JP2017155161A - Aqueous ink composition for writing instrument - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous ink composition suitable for writing instrument such as an aqueous ball point pen and a marking pen excellent in dry-up resistance without lowering dispersion stability of resin particles.SOLUTION: An aqueous ink composition for writing instrument contains at least 5 mass% or more of resin particles having an average particle size of 0.3 μm or more, and 0.05-10 mass% of sulfonic acid-modified polyvinyl alcohol.SELECTED DRAWING: None

Description

  The present invention relates to a water-based ink composition for a writing instrument suitable for a writing instrument such as an aqueous ball-point pen excellent in writing performance and dry-up resistance without reducing the dispersion stability of resin particles.

  Conventionally, resin particles may be blended for the purpose of imparting a specific function to a water-based ink composition for writing instruments. When such a writing instrument using ink is left in a state where the cap is removed, the ink dischargeability is reduced (drying up), the physical properties change such as the viscosity due to the decrease in the dispersion stability of the particles, and the writing property is lowered. The tendency to occur is seen. These fluctuations in physical properties and deterioration in writing properties are particularly easily affected by the amount and size of resin particles.

The mechanism that causes dry-up is presumed that the dispersion state of the resin particles collapses due to the volatilization of water and causes agglomeration, which reduces the ink dischargeability of the writing portion.
In order to suppress this, a method of creating a state like a “lid” by causing no aggregation or loose aggregation is conceivable. However, even if it is a loose agglomeration, a “bulky” agglomeration results in a dull state of ink with high viscosity, so that although dry-up resistance is manifested, this dama is transferred to the drawn line. There are issues such as degradation of quality.

  On the other hand, as an ink composition for writing instruments with improved dry-up resistance, for example, in an ink comprising at least a pigment having a particle diameter in a specific range, a humectant, and water, the humectant comprises urea and ethylene urea. An aqueous pigment ink composition (for example, refer to Patent Document 1) characterized in that the ratio is 1: 3 to 5: 1 by weight, a colorant containing colored resin particles, water, and shear thinning. An aqueous ink composition for ballpoint pens containing an agent and ethylene oxide-modified polyvinyl alcohol (PVA) is known (for example, see Patent Document 2).

  However, in the above-mentioned Patent Document 1, there are still problems such as insufficient dry-up resistance, and poor writing such as blurring. In the above-mentioned patent document 2, the non-drying property is certainly improved by blending ethylene oxide-modified PVA, but there is a problem that an ink agglomeration may occur at the beginning of writing after cap-off. There is also a problem that the viscosity increases with time.

JP-A-8-127746 (Claims, Examples, etc.) Japanese Patent Laying-Open No. 2015-120777 (Claims, Examples, etc.)

  The present invention has been made in view of the above-described problems of the prior art, and is intended to solve this problem. It has excellent dry-up resistance and writing performance without lowering the dispersion stability of the resin particles, and increases in viscosity over time. Another object of the present invention is to provide a water-based ink composition for writing tools suitable for writing tools such as water-based ballpoint pens and marking pens.

  As a result of intensive studies in view of the above-described conventional problems, the present inventors include at least resin particles having a specific average particle diameter and content and a specific modified polyvinyl alcohol in a specific range. Thus, the inventors have found that the above-described aqueous ink composition for writing instruments can be obtained, and have completed the present invention.

That is, the aqueous ink composition for a writing instrument of the present invention is as follows.
(1) At least 5% by mass of resin particles having an average particle size of 0.3 μm or more and 0.05 to 10% by mass of sulfonic acid-modified polyvinyl alcohol, Aqueous ink composition for writing instruments .
(2) The water-based ink composition for a writing instrument as described in (1) above, wherein the resin particles are core-shell type microcapsules.
(3) A writing instrument comprising the water-based ink composition for a writing instrument described in (1) or (2) above.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous | water-based for writing instruments suitable for writing instruments, such as a water-based ball-point pen and a marking pen which are excellent in dry-up resistance and writing performance, and do not raise a viscosity with time, without reducing the dispersion stability of resin particles. An ink composition is provided.

(A)-(c) is each drawing which shows typically the evaluation criteria (presence / absence of a drawing stroke) of the initial stroke state in Examples and Comparative Examples of the present invention, and (a) is written spirally. (B) and (c) are enlarged views of the portion A of (a), and (b) is a drawing line (evaluation: Drawing which shows (circle), (c) is drawing which shows the drawing line (evaluation: x) in which there is a drawing line deficiency and an initial stroke line state becomes inferior.

