JP2012012592A - Oil-based ink composition for ballpoint pen - Google Patents

Abstract

An oil-based ink composition for ballpoint pens having good handwriting performance without being affected by moisture absorption during writing after long-term storage, particularly writing after long-term storage under high temperature and high humidity.
An oil-based ink composition for ballpoint pens comprising at least a compound represented by the following general formula, an alkanediol having 4 to 7 carbon atoms, a resin, and a pigment. _{H 2 R 1 C (R 2} CH) nCR 3 H 2 ( expression). R ₁ and R ₃ represent H or — (OCH ₂ CH (CH ₃ )) m—OH. R ₂ represents — (OCH ₂ CH (CH ₃ )) m—OH. n and m represent an integer of 1 or more. Three or more carbons in the main chain to which — (OCH ₂ CH (CH ₃ )) m—OH is bonded are continuously arranged.
[Selection figure] None

Description

  The present invention relates to an oil-based ink composition for a ballpoint pen that is suitably used for a ballpoint pen using a so-called ballpoint pen tip in which a ball is partially held from the tip of a ball holder and held as a writing member.

  Conventionally, oil-based ink compositions for ballpoint pens include coloring materials such as dyes and pigments that are insoluble in water, organic solvents such as glycol ethers such as ethylene glycol monophenyl ether and aromatic alcohols such as benzyl alcohol, and the like. It consists at least of a resin whose main purpose is to prevent ink stickiness, pigment dispersion, ink viscosity adjustment, ink flow characteristic adjustment, and handwriting blur.

  The organic solvent used in such an oil-based ink composition for ballpoint pens has low water solubility and is difficult to absorb moisture, but absorbs moisture when in contact with the atmosphere for a long time. Oil-based inks for ballpoint pens using these organic solvents have a reduced ability to dissolve water-insoluble dyes and resins due to moisture absorption during long-term storage, especially long-term storage at high temperatures and high humidity. Solid particles such as pigments that are deposited or dispersed may agglomerate. When precipitation or aggregation occurs, ink leakage may occur due to low viscosity of the ink, or clogging of the ink flow path due to precipitation or aggregation or high viscosity of the ink may prevent the ball pen tip ball from rotating, As a result, writing is impossible or handwriting is blurred.

  Various researches have been made for a long time to prevent the precipitation of dyes and resins in the ink composition and the aggregation of pigments due to moisture absorption during long-term storage. A method of making a film of a polymer compound insoluble in water on the surface of the ink to suppress moisture absorption of the ink (Patent Document 1), improving the dissolution stability of the dispersion resin using benzyl alcohol, and a pigment having a sulfone group A method for stabilizing the dispersion of the pigment even after long-term storage by using a derivative (Patent Document 2), and a method for stabilizing the dispersion of the dispersant adsorbed on the pigment by using a specific surfactant (Patent Document 3). , A method of improving the solubility of the dispersion resin and the adsorption of the dispersion resin to the pigment by using a specific organic solvent such as diethylene glycol monophenyl ether or diethylene glycol monobenzyl ether, and stabilizing the dispersion of the pigment even after long-term storage (Patent Document 4) is known.

Japanese Patent Laying-Open No. 2005-213413 JP 2000-212696 A JP 2002-060669 A Japanese Patent Laid-Open No. 2002-275406

  These methods are a method of preventing moisture aggregation and pigment aggregation and resin precipitation due to moisture absorption by combining organic solvents with low water solubility and difficulty in absorbing moisture, and methods of protecting pigments and resins from moisture. is there. However, organic solvents with low water solubility tend to greatly affect the balance of the dissolution / dispersion system even with a small amount of moisture absorption, and are insufficient to prevent dye and resin precipitation and pigment aggregation.

In contrast, water-based inks do not cause dye or resin precipitation or pigment aggregation due to moisture absorption, and oil-based inks also use dyes or resins due to moisture absorption by using organic solvents with high water solubility. It is conceivable to prevent precipitation of pigment and aggregation of pigment.
When an organic solvent having high water solubility is used in the oil-based ink, dye or resin precipitation and pigment aggregation do not occur with a small amount of moisture absorption, compared to the case of using an organic solvent having low water solubility.
However, in long-term storage, particularly in long-term storage under high temperature and high humidity, the amount of moisture absorption increases, and eventually, precipitation of dyes and resins that do not dissolve in water and aggregation of pigments cannot be prevented.

  An object of the present invention is to provide an oil-based ink composition for ball-point pens having good handwriting performance without being affected by moisture absorption during writing after long-term storage, particularly after long-term storage under high temperature and high humidity. And

  That is, the first gist of the present invention is an oil-based ink composition for ballpoint pens comprising at least a compound represented by the following general formula (Formula 1), an alkanediol having 4 to 7 carbon atoms, a resin, and a pigment. The oil-based ink composition for ballpoint pens wherein the alkanediol having 4 to 7 carbon atoms is hexylene glycol is a second gist, and the compound represented by the general formula (Formula 1) is polyoxypropylene glyceryl. A third gist is an oil-based ink composition for ballpoint pens that is ether.

