JP2000104000A - Aqueous gloss ink composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To an ink storage tube having a pen tip attached to one end,
A water-based glossy ink composition that can be used for writing instruments that is directly filled with ink and an ink backflow preventer, and that can be written without blurring the handwriting even after leaving the pen tip exposed Providing things. SOLUTION: In an aqueous gloss ink composition containing at least a metal powder pigment and / or a pearl pigment, a pigment dispersant, a viscosity modifier, water and a water-soluble organic solvent, water is
A water-based glossy ink composition having a content of 50% by weight or less, a water-soluble organic solvent having a boiling point of 120 ° C or more, and a content of 30% by weight or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based glossy ink composition which can be used for a writing instrument in which an ink and an ink backflow preventer are directly filled in an ink storage tube having a pen tip attached to one end thereof. The present invention relates to a water-based glossy ink composition which can be written without blurring from the beginning even after being left with the tip exposed.

[0002]

2. Description of the Related Art In recent years, ballpoint pens have been proposed which have both the advantages of an oil-based ballpoint pen and the advantages of an aqueous ballpoint pen by directly filling aqueous ink into an ink storage tube to which a pen tip is attached. This type of ballpoint pen directly fills ink into an ink storage tube.
For this reason, this type of ballpoint pen has the property of having a high viscosity so that the ink does not leak naturally from the penpoint when the penpoint is turned down, and the ink viscosity decreases due to the high shear force caused by the rotation of the ball during writing. So-called gel ink is employed.

A ballpoint pen filled with the above gel ink is
The elastic member is loaded inside the cap and the pen tip is brought into close contact with the pen, thereby preventing the pen tip and the ink contained in the pen tip from drying. Therefore, when the cap is removed, the pen tip is not dry, so that writing can be performed from the beginning without blurring the handwriting.

[0004]

However, if the ball-point pen filled with the gel ink is left without writing the cap on the pen tip after writing, the pen tip and the ink contained in the pen tip are dried, so that the writing is performed. There is a problem that the written characters are blurred or the characters cannot be written at all.

SUMMARY OF THE INVENTION An object of the present invention is to allow a pen tip and ink contained in the pen tip to hardly dry even when the cap is left unattached to the pen tip, and to allow writing without blurring the handwriting from the beginning. It is an object of the present invention to provide a water-based glossy ink composition.

[0006]

The present invention provides a metal powder pigment and / or pearl pigment, a pigment dispersant, a viscosity modifier,
In an aqueous gloss ink composition containing at least water and a water-soluble organic solvent, water has a content of 50% by weight or less, a water-soluble organic solvent has a boiling point of 120 ° C or more, and The gist of the present invention is a water-based glossy ink composition having a content of 30% by weight or more.

Hereinafter, the present invention will be described in detail. The metal powder pigment and the pearl pigment used in the present invention are used for imparting metallic luster to handwriting or as a main colorant, and can be used without any particular limitation. For example, as metal powder pigments, various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, tin powder, and brass powder can be used. Also,
For pearl pigments, natural products such as fish scale foil, synthetic products such as basic lead carbonate, bismuth oxychloride, natural mica whose surface is coated with metal oxide, and synthetic mica whose surface is coated with metal oxide Goods can be used. The particle diameter of the metal powder pigment and the pearl pigment is desirably 50 μm or less. This is because if a metal powder pigment or a pearl pigment having a particle diameter of 50 μm or more is present, the metal powder pigment or the pearl pigment may clog the pen tip and hinder the ejection of ink, resulting in faint handwriting or a state in which writing is impossible. Because there is. The metal powder pigment and the pearl pigment can be used alone or in combination of two or more. The use amount of the metal powder pigment and the pearl pigment is preferably 1 to 40% by weight based on the total amount of the aqueous gloss ink composition.

