JP2009091393A - Water-based ink composition for writing utensil and writing utensil including the same in the inside - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based ink composition for a writing utensil, having wide practicability and providing good writing performance, by using a specific compound for chemically removing gas in ink, and to provide a writing utensil including the ink composition in the inside thereof. <P>SOLUTION: The water-based ink composition for the writing utensil contains at least a coloring agent, a water-soluble organic solvent, water and a phenylethanoid glycoside. The writing utensil is obtained by directly filling an ink-storing tube with the water-based ink composition for the writing utensil containing 0.1-3 wt.% of the phenylethanoid glycoside in the ink composition, and arranging an ink back flow-preventing body following the consumption of the ink at the rear end of the ink with close contact. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a water-based ink composition for a writing instrument and a writing instrument filled with the water-based ink composition for a writing instrument and an ink backflow preventive body that follows the ink consumption.

  Conventionally, an aqueous ballpoint pen ink composition containing a shear thinning agent such as a polymer polysaccharide has been disclosed as an ink having shear thinning among aqueous inks (see, for example, Patent Document 1).

This type of ink has a high viscosity when it is left to stand without shear stress, and is stably held in the mechanism. When writing, the ink in the vicinity of the ball is low due to the high shear force of the ball rotating at high speed. As a result, the ink is discharged from the gap between the ball and the ball container and transferred onto the paper surface. Since the ink transferred onto the paper surface is released from the shearing force, it becomes a high viscosity state again, and does not cause the blotting of the handwriting, which is a defect of the conventional aqueous ink composition.
Furthermore, ink leakage does not occur depending on the above-described shear thinning and a flow rate adjusting member (pen core) for adjusting the ink flow rate is not required, so that a writing instrument with a simple structure can be obtained.

  The conventional writing instrument using water-based ink exhibiting shear thinning has a simple structure, and the internal pressure of the writing instrument using the flow rate adjusting member does not enter air as the ink is consumed as in the writing instrument using the flow rate adjusting member. While there is little change and there is an advantage that the ink does not fall off, special considerations are required when preparing and filling the ink. This is to prevent the solvent in the ink from evaporating on the rear end surface of the ink, or to follow the ink consumption as the writing front end portion is in the upward state (upright state) to prevent the ink from flowing backward. This is because the backflow prevention body (liquid stopper) is filled, and since the ink exists in an airtight space that is blocked from the outside air, if the gas is mixed in the ink, the gas gathers over time and bubbles are generated. This is because the ink is generated and adversely affects the ink discharge at the time of writing, and if there is a bubble at the tip of writing, writing may become impossible.

  Apart from this, as a writing instrument of the type filled with the ink backflow preventive body, by providing a valve mechanism in the vicinity of the writing tip, it can be filled with an aqueous ink composition that does not exhibit shear thinning, As with, the presence of bubbles will adversely affect writing performance.

In order to solve the problems described above, defoaming treatment is mainly performed to remove the gas in the ink mechanically. However, it is difficult to perform sufficient defoaming by this method alone, and the gas remains in the ink. There is. In addition, when using a colorant that is insoluble in a solvent such as pigment, metal powder, titanium oxide, etc., if the specific gravity difference from the vehicle is large, the colorant will be contained in the ink container when processing such as centrifugal defoaming is performed. The problem of uneven distribution occurs.
Therefore, a method of chemically removing the gas in the ink is conceivable. For example, attempts to add an ascorbic acid derivative or α-tocopherol have been disclosed (see, for example, Patent Documents 2 to 3).
Japanese Patent Laid-Open No. 4-214782 Japanese Patent Publication No.7-113101 Japanese Patent Laid-Open No. 10-330672

However, among the compounds that chemically remove the gas in the ink, ascorbic acid derivatives tend to cause aggregation of the pigment in a system using a pigment as a colorant, which limits practical use. In addition, α-tocopherol is insoluble in water, so that it is separated over time and it is difficult to permanently develop a gas removal function.
The present invention provides a water-based ink composition for a writing instrument that has wide utility and can provide good writing performance by using a specific compound that chemically removes the gas in the ink described above, and a built-in ink composition for the same. Is to provide a writing instrument.

