JP4754225B2 - Water-based dye ballpoint pen - Google Patents

Description

The present invention relates to a water-based dye ballpoint pen. Furthermore, it is related with the water-based dye ball-point pen which incorporated the water-based ink composition for ball-point pens which was excellent in the anti-corrosion performance of the ball | bowl, and was provided with high writing performance.

Conventionally, as balls for ballpoint pens, balls such as silicon carbide balls, zirconia balls, cemented carbide balls, etc., containing silicon carbide, zirconia, tungsten carbide, etc. as the main component and a binder composed of metal as the other component, have been used. in use.
Since the balls mainly use metals such as cobalt, chromium, titanium, and nickel as binders, when used in water-based ballpoint pens, the binders can be used over time due to the action of dissolved oxygen in the ink. When the binder is lost in the ball, the crystal particles such as silicon carbide, zirconia, and tungsten carbide, which are the main components, drop off, or the eluted binder becomes a metal oxide and insolubilizes. It may become a so-called corrosive state such as adhering to the surface. Since the corrugation on the surface of the ball becomes large due to the corrosion, the rotation of the ball is obstructed and the writing feel becomes heavy, and the smooth outflow of the ink is obstructed and the handwriting is blurred.
In particular, among cemented carbide balls, balls containing tungsten or tungsten carbide as the main component and using metals such as cobalt and nickel as the binder are likely to corrode over time due to the high binder content. Has drawbacks.
Therefore, as a method for preventing this corrosion over time, a method of adding a rust preventive agent such as benzotriazole or benzothiadiazole or a sequestering agent to the ink has been disclosed (see Patent Documents 1 and 2).
Japanese Patent Publication No.49-45333 JP-A-8-41409

However, even when the above-mentioned rust preventive agent is added, elution of the metal that is the binder cannot be sufficiently suppressed, and as a result, the writing quality becomes heavy or the handwriting is faded. It was not enough.
In addition, when a sequestering agent is added, elution of the metal as a binding material can be suppressed, but the writing performance may be deteriorated because the lubrication performance at the time of writing decreases.

The present invention is built in an aqueous ballpoint pen according to the cemented carbide ball writing tip, the ball corrosion hardly proceeds over time, a good ballpoint water based ink composition for a writing feeling which can maintain excellent lubricating performance in the time of writing An aqueous dye ballpoint pen is provided.

The present invention applies tungsten carbide and / or tungsten carbide and a tungsten carbide ball and metal binder to the tip of the writing, incorporates a water-based ink composition in the ink containing tube, and prevents liquid ink backflow at the trailing edge of the ink. The water-based ink composition comprises at least a dye, water, a sequestering agent, and a phosphate ester, and a content ratio of the sequestering agent and the phosphate ester. 1:10 to 1: 500, the sequestering agent is added in an amount of 0.01 to 0.5% by weight based on the total amount of the ink composition, and the phosphate ester is 0.1% based on the total amount of the ink composition. An aqueous dye ballpoint pen characterized by being added in a range of ˜5% by weight is a requirement.
Furthermore, it is a requirement that the pH of the water-based ink composition is 7 to 13.

According to the present invention, in an aqueous ballpoint pen equipped with a cemented carbide ball at the tip of writing, it is possible to suppress long-term corrosion phenomena such as elution of the binding material and adhesion of insoluble matter to the ball surface, and high at the time of writing. Since the lubrication performance can be maintained, it is possible to provide a water-based dye ballpoint pen incorporating a water -based ballpoint pen ink composition that can maintain a smooth writing feeling without causing blurring or line skipping in the handwriting.

  The present invention contains a metal ion sequestering agent and a phosphate ester in a specific ratio in a water-based ink composition for ballpoint pens, so that a ball serving as a tip of writing has a metal such as cobalt, chromium, titanium, nickel, etc. Even when applied to a water-based ballpoint pen equipped with a cemented carbide ball used as a binder, corrosion phenomena such as adhesion of insoluble matter to the ball surface can be suppressed for a long period of time.

  The sequestering agent suppresses the elution of the metal binder into the ink and can prevent the corrosion phenomenon that insoluble matter (such as the oxide of the eluted metal binder) adheres to the ball surface over a long period of time. Yes, specifically, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), glycol etherdiaminetetraacetic acid (GETDA), nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA) and their alkali metal salts, ammonium salts, amine salts and the like can be exemplified, and they are used alone or in combination of two or more.

