JP6507926B2 - Oil-based ink for ballpoint pen - Google Patents

Description

  The present invention is an oil-based ink for a ballpoint pen which is excellent in color development of the handwriting, so that the handwriting does not jump when writing on a slippery paper surface, so-called coated paper writing performance is excellent and coated paper writing performance is excellent even after long-term aging. It is about

  Conventionally, as a dye for oil-based inks for ball point pens, a salt-forming dye composed of an acid dye and a basic substance is preferably used because it is excellent in the safety of the dye and the color development of the ink. It is also known to lower the viscosity of oil-based inks in order to obtain a light writing taste with these ink compositions.

  Patent Document 1 discloses a low viscosity ink in which a salt forming dye comprising an acid dye and a basic substance, a phosphate ester surfactant, and a polyoxyethylene alkylamine, an oxyethylene alkylamine or an alkylamine are used in combination. An ink which is lubricated, has a smooth writing taste and can be prevented from being worn between a ball and a ball seat, and is ink which is stable over time is disclosed.

  In Patent Document 2, a low viscosity of the ball surface is achieved by using a salt forming dye consisting of an acid dye and a basic substance, a solvent having a specific structure, and an additive of pyrrole, γ-lactam, indole and imidazole. There is disclosed an ink which improves the wetting of the ink and suppresses the paper slippage phenomenon on a writing surface which has been subjected to a surface treatment such as a sticky paper or a coated paper, in addition to a plain paper.

JP, 2009-108178, A JP, 2012-082338, A

  In Patent Document 1, an ink having excellent abrasion resistance and good stability over time is obtained, but the wetting of the ink on the ball surface is poor, and the ball slips at the time of writing on a writing surface having a smooth paper surface like coated paper. , There was a problem that line jump occurred.

In Patent Document 2, even if the writing surface has a smooth paper surface like coated paper, ink can sufficiently prevent line slippage without causing paper slippage as in coated paper, but pyrrole, which improves surface wettability, γ -Cyclic compounds of lactams, indoles, and imidazoles are prone to decyclization due to heat, oxidation, aging, etc., and when the ink is placed in a high temperature environment, substances that improve the writable properties of coated paper become ineffective. Also, even at room temperature, there are similar problems in the long run.
A salt forming dye comprising an acid dye and a basic substance is excellent in color development of the ink and provides clear handwriting, but a solvent used for a low viscosity oil-based ballpoint pen as disclosed in Patent Document 2 In some cases, the solubility is somewhat poor, and the dye may be precipitated over a long period of time. Patent Document 1 shows that the ink aging is good, but an ink composed only of benzyl alcohol having a good solubility as disclosed in this document and ethylene glycol monophenyl ether is effective phosphorus. Even in the case of the combination of an acid ester and an amine, such a solvent used for a low viscosity ink sometimes has insufficient solubility, and there has been a problem that the precipitated crystals deteriorate coated paper writing properties.

  Therefore, the present invention is an oil-based oil for ballpoint pens which is excellent in coloring properties of handwriting, so that writing does not jump when writing on slippery paper surface, so-called coated paper writing performance is excellent and coated paper writing performance is excellent even after long-term aging. The purpose is to provide ink.

  That is, according to the present invention, an oil-based ink for ball-point pen containing at least a salt-forming dye comprising an acid dye and a basic substance, triisopropanolamine and a phosphate ester is the first aspect, and the oil-based ink for ball-point pen is The oil-based ink for ball-point pens containing polyoxyethylene (hardened) castor oil is the second aspect.

  The oil-based ink for ball-point pens of the present invention is used for ball-point pens and has excellent coloring properties of the handwriting, so that the writing does not jump when writing on slippery paper surface. Although the reason for excellent paper writability has not been clarified in detail, it is possible to form a salt-forming dye composed of an acid dye and a basic substance, and a phosphate ester while maintaining good coloring of acid dye-derived handwriting. In addition, by adding triisopropanolamine to the ink, the wettability of the surface of the ball is improved, and even when the writing surface is smooth like a coated paper, the ball does not slip at the time of writing, so line fly can be prevented. There is no change in the properties of the oil-based ink for ball-point pens even with the passage of time in a high temperature environment, and the ink can be maintained in a good state without deterioration of the wettability of the ink over a long period of time. The ink composition is excellent in the dissolution stability of the dye and other components even in long-term aging without being affected by the type of solvent, and the precipitate and insoluble matter do not inhibit the rotation of the ball. It is surmised that an oil-based ink for ballpoint pens excellent in coated paper writing properties can be obtained.

  By further adding polyoxyethylene (hardened) castor oil to the oil-based ink for ballpoint pens of the present invention, it is possible to prevent line jump even in reverse writing, in which line jump is likely to occur in coated paper writing, and excellent coated paper writability can get.

Longitudinal sectional view showing the oil-based ballpoint pen refill of the present invention Longitudinal sectional view showing a ballpoint pen tip of the present invention An enlarged sectional view of a portion I of FIG. 2 Longitudinal section of sample 1 II-II 'cross-section arrow line view of FIG. 4 Longitudinal section of sample 2 The III-III 'line cross section arrow line view of FIG. 6 Longitudinal section of sample 3 The IV-IV 'line cross section arrow line view of FIG. 8

  The invention will be described in detail below.

  The organic solvent used in the present invention is not particularly limited as long as it is conventionally used in oil-based inks for ball point pens, and in particular, alcohols, glycols and glycol ethers are preferable from the viewpoint of safety and odor.

Specific examples of the organic solvent include ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether Ethylene glycol monoisopropyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol diisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono 2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol monobutyl ether , Polyethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether Ter, propylene glycol tertiary butyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Glycol ethers such as tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, 3-methyl-3-methoxy-1-butyl acetate, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene Glycol, octylene glycol, gu Glycols such as Lyselin, polyethylene glycol, 3-methyl-1,3 butanediol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, etc., benzyl alcohol, β-phenylethyl alcohol, α -Methyl benzyl alcohol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 3-methyl-3-methoxy Alcohols such as pentanol, lauryl alcohol, tridecyl alcohol, isodecyl alcohol, isotridecyl alcohol, methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexene Ethers such as silether and 2-ethylhexyl ether; esters such as 2-ethylhexyl acetate, isobutyl isobutyrate, ethyl lactate and butyl lactate can be mentioned. The partial use of a low boiling point organic solvent is suitable for reducing the viscosity of the ink and for reducing the writing taste. The low boiling point organic solvents which can be suitably used are organic solvents selected from glycols and glycol ethers having a boiling point of 140 ° C. or more and 200 ° C. or less. Specifically, hexylene glycol, 3-methoxy-1-butanol, 3-methoxy -3-Methyl-1-butanol, diethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether and the like can be mentioned.
Low-boiling organic solvents selected from glycols and glycol ethers having a boiling point of 140 ° C. or more and 200 ° C. or less in consideration of writing taste improvement due to low viscosity and pen tip drying resistance and high boiling point organic solvents having a boiling point exceeding 200 ° C. The weight ratio of the low boiling point organic solvent / high boiling point organic solvent is preferably 1.0 or more and 30.0 or less, and more preferably 1.3 or more and 6.0 or less.

  These organic solvents can be used alone or in combination, and the amount of use thereof is preferably 10.0% by weight or more and 90.0% by weight or less based on the total amount of the oil-based ink for ball point pen.

  As a coloring agent used in the present invention, a salt-forming dye comprising at least an acid dye and a basic substance is essential because it has high safety and excellent color development of the ink, but other conventionally known coloring agents may be used in combination Can also be used.

  As the basic substance used for salt formation in the above-described salt-forming dye comprising the acid dye and the basic substance, conventionally known basic dyes and basic substances can be used.

  Specific examples of salt-forming dyes comprising an acid dye and a basic dye which are conventionally known to be used in oil-based inks include VALIFAST RED 1308 (from C.I. Acid Yellow 23 and C.I. Basic Red 1). 1355 (C. I. Acid Yellow 23 and C. I. Basic Red 1), C. 1388 (C. I. Acid Yellow 23 and C. I. Basic Red 1). Salt forming dye), VALIFAST GREEN 1501 (salt forming dye comprising C.I. Acid Yellow 42 and C.I. Basic Blue 1), VALIFAST VIOLET 1701 (C.I. Acid Yellow 42 and C. I. Consists of .Basic Violet 1 and Salt forming dye), 1704 (salt forming dye consisting of CI Acid Yellow 36 and CI Basic Violet 1), 1173 (salt forming consisting of CI Acid Violet 17 and a methine dye) Dyes), VALIFAST BLUE 1603 (salt forming dye comprising C.I. Direct Blue 86 and C. I. Basic Blue 7), and 1621 (C.I. Direct Blue 87 and C. I. Basic Blue 7) Salt forming dyes) (above, produced by Orient Chemical Industry Co., Ltd.), and salt forming dyes of other acid dyes and basic dyes may be appropriately prepared and used according to conventionally known methods. it can. Moreover, as a specific example of the salt-forming dye which consists of an acid dye and a basic substance conventionally known to be used for oil-based ink, VALIFAST YELLOW 1101 (salt-forming salt which consists of a CI basic yellow 42 and a basic substance) Dyes), 1151 (salt forming dyes comprising CI Acid Yellow 42 and a basic substance), 1171 (salt forming dyes comprising CI Acid Yellow 42 and a basic substance), 1107 ( C. I. Salt forming dye consisting of Acid Yellow 42 and basic substance), 1109 (salt forming dye consisting of C. I. Acid Yellow 42 and basic substance), VALIFAST BLUE 1605 (C. I. Solvent Blue) Salt forming dye consisting of a salt forming dye consisting of 38 and a basic substance, VALIFAST Black 1815 (salt forming dye comprising CI Acid Black 1 and a basic substance) (above, manufactured by Orient Chemical Industry Co., Ltd.) can be mentioned, and the construction of other acid dyes and a basic substance can be mentioned. The salt dye can be appropriately prepared and used by a conventionally known method. These salt-forming dyes may be used alone or in combination in combination to adjust.

