JP2013095846A - Oil-based ink for writing implement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide oil-based ink for writing implements relating to an oil-based ink composition, more specifically, capable of writing on a surface which does not absorb ink, such as a resin plate, a metal plate, an enameled porcelain plate, a glass plate, a baking finished plate and a film, and does not easily generate so-called a whitening phenomenon, in which handwriting is observed to be whity depending on a process of drying of the handwriting.SOLUTION: The oil-based ink for writing implements comprises at least a colorant, a solvent and a polyglycerol-modified silicone having a polyglycerol group and ≥8 HLB.

Description

  The present invention relates to an oil-based ink for writing instruments, and more specifically, can be written on an ink non-absorbing surface of a resin plate, a metal plate, an enamel plate, a glass plate, a baked coating plate, a film, etc., and a clear handwriting The oil-based ink for writing instruments

Conventionally, a marking pen using an oil-based ink for a writing instrument containing an organic solvent as a main solvent can be written on either an ink absorbing surface such as paper or cloth, or an ink non-absorbing surface such as plastic, glass or metal. These oil-based inks for writing instruments can be erased with light rubbing with a dry cloth etc. by adding a release agent etc. There are erasable inks for boards. In general, the marking pen uses a fiber core for the pen tip, but recently, a ball-point pen type with a ball-point pen tip attached to the pen tip is also known.
The handwriting of these oil-based inks for writing instruments usually has a uniform and flat surface, but it absorbs moisture in the air before the handwriting dries, and the dye and resin in the handwriting deposits in a mottle and is uniform. A whitening phenomenon that makes it impossible to form a paint film, or causes a small hole or crack that is not coated with ink on a part of the paint film surface of the handwriting to lose its concealment or diffusely reflect the handwriting. Has the problem. This phenomenon is particularly noticeable under high humidity conditions where water droplets are attached to the non-absorbing surface, and the whitening phenomenon of handwriting is not only the whitening of the handwriting but also the deterioration of the hue and remarkably reduced fixability. It has the disadvantage of impairing the function.
In order to prevent this whitening phenomenon, diglycerin monofatty acid ester (Patent Document 1) that absorbs moisture in the atmosphere by having hydrophilicity and decaglycerin fatty acid ester of HLB11-18 (Patent Document 2) are used. , Because glycerin in the molecule absorbs moisture in the air, water no longer exists as droplets, and a resin that is incompatible with the water in the ink precipitates, and the pigment dispersed with the resin aggregates It is known that the whitening of the handwriting due to the irregular reflection of the handwriting by causing the dye or resin to deposit on the mottle and causing cracks.
In addition, a resin that is soluble in an oil-based ink solvent but compatible with water is added to absorb moisture in the atmosphere. Polyvinyl butyral having an average polymerization degree of 600 to 1000 and an average polymerization degree 300-500 polyvinyl butyral (Patent Document 3), ethanol-soluble phenol resin having a softening point of 60-100 ° C or a derivative thereof, and ethanol-soluble ketone resin having a softening point of 60-100 ° C (Patent Document 4) However, these resins selectively absorb moisture in the atmosphere, so that water does not exist as droplets, the resin does not coagulate and shrink, and small holes that are not coated with ink are generated. In addition, it is known that the resin deposits on the mottle and causes cracks to prevent whitening of the handwriting due to irregular reflection of the handwriting.

Japanese Patent Laid-Open No. 08-157763 JP 05-148444 A JP 2000-160088 A Japanese Patent Laid-Open No. 05-017717

However, since the inks described in Patent Documents 1 and 2 have a small number of hydroxyl groups in the hydrophilic group and do not have a large number of hydrophilic groups in the molecule, they can only take in water in the atmosphere. When writing under high humidity where water droplets are attached to the non-absorbing surface, water droplets on the coated surface at the time of writing cannot be taken in, and water will exist as droplets on the coated surface after writing, The effect of preventing whitening of the handwriting due to irregular reflection of the handwriting due to aggregation of pigments or resin in the ink or precipitation of the dye or resin on the mottle causes cracking.
In addition, since the resin used in the inks described in Patent Documents 3 and 4 is slightly compatible with water, when writing under high humidity where water droplets adhere to the non-absorbing surface, Water droplets on the coated surface at the time could not be taken in, and water was present as droplets on the coated surface after writing, resulting in small holes where ink was not applied due to the aggregation shrinkage of the resin, or the resin deposited in mottle The effect of preventing whitening of the handwriting due to irregular reflection of the handwriting due to cracking is not sufficient.