The pigment dispersant is used for the purpose of improving the dispersibility of the metal powder pigment and the pearl pigment and preventing the metal powder pigment and the pearl pigment from clogging the pen tip. The pigment dispersant used in the aqueous gloss ink composition of the present invention has a conventionally known dispersing action, a nonionic surfactant such as an ether type, an alkylphenol type, an ester type,
Fatty acids, alkyl sulfonic acids, alkali metal salts such as sulfosuccinic acid, alkanolamine salts, and anionic surfactants such as polycarboxylic acid type can be used. In particular, polyolefin-based emulsions and polyoxyethylene Fatty acid esters of glycerin borate are preferred. This is because the polyolefin-based emulsion and the fatty acid ester of polyoxyethylene diglycerin borate have a higher effect of preventing blurring of handwriting as compared with other surfactants having a dispersing action. Specific examples of the polyolefin-based emulsion include HYTEC E-43 as a polypropylene-based emulsion.
3N (ionicity of emulsion: nonionic), P-5
060 (same as nonion) and E-8045 (same as anion), and the polyethylene type is HYTEC E
-6000 (same as nonion), E-7058 (same as anion), E-4A (same as anion), and E-4B
(Nonion), E-1000 (Nonion)
(Above, manufactured by Toho Chemical Industry Co., Ltd.). In particular, when an aluminum powder pigment is used as a coloring agent,
In consideration of the temporal stability of the aluminum powder pigment, it is preferable to use a polyolefin-based emulsion in which the ionicity of the emulsion is nonionic. Specific examples of the fatty acid ester of polyoxyethylene diglycerin borate include Emalbon T-20, T-40, T-60,
T-80 and T-160 (Toho Chemical Industry Co., Ltd.)
Manufactured). Further, as those containing fatty acid esters of polyoxyethylene diglycerin borate, Dispants EN-120A and EN-130
(Both manufactured by Toho Chemical Industry Co., Ltd.). This is a mixture of a fatty acid ester of polyoxyethylene diglycerin borate and a fatty acid ester of diglycerin borate. Incidentally, specific examples of the fatty acid ester of diglycerin borate include emalbon S-20, S-40, S-60, and S-8.
And S-160 (both manufactured by Toho Chemical Industry Co., Ltd.). The amount of the pigment dispersant used is preferably from 0.1 to 10.0% by weight based on the total amount of the aqueous glossy ink composition.

The viscosity modifier is used for the purpose of regulating the viscosity of the aqueous gloss ink composition of the present invention and suppressing the sedimentation of the metal powder pigment and / or pearl pigment contained in the ink.
As the viscosity modifier to be used, those having a property that a high viscosity can be obtained even when the addition amount thereof is small and the viscosity is reduced by applying a high shearing force, that is, a so-called thixotropic property, are preferable. As a viscosity modifier that can be used,
For example, natural polymers such as guar gum, xanthan gum, locust bean gum, welan gum, ramzan gum, karaya gum, tragacanth gum, succinoglucan,
Cellulose polymers such as sodium carboxymethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose can be used. These can also be used alone or in combination of two or more.

Water is used as a solvent, and the amount of water used must be 50% by weight or less based on the total amount of the aqueous glossy ink composition. This means that the usage is 5
If the content is more than 0% by weight, the ink is easily dried, and the handwriting from the beginning tends to be blurred.

The water-soluble organic solvent used in the present invention is intended to prevent drying of the ink at the pen tip. It is necessary to use more than weight%. By the way, the water-soluble organic solvent having a boiling point of 120 ° C. or higher is an expression meaning that it includes a solvent having no clear boiling point, for example, polyethylene glycol. Specific examples of the water-soluble organic solvent include those having a boiling point of 120 ° C. or higher, such as ethylene glycol (boiling point: 197 ° C.), diethylene glycol (244 ° C.), propylene glycol (187 ° C.), and dipropylene glycol (23 ° C.).
2 ° C), 1,3-propanediol (213 ° C),
1,2-butylene glycol (190 ° C), 1,3-
Butylene glycol (207 ° C), 1,4-butylene glycol (235 ° C), 1,5-pentanediol (238 ° C), ethylene glycol monomethyl ether (124 ° C), ethylene glycol monoethyl ether (136 ° C) ° C), diethylene glycol monomethyl ether (194 ° C), diethylene glycol monoethyl ether (202 ° C), diethylene glycol diethyl ether (187 ° C), triethylene glycol dimethyl ether (216 ° C), 2-pyrrolidone (245 ° C), N-methyl-2-pyrrolidone (20
2 ° C.). When the boiling point is 250 ° C. or higher, for example, triethylene glycol (287 ° C.)
Tetraethylene glycol (327 ° C), glycerin (290 ° C), triethanolamine (360 ° C)
And polyethylene glycol having no clear boiling point. By the way, the boiling point is 250
When a large amount of a water-soluble organic solvent having a temperature of not less than ° C. is used, handwriting after writing becomes difficult to dry, and stains due to friction or transfer to paper may be generated. Therefore, when a water-soluble organic solvent having a boiling point of 250 ° C. or higher is used, the amount of the solvent is 15% by weight or less based on the total amount of the aqueous gloss ink composition.
It is preferable to use together with a water-soluble organic solvent having a boiling point of 120 to 250 ° C. The above water-soluble organic solvents can be used alone or in combination of two or more. The addition of the water-soluble organic solvent also makes it possible to prevent the ink from freezing at low temperatures.

