JPH10316922A - Water-base metallic gloss color ink for ballpoint pen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base metallic gloss color ink for ball-point pens, which can be delivered smoothly from the point of a ball-point pen by dispersing a specified amount of an aluminum powder pigment in a water-base vehicle containing a natural or semisynthetic polysaccharide; a specified amount of a metal chelating agent, a water-soluble organic solvent and water. SOLUTION: The ink composition contains 0.1-15 wt.% aluminum powder pigment and 0.1-5 wt.% metal chelating agent. The water-base vehicle optionally contains cyclodextrin as a dispersion stabilizer for the pigment. The aluminum powder pigment may be a leafing or non-leafing type having a mean particle diameter of 5-25 μm. The metal chelating agent is selected among ethylenediamine tetraacetic acid(EDTA), hydroxyethylenediamine triacetic acid (HWDA), glycol ether diamine tetraacetic acid(GEDTA) and alkali metal salts, ammonium salts and amine salts thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based metallic glossy ink for a ballpoint pen, which gives a writing surface of a metallic glossy color based on silver white on a writing surface.

[0002]

2. Description of the Related Art This type of ink is liable to react with an acidic component, a basic component or dissolved oxygen in an aqueous medium due to the properties of metallic aluminum, and as a result of these reactions, generates a gas such as hydrogen. . The gas generated in the ink in the ballpoint pen tends to cut off the ink flow path and hinder the outflow of ink from the pen tip during writing. As a means for suppressing the occurrence of this reaction, a perfluoroalkyl phosphate and / or a perfluoroalkyltrimethylammonium salt is contained in the ink (Japanese Patent Application Laid-Open No.
Means of incorporating N-fatty acid acyl-L-glutamate (JP-A-8-209053) have been proposed. However, these proposals also do not sufficiently satisfactorily suppress the reaction.

[0003]

SUMMARY OF THE INVENTION The present invention provides an aqueous metallic luster color for a ballpoint pen in which the generation of the gas in the ink in the ballpoint pen is suppressed as much as possible, so that the ink flow from the ballpoint pen tip is not interrupted during writing. It is intended to provide ink.

[0004]

SUMMARY OF THE INVENTION The aqueous metallic glossy ink for ballpoint pens of the present invention has an aluminum powder pigment dispersed in an aqueous vehicle containing a natural or semi-synthetic polysaccharide, a metal chelating agent, a water-soluble organic solvent and water. The ink composition contains 0.1 to 15% by weight of an aluminum powder pigment and 0.1 to 5% by weight of a metal chelating agent. The aqueous vehicle optionally contains cyclodextrin as a dispersion stabilizer for the pigments.

[0005] The aluminum powder pigment used may be of the leafing or non-leafing type as long as it has an average particle diameter in the range of 5 to 25 µm. Alpaste 96-2104 (Toyo Aluminum Co., Ltd., heating residue 60%) Alpaste WX
7830 (Toyo Aluminum Co., Ltd., heating residue 56
%) And the like. These aluminum powder pigments are used in the ink composition in the range of 0.1 to 15% by weight, preferably 0.3 to 10% by weight. When the ink content is less than 0.1% by weight, the handwriting hardly exhibits a metallic luster. When the content is more than 15% by weight, it is difficult to uniformly disperse the composition in the vehicle.

The metal chelating agents include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), glycol etherdiaminetetraacetic acid (GEDTA), nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), dihydroxy Ethylglycine (DHEG), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTH
A) and their alkali metal salts, ammonium salts or amine salts. These metal chelators supplement the trace amounts of metal ions present in the aqueous vehicle and prevent them from coming into contact with the aluminum powder pigment, thereby producing gas by the metal aluminum dissolution reaction caused by the metal ions. It is considered that it has the effect of suppressing The metal chelating agent accounts for 0.1 to 5% by weight, preferably 0.2%
To 3% by weight. If the addition is less than 0.1% by weight, a sufficient gas generation suppressing effect cannot be obtained, and 5% by weight
The effect is saturated by the addition up to, and the effect does not increase even if the amount is added more.

Next, a coloring agent selected from organic pigments, fluorescent pigments, and pearl pigments is used to obtain an ink that provides handwriting having a gold color, a copper color, or another metallic color. Examples of the organic pigment include azo-based, anthraquinone-based, condensed polyazo-based, thioindigo-based, metal complex salt-based, phthalocyanine-based, perinone-based, perylene-based, dioxazine-based, and quinacridone-based pigments. A processed easily dispersible processed pigment is also suitably used. These organic pigments are contained in the ink composition in an amount of 0.01%.
To 5% by weight, preferably 0.05 to 3% by weight.

