JP2009242491A - Oil-based ink for ballpoint pen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-based ink composition for a ballpoint pen hardly causing dripping. <P>SOLUTION: The oil-based ink for a ballpoint pen comprises at least a coloring material, ethylene glycol ether and/or diethylene glycol ether having a boiling point of 160.5-194°C and molecular weight of 118.18-134.17, ethylene glycol ether and/or diethylene glycol ether having a boiling point of 85.2-149.8°C and molecular weight of 76.1-104.15, and a polymer compound comprising an acrylic acid monomer unit as a principal component and having a (meth)acrylic acid alkyl ester monomer unit. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention is accommodated in a ballpoint pen that uses a ballpoint tip that has a ballpoint tip that holds a ball for transferring ink onto a writing surface such as paper as a part of the ballpoint holder and is held freely. The present invention relates to an oil-based ink for ballpoint pens using a solvent as a main medium.
Specifically, there is no blurring phenomenon such as excess ink generated from the tip of the pen when writing, dropping on the paper surface, or ink droplets collecting on the outer part of the tip of the ballpoint pen tip and The present invention relates to an oil-based ink composition for ballpoint pens that is difficult to generate.

Conventionally, oil-based ink compositions for ballpoint pens are used for coloring materials such as dyes and pigments, solvents such as glycols, glycol ethers, and high-boiling alcohols, and papers such as ketone resins, xylene resins, and rosin-derived resins. It consists of a resin whose main purpose is fixing, and a resin whose main purpose is to adjust viscosity, adjust flow characteristics, and prevent blistering, such as polyvinylpyrrolidone and polyvinyl butyral, if necessary.
Writing with this ball-point pen is a method in which ink circulated through the inner hole of the ball holder is transferred in contact with a writing object such as a paper surface and transferred by a rotating ball, thereby creating a handwriting / drawing line. At that time, ink that came out from the opening of the tip of the ball holder but did not become handwriting was also generated, such ink adhered to the outer periphery of the ball holder, and when starting to write, sometimes a lump of ink dropped during writing The so-called bloating phenomenon may occur. In particular, if there is a large amount of ink smearing from the opening at the front end that is not on the transfer direction, the amount of ink that has not been transferred to become handwriting increases, and the occurrence of the blur phenomenon increases.
Various researches have been made to prevent botting since ancient times. The specific means is to use a specific polyvinylpyrrolidone. (Refer to Patent Documents 1 and 2), numerical values related to viscosity and shear thinning are limited. (Patent Documents 3 and 4) are disclosed.
JP-A-8-239616 (paragraph numbers 0005 and 0006) JP 2001-139866 A (paragraph numbers 0003 and 0004) JP-A-6-313143 (paragraph numbers 0006 to 0008) JP-A-10-297158 (paragraph numbers 0003 to 0006)

  When polyvinylpyrrolidone is added to the ink, the cohesive strength of the ink increases, and the ability to pull the excess ink back into the ballpoint pen tip due to its stringiness increases, so that the so-called ink return effect can be increased and the loss can be reduced. However, if added to such an extent that the effect appears, the viscosity of the ink becomes high, and the ink ejection does not go smoothly, and there is a risk of blurring and line cracking in the handwriting.

  In addition, low-viscosity ink that gives shear thinning viscosity to reduce ink viscosity at the time of writing, enhances ink permeability to paper, penetrates excess ink at the tip of the chip into paper, and suppresses the phenomenon of blurring. There is a possibility that remarkable handwriting blur occurs, or the ball and the striker strike strongly, and the striker wears out and the rotation of the ball is hindered, resulting in blurring.

  That is, the present invention relates to a colorant, ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 160.5 ° C. to 194 ° C. and a molecular weight of 118.18 to 134.17, and a boiling point of 85.2. An oiliness for ballpoint pens comprising at least a compound represented by the following general formula (Equation 1) and an ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 76.1 to 104.15 in a range of from ℃ to 149.8 ℃. It is based on ink.