  As other colorants, conventionally known dyes and pigments used in oil-based inks for ballpoint pens other than the above-mentioned dyes can be used in combination, and the color can be freely adjusted in combination.

  Specific examples of dyes that can be used in combination include SPILON BLACK GMH SPECIAL, SPILON RED C-GH, SPILON RED C-BH, SPILON BLUE C-RH, SPILON BLUE BPNH, SPILON YELLOW C-GNH, SPILON YELLOW C-2 GH, SPILON VIOLET C-RH, S.I. P. T. ORANGE 6, S.I. P. T. BLUE 111, SOT Yellow-1, SOT Yellow-2, SOT Yellow-3, SOT Yellow-4, SOT Yellow-6, SOT Orange-1, SOT Orange-2, SOT Scarlet-1, SOT Red-1, SOT Red- 2, SOT Red-3, SOT Pink-1, SOT Brown-1, SOT Brown-2, SOT Blue-1, SOT Blue-2, SOT Blue-3, SOT Blue-4, SOT Violet-1, SOT Green- 1, SOT Green-2, SOT Green-3, SOT Brack-1, SOT Brack-2, SOT Brack-4, SOT Brack-5, SOT Brack-6, SOT Brack-8 ORIENT SPRIT BLACK AB, VALIFAST BLACK 3804, VALIFAST RED 1320, VALIFAST RED 1360, VALIFAST ORANGE 2210, VALIFAST BLUE 1601, VALIFAST BLUE 1631, VALIFAST BLUE 2601, VALIFAST YELLOW 1110, VALIFAST YELLOW 3104, VALIFAST YELLOW 1 011 Oil Colors Yellow 3G, Oil Colors Yellow GGS, Oil Colors Yellow # 105, Oil Colors Yellow # 107, Oil Colors Yell w # 136, Oil Colors Yellow # 140, Oil Colors Orange PS, Oil Colors Orange PR, Oil Colors Orange PR, Oil Colors Orange # 201, Oil Colors Pink OP, Oil Colors Pink OP # 312, Oil Colors Scarlet # 308, Oil Colors Red RR, Oil Colors Red 5B, Oil Colors Red # 330, Oil Colors Brown GR, Oil Colors Brown # 416, Oil Colors Brown BB, Oil Colors Green BG, Oil Colors Green # 502, Oil Colors Green # 533, Oil Colo s Blue BOS, Oil Colors Blue IIN, Oil Colors Blue # 603, Oil Colors Blue # 613, Oil Colors Violet # 730, Oil Colors Violet # 732, Oil Colors Black BY, Oil Colors Black BS, Oil Colors Black HBB, Oil Colors Black # 803, Oil Colors Black EB, Oil Colors Black EX, Neo Super Blue C-555, Rhodamine B Base, Soldan Red 3 R, Methyl Violet 2 B Base, Victoria Blue F4 R, C.I. I. Direct Black 17, 19, 22, 22, 32, 38, 51, 71, C.I. I. Direct Red 1, 4, 23, 31, 37, 39, 75, 80, 81, 83, 225, 226, 227, C.I. I. Direct Blue 1, 15, 41, 71, 86, 87, 106, 108, 199, C.I. I. Direct Yellow 4, 26, 26, 44, 50, C.I. I. Solvent Yellow 2, 6, 14, 15, 16, 16, 19, 33, 56, 61, 62, 79, 80, 82, 83: 1, 151 , C. I. Solvent Orange 1, 2, 5, 6, 14, 14, 37, 40, 41, 44, 45, 62, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 89, 91, 100, 100 109, 121, 122, 127, 132, 218, C.I. I. Disperse Red 9, C.I. I. Solvent Violeto 8, 13, 14, 15, 21: 1, 27, 27 C.I. I. Disperse Violet 1, C.I. I. Solvent Blue 2, 4, 5, 11, 12, 12, 35, 36, 38, 44, 45, 55, 67, 70, 73, C.I. I. Solvent Green 3, C.I. I. Solvent Bloom 3, 5, 20, 28, 37, C.I. I. Solvent Black 3, 5, 7, 22, 22, 22: 23, 27, 29, 34, 43, 123.

  Specific examples of usable pigments include carbon black, insoluble azo pigments, azo lake pigments, condensed azo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments Commonly known general pigments such as organic pigments such as pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, perinones, perylene pigments and the like can be used.

  Specific examples of carbon blacks that can be used in combination include Prinex 3, 25, 30, 35, 40, 45, 55, 60, 75, 80, 85, 90, 95 300, Special Black 4, 5, 100, 250, 550 (above, Degussa-Hyus Japan KK) Mitsubishi Carbon Black # 2700, # 2650, # 2600, # 2400, # 2400 # 2350, # 2300, # 2200, # 1000, # 990, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 750 650, # 52, # 50, # 47, # 45, # 45 L, # 44, # 40, # 33, # 32, # 30, # 25, # 25, # 20, The same # 10, the same # 5, the same # 95, the same # 260, CF9, MCF88, MA600, MA77, MA7, MA11, MA100, MA100R, MA100S, MA220, MA230 (all manufactured by Mitsubishi Chemical Corporation), Toka Black # 8500 / F, the same # 8300 / F, # 7550 SB / F, # 7400, # 7360 SB / F, # 7350 / F, # 7270 SB, # 7100 / F, ## 7050 (all manufactured by Tokai Carbon Co., Ltd.) And aniline black such as Diamond Black N (manufactured by Jade-Bon-Ken Color Co., Ltd.), Bone Black (manufactured by Mie Color Techno Co., Ltd.), and Iron-ized Black KN-320 (manufactured by Nippon Telecommunications Co., Ltd.) The iron black of can be mentioned. Specific examples of blue pigments include C.I. I. Pigment Blue 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 28, 28, 29, 36 60, 68, 76 and 80 can be mentioned. Specific examples of red pigments include C.I. I. Pigment Red 2, 3, 5, 8, 8, 14, 17, 22, 23, 31, 48, 1, 48: 2, 48: 3, 48: 4, 53 1: 1, 53: 2, 57: 1, 112, 122, 144, 146, 149, 166, 170, 175, 176, 177, 179, 184, the same 185, 187, 188, 202, 207, 208, 209, 210, 211, 213, 214, 242, 253, 254, 255, 256, 257, There can be mentioned H.264, H.266, H.268, H.270, H.272. Specific examples of yellow pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17. 55, 73, 74, 79, 81, 83, 93, 94, 95, 91 97, 109, 110, 111, 120, 128, 133, 136, 138, 139, 147, 151, 154, 155, 167, 173, 174, Examples are 175, 176, 180, 185, 191, 194 and 213. Specific examples of the orange pigment include C.I. I. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 62, 68, 72, 74. Specific examples of the green pigment include C.I. I. Pigment Green 7, 36, and 37. Specific examples of purple pigments include C.I. I. Pigment Violet 19 and 23 can be mentioned.

  Besides these pigments, processed pigments can also be used. Specific examples of them are Renol Yellow GG-HW30, HR-HW30, Orange Orange-RL-HW30, Red HF2B-HW30, FGR-HW30, F5RK-HW30, Carmine FBB-HW30, and Violet RL HW30, Blue B2G-HW30, CF-HW30, Green GG-HW30, Brown HFR-HW30, Black R-HW30 (all available from Clariant Japan Ltd.), UTCO-001 yellow, 012 yellow, Same as 021 orange, 031 red, 032 red, 042 violet, 052 blue, 052 blue, 062 green, 591 black, 592 black (all manufactured by Dainichi Seika Kogyo Co., Ltd.) It can be.

  The salt-forming dyes comprising the above-mentioned acid dyes and basic substances can be used alone or in combination, and can be freely used in combination with other dyes and pigments. The amount of the salt-forming dye comprising the acid dye and the basic substance can be suitably used in an amount of 5.0% by weight or more and 30.0% by weight or less based on the total amount of the oil-based ink for ball point pen.

  The amount of the coloring agent other than the salt-forming dye comprising the acid dye and the basic substance is within a range not to impair the goodness of color development of the handwriting by adding the salt-forming dye comprising the acid dye and the basic substance It can be used. If it exceeds 40.0% by weight with respect to the total amount of the oil-based ink for ballpoint pens, the dissolution taste at the time of blending is insufficient and the problem of heavy writing taste tends to occur due to the increase of solid content in the oil-based ink for ballpoint pens.

  The amount of triisopropanolamine used in the present invention is preferably 0.05% by weight or more and 10.0% by weight or less based on the total amount of the oil-based ink for ball point pen. More preferably, it is 0.1 wt% or more and 3.0 wt% or less. If the amount is less than 0.01% by weight, the coated paper scribing property and the prevention of the generation of crystals due to long-term aging are not sufficient, and even if it exceeds 10.0% by weight, no further improvement in performance is observed.