The sequestering agent can be added in an amount of 0.01 to 0.5% by weight, preferably 0.03 to 0.5% by weight, based on the total amount of the ink composition.
If it is less than 0.01% by weight, it is difficult to obtain the desired effect, and even if added over 0.5% by weight, no improvement in the corrosion inhibition effect is observed. do not do.

（式中Ｒ_１は８〜１８のアルキル基、アルケニル基、或いはフェニル基、アルキルフェニル基を示し、Ｒ_２はＯＨ、ＯＭ、Ｒ_１−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ｎを示し、Ｍはアルカリ金属、アルカノールアミンを示し、ｎは１〜３０の自然数を示す。） The phosphate ester can impart lubricating performance at the time of writing without interfering with the effect of the sequestering agent, and includes an aromatic or aliphatic functional group, an ethylene oxide group, and a phosphate group. Conventionally known materials such as phosphoric acid monoesters, diesters, triesters and the like are used, and for example, those given by the following general formula (1) can be applied.

(In the formula, R ₁ represents an alkyl group of 8 to 18, an alkenyl group, or a phenyl group or an alkylphenyl group; R ₂ represents OH, OM, R ₁ —O— (CH ₂ CH ₂ O) _n ; Represents an alkali metal or alkanolamine, and n represents a natural number of 1 to 30.)

  Specifically, Phosphanol RE-410, LE-500, RE-610, LE-700, RM-410, LM-400, LF-200, LF-205, RP- 710, LP-700, RS-410, LS-500, RD-510Y, RB-410, LB-400, RA-600, GB-520, RD-720, ML- 200, ML-210 (made by Toho Chemical Co., Ltd.), Prisurf A212E, A210G, AL, A212C, A215C, A208B, A208S, A208F (made by Daiichi Kogyo Seiyaku Co., Ltd.) it can.

The phosphoric acid ester can be added in an amount of 0.1 to 5% by weight, preferably 0.3 to 5% by weight, based on the total amount of the ink composition.
If the amount is less than 0.1% by weight, it is difficult to obtain the desired effect, and even if added over 5% by weight, no improvement in lubrication performance is observed, so no further addition is required.

The sequestering agent and phosphate ester are added to the ink composition so that the content ratio is in the range of 1:10 to 1: 500.
By adding at the above ratio, ball corrosion can be suppressed for a long time while maintaining excellent lubrication performance. When the ratio of the sequestering agent is high, the seat wear during writing increases, and when the ratio of phosphate ester is high, the dissolution stability in the ink decreases and the ink viscosity increases. May become heavy.

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.

The dyes can be used alone or in combination of two or more, and are used in the range of 1 to 25% by weight, preferably 2 to 15% by weight in the ink composition.

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, metal soap, polyalkylene glycol, ethylene oxide addition type cationic activity as required Lubricants such as additives, rust preventives such as benzotriazole, tolyltriazole, 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 and other preservatives or antifungal agents, urea, nonionic surfactants, sorbit, mannitol, sucrose, glucose, reduced starch hydrolysis Product, wetting agent such as sodium pyrophosphate, antifoaming agent, ink permeability The fluorine-based surfactants and nonionic surfactants to the above may be 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 based on alkyl esters of methacrylic acid, glucomannan, agar and carrageenan Carbohydrates having gelling ability extracted from seaweed such as benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymers, inorganic fine particles, nonionic surfactants having an HLB value of 8 to 12, and dialkylsulfosuccinic acid Metal salts and nets Can be exemplified a salt, further, be added in combination in the ink composition N- alkyl-2-pyrrolidone and anionic surfactant can have stable shear thinning.

The ink composition is applied by adjusting the pH to a neutral to alkaline range of 7 to 13, preferably a weak alkaline range of pH 7.3 to 11.
By adjusting the pH, dissolution stability of the sequestering agent and phosphate ester can be obtained, and it can work efficiently, and ball corrosion can be reliably suppressed while maintaining high lubrication performance.

