JP2004058615A - Manufacturing method of water-based ballpoint pen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based ballpoint pen which is free from bubbles occurring in ink with lapse of time, any obstruction in the flow of the ink and a blur during writing. <P>SOLUTION: A method of manufacturing the water-based ballpoint pen includes steps of filling ink consisting of at least a coloring agent, a water-soluble organic solvent, a reducing substance, and water in an ink storage tube having a member for rotatably holding a ball attached to one of its ends, filling a backflow preventive agent in the other end of the tube, and then centrifuging under a reduced pressure. <P>COPYRIGHT: (C)2004,JPO

Description

【００３８】
表１に示したように、インキ中に還元剤を添加し、かつ減圧下に遠心を実施した水性ボールペンは経時的な気泡の発生も無く良好であった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an aqueous ballpoint pen filled with an ink containing a coloring agent such as a pigment or a dye, a shear-thinning substance, a reducing substance, and the like in an aqueous medium mainly composed of water. The present invention relates to a method for manufacturing a water-based ball-point pen that prevents a bubble and / or a chip such as a ball gripping portion from generating bubbles and causing problems such as writing blur.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a method of manufacturing an aqueous ball-point pen, in particular, a method of preventing generation of bubbles over time in a ball-point pen tip as an ink storage tube and / or a ball-holding portion by removing dissolved gas in ink over time. A method for eliminating nuclei that grow into bubbles is known. As a method for removing dissolved oxygen in the ink, for example, the ink is added with a reducing substance that binds to oxygen in the ink, such as ascorbic acid, kojic acid, polyphenol, hydroquinone, sodium sulfite, etc., to remove dissolved oxygen. Before the ink is stored in the ink storage tube, a chemical method is used, or a physical method is used in which the ink is left under reduced pressure so that the amount of dissolved gas in the ink is reduced to a certain value or less. I have. Further, a physical method of efficiently removing dissolved gas mixed or dissolved in the ink by centrifuging the aqueous ball-point pen filled with the ink under reduced pressure is also performed.
[0003]
[Problems to be solved by the invention]
However, the above-described method is not sufficient to prevent the generation of bubbles over time, and the generated bubbles may block the ink flow path and cause problems such as blurring during writing.
That is, in the method of adding a reducing substance that binds to dissolved oxygen to the ink, the dissolved oxygen is eliminated, but in the method of leaving the ink under reduced pressure to reduce the dissolved gas to a certain value or less, the dissolved oxygen in the ink is removed. Although gas can be removed to some extent, air that has been entrained when filling the ink into the ink storage tube cannot be easily removed by centrifugation performed under normal pressure, and air bubbles may remain in the ink. Was.
Furthermore, in the method of centrifuging the ink-filled ball-point pen under reduced pressure, large air bubbles mixed in the ink can be easily removed, but dissolved gas cannot be removed by a short-time treatment. Since it requires a time-reduced centrifugation, the production takes too much time and is inefficient and uneconomical.
Aqueous ballpoint pens often entrap air from the pen tip during writing, but are left under reduced pressure to fill the ink with dissolved gas below a certain value, or to centrifuge the ink-filled ballpoint pen under reduced pressure. Since there is no means for removing air mixed in after production, air entrapped at the time of writing may block the ink flow path and cause problems such as ejection failure and blurring.
SUMMARY OF THE INVENTION It is an object of the present invention to provide an aqueous ballpoint pen that does not generate air bubbles in the ink even with the lapse of time, and does not hinder the flow of the ink or cause writing blur during writing.
[0004]
[Means for Solving the Problems]
That is, the present invention provides an ink comprising at least a colorant, a water-soluble organic solvent, a reducing substance, and water, and a backflow preventive agent on a pipe having a ballpoint pen tip attached to one end thereof at an interface opposite to the ballpoint pen tip of the ink. After storing so that the anti-reflux agent is located, there is a step of simultaneously making it exist under reduced pressure and applying a centrifugal force toward the ball-point pen tip by rotating the ball-point pen tip outside and rotating it. The gist of the invention is a method of manufacturing a ballpoint pen.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The details will be described below.