Phosphate ester is used to prevent abrasion of balls and ball receptacles, and when combined with a salt forming dye consisting of an acid dye and a basic substance, and triisopropanolamine, coated paper has good scribing properties and is aged over time A stable ink composition can be obtained. Specific examples include monoalkyl phosphoric acid, polyoxyethylene monoalkyl ether phosphoric acid, dialkyl phosphoric acid, polyoxyethylene dialkyl ether phosphoric acid, trialkyl phosphoric acid, polyoxyethylene trialkyl ether phosphoric acid, polyoxyethylene monostyrene And phenylether phosphate, polyoxyethylene distyrenated phenylether phosphate, perfluoroalkyl group / phosphate group-containing phosphate ester and the like. In addition, there is no problem in using these substances in solution.
As a commercially available thing, phosphanol BH-650, the same SM-172, the same ED-200, the same GF-339, the same RA-600, the same GF199, the same ML-200, the same ML-220, the same ML-240. , RD-510 Y, GF-185, RS-410, RS-610, RS-710, RL-210, RL-310, RB-410, RP-710, AK-25 The same GF702, the same RS-610NA, the same SC-6103, the same RD-720, the same LP-700, the same LS-500, the same LB400 (above, Toho Chemical Industry Co., Ltd.), Plysurf A207H, the A208B. A219B, A208S, A212S, A215C, AL, AL12 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), NIKKOL DLP-10, DOP-8N V, DDP-2, DDP-4, DDP-6, DDP-8, DDP-10, TLP-4, TCP-5, TOP-0 V, TDP-2, TDP- 6, TDP-8 (all, manufactured by Nikko Chemicals Co., Ltd.), Megafac F-510 (all, manufactured by DIC Corporation), among which monoalkyl phosphoric acid and polyoxyethylene monoalkyl ether can be mentioned. Phosphoric acid, dialkyl phosphoric acid, polyoxyethylene dialkyl ether phosphoric acid, trialkyl phosphoric acid, polyoxyethylene trialkyl ether phosphoric acid, polyoxyethylene mono-styrenated phenyl ether phosphoric acid ester, polyoxyethylene di-styrenated phenyl ether phosphorus The acid ester is excellent in the antiwear effect, and further, the carbon number of the alkyl group contained in the phosphoric acid ester is 1 When the load is 0 or more and 20 or less, wear of the ball and the ball seat is small even in heavy load writing, which is preferable.
Furthermore, in order to improve the wear resistance of the ball and the ball seat, one having an ethylene oxide group introduced into a phosphoric acid ester is preferably used. It is preferable that an ethylene oxide group is introduced in an amount of 1 mol or more and 20 mol or less in the phosphoric acid ester structure.
By keeping the HLB (Hydrophile-Lipophile Balance) of the phosphate ester suitable for use in oil-based inks for ballpoint pens, the phosphate esters do not separate in the ink and thus the ball and ball seat wear resistance is kept good over the long term It becomes possible. The preferable HLB range is 5 or more and 12 or less.

  Moreover, phosphoric acid esters having an aromatic ring in a hydrocarbon portion, one having a branched and saturated alkyl group, one having a branched and unsaturated alkyl group, one having a linear and saturated alkyl group, and a straight chain However, it is most preferable to use one having a linear unsaturated double bond as the hydrocarbon moiety in the phosphoric acid ester because the initial coatability of coated paper is further improved. is there. Specifically, monooleyl phosphate, polyoxyethylene monooleyl ether phosphate, dioleyl phosphate, polyoxyethylene dioleyl ether phosphate, trioleyl phosphate, polyoxyethylene trioleyl ether phosphate, monolinol phosphate, polylinole phosphate Oxyethylene monolinol ether phosphoric acid, dilinol phosphoric acid, polyoxyethylene dilinol ether phosphoric acid, trilinol phosphoric acid, polyoxyethylene trilinol ether phosphoric acid, and commercially available ones include phosphanol RB-410, LB-400 (above, Toho Chemical Industry Co., Ltd. product), NIKKOL DOP-8NV, TOP-10V (above, Nikko Chemicals Co., Ltd. product) can be mentioned.

  The amount of phosphoric acid ester used is preferably 0.05% by weight or more and 20.0% by weight or less, more preferably 0.1% by weight or more and 10.0% by weight or less, based on the total amount of the ballpoint pen oil ink. 0.3% by weight or more and 2.0% by weight is preferable. If the amount used is less than 0.05% by weight, the coatability of the coated paper and the prevention of crystal generation due to long-term aging and the writing taste are not sufficient, and if it exceeds 20.0% by weight, the content of the organic solvent in the ink As a result, the solubility of solid components in the ink, such as dye and resin, may be insufficient, which may lead to character distortion.

  A low viscosity ink having a viscosity of 5000 mPa · s or less at a temperature of 25 ° C. and a shear rate of 100 / s by using a low boiling point organic solvent as a part of the solvent in the combination of the above phosphoric ester and triisopropanolamine In this case, the writeability of coated paper can be maintained even over a long period of time, and there is a combination ratio excellent in preventing the crystal precipitation of a salt forming dye consisting of an acid dye and a basic substance. The value is preferably 1.0 or more and 5.0 or less, more preferably 2.0 or more and 3.5 or less.

Furthermore, by adding polyoxyethylene (hardened) castor oil, it is possible to prevent line skipping even in reverse writing, in which line skipping is apt to occur, as well as sequential writing in coated paper writing, and particularly excellent coated paper Writability is obtained. The polyoxyethylene (hardened) castor oil described in the oil-based ink for ballpoint pens of the present invention is polyoxyethylene hardened castor oil and polyoxyethylene castor oil.
Specific examples of polyoxyethylene (hardened) castor oil include NIKKOL HCO-5, HCO-10, HCO-20, HCO-30, HCO-40, HCO-50, HCO-60, and the like. HCO-80, HCO-100 (above, Nikko Chemicals Co., Ltd. product), EMALEX HC-5, HC-7, HC-10, HC-20, HC-30, HC-40, HC-50, HC-60, HC-80, HC-100 (above, manufactured by Nippon Emulsion Co., Ltd.), Braunone BR-404, BR-407, BR-410, BR-4135, BR-417, BR-420, BR-425, BR-430, BR-450, RCW-20, RCW-40, RCW-60, RCW-80, RCW-100 (more than ,Day Kasei Co., Ltd., Uniox HC-10, HC-20, HC-40, HC-60, HC-100, C-35 (manufactured by NOF Corporation). .
When the number of moles of ethylene oxide groups introduced into the polyoxyethylene (hardened) castor oil is in the range of 5 to 100 moles, it can be suitably used for the pen tip drying resistance.
The use amount of polyoxyethylene (hardened) castor oil is preferably 0.1% by weight or more and 15.0% by weight or less, more preferably 1.0% by weight or more and 8.0% by weight based on the total amount of the oil-based ink for ballpoint pen It is below. If the amount used exceeds 15.0% by weight, the content of the organic solvent in the oil-based ink for ballpoint pen decreases, so that the solubility of solid matter in the ink such as dye and resin is insufficient, and character distortion tends to occur. There is a fear. It is also possible to use polyoxyethylene (hardened) castor oil alone or in combination.

  Furthermore, water can also be added to the oil-based ink for ballpoint pens of the present invention. The water may be selected from tap water, ion exchange water, purified water, distilled water, pure water and the like. Among them, ion exchange water, purified water, distilled water, and pure water are preferable. The combination of triisopropanolamine, phosphoric ester, and water improves the writing taste and improves the initial coated paper writability. The amount thereof can be added in the range in which the ink does not become unstable with time, and is preferably 0.1% by weight or more and 15.0% by weight or less based on the total amount of the oil-based ink for ball point pen. More preferably, it is 0.5 wt% or more and 10.0 wt% or less. The method of adding water is not particularly limited, but even if water is added as it is to an ink in which components other than water are appropriately mixed, water is previously added to components used for oil-based inks such as coloring agents and resins. You may absorb moisture or absorb water.

  In addition to the above components, additives for lubricants, resins, rust inhibitors, and antifoaming agents can be used in combination as necessary.

Lubricants are added to smooth the rotation of the ball and to improve the wear prevention between the ball and the ball seat, and specific examples thereof include cutting oils, higher fatty acids, acyl amino acids and thiazoles. And polyethylene glycols and polyether-modified silicones. It is particularly preferable to use a polyether-modified silicone, since the writing feeling can be maintained in a good state over a long period of time.
These are used in an amount of 0.2% by weight or more and 4.5% by weight or less based on the total amount of oil-based ink for ball point pen. If it is added in excess of 4.5% by weight, the surface tension of the ink decreases, and the ink may leak when left to stand with the pen tip down.

  The resin is added for dispersion of solid matter such as pigment, improvement of fixing property, imparting of threading property, prevention of back reflection of handwriting, viscosity adjustment, and dissolution promotion of dye, and specific examples thereof include ester Gum, xylene resin, alkyd resin, polyvinyl pyrrolidone, acrylic ester resin, melamine resin, cellulose resin, condensation resin of ketones such as cyclohexanone, acetophenone and urea with formaldehyde, condensation resin of cyclohexanone and hydrogenated resin thereof Resin, maleic resin, copolymer of styrene and maleic ester, copolymer of styrene and acrylic acid or ester thereof, polyamide which is a condensation product of polymerized fatty acid and polyamines, epoxy resin, polyvinyl alkyl ether, Coumarone-indene resin, polyterpene, rosin resin and so on Hydrogen additive, rosin modified maleic resin, rosin modified phenolic resin, vinylpyrrolidone-vinyl acetate copolymer, polymethacrylic acid ester, polyoxyethylene, polyvinyl butyral resin, polyvinyl alcohol resin, polyvinyl acetal resin, acetic acid acetate Copolymers of vinyl and polyvinyl pyrrolidone, acrylic resin salts, copolymers of acrylic acid and alkyl methacrylates or salts thereof, cellulose derivatives such as hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, ethyl cellulose, hydroxypropylated guar gum, methyl cellulose Ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid, carboxyvinyl poly Polysaccharides over, etc., can be mentioned benzylidene sorbitol. In particular, polyvinyl butyral resin can be suitably used because its viscosity change with time is small and the dispersion stability and fixability of the pigment are excellent. Specific examples of polyvinyl butyral include Mowital B20H, B30B, B30H, B60T, B60H, B60HH, B70H manufactured by Hoechst Co., Ltd. S-LEC BH-3, BL-1, BL-2, BL manufactured by Sekisui Chemical Co., Ltd. -L, BL-S, BM-1, BM-2, BM-5, BM-S, BL-2H, BL-SH, BX-10, BX-L, BH-3, BH-6, BH-S , BX-1, BX-5, and the like. These resins can be used alone or in combination. The amount of these resins used is preferably 0.05% by weight or more and 30.0% by weight or less based on the total amount of the ballpoint pen oil ink.