  The water-based ink composition for a writing instrument of the present invention is required to contain at least a colorant, a water-soluble organic solvent, water, and a phenylethanoid glycoside. Furthermore, it is required that the phenylethanoid glycoside is contained in an ink composition in an amount of 0.1 to 3% by weight. Furthermore, a writing instrument in which the ink containing tube is directly filled with the water-based ink composition for a writing instrument and an ink backflow prevention body that follows as the ink is consumed is closely arranged at the rear end of the ink is required.

  Since the water-based ink composition for a writing instrument of the present invention expresses a remarkable bubble removing function without adversely affecting other additives by blending a phenylethanoid glycoside, the writing instrument using the ink is Bubbles do not occur over time, ink is smoothly led out to the writing tip, stable writing performance can be maintained, and good handwriting can be obtained continuously.

〔式中Ｒ_１はＨ又はアセチル基を、Ｒ_２はα−Ｌ−ラムノピラノースを、Ｒ_３はＨ又はトランス−カフェオイルを、Ｒ_４はＨ、トランス−カフェオイル、β−Ｄ−グルコピラノースのいずれかを、Ｒ_５はヒドロキシ基又はメトキシ基を示す。〕
前記フェニルエタノイド配糖体として具体的には、エキナコサイド、アクテオサイド、２′−アセチルアクテオサイド、シスタノサイドＡ、シスタノサイドＣ、イソアクテオサイド、チュブロサイドＡ等が例示でき、一種又は二種以上を併用して適用できる。 The phenylethanoid glycoside is a glycoside represented by the following general formula (1), which is industrially obtained by extraction and purification from kankanikuyuyo, etc., which is a plant parasitic on the root of Tamarix. It is what

[Wherein R ₁ represents H or acetyl group, R ₂ represents α-L-rhamnopyranose, R ₃ represents H or trans-caffeoyl, R ₄ represents H, trans-caffeoyl, β-D-glucose. In any of pyranose, R ₅ represents a hydroxy group or a methoxy group. ]
Specific examples of the phenylethanoid glycoside include echinacoside, acteoside, 2'-acetylacteoside, cystanoside A, cystanoside C, isoacteoside, tubuloside A, and the like. Can be applied.

  The phenylethanoid glycoside has high solubility in an aqueous solvent and exhibits an antioxidant action in a solution. Therefore, when added to an ink composition, the phenylethanoid glycoside exhibits a good oxygen absorbing ability. Therefore, it is presumed that the gas containing oxygen in the ink is prevented from collecting and forming bubbles. Moreover, it is possible to express a good oxygen absorption ability even in an acidic atmosphere.

The phenylethanoid glycoside can be added in an amount of 0.1 to 3% by weight, preferably 0.3 to 2% by weight in the ink composition.
If the amount is less than 0.1% by weight, it is difficult to obtain the desired bubble generation inhibiting effect, and even if the amount exceeds 3% by weight, no further bubble inhibiting effect can be obtained. I don't need it.

As the colorant, all dyes and pigments that can be dissolved or dispersed in an aqueous medium can be used, and specific examples thereof are illustrated below.
As the dye, an acid dye, a basic dye, a direct dye, or the like can be used.
As an acid dye,
New coccin (CI. 16255),
Tartrazine (C.I. 19140),
Acid Blue Black 10B (C.I. 20470),
Guinea Green (C.I.42085),
Brilliant blue FCF (C.I.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) or the like is used.

As basic dye,
Chrysoidine (C.I. 11270),
Methyl violet FN (C.I. 42535),
Crystal violet (C.I. 42555),
Malachite green (C.I. 42000),
Victoria Blue FB (C.I. 44045),
Rhodamine B (C.I. 45170),
Acridine orange NS (C.I. 46005),
Methylene blue B (C.I. 52015) or the like is used.

As a direct dye,
Congo Red (C.I. 22120),
Direct Sky Blue 5B (C.I. 24400),
Violet BB (C.I. 27905),
Direct deep black EX (CI 30235),
Caillas Black G Conch (C.I. 35225),
Direct Fast Black G (C.I. 35255),
Phthalocyanine blue (C.I. 74180) or the like is used.

