JP6998676B2 - Aqueous ink composition for writing tools and writing tools using it - Google Patents

Description

The present invention relates to a water-based ink composition for writing tools. More specifically, the present invention relates to a water-based ink composition for writing instruments, which is excellent in color development and fixability of handwriting ink when writing on paper, cloth or the like. The present invention also relates to a writing instrument using the composition.

Conventionally, ink compositions for writing instruments that can be written on paper or cloth have been known. Among them, water-based ink compositions using water as a main solvent have a small environmental load and high safety. It is being actively considered. In such an ink composition, by using a colorant or a fixing agent, the ink is fixed on the surface of paper or cloth, and an attempt is made to obtain a clear handwriting. (Patent Document 1)

Patent Document 1 describes an ink for writing instruments using a pigment, water, and a resin emulsion having a specific film forming temperature. The handwriting formed by this ink has high fixing property, and the handwriting written on the cloth is hard to be peeled off from the cloth during washing.

However, when writing on the surface of a cursive with a large gap between fibers such as paper and cloth using the ink composition described in Patent Document 1, the ink composition is covered through the gap between the fibers. Since it penetrates into the cursive and the colorant is difficult to stay on the surface of the cursive, the handwriting may become unclear.

Japanese Unexamined Patent Publication No. 2005-290237

According to the present invention, even when writing is performed on the surface of a cursive writing body having a large gap between fibers such as paper or cloth, the coloring agent is colored without passing through the gaps between the fibers and entering the inside of the cursive writing body. It is possible to fasten the agent on the fiber surface of the writing surface, and it is an object of the present invention to provide an ink composition for writing instruments having excellent color development and fixing property of handwriting.

The water-based ink composition for writing instruments according to the present invention is characterized by containing a pigment, etherified cellulose having a degree of etherification of 0.1 to 0.5, a poorly water-soluble resin, and water. ..

Further, the writing tool according to the present invention is characterized in that it contains the above composition.

According to the present invention, there is provided an ink composition for a writing instrument that exhibits excellent handwriting color development and high fixing property of a handwriting even when writing on the surface of a writing body having a large gap between fibers such as paper or cloth. Will be done.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, "part", "%", "ratio" and the like indicating the composition are based on mass unless otherwise specified.

The water-based ink composition for writing tools according to the present invention (hereinafter, may be referred to as "water-based ink composition" or "composition" in some cases) has a pigment and a degree of etherification of 0.1 to 0.5. It contains etherified cellulose, a polyolefin resin and / or an acrylic resin as a poorly water-soluble resin, and water. The polyolefin resin is a copolymer of ethylene and acrylic acid, and the acrylic resin is acrylic acid. One or more selected from ester resin, acrylic styrene resin, acrylic silicone resin, acrylic urethane resin, acrylic nitrile resin, acrylic styrene nitrile resin, acrylic vinegar resin, and methacrylic acid ester resin, and the etherified cellulose. When the total content of the water-insoluble resin is A and the total content of the poorly water-soluble resin is B, B / A is 0.5 ≦ B / A ≦ 40. Hereinafter, each component constituting the water-based ink composition according to the present invention will be described.

(Pigment)
In the present invention, the pigment can be arbitrarily selected from conventionally known inorganic pigments, organic pigments, and glossy brilliant pigments, and can be preferably used. Specifically, carbon black, titanium oxide, zinc oxide, iron black, yellow iron oxide, petals, metal oxides such as composite oxide pigments, and ultramarine as inorganic pigments, and azo as organic pigments. Pigments, indigo pigments, phthalocyanine pigments, quinacridone pigments, thioindigo pigments, slene pigments, perinone pigments, perylene pigments, phthalone pigments, dioxane pigments, isoindolinone pigments, metal complex pigments, Examples thereof include methine-azomethine-based pigments and diketopyrrolopyrrole-based pigments, and examples of glossy brilliant pigments include aluminum pigments and glass flake pigments. In the water-based ink composition of the present invention, it is preferable to use a metal oxide as the pigment, and it is particularly preferable to use titanium oxide. By using such a pigment, various colors can be used in combination with a complementary color pigment described later. This is because it is possible to realize various colors.

In the water-based ink composition of the present invention, the pigment is preferably surface-treated with a coating material, and the material of the coating material includes inorganic oxides such as silica, alumina, zirconia and zinc oxide, and molybdenum and the like. Metals, phosphates and the like are preferred. This is because by surface-treating the pigment with the above-mentioned coating material, aggregation of the pigments is suppressed in the ink and the dispersion of the pigment is stable, and the reaction between the pigment and water is suppressed to suppress the generation of bubbles. Because it can be done. Furthermore, when a pigment containing metal is subjected to shearing force from a mixer or the like during ink production, the pigment is deformed and damaged, and metal ions are suppressed from being eluted, so that the stability of the ink over time is improved. Is possible. Considering the dispersion stability in the ink described above, it is more preferable that the coating material of the pigment is an inorganic oxide containing silica or alumina.

Regarding the pigment, the coating amount of the pigment surface-treated by the coating material is such that the ratio of the mass of the coating material to 100 parts by mass of the pigment surface-treated by the coating material is 0.01% by mass to 20% by mass. It is preferably 0.1% by mass to 8.0% by mass, and more preferably. When the coating amount is within the above numerical range, it is possible to easily disperse the water-based ink composition and suppress the elution of the metal.

In the present invention, when a pigment surface-treated with an inorganic oxide is used, the pigment surface-treated with an inorganic oxide in the aqueous ink composition has a positive value or a negative value, considering the dispersion stability in the ink. It is preferable to have a surface charge of a negative value, and particularly when a pigment treated with an inorganic oxide containing silica is used, it is preferable to have a surface charge of a negative value, and the pigment is treated with an inorganic oxide containing alumina. When a pigment is used, it preferably has a positive value. Such pigments exhibit good dispersibility in the composition, but by combining with a pigment dispersant described later, dispersibility and redispersibility can be further enhanced. When the surface-treated pigment has the above-mentioned surface charge, the surface-treated pigment is preferably titanium oxide in consideration of dispersion stability in the ink.

The average particle size of the pigment is preferably 0.01 μm to 30 μm, more preferably 0.05 μm to 15 μm, and even more preferably 0.1 μm to 5 μm. When the average particle size of the pigment is within the above numerical range, the pigment does not easily enter the gaps between the fibers even when writing on a cursive with a large gap between fibers such as paper and cloth, and the color is clear. This is because it is easy to obtain. Further, when an aqueous ink composition containing a pigment whose average particle size is within the above numerical range is used for a writing instrument such as a marker, the ink ejection property can be improved. The average particle size of the pigment is, for example, 50% of the cumulative volume of the particle size distribution measured by the laser diffraction method using a laser diffraction type particle size distribution measuring machine (trade name "Microtrac HRA9320-X100", Nikkiso Co., Ltd.). It can be measured by the particle size (D50) of the hour. As used herein, the "average particle size" of a pigment refers to the volume-based average particle size unless otherwise specified.

