JP6049066B2 - Water-based ink composition for ballpoint pen and ballpoint pen incorporating the same - Google Patents

Description

  The present invention relates to a water-based ink composition for ballpoint pens. Furthermore, the present invention relates to a water-based ink composition for ballpoint pens having excellent lubricating performance and a ballpoint pen having high writing performance.

Conventionally, in a ballpoint pen incorporating a water-based ink having poor lubricity as compared with an oil-based ink, wear of the ball seat is likely to occur due to the rotation of the ball during writing. As a result, the ink flow path in the ballpoint pen tip may be deformed, resulting in defective ink ejection. For this reason, there is a problem that writing feeling is lost when writing, or writing defects such as handwriting blur are caused.
Therefore, in order to solve the above problems, attempts have been made to reduce wear of the ball seat by adding various compounds as a lubricant to the ink composition and improving the lubricating performance of the water-based ink (for example, (See Patent Documents 1 to 3).

JP 61-174278 A Japanese Patent Laid-Open No. 1-129081 JP-A-6-100824

The salt of N-acyl sarcosine used in Patent Document 1 is somewhat effective in an ink using a dye as a colorant, but particularly when a pigment that easily promotes wear of a ball seat is used. Further, seat wear could not be sufficiently suppressed, and ink ejection failure during writing sometimes occurred.
In addition, the dicarboxylic acid alkali salt and alkanolamide used in Patent Document 2 are effective in applying to an ink using a dye as a colorant, but a pigment that easily promotes wear of the ball seat. In the case of using, seat wear could not be sufficiently suppressed, resulting in ink ejection failure and shortening the writing distance.
On the other hand, the dicarboxylic acid monoamide used in Patent Document 3 can be applied without selecting a dye and a pigment as the colorant, but does not provide a sufficient lubricating effect. If the ball diameter is smaller than 0.4 mm, the number of rotations (rotational speed) of the ball with respect to the writing distance increases, which is a more severe condition, and seat wear tends to occur due to the longer writing distance. Become. Therefore, a more effective lubricant that can be applied to an extra fine ballpoint pen is required.

  In the case of using a pigment as a colorant, the present invention can suppress wear of the ball seat due to rotation of the ball by imparting a high lubricating effect to the water-based ink, which is a more disadvantageous condition for seat wear. Even when applied to an ultra-fine ballpoint pen, a water-based ink composition for ballpoint pens that can ensure good ink ejection properties over long distance writing and can maintain the same excellent writing feeling for the long term It provides a ballpoint pen that incorporates it.

The water-based ink composition for ballpoint pens of the present invention is required to contain at least a colorant, water, and polyoxyethylene polyoxypropylene alkyl ether phosphoric acid represented by the following general formula (1) .
Furthermore, it is a requirement that the colorant is a pigment.
Furthermore, it is a requirement that the ballpoint pen contains the water-based ink composition for ballpoint pens, and that the ballpoint pen includes a ball having a diameter of 0.4 mm or less at the writing tip.

  According to the present invention, high lubrication performance can be imparted, and the seat wear promoted by the pigment and the seat wear due to the high-speed rotation of the ball can be effectively suppressed. A water-based ballpoint pen ink composition capable of maintaining a uniform handwriting without causing poor handwriting such as blurring or blurring, and maintaining an excellent writing feeling equivalent to the initial for a long distance over a long period of time, and a ballpoint pen incorporating the same. Can be provided.

According to the present invention, by adding polyoxyethylene polyoxypropylene alkyl ether phosphoric acid to a water-based ink composition for ballpoint pens, a lubricating effect higher than that of the lubricant used so far is imparted, Abrasion can be effectively suppressed.
The polyoxyethylene polyoxypropylene alkyl ether phosphoric acid can be represented by, for example, the following general formula (1).