The reason why the oil-based ink composition for ballpoint pens of the present invention can prevent the ink from flocculating and settling and losing fluidity after being stored for a long time at high temperature and high humidity is presumed as follows.
The —OH group and the hydrophobic group in the molecular structure of the alkanediol having 4 to 7 carbon atoms used in the present invention are in contact with a functional group such as a hydrophilic group or a hydrophobic group present on the pigment surface, and electrostatic interaction / hydrophobicity. It is a solvent that is suitable for interaction, has good wettability with the pigment, and has excellent dispersion stability performance of the pigment.
Further, the alkanediol having 4 to 7 carbon atoms has a feature of high compatibility with water, and when the water is absorbed in the ink, the -OH group of the alkanediol having 4 to 7 carbon atoms. Directs water to hydrogen bond with water. When the —OH group of the alkanediol having 4 to 7 carbon atoms is hydrogen-bonded toward water, a hydrophobic group is collected in the opposite direction to the —OH group of the alkanediol having 4 to 7 carbon atoms. As a result, the hydrophobic group portion of the alkanediol in which any two hydrogen atoms of the aliphatic hydrocarbon having 4 to 7 carbon atoms bonded to water are substituted with a hydroxyl group exhibits strong hydrophobicity.
The compound represented by the above general formula (Formula 1) used in the present invention has a branched structure in which propylene oxide is added to glycerin. The polyoxypropylene chain possessed by the compound represented by the above general formula (Chemical Formula 1) is a hydrophilic and helical polyoxyethylene structure in which methyl groups are oriented outward, and is very hydrophobic. . Therefore, the polyoxypropylene chain of the compound represented by the general formula (Chemical Formula 1) is apparently bonded to the water by the hydrophobic interaction of alkanediol having 4 to 7 carbon atoms bonded to water, A complex composed of an alkanediol having 4 to 7 carbon atoms and a compound represented by the above general formula (Formula 1) can be formed.
Here, the compound represented by the general formula (Chemical Formula 1) has a structure in which a polyoxypropylene chain is bonded to a glycerin skeleton, the carbon at the 2-position of glycerin is arranged at the center of the triangular pyramid, and the three positions of the triangular pyramid are arranged. It is considered that a polyoxypropylene group is oriented toward the apex and hydrogen is oriented toward one apex. Therefore, between the polyoxypropylene groups of the compound represented by the above general formula (Chemical Formula 1) of a complex composed of water, an alkanediol having 4 to 7 carbon atoms and the compound represented by the above General Formula (Chemical Formula 1), The space in which hexylene glycol having 4 to 7 carbon atoms bonded to water can exist is limited. When alkanediol having 4 to 7 carbon atoms hydrogen-bonded to water enters this restricted space, the space becomes dense and hydrophobic groups exist, and water remains stable in the space. Cannot be performed, and water will be detached from the complex. The detached water is discharged into and out of the ink. The water discharged into the ink is again hydrogen-bonded with the other alkanediol having 4 to 7 carbon atoms present in the ink to form a complex with the compound represented by the above general formula (Formula 1). It is discharged again in or out of the ink.
On the other hand, by the elimination of water, a complex composed of water, an alkanediol having 4 to 7 carbon atoms and a compound represented by the following general formula (Formula 1) has an alkanediol having 4 to 7 carbon atoms and the above-mentioned Since it is separated from the compound represented by the general formula (Chemical Formula 1), the alkanediol in which any two hydrogen atoms of the aliphatic hydrocarbon having 4 to 7 carbon atoms are substituted with hydroxyl groups is water absorbed in the ink. Hydrogen bonds with water discharged from the complex.
As described above, the formation of a complex composed of water, an alkanediol having 4 to 7 carbon atoms and the compound represented by the above general formula (Formula 1) and the elimination of water are repeated to keep the moisture constant. Since a dripped ink layer is formed, it is presumed that the ink can be prevented from flocculating and settling and losing fluidity even after long-term storage at high temperature and high humidity.
In addition, the dispersion composed of water, the alkanediol having 4 to 7 carbon atoms, and the compound represented by the following general formula (Chemical Formula 1) is adsorbed on the pigment surface, thereby improving the dispersion stability of the pigment. By preventing water from adsorbing on the pigment surface and preventing water from adsorbing to the resin, it prevents thickening of the ink, and the pigment aggregates into coarse particles, and these coarse particles become ballpoint pen tips. It is presumed that good handwriting performance can be obtained without hindering the rotation.