  The gist of the present invention is an oil-based ink for writing instruments comprising a colorant, a solvent, and a polyglycerol-modified silicone having a polyglycerol group-containing HLB of 8 or more.

Polyglycerol-modified silicones with polyglycerol groups and HLB of 8 or more have high hydrophilicity despite a low modification rate, and the siloxane bond, which is the main skeleton, has an interatomic distance and bond compared to the carbon skeleton molecules. The corner is large and the whole molecule has a spiral structure.
Even under conditions of high humidity and water droplets on the non-absorbing surface, after the polyglycerol groups in the oil-based ink for writing instruments take in moisture, many hydroxyl groups in the polyglycerol groups finely disperse the water to the molecular level. Since water does not exist as droplets on the ink application surface on the absorption surface, it suppresses the precipitation of dyes and resins that do not dissolve in the water in the ink, and there are small holes that are not coated with ink due to cohesive shrinkage of the resin. It is possible to prevent the whitening phenomenon of the handwriting due to the occurrence of the occurrence or the resin depositing on the mottle and causing cracks to cause irregular reflection of the handwriting. In the course of drying the ink-coated surface on the non-absorbing surface, the solvent in the ink and the water molecules taken up by the hydroxyl groups are volatilized. It is excellent in properties, water molecules are also easily volatilized, and handwriting whitening phenomenon can be prevented in the course of drying the ink coated surface.

