JP2008163091A - Water-based ballpoint pen - Google Patents

Abstract

An object of the present invention is to provide an aqueous ballpoint pen that has good writing quality and is excellent in stability over time by suppressing metal salts and the like in the ballpoint pen tip.
The tip body is made of stainless steel, and at least water, a colorant, a water-soluble organic solvent, a neutralizer, ethylenediaminetetraacetic acid (EDTA), and a phosphate ester surfactant having an HLB of 13 or less. It is characterized by being an ink composition for water-based ballpoint pens, which is formed by using the added amount in combination at a specific ratio.
[Selection] Figure 1

Description

  The present invention relates to a water-based ballpoint pen, and more particularly to a water-based ballpoint pen that has good writing quality and excellent stability over time by suppressing precipitates in the ballpoint pen tip.

  Conventionally, a ballpoint pen provided with a ballpoint pen tip using a tip body made of a stainless steel material is well known. In the case of a water-based ballpoint pen using a chip body made of such a stainless steel material, precipitates such as metal salts generated by reaction of manganese ions and chromium ions such as manganese and chromium contained in the stainless steel material in the ink composition In order to prevent this, it has been proposed to add a rust inhibitor such as benzotriazole or a metal sequestering agent to the ink composition.

  Such water-based ballpoint pen ink compositions and water-based ballpoint pens using the same are disclosed in Japanese Patent Publication No. 49-45333 “Water-based ink for writing” and Japanese Patent Laid-Open No. 8-41409 “Ink composition for water-based ballpoint pen”. A water-based ballpoint pen ink composition is disclosed.

By the way, in order to improve the writing quality in JP-A-6-57194 "Aqueous ballpoint pen ink to be supplied directly to a pen body", an aqueous ballpoint pen ink composition in which a phosphate ester surfactant is added as a lubricant is disclosed. JP-A 2006-206658 discloses a water-based ballpoint pen in which a metal sequestering agent and a phosphate ester surfactant are added to “water-based ink composition for ballpoint pen and ballpoint pen incorporating the same”.
"Japanese Patent Laid-Open No. 49-45333" "JP-A-8-41409" "JP-A-6-57194" "Japanese Patent Laid-Open No. 2006-206658"

  However, Patent Documents 1 and 2 propose water-based ballpoint pen inks to which a rust preventive agent such as benzotriazole or benzothiadiazole compound is added, but the problem is that the lubricity is poor, the writing quality is poor, and the blurring occurs. Was holding.

  Further, as in Patent Document 3, when a phosphate ester surfactant is added as a lubricant in order to improve writing quality, the phosphate ester surfactant and metal ions such as manganese ions and chromium ions in the chip Reacts to generate a metal salt. Furthermore, the phosphoric acid ester surfactant having an HLB value of 13 or less improves the writing quality, but since the HLB value is low, the lipophilicity becomes strong and the solubility is poor. The metal salt produced by the reaction with the metal ions could not be dissolved and precipitates were generated, resulting in poor writing.

  Patent Document 4 discloses a water-based ink composition for ballpoint pens that suppresses corrosion of the ball by setting the content ratio of the sequestering agent and the phosphate ester surfactant to a specific ratio. In the case of using a stainless steel material, the content of the phosphate ester surfactant is too large relative to the sequestering agent, so that a sufficient suppression effect can be obtained as a suppression of metal salt precipitates on the chip body. Otherwise, there was a possibility that precipitates were generated in the ballpoint pen tip.

  As described above, the phosphate ester surfactant easily reacts with metal ions such as manganese ions and chromium ions contained in the stainless steel material, and generates a metal salt. It can be presumed that the addition amount of the sequestering agent necessary for suppressing the precipitation due to the metal salt is small.

  The object of the present invention is to provide a ballpoint pen tip using a tip body made of a stainless steel material, which has a good writing quality, and further suppresses precipitates due to metal salts in the tip body, thereby improving the stability over time. To provide a ballpoint pen.