As the colorant, a dye and / or pigment conventionally used in oil-based ink compositions for ballpoint pens can be used.
As the dye, a conventionally known oil-soluble dye can be used.
Specific examples of oil-soluble dyes include rhodamine B base (C.I. 45170B, manufactured by Taoka Dye Manufacturing Co., Ltd.), Soldan Red 3R (C.I. 21260, manufactured by Chugai Kasei Co., Ltd.), methyl violet 2B base ( C.I. 42535B, manufactured by National Airlines Div., USA), Victoria Blue F4R (C.I. 42563B), Nigrosine Base LK (C.I. 50415) (above, manufactured by BASF, Germany), Bali First Yellow # 3104 (C.I. 13900A), Bali First Yellow # 3105 (C.I. 18690), Orient Spirit Black AB (C.I. 50415), Bali First Black # 3804 (C.I. 12195), Bali First Yellow # 1109, Bali First Orange # 2 10, Bali First Red # 1320, Bali First Blue # 1605, Bali First Violet # 1701, Bali First Violet # 1704, Oil Blue # 613, Oil Yellow # 129, Nigrosine Base EX (above, manufactured by Orient Chemical Industry Co., Ltd.) ), Spiron Black GMH Special, Spiro Yellow C-2GH, Spiro Yellow C-GNH, Spiron Red C-GH, Spiron Red C-BH, Spiron Blue BPNH, Spiron Blue C-RH, Spiron Violet C-RH, S . P. T.A. Orange 6, S. P. T.A. Blue 111 (above, manufactured by Hodogaya Chemical Co., Ltd.).
A water-soluble dye can also be used in combination with an oil-soluble dye. Specific examples of water-soluble dyes include C.I. I. Direct Black 17, 19, 19, 22, 32, 38, 51, 71, C.I. I. Direct Yellow 4, 26, 44, 50, 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, and the like; I. Acid Black 1, 2, 24, 26, 31, 31, 52, 107, 109, 110, 119, 154, C.I. I. Acid Yellow 1, 7, 17, 19, 23, 25, 29, 38, 42, 49, 61, 72, 78, 110, 127, 135, 141, 142, C.I. I. Acid Red 8, 9, 9, 14, 26, 27, 35, 37, 51, 52, 57, 82, 83, 87, 92, 94, 111, 129, 131, 138, 186, 249, 254, 265, 276, C.I. I. Acid Violet 15, 17, 49, C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 40, 41, 43, 62, 78, 83, 90, 93, 100, 103, 104, 112, 113, 158, C.I. I. Acid Green 3, 9, 16, 25, 27, C.I. I. Acid dyes such as Acid Orange 56, C.I. I. Food dyes such as Food Yellow 3, Malachite Green (C.I. 42000), Victoria Blue FB (C.I. 44545), Methyl Violet FN (C.I. 42535), Rhodamine F4G (C.I. 45160), And basic dyes such as rhodamine 6GCP (C.I. 45160).

  Moreover, when using a pigment as a coloring agent, a conventionally well-known organic pigment and an inorganic pigment can be used.

  Specific examples of organic pigments include C.I. I. PIGMENT RED2, 3, 5, 17, 17, 38, 41, 48: 2, 48: 3, 49, 50: 1, 53: 1, 57: 1, 58: 2, 60, 63: 1, 63: 2, 64: 1, 88, 112, 122, 123, 144, 146, 149, 166, 168, 170, 176, 177, 178, 179, 180, 185, 190, 194, 202, 206, 207, 209, 216, 245, 254, 255, 256, 272, C.I. I. PIGMENT ORANGE 5, 10, 13, 16, 36, 40, 43, 61, 64, 71, 73, C.I. I. PIGMENT VIOLET 19, 23, 31, 33, 36, 37, 38, 50, C.I. I. PIGMENT BLUE 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 17, 17, 22, 25, the same 60, 66, C.I. I. PIGMENT BROWN 23, 25, 26, C.I. I. PIGMENT YELLOW 1, 3, 12, 13, 24, 83, 93, 94, 95, 97, 99, 108, 109, 110, 117, 120, the same 128, 139, 147, 151, 153, 166, 167, 173, C.I. I. PIGMENT GREEN 7, 10, 36, 37, C.I. I. And organic pigments such as PIGMENT BLACK 7.

  Also, as inorganic pigments, carbon black such as furnace black, channel black, thermal black, acetylene black, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, bitumen, cobalt blue, titanium yellow, turquoise, molybdate orange, Examples include titanium oxide.

  Specific examples of carbon black include Mitsubishi Carbon Black # 10B, # 20B, # 14, # 30, # 33, # 40, # 44, # 45, # 45L, # 50, # 55, # 95, # 260, # 900, # 1000, # 2200B, # 2300, # 2350, # 2400B, # 2650, # 2700, # 4000B, CF9 MA8, MA11, MA77, MA100, MA100, MA220, MA230, MA600 and MCF88 (Mitsubishi Chemical Corporation), Monarch 120, Monarch 700, Monarch 800, Monarch 880, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Mogal L, Legal 99R, Legal 250R, Legal 300R, Lega 330R, Legal 400R, Legal 500 and Legal 660R (above, manufactured by Cabot Corporation, USA), Printex A, Printex G, Printex U, Printex V, Printex 55, Printex 140U, Printex 140V, Print Tex 35, Printex 40, Printex 45, Printex Printex 85, Nine Pex 35, Special Black 4, Special Black 4A, Special Black 5, Special Black 6, Special Black 100, Special Black 250, Special Black 350, Special Black 550, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160 and Color Black S170 (above, manufactured by Degussa Japan Co., Ltd.), Raven 5000 Ultra II, Raven 2500 Ultra, Raven 1250, Raven 760 Ultra (above, Columbia Carbon Japan Co., Ltd.) Etc.

  These colorants can be used singly or in combination of two or more, and the amount used is preferably 3% by weight to 50% by weight with respect to the total ink composition.