[0008] The fluorescent pigment is a fluorescent dye such as rhodamine or flavin, which is obtained by copolymerizing an acrylic resin obtained by emulsion polymerization from a monomer such as styrene, (meth) acrylic acid, (meth) acrylic acid ester or acrylonitrile. Is preferably used, and 3 to 3
It is used in the range of 30% by weight, preferably 5 to 20% by weight.

The pearl pigment is an iris pigment obtained by coating the surface of mica pieces with a metal oxide such as titanium oxide or iron oxide, or a coloring agent such as carbon black or an organic pigment, and has an average particle diameter of 5 to 60 μm. Is preferably used. An ink using a pigment having a particle diameter of less than 5 μm can obtain only a handwriting with low gloss, and an ink using a pigment having a coarse particle diameter of more than 60 μm easily clogs in a capillary passage of the pen tip. This will make the outflow worse. These pearl pigments are used in the ink composition in the range of 1 to 20% by weight, preferably 2 to 15% by weight.

Examples of the polysaccharides added to thicken the ink include seed polysaccharides such as guar gum, locust bean gum and derivatives thereof, microbial xansan gum and succinoglycan, etc. Natural or semi-synthetic polysaccharides such as ginnan gum, alginic acid and its derivatives, and the resin-based polysaccharide, tarragant gum, are included in the ink composition in an amount of 0.1 to 0.8% by weight, preferably 0.2 to 0.8% by weight. It is used in the range of 0.5% by weight.

Cyclodextrin is used as a dispersion stabilizer for suppressing the sedimentation of pigments. It is considered that the pigment particles are wrapped in the ink to prevent the bare pigment particles from aggregating to form a hard cake. The cyclodextrin may be any of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and maltosyl cyclodextrin, and is used in an amount of 1 to 13% by weight, preferably 2 to 10% by weight in the ink composition.

The water-soluble organic solvent serves as a humectant for preventing the ink from drying out in the ballpoint pen, particularly at the tip of the ballpoint pen, thereby preventing writing from being performed, and is commonly used for ethylene glycol, glycerin, propylene glycol, and diethylene glycol. A non-volatile water-soluble organic solvent such as 2, 2-pyrrolidone is used in an amount of 5 to 40% by weight in the ink composition.

As other additives, a lubricant, a rust inhibitor, a surfactant, a water-soluble resin and the like may be added as required. As the lubricant, a polyoxyethylene monoether phosphate ester surfactant is suitably used, and when added, it is used in an amount of 0.1 to 3% by weight, preferably 0.3 to 2% by weight in the ink composition. Used.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The metallic glossy ink for a ballpoint pen of the present invention is prepared by the following formulation. A water-soluble organic solvent, a metal chelating agent, other additives, a preservative, and if added, cyclodextrin and an organic pigment are added to a predetermined amount of water, and the mixture is stirred by a disper to form a homogeneous mixture. A polysaccharide, an aluminum powder pigment and, if added, a pearl pigment were added to the mixed solution, and the mixture was subjected to high-speed stirring (about 5000 rpm) for about 2 hours using a disper. Then, the mixture was charged into a tabletop defoaming kneader H-NBK (Kokusan Co., Ltd.), and rotated under the conditions of rotation at 1300 rpm with rotation.
A defoaming treatment was performed for 5 minutes to obtain a sample ink.

[0015]

EXAMPLES The compositions of the inks of the examples prepared according to the above-mentioned formulas and the inks of comparative examples prepared according to the above-mentioned formulas are shown in Table 1. All the numerical values of the compositions in the table are expressed in parts by weight.
The compositions of the inks of Comparative Examples 1, 2 and 3 are the compositions in which the metal chelating agent in the compositions of the inks of Examples 1, 2 and 4 are replaced with an equal amount of water, respectively. Are compositions based on the inventions described in JP-A-6-192610 and JP-A-8-209053, respectively.

[Table 1]