前記一般式（１）において、Ｒはアルキル基であり、ａ及びｂは付加モル数を示す整数である。前記アルキル基Ｒは、炭素数１２〜１８である置換基、例えば、ラウリル基、ミリスチル基、パルミチル基、セチル基、ステアリル基、オレイル基等が適用できる。中でも、汎用性が高く、少量の添加で効果を発現できる点から、ミリスチル基、セチル基、オレイル基が特に好ましい。
また、エチレンオキサイドの付加モル数を示すａは、３〜２０の範囲が好ましく、より好ましくは５〜１５の範囲である。プロピレンオキサイドの付加モル数を示すｂは、１〜２０の範囲が好ましく、より好ましくは３〜８の範囲である。これらの範囲内の付加モル数のものは、潤滑効果が高いため好適に用いられる。
尚、前記一般式（１）において、具体的には、ａが１０、ｂが５、Ｒがセチル基の組み合わせ、ａが５〜８、ｂが２、Ｒがミリスチル基の組み合わせ、ａが５〜８、ｂが２、Ｒがオレイル基の組み合わせが特に好ましい。
また、インキ中に添加する際には、アルカリ金属塩やアミン塩として適用することもできる。

In the general formula (1), R is an alkyl group, and a and b are integers indicating the number of added moles. As the alkyl group R, a substituent having 12 to 18 carbon atoms, for example, lauryl group, myristyl group, palmityl group, cetyl group, stearyl group, oleyl group and the like can be applied. Among them, a myristyl group, a cetyl group, and an oleyl group are particularly preferable because they are highly versatile and can exhibit an effect when added in a small amount.
Moreover, a which shows the addition mole number of ethylene oxide has the preferable range of 3-20, More preferably, it is the range of 5-15. B which shows the addition mole number of propylene oxide has the preferable range of 1-20, More preferably, it is the range of 3-8. Those having an added mole number within these ranges are preferably used because they have a high lubricating effect.
In the general formula (1), specifically, a is 10, b is 5, R is a combination of cetyl groups, a is 5 to 8, b is 2, R is a combination of myristyl groups, and a is 5 A combination of ˜8, b = 2 and R = oleyl group is particularly preferred.
Moreover, when adding in ink, it can also be applied as an alkali metal salt or an amine salt.

The polyoxyethylene polyoxypropylene alkyl ether phosphoric acid can be added in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the total amount of the ink composition.
If it is less than 0.1% by weight, it is difficult to obtain a desired lubricating effect, and even if it exceeds 5% by weight, no improvement in the effect is observed, so no further addition is required.

As the colorant, all dyes and pigments that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof will be exemplified below.
As the dye, an acid dye, a basic dye, a direct dye, or the like can be used.
Examples of the acid dye include New Coxin (CI. 16255), Tartrazine (CI. 19140), Acid Blue Black 10B (CI. 20470), Guinea Green (CI. 42085), Brilliant Blue FCF. (CI.42090), Acid Violet 6B (C.I.42640), Soluble Blue (C.I.42755), Naphthalene Green (C.I.44025), Eosin (C.I.45380), Phloxin (C.I. 45410), erythrosine (C.I. 45430), nigrosine (C.I. 50420), acid flavin (C.I. 56205) and the like are used.
Examples of basic dyes include chrysoidine (C.I. 11270), methyl violet FN (C.I. 42535), crystal violet (C.I. 42555), malachite green (C.I. 42000), Victoria blue FB ( CI 44045), rhodamine B (C.I. 45170), acridine orange NS (C.I. 46005), methylene blue B (C.I. 52015) and the like are used.
As direct dyes, Congo Red (C.I. 22120), Direct Sky Blue 5B (C.I. 24400), Violet BB (C.I. 27905), Direct Deep Black EX (C.I. 30235), Kaya Las Black G Conch (C.I. 35225), Direct Fast Black G (C.I. 35255), Phthalocyanine Blue (C.I. 74180) and the like are used.