As the colorant used in the present invention, dyes and pigments used in conventional aqueous inks can be used, and any of dyes such as acid dyes, direct dyes, and basic dyes can be used. Examples thereof include Japananol Fast Black D Conch (CI Direct Black 17), Water Black 100L (19), Water Black L-200 (19), Direct Fast Black B (22), Direct Fast Black AB (32), Direct Deep Black EX (38), Direct Fast Black Conch (51), Kayalas Sprague VGN (71), Kayalas Direct Brilliant Yellow G (CI Direct Yellow 4) ), Direct Fast Yellow 5GL (26), Eizen Primula Yellow GCLH (44), Direct Fast Yellow R (50), Eizen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet G X (4), Direct Fast Scarlet 4BS (23), Eisen Direct Loadurin BH (31), Direct Scarlet B (37), Kayak Direct Scarlet 3B (39), Aizen Primula Pink 2BLH (75) ), Sumilight Red F3B (80), Aizen Primula Red 4BH (81), Kayalas Sprulbin BL (83), Kayalas Light Red F5G (225), Kayalas Light Red F5B (226), Kayaras Light Rose FR (227), Direct Sky Blue 6B (CI Direct Blue 1), Direct Sky Blue 5B (15), Sumilight Supra Blue BRR Conch (71), Daibogen Turquoise Blue S (71) 86), Water Blue # 3 (Same as above) 6), direct dyes such as Kayalas Star Koizu Blue GL (86), Kayaras Supra Blue FF2GL (106), Kayaras Splatter Blue FBL (199) and Acid Blue Black 10B (CI Acid Black). 1), Nigrosine (2), Suminol Milling Black 8BX (24), Kayanol Milling Black VLG (26), Suminol Fast Black BR Conk (31), Mitsui Nylon Black GL (52), Eisen Opal Black WH Extra Conc (52), Sumilan Black WA (52), Ranyl Black BG Extra Conc (107), Kayanol Milling Black TLB (109), Suminol Milling Black B (109), Kaya Nord Milling Black TLR ( 110), Eisen Opal Black New Conc (119), Water Black 187-L (154), Kayak Acid Brilliant Flavin FF (C.I. I. Acid Yellow 7: 1), Kayasil Yellow GG (17), Xylene Light Yellow 2G 140% (17), Suminol Leveling Yellow NR (19), Daiwa Trazine (23), Kayaktor Trazine (23) Suminol Fast Yellow R (25), Diacid Light Yellow 2GP (29), Suminol Milling Yellow O (38), Suminol Milling Yellow MR (42), Water Yellow # 6 (42), Kayanol Yellow NFG (49), Suminol Milling Yellow 3G (72), Suminol Fast Yellow G (61), Suminol Milling Yellow G (78), Kayanol Yellow N5G (110), Suminol Milling Yellow 4G 200% (141), Kayanol Yellow NG (135), Kayano Lumiling Yellow 5GW (127), Kayanol Milling Yellow 6GW (142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (9), Solar Rubin Extra (14), Daiwa New Koksin (18), Aizen Bonsaw RH (26), Daiwa Red No. 2 (27), Suminol Leveling Brilliant Red S3B (35), Kayasil Rubinol 3GS (37), Aizen Erythrosin (37) 51), Kayak Acid Rhodamine FB (52), Suminol Leveling Rubinol 3GP (57), Diacid Alizarin Rubinol F3G 200% (82), Eisen Eosin GH (87), Water Pink # 2 (52) 92), Eisen Acid Phloxine PB 92), Rose Bengal (94), Kayanol Milling Scarlet FGW (111), Kayanol Milling Rubin 3BW (129), Sumino All Milling Brilliant Red 3BN Conch (131), Sumino Milling Brilliant Red BS (131) 138), Eisen Opal Pink BH (186), Suminol Milling Brilliant Red B Conch (249), Kayaking Acid Brilliant Red 3BL (254), Kayaking Acid Brilliant Brilliant Red BL (265), Kayano Milling Red GW (276), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (17), Sumitomo Patent Pure Blue VX (CI Acid Blue) 1), Water Blue # 106 (1), Patent Blue AF (7), Water Blue # 9 (9), Daiwa Blue No. 1 (9), Spranol Blue B (15), Orient Solble Blue OBC (22), Suminol Leveling Blue 4GL (23), Mitsui Nylon Fast Blue G (25), Kayasil Blue AGG (40), Kayasil Blue BR (41), Mitsui Alizarin Safirol SE (43) , Suminol Leveling Sky Blue R Extra Conc (62), Mitsui Nylon Fast Sky Blue B (78), Sumitomobrilliant Indocyanine 6Bh / c (83), Sandran cyanine N-6B 350% (90), water Blue # 115 (90), Orient Soluble Blue OBB The same 93), Sumitomo brilliant blue 5G (the 103), Kaya Nord milling Ultra Sky SE (the 112), Kaya Nord milling cyanine 5R (the 113), Aizen Opal Blue 2GLH (the 158), Daiwa Guinea green B (C. I. Acid dyes such as Acid Green 3), Acid Brilliant Milling Green B (9), Daiwa Green # 70 (16), Kayanol Cyanine Green G (25), Suminol Milling Green G (27), and Aizenkachi Ron Yellow 3GLH (C.I. Basic Yellow 11), Eisenka Chiron Brilliant Yellow 5GLH (13), Sumiacryl Yellow E-3RD (15), Maxillon Yellow 2RL (19), Astrazon Yellow 7GLL (11) 21), Kayacryl Golden Yellow GL-ED (28), Astrazon Yellow 5GL (51), Eizen Katilon Orange GLH (CI Basic Orange 21), Eizen Katilon Brown 3GLH (30), Rhodamine 6 GCP (C.I. Black Red 1), Eizen Astra Phloxine (12), Sumiacryl Brilliant Red E-2B (15), Astrazon Red GTL (18), Eizen Chiron Brilliant Pink BGH (27), Maxilon Red GRL (17) 46), Aizen Methyl Violet (CI Basic Violet 1), Aizen Crystal Violet (3), Aizen Rhodamine B (10), Astrazone Blue G (CI Basic Blue 1), Astrazone Blue BG (3), methylene blue (9), maxilon blue GRL (41), Aizen Katilon Blue BRLH (54), Aizen Diamond Green GH (CI Basic Green 1), Aizen Malachite Green (4) ), Bismarck Blau G include basic dye (C.I. Basic Brown 1) and the like.
