JPH05271602A - Water-based ink for writing utensil - Google Patents

Abstract

PURPOSE:To enable an ink to have in a writing utensil the same color as that of the characters written with the ink to produce an improved display effect at a store counter. CONSTITUTION:This ink for use in a writing utensil, such as a ball-point pen or marking pen, which has an ink chamber and a barrel each made from a transparent or translucent material in order that the ink be visible from outside comprises a water-soluble dye such as an acid or direct dye, hollow particles of poly(methyl methacrylate), an acrylic-styrene copolymer, etc., and water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an ink containing portion,
The present invention relates to a water-based ink for a writing instrument used in a writing instrument in which the ink in the ink containing section can be visually recognized from the outside. It is particularly suitable for raw ink type ballpoint pens, marking pens and the like.

[0002]

2. Description of the Related Art Conventionally, a writing instrument has a pen tip attached to one end of a barrel which is a main body of the writing instrument, an ink containing portion is formed in the barrel, and ink in the ink containing portion is led out to the pen tip. A so-called refill type, in which a built-in writing instrument or a barrel having an ink storage portion inside and a pen tip attached to one end (so-called refill) is inserted and fixed in the barrel of the writing instrument body. Writing instruments are known. In the above writing instrument, the barrel of the writing instrument main body and the barrel of the refill are made of transparent or translucent material so that the remaining ink amount can be confirmed from the outside, or a part of the barrel is transparent or translucent. Is said. A water-based ink used for such a writing instrument contains a coloring material and water as main components.

When a water-soluble dye is used as the coloring material, the light incident on the ink in the liquid state is absorbed by the dye, and the color of the ink in the ink containing portion seen from the outside of the writing instrument is very similar to the handwriting. It will be different. For example, blue, green, yellow-green, sky blue, purple, brown, etc. are difficult to distinguish from black, and orange, pink, etc. are difficult to distinguish from red. Therefore, the color of the ink is usually displayed by making the tail plug, the cap, and the like the same color as the handwriting.

[0004]

However, in particular,
The barrel of the writing instrument body and the barrel of the refill are made of transparent or translucent material, or part of the barrel is transparent or translucent so that the remaining ink level can be checked from the outside. When a dye is used for the writing instrument, if the color of the ink in the ink containing portion is difficult to distinguish from blue or green, it has a drawback that the display effect at the store is low and the appearance is low. There is also a problem that the tail plugs and caps have to be made in different colors, which tends to increase costs. Therefore, an object of the present invention is to provide a water-based ink for a writing instrument that allows the ink color to be visually recognized from the outside.

[0005]

According to the present invention, there is provided a water-based ink for a writing instrument for use in a writing instrument which has an ink containing section and allows the ink in the ink containing section to be visually recognized from the outside. A water-based ink for a writing instrument, which is characterized in that it contains a dye, hollow polymer particles, and water.

The details will be described below. The writing instrument which has the ink containing section according to the present invention and allows the ink in the ink containing section to be visually recognized from the outside is a so-called ink in which the ink containing section is directly formed in the barrel as the writing instrument body as described above. It may be a built-in type or may be a so-called refill type in which the inside of the shaft cylinder serves as an ink containing portion and a refill having a pen tip attached to one end is inserted and fixed in the shaft cylinder which is the main body of the writing instrument. Further, an ink occlusion body such as a fiber bundle may be arranged in the ink containing portion. In order to make the ink inside the ink container visible from the outside of the writing instrument, in the case of the so-called ink built-in type, it is necessary to mold the barrel that is the main body with a transparent or translucent material. It is necessary to mold the refill and the writing instrument main body with a transparent or translucent material. Of course, only a part of the refill or the writing instrument main body may be transparent or semi-transparent. As the transparent or translucent material, polypropylene, polystyrene, methacrylic resin, polyethylene, polyphenylene ether resin, polyphenylene sulfide resin, polycarbonate, polybutadiene, ionomer resin, vinyl chloride resin, acetic acid fibrous resin, polysulfone resin, polymethylpentene, Polyethylene terephthalate, polyamide, polybutylene terephthalate,
Transparent or translucent grades of thermoplastic resins such as ethylene vinyl acetate copolymer, acrylonitrile / butadiene / styrene copolymer resin, acrylonitrile / styrene copolymer resin, and fluororesin can be used. The cross section of the refill or the barrel of the writing instrument main body is not limited to a circular cross section, but may be an oval shape or a square shape.