  As the pigment dispersant, a conventionally known pigment dispersant can be used regardless of whether it is a surfactant, a polymeric surfactant or a resin dispersant. The resin dispersants that can be used particularly well include low molecular weight polyvinyl butyral resins, ketone resins, urea resins, copolymers of styrene and acrylic acid or esters thereof, and copolymers of styrene and maleic acid or esters thereof. Examples thereof include styrene-α-methylstyrene-acrylic acid copolymer, polyacrylic acid, vinyl chloride / vinyl acetate copolymer resin, rosin ester resin, ethyl cellulose, and nitrocellulose. In addition to this, there are many types of high molecular weight surfactants in which polar groups are introduced into the molecule to improve pigment dispersion stability, but there are many products depending on the composition and structure of the polymer portion and the type of polar groups. As Solsperse 17000, Solsperse 20000, Solsperse 27000 (manufactured by Lubrizol).

  A resin that imparts fixability, dispersibility, viscosity adjustment, water resistance and the like, which has been conventionally added to oil-based inks for ballpoint pens, can also be added. For example, ketone resin, sulfoamide resin, acrylic resin, polymethacrylic acid ester, polyacrylic acid polymethacrylic acid copolymer, maleic acid resin, copolymer of styrene and maleic acid ester, styrene and acrylic acid or its ester Copolymer, ester gum, xylene resin, coumarone-indene resin, urea resin, polyamide resin, alkyd resin, phenol resin, alkylphenol resin, terpene phenol resin, rosin resin and its hydrogenated compounds, polyvinyl butyral, polyvinyl acetal, polyvinyl Alkyl ether, polyvinyl pyrrolidone, polyethylene oxide and the like can be mentioned, and these can be used alone or in combination. The total blending amount is preferably in the range of 0.1 to 30% by weight with respect to the total amount of the ink composition.

As the compound represented by the following general formula (Formula 1), a compound synthesized by addition polymerization of propylene oxide to a sugar alcohol may be used.
Specific examples of the sugar alcohol include tritol such as glycerin, tetritol such as erythritol and threitol, pentitol such as pentaerythritol, arabitol, ribitol and xylitol, sorbitol (glucitol), mannitol, galactitol (dulcitol), iditol, and taritol. Hexitol such as allitol, heptitol such as perseitol and boremitol, octitol, nonitol, decitol and the like.

  As what is marketed as a compound shown by the said General formula (Formula 1), as a polyoxypropylene glyceryl ether, Uniol SGP-65 (molecular weight 550), Uniol TG-1000 (molecular weight 1000), Uniol TG-2000 ( Molecular weight 2000), Uniol TG-3000 (molecular weight 3000), Uniol TG4000R (molecular weight 4000) (manufactured by NOF Corporation), New Pole GP-250 (Molecular weight 250), New Pole GP-400 (Molecular weight 420), New Pole GP-600 (Molecular weight 600), New Pole GP-1000 (Molecular weight 1050), New Pole GP-4000 (Molecular weight 4000), Sannix GP-250 (Molecular weight 250), Sannix GP-400 (Molecular weight 400), Sannicks P-600 (Molecular weight 600), Sannix GP1000 (Molecular weight 1000), Sannix GP-1500 (Molecular weight 1500), Sannix GP-3000 (Molecular weight 3000), Sannix, (Molecular weight 4000) (Sanyo Chemical Industries ( Mushiyuru C-060, Mushiyuru C-400 (above, manufactured by Toho Chemical Industry Co., Ltd.), UNIOL HS-1600D (molecular weight 1600), UNIOR HS-2000D (molecular weight 2100) (above) , NOF Corporation), New Pole SP-750 (molecular weight 690), Sanniks SP-750 (above, Sanyo Chemical Industries Co., Ltd.), polyoxypropylene methyl glucoside, GLUCAM P-10, GLUCAM P -20 (above, Nippon Lubrizol Co., Ltd.)), and the like.

  The compound represented by the above general formula (Formula 1) is preferably used in an amount of 0.1 to 30% by weight based on the total ink composition. Furthermore, it is particularly preferable that the ether is used in an amount of 10 to 50% by weight based on the amount of alkanediol having 4 to 7 carbon atoms.

  Moreover, it is preferable to use 0.1-30 weight% of compounds shown by the said general formula (Formula 1) with respect to all the ink compositions. Furthermore, the compound represented by the above general formula (Formula 1) is particularly preferable when the average molecular weight is in the range of 1100 or more and 1800 or less. For this reason, it is particularly preferable that the compounds represented by the above general formula (Formula 1) having different molecular weights are used in combination so that the average molecular weight is in the range of 1100 or more and 1800 or less. The average molecular weight is an arithmetic average of the molecular weights of the compounds represented by the above general formula (Formula 1).

The organic solvent uses alkanediol having 4 to 7 carbon atoms as the main solvent.
Specific examples of alkanediols in which any two hydrogen atoms of aliphatic hydrocarbons having 4 to 7 carbon atoms are substituted with hydroxyl groups include 2-methyl-1,3-propanediol and 1,2-butanediol. 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-2,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-1, 3-butanediol, 1,5-pentanediol, 1,2-pentanediol, 2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, 2,5-hexanediol Hexylene glycol (2-methyl-2,4-pentanediol), 2,4-dimethyl-2,4-pentanediol, 1,2-heptanediol, 1,6- Heptane diol, 1,7-heptane diol.
Of these alkanediols having 4 to 7 carbon atoms, hexylene glycol is particularly preferred.