[0006]
Pigments include organic pigments such as azo pigments, nitroso pigments, nitro pigments, basic dye pigments, acid dye pigments, vat dye pigments, mordant dye pigments, and natural dye pigments, loess, and barium. Inorganic pigments such as yellow, dark blue, cadmium red, barium sulfate, titanium oxide, red iron oxide, iron black, carbon black and the like can be mentioned, and these can be used alone or in combination.
Specific examples include aniline black (CI. 50440), cyanine black, naphthol yellow S (CI. 10316), Hansa yellow 10G (CI. 11710), Hansa yellow 5G (CI. 11660), and Hansa yellow. 3G (CI. 11670), Hansa Yellow G (CI. 11680), Hansa Yellow GR (CI. 11730), Hansa Yellow A (CI. 11735), Hansa Yellow RN (CI. 11740), Hansa Yellow R (CI. 12710), pigment yellow L (CI. 12720), benzidine yellow (CI. 21090), benzidine yellow G (CI. 21095), benzidine yellow GR (CI. 21100) ), Permanent Yellow NCG (CI. 20040), Balkan Fast E -5G (CI. 21220), Vulcan Fast Yellow R (CI. 21135), Tartrazine Lake (CI. 19140), Quinoline Yellow Lake (CI. 47005), Anslagen Yellow 6GL (C. 60520), permanent yellow FGL, permanent yellow H10G, permanent yellow HR, anthrapyrimidine yellow (CI. 68420), Sudane I (CI. 12055), permanent orange (CI. 12075), resole Fast Orange (C.I. 12125), Permanent Orange GTR (C.I. 12305), Hansa Yellow 3R (C.I. 11725), Vulcan Fast Orange GG (C.I. 21165), Benzidine Orange G (C.I. .21110), Persian Ole Di (CI. 15510), indanthrene brilliant orange GK (CI. 59305), indanthrene brilliant orange RK (CI. 59105), indanthrene brilliant orange GR (CI. 71105) , Permanent Brown FG (C.I. 12480), Para Brown (C.I. 12071), Permanent Red 4R (C.I. 12120), Para Red (C.I. 12070), Fire Red (C.I. 12085) ), Parachloroorthoaniline red (CI.12090), lysole fast scarlet, brilliant fast scarlet (CI.12315), brilliant carmine BS, permanent red F2R (CI.12310), permanent red F4R (C. ..I.1 2335), permanent red FRL (C.I. I. 12440), permanent red FRLL (C.I. 12460), permanent red F4RH (C.I. 12420), fast scarlet VD, Vulcan fast rubin B (C.I. 12320), Vulcan fast pink G (C.I. 12330), light fast red toner B (CI. 12450), light fast red toner R (CI. 12455), permanent carmine FB (CI. 12490), pyrazolone red (CI. 12120), Lisor Red (CI. 15630), Lake Red C (CI. 15585), Lake Red D (CI. 15500), Ansosine B (CI. 18030), Brilliant Scarlet G (CI. 15800), Lisor Rubin GK (CI. 158) 5), permanent red F5R (CI. 15865), brilliant carmine 6B (CI. 15850), pigment scarlet 3B (CI. 16105), Bordeaux 5B (CI. 12170), toluidine maroon (C. I. 12350), permanent Bordeaux F2R (CI. 12385), Helio Bordeaux BL (CI. 14830), Bordeaux 10B (CI. 15880), Bon Maroon Light (CI. 15825), Bonn Maroon Medium (CI. 15880), Eosin Lake (CI. 45380), Rhodamine Lake B (CI. 45170), Rhodamine Lake Y (CI. 45160), Alizarin Lake (CI. 58000) ), Thioindigo red B (CI. 73300), thioindigo Rune (CI. 73385), Permanent Red FGR (CI. 12370), PV Carmine HR, Watching Red, Monolight Fast Red YS (CI. 59300), Permanent Red BL, Fast Violet B, Methyl Violet Lake (C.I. 42535), Dioxazine Violet, Alkaline Blue Lake (C.I. 42750A, C.I. 42770A), Peacock Blue Lake (C.I. 42090), Peacock Blue Lake (C.I. 42025), Victoria Blue Lake (CI.44045), Phthalocyanine Blue (CI.74160), Fast Sky Blue (CI.74180), Indanthrene Blue RS (CI.69800), Indanth Renblue BC (CI.6 9825), indigo (C.I. I. 73000), Pigment Green B (CI. 10006), Naphthol Green B (CI. 10020), Green Gold (CI. 12775), Acid Green Lake, Malachite Green Lake (CI. 42000), And phthalocyanine green.
The use amount of these coloring agents is preferably 0.5 to 30% by weight based on the total amount of the ink. If it is less than 0.5% by weight, it is thin and does not fulfill the performance as a handwriting. If it exceeds 30% by weight, the dry-up in the chip increases and the writing performance tends to deteriorate.