The content of the pigment in the water-based ink composition is preferably 1% by mass to 40% by mass, more preferably 2% by mass to 30% by mass, based on the total mass of the water-based ink composition. When the content of the pigment is within the above numerical range, it is possible to prevent the ink ejection property from being lowered, and to maintain the sharpness and concealing property of the water-based ink composition and the handwriting formed by using the water-based ink composition. Can be done.

(Pigment dispersant)
The water-based ink composition of the present invention preferably contains a pigment dispersant. By combining the pigment dispersant and the pigment, it is possible to suppress the agglomeration of the pigments and improve the stability of the ink. The pigment dispersant used in the present invention is not particularly limited as long as it has an effect of enhancing the dispersibility of the pigment, but when a pigment surface-treated with an inorganic oxide is used, the dispersion stability of the pigment is taken into consideration. , It is preferable to use a pigment dispersant having an anionic adsorbent or a cationic adsorbent.

When a pigment surface-treated with an inorganic oxide containing silica is used in the composition of the present invention, the pigment dispersant preferably has a cationic adsorption group. Considering the stability of the ink composition, the acid basicity of the ink composition is preferably near neutral, but in this liquid property, the pigment in the ink composition has a negative surface charge. The cationic adsorption group is easily adsorbed on the pigment by the electric attraction, and the dispersion can be facilitated.
Specific examples of the pigment dispersant having a cationic adsorption group include DISPERBYK-184 and DISPERBYK-2055 (all manufactured by Big Chemie Co., Ltd.), which are preferably used. The pigment dispersant having a cationic adsorbent used in the present invention is not limited thereto. As the pigment dispersant, one kind or a plurality of kinds can be used.
Considering the dispersibility of the pigment, DISPERBYK-184 is particularly preferable as the pigment dispersant having a cationic adsorption group.

When a pigment surface-treated with an inorganic oxide containing alumina is used in the composition, the pigment dispersant preferably has an anionic adsorbent group. In the acid basicity, since the pigment has a positive surface charge, the anionic adsorbent group is easily adsorbed on the pigment by an electric attraction, and dispersion can be facilitated.
Specific examples of the pigment dispersant having an anionic adsorbent group include DISPERBYK-190, DISPERBYK-194N, and DISPERBYK-2010 (all manufactured by Big Chemie Co., Ltd.), which are preferably used. The pigment dispersant having an anionic adsorbent used in the present invention is not limited thereto. As the pigment dispersant, one kind or two or more kinds can be used. Considering the dispersibility of the pigment, DISPERBYK-190 is particularly preferable as the pigment dispersant having an anionic adsorbent.

The content of the pigment dispersant in the present invention is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 3% by mass in terms of the solid content of the active ingredient. Further, assuming that the total content of the pigment with respect to the total amount of the ink composition is A and the total content of the pigment dispersant with respect to the total amount of the ink composition is B, B / A is 0.005 ≦ B / A ≦ 0.5. It is preferable that there is, and it is more preferable that 0.01 ≦ B / A ≦ 0.2. When the content of the pigment dispersant and the ratio of the content of the pigment dispersant to the content of the pigment are within the above numerical ranges, the dispersibility of the pigment is good and the viscosity of the ink composition becomes excessively high. Can be suppressed.

(Etherated cellulose)
It is important that the water-based ink composition according to the present invention contains etherified cellulose.
The etherified cellulose is adsorbed on pigment particles, polyolefin particles described later, and complementary color pigments in an ink composition to form bulky aggregates of the pigment, so that the writing has a large gap between fibers such as paper and cloth. When writing on the body, the pigment is prevented from penetrating into the writing body through the gaps between the fibers, and the pigment is easily attached to the fibers on the surface of the writing body, so that the color development of the writing is good. It is something to do. Aetherylated cellulose is obtained by binding an organic group such as a methyl group or a carboxymethyl group to a hydroxyl group of one molecule of glucose constituting the cellulose, and specific examples thereof include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl. Examples thereof include cellulose, hydroxyethylmethyl cellulose, hydroxypropylmethyl cellulose and the like, which can be preferably used.
The etherified cellulose preferably used in the present invention is carboxymethyl cellulose, which ionizes in the ink composition, electrically repels each other and stably disperses, and forms a bulky aggregate of the pigment. , Improves the color development of handwriting. Further, the ink composition containing carboxymethyl cellulose is characterized by being excellent in stability against temperature changes and having a small change in ink viscosity with respect to temperature changes.

In the present invention, the etherified cellulose is preferably one having a degree of etherification of 0.1 to 0.5. The degree of etherification refers to the degree of substitution of a substituent such as a methyl group or a carboxymethyl group with respect to a hydroxyl group existing in an anhydrous glucose unit of cellulose. Since there are three hydroxyl groups in the unit, the degree of etherification can theoretically be "3.0". The etherified cellulose having the above-mentioned degree of etherification causes the ink composition to exhibit high dispersion stability without becoming excessively high viscosity, and the etherified cellulose is adsorbed with the pigment to form a bulkier aggregate. , Paper, cloth, etc., when writing on a cursive with large gaps between fibers, it prevents the pigment from penetrating into the cursive through the gaps between the fibers, and improves the color development of the cursive. do.
The degree of etherification is more preferably 0.15 to 0.4 in consideration of the dispersion stability and the improvement of the color development of the handwriting by forming bulky aggregates.

The water absorption of the etherified cellulose used in the present invention is preferably 10 g / g to 30 g / g. When the amount of water absorption is within the above range, the etherified cellulose stably disperses the ink composition without making the ink composition excessively high viscosity, and suppresses the ink from seeping out from the handwriting to the periphery of the handwriting during writing. Therefore, the color development of the handwriting can be improved.

Specific examples of the etherified cellulose used in the present invention include Sunrose SLD-F1 (carboxymethyl cellulose, etherification degree 0.20 to 0.30, water absorption 17.5 g / g), Sunrose SLD-FM (carboxy). Methyl cellulose, etherification degree 0.20 to 0.30, water absorption 19.0 g / g) (all manufactured by Nippon Paper Co., Ltd.) can be mentioned.
The etherified cellulose used in the present invention is not limited to these, but the etherified cellulose forms a three-dimensional network structure in the ink composition and retains the pigment in the network structure. It is preferably used because it has the effect of improving the dispersion stability of the pigment and suppressing the formation of a hard cake.

The content of the etherified cellulose in the present invention is preferably 0.01% by mass to 3.0% by mass, more preferably 0.05% by mass to 1.0% by mass, based on the total amount of the ink composition. Is more preferable. More preferably, it is 0.1% by mass to 0.5% by mass. When the content of the etherified cellulose is within the above range, the ink viscosity becomes too high and the deterioration of the ink ejection property at the time of writing is suppressed, and the ink is adsorbed with the pigment to form a bulky aggregate. It is possible to improve the color development of handwriting.

In the present invention, by using etherified cellulose and a poorly water-soluble resin described later in combination, when writing on a cursive with a large gap between fibers such as paper and cloth, the pigment is applied to the surface of the writing surface. , It can be more fixed and the color development of the handwriting can be further improved.