The invention is described in detail below.
As the colorant used in the present invention, dyes and / or pigments conventionally used in oil-based inks for writing instruments can be used. The dye used as the colorant may be soluble in a solvent, and examples thereof include nigrosine dyes, oil-soluble dyes, salt-forming oil-soluble dyes, metal-containing complex dyes, acid dyes, and direct dyes. For example, Solvent Yellow 2, 6, 14, 15, 16, 19, 21, 21, 33, 56, 61, 62, 79, 80, 82, 83: 1, 151, Solvent Orange 1, 2, 5, 6, 14, 37, 40, 41, 44, 45, 62, Solvent Red 1, 3, 8, 8, 23, 24, 25, 27, 30, 30, 49, 81, 82, 83, 84, 89, 91, 100, 109, 121, 122, 127, 132 218, Disperseed 9, Solvent Violet 8, 13, 14, 21, 21, 21: 1, 27, Disperse Violet 1, Solvent Blue 2, 4, 5, 11, 11, 12 25, 35, 36, 38, 44, 45, 5, 67, 70, 73, Solvent Green 3, Solvent Brown 3, 5, 20, 20, 28, Solvent Black 3, 5, 7, 22, 22, 22: 1 23, 27, 29, 34, 43, 123, Basic Blue 7, Japanol Fast Black D Conch (CI Direct Black 17), Water Black 100L (CI Direct Black 19), Water Black L-200 (CI Direct Black 19), Direct Fast Black B (CI Direct Black 22), Direct Fast Black AB (CI Direct Black 32), Direct Deep Black EX (C.I. I. Direct Black 38), Direct Fast Black Conch (C.I.D. Recto Black 51), Caillas Spragley VGN (CI Direct Black 71), Caillas Direct Brilliant Yellow G (CI Direct Yellow 4), Direct Fast Yellow 5GL (CI Direct Yellow 26), Eisen Primula Yellow GCLH (CI Direct Yellow 44), Direct Fast Yellow R (CI Direct Yellow 50), Eisen Direct Fast Red FH (CI Direct Red 1), Nippon Fast Scarlet GSX (C.I. I. Direct Red 4), Direct Fast Scarlet 4BS (C.I. Direct Red 23), Eisen Direct Rhodulin BH (C.I. Direct Red 31), Direct Scarlet B (C.I. Direct Red 3) 7) Kayak Direct Scarlet 3B (C.I. I. Direct Red 39), Eisen Primula Pink 2BLH (CI Direct Red 75), Sumilite Red F3B (CI Direct Red 80), Eisen Primula Red 4BH (CI Direct Red 81), Kayala Supra Rubin BL (C.I. Direct Red 83), Cayalas Light Red F5G (C.I. Direct Red 225), Cayalas Light Red F5B (C.I. Direct Red 226), Cayalas Light Rose FR (C.I. I. Direct Red 227), Direct Sky Blue 6B (C.I. Direct Blue 1), Direct Sky Blue 5B (C.I. Direct Blue 15), Sumilite Spula Blue BRR Conch (C.I. Direct Blue 71) , Dibogen Turquoise Blue S ( I. Direct Blue 86), Water Blue # 3 (C.I. Direct Blue 86), Kayara Star Coyze Blue GL (C.I. Direct Blue 86), Kayala Splash Blue FF2GL (C.I. Direct Blue 106) ), Caillas Splatter Turquoise Blue FBL (CI Direct Blue 199), Acid Blue Black 10B (CI Acid Black 1), Nigrosine (CI Acid Black 2), Suminol Milling Black 8BX (C CI Acid Black 24), Cyanol Milling Black VLG (CI Acid Black 26), Suminol Fast Black BR Conch (CI Acid Black 31), Mitsui Nylon Black GL (CI Acid Black) 52), Eisen Opal Rack WH Extra Conc (CI Acid Black 52), Sumilan Black WA (CI Acid Black 52), Ranil Black BG Extra Conc (CI Acid Black 107), Kayanol Milling Black TLB (C CI Acid Black 109), Suminol Milling Black B (CI Acid Black 109), Kayanol Milling Black TLR (CI Acid Black 110), Eisen Opal Black New Conch (CI Acid Black) 119), Water Black 187-L (CI Acid Black 154), Kayaku Acid Brilliant Flavin FF (CI Acid Yellow 7: 1), Kayasil Yellow GG (CI Acid Yellow 17), Xylene Light Yellow 2G 140% (C.I. I. Acid Yellow 17), Suminol Leveling Yellow NR (CI Acid Yellow 19), Daiwa Tarrazine (CI Acid Yellow 23), Kyakutor Trazin (CI Acid Yellow 23), Suminol Fast Yellow R (CI Acid Yellow 25), Diacid Light Yellow 2GP (CI Acid Yellow 29), Suminol Milling Yellow O (CI Acid Yellow 38), Suminol Milling Yellow MR (C.I. CI Acid Yellow 42), Water Yellow # 6 (CI Acid Yellow 42), Kayanol Yellow NFG (CI Acid Yellow 49), Suminol Milling Yellow 3G (CI Acid Yellow 72), Suminols Fast Yellow G (CI Acid Yellow 61), Suminols Millingue -G (C.I. Acid Yellow 78), Cyanol Yellow N5G (C.I. Acid Yellow 110), Suminoll Milling Yellow 4G 200% (C.I. Acid Yellow 141), Cyanol Yellow NG (C.I. Acid Yellow 135), Cyanol Milling Yellow 5 GW (CI Acid Yellow 127), Cyanol Milling Yellow 6 GW (CI Acid Yellow 142), Sumitomo Fast Scarlet A (CI Acid Red 8), Kayak Silk Scarlet (CI Acid Red 9), Solar Rubin Extra (CI Acid Red 14), Daiwa New Coxin (CI Acid Red 18), Eisenbonso RH (CI Acid Red) Red 26), Daiwa Red No. 2 (CI Acid Red 27), Minol Leveling Brilliant Red S3B (CI Acid Red 35), Kayasil Rubinol 3GS (CI Acid Red 37), Eisen Erythrosine (CI Acid Red 51), Kayaku Acid Rhodamine FB (CI) Acid Red 52), Suminol Leveling Lubinol 3GP (C.I. Acid Red 57), Diacid Alizarin Rubinol F3G 200% (C.I. Acid Red 82), Eisen Eosin GH (C.I. Acid Red 87) ), Water Pink # 2 (CI Acid Red 92), Eisen Acid Phloxin PB (CI Acid Red 92), Rose Bengal (CI Acid Red 94), Kayanol Milling Scarlet FGW (C.I.). I. Acid Red 111 ), Kayanol Milling Rubin 3BW (C.I.) I. Acid Red 129), Suminoall Milling Brilliant Red 3BN Conch (CI Acid Red 131), Suminol Milling Brilliant Red BS (CI Acid Red 138), Eisen Opal Pink BH (CI Acid Red 186) ), Suminol Milling Brilliant Red B Conch (C.I. Acid Red 249), Kayaku Acid Brilliant Red 3BL (C.I. Acid Red 254), Kayaku Acid Brilliant Red Br. Red (C.I. Acid Red 265) Cyanol Milling Red GW (CI Acid Red 276), Mitsui Acid Violet 6BN (CI Acid Violet 15), Mitsui Acid Violet BN (CI Acid Violet 17) Sumitomo Patent Pure Blue VX (CI Acid Blue 1), Water Blue # 106 (CI Acid Blue 1), Patent Blue AF (CI Acid Blue 7), Water Blue # 9 (C.I. I. Acid Blue 9), Daiwa Blue No. 1 (C.I. Acid Blue 9), Supranol Blue B (C.I. Acid Blue 15), Orient Soluble Blue OBC (C.I. Acid Blue 22), Suminol Leveling Blue 4GL (C.I. Acid Blue 23), Mitsui Nylon Fast Blue G (C.I. Acid Blue 25), Kayasil Blue AGG (C.I. Acid Blue 40), Kayasil Blue BR (C.I. Acid) Blue 41), Mitsui Alizarin Saphirol SE (CI Acid Blue 43) Suminol Leveling Sky Blue R Extra Conk (CI Acid Blue 62), Mitsui Nylon Fast Sky Blue B (CI Acid Blue 78), Sumitomo Brilliant Indocyanine 6Bh / c (CI Acid Blue 83) Sandrancyanine N-6B 350% (CI Acid Blue 90), Water Blue # 115 (CI Acid Blue 90), Orient Soluble Blue OBB (CI Acid Blue 93), Sumitomo Brilliant Blue 5G (C.I. Acid Blue 103), Cyanol Milling Ultra Sky SE (C.I. Acid Blue 112), Cyanol Milling Cyanine 5R (C.I. Acid Blue 113), Eisen Opal Blue 2GLH (C.I. Acid Blue 15 8) Daiwa Guinea Green B (C.I. I. Acid Green 3), Acid Brilliant Milling Green B (CI Acid Green 9), Daiwa Green # 70 (CI Acid Green 16), Cyanol Cyanine Green G (CI Acid Green 25), Sumi Nord Milling Green G (CI Acid Green 27), Maxilon Blue GRL (CI Acid Green 41), Eisen Cathillon Blue BRLH (CI Acid Green 54), Eisen Diamond Green GH (C.I. I. Basic Green 1), Eisen Malachite Green (CI Basic Green 4), Bismarck Brown G (CI Basic Brown 1), and the like can be used.
Examples of the pigment used as the coloring material include conventionally known carbon blacks such as Pigment Black 6 and 7 and the like, Pigment Blue 27 and 9, Pigment Violet 15 and Pigment Red 259 and other metal complex salt pigments, Pigment White 6 and Pigment Yellow. 42, metal oxide pigments such as Pigment Black 11 and Pigment Red 101, composite oxide pigments such as Pigment Yellow 53 and Pigment Brown 24, Pigment White 21, 22, 27, 28, 19, 19 24, body pigments such as kaolin clay, calcined clay, talc, bentonite, mica, muscovite, phlogopite, nepheline cinnite, metal powder pigments such as aluminum paste, aluminum flake powder, bronze powder, pigment white 1, 14 ,titanium dioxide Inorganic pigments such as pearlescent pigments such as coated mica, Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 82, 83, 84, 90, 90 : 1, 1, 151, 169, 172, 173, 174, 191, Pigment Orange 39, Pigment Yellow 18, 100, 104, 115, 117, Pigment Blue 1, 1: 2. 2, 3, 3, 8, 10, 11, 12, 14, 53, 62, 63, Pigment Violet 1, 2, 2: 2, 3, and 3 : 1, 3: 3, 4, 4, 5, 5: 1, 6: 1, 7: 1, 9, 12, 12, 20, 26, 27, 39, Pigment Green 1 2, 2, 3, 4, 8, 9, 10, 12, 45, Pigment Brown 3, etc. Lake pigment, Pigment Red 1, 3, 21, 112, 114, 146, 170, 187, 150, 185, 38, 41, Pigment Orange 5, 38, 36 , 16, 13, 34, Pigment Yellow 1, 3, 97, 167, 154, 12, 13, 14, 17, 55, 83, 81, 10, Insoluble azo pigments such as CI Pigment Brown 25, condensed azo pigments such as CI Pigment Red 144 and 166, Pigment Red 53, 53: 1, 53: 3, 50, 50: 1, 49, 49: 1 49: 2, 49: 3, 57: 1, 48: 1, 48: 2, 48: 3, 48: 4, 52: 1, 63: 1, 63: 2. 58: 2, 58: 4, 51, 60: 1, 64: 1, Azo lake pigments such as Pigment Orange 17, 18 and 19, Pigment Yellow 61 and 62, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15 : 5, 15: 6, 16, 17: 1, Pigment Green 7, 36, 37, etc. Phthalocyanine pigments, Pigment Red 122, 202, 206, 207, 209, Pigment Orange 48 Pigment Violet 19 and other quinacridone pigments, Pigment Red 168 and 177, Pigment Orange 51, Pigment Yellow 24 and 108, Pigment Blue 60 and other anthraquinone pigments, Pigment Red 123, 149, 178 and 179, 190, 224, Pigment Violet 29, Pigment Black 31, perylene pigments such as 32, perinone pigments such as pigment red 194 and pigment orange 43, indigo pigments such as pigment red 88 and 181, pigment brown 27, pigment blue 66 and 63, pigment violet 23, Dioxazine pigments such as 37, Quinophthalone pigments such as Pigment Yellow 138, Isoindolinone pigments such as Pigment Orange 61, Pigment Yellow 109, 110 and 173, Pigment Red 260, Pigment Orange 66 and 69, Pigment Isoindoline pigments such as yellow 139 and 185, azo metal complex pigments such as pigment yellow 150, pigment green 8 and pigment green 10, pigment red 257, pigment orange 68 and pigment Azomethine metal complex pigments such as Pigment Yellow 129, 153 and 65, diketopyrrolopyrrole pigments such as Pigment Red 254, 255, 264, 270 and 272, Pigment Orange 71 and 73, Pigment Blue 18 19、56、57、61、56: 1、61: 1 etc. Alkali Blue Pigment 、 Pigment Black 1 etc. Aniline Black 、 Basic Yellow 40 、 Basic Red 1 、 Basic Violet 10 、 Acid Yellow 7, Fluorescent dyes such as Acid Red 92, Acid Blue 9, Disperse Yellow 121, Disperse Blue 7, Direct Yellow 85, Fluorescent Brighting Whitex WS52, Solvent Yellow 44, Solvent Blue 5 and the like in a solid solution in a synthetic resin Among organic pigments such as pigments, one or two or more that can be stably dispersed as fine particles in oil-based ink for writing instruments can be selected and used.
The above colorants can be used alone or in combination, and the amount used is preferably 1 to 30% by weight based on the total amount of ink. If it is less than 1% by weight, the concentration is too low to make it difficult to confirm the handwriting.