The details of the contents of the raw materials in the table are described below according to the note numbers. (1) Aluminum paste 96-2104 (Toyo Aluminum Co., Ltd. product name) Average particle size 5-10 μm, heating residue 60% (2) Aluminum paste WX7830 (Toyo Aluminum Co., Ltd. product name) Average particle size 10 μm, heating Residue 56% (3) Aqueous pigment dispersion composed of 20% phthalocyanine blue pigment, 18% acrylic / styrene copolymer, 58% water, and 4% other (4) Iriodin 221 (product name of Merck Japan Ltd.) Particle size 5 to 25 μm, rutile type, fine blue color (5) Chilesto M-50 (product name of Chilesto Co., Ltd.) Emine amine salt solution, pH 7.0 (6) Chilesto NTB (product name of Kyresto Co., Ltd.) NTA Disodium salt, molecular weight 235, content 98%,
pH 6.5 (7) Chilesto 2C (product name of Chilesto Co.) EDTA trisodium salt trihydrate, molecular weight 412,
Content 99%, pH 7.0 (8) 2% Leosan (Sansei Co., Ltd. product) aqueous dispersion Leosan: semi-synthetic polysaccharide (succinoglycan) (9) 5% Chemicogel (product of Dainippon Pharmaceutical Co., Ltd.) Name) Aqueous dispersion Chemicogel: natural polysaccharide (xanthan gum) (10) Dexie Pearl K-100 (product name of Shimizu Port Sugar Co., Ltd.) 98% or more of total cyclodextrin, 70% or more of α-cyclodextrin in total (11) Plysurf M208B (Daiichi Kogyo Seiyaku Co., Ltd. product name) Polyoxyethylene monoether phosphate ester surfactant (12) F-top EF-132 (Mitsubishi Chemical Corporation product name) Perfluorotrimethylammonium salt (13) N-coconut fatty acid acyl-L-sodium glutamate: manufactured by Ajinomoto Co. (14) Topside 280: preservative manufactured by Palmchem Co., Ltd.

About the obtained sample ink, viscosity, pH
And other physical properties. The viscosity was measured using an ED type viscometer under three conditions of a rotor rotation speed of 1, 10, and 100 rpm, and the respective viscosity values were represented by η ₁ , η ₁₀ , and η ₁₀₀ . Table 2 shows the measured values. Next, 1 g of each of the sample inks was injected into a transparent plastic pipe-shaped ink inner cylinder having a ballpoint pen tip fitted at one end, and a grease-like liquid stopper (ink follower for preventing ink backflow) was filled at the other end. Centrifugal treatment was applied to the tip of the ballpoint pen for about 30 seconds with a centrifugal force of about 800 G of gravity to deaerate the inner cylinder of the ink. The processed ink inner cylinder was incorporated into a writing shaft cylinder to prepare a sample ballpoint pen, and after confirming that writing was possible, three sample ballpoint pens with caps fitted in a constant temperature bath maintained at 50 ° C. were set upright ( Pen point up) and inverted (point down)
An acceleration test was performed in which the device was left standing for 30 days. The aged sample ballpoint pen was taken out of the thermostat and left to reach room temperature, and the following items were tested.

(1) Presence or Absence of Air Bubbles In the sample pen left standing upright, in particular, with respect to the sample pen left standing upside down, it was observed whether air bubbles stayed at the interface between the ink and the liquid stopper. The evaluation of the results is as follows. ：: No air bubble generated △: Slight air bubble generation ×: Large air bubble generation In addition, stagnation of air bubbles at the pen tip causes ink shortage during writing, causing ink to flow to the interface between the ink and the liquid stopper. The retention of bubbles causes ink leakage (ink backflow) from the open end of the ink inner cylinder. (2) Initial brushability (writing performance) of sample ballpoint pen after test One line of paper having ruled lines at 7 mm intervals, about 12 m in width
The operation of drawing m continuous ellipses was repeated, and the number of blank lines required until normal handwriting was obtained was measured.
The evaluation of the results is as follows. ○: Writable in less than one line △: Two to five lines are required before writing becomes possible ×: Writable even in five lines

Table 2 shows the test results.

[Table 2] In Table 2, the handwriting color tone "silver white" and "meta blue" represent silver white and metallic blue, respectively.

[0020]

As can be seen from the test results, the aqueous metallic glossy ink for ball-point pens of the present invention can reliably suppress the generation of air bubbles even with aging at a high temperature by adding a metal chelating agent. Good writing performance within the period is promised.

Claims (4)

[Claims] 1. An aqueous ink comprising an aluminum powder pigment dispersed in an aqueous vehicle containing a natural or semi-synthetic polysaccharide, a metal chelating agent, a water-soluble organic solvent and water,
An aqueous metallic glossy ink for a ballpoint pen, characterized in that the ink composition contains 0.1 to 15% by weight of an aluminum powder pigment and 0.1 to 5% by weight of a metal chelating agent. 2. The metal chelating agent is ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), glycol etherdiaminetetraacetic acid (GEDTA), nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), dihydroxy Ethylglycine (DHEG), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTH
The aqueous metallic glossy color ink for ballpoint pens according to claim 1, wherein the aqueous metallic glossy ink is selected from the group consisting of A) and alkali metal salts, ammonium salts or amine salts thereof. 3. The aqueous metallic glossy ink for ball-point pens according to claim 1, wherein the aqueous vehicle further contains cyclodextrin. 4. The aqueous metallic glossy ink for ball-point pens according to claim 1, wherein a colorant selected from organic pigments, pearl pigments and fluorescent pigments is further added to the ink composition.