When the sum of the total content of the pigment with respect to the total amount of the ink composition and the total content of the complementary color pigment described later with respect to the total amount of the ink composition is A, and the total content of the etherified cellulose with respect to the total amount of the ink composition is B. The range of 0.001 ≦ B / A ≦ 0.1 is preferable, and the relationship of 0.002 ≦ B / A ≦ 0.05 is preferable. Considering more, 0.003 ≦ B / A ≤0.03 is preferable. Within the above numerical range, the pigment is more easily fixed on the surface of the writing surface to improve the color development property, and the viscosity of the ink composition does not become too high, so that the ink ejection property is good. This is because it is easy to have excellent writability.

(Slightly water-soluble resin)
The water-based ink composition according to the present invention contains a poorly water-soluble resin. The poorly water-soluble resin is a resin having a solubility in water (amount of solute in 100 g of water) of less than 1.0 g, and in the ink composition, the bulky aggregate, the pigment, and the polyolefin described later are described. By binding to particles and adhering to the surface to be written during writing, the fixing property and scratch resistance of the handwriting are improved, and the color development property of the handwriting is improved. Therefore, in the water-based ink composition of the present invention, it is important to use both of the etherified cellulose and the poorly water-soluble resin in combination because the fixing property and color development of the handwriting are further improved. ..
In the present invention, the poorly water-soluble resin is preferably used as an emulsion or a dispersion, whereby the poorly water-soluble resin can take a stable dispersed state.

Specific examples of the poorly water-soluble resin used in the ink composition of the present invention include acrylic resin, urethane resin, styrene-butadiene resin, alkyd resin, ketone resin, sulfoamide resin, maleic acid resin, and polyvinyl acetate resin. , Ethylene vinegar resin, vinyl chloride resin, copolymer of styrene and maleic acid ester, styrene-acrylonitrile resin, cyanate-modified polyalkylene glycol, ester gum, xylene resin, urea resin, urea aldehyde resin, phenol resin, Alkylphenol resin, terpenephenol resin, rosin-based resin and its hydrogenated compound, rosinphenol resin, polyvinyl butyral, polyvinyl acetal, polyvinylalkyl ether, polyamide resin, polyolefin resin, nylon resin, polyester resin, cyclohexanone-based resin and the like can be mentioned. It can be used preferably. It is possible to use one kind or two or more kinds of these.
Considering the improvement of the color development property of the handwriting, the fixing property of the handwriting, and the scratch resistance, the composition of the present invention may contain one or more selected from a polyolefin resin, an acrylic resin, a nylon resin, and a polyester resin. preferable. Considering the handwriting performance, the composition preferably contains a polyolefin resin or an acrylic resin, and particularly preferably contains a polyolefin resin.
By containing a polyolefin resin or an acrylic resin, the ink composition of the present invention can achieve both good color development, high fixability of handwriting, and excellent scratch resistance, and such an effect is achieved by etherified cellulose. It is effectively expressed by using the above-mentioned poorly water-soluble resin in combination.

Examples of the polyolefin resin used in the present invention include polymers using olefins such as ethylene, propylene, or butene as monomers, polymers and modified products of olefins and monomers other than olefins, and specific examples thereof. Polyethylene, polypropylene, polybutene, ethylene propylene copolymer, ethylene butene copolymer, propylene butene copolymer, ethylene propylene butene copolymer, polymer of ethylene and acrylic acid, copolymer of ethylene and methacrylic acid A combination, a polymer of ethylene and maleic anhydride, a polymer of ethylene and vinyl acetate and the like can be preferably used. Considering the color development and fixing properties of the water-based ink composition, the polyolefin resin used in the ink composition is more preferably a copolymer of ethylene and acrylic acid, and further, a copolymer of ethylene and acrylic acid. A self-emulsifying type obtained by modifying the polymer is particularly preferable.
As a specific example of the polyolefin resin suitable for the present invention, a polyolefin resin obtained by alkali-neutralizing a copolymer of ethylene and acrylic acid to form a self-emulsifying type (manufactured by Sumitomo Seika Co., Ltd., product name: Zyxen A type, L type, N type) and modified polyolefin resin (manufactured by Unitica Co., Ltd., product names: Arrowbase C series, D series, S series) can be mentioned.

Further, the acrylic resin used in the present invention is a polymer containing acrylic acid or methacrylic acid as a repeating unit, and it is possible to use a single acrylic resin or a plurality of kinds of acrylic resins. Specifically, acrylic acid ester resin, acrylic styrene resin, acrylic silicone resin, acrylic urethane resin, acrylic nitrile resin, acrylic styrene nitrile resin, acrylic vinegar resin, methacrylic acid ester resin and the like can be preferably used. Among these acrylic resins, an acrylic styrene resin is preferable, and a self-crosslinking acrylic styrene copolymer resin is more preferable, in consideration of further improving the fixing property and the abrasion resistance of the brush stroke.

The molecular weight of the acrylic resin is not particularly limited, but a mass average molecular weight of 1,000 to 1,000,000 is generally used.

Specific examples of the acrylic resin that can be used in the present invention include JONCRYL series (manufactured by BASF Corporation), Primal AC series (manufactured by Rohm and Hearth Japan Co., Ltd.), JSRAE series (manufactured by JSR Corporation), and so on. Examples include the MOVIN series (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), the Nikazol series (manufactured by Nippon Carbide Industry Co., Ltd.), and the Ultrasol series (manufactured by Aika Kogyo Co., Ltd.).

Further, the nylon resin and the polyester resin used in the present invention are not particularly limited as long as they have the effect of improving the color development property, the fixing property of the brush stroke and the abrasion resistance of the ink composition, and the nylon resin is an amide. A polymer having a repeating unit of bonding and an aliphatic skeleton, for example, Sepoljon PA (manufactured by Sumitomo Seika Co., Ltd.), which is a copolymerized nylon, can be mentioned, and examples of the polyester resin include Saturated copolymerized polyester resin (manufactured by Unitica Co., Ltd., product names: Elitel KA series, KT series), which is a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol, can be mentioned, and all of them are preferably used.

The content of the poorly water-soluble resin is preferably 0.1% by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass, based on the total amount of the ink composition. More preferably, it is 0.5 to 3% by mass. Further, when the total content of the etherified cellulose with respect to the total amount of the ink composition is A and the total content of the poorly water-soluble resin with respect to the total amount of the ink composition is B, 0.5 ≦ B / A ≦ 40. It is preferably in the range, preferably in the relationship of 2 ≦ B / A ≦ 20, and more preferably 3 ≦ B / A ≦ 15. If the content of the poorly water-soluble resin or the ratio between the content of the poorly water-soluble resin and the content of etherified cellulose is within the above numerical range, the fixability of the pigment on the writing surface is further enhanced and the pigment is excellent. This is because it is easy to write.

(solvent)
Examples of the solvent include water and a mixed solvent of water and an organic solvent. As water, conventional water such as ion-exchanged water, distilled water and tap water can be used, and when a mixed solvent of water and an organic solvent is used, ethanol, normal propanol, isopropanol or the like is used as the organic solvent. be able to. Although diols or triols having a relatively high boiling point such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and polyethylene glycol can be used, the blending amount thereof is preferably small. The content of the organic solvent is preferably 1% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, based on the total mass of the solvent. In particular, the content of diols or triols is preferably 1% by mass to 10% by mass. When the content of the organic solvent is within the above numerical range with respect to the total mass of the solvent, good dry-up performance and handwriting drying property can be achieved at the same time.

