JP2000007975A - Water-based ball-point pen ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a ball-point pen ink composition which, when used in a ball-point pen, can give less blotting writing, can reduce the abrasion of a ball socket, and is improved in writing performances and non-driability without markedly lowering the surface tension by incorporating a specified ether with a colorant containing a dye and/or a pigment, a thickener, and water. SOLUTION: This composition comprises 0.5-40 wt.%, particularly, 1-30 wt.% at least one ether selected between glycerol monomethyl ether and diglycerol monomethyl ether, 0.5-30 wt.%, particularly, 1-15 wt.% colorant containing a pigment and/or a water-soluble dye, 0.1-5 wt.% at least one water-soluble thickener selected among natural products such as Arabic rubber, tragacanth rubber, guar rubber, locust bean gum, alginic acid, pectin, carrageenan, gelatin, casein, lactoalbumin, lanolin, chitosan, and xanthone and semisynthetic products such as methylcellulose and ethylcellulose, and 30-90 wt.% water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a viscous aqueous ballpoint pen ink composition. Specifically, it has excellent lubrication and has the effect of reducing wear on the ball seat,
It relates to an ink that is excellent in durability and writing feeling.

[0002]

2. Description of the Related Art Conventional aqueous ballpoint pens have a viscosity of one to several
A product in which mPa's ink is impregnated into an occlusion body made of a fiber bundle or the like has been used. Such an ink occluding body in which the ink is permeated has a drawback that the remaining amount of the ink is difficult to recognize in appearance. In order to know the amount of ink remaining in the water-based ballpoint pen, increase the viscosity of the ink,
A method is adopted in which the ink is stored in a transparent container and the ink itself is held in an ink storage tube of a ballpoint pen.

[0003] This ink uses a dye or pigment as a colorant, and uses a high boiling water-soluble solvent such as glycol or glycerin in addition to water as a main component solvent in order to suppress ink drying at the pen tip (non-dryness). Is used. However, the lubricating property is poor as it is, and when the ball rotates during writing, the frictional resistance between the ball and the ball seat becomes large, which has various disadvantages. For example, the ball seat is worn, the ball sinks, the ball rattles, or the outflow of the ink becomes non-uniform. For the purpose of improving such disadvantages, attempts have been made to add a lubricity improver such as a surfactant.

Further, Japanese Patent Application Laid-Open No. 7-247 by the present applicant
No. 458 discloses that, as in the present application, the surface tension is not extremely reduced, so that handwriting is less likely to bleed, and has sufficient lubricity, reduces wear of the ball seat, provides a comfortable writing feeling, and provides non-dryness. Which is characterized by using a pigment and a dispersing agent. The present application is characterized in that not only a pigment but also a dye alone is used, and a thickener is used to obtain a gel ink.

[0005]

In the above-mentioned conventional method, sufficient lubricity cannot be obtained, the wear of the ball seat is not sufficiently prevented, and the phenomenon of writing failure due to the friction of the ball seat is completely solved. However, even if sufficient lubricity is obtained, there has been a problem that the surface tension of the ink is significantly reduced, and the handwriting is easily blurred. An object of the present invention is to not significantly reduce the surface tension, hardly penetrate the handwriting, and by providing sufficient lubricity, reduce ball seat wear due to smooth ball rotation, and significantly improve writing performance. An object of the present invention is to provide an ink for a water-based ball-point pen that improves comfort, gives a comfortable writing feeling, and is excellent in non-drying property.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, the ink composition contains glycerin monomethyl ether and / or diglycerin monomethyl ether, and a thickener is added. By blending, it was found that sufficient lubricity could be obtained using not only pigments but also dyes, and the above object could be achieved. Based on this finding, the present invention was completed. That is, the present invention provides a colorant comprising at least one ether selected from the group consisting of glycerin monomethyl ether and diglycerin monomethyl ether, a dye and / or a pigment,
An aqueous ballpoint pen ink composition comprising a thickener and water.

[0007] The aqueous ballpoint pen ink composition of the present invention comprises:
It contains at least one ether selected from the group consisting of glycerin monomethyl ether and diglycerin monomethyl ether, a coloring agent composed of a dye and / or a pigment, a thickener composed of various gums and celluloses, and water. The content of the ethers is preferably 0.5 to 40% by weight of the total composition, more preferably 1 to 30% by weight.