Examples of the pigment include inorganic pigments such as carbon black and ultramarine blue, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as water-dispersed pigments that are finely and stably dispersed in an aqueous medium in advance using a surfactant or the like. For example, C.I. I. Pigment Blue 15: 3B [Product Name: S.P. S. Blue GLL, pigment content 22%, manufactured by Sanyo Color Co., Ltd.], C.I. I. Pigment Red 146 [Product Name: S.P. S. Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.], C.I. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.], C.I. I. Pigment Red220 / 166 [Product name: TC Red FG, pigment content: about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.].
As the fluorescent pigment, a fluorescent pigment in the form of fine particles of a synthetic resin in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used.
In addition, pearl pigments, gold and silver metallic pigments, phosphorescent pigments, white pigments such as titanium dioxide, metal powders such as aluminum, thermochromic compositions, photochromic compositions, perfumes, etc. directly or microcapsules Examples of the capsule pigments are as follows.

The thermochromic composition includes (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reversible thermochromic composition comprising a reaction medium that determines the temperature at which the color reaction occurs. The composition is suitable and is encapsulated in microcapsules and applied as a reversible thermochromic microcapsule pigment.
Examples of the reversible thermochromic composition include those described in Japanese Patent Publication No. 51-44706, Japanese Patent Publication No. 51-44707, Japanese Patent Publication No. 1-29398, etc., at a predetermined temperature (discoloration point). Discolored before and after, decolored state in the temperature range above the high temperature side discoloration point, color development state in the temperature range below the low temperature side discoloration point, only one specific state exists in the normal temperature range among the two states, The other state is maintained as long as the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. A heat decolorable microcapsule pigment in which a reversible thermochromic composition having relatively small characteristics (ΔH = 1 to 7 ° C.) is encapsulated in a microcapsule can be applied.
Furthermore, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. Reversible heat with color memory in a specific temperature range when the color changes in a low temperature range below the complete color development temperature or in a high temperature range above the complete color erase temperature. A heat-decolorable microcapsule pigment in which the color-changing composition is encapsulated in microcapsules is also applicable.
Specifically, as the reversible thermochromic composition having color memory, a complete color development temperature can be obtained only in a freezing room, a cold district, etc., that is, −50 to 0 ° C., preferably −40 to − 5 ° C., more preferably −30 to −10 ° C., and complete decoloring temperature obtained from a frictional heat generated by a friction body, a heating body such as a hair dryer, that is, 50 to 95 ° C., preferably 50 to 90 ° C. More preferably, by specifying the range of 60 to 80 ° C. and specifying the ΔH value of 40 to 100 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).

The colorant can be used singly or in combination of two or more, and is used in the range of 1 to 30% by weight, preferably 2 to 25% by weight in the ink composition.
The lubricant of the present invention is particularly effective in pigment-based inks because it exhibits a high lubricating effect even in water-based inks using pigments in which seat wear is more likely to proceed.

Further, if necessary, a conventional general-purpose water-soluble organic solvent compatible with water can be used. Specifically, ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono Examples include ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, and N-methyl-2-pyrrolidone.
In addition, the said water-soluble organic solvent can be used 1 type or in combination of 2 or more types, and is used in 2 to 60 weight%, Preferably it is 5 to 35 weight%.

  Furthermore, a water-soluble resin can be added in order to impart adhesion and viscosity to the paper surface. Examples of the water-soluble resin include alkyd resins, acrylic resins, styrene maleic acid copolymers, cellulose derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin. The water-soluble resin can be used alone or in combination of two or more, and is used in the range of 1 to 30% by weight in the ink composition.

