JP7573433B2 - Water-based ink composition for writing implements and writing implements using the same - Google Patents

Description

The present invention relates to an aqueous ink composition for writing instruments, and more specifically, to an aqueous ink composition for writing instruments that suppresses the settling of metallic pigments, provides excellent color tone (metallic luster) in handwriting, and suppresses smearing of handwriting, and to a writing instrument using the same.

Conventionally, water-based ink compositions for writing instruments using metal pigments have been produced using metal pigments based on aluminum powder, brass powder, etc., glass flake pigments based on metal oxides or glass, or metal-coated resin film powder based on resin, to produce water-based ballpoint pens with water-based ink compositions for writing instruments that produce good handwriting.

Examples of such prior art include JP-A-8-151547, "Water-based metallic gloss color ink," which uses aluminum powder; JP-A-2001-262014, "Brilliant water-based ink composition," which uses a glass flake pigment having a structure in which flake-like glass is coated with a metal or the like; and Japanese Patent No. 4,346,000, "Brilliant water-based ink composition for ballpoint pens," in which aluminum is vapor-deposited onto a polyethylene terephthalate film powder on which aluminum is vapor-deposited.
In inks using metal powder pigments or pearl pigments as described above, the specific gravity of the pigment is larger than that of the solvent generally used in ink compositions, so the pigment is likely to settle in the ink and the ink has poor stability over time. To solve these problems, proposals have been made such as JP-A-11-12524 "Water-based glossy ink composition" which uses a fatty acid ester of polyoxyethylene diglycerin borate ester as a pigment dispersant, and JP-A-7-118592 "Water-based metallic glossy ink for ballpoint pens" which uses seed polysaccharides guar gum and locust bean gum as a gelling agent.

However, when the glittering water-based ink compositions of Patent Documents 1 to 4 are set to a low-viscosity ink with an ink viscosity of 100 (mPa·s) or less in an environment of 20° C. in order to set the ink viscosity to be suitable for marking pen inks, fountain pen inks, etc., or to increase the ink ejection amount to improve the metallic luster of handwriting, there is a problem that pigment sedimentation and the accompanying hard caking occur due to the high specific gravity of metal powder pigments and pearl pigments. Therefore, as a countermeasure against pigment sedimentation and the accompanying hard caking, it was necessary to insert a metallic stirrer into the ink reservoir tube to redisperse the pigment.
Furthermore, in Patent Document 5, a gelling agent is used to increase the ink viscosity and the ink viscosity is set to 10,000 to 150,000 (mPa·s), which makes it possible to suppress pigment sedimentation. However, the ink viscosity is too high and is not suitable for low-viscosity inks such as inks for marking pens and fountain pens. Furthermore, the ink ejection volume is small, which results in insufficient metallic gloss in handwriting and causes handwriting smearing.
Furthermore, metallic powder pigments have the problem that the metal reacts with water, resulting in the formation of air bubbles and the loss of metallic luster over time.

"Unexamined Japanese Patent Publication No. 8-151547" "JP 2001-262014 A" "Patent No. 4346000" "Unexamined Japanese Patent Publication No. 11-12524" "Unexamined Japanese Patent Publication No. 7-118592"

In view of the above problems, the object of the present invention is to provide a water-based ink composition for writing instruments that suppresses the settling of metal pigments, thereby eliminating the need to place a metal agitator in the ink reservoir, and that also provides excellent color tones in handwriting and suppresses smearing of handwriting, and a writing instrument using the same.

In order to solve the above problems, the present invention provides
"1. An aqueous ink composition for a writing instrument comprising water, a solvent, a metal pigment, and a polyamide resin, characterized in that the ink viscosity of the aqueous ink composition for a writing instrument is 100 (mPa·s) or less at a shear rate of 38.4 (sec ^-1 ) in an environment of 20°C.
2. The water-based ink composition for a writing instrument according to item 1, wherein the acid value of the polyamide resin is 50 (mgKOH/g) or less.
3. The water-based ink composition for a writing instrument according to item 1 or 2, wherein the content of the polyamide resin is 0.01 to 5% by mass based on the total amount of the ink composition.
4. The water-based ink composition for a writing instrument according to any one of items 1 to 3, wherein the solvent has a solubility parameter of 8 to 12.
5. The aqueous ink composition for a writing instrument according to any one of items 1 to 4, wherein the pH value of the aqueous ink composition for a writing instrument is 6 to 10.
6. A writing instrument, characterized in that the water-based ink composition for a writing instrument according to any one of items 1 to 5 is directly packed in an ink reservoir.
Let us assume that.