[0008] The first aqueous ballpoint pen ink composition of the present invention comprises a colorant comprising a dye and / or a pigment, a thickener comprising various gums, celluloses and water-soluble resins, and glycerin monomethyl ether and / or water. Or diglycerin monomethyl ether, preferably 0.5 to 40% by weight of the total composition of glycerin monomethyl ether, and 0.5 to 30% by weight of the total composition of the colorant.
An aqueous ballpoint pen ink composition comprising 0.1% to 5% by weight of a thickener, 0.1% to 5% by weight of the total composition, and 30% to 90% by weight of water of the total composition.

The second aqueous ballpoint pen ink composition of the present invention comprises a colorant comprising a dye and / or a pigment, a thickener comprising various gums, celluloses and water-soluble resins, and glycerin monomethyl ether and / or water. Alternatively, it is characterized by containing diglycerin monomethyl ether. Preferably, diglycerin monomethyl ether is used in an amount of 0.5 to 40% by weight of the total composition, and the colorant is used in an amount of 0.5 to 3% of the total composition.
An aqueous ballpoint pen ink composition comprising 0% by weight, 0.1 to 5% by weight of the total composition of a thickener and 30 to 90% by weight of water of the total composition.

[0010] The ether used in the ink composition of the present invention is at least one ether selected from the group consisting of glycerin monomethyl ether and diglycerin monomethyl ether. ~ 40% by weight is preferred, more preferably,
1 to 30% by weight. If the content is less than 0.5% by weight, sufficient lubricity cannot be obtained, and improvement in writability cannot be expected.
On the other hand, if it exceeds 40% by weight, the viscosity of the ink is increased, and the outflow from the pen tip deteriorates, which is not suitable.

The ether used in the ink composition of the present invention may be used as a mixture with a water-soluble organic solvent. Examples of the solvent include water-soluble polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; cellosolves such as ethylene glycol monomethyl ether (methyl cellosolve); and ethylene glycol monoethyl ether (ethyl cellosolve); And carbitols such as diethylene glycol monoethyl ether (ethyl carbitol), and glycol ethers such as ethylene glycol ethyl ether acetate. These have a higher boiling point than water, which is the main solvent, and are less likely to volatilize, and thus have the effect of improving the non-dryness of the ink. The content thereof is generally 40% by weight or less, preferably 5 to 40% by weight, based on the whole ink composition. If the content is more than 40% by weight, the ink easily penetrates when writing on paper, and the ink penetrates, and the solvent does not easily evaporate.

The colorant used in the ink composition of the present invention is a pigment and / or a water-soluble dye. There are no particular restrictions on the type of pigment, and any of inorganic and organic pigments conventionally used in aqueous ink compositions can be used. Examples of inorganic pigments include titanium oxide, carbon black, metal powder and metal oxide powder,
And organic pigments such as azo lakes, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dye lakes, nitro pigments, and the like.
And nitroso pigments.

Specifically, phthalocyanine blue (C.I.
L. 74, 160), phthalocyanine green (C.I.
L. 74, 260), Hansa Yellow 3G (CL1)
1,670), Disazo Yellow GR (CL.21,
100), permanent red 4R (CL 12,3)
35), Brilliant Carmine 6B (CL 15, 8)
50), quinacridone red (CL 46,500)
Etc. can be used. Also, a plastic pigment composed of particles of styrene or acrylic resin can be used. Hollow resin particles having voids inside the particles can be white, and pseudo-pigments in which the particles themselves are dyed with a dye can be used for multiple colors.

As the water-soluble dye, any of direct dyes, acid dyes, food dyes and basic dyes can be used. An example of a direct dye is described below. C. L. Direct Black 17, 19, 22, 22, 32, 51, 51
71, C.I. L. Direct Yellow 4, 26, 4
4, 50, C.I. L. Direct Red 1, 4, 4
3, same 31, same 37, same 39, same 75, same 80, same 8
1, 83, 225, 226, 227, C.I. L.
Direct Blue 1, 15, 15, 71, 86, 10
6, 119 and the like.

An example of the acid dye is described below. C.
L. Acid Black 1, 2, 24, 26, 3
1, 52, 107, 109, 110, 11
9, 154, C.I. L. Acid Yellow 7, 17, 19, 23, 25, 29, 38, 42, 4
9, 61, 72, 78, 110, 141, 127, 135, 142, C.I. L. Acid Red 8, 9, 14, 18, 26, 27, 35
37, 51, 52, 57, 82, 87, 92, 94, 115, 129, 131, and 18
6, 249, 254, 265, 276,

C. L. Acid Violet 18, 1
7, C.I. L. Acid Blue 1, 7, 9, 22,
23, 25, 40, 41, 43, 62, 78, 83, 90, 93, 103, 112,
113, 158, C.I. L. Acid Green 3, 9, 16, 16, 25, and 27.

