JPH08199108A - Water-based pigment ink for ball point pen - Google Patents

Abstract

PURPOSE: To prepare a water-born pigment ink for ball point pens, comprising a metallic powder pigment, a resin, a specific compound, a water-soluble organic solvent and water, showing excellent abrasion properties, smooth writing without line break and blurring. CONSTITUTION: This pigment ink comprises (A) 5-40wt.% of a metallic powder pigment such as brass or aluminum powder (preferably in the leaflet form), (B) 0.1-10wt.% of a water-soluble resin such as methyl-cellulose, CMC or pullulan as a viscosity controller, (C) 0.05-5wt.% of a compound of the formula (R1 is an 8-20C hydrocarbon; R2 is H, a 1-3C alkyl; X is a metal such as Na, K, NH3 , an amine such as MH2 C2 OH4 ), typically sodium N-oleyl-sarcosinate, (D) 10-40% of a water-soluble organic solvent such as ethylene glycol or sulfolane, and (E) 40-85wt.% of water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based pigment ink for use in a ballpoint pen, and more particularly to a water-based pigment ink for a ballpoint pen which uses a metal powder pigment as a colorant and has excellent abrasion resistance and provides a smooth writing appearance. .

[0002]

2. Description of the Related Art Conventionally, as a water-based pigment ink for ball-point pens, there is known one using a metal powder pigment as a coloring material and further containing a water-soluble resin, a water-soluble organic solvent and water.

[0003]

However, when a metal powder pigment is used as the coloring material, there is a problem that the dispersibility of the pigment is unstable and the pigment easily aggregates, and writing becomes impossible over time. Also, when used as ink for ballpoint pens, the ball seat of a synthetic resin or metal ballpoint pen tip wears due to friction with the ball during writing, and the clearance between the ball from which the ink is drawn out and the tip is blocked. There is a problem in that the ink is insufficiently led to the tip of the ball, and as a result, the handwriting is blurred and smooth writing cannot be performed.

[0004]

The present invention comprises a metal powder pigment,
The gist is a water-based pigment ink for a ballpoint pen, which contains at least a resin, a compound represented by Chemical formula 1, a water-soluble organic solvent, and water.

The details will be described below. The metal powder pigment is used as a coloring material, and examples thereof include brass powder and aluminum powder. As the brass powder, brass powders BS-605, BS607 (manufactured by Toyo Aluminum Co., Ltd.), bronze powder P-555, P-7 are used as a paste type.
77 (manufactured by Nakajima Metal Foil & Powder Industry Co., Ltd.), bronze powder 3L5, 3L7 (manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) and the like.

[0006] The aluminum powder is particularly preferably in the form of scales because the metallic luster appears more clearly. Aluminum powder is produced by a stamping method in which aluminum pieces are crushed with a friction reducing agent such as stearic acid or inorganic phosphoric acid in a stamping mill, or aluminum powder obtained by an injection method, a lubricant and a suitable liquid in a drum together with a hard ball. It is obtained by a ball mill method or the like in which the aluminum pieces are crushed by rotating the drum by rotating the drum. As a commercial product, it is usually available as an aluminum paste. Aluminum paste is made by grinding and polishing aluminum metal powder in a ball mill containing a high boiling point petroleum solvent (mineral spirit) and a degreasing agent such as stearic acid or inorganic phosphoric acid to form a very thin scale. Since it is made of aluminum fine particles, there is little danger of ignition and explosion, good storage stability, and easy handling in use.

The average particle diameter of the aluminum powder is 5 μm
It is preferable to use the above. This is because if the average particle size is less than 5 μm, the metallic luster of the handwriting is reduced, and unclear handwriting is likely to occur. Especially when used as an ink for ballpoint pens, the average particle size is 30μ.
m or less is preferable. This is because if the average particle diameter exceeds 30 μm, the ink discharge tends to be reduced with a pen tip having a size conventionally used as a ball-point pen, and it tends to be difficult to apply.