［式中、Ｒはアルキル又はアルキルアリル基を、nはエチレンオキサイド付加モル数を、Ｒ’はＨまたはＲＯ（ＣＨ_２ＣＨ_２Ｏ）_ｎ基を示す。］
３．前記ボールが、アルミナ、ジルコニア、窒化珪素、炭化珪素のいずれから選ばれるセラミック材からなることを特徴とした第１項または第２項に記載した水性ボールペン。」である。 In order to solve the above problems, the present invention
“1. A water-based ballpoint pen that has a ballpoint pen tip that rotatably holds a ball in a ball holding chamber of a tip body made of stainless steel at the tip of an ink containing cylinder, either directly or via a tip holder. In addition, at least water, a colorant, a neutralizing agent, a phosphate ester surfactant, and ethylenediaminetetraacetic acid are added to the ink containing cylinder, and the HLB of the phosphate ester surfactant is 13 or less, The addition amount of ethylenediaminetetraacetic acid is 0.1% by mass or more and 2.0% by mass or less with respect to the total mass of the ink composition, and the addition amount of the phosphate ester surfactant is 0.1% by mass or more and 5% or less. 0.0% by mass or less, and the ratio of the addition amount of the ethylenediaminetetraacetic acid and the phosphate ester surfactant is 1.0: 0.1 to 1.0: 5.0 Aqueous ballpoint pen, wherein a Rupen ink composition was filled directly.
2. The aqueous ballpoint pen described in item 1, wherein the phosphate ester surfactant is represented by the following general formula (1).

[Wherein, R represents an alkyl or alkylallyl group, n represents the number of moles of ethylene oxide added, and R ′ represents H or RO (CH ₂ CH ₂ O) _n group. ]
3. 3. The water-based ballpoint pen according to item 1 or 2, wherein the ball is made of a ceramic material selected from any of alumina, zirconia, silicon nitride, and silicon carbide. It is.

  The present invention is a water-based ballpoint pen equipped with a ballpoint pen tip using a tip body made of a stainless steel material, which has good writing quality and excellent temporal stability by suppressing deposits due to metal salts in the tip body. An aqueous ballpoint pen could be provided.

  The first feature of the present invention is a water-based ballpoint pen using a ballpoint pen tip using a tip body made of a stainless steel material. In the ink composition, phosphoric acid ester surface activity having ethylenediaminetetraacetic acid (EDTA) and HLB of 13 or less. It is to use the added amount of the agent together at a specific ratio.

  The phosphate ester surfactant is used to improve the writing quality because it can improve the lubricity between the ball and the chip body and obtain a smooth writing feeling.

  By the way, when a phosphate ester surfactant having an HLB value of 14 or more is used, it forms a highly hydrophilic metal salt and dissolves in water-based ink. For this purpose, it is important to use a phosphate ester surfactant having an HLB value of 13 or less. This is because the lower the HLB value, the higher the lipophilicity and the better the lubricity of the ball, thereby improving the writing quality.

  On the other hand, however, when a phosphate ester surfactant having an HLB value of 13 or less is used, a metal salt with strong lipophilicity is formed, so that it does not dissolve in the ink composition. There was a problem that.

  In order to solve these problems of improving writing quality and suppressing the generation of precipitates due to metal salts, the phosphate composition surfactant having an HLB value of 13 or less and the precipitates due to metal salts are suppressed in the ink composition. Therefore, it is important to use ethylenediaminetetraacetic acid (EDTA) in combination.

  As described above, in the present invention, a stainless steel material is used as the material of the chip body in the present invention. However, metal ions of the stainless steel material are eluted and react with a phosphate ester surfactant having an HLB value of 13 or less to make it lipophilic. However, by adding ethylenediaminetetraacetic acid, the ethylenediaminetetraacetic acid can wrap up the entire metal salt, and has the effect of dissolving and stabilizing the metal salt in the ink composition. This is because there is an effect of suppressing generation of precipitates.

As the phosphoric acid ester surfactant, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphoric acid diester, or derivatives thereof are suitable. Among them, it is most preferable to use a phosphate ester surfactant represented by the general formula as shown in Chemical Formula 1 in consideration of stability over time.

  Specific examples of the phosphate ester surfactant include the Prisurf series (Daiichi Kogyo Seiyaku Co., Ltd.) and the Phosphanol series (Toho Chemical Industry Co., Ltd.), Prisurf A212C (HLB value 9), A210G (HLB value 9), A207H (HLB value 7), AL (HLB value 5), A208B (HLB value 6), A208S (HLB value 7), A208F (HLB value 9), A212E (HLB value 10), Phosphanol RE-210 (HLB value 6), RE-410 (HLB value 9), RE-510 (HLB value 10), RS-410 (HLB value 9), RB -410 (HLB value 8), RM-410 (HLB value 5), RM-510 (HLB value 9), RL-210 (HLB value 5), RD-510Y (HLB value 10), M -200 (HLB value 10), such as the GB-520 (HLB value 6) and the like. These surfactants may be used alone or in combination of two or more. In addition, HLB can be calculated | required from HLB = 7 + 11.7log (Mw / Mo) and (Mw: molecular weight of a hydrophilic group, Mo: molecular weight of a lipophilic group) as a general formula.

