JP6611224B2 - Ballpoint pen - Google Patents

Description

The present invention relates to a ballpoint pen. Furthermore, it is related with the ball-point pen using the oil-based ink composition for ball-point pens which can suppress corrosion of a chip | tip.

  Conventionally, high-viscosity ink of 10,000 to tens of thousands of mPa · s has been used in oil-based ballpoint pens. Since the ballpoint pen using the high viscosity oil-based ink has a heavy writing feeling, an attempt to improve the lubricity between the ball constituting the chip and the ball seat by adding a fatty acid such as oleic acid to lighten the writing feeling. However, the ball seat was worn by writing with high writing pressure or writing over long distances. Therefore, a technique using benzotriazole or tolyltriazole as a lubricant has been disclosed in order to suppress the above-described wear (see, for example, Patent Document 1).

  In the technology of the patent document, benzotriazole or tolyltriazole as a lubricant alone or in combination with a higher fatty acid (oleic acid), benzotriazole or tolyltriazole forms a film on the surface of the ball seat, Lubricity (writing feeling) is improved by reducing the friction between the ball and the ball seat.

JP 2003-64290 A

  However, when the oil-based ink having the above configuration is stored in the form of a ballpoint pen for a long period of time, the ball seat will cause metal corrosion, resulting in inconveniences such as inability to obtain uniform handwriting and increased writing feeling. It was. In particular, when higher fatty acids are used in combination to further improve lubricity, or when the metal constituting the chip contains copper, corrosion is significant and writing may become impossible.

The present invention can impart an excellent lubricating effect even with oil-based inks with high ink viscosity, and even when used in combination with higher fatty acids or when the chip contains copper, the chip will corrode over time. The present invention provides a ballpoint pen that incorporates an oil-based ink composition for ballpoint pens that can exhibit excellent writing performance with a light writing feel and uniform handwriting over a long period of time.

The present invention relates to a colorant, an organic solvent selected from ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and 1- ( Any of 2-ethylhexylaminomethyl) benzotriazole, 1- (2-ethylhexylaminomethyl) methylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole The ball-point pen which contains the oil-based ink composition for ball-point pens containing the benzotriazole derivative which is, and the ball-point pen tip is a product made from white and white is a requirement.
Furthermore, it is a requirement that a higher fatty acid is contained in the ink composition and that the benzotriazole derivative is added in the range of 0.1 to 10% by weight in the total amount of the ink composition.

  According to the present invention, even if it is an oil-based ink having a high ink viscosity, an excellent lubricating effect is obtained, and even when a higher fatty acid is used or when a white chip containing copper is used, it depends on long-term aging. It is possible to provide a ballpoint pen that incorporates an oil-based ink composition for ballpoint pens that does not cause chip corrosion and can exhibit excellent writing performance with a light writing feeling and uniform handwriting over a long period of time.

  In the present invention, an excellent lubricating effect can be obtained even when the viscosity is high by adding the benzotriazole derivative of the general formula (1) to the oil-based ink composition for ballpoint pens. Further, by using a higher fatty acid in combination, a higher lubricating performance can be obtained, and an oil-based ink capable of suppressing metal corrosion such as chips conventionally caused by the combined use can be obtained.

The benzotriazole derivative of the general formula (1) is a benzotriazole having an aminomethyl group having a branched alkyl, and exhibits higher lubricating performance than the conventional benzotriazole and tolyltriazole by the action of the aminomethyl group. Moreover, it becomes possible to suppress metal corrosion when a higher fatty acid is used in combination.
Examples of the benzotriazole derivatives include 1- (2-ethylhexylaminomethyl) benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- (2-ethylhexyl). And aminomethyl) methylbenzotriazole and 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole.

  The benzotriazole derivative may be used alone or in combination with a higher fatty acid, and is not particularly limited, but is preferably 0.1% by weight to 10% by weight, preferably 0.8% in the ink composition. It is applied in the range of 5% to 5% by weight. In the blending amount, particularly high lubricating performance can be obtained.

The higher fatty acid is conventionally added to oil-based inks as a lubricant, and can be used in combination with the benzotriazole derivative to improve lubricating performance.
As the higher fatty acids, higher fatty acids having 6 to 22 carbon atoms, for example, saturated fatty acids such as lauric acid, myristic acid and stearic acid, and unsaturated fatty acids such as oleic acid, linolenic acid and linoleic acid are applicable. The higher fatty acids may be used alone or in combination of two or more, and are preferably applied in the range of 0.1% by weight to 10% by weight in the oil-based ink composition.