In addition to the above components, various additives used in conventional aqueous ink compositions for ballpoint pens can also be used.

For example, a resin can be added to improve the fixability of the handwriting on the surface to be written. Specific examples of the resin include, for example, resin emulsions such as styrene-acrylic, acrylic, styrene-butadiene, and vinyl acetate-based resins, alkali-soluble resins, and betaine-type acrylic resins.

Various pigments and dyes can be used as the complementary colorant. For example, pigments include carbon black,
Inorganic pigments such as titanium oxide, cobalt blue, iron oxide, ultramarine blue, navy blue and the like, organic pigments, fluorescent pigments and the like can be used. Alternatively, a dispersed pigment base in which a pigment is dispersed in an aqueous medium can be used. As the dye, conventionally known water-soluble dyes such as acid dyes, basic dyes and direct dyes can be used. These can also be used alone or in combination of two or more.

In addition, various additives such as benzothiazoline and omazine preservatives, rust preventives such as benzotriazole and various chelating agents, anionic and nonionic surfactants, and defoamers are also used. it can.

In producing the ink of the present invention, various conventionally known methods can be employed. For example, it can be easily obtained by blending each of the above components and stirring and mixing with a propeller stirrer, a stirrer such as a turbo mixer or a Henschel mixer, or mixing and grinding with a disperser such as a ball mill.

[0017]

In the aqueous gloss ink composition of the present invention, the water-soluble organic solvent contained in the ink has a hygroscopic property,
The water in the aqueous glossy ink composition is hardly lost. The metal powder pigment and the pearl pigment used in the present invention have a plate-like shape having a small thickness and a large planar area. It is expected that the loss of water in the aqueous gloss ink composition will form a layered structure in which the planes of these pigments face one another and stack. In this layered structure,
Since the area of the portion where the pigments are in contact with each other is large, the resulting contact resistance is also increased, and it is considered that a stable structure is obtained. When this is formed inside the pen tip or inside the pen tip, the ejection of ink is hindered, which causes a faint handwriting or a state in which writing is impossible. However, when the pigment dispersant in the aqueous glossy ink composition of the present invention is used, the pigment dispersant exists between the layered structures by adhering to the surface of the pigment, and the contact resistance between the pigments can be reduced. Becomes Therefore, since there is an effect of imparting fluidity, aggregation of the metal powder pigment and pearl pigment caused by loss of water in the aqueous glossy ink composition is prevented. From the synergistic effect described above, even when the cap is left unattached to the pen tip, the ink contained in the pen tip and the inside of the pen tip is difficult to dry and can be written without blurring the handwriting from the beginning. Conceivable.