The solvent used in the present invention can be used without limitation as long as it is a solvent that can be used in conventional oil-based inks for writing instruments, but known methyl alcohol, ethyl alcohol, normal-propyl alcohol, isopropyl alcohol, normal-butyl alcohol, isobutyl alcohol, Among lower alcohols having 4 or less carbon atoms such as secondary butyl alcohol and tertiary butyl alcohol, it is preferable to use one or a mixture of two or more. The amount used is determined in various mixing ratios in consideration of miscibility with other components used, but is preferably 30 to 90% by weight based on the total amount of ink.
Also, aromatic hydrocarbons such as xylene and toluene, lower aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, lower alcohol esters of lower fatty acids such as ethyl acetate and butyl acetate, and aliphatic hydrocarbons such as hexane and heptane Organic solvents such as cycloaliphatic hydrocarbons such as cyclohexane and ethylcyclohexane, glycol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and esters thereof, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mononormal butyl ether, propylene glycol mononormal propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Glycol ether solvents such as monoethyl ether, dipropylene glycol mononormal propyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, ethylene Glycol solvents such as recall, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, glycerin, polyethylene glycol, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, acetic acid isobutyl, acetic acid-n- Ester solvents such as amyl, 2-ethylhexyl acetate, isobutyl isobutyrate, ethyl lactate, n-butyl lactate, alcohols and their ethylene oxide and / or propylene oxide addition derivatives, β-phenylethyl alcohol, α-methyl Alcohol solvents such as benzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, isotridecyl alcohol, ethylene glycol monophenyl ether, propylene glycol The glycol ether solvents or the like having an aromatic ring such as monophenyl ether and ethylene oxide and / or propylene oxide adduct derivative alone or a mixture of a plurality of to be used.