The content of the solvent in the water-based ink composition is preferably 20% by mass to 90% by mass, more preferably 30% by mass to 80% by mass, based on the total mass of the composition. When the content of the solvent is within the above numerical range, each component can be stably dissolved or dispersed, and a bulky aggregate can be easily redispersible in the aqueous ink composition.

(Penetrating agent)
The water-based ink composition of the present invention lowers the surface tension of the ink composition by containing a penetrant, improves the wettability, and enhances the writeability on non-penetrating surfaces such as glass, plastic, and spinach, which easily repel ink. It is possible.
The penetrant used in the present invention is one of a phosphate ester-based surfactant, a surfactant having an acetylene bond, a fluorine-based surfactant, a silicone-based surfactant, and a succinic acid-based surfactant. It is preferable to select and use the above. By incorporating the above-mentioned surfactant into the water-based ink composition, the surface tension is lowered to improve the wettability of the water-based ink composition with respect to a non-permeable recording medium such as a film, and the non-permeable recording medium. It is possible to improve the writability by making the handwriting blurring and hollowing out of the handwriting good.

Among the penetrants, the penetrant preferable according to the present invention is a phosphate ester-based surfactant or a surfactant having an acetylene bond.
The phosphoric acid ester-based surfactant is a surfactant having a phosphoric acid group in its structure, and as described above, has the effect of lowering the surface tension of the aqueous ink composition and improving the writability of a non-permeable recording medium. When used as a writing ink for a ball pen, the phosphoric acid group is adsorbed on the metal surface of a ball, ball tip, etc., and exhibits lubricity, thereby suppressing wear of the ball seat and improving the writing quality. Brings an improving effect.

The phosphate ester-based surfactant used in the present invention has an HLB value = 7 + 11.7 log (Mw / Mo), (Mw) as a general formula in consideration of the effect of improving wettability and the dissolution stability in an ink composition. The HLB value obtained from (molecular weight of hydrophilic group; Mo; molecular weight of lipophilic group) is preferably 4 to 18, and more preferably 6 to 17.

Specific phosphate ester-based surfactants include Plysurf A212C (tridecyl alcohol), A208B (lauryl alcohol), and A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) from the Plysurf series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Short chain alcohol type), A215C (tridecyl alcohol type), A219B (lauryl alcohol type), A208N (mixed system of fatty alcohol with 12 carbon atoms and fatty alcohol with 13 carbon atoms), AL (same system) Styrene-based), and one type or two or more types can be preferably used.
Considering the effect of improving the wettability and the effect of improving the lubricity of the metal surface, among the above, plysurf A215C, A219B, 208N, and AL are more preferable, and ply is an aliphatic alcohol-based phosphoric acid ester. Surf A215C, A219B and A208N are particularly preferable.

The surfactant having an acetylene bond used in the present invention has an HLB value = 20 × (mass% of hydrophilic group) = 20 as a general formula in consideration of the effect of improving wettability and the dissolution stability in an ink composition. It is preferable that the HLB value obtained from × (total of the formula amounts of the hydrophilic groups / the molecular weight of the surfactant) has an HLB value of 4 to 18, more preferably 6 to 15, and 7 to 11 It is particularly preferable to have an HLB value of.

A surfactant having an acetylene bond has extremely high stability, and can continuously exert an effect of improving wettability to improve writeability. Examples of the surfactant having an acetylene bond include an acetylene alcohol-based surfactant and an acetylene glycol-based surfactant. In particular, an acetylene glycol-based surfactant is preferable because it is excellent in suppressing the generation of air bubbles, suppresses the foaming of the handwriting during writing, and easily exerts the effect of smoothing the surface of the handwriting.

Specific examples of the surfactant having an acetylene bond include Orfin D-10A, Orfin D-10PG, Orfin E1004, Orfin E1010, and Orfin E102.
0, Orfin E1030W, Orfin PD-001, Orfin PD-002W, Orfin PD-004, Orfin EXP. 4001, Orfin EXP. 4200, Orfin EXP. 4123, Orfin EXP. 4300, Surfinol 61, Surfinol 82, Surfinol 104 Series, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 2502, Dynol 604, Dynol 607 , Made by Nissin Chemical Industry Co., Ltd., acetylenol EH, acetylenol EL, acetylenol E
13T, acetylenol E40, acetylenol E60, acetylenol E81, acetylenol E100, acetylenol E200, acetylenol E300, acetylenol 85, and above, manufactured by Kawaken Fine Chemical Co., Ltd., can be mentioned as one or two.
Seeds or more can be preferably used. Among the above-mentioned surfactants, Dynol 604, Dynol 607, and Surfinol 2502 are particularly preferable in consideration of the effect of improving wettability and the effect of suppressing foaming of handwriting.
In the aqueous ink composition of the present invention, it is preferable to use the phosphoric acid ester-based surfactant in combination with a surfactant having an acetylene bond , and by using both in combination, the writeability on the non-penetrating surface is further enhanced.

The content of the penetrant in the present invention is preferably 0.001% by mass to 7% by mass, more preferably 0.01% by mass to 4% by mass. When the content is within the above numerical range, it is possible to achieve both improvement in wettability, lubricity of the metal surface, suppression of foaming of handwriting, and dissolution stability of the penetrant.

When a penetrant is used in combination, particularly when a phosphate ester-based surfactant and a surfactant having an acetylene bond are used in combination, the total content of the phosphate ester-based surfactant in the aqueous ink composition is set to A. Assuming that the total content of the surfactant having an acetylene bond in the aqueous ink composition is B, the ratio of A to B is preferably 0.5 ≦ A / B ≦ 15, and 1 ≦ A / B ≦ 5. Is more preferable. When the ratio of both A and B is within the above numerical range, it is possible to achieve both good writing property on the non-penetrating surface, lubricity, foaming inhibitory property of handwriting, and dissolution stability of the penetrant.

(Polyolefin resin particles)
Further, by using the polyolefin resin particles in the ink composition of the present invention, it is possible to impart high fixing property and scratch resistance to handwriting. Polyolefin resin particles are fine particles having surface lubricity, which are composed of polyolefins such as polyethylene and polypropylene, and mixtures thereof, and suppress the application of excessive force to the brush when the brush receives an external force such as scratching. This is a type of polyolefin resin different from the above-mentioned poorly water-soluble resin.
The polyolefin may be a linear polyolefin, a polyolefin having a branched chain, a modified polyolefin into which a functional group has been introduced, or the like. For example, when polyethylene is used as the polyolefin, low-density polyethylene, linear low-molecular-weight polyethylene, high-density polyethylene, modified polyethylene, modified high-density polyethylene and the like can be used. The molecular weight of these polyolefins is not particularly limited, but for example, a polyolefin having a mass average molecular weight of 500 to 100,000 is preferable, and a weight average molecular weight of 800 to 5,000 is more preferable. When the mass average molecular weight of the polyolefin resin particles is within the above numerical range, the water-based ink composition has higher slipperiness with respect to the writing line formed when writing is performed using a writing instrument such as a marker. Along with this, high scratch resistance can be imparted, and good handwriting can be obtained. The polyolefin resin particles may contain a material other than the polyolefin, if necessary.
In the water-based ink composition of the present invention, when the poorly water-soluble resin and the polyolefin resin are used in combination, the color development and fixing property of the handwriting and the scratch resistance of the handwriting are more likely to be improved, so that both can be used in combination. Preferably, by doing so, it is possible to write well when writing on a non-permeable recording medium.