  In the present invention, the corrosion of the metal ballpoint pen tip can be suppressed by keeping the pH of the ink in the appropriate range. The appropriate range is 3 or more and 10 or less, more preferably 5 or more and 8 or less.

  The dispersion of the pigments according to the invention is possible in a generally customary manner. For example, a pigment, a solvent, and a dispersant are mixed and uniformly stirred by a propeller stirrer or the like, and then the pigment is dispersed by a disperser. A dispersing machine such as a roll mill, a ball mill, a sand mill, a bead mill, a Henschel mixer, a homogenizer, a kneader, etc. is appropriately selected according to the amount of solvent of the ink and the pigment concentration.

  In order to produce the ink, after one or two or more kinds of coloring materials selected from the pigment and the dye dispersed above, a resin and a solvent are sufficiently mixed and stirred by a stirrer such as a homomixer etc. It can be obtained by mixing ingredients such as viscosity modifiers, dyes for color tone adjustment, lubricants, etc. and dissolving and mixing until it becomes more uniform, but the mixed ink may be dispersed with a dispersing machine if necessary. Or, the obtained ink may be filtered or centrifuged to remove coarse particles and insoluble components.

  The above-mentioned oil-based ink for a ballpoint pen is directly stored in the ink storage tube, and a ball as a writing member and a part of the ball are held protruding from the tip opening of the ink passage which is a through hole. A ball holder having a ball house portion defining a range in which the ball can move back and forth by forming the tip opening smaller in diameter than the diameter of the ball and forming a plurality of inward projections in the middle of the inner wall of the ink passage. The ballpoint pen tip is an oily ballpoint pen refill attached directly to the end of the ink container or through a tip holder. The ball holder of the above-mentioned ballpoint pen tip is mainly formed in a cylindrical metal member such as stainless steel through a through hole serving as an ink through hole and an inward projection using a cutting blade such as a drill or a broach. It is also possible to use a pipe material in which a through hole is formed. When a pipe material is used, the outer wall portion of the pipe material is pressed and deformed with a pin to form a concave portion, thereby forming a convex portion on the inner side wall portion corresponding to the portion. It becomes a direction protrusion.

The components of the ball that can be used in the ballpoint pen tip are: 75.0% by weight to 85.0% by weight of tungsten (element code: W); 9.0% by weight to 14.0% by weight cobalt (element code: Co) % Or less, chromium (element symbol: Cr) 0.0 wt% or more and 3.0 wt% or less, carbon (element symbol: C) 0.0 wt% or more and 6.0 wt% or less, Cr ₃ C ₃ 0.0 The thing of weight% or more and 5.0 weight% or less can be used. The surface roughness of the ball may be Ra 1.0 or more and 20.0 or less. A ball having a Vickers hardness (HV) of 1000 or more and 2000 or less can be used.
In addition to the above-mentioned cemented carbide, the component is 0.0 wt% or more and 95.0 wt% or less of silicon carbide (molecular formula: SiC), yttrium oxide-aluminum oxide (molecular formula: Y ₂ O ₃ -Al ₂ O ₃ ) 0.0 wt% or more and 5.0 wt% or less with a ball surface roughness of Ra 0.5 nm or more and 10.0 nm or less, or a component of 0.0 wt% or more of zirconium dioxide (molecular formula: ZrO ₂ ) 95.0 wt% or less, yttrium oxide (molecular formula: Y ₂ O ₃ ) 0.0 wt% or more and 5.0 wt% or less, ball surface roughness of 0.5 nm or more and 10.0 nm or less, or a component Ball surface roughness is 0. 0 with aluminum oxide (molecular formula: Al ₂ O ₃ ) 0.0 wt% or more and 99.9 wt% or less, chromium (element symbol: Cr) 0.0 wt% or more and 0.1 wt% or less. 5 nm or more 10.0 n The thing below m etc. are mentioned.
The ball diameter may be any of conventionally known 0.1 mm or more and 30.0 mm or less. It is preferable to use a ball diameter of 0.5 mm or less when it is desired to obtain fine writing, and it is preferable to use a ball diameter of 1.0 mm or more when obtaining bold writing.

In the case of stainless steel as a material of a ball holder that can be used in the above-mentioned ballpoint pen tip, the component is chromium (element symbol: Cr) 18.0% by weight or more and 22.0% by weight or less % To 3.0% by weight, manganese (element code: Mn) 0.0% to 2.0% by weight, silicon (element code: Si) 0.0 to 1.0% by weight, sulfur (Element symbol: S) 0.0% by weight or more and 0.2% by weight or less, Phosphorus (element code: P) 0.0% by weight or more and 0.1% by weight or less, Carbon (element code: C) 0.0 weight % Or more, 0.1% by weight or less, lead (element code: Pb) 0.0% by weight or more, 0.5% by weight or less, tellurium (element code: Te) 0.0% by weight or more, 0.1% by weight or less (Element symbol: Fe) 0.0 to 80.0% by weight Can be used. The chip has a Vickers hardness (HV) of 150 or more and 300 or less.
When the material of the ball holder is a copper alloy, the component is 55.0 wt% to 65.0 wt% of carbon (element symbol: C), 12.0 wt% to 18.0 wt% of nickel (element symbol: Ni) % Or less, manganese (element symbol: Mn) 0.0 wt% or more and 1.0 wt% or less, iron (element symbol: Fe) 0.0 wt% or more and 0.5 wt% or less, lead (element symbol: Pb) The thing of 0.0 weight% or more and 4.0 weight% or less and the thing of zinc (element symbol: Zn) 0.0 weight% or more and 30.0 weight% or less can be used. The chip has a Vickers hardness (HV) of 150 or more and 300 or less.
In addition, conventionally known materials such as resin and brass (brass) may be used as the material of the ball holder.

Then, the ball holder is pressed against the inner edge of the tip opening of the ball holder to improve the sealability of the ball holder, and a plurality of ball holders are provided inside for the purpose of preventing ink bleeding from the tip of the ballpoint It is also possible to provide a ballpoint pen tip provided with a coil spring for pressing the ball from the back through the center hole formed at the center of the inward protrusion to bias the ball forward. As a material of the coil spring, a stainless steel wire such as SUS304 is mainly used, but a hard steel wire or a piano wire can also be used. Also, resins such as polycarbonate and polyetheretherketone can be used. It is also possible to use nickel (element symbol: Ni) plated on the surface of stainless steel wire, hard steel wire or the like.
The pressing load of the ball in the state where the coil spring is installed in the ball holder can be used at 0.01 N or more and 1.50 N or less.

The example of the oil-based ball-point pen refill which filled the refill with the oil-based ink for ball-point pens using drawing as a specific example is explained in detail below.
FIG. 1 shows a longitudinal sectional view of an oil-based ballpoint pen refill. The ballpoint pen tip 1 rotatably holds a ball 2 as a writing member in a state where the ball 2 partially protrudes from a tip opening formed in the ball holder 3. The ink 5 is accommodated in the ink accommodating tube 4, and the ink follower 6 which is a high viscosity fluid incompatible with the ink 5 is disposed in contact with the rear end interface of the ink 5. Although this oil-based ballpoint pen refill is accommodated and used in an exterior body, illustration and description about an exterior are omitted. In addition, it is also possible to use a form called a so-called direct solution type in which the outer package itself is directly accommodated as the ink storage tube.

  As the ink storage tube 4, metals, and conventionally known resins such as polypropylene and polyethylene can be used. The inner diameter of the ink storage tube 4 may be 0.1 mm or more and 30.0 mm or less, preferably 0.5 mm or more and 15.0 mm or less. In addition to the illustrated straight pipe housing pipe, a housing pipe having a shape in which a plurality of different inner diameters are combined in multiple stages can also be used. When using a thing 0.5 mm or more in diameter, you may use together the cast which becomes a movable stopper for backflow prevention.

  The ink follower 6 improves the clear-drain property of the ink storage tube 4, improves the visibility of the remaining ink amount, improves the drying prevention property of the ink, and backflow of the ink when the writing tip is left facing upward (upright state) It is arranged for the purpose of preventing. As the ink follower 6, conventionally known ink followers can be used such as a fluid having a viscosity as high as that of polybutene, α-olefin, polyolefin, silicone or the like as a base material and appropriately using a gelling agent such as silica. The physical properties of the ink follower may be physical properties such as Newtonian fluid, thixotropy, shear thinning, etc., but Newtonian fluid is preferred. The viscosity of the ink follower is not particularly limited, but the viscosity of the ink follower at 25 ° C. and a shear rate of 100 / s is preferably 10 mPa · s to 100,000 mPa · s, and is 100 mPa · s to 30,000 mPa. S or less is most preferable. As commercially available products, as dimethyl silicone oils, SH200 C Fluid 5CS (viscosity 5 mPa · s), 6 CS (viscosity 6 mPa · s), 10 CS (viscosity 9 mPa · s), and 20 CS (viscosity 19 mPa · s) 30CS (viscosity 29 mPa · s), 50 CS (viscosity 48 mPa · s), 100 CS (viscosity 97 mPa · s), 200 CS (viscosity 190 mPa · s), 350 CS (viscosity 340 mPa · s), 500 CS (viscosity) 490 mPa · s), 1000 CS (viscosity 970 mPa · s), 3000 CS (viscosity 290 mPa · s), SH200 Fluid 10000 CS (viscosity 9700 mPa · s), 12500 CS (viscosity 12000 mPa · s), 30000 CS (viscosity 290) 00 mPa · s), 60000 CS (viscosity 59000 mPa · s), 100000 CS (viscosity 98000 mPa · s), 1,000,000 (viscosity 980000 mPa · s), BY11-040 (viscosity 1400 mPa · s), BY11-003 (viscosity 1400 mPa · s) ), BY11-007 (viscosity 1600 mPa · s), BY11- 014 (viscosity 12000 mPa · s), BY11-026 (viscosity 100000 mPa · s), BY25-320 (viscosity 8200 mPa · s) (all available from Toray Dow Corning, Inc.) And IF 4310 (viscosity 31000 ± 2000 mPa · s), 4311 (viscosity 24000 ± 2000 mPa · s), and 4312 (viscosity 3850 ± 450 mP) as a silicone oil to which shear thinning is imparted. · S) (manufactured by Dokumental Co., Ltd.) and the like. The use amount of the ink follower can be used in a range of 0.1% to 100.0% by weight based on the total amount of the oil-based ink for a ballpoint pen. However, when it is determined that the ink follower 6 is not particularly required, it does not have to be disposed.