The organic solvent is preferably used in an amount of 35 to 80% by weight based on the total ink composition.
The alkanediol having 4 to 7 carbon atoms may be used in combination with other organic solvents, and the amount of alkanediol having 4 to 7 carbon atoms may be used at 55 to 100% by weight of the total amount of the organic solvent. preferable. The organic solvent used in combination with the alkanediol having 4 to 7 carbon atoms can be used without particular limitation as long as it is conventionally used for oil-based inks for ballpoint pens, and alcohol, glycol, glycol ether and the like can be used. In addition, water can be used in combination with a small amount.

  Specific examples of the alcohol include benzyl alcohol, α-methylbenzyl alcohol, lauryl alcohol, tridecyl alcohol, isododecyl alcohol, isotridecyl alcohol and the like.

  Specific examples of glycol include ethylene glycol, diethylene glycol, propylene glycol and the like.

  Specific examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mononormal butyl ether, propylene glycol monomer Phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mononormal butyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mononormal butyl ether, And tripropylene glycol monophenyl ether.

  In addition, propylene glycol methyl ether acetate, propylene glycol diacetate, N-methyl-2-pyrrolidone and the like can be used.

  These organic solvents used in combination with 4 to 7 carbon atoms can be used alone or in combination of two or more.

  In addition to the above components, additives such as a pH adjuster, an antiseptic or an antifungal agent, a rust preventive, a lubricant or a wetting agent, and a seat wear inhibitor can be added as necessary.

  pH adjusters include ammonia, urea, monoethanolamine, diethanolamine, triethanolamine, sodium tripolyphosphate, sodium carbonate and other carbonates and alkali metal salts of phosphate, alkali metal hydroxides such as sodium hydroxide, preservatives or Antifungal agents such as phenol, sodium omadin, pentachlorophenol sodium, 1,2-benzisothiazoline 3-one, 2,3,5,6-tetrachloro-4 (methylsulfonyl) pyridine, sodium benzoate Acid, sorbic acid, alkali metal salts of dehydroacetic acid, benzimidazole compounds, rust preventives such as benzotriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, tolyltriazole, Lubricants and wetting agents include castor oil, polyoxyethylene adduct of castor oil, polyoxyethylene alkylamine, molybdenum disulfide, urea, ethylene urea, polyoxyethylene lauryl ether and other polyoxyethylene, polyoxypropylene or polyoxyethylene poly Derivatives of oxypropylene, glycerin such as tetraglyceryl distearate, derivatives of diglycerin or polyglycerin, sorbitan derivatives such as sorbitan monooleate, surfactants having a fluorinated alkyl group such as perfluoroalkyl phosphate, polyethylene of dimethylpolysiloxane Examples of polyether-modified silicones such as glycol adducts and seat wear inhibitors are alumina, silicon carbide, chromium oxide, boron carbide, zircon, Stone, jade stone, calcium fluoride, tungsten carbide, silica, diamond, garnet, aluminum nitride, silicon nitride or the like can be mentioned.

  A conventionally known method for producing an ink composition can be applied to the preparation of the oil-based ink composition for ballpoint pens of the present invention. That is, when a pigment is used, an oil-based ink composition for ballpoint pens can be obtained by dispersing the pigment together with other components using a dispersion mixer. It is particularly preferable to use heating to dissolve solids such as dyes at the time of production, and to use a filter or centrifugal separation to remove coarse particles such as pigments.

  Hereinafter, the present invention will be specifically described with reference to examples. In addition, the following compounding numerical value shows a weight part.

  Examples of blending ink compositions are shown below. In addition, the following compounding numerical value shows a weight part.