The shape of the polyolefin resin particles is not particularly limited, and can take any shape such as an amorphous shape, a spherical shape, a needle shape, a plate shape, and a square shape.

The average particle size of the polyolefin resin particles is preferably 0.1 μm to 35 μm. When the average particle size of the polyolefin resin particles is within the above numerical range, the water-based ink composition has higher slipperiness with respect to the writing line formed when writing is performed using a writing instrument such as a marker. Along with this, high scratch resistance can be imparted, and good handwriting can be obtained. Further, from the viewpoint of imparting high scratch resistance, it is more preferably 0.1 μm to 25 μm, further preferably 0.5 μm to 20 μm, and particularly preferably 0.5 μm to 15 μm. The average particle size of the polyolefin resin particles can be measured by the Coulter counter method.

Specific examples of the polyolefin resin particles that can be used in the present invention include Chemipearl W series, Chemipearl M series (all trade names are manufactured by Mitsui Chemicals, Inc.), CERAFLOUR series, Aquacer series, and Aquamat series (all are commercial products). Name, manufactured by Big Chemie Co., Ltd.).

The content of the polyolefin resin particles in the water-based ink composition is preferably 0.01% by mass to 10% by mass, preferably 0.2% by mass to 5% by mass, based on the total mass of the water-based ink composition. It is more preferable, and it is most preferably 0.5% by mass to 5% by mass. When the content of the polyolefin resin particles is within the above numerical range, the ink ejection property can be maintained and the writing line can be imparted with higher slipperiness.

(Complementary color pigment)
The water-based ink composition according to the present invention may contain a complementary color pigment in order to adjust the color of the obtained writing line. In particular, when white titanium oxide is selected as the main pigment particles, various colors can be realized by combining with the complementary color pigment. The complementary color pigment is not particularly limited, and pigments of various colors such as red, blue, yellow, green, white, and black can be used, and a pigment dispersion obtained by dispersing the pigment in a solvent is used. It is possible. Examples of complementary color pigments include SP series (manufactured by Fuji Dye Co., Ltd.), SANDYESUPERCOLOR series (manufactured by Sanyo Dye Co., Ltd.), EMACOL series (manufactured by Sanyo Dye Co., Ltd.), and Lumicol series (manufactured by Nippon Fluorescent Chemical Co., Ltd.) (Manufactured by Orient Chemical Industry Co., Ltd.), WA series (manufactured by Dainichi Seika Kogyo Co., Ltd.) and the like.

The content of the complementary color pigment in the water-based ink composition is preferably 0.01% by mass to 15% by mass, preferably 0.1% by mass to 10% by mass, based on the total mass of the water-based ink composition. Is more preferable.

(others)
In addition, the water-based ink composition may contain a constitutional material, a preservative, an antifoaming agent, a rust preventive agent, a pH adjusting agent, a bubble suppressing agent, a bubble absorbing agent, a shear thinning agent, a viscosity adjusting agent and the like, if necessary. It may be included.

(Aqueous ink composition for writing tools)
The viscosity of the aqueous ink composition according to the present invention is preferably low. The viscosity of the composition can be measured using an E-type rotational viscometer (manufactured by Brookfield). Specifically, the viscosity of the water-based ink composition at 20 ° C. is preferably 1 to 100 mPa · s when measured under the condition of a rotation speed of 100 rpm (shear rate 380 sec ^-1 ), and is preferably 2 to 70 mPa · s. Is more preferable. More preferably, it is 5 to 40 mPa · s. Further, when measured under the condition that the rotation speed is 10 rpm (shear rate 38 sec ^-1 ), it is preferably 1 to 600 mPa · s, and more preferably 5 to 200 mPa · s. More preferably, it is 10 to 100 mPa · s. At a rotation speed of 1 rpm (shear rate 3.8 sec ^-1 ), it is preferably 1 to 3000 mPa · s, and more preferably 10 to 1500 mPa · s. More preferably, it is 20 to 400 mPa · s. When the viscosity of the water-based ink composition is within the above numerical range, the ink ejection property when used for a writing instrument such as a marker can be improved, and the writing property on a non-permeable recording medium such as a film is improved. do.

The surface tension of the water-based ink composition is preferably 10 to 50 mN / m in an environment of 20 ° C. If the surface tension is within the above numerical range, it tends to be possible to prevent bleeding of the writing line and strike-through to the paper, and it is possible to improve the writing property by improving the handwriting blurring and hollowing out. .. Considering the writability of the non-permeable recording medium, the surface tension of the aqueous ink composition is preferably 20 to 30 mN / m, and in particular, in the present invention, a phosphate ester-based surfactant or an acetylene bond is used. It is preferable to use the surfactant contained in the structure because it is suitable for adjusting the surface tension of the water-based ink composition.
The surface tension is measured by a vertical plate method using a surface tension measuring instrument manufactured by Kyowa Interface Science Co., Ltd. and a platinum plate in an environment of 20 ° C.

The pH value of the water-based ink composition is preferably 6 to 10, and more preferably 7 to 9. When the pH value of the water-based ink composition is within the above numerical range, it is possible to suppress discoloration and excessively high viscosity of the ink composition, and an inorganic oxide having silica or alumina in the ink composition. When the pigment treated with the above is used, the dispersibility of the pigment can be further improved by further using the pigment dispersant.
Further, when etherified cellulose is used as in the present invention, if the pH value of the aqueous ink composition is set to 6 to 10 in order to obtain the above effects, the etherified cellulose is stabilized in the ink. Since it is easy to improve the dispersion stability of the pigment and the color development of the brush stroke, the pH value of the etherified cellulose is preferably 6 to 10, and more preferably, the pH value is 6 to 8. In the present invention, the pH value can be measured at 20 ° C. by, for example, an IM-40S type pH meter (manufactured by Toa DK Co., Ltd.).

The reason why the water-based ink composition according to the present invention exhibits excellent color development and fixability has not been clarified in detail, but it is presumed to be due to the following mechanism.

When a pigment is used as the water-based ink composition, the pigment is crushed and mixed so that the ink composition can obtain sufficient coloring power. The ink composition thus obtained has a vivid color tone, and while a clear cursive can be obtained when writing on a smooth or precise writing surface, a writing body having a large gap between fibers such as paper and cloth can be obtained. When writing in, the pigment crushed into fine particles passes through the gaps between fibers such as paper and cloth and enters the periphery of the part to be written and the inside of the cursive, and the color development of the cursive is deteriorated. ..

The water-based ink composition in the present invention further solves such a problem by combining etherified cellulose and a poorly water-soluble resin.