Food dyes are mostly contained in direct dyes or acid dyes, but examples of those not included are:
C. L. Food Yellow 3. One example of the basic dye is described below. C. L. Basic Yellow 1, 2, 21 and C.I. L. Basic Orange 2, 14,
32, C.I. L. Basic Red 1, 2, 9, 14, C.I. L. Basic Brown 12, Basic Black 2, and Basic Black 8.

These colorants may be used alone or in combination of two or more. The content in the total composition is usually 0.5 to 30% by weight, preferably 1 to 30% by weight.
-15% by weight. When stored for more than 30% by weight for a long period of time, the pigment may be aggregated or the dye may precipitate, causing the pen tip to be clogged, resulting in poor writing. 0.
If the content is less than 5% by weight, the coloring becomes weak and the hue of the handwriting cannot be recognized, which is not preferable.

When a pigment is used as a colorant, it is necessary to use a dispersant. This dispersant is adsorbed on the surface of the pigment to improve the affinity with water, and acts to stably disperse the pigment in water. Nonionic, anionic, surfactant and water-soluble resin are used. . Preferably, a water-soluble polymer is used.

The nonionic surfactants include higher fatty acid esters of polyoxyalkylenes, higher fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, etc. Specifically, fatty acid esters of glycerin, fatty acid esters of polyglycerin, propylene Glycol fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether,
Polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene castor oil, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxy Examples include ethylene alkylphenyl formaldehyde condensates.

Examples of the anionic surfactant include an alkylated sulfonate and an alkylallyl sulfonate of a higher fatty acid amide. Specific examples thereof include alkyl sulfates, polyoxyethylene alkyl ether sulfates, and N-acyl amino acids. Salts, N-acylmethyltaurine salts, polyoxyethylene alkyl ether acetates, alkyl phosphates, polyoxyethylene alkyl ether phosphates and the like.

Examples of the water-soluble resin include polyacrylic acid, acrylic acid copolymer, and maleic acid resin. Specifically, acrylic resin, styrene-acrylic resin, styrene-maleic acid resin, etc. Water-soluble. As an alkali metal forming a salt,
Representative examples of sodium and potassium include amines such as mono-, di-, or tri-propanolamine, methylethanolamine, methylpropanolamine, alcoholamines such as dimethylethanolamine, ammonia, morpholine and N-morpholine. Representative. The content of the dispersant is 0.1 to 10% by weight in the composition.

As the thickener, natural gum arabic,
Tragacanth gum, guar gum, locust bingham,
Alginic acid, pectin, carrageenan, gelatin, casein, lactalbumin, lanolin, chitosan, xanthan gum, ramzan gum, leosan gum, glucomannan, semi-synthetic methylcellulose, ethylcellulose,
Hydroxyethyl cellulose, carboxymethylcellulose, sodium starch glycolate, propylene glycol alginate, alkanolamine alginate, cationized and anionized guar gum,

Synthetic polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, sodium polyacrylate, polyacrylic acid, carboxyvinyl polymer, polyethylene oxide, copolymer of vinyl acetate and polyvinylpyrrolidone, alkali metal salt of acrylic resin, etc. Water soluble thickening resins can be used. The content of the thickener is 0.1 to 5% by weight in the composition.

The water used in the present invention is not particularly specified.
30 to 90% by weight is preferred. If the amount is less than 30% by weight, the relative solvent and the coloring agent increase, so that it is difficult to volatilize, and the handwriting becomes difficult to dry, which is not preferable. If the content is more than 90% by weight, the composition is liable to volatilize, the tip of the pen dries, and the writing becomes poor.

In addition to the above, the composition of the present invention may contain a lubricant, a preservative, a pH adjuster, and the like, if necessary. As the lubricant, fatty acid salts such as potassium ricinoleate, sodium ricinoleate, potassium oleate, and sodium oleate, aqueous cutting oil, and other surfactants mentioned as dispersants can be used.

As preservatives, phenol, isopropylmethylphenol, sodium pentachlorophenol, sorbic acid, potassium sorbate, 2-pyridine,
5-Chloro-2-methyl-4-isothiazoline-3one, 2,4-thiazolylbenzimidazole, paraoxybenzoate, and the like can be used.

As a pH adjuster, amines or bases, for example, various organic amines such as triethanolamine, diethanolamine, monoethanolamine and aminomethylpropanol, and alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide can be used. For example, an inorganic alkali agent or ammonia can be used.