For the purpose of imparting water resistance on the non-absorbing surface, film formation, adhesion to the writing surface, and adjusting the viscosity of the ink, natural resins and synthetic resins can be used. Specifically, rosin, rosin ester, Rosin-modified glycerol ester, rosin-modified maleic resin, rosin-modified phenol resin, rosin-based resin such as rosin-modified phenol glycerol ester, cellulose resin such as ethyl cellulose and acetyl cellulose, petroleum resin, ketone-based resin, polyvinyl butyral, vinyl chloride Water-soluble synthetic polymers such as vinyl acetate copolymer, vinylidene chloride-vinyl chloride copolymer, shellac, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, guar gum, locust bean gum and their derivatives Such as Child polysaccharides, xanthan gum, welan gum and microbial polysaccharides such as derivatives thereof, carrageenan, alginic acid and seaweed polysaccharides such as their derivatives, tragacanth and the like of the resin polysaccharides, and cellulose resins and the like. Specifically, as the phenol resin, Tamanol 100S, 510 (above, manufactured by Arakawa Chemical Co., Ltd.), Hitanol 1501, 2501 (above, manufactured by Hitachi Chemical Co., Ltd.), YP-90, YP-90L YS Polystar S145, # 2100, # 2115, # 2130, T80, T100, T115, T130, T145, Mighty Ace G125, 150 (above, Yashara Chemical Co., Ltd.), etc. As the ketone resin, ketone resin K-90 (Arakawa Chemical Industries, Ltd.), Halon 80, 110H (above, Honshu Chemical Co., Ltd.), Synthetic Resin AP, SK, 1201 (above, Huls) Germany)) as rosin resins, Hercolin D, Pentaline 255, 261 (above, manufactured by Rika Hercules Co., Ltd.), Remac T80, Harrier Star NL, Neotol C, Gum Rosin X (above, manufactured by Harima Chemical Co., Ltd.), Gum Rosin WW (produced in China), Ester Gum H (produced by Arakawa Chemical Industries, Ltd.), etc. Butyral # 2000-L, # 3000-1, # 3000-2, # 3000-4, # 3000-K (manufactured by Denki Kagaku Kogyo Co., Ltd.), ESREC BL-1, 4BL-3 , BL-S, BX-10 (above, manufactured by Sekisui Chemical Co., Ltd.), etc. as shellac, shellac NSC, shellac CS, shellac B. D. S. (Nippon Shellac Kogyo Co., Ltd.), shellac GBN-D, shellac PEARL-N811, shellac GBN-DF (above, Gifu Shellac Manufacturing Co., Ltd.) and the like.
These can be used alone or in combination, and the amount used is preferably 1 to 20% by weight based on the total amount of the oil-based ink for writing instruments. If it is less than 1% by weight, the fixability of the handwriting on the non-absorbing surface is insufficient, and if it exceeds 20% by weight, the viscosity of the ink becomes high and the ink ejection from the writing instrument pen tip becomes poor.