[0007]
When a pigment is used as the colorant, a dispersant may be used to stably disperse the pigment. As a dispersant, a water-soluble resin or a water-soluble resin conventionally used generally, or a dispersant used as a pigment dispersant such as an anionic or nonionic surfactant can be used. As an example, as a polymer dispersant, natural polymers such as lignin sulfonate and shellac, polyacrylate, salt of styrene-acrylic acid copolymer, salt of vinylnaphthalene-maleic acid copolymer, β-naphthalene Examples include anionic polymers such as sodium salts and phosphates of sulfonic acid formalin condensates, and nonionic polymers such as polyvinyl alcohol and polyethylene glycol. As surfactants, alkyl sulfates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids and salts thereof, N-acylmethyl taurine salts, polyoxyethylene alkyl ether acetates, alkyl sulfocarboxylates, α- Anionic surfactants such as olefin sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and nonionics such as polyoxyethylene alkyl ethers, sorbitan alkyl esters, and polyoxyethylene sorbitan alkyl esters Surfactants.
[0008]
One or more of these water-soluble resins and surfactants may be selected and used in combination. The amount used is preferably 0.05 to 20 parts by weight based on 10 parts by weight of the pigment. If the amount is less than 0.05 part by weight, the dispersing effect, which is the purpose of addition, is weak, and if the amount is more than 20 parts by weight, no further dispersing effect can be expected, which is uneconomical.
In the case of pigments, it is further advantageous to use an aqueous ink base dispersed in an aqueous medium in the production of pigment inks. Specifically, Fuji SP Black 8031, 8119, 8167, 8276, 8381, 8406, 8SP, Fuji SP Red 5096, 5111, 5193, 5193, 5220, Fuji SP Bordeaux 5500, Fuji SP Blue 6062, 6133 6134, 6401, Fuji SP Green 7051, Fuji SP Yellow 4060, 4178, Fuji SP Violet 9011, Fuji SP Pink 9524, 9527, Fuji SP Orange 534, FUJI SPB RUB (The above are manufactured by Fuji Dye Co., Ltd.), Emacol Black CN, Emacol Blue FBB, FB, KR, Emacol G reen LXB, Emacol Violet BL, Emacol Brown 3101, Emacol Carmine FB, Emacol Red BS, Emacol Orange R, Emacol Yellow FD, IRN, 3601, FGN, GN, and GN , 10G, Sandye Super Black K, C, Sandye Super Gray B, Sandye Super Brown SB, FRL, RR, Sandy Super Green L5G, GYB, GXB, Sandy Super Green H, FBL-160, FBB, Sandy Super Violet BL H / C, BL, Sandy Sup r Bordeaux FR, Sandy Super Pink FBL, F5B, Sandye Super Rubine FR, Sandy super Carmmine FB, Sandy Super Red FFF, RR, RB, Sandy Super Red FDG, RR, BS , 3R, Sandye Ywllow GG, F3R, IRC, FGN, GN, GRS, GSR-130, GSN-130, GSN, 10GN (all manufactured by Sanyo Dyeing Co., Ltd.), Rio Fast BlackFx 8012, 8313, 8169, Rio Fast Red Fx8209, 8172, Rio Fast Red S Fx 8315, 8316, Rio F st Blue FX 8170, Rio Fast Blue FX 8170, Rio Fast Blue S Fx 8312, Rio Fast Green S Fx 8314 (manufactured by Toyo Ink Co., Ltd.), NKW-2101, 1052, and 1022 , 2106, 2107, 2108, 2117, 2127, 2137, 2167, 2101P, 2102P, 2103P, 2104P, 2105P, 2106P, 2107P, 2108P, 2117P, 2117P 2127P, 2137P, 2167P, NKW-3002, 3003, 3004, 3005, 3007, 3077, 3008, 3402, 3404, 3405, 3407, 3408, 3377, 3677 2, 3603, 3604, 3605, 3607, 3677, 3608, 3702, 3703, 3704, 3705, 3777, 3708, 6013, 6038, and 6559 (Japan Fluorescent Co., Ltd.), Cosmo Color S1000F Series (Toyo Soda Co., Ltd.), Victoria Yellow G-11, G-20, Victoria Orange G-16, G-21, Victoria Red G-19, G -22, Victoria Pink G-17, Victoria G-23, Victoria Green G-18, Victoria G-24, Victoria Blue G-15, Victoria G-25 (all manufactured by Mikuni Pigment Co., Ltd.), Pollux PC5T1020, Pollux Pollux series such as Black PC8T135, Poluc Red IT1030 (Sumitoka Color Co., Ltd.) ) Are those like, these are what can be used in combination to select one or more.
[0009]
The reducing substance is used to combine with and remove dissolved oxygen in the ink. Specific examples thereof include ascorbic acid, erythorbic acid, kojic acid and salts and derivatives thereof, phenylenediamine, diaminodiphenylamine, aminophenol, hydroquinone, hydroquinonesulfonic acid and salts thereof, resorcin, catechol, pyrogallol, and phloroglucinol. , Gallic acid and its salts, catechin, tannic acid and its salts, polyphenols such as trihydroxybenzene, keto-enol isomers such as tert-butylphenol, hindered phenol, hindered amine, acetanilide, acetoacetanilide, hydroxylamine, oxyquinoline Sulfonic acid, thiourea dioxide, formamidine sulfinic acid, sulfite, bisulfite, thiosulfate, and the like, but are not limited thereto. If there a material having what most can be used.