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 writing tip portion (tip) of the ballpoint pen filled with the water-based ink composition for ballpoint pens has a more effective general-purpose mechanism than before, and a ball in which the vicinity of the tip of a metal pipe is pressed and deformed inward from the outer surface. A chip formed by holding a ball in the holding part, 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 a metal pipe or metal material A ball or the like held by a chip formed by cutting can be applied forward by a spring body.
The ball is obtained by sintering a group 4a, 5a, 6a metal or a carbide thereof together with a metal such as cobalt or nickel as a binder, and is made of a cemented carbide that is hard and difficult to wear. It is.
In particular, a cemented carbide ball using tungsten or tungsten carbide (tungsten carbide), which is chemically stable and has high hardness, among the metals of Group 4a, 5a, and 6a or their carbides, is preferably used. It is done.
In addition, titanium, vanadium, chromium, tantalum or a carbide thereof may be included as a metal of 4a, 5a, or 6a group.
Of the cobalt and nickel that function as the binder, cobalt is particularly apt to elute into water-based ink, and the ball surface becomes rough. Further, the elution of cobalt causes tungsten and tungsten carbide to fall off, making the ball surface even rougher. . Therefore, if the ball rotates while in contact with the ball seat, the wear of the seat becomes severe, and the gap between the ball and the ball holding portion in the axial direction (clearance) increases. It becomes easy to cause problems such as thickening and line skipping.
The balls having a diameter in the range of 0.1 mm to 2.0 mm are preferably used.

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 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.
In addition, the said shaft cylinder may accommodate the said refill in a shaft cylinder as a form of the refill for ball-point pens.

Furthermore, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
The ink storage tube may be configured as a ballpoint pen refill, in which the refill is stored in a shaft tube, or the shaft tube with a tip attached to a tip is used as an ink storage body in the shaft tube. You may fill ink directly.

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) Product name: FISCO BLACK 886, manufactured by Orient Chemical Industry Co., Ltd.
(2) Product name: Kirest 3D
(3) Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf AL
(4) λ-carrageenan, manufactured by Saneigen FFI Co., Ltd., trade name: carrageenin CSL-2

Preparation of ink After adding ingredients other than shear thinning agent to water, mixing and stirring, adding shear thinning agent, stirring at 400 rpm for 1 hour with a disper at 25 ° C, and filtering. Each ink was prepared.

Preparation of Ink Backflow Preventer Body In 85 parts of polybutene as a base oil, 15 parts of fatty acid amide as a thickener was added, and then kneaded with three rolls to obtain an ink backflow preventer body.

Preparation of Ballpoint Pen A stainless steel chip holding each WC-Co cemented carbide ball having a diameter of 0.5 mm is attached to one end of a polypropylene pipe (inner diameter: 3.8 mm) on a ballpoint pen refill. After filling, the ink backflow prevention body was disposed at the rear end, and then the ballpoint pen refill was incorporated into a shaft tube to prepare a sample ballpoint pen.

The following tests were conducted using the ink composition and the sample ballpoint pen.
Ball Corrosion Test Each sample ball-point pen was placed in a horizontal state in an environment of 50 ° C. for 60 days, and then the state of the ball surface was confirmed with an optical microscope (100 × magnification).

Written test After the sample ballpoint pen that was confirmed to be writable was left in a 50 ° C environment for 60 days in a horizontal position, the handwritten spiral circles were continuously written on JIS P3201 writing paper A. The state was confirmed visually.

Pedestal Abrasion Test A sample ball-point pen that was confirmed to be writable was left for 60 days in a horizontally placed environment at 50 ° C., and then was written 500 m on JIS P3201 writing paper A with a running tester. The amount of wear (μm) relative to the initial state of the pedestal portion at that time was measured.
The results of the test are shown in the following table.

The evaluation of the test results is as follows.
Ball corrosion test ○: No change from the initial stage.
X: It is coarse compared with the initial stage, or there is a deposit.
Writing test ○: Writing was smooth and good handwriting was shown.
(Triangle | delta): There exists a feeling of being caught at the time of writing, and a slight blur and a line jump are seen in a handwriting.
X: Written feeling is poor, and many blurs and line jumps are seen in the handwriting.

Claims (2)

A cemented carbide ball consisting of at least tungsten and / or tungsten carbide and a metal binder is applied to the writing tip, a water-based ink composition is built in the ink container, and a liquid ink backflow preventer is placed at the trailing edge of the ink. The water-based ink composition comprises at least a dye, water, a sequestering agent, and a phosphate ester, and the content ratio of the sequestering agent and the phosphate ester is 1:10. To 1: 500, the sequestering agent is added in the range of 0.01 to 0.5% by weight in the total amount of the ink composition, and the phosphate ester is 0.1 to 5% by weight in the total amount of the ink composition. A water-based dye ballpoint pen characterized by being added in the range of   The aqueous dye ballpoint pen according to claim 1, wherein the aqueous ink composition has a pH of 7 to 13.