Hereinafter, embodiments of the present invention will be described in detail.
The aqueous ink composition for a writing instrument of the present invention contains at least 5% by mass of resin particles having an average particle size of 0.3 μm or more and 0.05 to 10% by mass of sulfonic acid-modified polyvinyl alcohol. It is what.

<Resin particles>
The resin particles used in the present invention are not particularly limited in function and type. For example, the resin particle used as a coloring material, the resin particle for the purpose of a binder or a sealing effect may be sufficient. Further, the material constituting the resin particles is not limited. Examples thereof include acrylic resins, styrene resins, urethane resins, urea resins, epoxy resins, melamine resins, silicone resins and copolymers thereof, and various latex particles.

The resin particles used as the coloring material are composed of colored resin particles. For example, (1) Inorganic pigments such as carbon black and titanium oxide, phthalocyanine pigments, azo pigments, etc. in the resin particles Colored resin particles in which a colorant composed of a pigment such as an organic pigment is dispersed, (2) Colored resin particles in which the surface of the resin particle is coated with a colorant composed of the pigment, (3) Direct dye, acid dye on the resin particle Colored resin particles dyed with a colorant composed of a basic dye, a dye such as food dye, and (4) colored resin particles that are thermochromic or photochromic using a leuco dye, a photochromic dye, etc. Etc.
Examples of the resin component of the colored resin particles (1) to (3) above include at least one selected from the above-mentioned various resins, which are subjected to treatment such as crosslinking as necessary. Also good. Conventional methods for coloring these resins include a method of adding a colorant during polymerization of resin particles, a method of coating the surface of resin particles with a colorant by a hybridization method, and a method of dyeing resin particles with a dye. A known method is used.

As the thermochromic colored resin particles of the above 4), a leuco dye, a developer which is a component having an ability to develop the leuco dye, and a color change temperature in the coloration of the leuco dye and the developer are controlled. A thermochromic colored resin particle produced by microencapsulating a thermochromic composition containing at least a discoloring temperature adjusting agent so as to have a predetermined average particle diameter; As the colored resin particles, a photochromic dye (compound) that is colorless in an indoor lighting environment and has a property of developing a color in an ultraviolet irradiation environment, a photochromic dye produced by microencapsulating a fluorescent dye. Specific colored resin particles.
Examples of the microencapsulation method include interfacial polymerization method, interfacial polycondensation method, in situ polymerization method, liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melt dispersion cooling method, air A suspension coating method, a spray drying method, etc. can be mentioned, and it can select suitably according to a use, the shape of a microcapsule, and a structural characteristic.
As preferred resin particles, core-shell type microencapsulated resin particles are desirable from the viewpoint of exhibiting stability and more fulfilling functions.

  The resin particles for the purpose of the binder and sealing effect are not particularly limited. For example, polystyrene resin particles, polyurethane resin particles, acrylic resin particles, polyethylene wax emulsions, olefin wax emulsions such as polypropylene wax emulsions, etc. There may be mentioned at least one selected.

  The resin particles of the present invention, such as resin particles used as these coloring materials, and resin particles for the purpose of a sealing effect, exhibit a predetermined function (coloring power, dispersion stability, binder and sealing effect) From the standpoint of achieving a high degree of solving the problems of the present invention such as the dry-up described above, it is prepared to have a suitable average particle size.

In the present invention, the greater the content of the resin particles, the greater the average particle diameter, the greater the effect on the ink performance, the content of the resin particles is 5% by mass or more based on the total amount of the ink composition, As the average particle size becomes 0.3 μm or more, the problem of the present invention tends to become apparent.
The average particle size of the resin particles used and the content thereof vary depending on the function of the resin particles, the type of writing instrument, the use, etc., but the average particle size is 0.3 to 15 μm, and the content is based on the total amount of the ink composition. On the other hand, it is preferable to adjust to 5-30 mass%.
The “average particle size” defined in the present invention (including examples and the like) is a value of D50 calculated on a volume basis using a particle size distribution analyzer HRA9320-X100 (manufactured by Nikkiso Co., Ltd.).