  FIG. 2 shows a longitudinal sectional view of the ballpoint pen tip 1. Inside the ball holder 3 is disposed a coil spring 7 which pushes the ball 2 from the back to bias the front. After being inserted into the ball holder 3, the coil spring 7 is compressed to reduce the diameter of the rear end opening 3 a of the ball holder 3 in a state in which the coil spring 7 is compressed and compressed. It is fixed with the end biased. The coil spring 7 includes an expanding and contracting portion 7 a and a tip straight portion 7 b standing straight at the tip, and the tip straight portion 7 b passes through a through hole which is an ink passage of the ball holder 3 and the ball 2. The ball 2 is brought into circumferential contact with the inner edge of the tip opening 3b of the ball holder 3 by pushing the rear end of the ball 2 directly. When the through hole of the ball holder 3 is sufficiently large, the wound portion 7a may be brought into direct contact with the ball 2 and biased without forming the tip straight portion 7b of the coil spring 7.

  FIG. 3 shows an enlarged view of a portion I of the ballpoint pen tip 1. The ball holder 3 has a ball house portion 8, a center hole 9 and a rear hole 10 from the front end side as a passage of the ink which is penetrated by the manufacturing method of forming a through hole in the cylindrical metal member described above. An inward protrusion 11 is formed between the ball house 8 and the rear hole 10. The diameter of the tip opening 3b of the ball house 8 is reduced by caulking, and movement of the ball 2 in the front-rear direction by the diameter-reduced tip opening 3b and the inward protrusion 11 is performed. It defines the possible range. Further, a plurality of radial grooves 12 are formed in the annular shape at equal intervals on the inward protruding portion 11 by cutting. The radial groove 12 is in communication with the bore 9 and the rear hole 10, but not in communication with the bore 10 in order to prevent catching when the coil spring 7 is inserted. You can also keep it. Then, the concave ball transfer portion 13 is formed by pressing the ball 2 against the inward protruding portion 11, and the concave ball transfer portion 13 is in contact with the paper surface at the time of writing and the ball 2 is retracted. The position of the ball is stabilized to ensure smooth rotation with little unnecessary vibration and the like, and the ball 2 and the concave ball transfer portion 13 are shaped so as to contact in a substantially planar manner. Further, the radial groove 12 described above has an opening on the outer side than the concave ball transfer portion 13 of the inward protruding portion 11 and secures the ink supply to the ball house portion 8. The number of radial grooves 12 can be three or more and ten or less.

Based on the above-described example, a preparation example of a ballpoint pen tip will be described below. As Preparation Example 1, the portion shown in FIG. 4 which is a sectional view taken along the line II-II ′ of FIG. 4 and FIG. 4 is adjusted to be within the range of dimension values described below. One ballpoint pen tip sample was prepared. In FIG. 4, a state in which the ball 2 is in contact with the ball transfer portion 13 is indicated by a dotted line. Further, for convenience of explanation, in FIG. 5, the tip straight portion 7b of the ball 2 and the coil spring 7 is omitted.
(Preparation Example 1)
Ball diameter A1: 0.7 mm
Tip opening diameter B1: 0.655 mm or more and 0.665 mm or less Movement distance of ball in the front-rear direction C1: 0.015 mm or more and 0.020 mm or less Ball protrusion length D1: 0.20 mm or more and 0.22 mm or less Ball house part diameter E1: 0.720 mm or more and 0.730 mm or less Medium hole diameter F1: 0.35 mm or more and 0.37 mm or less Hole diameter G1: 0.70 mm or more and 0.90 mm or less Radial groove width H1: 0.090 mm or more and 0.110 or less Ball transfer portion diameter J1 : 0.620 mm or more and 0.640 mm or less The number of radial grooves is 6, the wire diameter of the coil spring is 0.12 mm, and the pressure load of the ball in the state where the coil spring is disposed in the ball holder is 0.147 N or more 0 It was less than .216N.

Further, as Preparation Example 2, the portion shown in FIG. 7 which is a sectional view taken along the line III-III 'in FIG. 6 and FIG. A ballpoint pen tip sample of 5 mm was made. Note that, in FIG. 6, a state in which the ball 2 is in contact with the ball transfer portion 13 is indicated by a dotted line. Further, for convenience of explanation, in FIG. 7, the tip straight portion 7b of the ball 2 and the coil spring 7 is omitted.
(Production Example 2)
Ball diameter A2: 0.5 mm
Tip opening diameter B2: 0.465 mm or more and 0.480 mm or less Movement distance of ball in the back and forth direction C2: 0.011 mm or more and 0.017 mm or less Ball protrusion length D2: 0.149 mm or more and 0.159 mm or less Ball house part diameter E2: 0.520 mm or more and 0.530 mm or less Medium hole diameter F2: 0.22 mm or more and 0.28 mm or less Hole diameter G2: 0.50 mm or more and 0.70 mm or less Radial groove width H2: 0.065 mm or more and 0.075 mm or less Ball transfer portion diameter J2 The number of radial grooves is 5, the wire diameter of the coil spring is 0.12 mm, and the pressure load of the ball in the state where the coil spring is disposed in the ball holder is 0.147 N or more 0 It was less than .216N.

Further, as Preparation Example 3, the portion shown in FIG. 8 which is a sectional view taken along the line IV-IV ′ of FIG. 8 and FIG. 8 is adjusted to be within the range of dimensional values described below. A ball pen tip sample of 2 mm was made. Note that, in FIG. 8, a state in which the ball 2 is in contact with the ball transfer portion 13 is indicated by a dotted line. Further, for convenience of description, the ball 2 and the tip straight portion 7b of the coil spring 7 are omitted in FIG.
(Preparation Example 3)
Ball diameter A3: 0.2 mm
Tip opening diameter B3: 0.170 mm or more and 0.195 mm or less Movement distance of ball in the back and forth direction C3: 0.005 mm or more and 0.015 mm or less Ball protrusion length D3: 0.05 mm or more and 0.09 mm or less Ball house part diameter E3: 0.205 mm or more and 0.240 mm or less Medium hole diameter F3: 0.11 mm or more and 0.15 mm or less Hole diameter G3: 0.20 mm or more and 0.60 mm or less Radial groove width H3: 0.02 mm or more and 0.07 mm or less Ball transfer portion diameter J3 : 0.10 mm or more and 0.19 mm or less The number of radial grooves is 3, the wire diameter of the coil spring is 0.10 mm, and the pressure load of the ball in the state where the coil spring is disposed in the ball holder is 0.078 N or more .196 N or less.

  The writing property of the ink is improved by combining it with a low viscosity ink having a viscosity of 5 mPa · s or more and 5000 mPa · s or less at a shear rate of 100 / s at a temperature of 25 ° C. in combination with the ballpoint pen tip. It is more preferable to set the viscosity range at a temperature of 25 ° C. and a shear rate of 100 / s to 50 mPa · s or more and 3000 mPa · s or less in consideration of the leakability of the ink and the like.

  EXAMPLES The present invention will be more specifically described by way of the following examples, but the present invention is not limited by these examples.

  Although the ratio of triisopropanolamine and phosphoric acid ester is calculated in the examples, molecular weight is calculated using the average molar number of addition described in the catalog for the molar number of phosphoric acid ester added. In the case of a mixture of phosphoric acid monoester, diester and triester, the blending ratio of the triester is small, so that 50: 50 by weight ratio of phosphoric acid monoester and diester is included and the weighted average is considered. The molecular weight is calculated by Moreover, the substance described over several ranges as carbon number of the alkyl group in phosphoric acid ester is 12 or more and 15 or less performs carbon number of the alkyl group, and performs calculation of molecular weight.

  The viscosities in the examples were measured using a Physica MCR 302 (manufactured by Anton Paar) with a rotor CP20-1.

Example 1
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
2.00% by weight
VALIFAST YELLOW 1171 (C.I. Acid Yellow 42 and a salt-forming dye comprising a basic substance, manufactured by Orient Chemical Industry Co., Ltd.) 18.00% by weight
VALIFAST VIOLET 1704 (Cation dye consisting of C. I. Acid Yellow 36 and C. I. Basic Violet 1, Orient Chemical Industry Co., Ltd.)
12.00% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 5.00% by weight
Benzyl alcohol (organic solvent) 10.00 wt%
3-methoxy-1-butanol (organic solvent) 14.30% by weight
NIKKOL TOP-0 V (phosphate, trioleyl phosphate, molecular weight 879.4,
HLB 2.5, manufactured by Nikko Chemicals Co., Ltd. 10.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
2.20% by weight
Braunone BR-450 (Polyoxyethylene castor oil, manufactured by Aoki Yushi Kogyo Co., Ltd.)
8.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
0.25 wt%
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.25 wt%
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
NIKKOL BL-9 EX (polyoxyethylene lauryl ether, Nikko Chemicals
Co., Ltd. 3.00% by weight
Ion exchange water 2.00% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 1.0. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 500 mPa · s at a shear rate of 100 / s, and the pH was 4.5.