[0018]

Example 1 Example 1 Aluminum paste (WXMU75, aluminum powder content 60% by weight, manufactured by Toyo Aluminum Co., Ltd.) 4.0 parts by weight Colorant (EM Green G, green dispersion pigment, nonvolatile content: 44% by weight, 9.0 parts by weight Pigment dispersant (Dispant EN-120A, mixture of oleic acid ester of polyoxyethylene diglycerin borate and oleic acid ester of diglycerin borate, Toho Chemical Co., Ltd.) 1.0 part by weight Xanthan gum (Kelzan AR, manufactured by Kelco, USA) 0.8 part by weight Resin emulsion (Johncryl 450, styrene-acrylic type, manufactured by Johnson Polymer Co., Ltd.) 1.0 part by weight Part water 40.8 parts by weight ethylene glycol 38.0 parts by weight glycerin 5.0 parts by weight 0.2 parts by weight of a preservative (Proxel GXL, 1,2-benzisothiazolin-3-one, manufactured by ICI Japan) 0.2 parts by weight of an antifoaming agent (YMA6509, silicone emulsion, manufactured by Toshiba Silicon Corporation) Among the above ingredients, xanthan gum was added to 20 g of water, mixed with stirring, and completely dissolved. The remainder of the water was mixed with all the other ingredients and dispersed for 5 minutes with a turbomixer. The whole amount of the above xanthan gum aqueous solution is added to this, and 3
The mixture was stirred for 0 minutes to obtain a green ink having glossy handwriting.

Example 2 Aluminum paste (WXM0630, aluminum powder content 60% by weight, manufactured by Toyo Aluminum Co., Ltd.) 6.0 parts by weight Pigment dispersant (HYTEC E-4B, polyolefin emulsion, Toho Kagaku Kogyo Co., Ltd.) )) 1.0 parts by weight Xanthan gum (Roadpol 23, manufactured by Rhone Poulin Japan KK) 0.9 parts by weight Resin emulsion (Movinyl DM772, acrylic, manufactured by Hoechst Gosei Co., Ltd.) 1.0 parts by weight Water 45.9 parts by weight Ethylene glycol 30.0 parts by weight Glycerin 15.0 parts by weight Preservatives (Proxel GXL, as described above) 0.2 parts by weight Silver ink having gloss on handwriting in the same manner as in Example 1 above I got

Example 3 Pearl pigment (MC-302-F, manufactured by Nippon Koken Kogyo Co., Ltd.) 15.0 parts by weight Aluminum paste (WXM0630, as described above) 3.0 parts by weight Pigment dispersant (Emalbon T-20, Lauric ester of polyoxyethylene diglycerin borate ester, manufactured by Toho Chemical Industry Co., Ltd. 1.0 part by weight Welan gum (K1A96, manufactured by Kelco, USA) 0.2 part by weight Guar gum (Mappro CSA 200/50) Resin emulsion (Acronal YJ-1800D, acrylic, Mitsubishi Chemical B ASF Co., Ltd.) 2.0 parts by weight Water 43.2 parts by weight Propylene glycol 25.0 parts by weight Part 2-pyrrolidone 10.0 parts by weight Preservative (Proxel GXL, as described above) 0.2 parts by weight Antifoam TSA7341, silicone emulsions, manufactured by Toshiba Silicon Co.) in the same manner as in Example 1 0.5 parts by weight The above components, to give a golden inks having gloss handwriting.

Example 4 Pearl pigment (TP-350, manufactured by Teika Co., Ltd.) 20.0 parts by weight Colorant (Kayacyl Rhodamine FB, acid dye, manufactured by Nippon Kayaku Co., Ltd.) 2.0 parts by weight Water 43. 8 parts by weight 1,4-butylene glycol 30.0 parts by weight Xanthan gum (Kelzan D, manufactured by Kelco, USA) 0.5 part by weight Resin emulsion (Joncryl 775, styrene-acrylic, manufactured by Johnson Polymer Co., Ltd.) 1 0.5 parts by weight Preservative (Proxel GXL, described above) 0.2 parts by weight Pigment dispersant (HYTEC E-433N, polyolefin emulsion, manufactured by Toho Chemical Industry Co., Ltd.) 2.0 parts by weight In the same manner as in the above, a red ink having handwriting gloss was obtained.