The amount of these reducing substances used is preferably 0.05% by weight to 5% by weight, and more preferably 0.1% by weight to 2% by weight, based on the whole ink. If it is less than 0.05%, the effect of removing oxygen in the ink is weak, and if it is added in excess of 5% by weight, no further effect of removing oxygen is obtained, and there is no point in adding.
[0010]
In the present invention, when the pen tip is left down, the viscosity of the ink can be adjusted to prevent the ink from leaking from the pen tip. The viscosity of the ink can be adjusted by appropriately adjusting and using a thickening substance and / or a shear-thinning substance so as to obtain a desired viscosity. Specific examples thereof include polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, carboxyethylcellulose, collagen, HPC-SL, L, M, and H (all manufactured by Nippon Soda Co., Ltd.), Avicel PH-101. , 102, 301, M06, TG-101 (all manufactured by Asahi Kasei Corporation) and the like, Kelzan, Kelzan S, Kelzan F, Kelzan AR, Kelzan M, and Kelzan D (all, Sansei (Co., Ltd.) Xanthan gum such as Kojin, Kojin F, Kojin T and Kojin K (all manufactured by Kojin Co., Ltd.), succinoglucan such as leozan (manufactured by Sansho Co., Ltd.), K1A96 (manufactured by Sancho Co., Ltd.) Wellan gum such as K1A112, K7C2433 (above, manufactured by Sancho Co., Ltd.), etc .; Jaguar 8111; Guar gums such as HP-8, HP-60, and CP-13 (all manufactured by Sancho Corporation), water-soluble polysaccharides such as pullulan (manufactured by Hayashibara Corporation), GX-205, NA-010 Water-soluble synthetic polymers such as N-vinylacetamide polymerized cross-linked products such as (manufactured by Showa Denko KK), smecton SA (smectite, manufactured by Kunimine Industry Co., Ltd.), kunipia-F, kunipia-G (montmorillonite, kunimine industry) Co., Ltd.), Wenger HV, FW, 15, 15 (Bentonite, manufactured by Toyojun Yoko Co., Ltd.), Esven, C, W, N400 (quaternary ammonium cation-modified montmorillonite, Co., Ltd.) And inorganic clay minerals such as Toyohyun Yoko).
Among these, xanthan gum has a large shear thinning property, so that the viscosity of the ink is greatly reduced during writing, and as a result, it is difficult for spots and line breaks to occur during writing, stability against temperature change, stability against pH Is particularly preferable from the viewpoint of stability against salts.
The above-mentioned shear-thinning substances can be used as a mixture of a plurality of types.However, the amount of use thereof cannot be said unconditionally because it depends on the properties of each of the shear-thinning substances. In consideration of ink leakage and the like, it is preferable that the ink viscosity is 30,000 mPa · s or less at a shear rate of 10 sec-1.
[0011]
Various resins can be used in combination as a binder in order to fix the colorant of the ink to the paper surface. Specifically, shellac, styrene-maleic acid copolymer, alkali metal salt of styrene-acrylic acid copolymer, amine salt, ammonium salt thereof, alkali metal salt of α-methylstyrene-acrylic acid copolymer, A water-soluble resin such as the same amine salt and the same ammonium salt can be used. Further, a water-insoluble resin such as an acrylic resin, a vinyl acetate resin, and a styrene-butadiene copolymer can also be used. The water-insoluble resin is used in the form of an aqueous emulsion.
[0012]
Water is used as the main solvent.
Various water-soluble organic solvents are used together with water for the purpose of preventing drying of the ink and preventing freezing at low temperatures. Specifically, alcohols such as ethanol, 1-propanol, 2-propanol and butyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, hexylene glycol, 2-ethyl 1,3- Hexane glycol, glycerin, triethylene glycol, dipropylene glycol, diglycerin, polyethylene glycol, glycol such as polypropylene glycol, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, ether such as diethylene glycol ethyl ether, thiodiglycol, Thiodiglycolic acid and its salts and derivatives thereof, Thiodipropionic acid and its salts and derivatives thereof, dithiodiglycol, N-methylpyrrolidone 2-phenoxyethanol, etc. can be used.
These can be used alone or in combination of two or more. The amount used is preferably 0.5 to 40% by weight based on the total amount of the ink. If the amount is less than 0.5% by weight, the effect of preventing drying of the coated portion may be weak and may not be used. Even if it is added in excess of 60% by weight, the effect is not improved and the meaning of the addition cannot be found.
[0013]
In addition to the above components, various additives conventionally used in aqueous inks for writing instruments can be used as needed.
For example, sugar alcohols such as sorbitol and xylitol are used to prevent evaporation of the ink, and polyethylene glycol, polyoxyethylene glycol polyoxypropylene glycol, alkali metal salts and amine salts of oleic acid, and acyl salts are used to improve the writing feel. A lubricant such as an amino acid, an alkali metal salt such as taurine and methyl taurine, and an amine salt can be used.