The compound represented by the general formula (Equation 1) has a plurality of hydrophilic groups and is bonded to a solvent having a hydrophilic group. When the solvent has a hydrophobic group together with a hydrophilic group, the compound represented by the general formula (Equation 1) becomes gel-like particles swollen with the solvent due to steric hindrance between the hydrophobic groups. If the molecular chain of the solvent is long, steric hindrance occurs. It is considered that the distance between the hydrophobic groups is also increased, and the size of the swollen gel particles is considered to be affected by the molecular weight of the solvent. When a solvent having a boiling point and a molecular weight different from each other is used as a solvent for swelling the compound represented by the general formula (Equation 1), the size of the gel-like particles is limited within a certain range in the drying process due to the difference in the evaporation speed of the solvent. It is assumed that it can be changed in That is, ethylene glycol ether having a boiling point in the range of 160.5 ° C. or higher and 194 ° C. or lower and a molecular weight of 118.18 or higher and 134.17 or lower as a solvent for swelling the compound represented by the general formula (Formula 1) and / or When diethylene glycol ether and ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 85.2 ° C. to 149.8 ° C. and a molecular weight of 76.1 to 104.15 are used, the boiling point is 85.2 ° C. The boiling point is 160.5 ° C. or more in the gel particles swollen by ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 76.1 or more and 104.15 or less previously vaporized and swollen in the range of 149.8 ° C. or less. In a range of 194 ° C. or lower and a molecular weight of 118.18 or higher and 134.17 or lower. Since the ratio of the ethylene glycol ether and / or diethylene glycol ether increases that, in the gelling particles moves to swollen state due to the large solvent molecular weight, gel-like particles is increased.
By the way, the ink used for the ballpoint pen passes through a minute gap in the ballpoint pen and becomes a handwriting, but the ink drying occurs mainly at the opening of the ballpoint pen tip that is the contact portion with the outside world Part.
That is, in the process up to the opening of the ball-point pen tip, since the two kinds of solvents described above are mixed in the gel-like particles, the gel-like particles are small and pass through the fine ink passage. However, the ink that has reached the opening of the ball-point pen tip is vaporized from the above-mentioned low boiling point solvent when not writing, and the size of the gel-like particles grows in the portion and the gel-like particles are covered. Such a state is formed.
Therefore, it is possible to suppress the outflow of more ink at the time of non-writing, and it is possible to suppress ink leakage at the time of non-use and dropping of the ink at the time of re-writing due to ink accumulation near the opening of the ball-point pen tip. be able to.

The invention is described in detail below.
As the colorant, generally used dyes and pigments can be used. Examples of dyes include SPILON BLACK GMH SPECIAL, SPILON RED C-GH, SPILON RED C-BH, SPILON BLUE C-RH, SPILON BLUE BPNH, SPILON YELLOW C-2GH, SPILON VIOLET C-RH, S. P. T.A. ORANGE6, S. P. T.A. BLUE111, SOT Yellow-1, SOT Yellow-2, SOT Yellow-3, SOT Yellow-4, SOT Yellow-6, SOT Orange-1, SOT Orange-2, SOT Scallet-1, SOT Red-1, SOT Red- 2, SOT Red-3, SOT Pink-1, SOT Brown-1, SOT Brown-2, SOT Blue-1, SOT Blue-2, SOT Blue-3, SOT Blue-4, SOT Violet-1, SOT Green- 1, SOT Green-2, SOT Green-3, SOT Black-1, SOT Black-2, SOT Black-4, SOT Black-5, SOT Black-6, SOT Black-8 (above, Hodogaya Chemical INDUSTRIAL CO., LTD. 2601, VALIFAST YELLOW 1110, VALIFAST YELLOW 3104, VALIFAST YELLOW 3105, VALIFAST YELLOW 1109, Oil Colors Yellow # 101, Oil Colors Yellow 3G, Oil Col rs Yellow GGS, Oil Colors Yellow # 105, Oil Colors Yellow # 107, Oil Colors Yellow # 136, Oil Colors Yellow # 140, Oil Colors Orange PS, Oil Colors Orange Colors 201, Orange Colors PR Colors Pink # 312, Oil Colors Scarlet # 308, Oil Colors Red RR, Oil Colors Red 5B, Oil Colors Red # 330, Oil Colors Brown GR, Oil Colors Brown # 416, Oil Bowl Golds, Oil Bowls # 416 n BG, Oil Colors Green # 502, Oil Colors Green # 533, Oil Colors Blue BOS, Oil Colors Blue IIN, Oil Colors Blue # 603, Oil Colors Violet # 730, Oil Colors Violet # 730 Black BS, Oil Colors Black HBB, Oil Colors Black # 803, Oil Colors Black EB, Oil Colors Black EX (manufactured by Orient Chemical Industry Co., Ltd.), Neo Super Blue C-555 (manufactured by Chuo Synthetic Chemical Co., Ltd.) Rhodamine B base, Soldan red 3R, Methyl violet 2B base, ECTS rear Blue F4R, and the like.
As the pigment, those generally used can be used. For example,
Carbon black, insoluble azo pigment, azo lake pigment, condensed azo pigment, diketopyrrolopyrrole pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, anthraquinone pigment, dioxazine pigment, Conventionally known general pigments such as organic pigments such as indigo pigments, thioindigo pigments, quinophthalone pigments, perinone and perylene pigments can be used. These may be used alone or in combination of two or more.