Examples of the pigment include inorganic pigments such as carbon black and ultramarine, and organic pigments such as copper phthalocyanine blue and benzidine yellow, as well as water dispersion finely and stably dispersed in an aqueous medium in advance using a surfactant or resin. Pigment products and the like are used. I. Pigment
Blue 15: 3B [Product name: Sandye Super Blue GLL, pigment content 24%, manufactured by Sanyo Dye Co., Ltd.]
C. I. Pigment Red 146 [Product name: Sandye Super Pink FBL, pigment content 21.5%, manufactured by Sanyo Dye Co., Ltd.]
C. I. Pigment Yellow 81 [Product name: TC Yellow FG, pigment content about 30%, manufactured by Dainichi Seika Kogyo Co., Ltd.]
C. I. Pigment Red 220/166 [Product name: TC Red FG, pigment content of about 35%, manufactured by Dainichi Seika Kogyo Co., Ltd.].
As the resin for dispersing the pigment, polyamide resin, polyurethane resin, polyester resin, epoxy resin, melamine resin, phenol resin, silicone resin, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, Examples thereof include polystyrene, acrylic acid resin, maleic acid resin, gum arabic, cellulose, dextran, casein, and derivatives thereof, and copolymers of the above-described resins.
As the fluorescent pigment, a fluorescent pigment in the form of fine particles of synthetic resin in which various fluorescent dyes are formed into a solid solution in a resin matrix can be used.
In addition, white pigments such as titanium dioxide, metal powders such as aluminum, natural mica, synthetic mica, alumina, pearl pigments in which the surface of the core material is coated with a metal oxide such as titanium dioxide, cholesteric liquid crystal type glitter A functional pigment or the like can also be used.
Furthermore, a microcapsule pigment encapsulating a reversible thermochromic composition, or a thermochromic pigment such as a microcapsule pigment encapsulating a dye or pigment together with the reversible thermochromic composition can also be used.
The pigments 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, as the water-soluble organic solvent, conventional general-purpose solvents compatible with water are used, and ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiol Diethylene glycol, hexylene glycol, 1,3-butanediol, neoprene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol Monoethyl ether, 2-pyrrolidone, N- methyl-2-pyrrolidone.
In addition, the said water-soluble organic solvent can also use 1 type, or 2 or more types together, It is 2-60 weight% in an ink composition, Preferably it is used in 5-35 weight%.

In addition, a pH adjuster, an antiseptic, or an antifungal agent can be added as necessary.
Examples of the pH adjuster include inorganic salts such as ammonia, sodium carbonate, sodium phosphate, sodium hydroxide and sodium acetate, organic basic compounds such as water-soluble amine compounds such as triethanolamine and diethanolamine, lactic acid and citric acid. Etc.
Examples of the preservative or antifungal agent include carboxylic acid, sodium salt of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6 -Tetrachloro-4- (methylsulfonyl) pyridine and the like.
Furthermore, an antifoaming agent such as a fluorine-based surfactant that improves the permeability of the solvent, a nonion, an anion, a cationic surfactant, or dimethylpolysiloxane may be added.

  In addition, one or more water-soluble resins such as alkyd resin, acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin may be added within the range that does not impair drying resistance, or urea In addition, one or more wetting agents such as nonionic surfactants, sorbitol, mannitol, sucrose, glucose, reduced starch hydrolyzate, sodium pyrophosphate can be added.

A shear thinning agent can be added to the water-based 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 Thickening polysaccharides having gelling ability extracted from seaweed such as benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, poly Tylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, etc. have an HLB value of 8 to Twelve nonionic surfactants, salts of dialkyl or dialkenylsulfosuccinic acid and the like can be exemplified, and they can be used alone or in combination.
Furthermore, a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, a mixture of polyvinyl alcohol and an acrylic resin can also be used.
The shear thinning agent can be used in the range of 0.1 to 20% by weight in the ink composition.

In addition, a rust preventive agent, a lubricant, etc. can be added as needed.
Examples of the rust inhibitor include benzotriazole and derivatives thereof, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, sodium thiosulfate, ethylenediaminetetraacetate, saponin, and dialkylthiourea.
Examples of the lubricant include metal soap, polyalkylene glycol fatty acid ester, ethylene oxide addition type cationic activator, phosphate ester activator, thiocarbamate, dimethyldithiocarbamate and the like.
A particularly preferably used lubricant is a phosphate ester surfactant described in JP-B-1-13508.