[0014]
Furthermore, various surfactants such as anionic, nonionic and cationic surfactants, surface tension regulators such as silicone surfactants and fluorine surfactants, sodium dehydroacetate, 1,2-benzoisothiazalin-3-one, etc. Rust inhibitors such as benzotriazole and ethylenediaminetetraacetic acid, and alkalinizing agents such as sodium hydroxide, alkanolamine, amine and ammonium as pH adjusters.
[0015]
As the ballpoint pen tip, a metal tip using metal for the ball holder and a resin tip mainly using synthetic resin can be used. As a material of the ball holder using metal, generally used materials such as nickel silver, brass and stainless steel can be used. In addition, as a main material of a ball holder mainly made of a synthetic resin, a general molding resin can be used, and 100% of these synthetic resins may be used for molding. Specifically, polyacetal resin, polybutylene terephthalate resin, aromatic nylon resin, modified polyphenylene ether resin, polyacrylate resin and the like can be used. Polyacetal resin, polyethylene terephthalate resin, and polybutylene terephthalate resin are particularly preferable from the viewpoint of smooth writing feel.
Various fillers can be added to these resins for the purpose of improving lubricity, improving wear resistance, improving strength, and the like. Examples of the filler include molybdenum, potassium titanate, glass fiber, calcium carbonate, mica and the like. The amount of these fillers is preferably 30% or less. If it exceeds 40%, the filler may be unevenly formed at the time of molding and the shape of the chip may be impaired.
[0016]
As an example of a ball material to be gripped by the ball holder, a ball made of tungsten carbide, a ball made mainly of silicon carbide, a ball made mainly of zirconia, or the like can be used.
[0017]
Polyethylene, polypropylene, fluororesin, silicone resin, and the like can be used as the material of the ink container for directly filling the ink, but polypropylene is preferable in consideration of moisture permeability, transparency, cost, and the like.
[0018]
In the manufacture of the ballpoint pen of the present invention, there is no particular problem in filling the ink by filling the ink containing a reducing substance to be removed by combining with dissolved oxygen by a conventional method. In order to centrifuge the ballpoint pen filled with ink under reduced pressure, a method of gradually and / or rapidly reducing the pressure while centrifuging, a method of first reducing the pressure and then centrifuging, and a method of reducing the pressure while centrifuging and then reducing the pressure After that, there is a method of reducing the pressure again, and in some cases, a method of repeatedly reducing and reducing the pressure.
In the method of reducing the pressure gradually and / or at a stretch while centrifuging, the ink is suppressed by the centrifugal force. Therefore, even if the bubbles expand rapidly when the pressure is reduced, the ink and / or the backflow preventer does not leak from the ink storage tube. Productive advantage.
The method of decompressing while centrifuging and then depressurizing and then depressurizing again, or the method of repeating this depressurizing and depressurizing, increases or decreases the bubbles in the ink, so ink is stored. This is effective for more completely removing fine bubbles adhering to a tube wall or the like.
The method of first depressurizing and then centrifuging has the advantage that it is easy to remove the air bubbles in a short time by centrifuging the air bubbles since the air bubbles can be made the largest because no pressure is applied to the air bubbles.
In these methods, changing the conditions of centrifugation while performing reduced-pressure centrifugation is an effective method for removing dissolved oxygen and / or existing bubbles.
Here, the degree of pressure reduction during centrifugation is higher if the air pressure is lower than the atmospheric pressure, and the effect of air bubble removal is higher. The lower the pressure is, the higher the effect is. However, empirically, the pressure is reduced to 300 mmHg or less. More preferably, it is more preferable to set the pressure to 50 mmHg or less because the air bubble removing effect is high. However, since the components in the ink contain a volatile substance, for example, water, it is necessary to keep the pressure at a level that does not cause the components in the ink to boil.
The conditions of centrifugation need to be changed depending on the condition of each ink and ballpoint pen, so it cannot be said unconditionally, but the higher the number of revolutions and the stronger the centrifugal force, the better the effect of removing air bubbles in the ink. In the case where the ink contains a component that settles in the ink, centrifugation may be performed by appropriately selecting a rotation speed that does not cause clogging due to the settling.
The centrifugation time is a trade-off with the centrifugal rotation speed, but the longer the time, the more the air bubble removal effect increases.Therefore, considering the production efficiency and the high rate of air bubble removal, take into account the centrifugal rotation speed and the degree of pressure reduction. Need to be measured.
[0019]
[Action]
In the present invention, dissolved oxygen is eliminated by adding a substance that chemically dissolves oxygen to remove dissolved oxygen to the ink, and the partial pressure of each gas dissolved in the ink and the partial pressure of the atmosphere are removed. By disturbing the equilibrium, the gas present in the ink acts to maintain equilibrium with the atmosphere, and as a result, the dissolved gas in the ink flows out to the atmosphere, so that the dissolved gas is eliminated from the ink. Thereby, it is presumed that fine bubbles that cause the generation of bubbles over time and the dissolved gas that collects in these fine bubbles to form large bubbles are removed, thereby preventing the generation of bubbles over time.
In the present invention, a centrifugal treatment is performed under reduced pressure during the production of a ballpoint pen. This makes it possible to remove gas such as air entrained when the ink container is filled with ink, thereby preventing fine bubbles present in the ink from gathering over time to form large bubbles.
By performing both of the above two means, it is possible to prevent the initial bubble removal and the generation of bubbles over time. It is presumed that no problem occurs.