The polyglycerol-modified silicone having a polyglycerol group and having an HLB of 8 or more used in the present invention allows water to be dispersed finely to a molecular level by many hydroxyl groups in the polyglycerol group after water is taken into the ink. It is used as an anti-whitening agent for handwriting without water present as a liquid medium. Among them, polyglycerol-modified silicones with polyglycerol groups at both ends have a linear polysiloxane moiety because the siloxane bond, which is the main skeleton, has a larger interatomic distance and bond angle than the carbon skeleton molecules, and is highly hydrophobic and oleophobic. Floats on the ink-atmosphere interface side, so that the ink itself after writing is difficult to absorb moisture during the handwriting drying process, and after the handwriting is dried, a large chain silicone part floats on the surface of the handwriting, and the water resistance and fixing of the handwriting It is preferable because it has excellent properties. In order to improve the clarity and fixability of the handwriting, it is preferable to use a linear polyglycerol-modified silicone in which both terminal groups are polyglycerol groups.
Examples of the polyglycerol-modified silicone having an HLB of 8 or more include bis (PG-3-oxyphenylpropyl) dimethicone, (PG-3-oxyphenylpropyl) dimethicone, and Kao Corp. Sofcare GS-G. Is preferably 0.5 to 20% by weight based on the total amount of oil-based ink. If the amount is less than 0.5% by weight, the effect of preventing whitening of the handwriting is insufficient, and if it exceeds 20% by weight, the viscosity of the ink increases and the ink ejection from the writing instrument nib becomes worse.

  In addition, if necessary, as a wetting agent, glycols, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, etc., as a viscosity modifier, celluloses such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, etc. Various additives can be appropriately selected and used.

Furthermore, additives such as a nonionic surfactant, an anionic surfactant, a rust preventive, a handwriting smudge-preventing agent, a handwriting smoothness-imparting material, and water may be used as necessary. Moreover, when using as ink for writing boards, handwriting erasers, such as fatty acid ester and a liquid paraffin, may be used.
Even if these additives are present in the ink, the HLB having a polyglycerol group does not adversely affect the hand whitening-preventing action of polyglycerol-modified silicone having 8 or more.

  In producing the oil-based ink for writing instruments of the present invention, various conventionally known methods can be employed. For example, it can be easily obtained by blending the above components and mixing and dispersing them with a high-speed stirrer such as a homomixer or lab mixer, or a dispersing machine such as a ball mill, sand mill or bead mill.

  Hereinafter, the present invention will be described in detail with reference to examples.