  If the addition amount of the phosphate ester surfactant is less than 0.1% by mass with respect to the total amount of the ink composition, the desired lubricity cannot be obtained, the writing quality is poor, and there is a risk of blurring in the handwriting. If it exceeds 5.0% by mass, the ink aging may become unstable, so the content is set to 0.1 to 5.0% by mass with respect to the total amount of the ink composition. Further, in order to further improve the writing feeling and obtain good ink aging, the addition amount of the phosphate ester surfactant is most preferably 0.5 to 2.0% by mass with respect to the total amount of the ink composition.

  Moreover, when the addition amount of ethylenediaminetetraacetic acid is less than 0.1% by mass with respect to the total amount of the ink composition, the effect of suppressing precipitation of metal salt may be weakened, and when it exceeds 2.0% by mass. Since the ink aging becomes unstable, the content is set to 0.1 to 2.0% by mass with respect to the total amount of the ink composition. More preferably, the addition amount of ethylenediaminetetraacetic acid is 0.5 to 1.0% by mass with respect to the total amount of the ink composition. In order to dissolve ethylenediaminetetraacetic acid in water, alkali metal neutralized products such as 2 or 4 sodium salt of ethylenediaminetetraacetic acid can also be used.

  Furthermore, the ratio of the addition amount of ethylenediaminetetraacetic acid and phosphate ester surfactant is 1.0: 0.1 to 1.0: 5.0. This is because when the ratio of the addition amount of phosphate surfactant to the addition amount 1 of ethylenediaminetetraacetic acid is less than 0.1, even if the addition amount of ethylenediaminetetraacetic acid is 2.0% by mass, The addition amount of is small, sufficient lubricity cannot be obtained, and the writing quality is inferior.

  In addition, when the ratio of the addition amount of the phosphate ester surfactant to the addition amount 1 of ethylenediaminetetraacetic acid exceeds 5.0, the amount of phosphate ester relative to ethylenediaminetetraacetic acid is large, so that the dissolution stability cannot be maintained. It is not possible to suppress the formation of metal salt precipitates. Therefore, the ratio of the addition amount of ethylenediaminetetraacetic acid and phosphate ester surfactant is in the range of 1.0: 0.5 to 1.0: 5.0. By adding ethylenediaminetetraacetic acid and a phosphate ester surfactant in the above ratio range, the solubility of the metal salt formed by the reaction can be secured, and the metal salt precipitate can be suppressed.

  Therefore, ethylenediaminetetraacetic acid: phosphate ester surfactant is most preferably in the range of 1.0: 0.1 to 1.0: 2.0.

  Further, the ball-point pen tip ball is not particularly limited, but a cemented carbide ball mainly composed of tungsten carbide uses cobalt, nickel, or the like as its binder. Since cobalt and nickel have strong reactivity with ethylenediaminetetraacetic acid, the cobalt, nickel, and the like of the binder are corroded with time, and rotational resistance is generated, so the writing quality may be inferior. For this reason, it is more preferable to use a ball of ceramic material containing silicon carbide, alumina, zirconia, silicon nitride, or the like, which hardly corrodes.

  In addition, a neutralizing agent may be added to the aqueous ballpoint pen ink composition used in the present invention for the purpose of neutralizing ethylenediaminetetraacetic acid or a phosphate ester surfactant. Specifically, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, triethylamine, diisopropanolamine, diethylamine, dipropylamine, amylamine and other organic amines, sodium hydroxide, potassium hydroxide, hydroxide Examples thereof include alkali metal salts such as lithium. These neutralizing agents may be used alone or in combination of two or more.

  In the present invention, a resin may be used as an ink viscosity adjusting agent. Specifically, water-soluble resins such as acrylic resins, alkyd resins, cellulose derivatives, polyvinyl pyrrolidone, and polyvinyl alcohol, xanthan gum, cross-linked acrylic acid polymers, cross-linked acrylamide polymers, shearing succinoglycans, gar gums, etc. Examples include a viscosity reducing agent. You may use these individually or in mixture of 2 or more types.

  Moreover, if the addition amount of the resin is less than 0.1% by mass relative to the total amount of the ink composition, it is difficult to obtain a desired ink viscosity, and if it exceeds 30% by mass, the writing performance may be deteriorated. Therefore, 0.1 mass% or more and 30 mass% or less are preferable.