The present invention stabilizes the dispersibility of metal pigments in an aqueous ink composition for writing instruments, inhibits the settling of metal pigments, and produces handwriting with even shading, excellent color tones, and inhibits smudges in handwriting.

The present invention is characterized in that, even when a metal pigment having a large specific gravity is used under harsh conditions of 100 (mPa·s) or less at a 20°C environment and a shear rate of 38.4 (sec ^-1 ), the inclusion of a polyamide-based resin makes it possible to suppress sedimentation of the metal pigment, produce handwriting with no shading, achieve excellent handwriting color tone (metallic luster), and suppress blurring of the handwriting.

(Polyamide resin)
The polyamide resin used in the present invention is a resin having an amide bond, and by being contained in the aqueous ink composition for writing instruments, even if a metal pigment with a large specific gravity is used under harsh conditions of a 20°C environment, a shear rate of 38.4 (sec ^-1 ), and 100 (mPa.s) or less, the metal pigment dispersibility is stabilized, the metal pigment sedimentation is suppressed, and the handwriting is uniform and has good color tone (metallic luster). This is because the polyamide resin forms a three-dimensional network structure through interaction with water and a solvent, and the metal pigment is caught in the three-dimensional network structure formed by the polyamide resin, thereby suppressing the sedimentation of the metal pigment, stabilizing the metal pigment dispersibility, and suppressing the sedimentation of the metal pigment. Furthermore, the polyamide resin can be suitably used because it can improve the orientation of the metal pigment, resulting in uniform and good color tone of the handwriting. In particular, when a metal pigment containing metal powder is used, it is more effective because the orientation of the metal powder is increased, which tends to affect the metallic luster of the handwriting.

Examples of the polyamide-based resin include polyamide and modified polyamide. The acid value of the polyamide-based resin is preferably 50 (mgKOH/g) or less. This is because the polyamide-based resin is likely to form a stable structure that allows metal pigments to be easily caught in the three-dimensional network structure, which inhibits the sedimentation of the metal pigment and improves the color tone (metallic gloss) of the handwriting. In consideration of the inhibition of the sedimentation of the metal pigment, the acid value is preferably 40 (mgKOH/g) or less, and more preferably, the acid value is 30 (mgKOH/g) or less, and more preferably, the acid value is 10 to 30 (mgKOH/g).
The acid value of the polyamide resin can be determined by a known method, for example, by dissolving the resin in a 1:1 solution of xylene and dimethylformamide, titrating it with a 0.1 mol/L potassium hydroxide-ethanol solution by potentiometric titration, and calculating the acid value from the titration amount of the potassium hydroxide solution up to the end point. In detail, this can be done based on "JIS-K2501-2003 Petroleum products and lubricants - Neutralization number test method".

Polyamide-based resins are preferably made into polyamide salts because they are more likely to form a stable structure in the ink when neutralized with a neutralizing agent, and from a more consideration, polyamide amine salts are more preferable. Specific examples of polyamide-based resins include Disparlon AQ-600, Disparlon AQ-607, Disparlon AQ-610, Disparlon AQ-630, and Disparlon AQ-633E (all manufactured by Kusumoto Chemicals Co., Ltd.).

If the content of polyamide resin is less than 0.01% by mass relative to the total amount of the ink composition, the desired sedimentation of the metal pigment is inhibited and the color tone of the handwriting is not obtained, and if it exceeds 5% by mass, the ink ejection properties tend to deteriorate and the color tone of the handwriting tends to deteriorate, so 0.01 to 5% by mass is preferable, and from further consideration, 0.1 to 3% by mass is even more preferable, and from further consideration, 0.3 to 3% by mass is even more preferable, and 0.5 to 2% by mass is even more preferable.