(Example 2)
VALIFAST YELLOW 1171 (C.I. Acid Yellow 42 and a salt-forming dye consisting of a basic substance, ORIENT Chemical Industry Co., Ltd.) 5.00% by weight
VALIFAST VIOLET 1704 (Cation dye consisting of C. I. Acid Yellow 36 and C. I. Basic Violet 1, Orient Chemical Industry Co., Ltd.)
Made of 20.00% by weight
Benzyl alcohol (organic solvent) 17.50% by weight
3-methoxy-1-butanol (organic solvent) 38.68% by weight
NIKKOL TOP-0 V (phosphate, trioleyl phosphate, molecular weight 879.4,
HLB 2.5, 0.50% by weight, manufactured by Nikko Chemicals Co., Ltd.
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.30% by weight
Emarex HC-20 (polyoxyethylene hydrogenated castor oil, manufactured by Nippon Emulsion Co., Ltd.)
2.00% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
3.00% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
NIKKOL BL-9 EX (polyoxyethylene lauryl ether, Nikko Chemicals
Co., Ltd. 3.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 2.8. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 270 mPa · s, and the pH was 7.0.

(Example 3)
VALIFAST BLUE 1605 (C.I. Solvent Blue 38 and salt forming dye comprising basic substance, ORIENT Chemical Industry Co., Ltd.) 1.00% by weight
VALIFAST YELLOW 1171 (C.I. Acid Yellow 42 and a salt-forming dye consisting of a basic substance, made by Orient Chemical Industry Co., Ltd.) 3.00% by weight
VALIFAST GREEN 1501 (salt forming dye consisting of C.I. Acid Yellow 42 and C.I. Basic Blue 1, made by Orient Chemical Co., Ltd.)
5.00 wt%
Ethylene glycol monophenyl ether (organic solvent) 34.00% by weight
Benzyl alcohol (organic solvent) 46.65% by weight
NIKKOL DDP-2 (phosphate, di (C12-15) palace-2 phosphate,
Molecular weight 630.8, HLB 6.5, Nikko Chemicals Co., Ltd. product) 0.25% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.30% by weight
NIKKOL HCO-50 (polyoxyethylene hydrogenated castor oil, manufactured by Nikko Chemicals Co., Ltd.) 0.30% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
5.00 wt%
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Ion-exchanged water 4.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a green oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 4.0. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 1000 mPa · s at a shear rate of 100 / s, and the pH was 7.5.

(Example 4)
VALIFAST BLUE 1605 (C.I. Solvent Blue 38 and salt forming dye comprising basic substance, ORIENT Chemical Industry Co., Ltd.) 1.00% by weight
VALIFAST YELLOW 1171 (C.I. Acid Yellow 42 and a salt-forming dye consisting of a basic substance, made by Orient Chemical Industry Co., Ltd.) 3.00% by weight
VALIFAST GREEN 1501 (salt forming dye consisting of C.I. Acid Yellow 42 and C.I. Basic Blue 1, made by Orient Chemical Co., Ltd.)
5.00 wt%
Ethylene glycol monophenyl ether (organic solvent) 34.00% by weight
Benzyl alcohol (organic solvent) 40.70% by weight
NIKKOL DDP-2 (phosphate, di (C12-15) palace-2 phosphate,
Molecular weight 630.8, HLB 6.5, Nikko Chemicals Co., Ltd. product) 2.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
1.30% by weight
NIKKO LHCO-50 (Polyoxyethylene Cured Castor Oil, Nikko Chemicals Co., Ltd.)
Made of 3.50% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
5.00 wt%
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Ion-exchanged water 4.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a green oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 2.1. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 950 mPa · s, and the pH was 6.7.

(Example 5)
SPILON RED C-GH (coloring agent, xanthene oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 3.00% by weight
VALIFAST RED 1308 (C.I. Acid Yellow 23 and C.I.
Salt forming dye made of Basic Red 1 (Orient Chemical Industry Co., Ltd.)
3.00% by weight
VALIFAST GREEN 1501 (C.I. Acid Yellow 42 and C.I.
I. Salt-forming dye consisting of Basic Blue 1 and Orient Chemical Industry Co., Ltd.)
13.00 wt%
Diethylene glycol monomethyl ether (organic solvent) 10.38% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 9.10% by weight
Ethylene glycol monophenyl ether (organic solvent) 34.00% by weight
NIKKOL DDP-2 (phosphate, di (C12-15) palace-2 phosphate,
Molecular weight 630.8, HLB 6.5, Nikko Chemicals Co., Ltd. product) 5.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
3.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation)
3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
NIKKOL BL-9 EX (polyoxyethylene lauryl ether, Nikko Chemicals
Co., Ltd. 3.00% by weight
Ion-exchanged water 0.50% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 2.0. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 650 mPa · s, and the pH was 6.5.

(Example 6)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
7.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 2.00% by weight
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and methine dye, ORInt Chemical Industry Co., Ltd.) 7.00% by weight
VALIFAST YELLOW 1171 (C.I. Acid-yellowing dye comprising a salt of Yellow 42 and a basic substance, ORIENT Chemical Industry Co., Ltd.) 1.00% by weight
VALIFAST VIOLET 1704 (Cation dye consisting of C. I. Acid Yellow 36 and C. I. Basic Violet 1, Orient Chemical Industry Co., Ltd.)
Made of 3.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 26.00% by weight
3-methoxy-1-butanol (organic solvent) 21.98% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. 8.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
10.00 wt%
Braunone BR-425 (polyoxyethylene castor oil, manufactured by Aoki Yushi Kogyo Co., Ltd.)
1.00 wt%
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 4.8. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 520 mPa · s at a shear rate of 100 / s, and the pH was 8.0.

(Example 7)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
2.00% by weight
OIL BLUE 613 (coloring agent, triallylmethane oil dye, manufactured by Orient Chemical Industry Co., Ltd.) 1.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 1.00% by weight
VALIFAST VIOLET 1731 (C. I. Acid Violet
Salt-forming dye comprising 17 and methine-based dye, manufactured by Orient Chemical Industry Co., Ltd.
10.00 wt%
VALIFAST RED 1308 (C.I. Acid Yellow 23 and C.I.
Salt forming dye made of Basic Red 1 (Orient Chemical Industry Co., Ltd.)
2.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 20.68% by weight
Ethylene glycol monophenyl ether (organic solvent) 18.70% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. product 13.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
12.00% by weight
NIKKOL HCO-10 (polyoxyethylene hydrogenated castor oil, manufactured by Nikko Chemicals Co., Ltd.) 3.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Ion-exchanged water 0.10% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 3.6. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 550 mPa · s, and the pH was 7.4.

(Example 8)
VALIFAST BLUE 1605 (salt forming dye consisting of a salt forming dye consisting of CI Solvent Blue 38 and a basic substance, manufactured by Orient Chemical Co., Ltd.)
14.00 wt%
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and a methine dye, made by Orient Chemical Industry Co., Ltd.) 14.00% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 28.46% by weight
Benzyl alcohol (organic solvent) 31.82% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. 0.10% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.10% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
5.00 wt%
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
NIKKOL BL-9 EX (polyoxyethylene lauryl ether, Nikko Chemicals
30.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a blue oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 3.9. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 300 mPa · s at a shear rate of 100 / s, and the pH was 7.4.

(Example 9)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
2.00% by weight
SPILON RED C-GH (coloring agent, xanthene oil-based dye, Hodogaya Chemical Industry Co., Ltd. 2.00% by weight
VALIFAST BLUE 1605 (C.I. Solvent Blue 38 and a salt forming dye consisting of a basic substance, made by Orient Chemical Co., Ltd.) 3.00% by weight
VALIFAST YELLOW 1171 (C.I. Acid Yellow 42 and a salt-forming dye consisting of a basic substance, made by Orient Chemical Industry Co., Ltd.) 3.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 22.00% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 19.90% by weight
Ethylene glycol monophenyl ether (organic solvent) 18.89% by weight
Phosphanol RS-610 (Phosphate ester, mixture of phosphoric monoester, diester and triester of polyoxyethylene (10) tridecyl ether, molecular weight 103
0.3, HLB 10.5, Toho Chemical Industry Co., Ltd. 0.06% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.05% by weight
NIKKOL HCO-100 (Polyoxyethylene hydrogenated castor oil, Nikko Chemicals Co., Ltd.)
Made of 0.10% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
Ion-exchanged water 13.00% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar amount of triisopropanolamine / phosphate is 4.5. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 530 mPa · s at a shear rate of 100 / s, and the pH was 7.7.

(Example 10)
VALIFAST YELLOW 1171 (C.I. Acid Yellow 42 and a salt-forming dye consisting of a basic substance, ORIENT Chemical Industry Co., Ltd.) 5.00% by weight
VALIFAST VIOLET 1704 (Cation dye consisting of C. I. Acid Yellow 36 and C. I. Basic Violet 1, Orient Chemical Industry Co., Ltd.)
Made of 20.00% by weight
3-methoxy-1-butanol (organic solvent) 43.68% by weight
NIKKOL TOP-0 V (phosphate, trioleyl phosphate, molecular weight 879.4,
HLB 2.5, 0.20% by weight, manufactured by Nikko Chemicals Co., Ltd.
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.10% by weight
Emarex HC-20 (polyoxyethylene hydrogenated castor oil, manufactured by Nippon Emulsion Co., Ltd.) 15.00% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
3.00% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
NIKKOL BL-9 EX (polyoxyethylene lauryl ether, Nikko Chemicals
Co., Ltd. 3.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 2.3. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 310 mPa · s, and the pH was 6.5.

(Example 11)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
2.00% by weight
OIL BLUE 613 (coloring agent, triarylmethane-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 1.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, Hodogaya Chemical Industry 1.00 wt%
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and methine dye, made by Orient Chemical Industry Co., Ltd.) 10.00% by weight
VALIFAST RED 1308 (C.I. Acid Yellow 23 and C.I.
Salt forming dye made of Basic Red 1 (Orient Chemical Industry Co., Ltd.)
2.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 24.28% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 19.40% by weight
Ethylene glycol monophenyl ether (organic solvent) 19.00% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. 1.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.80% by weight
NIKKOL HCO-10 (Polyoxyethylene Cured Castor Oil, Nikko Chemicals Co., Ltd.)
Made of 2.50% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Ion-exchanged water 0.50% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 3.1. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 560 mPa · s, and the pH was 7.2.