Carbon black can be used as the black pigment. For example, Printex 3, 25, 30, 35, 40, 45, 55, 60, 75, 80, 85, 90, 95, 300, Special Black 4, 5, 100, 250, 550 (Degussa Huls Japan Co., Ltd.) Mitsubishi Carbon Black # 2700, # 2650, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52 # 50, # 47, # 45, # 45L, # 44, # 40, # 33, # 32, # 30, # 25, # 20, # 10, # 5, # 95, # 260, CF9, MCF88, MA600, MA77, MA7, MA11, MA11, MA100, MA100R, MA100S, MA100S, MA220, MA230 (Mitsubishi Chemical Corporation), Talker Black # 8500 / F, # 8300 / F, # 7550SB / F, # 7400, # 7360SB / F, # 7350 / F, # 7270SB, # 7100 / F, # 7050 (above, manufactured by Tokai Carbon Co., Ltd.). Examples of blue pigments include C.I. I. Pigment Blue 2, 9, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 16, 17, 28, 29, 36, 60, 68, 76, 80, etc. can be used. Examples of red pigments include C.I. I. Pigment Red 2, 3, 5, 8, 14, 17, 17, 22, 31, 31, 48: 1, 48: 2, 48: 3, 48: 4, 53 : 1, 53: 2, 57: 1, 112, 122, 144, 146, 149, 166, 170, 175, 176, 177, 179, 184, same 185, 187, 188, 202, 207, 208, 209, 210, 211, 213, 214, 242, 253, 254, 255, 256, 257, 264, 266, 268, 270, 272, etc. can be used. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 79, 81, 83, 93, 94, 95, the same 97, 109, 110, 111, 120, 128, 133, 136, 138, 139, 147, 151, 154, 155, 167, 173, 174, 175, 176, 180, 185, 191, 194, 213, etc. can be used. Examples of orange pigments include C.I. I. Pigment Orange 5, 13, 13, 16, 34, 36, 38, 43, 62, 68, 72, 74, and the like. Examples of green pigments include C.I. I. Pigment Green 7, 36, 37, etc. can be used. Examples of purple pigments include C.I. I. Pigment Violet 19, 23 and the like can be used.
These dyes and pigments are preferably used in an amount of 1 to 40% by weight, more preferably 1 to 30% by weight, based on the total amount of oil-based ink for ballpoint pens. If the amount used is less than 1% by weight, the handwriting is too thin and difficult to read. On the other hand, when the amount is more than 40% by weight, it becomes easy to cause a problem that writing becomes unsatisfactory due to clogging due to sedimentation with time, and an increase in the solid content in oil-based ink for ballpoint pens.

Ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 160.5 ° C. or more and 194 ° C. or less and a molecular weight of 118.18 or more and 134.17 or less are the main medium of the ink. Mononormal butyl ether (boiling point 171.2 ° C., molecular weight 118.18), ethylene glycol monoisobutyl ether (boiling point 160.5 ° C., molecular weight 118.18), diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15), diethylene glycol dimethyl ether (Boiling point 162.5 ° C., molecular weight 134.17). These solvents can be used alone or in combination.
When the boiling point exceeds 194 ° C., the gel-like particles in the ink become too large and do not reach the opening of the ball-point pen tip, and only the ink accumulates in the opening, preventing boiling. The boiling point is less than 160.5 ° C. When ethylene glycol ether and / or diethylene glycol ether is used, the solvent evaporates too quickly, and the amount may be reduced during long-term storage, making writing impossible.
An ethylene glycol ether and / or diethylene glycol ether having a boiling point of 160.5 ° C. or higher and 194 ° C. or lower and a molecular weight of 118.18 or higher and 134.17 or lower, and a boiling point of 85.2 ° C. or higher and 149.8 ° C. or lower; The total amount of ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 76.1 or more and 104.15 or less is preferably 10% by weight or more and 80% by weight or less based on the total amount of the ink.

An ethylene glycol ether and / or diethylene glycol ether having a boiling point of 85.2 ° C. or higher and 149.8 ° C. or lower and a molecular weight of 76.1 or higher and 104.15 or lower has a boiling point of 160.5 ° C. or higher and 194 ° C. or lower. Used as a main ink medium together with ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 118.18 or more and 134.17 or less, ethylene glycol methyl ether (boiling point 124.5 ° C., molecular weight 76.1), ethylene glycol Ethyl ether (boiling point 135 ° C., molecular weight 90.12), ethylene glycol dimethyl ether (boiling point 85.2 ° C., molecular weight 90.12), ethylene glycol mononormal propyl ether (boiling point 149.8 ° C., molecular weight 104.15), ethylene glycol Over mono isopropyl ether (boiling point 141.8 ° C., molecular weight 104.15) is.
In particular, ethylene glycol mononormal propyl ether and ethylene glycol monoisopropyl ether are preferably used in order to prevent blurring of handwriting while preventing blur.

An ethylene glycol ether and / or diethylene glycol ether having a boiling point of 160.5 ° C. or higher and 194 ° C. or lower and a molecular weight of 118.18 or higher and 134.17 or lower, and a boiling point of 85.2 ° C. or higher and 149.8 ° C. or lower. The weight ratio of ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 76.1 or more and 104.15 or less is preferably 1: 1 or more and 20: 1 or less from the viewpoint of the size of the swollen gel particles. When the amount of ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 85.2 ° C. or higher and 149.8 ° C. or lower and molecular weight of 76.1 or higher and 104.15 or lower is greater than 1: 1, the opening of the ball-point pen tip There is a risk that the amount of evaporation from the water will increase, and the weight will be reduced during long-term storage, making it impossible to write.
If the amount of ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 85.2 ° C. or higher and 149.8 ° C. or lower and a molecular weight of 76.1 or higher and 104.15 or lower is less than 20: 1, There is a possibility that the gel-like particles become too large, hindering the rotation of the ball and increasing the writing quality.