Specific examples of the aluminum powder include Alpaste WB0230, WX0630 (above, manufactured by Toyo Aluminum Co., Ltd.), and Superfine 22000W.
N, the same No. 18000 WN (above, Daiwa Metal Powder Co., Ltd.), aluminum powder AA12, No900, N
o. 18,000 (above, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) and the like.

The above metal powder pigments can be used alone or in combination. The amount used is preferably 5 to 40% by weight with respect to the total amount of the aqueous pigment ink for ballpoint pens. When the amount used is less than 5% by weight, the metallic luster on the handwriting is reduced, and when the amount used exceeds 40% by weight, the solid content increases and the fluidity decreases, tending to result in poor ink ejection. The types of pigments to be used and the proportions when they are mixed and used are appropriately selected.

The water-soluble resin is used as a fixing agent for handwriting and as a viscosity adjusting agent.
The fixing agent (binder resin) is used for forming a film of a handwriting or dispersing a pigment, and a water-soluble resin such as a water-soluble acrylic resin, a water-soluble styrene-acrylic resin or a water-soluble styrene-maleic acid resin, Examples thereof include water-dispersible resins such as acrylic emulsions, vinyl acetate emulsions and urethane emulsions, and the amount thereof is preferably 0.1 to 20% by weight based on the total amount of the aqueous pigment ink.
Resins used as viscosity modifiers are water-soluble cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, pullulan, xanthan gum, welan gum, rhamsan gum, succinoglucan, dextran and other microorganism-producing polysaccharides or derivatives thereof, and traganci gum. , Water-soluble plant polysaccharides or their derivatives such as guar gum, guar gum, locust bean gum, tara gum, karaya gum, arabinogalactan gum, gati gum, quisseed gum, silium seed gum, gum arabic, pectin, starch, carrageenan, alginic acid, etc. Seaweed-type polysaccharides or their derivatives, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polyethylene oxide, polyvinyl chloride Known resins such as water-soluble synthetic polymer pyrrolidone or the like can be used alone or in combination, the amount used is preferably 0.1 to 10 wt% of the aqueous pigment ink total amount.

In particular, microbial-based xanthane gum is excellent in that it has stable physical properties even when used in combination with aluminum powder, and has little change in viscosity. This is because when aluminum powder begins to dissolve in water as ions due to the trace amount of electrolyte contained in the ink, water-soluble resins commonly used for preventing the sedimentation of pigments and adjusting the viscosity of the ink, such as cellulose-based and polyoxy resin. Due to the action of aluminum ions, ethylene and the like tend to increase or decrease in viscosity due to gelation, hydrolysis or partial insolubilization. On the other hand, xansan gum has glucuronic acid, which is its side chain, By virtue of the ionic bond between and the aluminum ion, the viscosity is slightly increased, the viscosity stability can be maintained even after long-term storage, and the deterioration of the ink can be suppressed. In addition, dextran has the property of being excellent in stability over time in an ink using a metal powder pigment. This dextran is a homopolysaccharide consisting of D-glucose produced mainly by bacteria of the genus Leuconostoc, but it is also obtained from other bacteria, and generally D-glucose is α-1, It is a 6-bonded polysaccharide and may have α-1,4 bond and α-1,3 bond in addition to this.
Examples of the dextran derivative include dialkyl dextran, dextran sodium sulfate, dextran benzyl ether and the like. In addition, dextran is
Those having an intrinsic viscosity of 0.15 to 0.90 are preferable,
The amount used is 0.5 to 15 with respect to the total amount of the aqueous pigment ink.
Weight percent is preferred. This is because dextran having an intrinsic viscosity of less than 0.15 exerts sufficient protective colloidal property for a substance having a small specific gravity such as an ordinary pigment, but has a specific gravity such as that of the metal powder pigment used in the present invention. This is because a large pigment may not have sufficient protective colloid properties, and when it exceeds 0.90, the protective colloid layer becomes too thick and the metal powder pigments tend to be entangled with each other and easily aggregate.