(Metal Pigments)
In the present invention, a metal pigment is used as a colorant. Examples of the metal pigment include metal powders of aluminum, brass, stainless steel, bronze, titanium oxide, iron oxide, aluminum oxide, zinc oxide, and the like, metal powders of alloys, and pigments containing at least these metals. Specifically, metal powders of aluminum powder, brass powder, stainless steel powder, bronze powder, titanium oxide, and the like may be used as metal pigments as they are, or metal pigments in which a colorant is adsorbed onto these metal pigments may be used. In addition, the metal powder pigments such as aluminum powder may be processed and dispersed in advance with a surfactant, resin, solvent, and the like to form a paste-like pigment dispersion or a liquid metal pigment dispersion, or the metal powder pigments such as aluminum powder may be processed or dispersed with wax, surfactant, resin, and the like to form a solid metal pigment that does not contain a solvent.
Examples of metal pigments include aluminum paste pigments, aluminum powder pigments, titanium oxide pigments, metal vapor deposition powder pigments (pigments in which a metal thin film is coated with a resin), glass flake pigments, and pearl pigments.

The metallic pigment is preferably a metallic pigment coated with a coating material such as silica, molybdenum, or a phosphoric acid compound such as a phosphate, a phosphonic acid, or a phosphoric acid ester, etc. This is because by using a metallic pigment coated with a coating material such as silica, the three-dimensional network structure formed by the polyamide resin and the metallic pigment are stably entangled in the network structure, which makes it easier to suppress sedimentation of the metallic pigment.
Furthermore, metal pigments coated with a coating material such as silica are preferred because they have low reactivity with water and solvents and high stability, and therefore are less susceptible to bubble generation and deterioration of metallic luster over time, and among the above coatings, silica coating and phosphate compound coating are preferred because of their low reactivity with water and solvents and high stability. From further consideration, phosphate compound coating is more preferred.

In addition, regarding the amount of coating of the metal pigment with the silica or the like, it is preferable that the total mass of the coating material such as the silica or the phosphate compound (coating material/metal powder) is 0.001 to 0.5 times the total mass of the metal powder in the total amount of the ink composition. This is because if it is less than 0.001 times, it will be adsorbed to the entire surface of the metal powder, making it difficult to coat, and it will be difficult to obtain the above-mentioned effects such as suppressing the sedimentation of the metal pigment, and if it exceeds 0.5 times, the coating material will tend to be in excess of the metal powder, and the excess will tend to precipitate or generate metal salt precipitates. From further consideration, it is preferable that the content ratio is 0.01 to 0.3 times by mass, and even more preferably 0.01 to 0.1 times.

Among the phosphoric acid compound coatings, phosphonic acid coatings are preferred, and alkylphosphonic acid coatings are even more preferred. This is a phosphonic acid compound having an alkyl group, and both the phosphonic acid group and the alkyl group of the alkylphosphonic acid are easily adsorbed to the metal powder, so the adsorption is stable for a long period of time, resulting in better long-term stability over time than conventional metal pigments, and the above-mentioned effects are likely to be sustained for a long period of time. In particular, taking into consideration the dispersibility of the metal pigment, it is preferable to use a metal pigment in which the metal powder has been surface-treated with an alkylphosphonic acid, and more preferably, to use a metal pigment in which the metal powder has been surface-treated in advance with an alkylphosphonic acid.

The alkylphosphonic acid improves the adsorption to metal powder, suppresses the elution of metal ions, improves pigment sedimentation suppression (dispersibility of metal pigments), and improves ink stability over time by suppressing metal salt precipitation. In consideration of the metallic luster of the handwriting, the alkyl group preferably has 1 to 20 carbon atoms. This is because the longer the alkyl group, the wider the adsorption area and the easier it is to adsorb to metal powder. From further consideration, the alkyl group preferably has 1 to 12 carbon atoms, and from further consideration, the alkyl group has 6 to 10 carbon atoms, and most preferably the alkyl group has 8 carbon atoms. Furthermore, the alkyl group is not limited to a straight-chain structure or a branched-chain structure, but an alkyl group with a straight-chain structure is preferable because it has a wider adsorption area and is easier to adsorb to metal powder, and is more preferable because it tends to improve metal pigment sedimentation suppression (dispersibility of metal pigments).