The compound represented by the general formula (Equation 1) has a boiling point of 160.5 ° C. or more and 194 ° C. or less and a molecular weight of 118.18 or more and 134.17 or less, and a boiling point of ethylene glycol ether and / or diethylene glycol ether. By using ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 76.1 to 104.15 in the range of 85.2 ° C. or higher and 149.8 ° C. or lower, the swelling is small, By evaporating from the solvent having a low boiling point as described above, the size of the gel-like particles grows to form a state in which the gel-like particles are covered, thereby preventing bottling. Specific examples thereof include PEMULEN TR-1, PEMULEN TR-2 (above, BF Goodrich, USA) and the like.
The amount used is preferably 0.1% by weight or more and less than 2% by weight based on the total amount of the ink. If it is less than 0.1% by weight, the gel-like particles will not be in a state of covering and cannot be prevented. On the other hand, when the amount is 2% by weight or more, the gel-like particles are likely to aggregate, and the gel-like particles do not reach the opening of the ball-point pen tip, so that the void cannot be prevented.

Furthermore, when polypropylene glycol is used in combination, the ink and the ink inside the ball-like pen tip are in a state where the gel-like particles are capped and the gel-like particles are capped. Ethylene glycol having a boiling point in the range of 85.2 ° C. or higher and 149.8 ° C. or lower and a molecular weight of 76.1 or higher and 104.15 or lower as it volatilizes and passes through a state where the gel-like particles are covered. By supplementing ether and / or diethylene glycol ether even temporarily, scumming can be suppressed by arranging abundant ink inside the state where the gel-like particles are covered. Specific examples of polypropylene glycol include Uniol D400, 700, 1000, 1200, 2000, 4000 (manufactured by Nippon Oil & Fats Co., Ltd.), Exenol 420, 720, 1020, 2020, 3020, 3021 and 510 (above manufactured by Asahi Glass Co., Ltd.).
These can be used alone or in combination of two or more, and the amount used is preferably 0.5% by weight or more and 10% by weight or less based on the total amount of the ink. If the amount is less than 0.5% by weight, the effect of preventing the first brush blurring is reduced.

The ink of the present invention may be an oil-soluble resin for adjusting the viscosity and promoting dissolution of the dye, in addition to improving the fixing property and preventing the show-through of the handwriting. Oil-soluble resins include cyclohexanone, acetophenone, urea and other ketone and formaldehyde condensation resins, cyclohexanone condensation resins and hydrogenated resins, maleic acid resins, copolymers of styrene and maleic esters, styrene and Copolymers with acrylic acid or its esters, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetal, polyamides that are condensates of polymerized fatty acids and polyamines, epoxy resins, polyvinyl alkyl ethers, coumarone-indene resins, polyterpenes, xylene resins, Rosin resin and its hydrogenated product, rosin-modified maleic acid resin, vinylpyrrolidone-vinyl acetate copolymer, polymethacrylic acid ester, polyacrylic acid-polymethacrylic acid copolymer, polyoxyethylene and vinyl Such as Nord resin and the like.
These resins can be used alone or in combination. The amount used is preferably 0.05% by weight or more and 30% by weight or less based on the total amount of the oil-based ink composition for ballpoint pens.

The ink of the present invention is sheared to prevent ink leakage from the gap between the ball and the chip when not in use, and to prevent backflow of ink when the writing tip is left in an upright state (upright state). You may give thinning. As shear thinning agents, cellulose derivatives such as hydroxypropyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, ethyl cellulose, water-soluble polysaccharides such as hyaluronic acid, benzylidene sorbitol, silica, bentonite inorganic compounds, organic bentonite, etc. can also be used. is there.
In addition, when shear thinning is applied, the purpose is to make writing quality lighter by preventing leakage of ink for ballpoint pens when the pen tip is left facing down and by making the viscosity decrease during writing optimal. The shear thinning index at 25 ° C. is preferably 0.3 or more and 0.9 or less.

A dispersant may be used to disperse the pigment. Although what is normally used can be used, polyvinyl butyral is preferable.
In addition to the above components, organic solvents, lubricants and viscosity modifiers, rust preventives, antiseptics, antifoaming agents, anti-scratch agents, dispersants, and stringiness-imparting agents used as ink raw materials for oil-based ballpoint pens as necessary In addition, additives such as leveling property-imparting agents can be used in combination as long as the formation of gel-like particles is not inhibited.
As the organic solvent, a solvent usually used for oil-based inks for ballpoint pens can be used as long as it does not hinder the formation of gel particles. Specific examples include phenyl cellosolve, benzyl alcohol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene Examples include propylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, isobutyl diglycol, phenyl diglycol, phenyl triglycol, benzyl glycol, benzyl diglycol, benzyl triglycol, and hexylene glycol.
Lubricants are used to give smooth writing, but cutting oils, higher fatty acids, phosphate esters, acylamino acids, thiazoles, polyethylene glycols or their alkyl ethers form gel particles. Can be used as long as they are not hindered.
When using phosphoric esters, when used in combination with polyoxyethylene alkylamine, not only the lubricity but also the effect of suppressing scratching of the first brush is obtained. Furthermore, when used in combination with polypropylene glycol, the effect of suppressing initial brush blurring is enhanced.