The compound represented by the above chemical formula 1 is used for imparting lubricity to the aqueous pigment ink for ballpoint pens of the present invention, and is N-oleoyl sarcosine sodium, N-myristoyl sarcosine sodium, N-lauroyl glycine sodium, N-oleoyl sarcosine ammonium, N-myristoyl sarcosine ammonium, N-lauroyl glycine ammonium, oleoyl sarcosine, cocoyl sarcosine sodium, palmitoyl sarcosine sodium, lauroyl sarcosine, potassium lauroyl sarcosine, sodium lauroyl sarcosine, sodium lauroyl methylalanine and the like can be mentioned. . The amount used is 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the total amount of the aqueous pigment ink for ballpoint pens.
% By weight. If the amount is less than 0.05% by weight, the effect is small, and if the amount is more than 5% by weight, no further effect is exerted, which is disadvantageous in cost.

The water-soluble organic solvent is ethylene glycol,
Glycols such as diethylene glycol and propylene glycol, ethylene glycol monomethyl ether,
Glycol ethers such as ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, carbitols such as diethylene glycol monoethyl ether, sulfolane, thiodiethylene glycol, acetin, etc., which can be used alone or in combination, The amount used is 1 to 50% by weight, preferably 10% by weight, based on the total amount of the water-based pigment ink for ballpoint pens.
-40% by weight.

Water is used as a main solvent, and its amount is 40 with respect to the total amount of the water-based pigment ink for ballpoint pens.
~ 85%.

In addition to the above components, if necessary, antiseptic and fungicides such as 1,2-benzisothiazolin-3-one, pentachlorophenol and cresol, rust preventives such as benztriazole, dispersants and viscosity modifiers. , Various additives such as color pigments and various surfactants can be used appropriately.

The preparation of the water-based pigment ink for this ballpoint pen is as follows.
A conventionally known ink manufacturing method can be applied.
That is, an aqueous pigment ink for a ballpoint pen can be obtained by mixing the above components and dispersing the pigment together with other components by a dispersion mixer. It should be noted that, during production, heating for removing bubbles generated, mechanical degassing under reduced pressure, and the like are particularly preferable methods.

[0017]

It is not clear why the water-based pigment ink for ballpoint pens of the present invention is excellent in abrasion resistance, but it is presumed as follows. When used in an aqueous pigment ink, the compound represented by the above chemical formula 1 used in the present invention exhibits an excellent abrasion resistance without damaging the pigment dispersion system. This is because the compound represented by Chemical formula 1 is chemically adsorbed on the surface of the metal powder pigment.

[0018]

EXAMPLES Examples and comparative examples will be shown below. Example 1 Alpaste WX0630 10.0 parts by weight John Krill J775 (binder resin, styrene-acrylic acid copolymer emulsion, manufactured by Johnson Polymer Co., Ltd.) 0.5 parts by weight Kelzan AR (viscosity modifier, zansan gum, three Crystal Co., Ltd.) 1.0% by weight N-oleoyl sarcosine sodium 1.0 part by weight Ethylene glycol 20.0 parts by weight Propylene glycol 10.0 parts by weight Water 57.5 parts by weight The above components are mixed and the lower blade is mixed. The mixture was stirred for 30 minutes with a dispersion stirrer to obtain a silver aqueous pigment ink for ballpoint pens.

Comparative Example 1 A silver-colored aqueous pigment ink for ballpoint pens was obtained in the same manner as in Example 1 except that N-oleoyl sarcosine sodium was removed and water was added in that amount.

Example 2 Brass powder BS605 20.0 parts by weight John Cryl J61J (binder resin, styrene-acrylic acid copolymer ammonium salt, manufactured by Johnson Polymer Co., Ltd.) 2.0 parts by weight N-myristoyl sarcosine sodium 2 0.0 parts by weight Glycerin 20.0 parts by weight Ethylene glycol 20.0 parts by weight Water 35.8 parts by weight Proxel GXL (antifungal agent) 0.2 parts by weight The above components are mixed and mixed with a lower blade dispersion stirrer 30 After stirring for a minute, a golden water-based pigment ink for ballpoint pens was obtained.