Example 1
Printex 35 (pigment, manufactured by Degussa Huls Japan Co., Ltd.) 27.00
S Lec BL-1 (polyvinyl butyral, dispersant, manufactured by Sekisui Chemical Co., Ltd.) 4.00
Hexylene glycol 47.48
Hilac 901 (Ketone resin, manufactured by Hitachi Chemical Co., Ltd.) 3.00
PVP K-90 (polyvinylpyrrolidone, manufactured by ISP Japan Co., Ltd.) 0.50
AKP-30 (high purity alumina powder, manufactured by Sumitomo Chemical Co., Ltd.) 0.02
UNIOR TG-1000 (polyoxypropylene glyceryl ether, manufactured by NOF Corporation)
13.68
UNIOR TG-3000 (polyoxypropylene glyceryl ether, manufactured by NOF Corporation)
4.32
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 2
Special Black # 4 (pigment, manufactured by Degussa Huls Japan Co., Ltd.) 30.00
Jonkrill 678 (styrene-acrylic acid copolymer, dispersant, BASF Japan Ltd.)
(Made) 8.00
Hexylene glycol 36.98
Ketone resin K-90 (ketone resin, manufactured by Arakawa Chemical Industries, Ltd.) 5.00
AKP-30 (described above) 0.02
UNIOR TG-1000 (mentioned above) 15.20
UNIOR TG-2000 (polyoxypropylene glyceryl ether, manufactured by NOF Corporation)
4.80
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 3
Printex 35 (described above) 10.00
Mitsubishi Carbon Black MA220 (pigment, manufactured by Mitsubishi Chemical Corporation) 15.00
S REC BL-1 (mentioned above) 10.00
Hexylene glycol 33.40
Ketone resin K-90 (described above) 2.00
Hi-Rack 901 (mentioned above) 2.00
PVP K-90 (described above) 0.60
UNIOR TG-1000 (described above) 23.76
UNIOR TG-3000 (described above) 3.24
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 4
Mitsubishi Carbon Black MA220 (mentioned above) 20.00
Oil black HBB (dye, manufactured by Orient Chemical Co., Ltd.) 10.00
S REC BL-1 (mentioned above) 5.00
Hexylene glycol 49.56
Hi-Rack 901 (mentioned above) 7.00
PVP K-90 (described above) 0.40
AKP-30 (described above) 0.04
UNIOR TG-1000 (mentioned above) 1.76
UNIOR TG-3000 (described above) 6.24
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 5
Printex 35 (described above) 30.00
ESREC BL-1 (mentioned above) 15.00
Hexylene glycol 25.00
Ethylene glycol monophenyl ether 13.47
Ketone resin K-90 (described above) 6.00
PVP K-90 (described above) 0.50
AKP-30 (described above) 0.03
UNIOR TG-1000 (mentioned above) 9.30
UNIOR TG-2000 (described above) 0.70
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 6
Printex 35 (described above) 27.00
S Lec BL-1 (described above) 4.00
Hexylene glycol 47.38
Hi-Rack 901 (mentioned above) 4.00
PVP K-90 (described above) 0.60
AKP-30 (described above) 0.02
UNIOR TG-1000 (mentioned above) 17.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 7
Special Black # 4 (mentioned above) 20.00
S Lec BL-1 (described above) 3.00
Hexylene glycol 61.26
Ketone resin K-90 (described above) 3.00
PVP K-90 (described above) 0.70
AKP-30 (described above) 0.04
UNIOR TG-2000 (mentioned above) 12.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 8
Mitsubishi Carbon Black MA220 (mentioned above) 25.00
S REC BL-1 (mentioned above) 10.00
Hexylene glycol 50.58
Hi-Rack 901 (mentioned above) 7.00
PVP K-90 (described above) 0.40
AKP-30 (described above) 0.02
UNIOR RG-3000 (mentioned above) 7.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 9
Special Black # 4 (mentioned above) 30.00
ESREC BL-1 (mentioned above) 15.00
Hexylene glycol 27.63
Benzyl alcohol 4.87
Ketone resin K-90 (described above) 5.00
Hi-Rack 901 (mentioned above) 2.00
PVP K-90 (described above) 0.50
UNIOR SGP-65 (polyoxypropylene glyceryl ether, manufactured by NOF Corporation)
15.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 10
C. I. Pigment Red 254 23.00
S Lec BL-1 (described above) 8.00
Hexylene glycol 31.44
Ethylene glycol monophenyl ether 11.63
High rack 901 (mentioned above) 10.00
PVP K-90 (described above) 0.90
AKP-30 (described above) 0.03
UNIOR TG-700 (polyoxypropylene glyceryl ether, manufactured by NOF Corporation)
15.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a red ballpoint pen ink.