The aqueous ink composition of the present invention has excellent lubricity and improves writing performance. Although the detailed action is not clear, the glycerin monomethyl ether used in the present invention, the hydroxyl group in the structure of diglycerin monomethyl ether, and the oxygen of the ether bond show an adsorbing action on the metal surface, and the metal surface has a hydrophobic group or the like. Can be covered with hydrocarbon chains. It is also assumed that the viscosity of glycerin monomethyl ether or diglycerin monomethyl ether itself provides lubricity by forming a lubricating film between the ball and the ball seat. Furthermore, since the surface tension in the ink is not reduced, it is considered that when used for a ballpoint pen, bleeding is small and good lubricity is obtained. The ballpoint pen using the ballpoint pen ink of the present invention is a direct liquid type. The ball-point pen includes a tube for directly storing the ink of the present invention, a pen tip including a ball and a tip holder, and the like.

[0030]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The evaluation of the inks obtained in each of the examples and comparative examples was performed by the following writing test. Table 1 shows the results. The ball sink measurement method in the writing test, and the determination of the brush feeling and the bleeding state of the handwriting were performed according to the following criteria.

Ball sinking: The worn depth of the ball seat after writing 500 m with a spiral writing tester at a writing angle of 60 degrees, a writing speed of 5.5 m / min, and a load of 100 g, ie, a ball protruding from the holder. Was measured for the reduced length of the protrusion length.

Writing feeling: ：: Soft and stable writing taste ：: Rugged hard writing taste ×: Rugged hard writing taste with broken lines and directionality.

Bleeding of handwriting: ：: clear handwriting without bleeding Δ: blurred, unclear handwriting ×: bleeding, very unclear handwriting

Example 1 A red aqueous ballpoint pen dye ink was prepared with the following composition. Each component was stirred at room temperature for 3 to 4 hours and then filtered. Weight% Dye: Eosin (CL Assid 87) 4.0 Ether: Glycerin monoethyl ether 10.0 Thickener: Guar gum 0.5 Lubricant: Potassium oleate 0.5 Preservative: Benzotriazole 0. 1 Purified water: 84.9 total 100.0

Example 2 A black aqueous ballpoint pen pigment ink was prepared with the following composition. After stirring and mixing each component of the following components except for sodium polyacrylate and part of purified water with a stirrer, the mixture was dispersed in a sand mill for 5 hours.
Furthermore, coarse particles were removed by a centrifugal separator, and then sodium polyacrylate dissolved in the remaining purified water was slowly added with stirring at room temperature, followed by further stirring for 3 to 4 hours, followed by filtration. . Weight% Pigment: Carbon black (Mitsubishi Chemical "MA-100") 7.0 Ether: Glycerin monomethyl ether 15.0 Dispersant: Styrene acrylate fatty ammonium salt 2.0 Thickener: Sodium polyacrylate 0.5 Lubricant: potassium linoleate 0.2 pH adjuster: triethanolamine 0.5 Preservative: 1,2-benzisothiazolin-3-one (Zeneca Corporation Proxel BDN) 0.1 Rust inhibitor: benzotriazole 0 ..2 Purified water: 74.5 total 100.0

Example 3 A pink aqueous ballpoint pen pigment ink was prepared with the following composition. Each component was stirred at room temperature for 3 to 4 hours and then filtered. Weight% Pigment: Synthetic resin emulsion dyed with fluorescent dye [NKW-2317 (manufactured by Nippon Fluorescent Co., Ltd.)] 50.0 Ether: Diglycerin monomethyl ether 10.0 Thickener: Xanthan gum 0.4 Lubrication Agent: Potassium oleate 0.2 Preservative: Phenol 0.2 Rust inhibitor: Benzotriazole 0.2 Purified water: 49.0 Total 100.0

Example 4 A white aqueous ballpoint pen pigment ink was prepared with the following components. Each component at room temperature 3-4
After stirring for hours, it was obtained by filtration. After stirring and mixing a part of the following components with titanium oxide, a dispersant and purified water with a stirrer, dispersed in a sand mill for 5 hours, and then slowly adding the remaining components while stirring at room temperature. 3 ~
The mixture was stirred for 4 hours and filtered. Weight% Pigment: Titanium oxide 10.0 White plastic pigment (Rohm & Haas Co., Ltd. Rope Lake OP-62) 50.0 Ether: Diglycerin monomethyl ether 8.0 Dispersant: Styrene acrylate fatty ammonium salt 2.0 Thickener: sodium polyacrylate 1.0 Lubricant: potassium linoleate 0.1 Preservative: 1,2-benzisothiazolin-3-one (Zeneca Corporation Proxel BDN) 0.1 Rust inhibitor: benzotriazole 0.2 Purified water: 28.6 Total 100.0