In addition, if you want to suppress the settling of metal pigments (metal pigment dispersibility) and improve the color tone of the handwriting (metallic gloss), it is preferable to use aluminum paste pigments or metal vapor deposition powder pigments, and if you take this into consideration, it is more preferable to use aluminum paste pigments.

Among metal pigments, those using aluminum powder are preferred because the metallic luster of the handwriting is good, the specific gravity is relatively low among metals, and the metal powder is less likely to settle. Regarding the shape of the metal powder, if it is shaped like a scale, a corner, or a plate, it is likely to be caught in the three-dimensional mesh structure formed by the polyamide resin and the fatty acid amide, suppressing the settlement of the metal pigment, and further, such a shape is preferred because it makes it easier for light to be diffused and the metallic luster becomes clearer. There are also leafing and non-leafing types, and the leafing type is more preferred because the metal powder floats and is arranged on the surface of the ink film, making it easier to achieve good metallic luster of the handwriting.

The size of the metal pigment is preferably 1 to 50 μm in average particle diameter, because the above range makes it easy to be caught in the three-dimensional network structure formed by the polyamide resin, suppresses the sedimentation of the metal pigment, and makes it easy to obtain a good color tone (metallic luster), and furthermore, makes it difficult for the metal pigment in the ink to clog the pen tip. In particular, in consideration of making it easy to be caught in the three-dimensional network structure and suppressing the sedimentation of the metal pigment, the average particle diameter is preferably 3 to 20 μm, and most preferably 5 to 15 μm. Here, the average particle diameter can be determined by the laser diffraction method, specifically, the particle diameter (D50) at 50% cumulative volume of the particle size distribution measured based on values calibrated using standard samples and other measurement methods using a laser diffraction type particle size distribution measuring instrument (product name "MicrotracHRA9320-X100", Nikkiso Co., Ltd.).
Since the metal powder exerts the above-mentioned effects in a dispersed state in the ink composition, it is preferable to determine the particle size in the dispersed state.

In addition, in the total amount of ink composition, the mass ratio of polyamide resin to the total mass of metallic pigment (polyamide resin/metallic pigment) is preferably 0.1 to 3 times. This is because if it is less than 0.1 times, it is difficult to obtain the above-mentioned effects such as suppressing metallic pigment sedimentation and good color tone of handwriting, and if it exceeds 3 times, the ink viscosity is too high, the ink ejection amount is likely to be small, and the color tone of handwriting is likely to be affected. From further consideration, it is preferable that the content ratio is 0.3 to 2 times by mass, and even more preferably 0.5 to 1.5 times.