The water-soluble dye used in the water-based ink is a coloring material, and is a conventionally known acid dye, direct dye, basic dye,
Any of the food dyes can be used. Acid dyes include C.I. I. Acid Red 87, C.I. I. Acid Blue 9, C.I. I. Acid Yellow 23, C.I. I. Acid Red 92, C.I. I. Acid Black 2, C.I.
I. Acid Violet 49 and the like. Direct dyes include C.I. I. Direct Black 19, C.I.
I. Direct Black 154, C.I. I. Direct Blue 86, C.I. I. Direct Red 1, C.I. I. Direct Blue 15, C.I. I. Direct Yellow 4 and the like can be mentioned. Examples of the basic dye include C.I. I Basic Blue 7, C.I. I. Basic Red 1, C.I. I. Basic Blue 26, C.I. I. Basic Green 4, C.I.
I. Basic Yellow 21 and the like can be mentioned. Most of the food dyes are contained in acid dyes or direct dyes, but as another example, C.I. I. Food yellow 3
Is mentioned. One kind or a mixture of two or more kinds can be used, and the amount used is 0.2 to 2 with respect to the total amount of the water-based ink for writing instruments.
0% by weight is preferred.

Hollow polymer particles are used to make the color of the water-based ink for writing instruments visible from the outside, and are known in the prior art by the composite particle emulsion method,
It can be obtained by an emulsion method of particles having a heterogeneous structure or a method of containing a volatile component. As the polymer, polyvinyl alcohol, polymethyl methacrylate, polyamide,
Polystyrene, polyvinyl chloride, an acrylic-styrene copolymer and the like can be used, but an acrylic-styrene copolymer is preferable in consideration of the hardness of the shell and the like. or,
The specific gravity is preferably 1 or less, and the particle diameter is preferably 1 μm or less. Specific examples of acrylic-styrene copolymers include ROPAQ
UE OP42, OP62, OP84 (Rome and Haas, USA), Primal OP42M
(Manufactured by Nippon Acrylic Co., Ltd.), SX863 (A), SX8
64 (B), SX865 (B) (above, manufactured by Nippon Synthetic Rubber Co., Ltd.) and the like. These are water-based emulsions and are hollow particles in which water is contained in a polymer shell. is there. The above-mentioned hollow polymer particles can be used alone or in combination of two or more, and the amount thereof is preferably 1 to 40% by weight in terms of solid content based on the total amount of the aqueous ink.

Water is used as a main solvent, and the amount thereof is preferably 40 to 95% by weight based on the total amount of the aqueous ink for writing instruments.

In addition to the above essential components, alcohols such as methanol, ethanol, propanol, and isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butylene glycol, in order to retain moisture or prevent freezing. Glycols such as thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, N-methyl-2-
Water-soluble organic solvents such as pyrrolidone, sorbit, sorbitan, acetin and glycerin can be used alone or in admixture of two or more.

Further, known moisturizing aids such as urea, thiourea, ethyleneurea or their derivatives, and water-soluble materials such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, pullulan, xanthane gum, tragacanth gum, guar gum and gum arabic. Natural polymer materials, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, water-soluble synthetic polymer materials such as polyethylene oxide, styrene-acrylic acid copolymer, styrene-maleic acid copolymer, rosin-modified maleic acid resin, Alkali metal salt of alkali-soluble polymer such as shellac, ammonium salt,
An amine salt may be used as a viscosity modifier or a dispersion stabilizer for hollow polymer particles, and a handwriting protective agent such as an aqueous resin emulsion or an aqueous resin microemulsion.

Other additives such as surfactants, preservatives, antifungal agents, rust preventives, pH adjusters, fragrances and defoamers may be used alone or in admixture of two or more. it can.

The water-based ink for a writing instrument of the present invention can be easily obtained by stirring and mixing the above components using a conventionally known stirrer.

[0014]

The hollow resin particles used in the water-based ink according to the present invention have a high light scattering ability. Therefore, it is presumed that the water for the writing instrument is an ink having excellent color visibility even when it is a dye ink because the light incident on the ink is reflected by the hollow resin particles. It

[0015]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples and comparative examples, "part" means "part by weight".

Example 1 C. I. Direct Blue 86 7.0 parts Propylene glycol 7.0 parts Thiodiglycol 5.0 parts Guar gum (viscosity modifier) 0.1 parts Ammonium salt of styrene-acrylic acid copolymer 1.0 parts Benzotriazole (rust inhibitor ) 0.2 part Sodium hydroxide (pH adjuster) 1.0 part SX864 (B) (solid content 40%) 50.0 parts Water 28.7 parts The above components are mixed and stirred with a stirrer for 2 hours. A blue water-based ink was obtained.

Comparative Example 1 A blue water-based ink was obtained in the same manner as in Example 1 except that SX864 (B) was removed and 0.3 part of guar gum and 49.7 parts of water were added.

Example 2 C. I. Acid Yellow 42 3.0 parts C.I. I. Acid Blue 9 4.0 parts Glycerin 5.0 parts Ethylene glycol 12.0 parts Alcox E-75 (viscosity modifier, polyethylene oxide, manufactured by Meisei Chemical Industry Co., Ltd.) 1.0 part Emulgen A-60 (nonionic) -Type surfactant, polyoxyethylene derivative, manufactured by Kao Co., Ltd. 0.8 part Proxel GXL (preservative: manufactured by British ICI) 0.2 part Primal OP42M (solid content 42.5%) 45.0 parts Water 29.0 parts The above components were mixed and stirred with a stirrer for 2 hours to obtain a green aqueous ink.