  The colorant is not particularly limited, such as a dye or a pigment, and can be appropriately selected and used. As the dye, direct dyes, acid dyes, basic dyes, metal-containing dyes, various water-soluble salt-forming dyes, and the like can be used. Examples of pigments include inorganic, organic, and processed pigments. Specifically, carbon black, aniline black, ultramarine, yellow lead, titanium oxide, iron oxide, phthalocyanine, azo, quinacridone, quinophthalone, selenium , Triphenylmethane, perinone, perylene, glyoxazine, aluminum pigment, pearl pigment, fluorescent pigment, phosphorescent pigment, and complementary color pigment. In addition, a microcapsule pigment in which a colored body in which a pigment is dispersed in a medium as a colored resin particle body is encapsulated or solidified in a shell made of a resin wall film forming substance by a known microencapsulation method may be used. good. Further, colored resin particles in which the pigment is covered with a transparent or translucent resin or the like, or colored resin particles or colorless resin particles colored with a pigment or a dye can also be used. These dyes and pigments may be used alone or in combination of two or more. The addition amount is preferably 1% by mass to 20% by mass with respect to the total amount of the ink composition.

  Other additives include water-soluble stability, water evaporation and drying prevention, water-soluble organic solvents such as glycerin and ethylene glycol, humectants such as urea and sorbit, 1,2 benzoisothiazoline-3-one An antibacterial agent such as can be added. Silicone, acetylene glycol, and fluorine surfactants other than phosphate ester surfactants can also be added to improve wettability and water resistance. These can be used alone or in combination of two or more. It can also be blended.

Next, an Example is shown and this invention is demonstrated.
Example 1
The tip of the ink storage cylinder is provided with a ballpoint pen tip that rotatably holds a silicon carbide ball having a ball diameter of φ0.7 mm in a ball holding chamber of a chip body made of stainless steel material. A refill directly filled with a water-based ballpoint pen ink composition 6 and a grease-like ink follower 7 obtained by the following formulation 1 was used as a knock type gel ink ballpoint pen (trade name: G-Knock) manufactured by Pilot Corporation. A water-based ballpoint pen 1 of the present invention was prepared.

Ink formulation 1
Water 28.0 parts by mass Water-soluble organic solvent (glycerin) 20.0 parts by mass Ethylenediaminetetraacetic acid 0.5 parts by mass Phosphate ester surfactant (Plysurf A-208S) 1.0 part by mass neutralizing agent (tri Ethanolamine) 2.8 parts by mass humectant (urea) 7.5 parts by mass antibacterial agent (1,2 benzoisothiazolin-3-one) 0.2 parts by mass colorant (fluorescent pigment: NKW-2100 series ( Solid content about 50%)) 40.0 parts by mass Resin (succinoglycan) 0.24 parts by mass

  Ink formulation 1 is first water, water-soluble organic solvent, ethylenediaminetetraacetic acid, phosphate ester surfactant (Pricesurf A-208S; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), neutralizer, moisturizer, Base ink is prepared by heating and stirring the fungicide with a magnetic hot stirrer.

  Then, while heating the base ink prepared above, the resin was added and thoroughly mixed and stirred using a homogenizer stirrer until uniform, and then a colorant (fluorescent pigment: NKW-2100 series series (Japan) Fluorescent Chemical Co., Ltd.)) is added and stirred until further uniform. Then, it filtered using the filter paper, and obtained the ink composition for water-based ball-point pens of the ink compounding 1.

Examples 2-16
A water-based ballpoint pen ink composition was prepared in the same procedure as ink formulation 1 except that the components were changed to the formulations and ball materials shown in Tables 1 and 2, and Example 2 was repeated in the same manner as Example 1. Sixteen aqueous ballpoint pens were obtained.

Comparative Examples 1-18
A water-based ballpoint pen ink composition was prepared in the same procedure as ink formulation 1 except that the components were changed to the formulations and ball materials shown in Tables 3 and 4, and Comparative Example 2 was performed in the same manner as in Example 1. 18 aqueous ballpoint pens were obtained.

Tests and Evaluations The following tests and evaluations were performed using the aqueous ballpoint pens prepared in Examples 1 to 16 and Comparative Examples 1 to 18. The writing taste was evaluated using copy paper (PPC paper) as a writing test paper.

Written taste: A hand-written sensory test was performed and evaluated.
Smooth and good ・ ・ ・ ◎
Somewhat inferior
Heavy and inferior

Time-lapse test of chip body: The ink in the chip body was observed with a microscope after leaving the ballpoint pen refill in an environment of 50 ° C. and 0% humidity for 3 months.
Good without deposits ... ◎
Slightly generated precipitates, but no problem in practical use ... ○
Precipitates are generated and the practicality is poor.