<Sulfonic acid-modified polyvinyl alcohol>
The sulfonic acid-modified polyvinyl alcohol used in the present invention is polyvinyl alcohol (hereinafter abbreviated as “PVA”) “general formula, — [CH ₂ —CH (OH)] m— [CH ₂ —CH (OCOCH ₃ ] n—”. In the formula, at least part of the hydroxyl group, acetic acid group, and terminal group is modified with a sulfonic acid group, and any vinyl alcohol polymer containing a predetermined amount of the sulfonic acid group can be used without any particular limitation.
As a synthesis method of sulfonic acid-modified polyvinyl alcohol, for example, a monomer having a sulfonic acid group is polymerized with vinyl acetate, and then a part or all of vinyl acetate is saponified to obtain vinyl alcohol. It can also be synthesized by bonding a compound having a sulfonic acid group to the hydroxyl group of polyvinyl alcohol.
Examples of the monomer having a sulfonic acid group include ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and salts thereof.
As sulfonic acid modification polyvinyl alcohol, what was synthesize | combined suitably may be sufficient and a commercial item may be sufficient.

In the present invention, the sulfonic acid-modified polyvinyl alcohol to be used in the ink composition using the above-described resin particles does not reduce the effect of the present invention, that is, the dispersion stability of the resin particles, and does not deteriorate the dry-up property and the drawn line. It has excellent writing performance with no deterioration in quality, and exhibits a function that does not increase in viscosity over time. Among them, from the viewpoint of the stability of the ink over time and the viscosity imparting property, the saponification degree {[m / (m + n)] × 100} is preferably 70 mol% or more, and more preferably 85 mol. % Or more is desirable.
In addition, in the sulfonic acid-modified polyvinyl alcohol having the saponification degree, the degree of polymerization (m + n) is preferably 1000 or less from the viewpoint of further exerting the effects of the present invention without impairing writing feeling and colorability. Preferably, it is 500 or less, and particularly preferably 100 to 300.
Specific examples of the sulfonic acid-modified polyvinyl alcohol that can be used include Gosennex L-3266, CKS-50, and the like manufactured by Nippon Synthetic Chemical Industry.
These sulfonic acid-modified polyvinyl alcohols may be used alone or in combination of two or more.

The content of the sulfonic acid-modified polyvinyl alcohol used in the present invention is 0.05 to 10% by mass, preferably 0.1 to 5% by mass with respect to the total amount of the ink composition.
If the content is less than 0.05%, the intended effect of the present invention cannot be obtained. On the other hand, if the content exceeds 10% by mass, the viscosity of the ink increases, which is not preferable.

  In the water-based ink composition for a writing instrument of the present invention, in addition to the above components, the coloring material, the balance being water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.), and an anionic interface The effects of the present invention include activators, components usually used in writing instrument aqueous ink compositions, such as water-soluble organic solvents, thickeners, lubricants, rust preventives, antiseptics or antibacterial agents, and pH adjusters. It can contain suitably in the range which is not impaired.

In the present invention, when resin particles are used as a color material, other color materials (coloring agents) other than the colored resin particles can be used together as complementary color components, and when resin particles are not used as a color material, ink coloring Can be used for ingredients.
Color materials that can be used include dyes that dissolve or disperse in water, conventionally known inorganic and organic pigments such as titanium oxide, and a multilayer coating of iron oxide, titanium oxide, etc. on the surface layer using silica or mica as a base material. A pigment or the like can be used in an appropriate amount within a range not impairing the effects of the present invention.
Examples of the dye include acid dyes such as eosin, fuoxin, water yellow # 6-C, acid red, water blue # 105, brilliant blue FCF, and nigrosine NB; direct black 154, direct sky blue 5B, violet B00B, and the like. Dyes; basic dyes such as rhodamine and methyl violet can be used.