Example 11
Printex 35 (described above) 12.00
Oil black HBB (mentioned above) 15.00
S Lec BL-1 (described above) 8.00
Hexylene glycol 40.95
Ketone resin K-90 (described above) 4.00
AKP-30 (described above) 0.05
UNIOR HS-1600D (Polyoxypropylene Sorbit, manufactured by NOF Corporation)
20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 12
Special Black # 4 (mentioned above) 15.00
Oil black HBB (mentioned above) 10.00
S REC BL-1 (mentioned above) 10.00
Hexylene glycol (described above) 37.28
Ethylene glycol monophenyl ether 5.08
High rack 901 (mentioned above) 8.00
PVP K-90 (described above) 0.60
AKP-30 (described above) 0.04
UNIOR HS-2000D (Polyoxypropylene Sorbit, manufactured by NOF Corporation)
14.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 13
Printex 35 (described above) 27.00
S Lec BL-1 (described above) 8.00
Hexylene glycol 19.11
Dipropylene glycol 23.37
Hi-Rack 901 (mentioned above) 4.00
PVP K-90 (described above) 0.50
AKP-30 (described above) 0.02
UNIOR TG-1000 (mentioned above) 13.68
UNIOR TG-3000 (described above) 4.32
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 14
Special Black # 4 (mentioned above) 20.00
S Lec BL-1 (described above) 3.68
Hexylene glycol (mentioned above) 12.74
Ethylene glycol monophenyl ether (mentioned above) 50.96
Ketone resin K-90 (described above) 3.00
PVP K-90 (described above) 0.60
AKP-30 (described above) 0.02
UNIOR TG-1000 (described above) 6.84
UNIOR TG-2000 (described above) 2.16
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 15
Printex 35 (described above) 27.00
S Lec BL-1 (described above) 4.00
Hexylene glycol 47.48
High rack 901 (mentioned above) 3.00
PVP K-90 (described above) 0.50
AKP-30 (described above) 0.02
Newpol GP-400 (polyoxypropylene glyceryl ether, Sanyo Chemical Industries, Ltd.)
13.68)
Newpol GP-1000 (polyoxypropylene glyceryl ether, manufactured by Sanyo Chemical Industries, Ltd.) 4.32.
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 16
Mitsubishi Carbon Black MA220 (mentioned above) 20.00
Oil black HBB (dye, manufactured by Orient Chemical Co., Ltd.) 10.00
S REC BL-1 (mentioned above) 5.00
Hexylene glycol 49.56
Hi-Rack 901 (mentioned above) 7.00
PVP K-90 (described above) 0.40
AKP-30 (described above) 0.04
SANNICS GP-600 (polyoxypropylene glyceryl ether, manufactured by Sanyo Chemical Industries, Ltd.) 1.76
Newpole GP-1000 (polyoxypropylene glyceryl ether, manufactured by Sanyo Chemical Industries, Ltd.) 6.24
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 17
Printex 35 (described above) 27.00
S Lec BL-1 (described above) 4.00
Hexylene glycol 47.38
Hi-Rack 901 (mentioned above) 4.00
PVP K-90 (described above) 0.60
AKP-30 (described above) 0.02
Musyule C-400 (polyoxypropylene glyceryl ether, manufactured by Toho Chemical Industry Co., Ltd.) 17.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Example 18
Printex 35 (described above) 12.00
Oil black HBB (mentioned above) 15.00
S Lec BL-1 (described above) 8.00
Hexylene glycol 40.95
Ketone resin K-90 (described above) 4.00
AKP-30 (described above) 0.05
New Pole SP-750 (Polyoxypropylene Sorbit, manufactured by Sanyo Chemical Industries)
20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 1
Printex 35 (described above) 27.00
S Lec BL-1 (described above) 4.00
Hexylene glycol (mentioned above) 65.38
High rack 901 (mentioned above) 3.00
PVP K-90 (described above) 0.60
AKP-30 (described above) 0.02
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 2
Printex 35 (described above) 27.00
ESREC BL-1 (mentioned above) 7.00
Hexylene glycol (mentioned above) 40.98
Ketone resin K-90 (described above) 5.00
AKP-30 (described above) 0.02
UNIOX G-1200 (polyoxyethylene glyceryl ether, manufactured by NOF Corporation)
20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 3
Special Black # 4 (mentioned above) 10.00
Mitsubishi Carbon Black MA220 (mentioned above) 15.00
S REC BL-1 (mentioned above) 5.00
Ethylene glycol monophenyl ether 45.20
Ketone resin K-90 (described above) 2.00
Hi-Rack 901 (mentioned above) 2.00
PVP K-90 (described above) 0.80
AKP-30 (described above) 0.02
UNIOR TG-1000 (mentioned above) 20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 4
Special Black # 4 (mentioned above) 20.00
Oil black HBB (mentioned above) 10.00
S Lec BL-1 (described above) 8.00
Benzyl alcohol 36.40
Hi-Rack 901 (mentioned above) 7.00
PVP K-90 (described above) 0.60
AKP-30 (described above) 0.02
UNIOR TG-1000 (mentioned above) 18.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 5
Printex 35 (described above) 30.00
ESREC BL-1 (mentioned above) 15.00
Ethylene glycol (mentioned above) 20.00
Tripropylene glycol monomethyl ether 8.00
Ketone resin K-90 (described above) 6.00
PVP K-90 (described above) 1.00
AKP-30 (described above) 0.03
UNIOR TG-1000 (mentioned above) 20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 6
Special Black # 4 (mentioned above) 25.00
ESREC BL-1 (mentioned above) 12.00
Dipropylene glycol 34.18
High rack 901 (mentioned above) 10.00
PVP K-90 (described above) 0.80
AKP-30 (described above) 0.02
UNIOR TG-1000 (mentioned above) 18.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 7
Mitsubishi Carbon Black MA220 (mentioned above) 25.00
S Lec BL-1 (described above) 3.68
Benzyl alcohol 63.90
Hi-Rack 901 (mentioned above) 7.00
PVP K-90 (described above) 0.40
AKP-30 (described above) 0.02
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 8
Special Black # 4 (mentioned above) 30.00
S Lec BL-1 (mentioned above) 20.00
Ethylene glycol 42.18
Ketone resin K-90 (described above) 5.00
Hi-Rack 901 (mentioned above) 2.00
PVP K-90 (described above) 0.80
AKP-30 (described above) 0.02
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 9
C. I. Pigment Red 254 22.00
ESREC BL-1 (mentioned above) 15.00
Hexylene glycol 32.17
High rack 901 (mentioned above) 10.00
PVP K-90 (described above) 0.80
AKP-30 (described above) 0.03
Unilube 50TG32 (polyoxyethylene polyoxypropylene glyceryl ether, manufactured by NOF Corporation) 20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a red ballpoint pen ink.