[0020]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. In the examples, “parts” means “parts by weight”.
[0021]
Ink sample 1
Water Black # 108-L (CI Direct Black 19
40.0 parts (14% aqueous solution, manufactured by Orient Chemical Industry Co., Ltd.)
Kerzan AR (xanthan gum, shear-thinning resin, Sansei Co., Ltd.) 0.2 part
Ethylene glycol 10.0 parts
Glycerin 10.0 parts
Benzotriazole 0.5 parts
Sodium ascorbate 0.5 parts
Proxel GXL (1,2-benzisothiazolin-3-one, preservative, I
0.3 parts by CI Corporation
38.5 parts of ion exchange water
In the above components, the entire amount of Kelzan AR and 5.0 parts of water were stirred with a lab mixer for 30 minutes to uniformly dissolve and prepare a Kelzan aqueous solution. The remaining components were mixed, mixed and stirred for 1 hour, added with a Kelzan AR aqueous solution, and further stirred for 2 hours, and the shearing speed was 10 sec. ^-1 , A black ink having a viscosity of 70 mPa · s was obtained.
[0022]
Ink sample 2
Water Red # 2 (CI ACID RED87, manufactured by Orient Chemical Industry Co., Ltd.) 5.0 parts
Water Yellow # 6C (CI ACID YELLOW 23, manufactured by Orient Chemical Industry Co., Ltd.) 3.0 parts
Kerzan AR 0.5 copy
Ethylene glycol 25.0 parts
Glycerin 10.0 parts
0.1 part of sarcosinate OH (N-oleoyl sarcosine, surfactant, manufactured by Nikko Chemicals Co., Ltd.)
Benzotriazole 0.5 parts
Proxel GXL 0.3 parts
0.3 parts of potassium hydroquinone sulfonate (reducing agent, manufactured by Samsung Chemical Industry Co., Ltd.)
AKP-20 (alumina, particle size 0.5 μm, manufactured by Sumitomo Chemical Co., Ltd.) 0.01 part
55.29 parts of ion-exchanged water
In the above components, the entire amount of Kelzan AR and 5.0 parts of water were stirred with a lab mixer for 30 minutes to be uniformly dissolved to prepare a Kelzan aqueous solution. Next, AKP-20 and the entire amount of glycerin were mixed and uniformly stirred, followed by stirring with a homogenizer for 15 minutes to prepare an alumina dispersion. The remaining components were mixed and stirred for 1 hour, and then an aqueous Kelzan AR solution and an alumina dispersion were added. The mixture was further stirred for 2 hours to obtain a red ink having a viscosity of 350 mPa · s.
[0023]
Ink sample 3
FUJI SP BLACK 8922 (20% dispersion of carbon black, manufactured by Fuji Dye Co., Ltd.) 25.0 parts
Ethylene glycol 10.0 parts
Glycerin 10.0 parts
Benzotriazole 0.5 parts
Proxel GXL (1,2-benzisothiazolin-3-one, preservative, I
0.3 parts by CI Corporation
0.3 parts of Pemulen TR-1 (crosslinked acrylic acid and acrylate copolymer, manufactured by BF Goodrich)
Sodium sulfite 1.0 part
52.9 parts of ion-exchanged water
Among the above components, the whole amount of Pemulen TR-1 and 10 parts of water were stirred for 1 hour with a laboratory mixer to prepare an aqueous solution of Pemulen TR-1. An aqueous solution of Pemulen TR-1 was added to a liquid obtained by mixing the remaining components and stirring for 1 hour until the mixture became uniform, and the mixture was further stirred for 2 hours to obtain a black ink having a viscosity of 260 mPa · s.
[0024]
Ink sample 4
Daiwa Blue # 1 (CI Acid Blue 9, manufactured by Daiwa Kasei Co., Ltd.) 4.0 parts
Water Red # 2 0.4 parts
Ethylene glycol 12.0 parts
Thiodiglycol 6.0 parts
Glycerin 3.0 parts
Benzotriazole 0.5 parts
0.2 parts of Proxel GXL (1,2-benzisothiazolin-3-one, preservative, manufactured by ICI Corporation)
Kerzan AR 0.5 parts
Pemulen TR-1 0.5 parts
Sodium ascorbate 1.0 part
71.9 parts of ion exchange water
Among the above components, the whole amount of Pemulen TR-1 and 10 parts of water were stirred for 1 hour with a laboratory mixer to prepare an aqueous solution of Pemulen TR-1. In addition, the entire amount of Kelzan AR and 10 parts of water were stirred for 1 hour with a laboratory mixer to prepare a Kelzan AR aqueous solution. An aqueous solution of Pemulen TR-1 and an aqueous solution of Kelzan AR were added to the liquid obtained by mixing the remaining components and stirring for 1 hour until the mixture became uniform, and the mixture was further stirred for 2 hours to obtain a blue ink having a viscosity of 3000 mPa · s.
[0025]
Comparative sample 1 of ink
A black ink having a viscosity of 62 mPa · s was obtained in the same manner as in Example 1 of the ink except that sodium ascorbate was removed and water was added to the ink in Example 1 of the ink.