Example 1
Fuji AS Black 810 (processed pigment coated with black pigment with polyvinyl butyral, manufactured by Fuji Dye Co., Ltd.) 8.0 parts by weight ethanol 50.0 parts by weight isopropyl alcohol 32.0 parts by weight carbinol-modified silicone oil (anti-bleeding agent) ) 1.0 part by weight Mighty Ace G125 (fixing resin, manufactured by Yasuhara Chemical Co., Ltd.) 7.0 parts by weight (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB8.0) 2.0 parts by weight The components were mixed by stirring and dissolved to obtain a black oil-based ink for writing instruments.

Example 2
Balifast Black 3806 (dye, manufactured by Orient Co., Ltd.) 16.0 parts by weight ethanol 40.0 parts by weight propylene glycol monomethyl ether 20.9 parts by weight benzyl alcohol 10.0 parts by weight Harimac T80 (fixing resin, Harima Kasei Co., Ltd.) 9.0 parts by weight Bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0) 0.1 parts by weight Isopropyl sebacate (dibasic acid ester) 4.0 parts by weight Were mixed by stirring and dissolved to obtain a black oil-based ink for a writing instrument.

Example 3
Varifast Black 3806 (Dye, manufactured by Orient Co., Ltd.) 12.0 parts by weight Ethanol 31.0 parts by weight Propylene glycol monomethyl ether 5.0 parts by weight 3-methoxy-3-methyl-1-butanol 15.0 parts by weight Harimac T80 (fixing resin, manufactured by Harima Chemicals Co., Ltd.) 14.0 parts by weight Bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0) 20.0 parts by weight isopropyl adipate (dibasic acid) Ester) 3.0 parts by weight The above components were mixed by stirring and dissolved to obtain a black oil-based ink for a writing instrument.

Example 4
Varifast Black 3806 (dye, manufactured by Orient Co., Ltd.) 12.0 parts by weight ethanol 41.5 parts by weight propylene glycol monomethyl ether 20.0 parts by weight benzyl alcohol 5.0 parts by weight Harimac T80 (fixing resin, Harima Kasei Co., Ltd.) 16.0 parts by weight DK ester F90 (sucrose fatty acid ester, HLB9.5, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
1.0 parts by weight Isopropyl sebacate (dibasic acid ester) 3.0 parts by weight Bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0) 1.5 parts by weight The mixture was dissolved to obtain a black oil-based ink for a writing instrument.

Comparative Example 1
An oily ink for writing instruments was obtained in the same manner as in Example 4 except that ethanol was added instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0).

Comparative Example 2
In the same manner as in Example 4, except that diglycerin monolaurate (HLB9.4) was added instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0) An oil-based ink was obtained.

Comparative Example 3
In Example 4, the same procedure was followed except that diaminopropyltetramethyldisiloxane (amino-modified silicone) was added instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0). An oil-based ink for writing instruments was obtained.

Comparative Example 4
In Example 4, the same procedure was followed except that polyethylene glycol-3 dimethicone (polyether-modified silicone) was added instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0). An oil-based ink for writing instruments was obtained.

Comparative Example 5
In Example 4, polyglyceryl-3 polydimethylsiloxyethyl dimethicone (polyglycerin-modified silicone, HLB4.5) was added instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0). Except that, oil-based ink for writing instruments was obtained in the same manner.

Comparative Example 6
In Example 4, polyglyceryl-3 disiloxane dimethicone (polyglycerin-modified silicone, HLB 7.0) was added instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB 12.0). In the same manner, oil-based ink for writing instruments was obtained.

Comparative Example 7
In Example 4, lauryl polyglycerin-3 polydimethylsiloxyethyl dimethicone (polyglycerol-modified silicone, HLB4.0) was used instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0). An oily ink for writing instruments was obtained in the same manner except that it was added.

Comparative Example 8
In Example 4, an oil-based ink for writing instruments was obtained in the same manner except that decagyl distearate was added instead of bis (PG-3-oxyphenylpropyl) dimethicone (polyglycerol-modified silicone, HLB12.0). It was.

Comparative Example 9
Varifast Black 3806 (Dye, manufactured by Orient) 12.0 parts by weight Ethanol 31.0 parts by weight Propylene glycol monomethyl ether 20.0 parts by weight 3-methoxy-3-methyl-1-butanol 15.0 parts by weight Harimac T80 (fixing resin, manufactured by Harima Chemicals Co., Ltd.) 14.0 parts by weight ESRECK BL-1 (polyvinyl butyral, average polymerization about 300,
Sekisui Chemical Co., Ltd.) 1.0 part by weight Denkabutyral # 3000-2 (polyvinyl butyral, average polymerization degree of about 700,
4.0 parts by weight Isopropyl adipate (dibasic acid ester) 3.0 parts by weight The above components were mixed by stirring and dissolved to obtain a black oil-based ink for a writing instrument.