In the case of the water-based ink composition according to the present invention, the crushed pigment particles and the etherified cellulose are adsorbed to form bulky aggregates. As a result, when writing on a cursive with large gaps between fibers such as paper and cloth, bulky aggregates do not pass through the gaps between the fibers and are easily adsorbed on the fibers on the surface of the writing surface. Therefore, it is considered that the color development and the fixing property of the handwriting are improved.
In addition, since the ink composition in which aggregates are formed by etherified cellulose exhibits pseudoplastic viscous behavior, the viscosity of the handwritten ink composition, which was lowered by the operation during writing, is immediately restored by being allowed to stand. It is considered that the suppression of ink bleeding from the handwriting contributes to the improvement of color development and the fixing property of the handwriting. Further, the poorly water-soluble resin can further improve the fixing property and the abrasion resistance of the pigment and the bulky aggregate by binding to the pigment and the bulky aggregate, so that the color development property of the handwriting is further improved. be able to.

By further containing a penetrant, the ink composition of the present invention lowers the surface tension of the ink composition, improves the wettability, and enhances the writeability on non-penetrating surfaces such as glass, plastic, and spinach, which easily repel ink. It is possible.

Further, the water-based ink composition according to the present invention contains polyolefin resin particles, so that the abrasion resistance is significantly improved. The reason for this is presumed to be as follows. The handwriting formed by using the aqueous ink composition containing the polyolefin resin particles is formed by arranging the bulky aggregate and the polyolefin resin particles on the surface to be written. Since the surface of the polyolefin resin particles has a small frictional resistance, when the surface of the handwriting is scratched, excessive external force is suppressed from being applied to the handwriting, and the handwriting is not affected by peeling. Then, as the scraping progresses, the polyolefin resin particles are deformed by the force applied or frictional heat to cover the surface of the handwriting. As a result, it is presumed that the surface of the handwriting is coated with the polyolefin resin, the friction coefficient of the surface of the handwriting is lowered by the polyolefin resin, and the handwriting is protected.

The water-based ink composition according to the present invention can be produced by any conventionally known method. Specifically, each of the above components can be blended in a required amount and mixed with various stirrers such as a propeller stirrer, a homodisper, or a homomixer, or various dispersers such as a bead mill, and the like can be produced.

(Stationery)
The water-based ink composition of the present invention is used for writing tools such as marking pens and ballpoint pens using a pen nib such as a fiber tip, felt tip, plastic tip or a ballpoint pen tip, and a fountain pen using a metal pen tip. Can be done. Among them, in order to improve the writability of a non-permeable recording medium such as a film, it is preferable that the pen tip is a pen core or a ballpoint pen tip made of a fiber tip, a felt tip, or a plastic tip. Furthermore, it is more preferable to use it for a marking pen or a ballpoint pen.
The pore diameter of the pen core can be arbitrarily set as long as the pore diameter is such that bulky aggregates can pass through, and the porosity is preferably 50 to 80%. When the porosity of the pen core is within the above numerical range, the pigment is not clogged and an appropriate ink ejection amount can be maintained.

The writing tool of the present invention may be configured to be directly filled with the water-based ink composition, or may be provided with an ink container or an ink storage body capable of filling the water-based ink composition. Further, in order to redistribute the pigment, it is preferable that the ink container contains a stirrer such as a stirrer ball for stirring the ink. Further, the shape of the stirring body may be a spherical body, a rod-shaped body, or the like. The material of the stirrer is not particularly limited, and specific examples thereof include metal, ceramic, resin, glass, etc. Among these, if the stirring power for redispersing the pigment is taken into consideration. , It is preferable to use a metal material, and considering the cost, it is preferable to use a glass material. The agitator may be made of a plurality of materials or a plurality of types of materials.

The haunting mechanism of the writing instrument of the present invention is not particularly limited, and examples thereof include a cap type having a cap covering the pen tip, a knock type, a rotary type, and a slide type. Further, it may be a haunting type that can accommodate the pen tip in the barrel.

Further, the ink supply mechanism in the writing tool is not particularly limited, and for example, (1) a mechanism provided with an ink guide core made of a fiber bundle or the like as an ink flow rate adjusting member and supplying a water-based ink composition to a pen tip. (2) A mechanism for supplying a water-based ink composition to the pen tip by interposing a comb-groove-shaped ink flow rate adjusting member, and (3) an ink flow rate adjusting member by a valve mechanism, and pen for the water-based ink composition. Examples thereof include a mechanism for supplying water first, and (4) a mechanism for directly supplying the water-based ink composition to the pen tip from an ink container or a shaft cylinder provided with a pen tip.

In one embodiment, the writing instrument is a marking pen, and the pen tip is not particularly limited, and may be, for example, a fiber tip, a felt tip, a plastic tip, or the like, and the shape thereof may be bullet-shaped, chisel-shaped, or the like. It may be a brush pen type or the like.

In one embodiment, the writing instrument is a ballpoint pen, preferably a ballpoint pen provided with an ink backflow preventive body.

The present invention will be described below with reference to various examples.
(Example 1)
An ink composition for writing utensils was obtained by stirring and mixing the following raw materials and blending amounts at room temperature for 1 hour. The viscosity of the obtained aqueous ink composition was measured with an E-type rotary viscometer (DV-II + Pro, cone-type rotor CPE-42, manufactured by Brookfield), and the viscosity index was calculated based on the viscosity. Specifically, the viscosity at 20 ° C. and a shear rate of 38 sec ^-1 (rotational speed of 10 rpm) is 9.12 mPa · s. Further, as a result of measuring the pH of the aqueous ink composition at 20 ° C. using an IM-40S type pH meter (manufactured by DKK-TOA CORPORATION), the pH was 8.6.
The surface tension of the obtained water-based ink composition was measured by a surface tension measuring instrument (20 ° C. environment, vertical flat plate method, manufactured by Kyowa Interface Science Co., Ltd.) and found to be 42.5 mN / m.
・ Pigment 30% by mass
(Silica, titanium oxide surface-treated with alumina, average particle diameter 0.26 μm, manufactured by Sakai Chemical Industry Co., Ltd., trade name: GTR-100)
・ Pigment dispersant 1.5% by mass
(Pigment dispersant having a cationic adsorbent, solid content 52%, manufactured by Big Chemie Co., Ltd., trade name: DISPER BYK-184)
・ 0.25% by mass of etherified cellulose
(Carboxymethyl cellulose (etherification degree 0.2-0.3, manufactured by Nippon Paper Industries, Ltd., trade name: Sunrose SLD-F1)
・ 10% by mass of sparingly water-soluble resin
(Self-emulsifying polyolefin dispersion, solid content 25%, manufactured by Sumitomo Seika Chemical Co., Ltd., product name: Zyxen L)
・ Diethylene glycol 2% by mass
・ Antifoaming agent 0.3% by mass
(Silicone defoamer, manufactured by Big Chemie Co., Ltd., trade name BYK-024)
・ Preservative 0.2% by mass
(Benzoisothiazolin-3-one, manufactured by Lonza Japan Co., Ltd., trade name: Proxel XL-2)
・ Ion-exchanged water 55.75% by mass