In addition, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, 2,5-dimercapto- Rust preventives such as 1,3,4-thiadiazole, saponin, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3 , 5,6-tetrachloro-4- (methylsulfonyl) pyridine, etc., antiseptic or antifungal agent, urea, nonionic surfactant, sorbit, mannitol, sucrose, glucose, reduced starch hydrolyzate, pyrophosphate Wetting agents such as sodium, antifoaming agents, fluorosurfactants and noni that improve ink permeability The emissions-based surfactant may be used.
Furthermore, ascorbic acids, erythorbic acids, α-tocopherol, catechins, synthetic polyphenols, kojic acid, alkylhydroxylamine, oxime derivatives, α-glucosylrutin, α-lipoic acid, phosphonate, phosphinate, sulfite, sulfoxyl Bubbles can also be removed chemically by adding acid salts, dithionites, thiosulfates, thiourea dioxide or the like.
Further, oligomers of N-vinyl-2-pyrrolidone, oligomers of N-vinyl-2-piperidone, N-vinyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, ε-caprolactam, N-vinyl-ε-caprolactam By adding a thickening inhibitor such as an oligomer, it is possible to enhance the function in the intruding form.
Furthermore, other lubricants can be used in combination, for example, metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic surfactant, phosphate ester type surfactant, β-alanine type surfactant, N-acyl. Amino acids, N-acylmethyltaurine, 2,5-dimercapto-1,3,4-thiadiazole and its salts and oligomers, 3-amino-5-mercapto-1,2,4-triazole, thiocarbamate, dimethyldithiocarbamine Acid salts, α-lipoic acid, condensates of N-acyl-L-glutamic acid and L-lysine, salts thereof, and the like are used.

A shear thinning agent can also be added to the ink composition.
As the shear thinning agent, a water-soluble or dispersible substance is effective, and xanthan gum, welan gum, and succinoglycan whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose (average molecular weight) About 1,000 to 8 million), guar gum, locust bean gum and derivatives thereof, hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 mainly composed of alkyl esters of methacrylic acid, glucomannan, agar and carrageenan Such as carbohydrates having gelling ability extracted from seaweed such as benzylidene sorbitol and benzylidene xylitol or derivatives thereof, cross-linkable acrylic acid polymer, poly N-vinylcarboxylic acid amide, inorganic fine particles, nonion having HLB value of 8-12 Surfactant, dialki Examples thereof include metal salts and amine salts of sulfosuccinic acid, and even when N-alkyl-2-pyrrolidone and an anionic surfactant are used in combination in the ink composition, stable shear thinning can be imparted. .

Furthermore, an ink backflow preventer (liquid stopper) can be disposed at the rear end of the ink composition filled in the ink containing tube.
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 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.

The structure of the tip end (tip) of the ballpoint pen that is filled with the water-based ink composition for ballpoint pens is effective for a conventional general-purpose mechanism. 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.
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 0.15mm-1.0mm is suitable. Used for. In particular, when the ball diameter is as small as 0.4 mm or less, the number of rotations of the ball with respect to the writing distance increases, so that the ink of the present invention works more suitably. Therefore, as the ball diameter becomes smaller, such as 0.38 mm, 0.35 mm, 0.3 mm, 0.28 mm, 0.25 mm, 0.18 mm, etc., the ink of the present invention works very advantageously.
Among the ball materials, a cemented carbide ball having a high hardness is likely to cause seat wear, so that the water-based ink composition of the present invention is particularly useful.

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 water-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.
When the ink composition is low in viscosity, the ink composition accommodated in the shaft cylinder includes a method of mounting an ink retaining member at the front of the shaft cylinder and storing the ink composition directly in the shaft cylinder, Examples of the method include impregnating the ink composition into a material body or a fiber processed body.

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 outer shaft front end opening.
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.