(Example 12)
VALIFAST YELLOW 1108 (coloring agent, azo-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 3.00% by weight
VALIFAST RED 1308 (C.I. Acid Yellow 23 and C.I.
Salt forming dye made of Basic Red 1 (Orient Chemical Industry Co., Ltd.)
10.00 wt%
Diethylene glycol monomethyl ether (organic solvent) 40.00 wt%
Ethylene glycol monoisopropyl ether (organic solvent) 18.50% by weight
Phosphanol RS-610 (Phosphate ester, mixture of phosphoric monoester, diester and triester of polyoxyethylene (10) tridecyl ether, molecular weight 103
0.3, HLB 10.5, Toho Chemical Industry Co., Ltd. 3.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
1.50% by weight
Braunone BR-404 (polyoxyethylene castor oil, manufactured by Aoki Yushi Kogyo Co., Ltd.)
5.00 wt%
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
3.00% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
NIKKOL BL-9 EX (polyoxyethylene lauryl ether, Nikko Chemicals
Co., Ltd. 3.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a red oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 2.7. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 320 mPa · s at a shear rate of 100 / s, and the pH was 6.8.

(Example 13)
VALIFAST YELLOW 1108 (coloring agent, azo-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 2.00% by weight
VALIFAST YELLOW 1171 (C.I. Acid Yellow 42 and a salt-forming dye consisting of a basic substance, manufactured by Orient Chemical Industry Co., Ltd.) 13.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 14.00% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 12.50% by weight
Ethylene glycol monophenyl ether (organic solvent) 5.00% by weight
NIKKOL DDP-2 (phosphate, di (C12-15) palace-2 phosphate, molecular weight 630.8, HLB 6.5, manufactured by Nikko Chemicals Co., Ltd.) 20.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
7.00% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
3.00% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
Ion-exchanged water 10.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a yellow oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 1.2. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 300 mPa · s at a shear rate of 100 / s, and the pH was 5.0.

(Example 14)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
2.00% by weight
SPILON RED C-GH (coloring agent, xanthene oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 1.00% by weight
OIL BLUE 613 (coloring agent, triarylmethane-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 3.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 2.00% by weight
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and methine dye, ORInt Chemical Industry Co., Ltd.) 7.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 26.00% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 12.00% by weight
Ethylene glycol monophenyl ether (organic solvent) 25.88% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. product 1.20% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
1.00 wt%
NIKKOL HCO-10 (polyoxyethylene hydrogenated castor oil, manufactured by Nikko Chemicals Co., Ltd.) 2.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
0.10% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Ion-exchanged water 0.30% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 3.2. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 520 mPa · s at a shear rate of 100 / s, and the pH was 7.0.

(Example 15)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
5.00 wt%
SPILON RED C-GH (coloring agent, xanthene oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 3.00% by weight
OIL BLUE 613 (coloring agent, triarylmethane-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 3.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 4.00% by weight
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and methine dye, ORIENT CHEMICAL CO., LTD.) 6.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 24.88% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 16.00% by weight
Ethylene glycol monophenyl ether (organic solvent) 16.00% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. 1.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.80% by weight
NIKKOL HCO-10 (polyoxyethylene hydrogenated castor oil, manufactured by Nikko Chemicals Co., Ltd.) 3.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
0.30% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Ion-exchanged water 0.50% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 3.1. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 520 mPa · s at a shear rate of 100 / s, and the pH was 7.8.

(Example 16)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
7.00% by weight
SPILON RED C-GH (coloring agent, xanthene oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 2.00% by weight
OIL BLUE 613 (coloring agent, triarylmethane-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 1.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 3.00% by weight
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and methine dye, made by Orient Chemical Industry Co., Ltd.) 4.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 22.00% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 21.08% by weight
Ethylene glycol monophenyl ether (organic solvent) 15.00% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. 1.50% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
1.20% by weight
NIKKOL HCO-10 (Polyoxyethylene Cured Castor Oil, Nikko Chemicals Co., Ltd.)
Made of 3.50% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
0.70% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Ion-exchanged water 1.50% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 3.1. When the viscosity and pH were measured at a measurement temperature of 25 ° C., the viscosity was 820 mPa · s at a shear rate of 100 / s, and the pH was 7.5.

(Example 17)
Printex 35 (coloring agent, carbon black, manufactured by Degus-Hurs Japan Ltd.)
5.00 wt%
SPILON RED C-GH (coloring agent, xanthene oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 3.00% by weight
OIL BLUE 613 (coloring agent, triarylmethane-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 3.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 3.00% by weight
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and methine dye, made by Orient Chemical Industry Co., Ltd.) 10.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 19.93% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 15.65% by weight
Ethylene glycol monophenyl ether (organic solvent) 15.00% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. 0.80% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.60% by weight
NIKKOL HCO-10 (Polyoxyethylene Cured Castor Oil, Nikko Chemicals Co., Ltd.)
Made of 4.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
1.00 wt%
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, manufactured by NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Ion-exchanged water 2.50% by weight
Among the above components, half of each organic solvent and the entire amount of S-Leak BL-1 are stirred at room temperature, mixed and dissolved, and then the entire amount of Printex 35 is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd. Through 10 times using zirconia beads having a diameter of 0.3 mm, a black paste was obtained.
Then, the whole amount of the remaining material was added to the paste and stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 2.9. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 920 mPa · s, and the pH was 7.5.

(Example 18)
FUJI FAST RED 8800 (Colorant, CI Pigment Red
254, 5.00% by weight of Fuji pigment
SPILON RED C-GH (coloring agent, xanthene oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 5.00% by weight
VALIFAST YELLOW 1108 (coloring agent, azo-based oily dye, manufactured by Orient Chemical Industry Co., Ltd.) 1.00% by weight
SPILON YELLOW C-GNH (coloring agent, indolinone based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 1.00% by weight
VALIFAST RED 1308 (C.I. Acid Yellow 23 and C.I.
Salt forming dye made of Basic Red 1 (Orient Chemical Industry Co., Ltd.)
5.00 wt%
Diethylene glycol monomethyl ether (organic solvent) 10.00% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 21.08% by weight
Ethylene glycol monophenyl ether (organic solvent) 30.00% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. product 0.50% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.20% by weight
NIKKOL HCO-10 (polyoxyethylene hydrogenated castor oil, manufactured by Nikko Chemicals Co., Ltd.)
2.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
0.70% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
Ion exchange water 2.00% by weight
Among the above components, half of each organic solvent and all of S-Leak BL-1 are stirred, mixed and dissolved at room temperature, and then the whole of FUJI FAST RED 8800 is added and further stirred, and then Dynomill (Bead Mill, Inc. 10 times through zirconia beads (diameter of 0.3 mm), to obtain a red paste.
Then, the whole amount of the remaining material was added to the paste, and the mixture was stirred at 70 ° C. for 4 hours to obtain a red oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 1.5. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 1200 mPa · s, and the pH was 5.5.

(Example 19)
CROMOPHTAL Blue A3R (coloring agent, CI Pigment Blue
60, 5.00% by weight, manufactured by Ciba Japan Ltd.
OIL BLUE 613 (coloring agent, triallylmethane oil dye, manufactured by Orient Chemical Industry Co., Ltd.) 5.00% by weight
VALIFAST BLUE 1605 (salt forming dye comprising salt forming dye consisting of CI Solvent Blue 38 and a basic substance, manufactured by Orient Chemical Co., Ltd.)
3.00% by weight
VALIFAST VIOLET 1731 (C.I. Acid-forming dye comprising CI Violet Violet 17 and methine dye, ORIENT CHEMICAL CO., LTD.) 2.00% by weight
Diethylene glycol monomethyl ether (organic solvent) 40.00 wt%
Ethylene glycol monoisopropyl ether (organic solvent) 5.18% by weight
Ethylene glycol monophenyl ether (organic solvent) 10.00% by weight
Phosphanol LB-400 (Phosphate, a mixture of phosphoric monoester, diester and triester of polyoxyethylene (4) oleyl ether, molecular weight 737.9,
HLB 8.6, Toho Chemical Industry Co., Ltd. 1.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
0.80% by weight
NIKKOL HCO-10 (polyoxyethylene hydrogenated castor oil, manufactured by Nikko Chemicals Co., Ltd.)
3.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
S-LEC BH-3 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
1.00 wt%
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Uniol D 2000 (polypropylene glycol, NOF Corporation) 3.00% by weight
AKP-20 (alumina fine particles, manufactured by Sumitomo Chemical Co., Ltd.) 0.02% by weight
NIKKOL BL-9 EX (polyoxyethylene lauryl ether, Nikko Chemicals
Co., Ltd. 3.00% by weight
Ion-exchanged water 5.00% by weight
Among the above components, half of each organic solvent and the whole amount of S-Leak BL-1 are stirred, mixed and dissolved at room temperature, and then the whole amount of CROMOP HTAL Blue A3R is added and further stirred, and then Dynomill (bead mill, Shinmaru Co., Ltd.) Through 10 times using zirconia beads with a diameter of 0.3 mm, a blue paste was obtained.
Then, the whole amount of the remaining material was added to this paste, and the mixture was stirred at 70 ° C. for 4 hours to obtain a blue oil-based ink for ball point pen. The molar conversion of triisopropanolamine / phosphate is 3.1. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 900 mPa · s, and the pH was 7.5.