  Furthermore, a general-purpose lubricant can be added as required, and nonionic surfactants having a long-chain alkyl group, polyether-modified silicone oil, thiophosphite tri (alkoxycarbonylmethyl ester) and thiophosphite trioxide. (Alkoxycarbonylethyl ester) thiophosphorous triester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid diester, or These metal salts, ammonium salts, amine salts, alkanolamine salts and the like can be exemplified.

Conventional organic solvents for oil-based ballpoint pens can be used as the organic solvent, for example, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, tert -Amyl alcohol, benzyl alcohol, ethylene glycol, hexylene glycol, diethylene glycol, propylene glycol, benzyl glycol, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene Glycol monophenyl ether, diethylene glycol monoethyl ether Diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monophenyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol Propylene glycol monophenyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 3-methyl-1,3-butanediol, 1,3-butanediol, n-heptane, n-octane, isooctane, methylcyclohexane , Ethylcyclohexane, toluene, xylene, ethylbenzene, methyl isobutyl ketone, methyl n-pro Luketone, methyl n-butyl ketone, di-n-propyl ketone, n-butyl formate, isobutyl formate, methyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl propionate, n-butyl propionate And methyl butyrate, ethyl butyrate, dimethyl carbonate, diethyl carbonate, propyl carbonate and the like.
The organic solvent may be used singly or in combination of two or more in the ink composition in the range of 40 to 95% by weight.

As the colorant, general-purpose dyes and pigments conventionally applied to oil-based inks are appropriately used.
Examples of the dye include organic solvent-soluble dyes classified as solvent dyes in the color index.
Specific examples of the solvent dye include Balifast Black 3806 (CI Solvent Black 29), 3807 (Trimethylbenzylammonium salt of the dye of CI Solvent Black 29), Spirit Black SB (C.I. Solvent Black 5), Spiron Black GMH (CI Solvent Black 43), Bali Fast Red 1308 (Salt Form of Dye of CI Basic Red 1 and Dye of CI Acid Yellow 23), Bali Fast Yellow AUM (Salt of CI Basic Yellow 2 dye and CI Acid Yellow 42 dye), Spiron Yellow C2GH (organic acid salt of CI Basic Yellow 2 dye) Ron Violet CRH (CI Solvent Violet 8-1), Balifu Strioviolet 1701 (salt salt of CI Basic Violet 1 and CI Acid Yellow 42 dyes), Spiron Red CGH (organic acid salt of CI Basic Red 1 dye), Spiron Pink BH (C.I. CI Solvent Red 82), Nigrosine Base EX (CI Solvent Black 7), Oil Blue 613 (CI Solvent Blue 5), Neozapon Blue 808 (CI Solvent Blue 70) and the like. It is done.
Examples of the pigment include inorganic pigments such as carbon black, ultramarine, and titanium dioxide pigment, azo pigments, phthalocyanine pigments, indigo pigments, thioindigo pigments, selenium pigments, quinacridone pigments, anthraquinone pigments, selenium pigments, diketopyrrolo Organic pigments such as pyrrole pigments, dioxazine pigments, perylene pigments, perinone pigments, isoindolinone pigments, aluminum pigments, metal pigments whose surfaces are treated with colored resins, transparent or colored transparent films such as aluminum Metallic pigment, gold, silver, platinum, copper, with a thickness of 0.01 to 0.1 μm, obtained by peeling a metallic vapor deposited film such as aluminum formed on a substrate such as a metallic luster pigment, film, etc. Colloidal particles with an average particle size selected from 5 to 30 nm, fluorescent pigments, luminous pigments, thermal discoloration Pigments, natural mica as a core material, synthetic mica, glass pieces, alumina, pearl pigment and the like to the surface of the transparent film pieces were coated with a metal oxide such as titanium oxide.
The colorant may be used alone or in combination of two or more, and is used in the range of 3 to 40% by weight in the ink composition.

Furthermore, a resin can be added for the purpose of imparting blurring of handwriting, improving fixability, fastness and the like. The resin is not particularly limited as long as it is soluble in the organic solvent, and examples thereof include ketone resins, amide resins, alkyd resins, rosin-modified resins, rosin-modified phenol resins, and phenol resins. , Xylene resin, polyvinyl butyral resin, terpene resin, coumarone-indene resin, polyvinyl pyrrolidone, polyethylene oxide, polymethacrylate, ketone-formaldehyde resin, α- and β-pinene / phenol polycondensation resin, polyvinyl butyral resin, acrylic Examples thereof include resins and polyacrylic acid-polymethacrylic acid copolymers.
These resins may be used singly or in combination of two or more, and are used in the range of 0.5 to 40% by weight, preferably 1 to 35% by weight in the ink composition. If the amount is less than 0.5% by weight, sufficient effects such as suppression of handwriting on paper, improvement of fixing property, imparting fastness and the like cannot be exerted. If the amount exceeds 40% by weight, the solubility of the resin in the solvent decreases. In addition, the fluidity of the ink may be reduced.