Examples will be described below, but the present invention is not limited to these examples.
The composition of the water-based ink 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) Fuji Pigment Co., Ltd., trade name: Fuji SP Blue 6455 (solid content: 27.5%)
(2) Fuji Pigment Co., Ltd., trade name: Fuji SP Black 8065 (solid content: 25.0%)
(3) Product name: Water Black 191L (20% aqueous solution), manufactured by Orient Chemical Co., Ltd.
(4) Product name: Aluminum paste WXM0630 (solid content: 65.0%), manufactured by Toyo Aluminum Co., Ltd.
(5) POP (5) POE (10) Cetyl ether phosphate (6) POP (2) POE (5) Myristyl ether phosphate (7) POP (2) POE (8) Oleyl ether phosphate (8) POE ( 9) Lauryl ether phosphate (9) Product name: Proxel XL-2 manufactured by Avicia
(10) Alkali thickened acrylic emulsion, manufactured by Rohm & Haas Japan, trade name: Primal ASE-60
(11) Product name: Kelzan ST, manufactured by Sanki Co., Ltd.

Preparation of ink After adding each component to water and stirring at 400 ° C. for 1 hour with a disper at 20 ° C., those containing a shear thinning agent are added and stirred for another hour to add each ink. Prepared.

Preparation of Ink Backflow Preventing Body After adding 1.5 parts of fatty acid amide as a thickener to 98.5 parts of polybutene as a base oil, an ink backflow preventing body was obtained by kneading with 3 rolls.

Production of Ballpoint Pen A A stainless steel chip holding a cemented carbide ball having a diameter of 0.4 mm is attached to one end of a polypropylene pipe with the ink compositions of Examples 1, 2, 4 and Comparative Examples 1, 2, 4. After 1.0 g was filled in the fitted ballpoint pen refill and the ink backflow preventer was disposed at the rear end of the ink, the ballpoint pen refill was assembled on the outer shaft, and a cap was attached to prepare a sample ballpoint pen.

Production of Ballpoint Pen B The pen composition ballpoint pen (Hi-TecpointV5, manufactured by Pilot Corporation) having the pen tip for holding a cemented carbide ball having a diameter of 0.5 mm was used for the ink compositions of Example 3 and Comparative Example 3 A sample ball-point pen was prepared by filling 2.0 g of the ink storage part and fitting a cap.

The following tests were conducted using the sample ballpoint pen.
Written test A sample ball-point pen that has been confirmed to be writable can be written on the old JIS P3201 writing paper A continuously with an automatic writing tester, and the situation of the handwriting and the ink to be filled are completely consumed. I checked if it was possible. The tester was used under the conditions of a writing load of 100 g, a writing angle of 70 °, and a writing speed of 4 m / min.
Abrasion test A sample ball-point pen that has been confirmed to be writable can be worn by an automatic writing tester with respect to the initial state of the ball seat after the spiral circle is continuously written 1000 m on JIS P3201 writing paper A (pen) The amount of ball sinking in the upward upward state) was measured.
The tester was used under the conditions of a writing load of 100 g, a writing angle of 70 °, and a writing speed of 4 m / min. Moreover, a measured value is an average value of what was tested 5 each.
The results of each test are shown in the following table.

The evaluation of the test results is as follows.
Written test ○: A good handwriting could be formed, and all the ink contained could be written.
X: Line skipping or blurring occurred in the handwriting, and writing was not possible on the way, and ink remained.

Claims (4)

A water-based ink composition for ballpoint pens containing at least a colorant, water, and polyoxyethylene polyoxypropylene alkyl ether phosphoric acid represented by the following general formula (1) .

[In the said General formula (1), R is an alkyl group, a and b are integers which show the addition mole number. The alkyl group R is a substituent having 12 to 18 carbon atoms, a indicating the number of added moles of ethylene oxide is 3 to 20, and b indicating the number of added moles of propylene oxide is 1 to 20. It is a range. ]   The water-based ink composition for ballpoint pens according to claim 1, wherein the colorant is a pigment.   A ballpoint pen incorporating the water-based ink composition for ballpoint pens according to claim 1 or 2. The ball-point pen according to claim 3, wherein the ball-point pen includes a ball having a diameter of 0.4 mm or less at a writing tip.