Comparative Example 2 A green water-based ink was prepared in the same manner as in Example 2 except that Primal OP42M was removed and 0.4 parts of Alcox E-75 and 44.6 parts of water were added. Obtained.

Example 3 C. I. Acid Red 52 0.2 parts C.I. I. Acid Red 92 0.7 parts Glycerin 4.5 parts Ethylene glycol 15.0 parts Guar gum 0.2 parts Proxel BD (preservative: manufactured by British ICI) 0.2 parts SX865 (B) (solid content 48%) 20 0.0 parts Water 59.2 parts The above components were mixed and stirred with a stirrer for 2 hours to obtain a pink aqueous ink.

Comparative Example 3 In Example 3, SX865
A pink aqueous ink was obtained in the same manner as in Example 3, except that 0.2 part of guar gum and 19.8 parts of water were added except for (B).

Example 4 C. I. Acid Blue 9 2.0 parts Glycerin 5.0 parts Ethylene glycol 20.0 parts Sodium salt of styrene-maleic acid copolymer 3.0 parts Emulgen A-60 0.5 parts Proxel GXL 0.2 parts SX863 (A) (Solid content: 20%) 40.0 parts Water 29.3 parts The above components were mixed and stirred with a stirrer for 2 hours to obtain a sky-colored water-based ink.

Comparative Example 4 A sky-colored water-based ink was obtained in the same manner as in Example 4 except that SX863 (A) was removed and that amount of water was added.

Example 5 C. I. Acid Red 92 1.0 part Glycerin 10.0 parts Ethylene glycol 10.0 parts Sodium salt of styrene-acrylic copolymer 8.0 parts ROPAQUE OP62 (solid content 37.5%) 25.0 parts Water 46.0 Parts The above components were mixed and stirred with a stirrer for 2 hours to obtain a pink aqueous ink.

Comparative Example 5 In Example 5, except for ROPAQUE OP62,
A pink aqueous ink was obtained in the same manner as in Example 5 except that water was added in that amount.

Example 6 C. I. Acid Yellow 42 4.2 parts C.I. I. Acid Red 87 1.0 part Thiodiglycol 5.0 parts Ethylene glycol 10.0 parts Amine salt of styrene-acrylic acid copolymer 6.0 parts SX865 (B) 30.0 parts Water 43.8 parts The above components Was mixed and stirred with a stirrer for 2 hours to obtain an orange aqueous ink.

Comparative Example 6 An orange aqueous ink was obtained in the same manner as in Example 6 except that SX865 (B) was removed and water was added in that amount.

Comparative Example 7 (black ink for color comparison) C.I. I. Acid Black 2 10.0 parts Ethylene glycol 15.0 parts Thiodiglycol 8.0 parts Water 67.0 parts The above components were mixed and stirred with a stirrer for 2 hours to obtain a black aqueous ink.

Comparative Example 8 (red ink for color comparison) C.I. I. Basic Red 14 2.0 parts Glycerin 5.0 parts Ethylene glycol 10.0 parts Proxel GXL 0.2 parts Water 82.8 parts The above components were mixed and stirred with a stirrer for 2 hours to obtain a red aqueous ink. ..

The above Examples 1, 2, 3 and Comparative Example 1,
The water-based inks obtained in Nos. 2, 3, 7, and 8 were commercially available ball-point pens that were refill type writing instruments (hybrid, product code: K105, manufactured by Pentel Co., Ltd., the ink storage material was polypropylene, and the main barrel material was acrylonitrile. -Styrene copolymer resin, both of which are transparent) and filled in Examples 4, 5, 6 and Comparative Examples 4, 5, 6, 7, 8
The water-based ink obtained in (1) was filled in a commercially available water-based fluorescent marker (Exo Data Checker, product code: SL25, manufactured by Pentel Co., ink storage material: transparent with polypropylene) that is a writing instrument with built-in ink. .. When the color tone of the ink was visually confirmed from the appearance, Examples 1 to 1
6 and Comparative Examples 7 and 8 each had a color tone equivalent to that of handwriting, but Comparative Examples 1 and 2 and Comparative Example 4 were indistinguishable from Comparative Example 7, and Comparative Examples 3 and 5 and 6 were Comparative Examples. It was indistinguishable from 8.

[0031]

As described above in detail, the aqueous ink for a writing instrument of the present invention is used in a raw ink type writing instrument in which the ink can be visually recognized from the outside, unlike the conventional aqueous ink for a writing instrument using a dye. In this case, since the ink color has excellent visibility, it has the advantages that it has a high display effect in stores and has a good aesthetic appearance.

Claims (1)

[Claims] 1. A water-based ink for a writing instrument for use in a writing instrument having an ink containing portion, wherein the ink in the ink containing portion can be visually recognized from the outside, wherein the aqueous ink is a water-soluble dye and hollow polymer particles. A water-based ink for a writing instrument, which contains water and water.