Furthermore, in the oil-based ink composition of the present invention, an antioxidant, an ultraviolet absorber, a rust inhibitor, a viscosity modifier, a pigment dispersant, an antifoaming agent, and a shear thinning agent are provided in addition to the above components as necessary. Various additives such as surfactants can be used.
The additive is a so-called conventional additive, and can be appropriately used as necessary from known compounds.

As the antioxidant, dibutylhydroxytoluene, nordihydroxytoluene, flavonoids, butylhydroxyanisole, ascorbic acid derivatives, α-tocopherol, catechins and the like can be used.
As UV absorbers, 2- (2'-hydroxy-3'-t-butyl 5'-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) Benzotriazole, p-benzoic acid-2-hydroxybenzophenone, and the like can be used.
As the rust preventive agent, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin and the like can be used.
As the antifoaming agent, dimethylpolysiloxane or the like can be used.

Further, by adding a shear thinning agent, it is possible to prevent the ink from flowing backward when the writing tip is left facing upward (upright state).
As the shear thinning agent, a conventionally known compound can be used. For example, a crosslinkable acrylic resin, a crosslinkable acrylic resin emulsion type, a crosslinkable N-vinylcarboxylic acid amide polymer or a copolymer. Non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer Non-crosslinked N-vinylcarboxylic acid amide polymer or copolymer aqueous solution, hydrogenated castor oil, fatty acid amide wax, oxidized polyethylene wax and other waxes , Fatty acid metal salts such as aluminum stearate, aluminum palmitate, aluminum octylate, aluminum laurate, dibenzylidene sorbitol, dextrin fatty acid ester, N-acyl amino acid compound, smectite inorganic compound, montmorillonite inorganic compound, bentonite inorganic Compound, Kutoraito phosphate mineral, silica and the like.

The structure of the writing tip (tip) of the ballpoint pen filled with the oil-based ink composition for the ballpoint pen is effective by a conventional general-purpose mechanism, and the ball holder in which the vicinity of the tip of the metal pipe is pressed and deformed inward from the outer surface. A chip formed by holding a ball in the holding part, or a chip formed by holding a ball in a ball holding part formed by cutting a metal material with a drill or the like, or cutting a metal pipe or metal material A ball or the like held by a chip formed by processing is urged forward by a spring body can be applied. In particular, in the present invention, metal corrosion over time can be suppressed, and therefore it is possible to use a material containing copper such as white and white which is inexpensive and can provide a soft writing feeling.
Moreover, the said ball | bowl can apply the general purpose thing which consists of a cemented carbide alloy, stainless steel, a ruby, a ceramic, etc., and the thing of the range of diameter 0.1mm-2.0mm, Preferably 0.2mm-1.0mm is suitable. Used for.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, or polyethylene terephthalate is preferably used as the shaft cylinder that accommodates the oil-based ink composition in terms of low ink evaporation and productivity.
In addition to directly connecting the tip to the shaft tube, the shaft tube and the chip may be connected via a connecting member.
The ink composition accommodated in the shaft cylinder includes a method of mounting an ink retaining member on the front of the shaft cylinder according to the viscosity, and storing the ink composition directly in the shaft cylinder, and a porous body or a fiber processed body It is also possible to use a method in which the ink composition is impregnated and accommodated.

Furthermore, by using a transparent, colored transparent, or translucent molded body as the shaft tube, it is possible to confirm the ink color, the remaining amount of ink, and the like.
The shaft tube may be a ballpoint pen refill that accommodates the refill in the outer shaft, or the shaft tube with the tip mounted on the tip itself is used as an ink container and directly in the shaft tube. You may fill with ink.