In the present invention, it is usually possible to disperse the pigment by a general method. For example, a pigment, an ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 160.5 ° C. or more and 194 ° C. or less and a molecular weight of 118.18 or more and 134.17 or less and / or a boiling point of 85.2 ° C. or more and 149 After mixing ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 76.1 or less and 104.15 or less with a dispersing agent and stirring uniformly with a propeller stirrer, etc., Disperse the pigment. A dispersing machine such as a roll mill, a ball mill, a sand mill, a bead mill, or a homogenizer is appropriately selected depending on the amount of solvent of the ink and the pigment concentration.
In order to produce the ink, a dye, the pigment dispersed above, an oil-soluble resin, an ethylene glycol ether having a boiling point in the range of 160.5 ° C. or higher and 194 ° C. or lower and a molecular weight of 118.18 or higher and 134.17 or lower; And / or diethylene glycol ether, ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 85.2 ° C. to 149.8 ° C. and a molecular weight of 76.1 to 104.15, and the above general formula (Formula 1) After sufficiently mixing and stirring the compound represented by the above with a stirrer such as a homomixer, other components such as a viscosity adjusting agent, a solvent, an oily dye for adjusting the color tone, a lubricant, etc. are mixed to make it even more uniform. In some cases, the mixed ink is further dispersed with a disperser, or the obtained ink is filtered. It is or or excluding coarse particles and insoluble components over the centrifuge no problem.
In addition, the viscosity of the ink of the present invention is 500 mPa · s or more and 5000 mPa · s or less when the shear rate is 1 / s in consideration of ink discharge or ink leakage from the pen tip when the pen tip is left facing down. Preferably, when shear thinning is applied, it is preferable that the viscosity be 1000 mPa · s or more and 100,000 mPa · s or less at 1 / s, and 300 mPa · s or more and 5000 mPa · s or less at 10 / s.

Hereinafter, it demonstrates still in detail based on an Example and a comparative example. In each example, “part” simply means “part by weight”.
Example 1
Printex 35 (carbon black, manufactured by Degussa Huls Japan Co., Ltd.) 5.0 parts Neo Super Blue C-555 (CI Solvent Blue 70, manufactured by Chuo Synthetic Chemical Co., Ltd. 17.3 parts SPILON RED C-GH (Oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.) 4.6 parts VALIFAST YELLOW 1151 oil-based dye, manufactured by Orient Chemical Industry Co., Ltd.)
3.1 parts diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15)
44.4 parts ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15) 17.0 parts ESREC BL-1 (polyvinyl butyral, dispersant, manufactured by Sekisui Chemical Co., Ltd.) 1.6 parts PEMULEN TR -2 (compound represented by the above general formula (Formula 1), manufactured by BF Goodrich, USA) 1.0 part Phosphanol LB400 (phosphate ester surfactant, lubricant, Toho Chemical Co., Ltd.) )) 1.5 parts Amite 105 (POE coconut amine, surfactant, manufactured by Kao Corporation) 1.0 parts Uniol D2000 (polypropylene glycol, first brush anti-scratch agent, Nippon Oil & Fats Co., Ltd.)
3.5 parts Among the above components, the total amount of diethylene glycol monomethyl ether, the total amount of ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15), and the total amount of ESREC BL-1 are stirred at 70 ° C. After mixing and dissolving, this was allowed to cool to room temperature, and then the entire amount of Printex 35 was added, and 10 times were passed through a dyno mill (bead mill, manufactured by Shinmaru Enterprise Co., Ltd.) using zirconia beads having a diameter of 0.3 mm. A paste of was obtained.
Next, the total amount of Neo Super Blue C-555, the total amount of SPILON RED C-GH, the total amount of VALIFAST YELLOW 1151, the total amount of Phosphanol LB400, the total amount of Amate 105, the total amount of Uniol D2000, The total amount of PEMULEN TR-2 was added, and the mixture was stirred and mixed at 70 ° C. for 3 hours, and then allowed to cool to room temperature to obtain a black ballpoint pen oil ink.
The viscosity of this product was 1420 mPa · s at a shear rate of 1 / s.