Example 5 Aluminum paste (WB0230, manufactured by Toyo Aluminum Co., Ltd.) 10.0 parts by weight Resin (Johncryl 1535, styrene-acrylic type, manufactured by Johnson Polymer Co., Ltd.) 2.0 parts by weight Water 47.5 Parts by weight 1,3-propanediol 35.0 parts by weight triethanolamine 3.0 parts by weight Locust bean gum (Mayprodin 200, manufactured by Mayhall Chemical Co., Switzerland) 0.5 parts by weight Preservative (Proxel GXL) 0.2 parts by weight Pigment dispersant (BT-12, polyoxyethylene secondary alkyl ether, manufactured by Nikko Chemicals Co., Ltd.) 1.5 parts by weight Defoamer (BYK-026, silicone emulsion, Germany) , Manufactured by BYK-Chemie) 0.3 parts by weight The above-mentioned components were glossed in the handwriting in the same manner as in Example 1. To obtain a color ink.

Comparative Example 1 A green ink having a glossy handwriting was obtained in the same manner as in Example 1 except that water was used instead of ethylene glycol of Example 1.

Comparative Example 2 A silver ink having a glossy handwriting was obtained in the same manner as in Example 2 except that water was used in place of ethylene glycol and glycerin.

Comparative Example 3 A silver ink having a glossy handwriting was obtained in the same manner as in Example 3 except that water was used in place of 2-pyrrolidone.

Comparative Example 4 In place of 1,4-butylene glycol in Example 4, ethylene glycol diglycidyl ether (boiling point: 112 ° C.)
Was used in the same manner as in Example 4 to obtain a red ink having gloss in handwriting.

Comparative Example 5 Pearl pigment (TP-350, as described above) 5.0 parts by weight Aluminum paste (WXM0630, as described above) 3.0 parts by weight Water 53.3 parts by weight Diethylene glycol diethyl ether 30.0 parts by weight Xanthan gum (Kelzan D) 0.5 parts by weight Resin (Yukaformer W, 30% aqueous solution of betaine type acrylic resin, manufactured by Mitsubishi Chemical Corporation) 6.0 parts by weight Preservative (Proxel GXL, as described above) 0.2 parts by weight Pigment 2.0 parts by weight of dispersant (TAMNO-5, polyoxyethylene oleylamine, manufactured by Nikko Chemicals Co., Ltd.) 2.0 parts by weight In the same manner as in Example 1, a silver ink having gloss on handwriting was obtained.

The water-based glossy ink compositions obtained from Examples 1 to 5 and Comparative Examples 1 to 5 were transparently formed by a polypropylene hollow shaft cylinder having a stainless steel ballpoint pen tip (ball material: cemented carbide) connected to one end. A test ballpoint pen was assembled after filling a water-based glossy ink composition of the present invention and an ink backflow preventer into a simple ink container. (Pentel Corporation)
Manufactured by the same method using the same parts as those of K105. The following test was performed using this.

(Confirmation of Prevention of Drying of Pen Tip: Writing Test) The test ballpoint pen assembled by the above method was allowed to stand horizontally at room temperature for 2 days at room temperature with the cap removed, and then a straight line was written on the paper surface and handwriting was performed. The writing distance until the fading disappeared was measured. Writing paper A (JIS P 3201)
It was used.

[0030]

[Table 1]

[0031]

As described in detail above, the water-based glossy ink composition according to the present invention is obtained by directly filling an ink container with a pen tip attached to one end with ink and an ink backflow preventer. Regarding the aqueous gloss ink composition that can be used for writing instruments, even after leaving the pen tip exposed,
It is a water-based glossy ink composition that can be written without blurring.

Continued on front page F-term (reference) 4J039 AB02 AB07 AD01 BA06 BA32 BC07 BC09 BC10 BC12 BC13 BC20 BC35 BC49 BC58 BE01 BE12 BE22 BE23 CA06 DA02 DA05 DA08 EA11 EA44 GA11 GA12 GA27

Claims (2)

[Claims] 1. An aqueous gloss ink composition comprising at least a metal powder pigment and / or a pearl pigment, a pigment dispersant, a viscosity modifier, water and a water-soluble organic solvent, wherein water is
A water-based glossy ink composition having a content of 50% by weight or less, a water-soluble organic solvent having a boiling point of 120 ° C or more, and a content of 30% by weight or more. 2. The water-based glossy ink composition according to claim 1, wherein the pigment dispersant is a polyolefin emulsion and / or a fatty acid ester of polyoxyethylene diglycerin borate.