  The water-based ink composition for a writing instrument of the present invention is filled in a marking pen or a ballpoint pen having a fiber tip, a felt tip, a plastic tip or a ballpoint tip attached to the tip of the writing.

  The structure and shape of the ballpoint pen itself are not particularly limited, and a conventional one can be applied. For example, the ballpoint pen has an ink containing tube filled with an ink composition, and the ink containing tube has a ball. An example is a ballpoint pen that communicates with a tip attached to the tip, and further has a liquid stopper for backflow prevention in close contact with the end face of the ink.

The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or a metal material is cut by a drill or the like A chip formed by holding the ball in the ball holding part formed by the above, or a ball held in a chip formed by cutting a metal pipe or metal material, and the like that is urged forward by a spring body, etc. Can be applied.
The ball may be cemented carbide, stainless steel, ruby, ceramic, or the like.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, or polyethylene terephthalate is preferably used as the ink storage tube for storing the water-based ink composition in terms of low ink evaporation and productivity. Further, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining ink amount, and the like can be confirmed.
In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member.
The ink storage tube may be a refill type in which the refill is stored in a shaft tube, or the shaft tube itself having a tip attached to a tip is used as an ink container, and ink is directly applied to the shaft tube. It may be filled.

The back end of the ink composition housed in the ink housing tube is filled with an ink backflow prevention body.
The ink backflow preventer can be either liquid or solid, and the liquid ink backflow preventive includes non-volatile media such as polybutene and silicone oil. Aluminum silicate or the like can also be added.
Moreover, a resin molding is mentioned as a solid ink backflow prevention body.
Further, the liquid and solid ink backflow preventers can be used in combination.

  The water-based ink composition for writing instruments of the present invention is charged with a dye or pigment (pigment dispersion), a water-soluble organic solvent, a phenylethanoid glycoside, and, if necessary, a shear thinning agent and various additives in an aqueous medium. If necessary, it is prepared by heating and stirring, dissolving and dispersing, and is used by filling in a writing instrument such as a ballpoint pen, a sign pen, a felt pen, and a brush pen.

Examples will be described below, but the present invention is not limited to these examples.
Table 1 shows compositions of water-based inks for ballpoint pens of Examples and Comparative Examples. 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) Sanyo Dye Co., Ltd., trade name: Sundai Super Color Blue GLL
(2) Eisen Hodogaya Co., Ltd., trade name: Phloxine (3) Orient Chemical Industry Co., Ltd., trade name: Water Black 100L, C.I. I. Direct Black 19, dye content 20%
(4) Product name: Kanka extract P25 (active ingredient 50%), manufactured by Oriza Oil Chemical Co., Ltd.
(5) Phosphate ester surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf AL
(6) Phosphate ester surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Prisurf A212C
(7) Product name: Kirest M-50, manufactured by Kirest Co., Ltd.

Preparation of ink Each raw material was mixed in the blending amounts of the above Examples and Comparative Examples, and the mixture was stirred and dissolved at 20 ° C. for 3 hours to obtain a writing instrument aqueous ink composition.

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 pens Each of the ink compositions is filled in a ballpoint refill in which a stainless steel chip holding a ball of a hard metal having a diameter of 0.4 mm is fitted to one end of a polypropylene pipe, and the rear end is filled with the ink composition. After arranging the ink backflow prevention body, the ballpoint pen refill was incorporated into a shaft tube to prepare a sample ballpoint pen.

After leaving the sample ball-point pen at 50 ° C. for 60 days, the presence or absence of bubbles in the ink containing tube and the state of the handwriting by a writing test (written on JIS P3201 writing paper A) were visually observed.
The results are shown below.

The criteria in the table are as follows.
Written test ○: Good handwriting is obtained.
X: Scratch and line skipping are seen in the handwriting.

Claims (3)

  A water-based ink composition for a writing instrument comprising at least a colorant, a water-soluble organic solvent, water, and a phenylethanoid glycoside.   The water-based ink composition for a writing instrument according to claim 1, comprising 0.1 to 3% by weight of the phenylethanoid glycoside in the ink composition.   A writing instrument comprising the ink back tube directly filled in the ink containing tube with the water-based ink composition for a writing instrument according to claim 1 or 2 and closely arranged at the rear end of the ink.