Comparative Example 10
Mitsubishi Carbon Black MA220 (mentioned above) 10.00
Oil black HBB (mentioned above) 10.00
ESREC BL-1 (mentioned above) 7.00
Hexylene glycol 50.36
Ketone resin K-90 (described above) 2.00
High rack 901 (mentioned above) 5.00
PVP K-90 (described above) 0.60
AKP-30 (described above) 0.04
UNILOVE 43TT-2500 (polyoxyethylene polyoxypropylene trimethylolpropane) 15.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 11
Printex 35 (described above) 12.00
Oil black HBB (mentioned above) 15.00
S Lec BL-1 (described above) 8.00
Hexylene glycol 42.63
Ketone resin K-90 (described above) 4.00
PVP K-90 (described above) 0.30
AKP-30 (described above) 0.07
Unilube DGP-700 (polyoxypropylene diglyceryl ether, NOF Corporation)
(Made) 18.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 12
Special Black # 4 (mentioned above) 15.00
Oil black HBB (mentioned above) 10.00
S Lec BL-1 (described above) 4.00
Hexylene glycol 42.58
High rack 901 (mentioned above) 8.00
PVP K-90 (described above) 0.40
AKP-30 (described above) 0.02
Unilube 5TP-300KB (polyoxyethylene polyoxypropylene pentaerythritol ether, manufactured by NOF Corporation) 20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 13
Printex 35 (described above) 27.00
S REC BL-1 (mentioned above) 5.00
Hexylene glycol 37.48
Ketone resin K-90 (described above) 5.00
PVP K-90 (described above) 0.50
AKP-30 (described above) 0.02
Glycerin 25.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

Comparative Example 14
Printex 35 (described above) 27.00
S Lec BL-1 (described above) 6.00
Hexylene glycol 42.48
Hi-Rack 901 (mentioned above) 4.00
PVP K-90 (described above) 0.50
AKP-30 (described above) 0.02
UNIOR D-2000 (polypropylene glycol, manufactured by NOF Corporation) 20.00
The mixture of the above components was stirred with a propeller stirrer at 60 ° C. for 4 hours to obtain a black ballpoint pen ink.

  As mentioned above, the following test was done about the ink obtained by the Example and the comparative example. The results are shown in Table 1.

Preparation of test sample The ballpoint pen inks obtained in Examples 1 to 18 and Comparative Examples 1 to 14 were used to form a 0.7 mm diameter carbide ball using a stainless steel ball holder and open the tip of the ball holder. Ink of a knock-type ballpoint pen (Rolly, product code BP127, manufactured by Pentel Co., Ltd.) that accommodates a refill body that connects a ballpoint pen tip held in a state of partially protruding from the part and a polypropylene pipe formed by extrusion molding The container tube was filled with 0.25 g, and centrifuged at a rotational speed of 1700 rpm for 10 minutes using a commercially available centrifuge (H-103NR, Kokusan Co., Ltd.) to obtain a test ballpoint pen sample.

  Forced heating and humidification over time writing stability test: The ballpoint pen sample filled with the inks of Examples 1 to 18 and Comparative Examples 1 to 14 can be left in a thermostatic bath at 80 ° C. and 80% humidity for 1 month, handwritten and written. I confirmed. As evaluation criteria, x was written when it was not possible to write at all, Δ was written but the handwriting was faint, ◯ was slightly changed compared to before the test, and ◎ was written as before the test.

  Forced heating and humidification post-line jump test: A ballpoint pen sample filled with the inks of Examples 1 to 18 and Comparative Examples 1 to 14 was left in a thermostatic bath at 80 ° C. and 80% humidity for 1 month, and then a spiral writing tester Then, writing was performed at a writing speed of 7 cm / sec, a writing load of 150 g, and a writing angle of 70 °, and the handwriting was visually determined.

Viscosity measurement after forced heating and humidification: The initial viscosity of the inks of Examples 1 to 18 and Comparative Examples 1 to 14 and the viscosity after being left in a thermostatic bath at 80 ° C. and a humidity of 80% for 1 month were measured.
The viscosity was measured with VICOANALYSER VAR-100 (manufactured by Reologica, Sweden). Measurement conditions include a temperature 25 ° C., shear rate 3000 s ^-1 from a shear rate of ^{1s -1,} delay time 5 seconds, integration time 5 seconds at 20mm cone plate (1 °), the value of the shear rate 0.1s ^-1 I read it.

  Particle size measurement after forced heating and humidification: The initial particle size of the inks of Examples 1 to 18 and Comparative Examples 1 to 14 and the particle size after being left in a constant temperature bath at 80 ° C. and 80% humidity were measured. . The particle size was measured before and after forced heating and humidification over time writing stability test using SALD-7100 (Nanoparticle size distribution measuring device, manufactured by Shimadzu Corporation).

  As described above in detail, the ink for the ballpoint pen of the present invention collects ink at the tip of the ballpoint pen tip during writing and causes a phenomenon that the ink adheres to the outer surface of the ball holder, so-called ink adhesion, and the density of the handwriting density and the handwriting. It is a good one without the phenomenon that ink does not get on the center of the ink.

Claims (3)

An oil-based ink composition for ballpoint pens comprising at least a compound represented by the following general formula (Formula 1), an alkanediol having 4 to 7 carbon atoms, a resin, and a pigment.

The oil-based ink composition for ballpoint pens according to claim 1, wherein the alkanediol having 4 to 7 carbon atoms is hexylene glycol. The oil-based ink composition for ballpoint pens according to claim 1, wherein the general formula (Formula 1) is polyoxypropylene glyceryl ether.