Comparative Example 2 A gold aqueous pigment ink for ballpoint pens was obtained in the same manner as in Example 2 except that N-myristoyl sarcosine sodium was removed and water was added in that amount.

Example 3 Alpaste WB0230 8.0 parts by weight DURIMER AC-20L (binder resin, sodium salt of acrylic acid resin, manufactured by Nippon Pure Chemical Co., Ltd.) 10.0 parts by weight N-lauroylglycine ammonium 4. 0 parts by weight Propylene glycol 20.0 parts by weight Water 51.5 parts by weight Copper phthalocyanine blue 5.0 parts by weight Benztriazole 0.5 parts by weight The above components are mixed and stirred with a lower blade type dispersion stirrer for 30 minutes to obtain metallic. A blue water-based pigment ink for ballpoint pens was obtained.

Comparative Example 3 A metallic blue aqueous pigment ink for ballpoint pens was obtained in the same manner as in Example 3, except that N-lauroylglycine ammonium was removed and water was added in that amount. .

Example 4 Bronze powder P-777 10 parts by weight John Kryl J-511 (binder resin, styrene-acrylic acid copolymer emulsion, manufactured by Johnson Polymer Co., Ltd.) 5 parts by weight N-oleoyl sarcosine sodium 1 Parts by weight diethylene glycol 15 parts by weight ethylene glycol 20 parts by weight water 49 parts by weight The above components were mixed and stirred with a lower blade type dispersion stirrer at 50 ° C. for 30 minutes to obtain a golden ink.

Example 5 Bronze powder P-777 10.00 parts by weight John Cryl J62 (binder resin, styrene-acrylic acid copolymer ammonium, manufactured by Johnson Polymer Co., Ltd.) 10.00 parts by weight N-oleoyl sarcosine Sodium 0.02 parts by weight Diethylene glycol 15.00 parts by weight Ethylene glycol 20.00 parts by weight Water 44.98 parts by weight The above components are mixed and stirred with a lower blade type dispersion stirrer for 30 minutes, and then a golden aqueous pigment ink for ballpoint pens. Got

Preparation of test samples: The water-based pigment inks for ball-point pens obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were commercially available water-based ball-point pens (K105, manufactured by Pentel Co., Ltd.,
The pen tip consisted of a stainless steel tip and a cemented carbide ball), and 0.8 g was filled in a writing instrument similar to that described above to prepare a test sample.

Abrasion resistance test: Each of the above test samples was written using a commercially available rotation type continuous writing force measuring machine (spiral machine) to write 7c.
The ball sinking is measured from the difference between the ball protrusion after continuous writing for 500 m and the ball protrusion before writing at m / sec, a load of 100 g, and an angle of 70 °.

First-time brush fading test: After handwriting each of the test samples described above, the test sample was handwritten and the temperature was 5 in a horizontal direction with the cap removed.
Let stand for 24 hours under conditions of 0 ° C and 30% humidity. After taking it out, it is left for 2 hours in a room at a temperature of 22 ° C. and a humidity of 60% to return to room temperature, and then handwritten in a straight line. Measure the length from the beginning of writing to the position of the handwriting that was normally written with a ruler.

Writing smoothness test: Each of the above test samples is handwritten and the smoothness of the writing is evaluated organoleptically (smooth; ◯, somewhat good; Δ, bad; ×).

[0030]

[Table 1]

[0031]

As described above in detail, the water-based pigment ink for ball-point pens according to the present invention has excellent effects such as excellent abrasion resistance, giving a smooth writing appearance, and being free from unwriting and scratching. are doing.

Claims (1)

[Claims] 1. An aqueous pigment ink for a ballpoint pen, which contains at least a metal powder pigment, a resin, a compound represented by Chemical formula 1, a water-soluble organic solvent, and water. Embedded image (In the formula, R ₁ is a saturated or unsaturated hydrocarbon having 8 to 20 carbon atoms, R ₂ is H or an alkyl group having 1 to 3 carbon atoms, and X is N.
a, metal such as K or amine such as NH ₃ , NH ₂ C ₂ H ₄ OH)