(Examples 2 to 31, Comparative Examples 1 to 8)
The types and amounts of the components to be blended were changed with respect to Example 1 as shown in Tables 1 to 5, and the ink compositions of Examples 2 to 31 and Comparative Examples 1 to 8 were obtained.
The positive and negative signs of the pigment surface charge values in the ink compositions of Examples 1 to 31 and Comparative Examples 1 to 8 were as follows.
-Examples 1 to 8, 11 to 27, 29 to 31 (negative value)
-Comparative examples 1 to 8 (negative value)
-Examples 9 to 10, 28 (positive value)

上記実施例で使用した材料の詳細は以下の通りである。
・顔料（１）シリカ、アルミナにより表面処理された酸化チタン（平均粒子径：０．２６μｍ、堺化学工業株式会社製、商品名：ＧＴＲ－１００）
・顔料（２）シリカ、アルミナにより表面処理された酸化チタン（平均粒子径：０．２５μｍ、テイカ株式会社製、商品名：ＪＲ－７０７）
・顔料（３）シリカ、アルミナ、酸化亜鉛により表面処理された酸化チタン（平均粒子径：０．２７μｍ、テイカ株式会社製、商品名：ＪＲ－７０１）
・顔料（４）アルミナにより表面処理された酸化チタン（平均粒子径：０．２３μｍ、堺化学工業株式会社製、商品名：Ｒ－３２）
・顔料（５）アルミナにより表面処理された酸化チタン（平均粒子径：０．２１μｍ、テイカ株式会社製、商品名：ＪＲ－４０５）
・顔料分散剤（１）カチオン性吸着基を有する顔料分散剤（固形分含有量５２％、ビッグケミー株式会社製、商品名：ＤＩＳＰＥＲ ＢＹＫ－１８４）
・顔料分散剤（２）アニオン性吸着基を有する顔料分散剤（固形分含有量４０％、ビックケミー株式会社製、商品名：ＤＩＳＰＥＲ ＢＹＫ－１９０）
・エーテル化セルロース（１）カルボキシメチルセルロース（エーテル化度０．２～０．３、日本製紙株式会社製、商品名：サンローズＳＬＤ－Ｆ１）
・エーテル化セルロース（２）カルボキシメチルセルロース（エーテル化度０．２～０．３、日本製紙株式会社製、商品名：サンローズＳＬＤ－ＦＭ）
・エーテル化セルロース（３）ヒドロキシプロピルメチルセルロース（エーテル化度１．９、信越化学工業株式会社製、商品名：メトローズ６０ＳＨ－５０）
・難水溶性樹脂（１）自己乳化型ポリオレフィン樹脂ディスパージョン（固形分含有量２５％、住友精化株式会社製、商品名：ザイクセンＬ）
・難水溶性樹脂（２）アクリル樹脂エマルション（固形分含有量４２％、ＢＡＳＦ株式会社製、商品名：ＪＯＮＣＲＹＬ ＰＤＸ－７３７０）
・ポリオレフィン樹脂粒子（１）変性ポリエチレンワックス（平均粒子径：８μｍ、固形分：１００％、ビックケミー株式会社製、商品名：ＣＥＲＡＦＬＯＵＲ９２９）
・ポリオレフィン樹脂粒子（２）変性ポリエチレンワックス（平均粒子径：６μｍ、固形分：１００％、ビックケミー株式会社製、商品名：ＣＥＲＡＦＬＯＵＲ９２５）
・ポリオレフィン樹脂粒子（３）低密度ポリエチレン（平均粒子径：６μｍ、４０％ディスパージョン、三井化学株式会社製、商品名：ケミパールＭ２００）
・ポリオレフィン樹脂粒子（４）低分子ポリエチレン（平均粒子径：０．６μｍ、 ４０％ディスパージョン、三井化学株式会社製、商品名：ケミパールＷ４００５）
・補色顔料（１）ＳＡＮＤＹＥＳＵＰＥＲＣＯＬＯＵＲ ＢＬＵＥ ＧＬＬ－Ｅ（有機顔料水分散体、固形分含有量３２％、山陽色素株式会社製）
・補色顔料（２）ＳＡＮＤＹＥＳＵＰＥＲＣＯＬＯＵＲ ＲＥＤ １３２１－Ｅ（有機顔料水分散体、固形分含有量３５％、山陽色素株式会社製）
・浸透剤（１）リン酸エステル系界面活性剤（第一工業製薬株式会社製、商品名：プライサーフＡ２０８Ｎ、ＨＬＢ：７）
・浸透剤（２）リン酸エステル系界面活性剤（第一工業製薬株式会社製、商品名：プライサーフＡ２１９Ｂ、ＨＬＢ：１６．２）
・浸透剤（３）アセチレン結合を有する界面活性剤（日信化学工業株式会社製、商品名：ダイノール６０４、ＨＬＢ：８）
・粘度調整剤（１）架橋型アクリル酸重合体（和光純薬工業株式会社製、商品名：ハイビスワコー１０４）
・粘度調整剤（２）架橋型アクリル酸重合体（和光純薬工業株式会社製、商品名：ハイビスワコー１０５）
・消泡剤 シリコーン系消泡剤（ビッグケミー株式会社製、商品名：ＢＹＫ－０２４）
・防腐剤 ベンゾイソチアゾリン－３－オン（ロンザジャパン株式会社、商品名：Ｐｒｏｘｅｌ ＸＬ－２）
・ｐＨ調整剤
・ジエチレングリコール