(Example 2)
SPILON VIOLET C-RH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.)
15.0 parts SPILON YELLOW C-GNH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.)
10.0 parts ethylene glycol mononormal butyl ether (boiling point 171.2 ° C, molecular weight 118.18) 31.0 parts ethylene glycol mononormal propyl ether (boiling point 149.8 ° C, molecular weight 104.15) 29.7 parts Hilac 110H (Ketone resin, viscosity modifier, manufactured by Hitachi Chemical Co., Ltd.) 6.0 parts PEMULEN TR-2 (compound represented by the above general formula (Formula 1), BF Goodrich, USA) 1.5 parts Naimine O-205 (polyoxyethylene oleylamine, surfactant, manufactured by NOF Corporation) 1.0 part Phosphanol RP710 (POE alkyl ether phosphate, lubricant, manufactured by Toho Chemical Industry Co., Ltd.) 0.8 Uniol D1200 (polypropylene glycol, anti-scratch agent for the first brush, Nippon Oil & Fats Co., Ltd.)
Product) 5.0 parts The above ingredients were stirred at 70 ° C. and dissolved uniformly to obtain a black oil-based ink for ballpoint pens. The viscosity at a shear rate of 1 / s was 3380 mPa · s.

(Example 3)
NOVOPERM RED F3RK70 (C.I. Pigment Red 170,
5.0 parts SPILON RED C-GH 15.6 parts SPILON RED C-BH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.) 0.8 parts SPILON YELLOW C-GNH 3.8 Part ESREC BL-1 1.6 parts PEMULEN TR-2 (compound represented by the above general formula (formula 1), BF Goodrich, USA) 0.6 part ethylene glycol monoisobutyl ether (boiling point 160.5 ° C, molecular weight 118.18)
53.1 parts ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15) 13.5 parts Phosphanol RP710 1.5 parts Niimine O-205 1.0 part Uniol D2000 3.5 parts Of these, the total amount of ethylene glycol monoisobutyl ether, the total amount of ethylene glycol monoisopropyl ether, and the total amount of S-LEC BL-1 were stirred and mixed and dissolved at 70 ° C., then allowed to cool to room temperature, and then NOVOPER RED F3RK70 The whole amount was added and passed through 10 times with a dyno mill (bead mill, manufactured by Shinmaru Enterprise Co., Ltd.) using zirconia beads having a diameter of 0.3 mm to obtain a red paste.
This paste was then added to the total amount of SPILON RED C-GH, the total amount of SPILON RED C-BH, the total amount of SPILON YELLOW C-GNH, the total amount of phosphanol RP710, the total amount of Naimine O-205, and PEMULEN TR. -2 was added, and the mixture was stirred and mixed at 70 ° C. for 3 hours, and then allowed to cool to room temperature to obtain a red oil-based ink for ballpoint pens. The viscosity of this product was 660 mPa · s at a shear rate of 1 / s.

Example 4
SPILON VIOLET C-RH 15.0 parts SPILON YELLOW C-GNH 10.0 parts ethylene glycol monoisobutyl ether (boiling point 160.5 ° C., molecular weight 118.18)
56.5 parts ethylene glycol mononormal propyl ether (boiling point 149.8 ° C., molecular weight 104.15) 9.1 parts Hilac 110H 6.0 parts PEMULEN TR-1 (compound represented by the above general formula (formula 1), B. F. Goodrich, USA) 1.0 part Nymine O-205 (polyoxyethylene oleylamine, manufactured by NOF Corporation)
1.0 part Phosphanol RP710 (POE alkyl ether phosphate, manufactured by Toho Chemical Industry Co., Ltd.)
1.0 part Uniol D700 (polypropylene glycol, anti-scratch agent for the first brush, Nippon Oil & Fat Co., Ltd.)
Product) 0.4 part The above ingredients were stirred at 70 ° C. and dissolved uniformly to obtain a black oil-based ink for ballpoint pens. The viscosity at a shear rate of 1 / s was 1880 mPa · s.

(Example 5)
SPILON VIOLET C-RH 15.0 parts SPILON YELLOW C-GNH 10.0 parts diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15)
52.0 parts ethylene glycol mononormal propyl ether (boiling point 149.8 ° C., molecular weight 104.15) 8.1 parts phenyl glycol 5.0 parts PEMULEN TR-1 (compound represented by the above general formula (Formula 1), B F. Goodrich, USA) 0.6 parts PVP-k90 4.0 parts Nymeen O-205 (polyoxyethylene oleylamine, manufactured by Nippon Oil & Fats Co., Ltd.)
1.0 part Phosphanol RP710 (POE alkyl ether phosphate, manufactured by Toho Chemical Industry Co., Ltd.)
1.5 parts Uniol D4000 (polypropylene glycol, anti-scratch agent for the first brush, Nippon Oil & Fats Co., Ltd.)
2.8 parts The above components were stirred at 70 ° C. and dissolved uniformly to obtain a black ballpoint pen oil-based ink. The viscosity at a shear rate of 1 / s was 1830 mPa · s.