Examples of organic pigments include azo lakes, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, and nitroso pigments. More specifically, carbon black, titanium black, zinc white, red pepper, aluminum, chromium oxide, iron black, cobalt blue, iron oxide yellow, viridian, zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, yellow lead, Inorganic pigments such as molybdate orange, zinc chromate, strontium chromate, white carbon, clay, talc, ultramarine, precipitated barium sulfate, barite powder, calcium carbonate, lead white, pale white, bituminous, manganese violet, aluminum powder, brass powder , C.I. I. Pigment blue 15, C.I. I. Pigment blue 17, C.I. I. Pigment blue 27, C.I. I. Pigment red 5, C.I. I. Pigment red 22, C.I. I. Pigment red 38, C.I. I. Pigment red 48, C.I. I. Pigment red 49, C.I. I. Pigment red 53, C.I. I. Pigment red 57, C.I. I. Pigment red 81, C.I. I. Pigment red 104, C.I. I. Pigment red 146, C.I. I. Pigment red 245, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 34, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 167, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 16, C.I. I. Pigment violet 1, C.I. I. Pigment violet 3, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 50, C.I. I. And organic pigments such as CI Pigment Green 7.
These color materials can be used alone or in admixture of two or more.

Examples of the anionic surfactant that can be used include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyphosphates, and the like. Examples thereof include oxyethylene alkyl sulfate ester salts, polyoxyethylene alkyl allyl sulfate salts, naphthalene sulfonic acid formalin condensate salts, and polyoxyethylene alkyl phosphate esters. Among these, those having an aromatic ring are preferable, and naphthalenesulfonic acid formalin condensate salt is particularly preferable. These anionic surfactants have the effect of further stabilizing the ink physical properties.
The content of these anionic surfactants is appropriately adjusted in the range of 0.05 to 10% by mass with respect to the total amount of the ink composition.

Water-soluble organic solvents that can be used include alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, 3-butylene glycol, thiodiethylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like These may be used alone or in combination of two or more.
The content of these water-soluble organic solvents is appropriately adjusted for each ink composition, and is generally in the range of about 10% by mass to 30% by mass with respect to the total amount of the ink composition.
In order to exhibit a function excellent in drawn line drying properties, it is an effective means to make the content of these water-soluble organic solvents 10% by mass or less, but on the other hand, the dry-up resistance is easily impaired. According to the present invention, even when the content is 10% by mass or less, further 7% by mass or less, and further 5% by mass or less, the dry-up resistance is not impaired.

  As the thickener that can be used, for example, at least one selected from the group consisting of synthetic polymers, cellulose, and polysaccharides is desirable. Specifically, gum arabic, gum tragacanth, guar gum, locust bean gum, alginic acid, carrageenan, gelatin, xanthan gum, welan gum, succinoglycan, diutane gum, dextran, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch glycolic acid and Examples thereof include polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic acid and salts thereof, polyethylene oxide, copolymers of vinyl acetate and polyvinyl pyrrolidone, styrene-acrylic acid copolymers and salts thereof.

Lubricants include nonionic compounds such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of sugars, polyoxyalkylene higher fatty acid esters, etc., which are also used as pigment surface treatment agents, alkyl sulfonic acids of phosphoric acid esters and higher fatty acid amides. Examples thereof include salts, anionic compounds such as alkyl allyl sulfonates, polyalkylene glycol derivatives, fluorosurfactants, and polyether-modified silicones.
Also, as rust preventives, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, saponins, etc., as preservatives or fungicides, phenol, sodium omadin, sodium benzoate, benzisothiazoline, benzimidazole series Compound etc. are mentioned.
Examples of pH adjusters include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, amine compounds such as triethanolamine, diethanolamine, monoethanolamine, dimethylethanolamine, morpholine and triethylamine, ammonia, etc. Is mentioned.

  The aqueous ink composition for a writing instrument of the present invention comprises 5% by mass or more of resin particles having an average particle diameter of 0.3 μm or more, 0.05 to 10% by mass of sulfonic acid-modified polyvinyl alcohol, and an anionic surfactant. , Water-soluble organic solvent, and other components are combined as needed according to the application of the writing instrument (ball pen, marking pen, etc.) and further mixed by agitator such as homomixer, homogenizer or disper. Accordingly, an aqueous ink composition for a writing instrument can be prepared by removing coarse particles in the ink composition by filtration or centrifugation.

The water-based ink composition for a writing instrument of the present invention is mounted on a ballpoint pen, a marking pen, or the like having a pen tip such as a ballpoint pen tip, a fiber tip, a felt tip, or a plastic tip.
As the ballpoint pen in the present invention, the water-based ink composition for writing instruments having the above composition is accommodated in a ballpoint pen ink container (refill), and is not compatible with the water-based ink composition housed in the ink container. Examples of the ink follower include substances having a small specific gravity with respect to the water-based ink composition, such as polybutene, silicone oil, mineral oil, and the like.
The structure of the ballpoint pen and the marking pen is not particularly limited. For example, a collector structure (ink holding mechanism) in which the shaft tube itself is used as an ink container and the water-based ink composition for a writing instrument having the above configuration is filled in the shaft tube. It may be a direct liquid ballpoint pen or a marking pen provided.

