handwriting are measured at the same position immediately after writing and 10 minutes later. At each location, the ratio is obtained by dividing the handwriting width after 10 minutes of writing by the handwriting width immediately after writing. When the obtained ratio value is close to 1, it is evaluated as a good ink with a small handwriting spread. The results are shown in Table 1.

The inks of Examples 1 to 6 were all good in that the writing surface was not spread because the writing surface was modified to ink repellency by the modified silicone having an alcoholic hydroxyl group in the structure and the dibasic acid ester. It was.
In Examples 1, 6, and 7, the effect of suppressing the spread of the handwriting was obtained regardless of the modification positions of both terminals, one terminal, and the side chain of the silicone oil. In Examples 2 and 3, the effect of suppressing the spread of the handwriting was obtained regardless of the amount of the modified silicone having an alcoholic hydroxyl group in the structure. In Examples 4 and 5, when the addition amount of the dibasic acid ester is large, the dibasic acid ester is hardly volatile, so the drying property of the ink is slightly lowered, but the effect of suppressing the spread of the handwriting Was obtained unchanged. Similarly, with the phenol-modified silicone oil of Example 8, the effect of suppressing the spread of the handwriting was obtained.

As described above, the oil-based ink of the present invention is a good handwriting that does not spread and spread when the handwriting is written on a non-absorbing surface, particularly a highly hydrophilic surface such as a glass surface or a metal surface. Is obtained.

Claims (1)

An oil-based ink composition comprising a colorant, a solvent, a modified silicone oil having an alcoholic hydroxyl group in its structure, and a dibasic acid ester.