[0026]
Comparative sample 2 of ink
A red ink having a viscosity of 347 mPa · s was obtained in the same manner as in Example 2 of the ink except that potassium hydroquinonesulfonate was removed and the amount of water was increased in Example 2 of the ink.
[0027]
Comparative sample 3 of ink
A red ink having a viscosity of 254 mPa · s was obtained in the same manner as in Example 3 of the ink except that the amount of water was increased by removing sodium sulfite in Example 3 of the ink.
[0028]
Production Example 1
The ink of Ink Sample 1 was placed in a polypropylene ink container having an inner diameter of 4 mm and a length of 85 mm in which a stainless steel chip having a 0.7 mm diameter carbide ball held at one end was attached via a chip holder. The ink was charged with 8 g, and the back end of the ink was charged with 0.2 g of a backflow inhibitor obtained by gelling polybutene with a gelling agent. The nib capped with a hot-melt adhesive was placed in a reduced-pressure centrifuge, and the pressure was reduced to 20 mmHg while centrifuging at 1000 rpm. After maintaining it for 15 minutes, the pressure was returned to the atmospheric pressure, the centrifugation was stopped, and the aqueous ballpoint pen was obtained.
[0029]
Production Example 2
Using the same parts as in ball-point pen manufacturing example 1, the ink of ink sample 2 was filled therein, the back end of the ink was filled with 0.1 g of a backflow inhibitor gelling an α-olefin oligomer, and a polypropylene float was further added. Was inserted. The pen tip was capped with a hot melt adhesive, placed in a reduced pressure centrifuge, centrifuged at 1000 rpm for 5 minutes, and the pressure was reduced to 30 mmHg while maintaining 1200 rpm. After maintaining for 5 minutes in this state, the centrifugation was relaxed to 500 rpm, and the pressure was reduced to 10 mmHg and maintained for 5 minutes. The centrifugation was returned to 1200 rpm again while maintaining the pressure, and this was maintained for 5 minutes. Thereafter, the reduced pressure was returned to the atmospheric pressure, and then the centrifugation was stopped to obtain an aqueous ballpoint pen.
[0030]
Production Example 3
The ink of Hybrid K106 manufactured by Pentel Co., Ltd. was drained, and the ink of Ink Sample 3 was filled instead. This was centrifuged under reduced pressure in the same manner as in Production Example 1 of a ballpoint pen to obtain an aqueous ballpoint pen.
[0031]
Production Example 4
The ink of Engel (ball diameter 0.7 mm) manufactured by Pentel Co., Ltd. was drained, and the ink of Ink Sample 4 was filled instead. This was centrifuged under reduced pressure in the same manner as in Production Example 2 of a ballpoint pen to obtain an aqueous ballpoint pen.
[0032]
Comparative Production Example 1
An aqueous ballpoint pen was obtained in the same manner as in Ballpoint Pen Production Example 1, except that the ink of Comparative Example 1 was filled.
[0033]
Comparative Production Example 2
An aqueous ballpoint pen was obtained in the same manner as in Ballpoint Pen Production Example 2 except that the ink of Comparative Sample 2 was filled.
[0034]
Comparative Production Example 3
The ink of Comparative Sample 3 was placed in a polypropylene ink container having an inner diameter of 4 mm and a length of 85 mm in which a stainless steel chip having a 0.7 mm diameter carbide ball held at one end was attached via a chip holder. The ink was filled with 0.8 g, and the back end of the ink was filled with 0.2 g of a backflow preventing agent obtained by gelling polybutene with a gelling agent. The tip of this pen was capped with a hot-melt adhesive, placed in a vacuum centrifuge, and centrifuged at 1000 rpm for 15 minutes to obtain an aqueous ballpoint pen.
[0035]
Comparative Production Example 4
An aqueous ballpoint pen was obtained in the same manner as in Comparative Example 3 except that the ink of Comparative Sample 3 was filled with the ink of Ink Sample 3.
[0036]
【The invention's effect】
The water-based ballpoint pens obtained above were left in a constant temperature room at 50 ° C. for one month so that the tips of each of the 50 ballpoint pens are turned down, and then the pens were softened with a soft X-ray apparatus (SOFRON-405 manufactured by Soflon Corp.). Photographs were taken to check for air bubbles.
Separately, after leaving it in a constant temperature room at 50 ° C for 50 months so that the tips of the pens are facing upwards by 50 pens each time, write a circle with a diameter of about 2 cm continuously to write the handwriting. It was confirmed visually. Table 1 shows the results.
[0037]
[Table 1]

[0038]
As shown in Table 1, the aqueous ballpoint pen obtained by adding the reducing agent to the ink and centrifuging the ink under reduced pressure was good without generation of bubbles over time.

Claims (2)

An ink comprising at least a colorant, a water-soluble organic solvent, a reducing substance, and water, and a backflow preventive agent. A backflow preventive agent is located at the interface opposite to the ballpoint pen tip of the ink in a pipe having a ballpoint pen tip attached to one end. A method for producing an aqueous ball-point pen, comprising the steps of simultaneously placing the ball-point pen under reduced pressure and placing the ball-point pen tip outside and rotating it to apply a centrifugal force toward the ball-point pen tip. The method of claim 1 wherein the ink comprises a shear thinning material.