Ink aging test: The ballpoint pen refill was allowed to stand for 3 months in an environment of 50 ° C. and 0% humidity, and the state of the ink in the refill was observed with a microscope.
No precipitate is present ... ◎
Precipitates existed, but there are no practical problems
Precipitate is present, causing scumming or poor writing, etc. ×

    In Examples 1 to 16, good writing quality, a chip body aging test, and an ink aging test were good, or a performance with no practical problem was obtained. In particular, the use of ceramic balls containing silicon carbide, alumina or the like as a component was better in writing than cemented carbide.

  In Comparative Examples 1 and 2, since ethylenediaminetetraacetic acid was not added, precipitates were generated.

  In Comparative Examples 3 and 4, since a phosphate ester surfactant having HLB14 or higher was used, writing was heavy.

  In Comparative Examples 5 to 10, since the addition amount of ethylenediaminetetraacetic acid was large, the temporal stability of the ink was poor.

  In Comparative Examples 11 and 12, since 1.0: 5.0 was exceeded, the amount of phosphate ester was large, so that a metal salt was formed in an amount that could not maintain dissolution stability, and a metal salt precipitate was generated. Oops.

  In Comparative Examples 13 and 14, the phosphate ester surfactant was not added, so that sufficient lubricity was not obtained and the writing quality was heavy.

  In Comparative Examples 15 and 16, the content of the phosphate ester surfactant was large, and the ink aging was unstable.

  In Comparative Examples 17 and 18, since a surfactant other than the phosphate ester surfactant was added, the writing was heavy.

  Although not shown, when a coil spring that presses a ball made of stainless steel is disposed in the ballpoint pen tip, the phosphate ester surfactant and the metal ions of the coil spring are disposed in the same manner as the tip body. Since the metal salt may be generated by this reaction, the effect of the present invention is remarkable.

Furthermore, in the ink composition to which a large particle size such as a pigment is added, the writing quality may be deteriorated due to rotation inhibition between the ball and the chip body, and a ball having a ball diameter of 0.7 mm or less was used. Since the ball pen has a small contact area between the ball and the ball seat, and there is a possibility that the writing quality is deteriorated due to a high load applied to the unit area, the effect of the present invention is remarkable.

  The present invention relates to a water-based ballpoint pen, and more specifically, in a ballpoint pen tip using a tip body made of stainless steel, the addition amount of a phosphate ester surfactant having ethylenediaminetetraacetic acid (EDTA) and HLB of 13 or less is specified ratio. By using together, it is possible to provide an aqueous ballpoint pen that has good writing quality and is excellent in stability over time by suppressing metal salts and the like in the ballpoint pen tip. Therefore, it can be widely used as a ballpoint pen, such as a cap type and a knock type.

It is a longitudinal cross-sectional view which shows the water-based ball-point pen of this invention. It is an external view in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Water-based ball-point pen 2 Ink storage cylinder 3 Ball-point pen tip 4 Ball 5 Tip holder 6 Water-based ball-point pen ink composition 7 Ink follower

Claims (3)

A water-based ballpoint pen comprising a ballpoint pen tip that rotatably holds a ball in a ball holding chamber of a tip body made of a stainless steel material, directly or via a tip holder, at the tip of an ink containing cylinder, At least water, a coloring agent, a neutralizing agent, a phosphate ester surfactant, and ethylenediaminetetraacetic acid are added to the ink containing cylinder, and the HLB of the phosphate ester surfactant is 13 or less, and the ethylenediaminetetraacetic acid Is 0.1% by mass or more and 2.0% by mass or less with respect to the total mass of the ink composition, and the addition amount of the phosphate ester surfactant is 0.1% by mass or more and 5.0% by mass. %, And the ratio of the addition amount of the ethylenediaminetetraacetic acid and the phosphate ester surfactant is 1.0: 0.1 to 1.0: 5.0 The aqueous ballpoint pen the emissions ink composition characterized by being packed directly. The aqueous ballpoint pen according to claim 1, wherein the phosphate ester surfactant is represented by the following general formula (1).

[Wherein, R represents an alkyl or alkylallyl group, n represents the number of moles of ethylene oxide added, and R ′ represents H or a RO (CH ₂ CH ₂ O) _n group. ] The water-based ballpoint pen according to claim 1 or 2, wherein the ball is made of a ceramic material selected from any of alumina, zirconia, silicon nitride, and silicon carbide.

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