The water-based ink composition for a writing instrument comprising the resin particles of the present invention thus configured is excellent in writing performance without reducing the dispersion stability of the resin particles and without reducing the dry-up resistance and the drawing quality. The water-based ink composition for writing instruments that does not increase in viscosity over time is presumed as follows.
Conventionally, when an aqueous ink composition for a writing instrument containing resin particles is used, the dispersion state collapses due to volatilization of moisture, and aggregation of resin particles occurs in the ink, or aggregation occurs in the writing part. The problem of dry-up that ink ejection is hindered and writing is poor occurs. Furthermore, in order to suppress dry-up, there is a method of causing loose agglomeration by containing modified ethylene oxide PVA or the like. However, even if it is a loose agglomeration, an ink having a high viscosity is a “bulky” agglomeration. However, although the dry-up resistance is exhibited, there is a problem in that the quality of the drawn line is deteriorated because the dama is transferred to the drawn line.
In the conventional water-based ink composition for writing instruments, as the content of the resin particles used is larger and the average particle diameter is larger, the above-mentioned problem tends to be manifested. By including 0.05 to 10% by mass of sulfonic acid-modified polyvinyl alcohol in the ink composition using the resin particles, a loose aggregate having an appropriate bulkiness can be formed even if moisture is volatilized. It exhibits excellent dry-up resistance without lowering the dispersion stability of the resin particles, excellent writing performance with no deterioration in drawing quality that causes writing strokes to be ink-damped, and functions that do not increase in viscosity over time It becomes.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example etc.

[Examples 1 to 9 and Comparative Examples 1 to 5]
Each water-based ink composition for writing instruments was prepared according to the formulation shown in Table 1 below.
The thermochromic microcapsule pigments 1 and 2 which are resin particles used as the coloring material in Examples 1 and 2 were obtained by the following production methods 1 and 2. The modified ethylene oxide polyvinyl alcohol (PVA) used in Comparative Example 5 was obtained by the following production method 3.
(Production Example 1: Thermochromic microcapsule pigment 1)
As a leuco dye, 1 part by mass of ETAC (manufactured by Yamada Chemical Co., Ltd.) (hereinafter simply referred to as “part”), 2 parts of bisphenol A as a developer, and 24 parts of myristyl myristate as a color change temperature adjusting agent are 100 ° C. And melted to obtain 27 parts of a homogeneous composition.
As a capsule film agent, 10 parts of an isocyanate and 10 parts of a polyol were added to a uniform hot solution of 27 parts of the composition obtained above and stirred and mixed. Subsequently, 60 parts of 12% polyvinyl alcohol aqueous solution was used as a protective colloid and emulsified at 25 ° C. to prepare a dispersion. Subsequently, using 5 parts of 5% polyvalent amine, it was treated at 80 ° C. for 60 minutes to obtain a core-shell type microcapsule.
(Production Example 2: Thermochromic microcapsule pigment 2)
As a leuco dye, 1 part of RED520 dye (manufactured by Yamada Chemical Co., Ltd.), as a developer, 2 parts of 4,4 ′-(2-ethylhexylidene) bisphenol, and as a color changing temperature regulator, 4,4 ′ -(Hexafluoroisopropylidene) bisphenol dimyristate 24 parts was heated and melted at 100 ° C to obtain 27 parts of a homogeneous composition.
Using a uniform hot solution of 27 parts of the composition obtained above as a protective colloid agent, 40 parts of methyl vinyl ether / maleic anhydride copolymer resin (Gantretz AN-179: manufactured by ISP Co., Ltd.) was adjusted to pH 4 with NaOH. While gradually adding to 100 parts of the dissolved 90 ° C. aqueous solution, the mixture is heated and stirred to disperse into oil droplets having a diameter of about 0.5 to 1.0 μm, and then as a capsule film agent, melamine resin (Sumitex resin) M-3 (manufactured by Sumitomo Chemical Co., Ltd.) 20 parts was gradually added and treated at 90 ° C. for 30 minutes to obtain core-shell type microcapsules.