(Example 6)
HOSTAPERM P-BFS (CI Pigment Blue 15: 4, manufactured by Clariant Japan Co., Ltd.) 7.0 parts SPILON RED C-BH 4.0 parts Neo Super Blue C-555 16.0 parts ESREC BL-1 6 parts PEMULEN TR-1 (compound represented by the above general formula (Formula 1), BF Goodrich, USA) 0.8 parts diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15)
25.0 parts ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15) 39.6 parts Phosphanol RP710 1.5 parts Niimine O-205 1.0 part Uniol D2000 3.5 parts Among them, the total amount of diethylene glycol monomethyl ether, the total amount of ethylene glycol monoisopropyl ether, and the total amount of S-REC BL-1 were stirred and mixed and dissolved at 70 ° C., and then allowed to cool to room temperature, and then the total amount of HOSTAPERM P-BFS Was added 10 times with a dyno mill (bead mill, manufactured by Shinmaru Enterprise Co., Ltd.) using zirconia beads having a diameter of 0.3 mm to obtain a red paste.
Next, the total amount of SPILON RED C-BH, the total amount of Neo Super Blue C-555, the total amount of phosphanol RP710, the total amount of Naimine O-205, and the total amount of PEMULEN TR-1 were added to this paste, The mixture was stirred and mixed at 0 ° C. for 3 hours, and then allowed to cool to room temperature to obtain a red ballpoint pen oil ink. The viscosity of this product was 920 mPa · s at a shear rate of 1 / s.

(Example 7)
HOSTAPERM P-BFS (CI Pigment Blue 15: 4, manufactured by Clariant Japan Co., Ltd.) 7.0 parts SPILON RED C-BH 4.0 parts Neo Super Blue C-555 16.0 parts ESREC BL-1 6 parts PEMULEN TR-2 (compound represented by the above general formula (Equation 1), BF Goodrich, USA) 0.5 parts diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15)
61.9 parts ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15) 3.0 parts Phosphanol RP710 1.5 parts Niimine O-205 1.0 part Uniol D2000 3.5 parts Among them, the total amount of diethylene glycol monomethyl ether, the total amount of ethylene glycol monoisopropyl ether, and the total amount of S-REC BL-1 were stirred and mixed and dissolved at 70 ° C., and then allowed to cool to room temperature, and then the total amount of HOSTAPERM P-BFS Was added 10 times with a dyno mill (bead mill, manufactured by Shinmaru Enterprise Co., Ltd.) using zirconia beads having a diameter of 0.3 mm to obtain a red paste.
Next, the total amount of SPILON RED C-BH, the total amount of Neo Super Blue C-555, the total amount of Phosphanol RP710, the total amount of Naimine O-205, and the total amount of PEMULEN TR-2 were added to this paste, The mixture was stirred and mixed at 0 ° C. for 3 hours, and then allowed to cool to room temperature to obtain a red ballpoint pen oil ink. The viscosity of this product was 920 mPa · s at a shear rate of 1 / s.

(Example 8)
In Example 1, the same procedure was performed except that ethylene glycol methyl ether (boiling point 124.5 ° C., molecular weight 76.1) was added instead of ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15). A black ballpoint pen oil-based ink was obtained. The viscosity of this ink was 993 mPa · s at a shear rate of 1 / s.

Example 9
In Example 2, the same procedure was followed except that ethylene glycol ethyl ether (boiling point 135 ° C., molecular weight 90.12) was added instead of ethylene glycol mononormal propyl ether (boiling point 149.8 ° C., molecular weight 104.15). A black oil-based ink for ballpoint pens was obtained. The viscosity of this ink was 2640 mPa · s at a shear rate of 1 / s.

(Example 10)
In Example 3, the same procedure was followed except that ethylene glycol dimethyl ether (boiling point 85.2 ° C., molecular weight 90.12) was added instead of ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15). A black oil-based ink for ballpoint pens was obtained. The viscosity of this ink was 530 mPa · s at a shear rate of 1 / s.

(Comparative Example 1)
In the same manner as in Example 1, except that isobutyl diglycol (boiling point 220 ° C., molecular weight 162.23) was added instead of diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15), black oil-based ink for ballpoint pens was used. Got. The viscosity of this ink was 1530 mPa · s at a shear rate of 1 / s.

(Comparative Example 2)
In Example 2, the same procedure was followed except that ethylene glycol monohexyl ether (boiling point 208.1 ° C., molecular weight 146.23) was used instead of diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15). An oil-based ink for ballpoint pens was obtained. The viscosity of this ink was 2390 mPa · s at a shear rate of 1 / s.

(Comparative Example 3)
In Example 2, the same procedure was followed except that ethylene glycol mononormal propyl ether (boiling point 149.8 ° C., molecular weight 104.15) was removed and diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15) was added accordingly. Oil-based ink for ballpoint pens was obtained. The viscosity of this ink was 3530 mPa · s at a shear rate of 1 / s.

(Comparative Example 4)
In Example 2, the same procedure was followed except that diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15) was removed and ethylene glycol monoisopropyl ether (boiling point 141.8 ° C., molecular weight 104.15) was added accordingly. An oil-based ink for ballpoint pens was obtained. The viscosity of this ink was 2640 mPa · s at a shear rate of 1 / s.

(Comparative Example 5)
In Example 2, PEMULEN TR-2 (the compound represented by the above general formula (Equation 1), BF Goodrich, USA) was pulled out, and to that extent ESREC BH-3 (polyvinyl butyral, viscosity modifier, Sekisui Chemical Co., Ltd.) A black oil-based ink for ballpoint pens was obtained in the same manner except that Kogyo Co., Ltd. was added. The viscosity of this ink was 2840 mPa · s at a shear rate of 1 / s.