(Comparative example 1)
Spiron black GMH-S (coloring agent, oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.)
20.00 wt%
VALIFAST VIOLET 1701 (Cation dye comprising C.I. Acid Yellow 42 and C.I. Basic Violet 1, Orient Chemical Industry Co., Ltd.)
Made of 18.00% by weight
Benzyl alcohol (organic solvent) 23.00% by weight
Ethylene glycol monophenyl ether (organic solvent) 23.50% by weight
Plysurf A 215 C (phosphate ester, Dai-ichi Kogyo Seiyaku Co., Ltd. product) 2.00% by weight
Naimine L207 (polyoxyethylene alkylamine, manufactured by NOF Corporation)
2.00% by weight
Oleic acid 2.00% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hirak 110H (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 7.00% by weight
Ion exchange water 2.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 850 mPa · s at a shear rate of 100 / s, and the pH was 7.1.

(Comparative example 2)
SPILON YELLOW C-GNH (coloring agent, indolinone-based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 10.00% by weight
SPILON VIOLET C-RH (coloring agent, triarylmethane-based oily dye, manufactured by Hodogaya Chemical Industry Co., Ltd. 19.50% by weight
VALIFAST VIOLET 1701 (Cation dye comprising C.I. Acid Yellow 42 and C.I. Basic Violet 1, Orient Chemical Industry Co., Ltd.)
Made of 2.80% by weight
Mydol 10 (surfactant, manufactured by Kao Corporation) 0.20% by weight
Marquide No. 32 (maleic resin, manufactured by Arakawa Chemical Industries, Ltd.) 7.50% by weight
3-Methyl-1-phenyl-5-pyrazolone (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.00% by weight
3-methoxy-3-methyl-1-butanol (organic solvent) 55.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 500 mPa · s at a shear rate of 100 / s, and the pH was 6.8.

(Comparative example 3)
SPILON RED C-GH (coloring agent, xanthene oil-based dye, manufactured by Hodogaya Chemical Industry Co., Ltd.) 3.00% by weight
VALIFAST RED 1308 (C.I. Acid Yellow 23 and C.I.
Salt forming dye made of Basic Red 1 (Orient Chemical Industry Co., Ltd.)
3.00% by weight
VALIFAST GREEN 1501 (C.I. Acid Yellow 42 and C.I.
I. Salt-forming dye consisting of Basic Blue 1 and Orient Chemical Industry Co., Ltd.)
13.00 wt%
Diethylene glycol monomethyl ether (organic solvent) 34.80% by weight
Ethylene glycol monoisopropyl ether (organic solvent) 20.20% by weight
Ethylene glycol monophenyl ether (organic solvent) 5.00% by weight
Triisopropanolamine (molecular weight 191.3, manufactured by Tokyo Chemical Industry Co., Ltd.)
1.50% by weight
NIKKOL HCO-50 (polyoxyethylene hydrogenated castor oil, manufactured by Nikko Chemicals Co., Ltd.) 2.00% by weight
S-LEC BL-1 (resin, polyvinyl butyral, manufactured by Sekisui Chemical Co., Ltd.)
2.5% by weight
PVPK-90 (resin, polyvinyl pyrrolidone, manufactured by ISP Japan Co., Ltd.)
0.50% by weight
Hi-Rack 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 10.00% by weight
L7002 (polyether modified silicone, manufactured by Toray Dow Corning Co., Ltd.)
0.50% by weight
Ion-exchanged water 4.00% by weight
The above components were stirred at 70 ° C. for 4 hours to obtain a black oil-based ink for ball point pen. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity was 700 mPa · s at a shear rate of 100 / s, and the pH was 9.0.

(Comparative example 4)
A black oil-based ballpoint ink was obtained in the same manner as in Example 1 except that the total amount of triisopropanolamine was replaced with triethanolamine in Example 1. When the viscosity and pH at a measurement temperature of 25 ° C. were measured, the viscosity at a shear rate of 100 / s was 490 mPa · s, and the pH was 4.4.

Preparation of test ballpoint pen 0.2 g of polypropylene ink container tube (outside diameter φ 3.0 mm, inside diameter φ 1.8 mm) in which the inner surface was treated with silicone for the oil-based ink for ballpoint pens of Examples 1-19 and Comparative Examples 1 to 4 After filling, the ballpoint pen tip prepared in the ballpoint pen tip preparation example 1 is directly attached to the tip of the ink storage tube, and filled with SH200 Fluid 12500CS as an ink follower, then centrifugal force (1000 revolutions / minute for 5 minutes in a centrifugal machine) ) Was added to degas the bubbles in the ink to prepare a test ballpoint pen refill.

Initial coated paper writing test 1 (Sequential writing)
Using the ballpoint pen for the above-mentioned test immediately after making each of the examples and comparative examples, using 10 pieces each in each example and using the TRIBO-MASTER (TYPE: TL201SA) made by Trinity Lab, coated paper made by Oji Paper Co., Ltd. (OK top coat +) An average value of the total distance (mm) of line jump when writing was made at a writing angle of 70 °, a load of 1.47 N, and a writing speed of 7 cm / sec on 10 cm was determined.

Initial coated paper writing test 2 (reverse written)
Using the ballpoint pen for the above-mentioned test immediately after making each of the examples and comparative examples, using 10 pieces each in each example and using the TRIBO-MASTER (TYPE: TL201SA) made by Trinity Lab, coated paper made by Oji Paper Co. (OK top coat +) An average value of the total distance (mm) of line jump when writing was made at a writing angle of 110 °, a load of 1.47 N and a writing speed of 7 cm / sec on 10 cm was determined.

Coated paper writable heat resistance confirmation test Ten ball pens for the above test are stored for 24 hours in a 70 ° C. thermostatic chamber for each example and comparative example, and allowed to cool at room temperature for 24 hours. Using TRIBO-MASTER (TYPE: TL201SA) on Oji Paper Co., Ltd. coated paper (OK top coat +) writing angle 70 °, load 1.47 N, writing speed 7 cm / sec in order The average value of the total distance (mm) of line fly when writing was made 10 cm was determined.

Long-term time-lapsed coated paper writability confirmation test After storing ballpoint pens for the above test for 10 months per each example and comparative example in a thermostatic bath at 50 ° C and 30% RH for 3 months and letting them cool at room temperature for 24 hours Writing angle 70 °, load 1.47 N, writing speed 7 cm / sec on Oji Paper Co., Ltd. coated paper (OK top coat +) using TRIBO-MASTER (TYPE: TL201SA) manufactured by Trinity Lab The average value of the total distance (mm) of line jump when writing was made 10 cm was determined.

Generation confirmation test of long-term aging crystal The ink was taken out from the pen point of the ballpoint pen used in the long-term 1-coated paper writing performance confirmation test, and the crystal was observed with a polarizing microscope (CX31-P, manufactured by Olympus Corporation).
There was no crystal ·················
The crystal has been confirmed ... · · · · · · · · · ×
And The results are shown in Table 1.

  The oil-based ink for ball-point pens of Examples 1 to 19 is excellent in the color development of the handwriting since it contains a salt-forming dye having acid dye and basic substance, triisopropanolamine and a phosphate ester with good writing taste, It was possible to obtain a coated paper which is excellent in writability and which is excellent in writability on coated paper even after a long period of time.

  Furthermore, in Examples 1 to 4, 6, 7, 9 to 12 and 14 to 19, in addition to a salt forming dye comprising an acid dye and a basic substance, triisopropanolamine and a phosphate ester, polyoxyethylene (cured) By containing the castor oil, it was possible to obtain a sheet excellent in coated paper writing properties in reverse writing.

On the other hand, Comparative Example 1 is an oil-based ink for a ballpoint pen using polyoxyethylene alkylamine described in Patent Document 1 instead of triisopropanolamine, but the color development is good and crystals are generated even after long-term aging. Although it does not, the wettability of the ball is so poor that coated paper writing can not be obtained.
Comparative Example 2 is the oil-based ink for ball point pen of Patent Document 2, but
Since the acid dye and the cyclic compound that improves the coatability of the coated paper are included, the coloration is good, and the coatability of the coated paper in the initial stage is excellent, but if the ink is placed in a high temperature environment, the coated paper will be written. Substances that improve the properties become ineffective, and over time, the coated paper can not be drawn. Furthermore, the solvent used for a low viscosity oil-based ballpoint pen is somewhat less soluble, and the dye has been deposited over a long period of time.
Comparative Example 3 is an ink containing a salt forming dye comprising an acid dye and a basic substance, and triisopropanolamine, and although color development is good, coated paper scribing properties can not be obtained, and crystallization can not be prevented after long-term aging.
Comparative Example 4 contains triethanolamine as an amine other than triisopropanolamine, but although color development is good, coated paper writing properties can not be obtained, and crystal precipitation after long-term aging can not be prevented.

  As described above in detail, the present invention is excellent in the coloring properties of the handwriting, so that the handwriting does not jump when writing on a slippery surface, so-called coated paper writing performance is excellent, and coated paper writing is possible even after a long time Related to oil-based ink for ballpoint pens with excellent properties

Reference Signs List 1 ballpoint pen tip 2 ball 3 ball holder 3a rear end opening 3b tip opening 4 ink storage tube 5 ink 6 ink follower 7 coil spring 7a winding portion 7b tip straight portion 8 ball house portion 9 center hole 10 back hole 11 inside Protrusion 12 Radial groove 13 Ball transfer part A1, A2, A3 Ball diameter B1, B2, B3 Tip opening diameter C1, C2, C3 Longitudinal movement distance of ball D1, D2, D3 Ball projection length E1, E2, E3 Ball house diameter F1, F2, F3 Medium pore size G1, G2, G3 Post pore size H1, H2, H3 Radial groove width J1, J2, J3 Ball transfer area diameter

Claims (2)

An oil-based ink for a ballpoint pen comprising at least a salt-forming dye comprising an acid dye and a basic substance, triisopropanolamine and a phosphate ester. The oil-based ink for ball-point pen according to claim 1, wherein the oil-based ink for ball-point pen contains polyoxyethylene (cured) castor oil.

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