Comparative Example 10
In Comparative Example 9, instead of Denkabutyral # 3000-2 (polyvinyl butyral, average polymerization degree of about 700, manufactured by Denki Kagaku Kogyo Co., Ltd.), Hitanol 2501 (phenol resin, softening point 75-90 ° C., Hitachi Chemical Co., Ltd.) The oil-based ink for writing instruments was obtained in the same manner except that (Made) was added.

The above-mentioned oil-based inks for writing instruments obtained in Examples 1 to 4 and Comparative Examples 1 to 10 were prepared by using a fiber core pen tip and a cotton pad (Pentel Pen <Green Label> NN50 <Round Core>, Pentel Co., Ltd.) A member other than the ink used in the production) was filled to obtain a writing instrument for testing oil-based ink for writing instruments. Using this test writing instrument, the degree of whitening phenomenon of the handwriting on the non-absorbing surface and the handwriting fixability were evaluated.

Degree of whitening phenomenon of handwriting The writing board (FB-115Wc, enamel board surface, manufactured by KOKUYO Co., Ltd.) is left for 10 minutes under the conditions of 25 ° C. and 80% humidity. After visually confirming that there is a 10 mm x 60 mm rectangular writing surface by shifting each time a 10 mm straight line is written using the above test writing instrument, let it stand for 10 minutes or longer on the spot. A sample was used.
The brightness of the writing surface of the test sample was measured with a color computer (NF777, manufactured by Nippon Denshoku Industries Co., Ltd.). The degree of whitening phenomenon of the handwriting was confirmed by this comparison as an index that the handwriting looks whiter as the lightness is higher.

Handwriting fixability test on non-absorbing surface A polypropylene (PP) OHP sheet [thin mouth] (manufactured by Ricoh Educational Equipment Co., Ltd.) is allowed to stand for 10 minutes under conditions of 25 ° C. and humidity of 80%. After visually confirming that water droplets are attached, write a 10 mm x 60 mm rectangular writing surface by shifting each time a 10 mm straight line is written using the above-mentioned test writing tool. The test sample was left for more than a minute.
Next, the test sample is placed in an environment of 25 ° C. and 30% humidity, and a high quality paper is stacked on it, a weight (50 mm in diameter on the bottom surface, 500 g in mass) is placed on it, and the high quality paper is moved back and forth 10 times left and right. Was scraped with fine paper. The area of the applied 10 mm × 60 mm rectangle was taken as 100%, the area of the handwriting remaining in the 10 mm × 60 mm rectangle after the test was measured, and the ratio was calculated.

The inks of Examples 1 to 4 were obtained by adding water absorbed in the course of drying the handwriting even under high humidity to a molecular level by adding polyglycerol-modified silicone having an HLB having a polyglycerol group of 8 or more. Water does not exist as droplets, the resin in the ink agglomerates, the dye or resin deposits on the mottle and causes cracks, and the handwriting appears to be whitish due to the irregular reflection of the handwriting. The whitening phenomenon can be prevented, and a good fixability when writing on the non-absorbing surface was obtained.
Among them, in the inks of Examples 2 to 4, since the side chain of the linear polyglycerol-modified silicone composed of a polyglycerol group is not polyglycerol-modified, the surface of the handwriting can be more hydrophilic and oleophilic. The fixing property on the non-absorbing surface was better than that of Example 1.
In particular, in the ink of Example 4, since a linear polyglycerol-modified silicone having both terminal groups composed of polyglycerol groups was used in a preferable addition amount, better results could be obtained.

  On the other hand, Comparative Examples 1 to 10 do not contain polyglycerol-modified silicone having an HLB having a polyglycerol group of 8 or more. Because there is a small hole where ink is not applied in the handwriting on the non-absorbing surface, the resin in the ink may agglomerate or the dye or resin may deposit on the mottle and cause cracks. As a result, a whitening phenomenon that causes the handwriting to appear whitish due to irregular reflection of the handwriting occurs, and the fixability when writing on the non-absorbing surface is lost.

Claims (1)

An oil-based ink for a writing instrument comprising a colorant, a solvent, and a polyglycerol-modified silicone having a polyglycerol group-containing HLB of 8 or more.