(Comparative Example 6)
NOVOPERM RED F3RK70 (CI Pigment Red 170, manufactured by Clariant Japan Co., Ltd.) 5.0 parts SPILON RED C-GH 15.6 parts SPILON RED C-BH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.) 0.8 parts SPILON YELLOW C-GNH 3.8 parts ESREC BL-1 1.6 parts PEMULEN TR-2 (compound represented by the above general formula (Formula 1), manufactured by BF Goodrich, USA) 0. 8 parts Hilac 110H 4.0 parts ethylene glycol monophenyl ether (boiling point 244.7 ° C., molecular weight 138.17)
50.2 parts ethylene glycol monobenzyl ether (boiling point 256.0 ° C., molecular weight 152.19)
12.2 parts Phosphanol RP710 1.5 parts Nymine O-205 1.0 part Uniol D2000 3.5 parts Among the above components, the total amount of ethylene glycol monophenyl ether, the total amount of ethylene glycol monobenzyl ether, and ESREC The whole amount of BL-1 was stirred at 70 ° C., mixed and dissolved, and then allowed to cool to room temperature, then the whole amount of NOVOPERM RED F3RK70 was added, and the diameter was 0.3 mm with a dyno mill (bead mill, manufactured by Shinmaru Enterprise Co., Ltd.). A red paste was obtained by passing 10 times using zirconia beads.
This paste was then added to the total amount of SPILON RED C-GH, the total amount of SPILON RED C-BH, the total amount of SPILON YELLOW C-GNH, the total amount of phosphanol RP710, the total amount of Naimine O-205, and PEMULEN TR. -2 and the total amount of Hilac 110H were added, stirred and mixed at 70 ° C. for 3 hours, and then allowed to cool to room temperature to obtain a red ballpoint pen oil ink. The viscosity of this product was 1220 mPa · s at a shear rate of 1 / s.

(Comparative Example 7)
SPILON VIOLET C-RH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.)
15.0 parts SPILON YELLOW C-GNH (oil-based dye, manufactured by Hodogaya Chemical Co., Ltd.)
10.0 parts diethylene glycol monomethyl ether (boiling point 194 ° C., molecular weight 120.15)
34.5 parts ethylene glycol mononormal propyl ether (boiling point 149.8 ° C., molecular weight 104.15) 26.6 parts Hilac 110H (ketone resin, viscosity modifier, manufactured by Hitachi Chemical Co., Ltd.) 6.0 parts PVP- k90 (polyvinyl pyrrolidone, viscosity modifier, manufactured by ISP, USA) 6.0 parts Niimine O-205 (polyoxyethylene oleylamine, surfactant, manufactured by NOF Corporation) 1.0 part Phosphanol RP710 (POE) Alkyl ether phosphoric acid, lubricant, manufactured by Toho Chemical Industry Co., Ltd.) 0.7 parts Uniol D1200 (polypropylene glycol, anti-scratch brush, manufactured by Nippon Oil & Fats Co., Ltd.) 0.2 parts The above ingredients are stirred at 70 ° C. And uniformly dissolved to obtain a black oil-based ink for ballpoint pens. The viscosity at a shear rate of 1 / s was 1210 mPa · s.

As mentioned above, the following test was done about the ink composition obtained by the Example and the comparative example. The results are shown in Table 1.
The viscosity is measured by attaching a φ20 parallel rotor to a rheometer VAR-100 manufactured by Jusco International Co., Ltd., adjusting the clearance between the sample stage to 0.2 mm, and setting the shear rate to 1 at a constant speed. / S was performed at 25 ° C.

(Preparation of test ballpoint pen)
The oil-based ballpoint pen ink obtained in the above Examples and Comparative Examples was filled with 0.3 g of the parts cleaned by removing the ink from a commercially available oil-based ballpoint pen (Jetstream, manufactured by Mitsubishi Pencil Co., Ltd. (ball diameter φ0.7)). Then, centrifugal force was applied with a centrifuge to degas bubbles in the ink, and a test ballpoint pen was produced.

  Bite test: The size of the area where ink adheres to the area other than the handwriting on the paper when the "Date of Diet" is repeatedly written on a 400-character manuscript paper (manufactured by KOKUYO Co., Ltd., product number: K-10) The length (length of the longest part) and number were evaluated.

  As described above in detail, the ink of the present invention relates to an oil-based ink for ballpoint pens that is less likely to cause voids.

Claims (1)

A colorant, an ethylene glycol ether and / or diethylene glycol ether having a boiling point in the range of 160.5 ° C. or more and 194 ° C. or less and a molecular weight of 118.18 or more and 134.17 or less, and a boiling point of 85.2 ° C. or more and 149.8 ° C. An oil-based ink for ballpoint pens comprising at least an ethylene glycol ether and / or diethylene glycol ether having a molecular weight of 76.1 or more and 104.15 or less in the following range and a compound represented by the following general formula (Formula 1).