The details of the materials used in the above examples are as follows.
-Pigment (1) Titanium oxide surface-treated with silica and alumina (average particle size: 0.26 μm, manufactured by Sakai Chemical Industry Co., Ltd., trade name: GTR-100)
-Pigment (2) Titanium oxide surface-treated with silica and alumina (average particle size: 0.25 μm, manufactured by TAYCA CORPORATION, trade name: JR-707)
Pigment (3) Titanium oxide surface-treated with silica, alumina, and zinc oxide (average particle size: 0.27 μm, manufactured by TAYCA Corporation, trade name: JR-701).
-Pigment (4) Titanium oxide surface-treated with alumina (average particle size: 0.23 μm, manufactured by Sakai Chemical Industry Co., Ltd., trade name: R-32)
Pigment (5) Titanium oxide surface-treated with alumina (average particle size: 0.21 μm, manufactured by TAYCA CORPORATION, trade name: JR-405)
-Pigment dispersant (1) Pigment dispersant having a cationic adsorbent (solid content 52%, manufactured by Big Chemie Co., Ltd., trade name: DISPER BYK-184)
-Pigment dispersant (2) Pigment dispersant having an anionic adsorbent (solid content 40%, manufactured by Big Chemie Co., Ltd., trade name: DISPER BYK-190)
-Aetherylated cellulose (1) Carboxymethyl cellulose (etherified degree 0.2-0.3, manufactured by Nippon Paper Industries, Ltd., trade name: Sunrose SLD-F1)
-Aetherized cellulose (2) Carboxymethyl cellulose (etherified degree 0.2-0.3, manufactured by Nippon Paper Industries, Ltd., trade name: Sunrose SLD-FM)
-Aetherylated cellulose (3) Hydroxypropylmethylcellulose (etherified degree 1.9, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: Metrose 60SH-50)
・ Slightly water-soluble resin (1) Self-emulsifying polyolefin resin dispersion (solid content 25%, manufactured by Sumitomo Seika Chemical Co., Ltd., trade name: Zyxen L)
-Slightly water-soluble resin (2) Acrylic resin emulsion (solid content 42%, manufactured by BASF Corporation, trade name: JONCRYL PDX-7370)
Polyolefin resin particles (1) Modified polyethylene wax (average particle size: 8 μm, solid content: 100%, manufactured by Big Chemie Co., Ltd., trade name: CERAFLOUR929)
-Polyolefin resin particles (2) Modified polyethylene wax (average particle size: 6 μm, solid content: 100%, manufactured by Big Chemie Co., Ltd., trade name: CERAFLOUR 925)
-Polyolefin resin particles (3) Low density polyethylene (average particle diameter: 6 μm, 40% dispersion, manufactured by Mitsui Chemicals, Inc., trade name: Chemipearl M200)
-Polyolefin resin particles (4) Small molecule polyethylene (average particle size: 0.6 μm, 40% dispersion, manufactured by Mitsui Chemicals, Inc., trade name: Chemipearl W4005)
Complementary color pigment (1) SANDYESUPERCOLOR BLUE GLL-E (organic pigment aqueous dispersion, solid content 32%, manufactured by Sanyo Dye Co., Ltd.)
Complementary color pigment (2) SANDYESUPERCOLOR RED 1321-E (organic pigment aqueous dispersion, solid content 35%, manufactured by Sanyo Dye Co., Ltd.)
・ Penetrant (1) Phosphoric acid ester-based surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Plysurf A208N, HLB: 7)
・ Penetrant (2) Phosphoric acid ester-based surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Plysurf A219B, HLB: 16.2)
Penetrant (3) Surfactant having an acetylene bond (manufactured by Nissin Chemical Industry Co., Ltd., trade name: Dynol 604, HLB: 8)
-Viscosity adjuster (1) Cross-linked acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd., trade name: Hibiswaco 104)
-Viscosity adjuster (2) Cross-linked acrylic acid polymer (manufactured by Wako Pure Chemical Industries, Ltd., trade name: Hibiswaco 105)
-Defoaming agent Silicone-based defoaming agent (manufactured by Big Chemie Co., Ltd., product name: BYK-024)
・ Preservative benzoisothiazolin-3-one (Lonza Japan Co., Ltd., trade name: Proxel XL-2)
・ PH adjuster ・ Diethylene glycol

(Testing and evaluation with ballpoint pen and marking pen)
The prepared water-based ink composition was evaluated as follows. The results obtained were as shown in Tables 1-5.
As the ballpoint pen used in the evaluation test, the following ballpoint pen was prepared and used.
Ballpoint pen: A ballpoint pen tip that rotatably holds a ball with a ball diameter of 1.0 mm is attached to the tip of an ink storage cylinder (made of nylon), and it is directly attached to the ink storage cylinder containing a metal ball with a diameter of 5.0 mm. The following tests and evaluations were carried out as ballpoint pens filled with the water-based ink compositions obtained in Examples 1 to 26 and Comparative Examples 1 to 5.
As the marking pen used in the evaluation test, the following marking pen was prepared and used.
Marking pen: A spherical agitator made of a metal material with a diameter of 8 mm and an ink composition with a volume of 6 cm ³ are built into the ink container (inner dimensions: length 80 mm, diameter 16 mm) of the marking pen equipped with a pen tip. Then, the water-based ink compositions obtained in Examples 27 to 31 and Comparative Examples 6 to 8 were filled, the pen tip was impregnated with the water-based ink composition, and the pen tip was made of bullet-shaped polyester having a pore ratio of 60%. The following tests and evaluations were conducted as a marking pen using a fiber nib.

(Evaluation of handwriting color development)
Writing was performed on the writing test medium using the above-mentioned ballpoint pen and marking pen. The color development of the handwriting at that time was visually observed. A cotton cloth (Nisshinbo, 60th, cotton lawn) and a plastic film (polypropylene) were used as a medium for the writing test.
A: There is no color unevenness in the handwriting and it is clear. B: There is some color unevenness in the handwriting, but there is no problem in practical use. C: There is color unevenness in the handwriting and the density is low. Things of practical concern

(Evaluation of abrasion resistance test)
Writing was performed on a cotton cloth (Nisshinbo, 60th count, cotton loan) and a plastic film (polypropylene) using the above ballpoint pen and marking pen. After leaving this writing line for one day, it was rubbed and rubbed 50 times with a cotton cloth (Nisshinbo, 60th, cotton loan) under a load of 200g using a Gakushin type friction fastness tester (manufactured by Tester Sangyo Co., Ltd.). The later handwriting was compared with the initial handwriting, and the abrasion resistance was evaluated according to the following criteria.
A: No handwriting peeling B: Some handwriting peeling but no practical problem C: Handwriting peeling D: Many handwriting peeling and impractical

(Evaluation of writeability)
A writing test was conducted using the above ballpoint pen and marking pen. The color development of the handwriting at that time was visually observed. A plastic film (made of polypropylene) was used as a medium for the writing test.
A: No cissing, no blemishes, good handwriting B: Some cissing, blemishes but no practical problems C: Repelling, blemishes D: Severe cissing, blemishes, handwriting can be recognized What is impractical

(Evaluation of writing taste)
Writing was performed on a writing test medium using the above ballpoint pen, and the writing taste at that time was sensory evaluated. As a medium for the writing test, black paper (manufactured by Nagatoya Shoten Co., Ltd., color paper B5 medium-thick black, thickness 0.09 mm, density 80 g / m ²² ) was used.
A: The writing taste was extremely smooth.
B: Smooth writing taste C: I felt a little heavy writing taste, but it was a level that was not a problem in practice.
D: It was heavy and slippery.

Claims (7)

It contains a pigment, etherified cellulose having a degree of etherification of 0.1 to 0.5, a polyolefin resin and / or an acrylic resin as a poorly water-soluble resin , and water, and the polyolefin resin is ethylene and acrylic acid. The acrylic resin is selected from acrylic acid ester resin, acrylic styrene resin, acrylic silicone resin, acrylic urethane resin, acrylic nitrile resin, acrylic styrene nitrile resin, acrylic vinegar resin, and methacrylic acid ester resin. When one kind or two or more kinds, the total content of the etherified cellulose is A, and the total content of the poorly water-soluble resin is B, B / A is 0.5 ≦ B / A ≦ 40. A water-based acrylic composition for writing tools, which is characterized by being in the range of. The ink composition for writing utensils according to claim 1, which contains a phosphoric acid ester-based surfactant and / or a surfactant having an acetylene bond. The ink composition for writing utensils according to claim 2, which contains a phosphoric acid ester-based surfactant and a surfactant having an acetylene bond. The water-based ink composition for writing tools according to claim 3, wherein the total content of the phosphoric acid ester-based surfactant is 0.5 to 15 times the total content of the surfactant having an acetylene bond. The water-based ink composition for writing tools according to claim 4, wherein the total content of the phosphoric acid ester-based surfactant is 1 to 5 times the total content of the surfactant having an acetylene bond. The water-based ink composition for stationery according to any one of claims 2 to 5, wherein the surfactant having an acetylene bond is an acetylene glycol-based surfactant. A writing instrument comprising the composition according to any one of claims 1 to 6.