  A water-based ballpoint pen was produced using each ink composition obtained above. Specifically, using an axis of a ballpoint pen [Mitsubishi Pencil Co., Ltd., trade name: Signo UM-100], an inner diameter of 4.0 mm, a length of 113 mm, a polypropylene ink containing tube, and a stainless steel tip (a cemented carbide ball, A water ballpoint pen is manufactured by filling each water-based ink with a refill consisting of a joint connecting the receiving tube and the tip with a ball diameter of 0.7 mm, and an ink follower mainly composed of mineral oil at the rear end of the ink. did.

Using each of the obtained water-based ballpoint pens, dry-up resistance, initial stroke state, and pen body stability were evaluated by the following evaluation methods. In addition, ink aging stability (initial viscosity and viscosity after aging) of each obtained water-based ink composition for writing instruments was evaluated.
These evaluation results are shown in Table 1 below.

[Dry-up resistance evaluation method]
Each obtained water-based ballpoint pen is left to stand downward for 10 days in a constant temperature and humidity chamber of 25 ° C. and 60% RH with the pen tip exposed, and then a circle having a diameter of about 2 cm is continuously drawn on the PPC paper. Thus, 20 round spiral writing was performed, and the dry-up resistance was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: There is no blur and good writing can be made.
Δ: Scratch occurs within 5 laps.
X: Scratch exceeding 5 laps occurred.

[Evaluation method of initial stroke state]
About the example of (circle) evaluation in the said test, the initial drawing state of writing was evaluated based on the following evaluation criteria and FIG.
○: Draw line dama (a state in which a lump was first crushed and a lump was dropped) was not observed and was uniform [see FIG. 1 (b)].
X: Draw lines are observed [see FIG. 1 (c)].

[Evaluation method of pen body stability over time]
Each water-based ballpoint pen obtained was stored for 1 month at 50 ° C. and 65% RH, and then written speed using a writing tester (Minitech writing tester, Mitsubishi pencil) according to JIS standard: S6039-2001. A writing test is performed by spiral writing on a writing test paper compliant with JIS standard P3201 under writing conditions of 4.5 m / min, a writing angle of 60 °, and a writing weight of 1.96 N, and a drawn line at an arbitrary position of 0 to 100 m The density and the drawn line density at an arbitrary position of 300 to 400 m were compared.
○: There is no difference in drawn line density.
Δ: A slight difference is observed in the drawn line density.
X: A clear difference is observed in the drawn line density.

[Evaluation method of ink aging stability]
Each ink composition obtained was filled in a glass bottle and the viscosity value (shear rate 3.83 / s) after storage for 1 month under the conditions of 50 ° C. and 65% RH was compared with the initial value (immediately after production). The smaller the difference in viscosity value between the initial ink viscosity and the time after storage for one month, the better the ink stability.

As is clear from the results of Table 1 above, the aqueous ink compositions for writing instruments of Examples 1 to 9 according to the present invention are more stable in dispersion of resin particles than Comparative Examples 1 to 5 outside the scope of the present invention. It has been found that a water-based ink composition for a writing instrument can be obtained without reducing the dryness, without any improvement in dry-up resistance and drawing quality, and excellent writing performance and no increase in viscosity over time.
Looking at Comparative Examples 1 to 5, Comparative Examples 1 to 4 contain the same resin particles as in Examples 1 to 4, and are aqueous ink compositions for writing instruments that do not contain sulfonic acid-modified polyvinyl alcohol. Comparative Example 5 contains a modified ethylene oxide polyvinyl alcohol copolymer (PVA) described in JP-A-2015-120777 instead of sulfonic acid-modified polyvinyl alcohol. In these cases, the effects of the present invention are included. It was confirmed that it was not possible to demonstrate.

  A water-based ink composition for writing tools suitable for writing tools such as water-based ballpoint pens and marking pens can be obtained.

Claims (3)

  A water-based ink composition for a writing instrument, comprising at least 5% by mass of resin particles having an average particle size of 0.3 μm or more and 0.05 to 10% by mass of sulfonic acid-modified polyvinyl alcohol.   The water-based ink composition for a writing instrument according to claim 1, wherein the resin particles are core-shell type microcapsules.   A writing instrument comprising the aqueous ink composition for a writing instrument according to claim 1 or 2 mounted thereon.

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