The ballpoint pen using the shaft tube can be applied to either a cap type or a retractable type. The retractable ballpoint pen is stored in the outer shaft with the writing tip provided on the ballpoint pen refill exposed to the outside air, and the writing tip protrudes from the opening of the outer shaft by the operation of the retracting mechanism. Anything can be used.
Examples of the operation method of the retracting mechanism include a knock type, a rotary type, and a slide type.
The knock type has a knock portion on the outer shaft rear end portion or the outer shaft side surface, and by pressing the knock portion, the writing pen tip portion of the ballpoint pen refill is caused to protrude or retract from the outer shaft front end opening portion, or on the outer shaft. By pressing the provided clip portion, a configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the outer shaft front end opening portion can be exemplified.
The rotary type can be exemplified by a configuration in which a rotating portion (rear shaft or the like) is provided on the outer shaft, and the writing tip portion of the ballpoint pen refill is projected and retracted from the outer shaft front end opening by turning the rotating portion.
The slide type has a slide part on the side surface of the shaft tube, and the writing tip part of the ball-point pen refill is projected and retracted from the front end opening part of the outer shaft by operating the slide, or the clip part provided on the outer shaft is slid. By doing so, it is possible to exemplify a configuration in which the writing tip portion of the ballpoint pen refill is projected and retracted from the front end opening portion of the outer shaft.
The retractable ballpoint pen may be a composite retractable ballpoint pen that accommodates a plurality of ballpoint pen refills in addition to the one that accommodates a single ballpoint refill in the outer shaft. Further, the ink storage tube constituting the ballpoint pen refill may be made of resin or metal.

An ink backflow preventer (liquid stopper) may be disposed at the rear end of the ink stored in the ballpoint pen refill.
As the ink backflow preventer, either liquid or solid can be used, and examples of the liquid ink backflow preventer include non-volatile media such as polybutene, α-olefin oligomer, silicone oil, and refined mineral oil. If desired, silica, aluminum silicate, swellable mica, fatty acid amide, fatty acid dextrin, and the like can be added to the medium. Moreover, a resin molding is mentioned as a solid ink backflow prevention body. The liquid and solid ink backflow preventers can be used in combination.

Examples will be described below, but the present invention is not limited to these examples.
The composition of oil-based inks for ballpoint pens of Examples and Comparative Examples is shown in the following table. In addition, the numerical value of a composition in a table | surface shows a weight part.

The contents of the raw materials in the table will be described along the note numbers.
(1) Product name: Spiron Black GMH-S, manufactured by Hodogaya Chemical Co., Ltd.
(2) Made by Orient Chemical Industry Co., Ltd., trade name: Bali Fast Violet 1701
(3) Product name: Bali Fast Blue 1621, manufactured by Orient Chemical Co., Ltd.
(4) Pigment dispersant, manufactured by Sekisui Chemical Co., Ltd., trade name: ESREC BL-10
(5) Product name: Naimine L207, manufactured by NOF Corporation
(6) Made by Hitachi Chemical Co., Ltd., trade name: Hilac 110H
(7) Product name: K-90, manufactured by ISP Japan Co., Ltd.
(8) 1- (2-ethylhexylaminomethyl) benzotriazole (9) 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole (10) 1- [N, N-bis (2-Ethylhexyl) aminomethyl] methylbenzotriazole

Preparation of ink Each ink was prepared by adding each component to an organic solvent and stirring at 60 ° C. with a disper at 400 rpm for 3 hours.

Preparation of ball-point pen refill In the ink containing cylinder connected to the tip of a polypropylene pipe, a white cutting tip (made by PREMEC, code. 2383) holding a carbide ball having a diameter of 0.7 mm rotatably. Ballpoint pen refills were obtained by filling the oil-based inks obtained in Examples and Comparative Examples.

  The ballpoint pen refill was placed horizontally at 20 ° C. for 3 years, and then the following test was performed using the ballpoint refill.

Writing test Each ball-point pen refill that has been confirmed to be writable is assembled into the exterior of the Super Grip manufactured by Pilot Corporation to form a ball-point pen, and then a handwritten spiral circle written on JIS P3201 writing paper A. The feeling was confirmed.

Corrosion test After the ball was pulled forward from the tip of each ballpoint pen refill, the ball seat portion of the tip was observed at 200 times and 1000 times using a microscope.

The test results are shown in the following table.

The contents of the test result evaluation symbols are as follows.
Writing test ○: A smooth writing feeling can be obtained stably.
X: It is a rough feeling or a heavy writing feeling.
Corrosion test ○: Metallic luster, no corroded part.
X: The metallic luster is lost, and further a corroded part is seen.

Claims (3)

A colorant, an organic solvent selected from ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and 1- (2-ethyl Benzotriazole which is any one of xylaminomethyl) benzotriazole, 1- (2-ethylhexylaminomethyl) methylbenzotriazole, and 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole A ballpoint pen that contains an oil-based ink composition for ballpoint pens containing a derivative, and the ballpoint pen tip is made of white and white.   The ballpoint pen according to claim 1, wherein a higher fatty acid is contained in the ink composition. The ballpoint pen according to claim 1 or 2, wherein the benzotriazole derivative is added in an amount of 0.1 to 10% by weight based on the total amount of the ink composition.