Example 5 A black aqueous ballpoint pen pigment ink was prepared with the following composition. After stirring and mixing each component of the following components except for sodium polyacrylate and part of purified water with a stirrer, the mixture was dispersed in a sand mill for 5 hours.
Furthermore, coarse particles were removed by a centrifugal separator, and then sodium polyacrylate dissolved in the remaining purified water was slowly added with stirring at room temperature, followed by further stirring for 3 to 4 hours, followed by filtration. . Weight% Pigment: Carbon black (Mitsubishi Chemical "MA-100") 7.0 Ether: Glycerin monomethyl ether 15.0 Solvent: 10.0 Dispersant: Styrene acrylate fatty ammonium salt 2.0 Thickener: Poly Sodium acrylate 0.5 Lubricant: potassium linoleate 0.2 pH adjuster: triethanolamine 0.5 Preservative: 1,2-benzisothiazolin-3-one (Zeneca Corporation Proxel BDN) 0.1 Rust agent: benzotriazole 0.2 Purified water: 63.0 Total 100.0

Comparative Example 1 A red ball-point pen dye ink was prepared in the same manner as in Example 1 except that glycerin monomethyl ether was not used and the same amount of ethylene glycol was used instead.

Comparative Example 2 A black ballpoint pen pigment ink was prepared in the same manner as in Example 2 except that the same amount of ethylene glycol was used instead of glycerin monomethyl ether.

Comparative Example 3 A pink ballpoint pen pigment ink was prepared in the same manner as in Example 3 except that the same amount of ethylene glycol was used instead of diglycerin monomethyl ether.

Comparative Example 4 A white ball-point pen pigment ink was prepared in the same manner as in Example 3, except that diglycerin monomethyl ether was not used and the same amount of ethylene glycol was used instead.

Comparative Example 5 A black ballpoint pen pigment ink was prepared in the same manner as in Example 2, except that 25 parts by weight of ethylene glycol was used instead of glycerin monomethyl ether.

An aqueous ballpoint pen was charged with the inks obtained in Examples 1 to 5 and Comparative Examples 1 to 5 into a polypropylene tube, and one end of which was fitted with a nib assembled using a ball and a tip holder. Table shows the results of examining the ball sinking, writing feel, and the bleeding state of the handwriting in a pair and a writing test.
It is shown in FIG.

[0045]

[Table 1]

[0046]

The water-based ballpoint pen ink composition of the present invention, when used in a ballpoint pen, has less blur of handwriting,
It provides good lubricity, has little wear on the ball seat due to the rotation of the ball, maintains proper ink outflow, and gives a smooth brush feel. In addition, since the ink drying property at the pen tip is suppressed, there is an effect that the ink is hardly worn out.

Claims (4)

[Claims] 1. An aqueous ballpoint pen ink containing at least one ether selected from the group consisting of glycerin monomethyl ether and diglycerin monomethyl ether, a coloring agent containing a dye and / or a pigment, a thickener, and water. Composition. 2. The method according to claim 1, wherein at least one ether selected from the group consisting of glycerin monomethyl ether and diglycerin monomethyl ether is used in an amount of from 0.5 to 40% of the total composition.
The aqueous ball-point pen ink composition according to claim 1, which is contained by weight. 3. The composition according to claim 1, wherein the content of glycerin monomethyl ether and diglycerin monomethyl ether is 0.1%.
2. The composition according to claim 1, comprising 5 to 40% by weight, 0.5 to 30% by weight of a coloring agent containing a dye and / or a pigment, 0.1 to 5% by weight of a thickener and 30 to 90% by weight of water. Aqueous ballpoint pen ink composition. 4. The thickening agent is a natural gum arabic, tragacanth gum, guar gum, locust bingham, alginic acid, pectin, carrageenan, gelatin, casein, lactalbumin, lanolin, chitosan, xanthan gum, ramzan gum, leozan gum, glucomannan, half Synthetic methyl cellulose, ethyl cellulose,
Hydroxyethyl cellulose, carboxymethylcellulose, sodium starch glycolate, propylene glycol alginate, alkanolamine alginate, cationized and anionized guar gum, synthetic polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, sodium polyacrylate, polyacrylic acid, The carboxyvinyl polymer, polyethylene oxide, a copolymer of vinyl acetate and polyvinylpyrrolidone, and at least one water-soluble thickening resin selected from the group consisting of alkali metal salts of acrylic resins. Aqueous ballpoint pen ink composition.