Specific examples of metal pigments include aluminum paste pigments such as WXM0630, WB0230, 400SW, and FM4010WG (all manufactured by Toyo Aluminium K.K.); colored aluminum pigments such as F503RG, F503BG, F500SI, F500RE, F500RE, and F500BL (all manufactured by Toyo Aluminium K.K.); the Chromal series; and solid RotosafeAqua 250 042, 250 022, and 260 003 (all manufactured by ECKART K.K.).
Examples of aluminum powder include AA12, AA8, No. 900, and No. 18000 (all manufactured by Fukuda Metal Foil and Powder Co., Ltd.).
Metal-deposited powder pigments include LG Silver #500, #325, and #200 (all manufactured by Oike Kogyo Co., Ltd.), which are made by vacuum-depositing aluminum on synthetic resin, protecting the metal layer with resin, and pulverizing it into flakes.Furthermore, LG R. Gold #500, LG B. Gold #500, LG R. Gold #325, LG B. Gold #325, LG Red #325, LG Blue #325, LG Green #325, LG Violet #325, LG Black #325, LG Copper #325, LG R. Gold #200, LG B. Gold #200, Red #200, Blue #200, Green #200, Violet #200, Black #200, and Copper #200 (all manufactured by Oike Kogyo Co., Ltd.).
Examples of glass flake pigments include Metashine REFSX-2015PS, REFSX-2025PS, REFSX-2040PS, RCFSX-5030NS, REFSX-5030NB, REFSX-5030PS, REFSX-2015PS, and REFSX-5090GG (all manufactured by Nippon Sheet Glass Co., Ltd.), which are glass flakes coated with metal by electroless plating.
Examples of pearl pigments include Iriodin 120 Luster Satin, Iriodin 123 Bright Luster Satin, Iriodin 201 Rutile Fine Gold, Iriodin 211 Rutile Fine Red, Iriodin 221 Rutile Fine Blue, Iriodin 223 Rutile Fine Lilac, Iriodin 231 Rutile Fine Green, Iriodin 302 Gold Satin, Iriodin 323 Royal Gold Satin, Iriodin 520 Bronze Satin, Iriodin 522 Red Brown Satin, and Iriodin 524 Red Satin (all manufactured by Merck Japan Ltd.).
Examples of titanium oxide pigments include Titone SR-1, Titone R-650, Titone R-3L, Titone A-110, Titone A-150, Titone R-5N, Titone R-7E (all manufactured by Sakai Chemical Industry Co., Ltd.), Typeake R-580, Typeake R-550, Typeake R-780, Typeake R-780-2, Typeake R-930, Typeake A-100, Typeake A-220, Typeake CR-58 (all manufactured by Ishihara Sangyo Kaisha, Ltd.), Kronos KR-310, Typeake KR-380, Typeake KR-480, Typeake KA-10, Typeake KA-20, Typeake KA-30 (all manufactured by Titanium Industries Co., Ltd.), Typeake R-900, Typeake R-931, Typeake R-960, Typeake R-960VHG (all manufactured by DuPont Japan Limited). In addition, it is preferable to use a commercially available aqueous dispersion of titanium oxide such as LIOFAST WHITE H201, EM WHITE H, EMWHITE FX9048 (all manufactured by Toyo Ink Co., Ltd.), Pollux White PC-CR (manufactured by Sumitomo Color Co., Ltd.), FUJISP WHITE 11, 1011, 1036, and 1051 (all manufactured by Fuji Color Co., Ltd.), since this allows the dispersion step to be omitted in terms of production and allows ink to be easily produced.

If the content of the metallic pigment is less than 1% by mass of the total ink composition, the desired metallic luster of the handwriting cannot be obtained, and if it is 10% by mass or more, the pigment may settle and the ink may be easily affected in terms of its stability over time. Therefore, the content is preferably 1 to 10% by mass, more preferably 1 to 7% by mass, and most preferably 1 to 5% by mass.

(solvent)
In the present invention, it is preferable to use a solvent in consideration of the solubility of the ink components, dispersion stability, prevention of water evaporation and drying, etc.
When using a polyamide-based resin as in the present invention, taking into consideration the effect of inhibiting sedimentation of the metal pigment by stably facilitating the formation of a three-dimensional network structure in the ink, it is preferable to use a solvent with a solubility parameter (SP value) of 8 to 12, and from this perspective it is more preferable to use a solvent with a solubility parameter (SP value) of 8.5 to 10.5.
Specifically, propylene glycol monomethyl ether (SP value 10.2), propylene glycol monopropyl ether (SP value 9.4), propylene glycol monobutyl ether (SP value 9.0), dipropylene glycol monomethyl ether (SP value 9.1), triethylene glycol monomethyl ether (SP value 11.2), tripropylene glycol monomethyl ether (SP value 9.1), ethylene glycol-2-ethylhexyl ether (SP value 9.0), diethylene glycol-2-ethylhexyl ether (SP value 9.2), ethylene glycol isopropyl ether (SP value 9.2), diethylene glycol monobutyl ether (SP value 9.5), 2-ethylhexanol (SP value 9.6), P value 9.5), 3-methoxy-3-methylbutanol (SP value 9.3), hexylene glycol (SP value 10.5), diethylene glycol monomethyl ether (SP value 10.7), triethylene glycol monomethyl ether (SP value 11.2), phenyl glycol (SP value 11.5), tetraethylene glycol dimethyl ether (SP value 9.4), diethylene glycol ethyl methyl ether (SP value 8.9), triethylene glycol monobutyl methyl ether (SP value 8.9), etc., and in consideration of stability with polyamide resins, it is preferable to use propylene glycol monomethyl ether (SP value 10.2) and propylene glycol monobutyl ether (SP value 9.0).

As the solvent, it is preferable to use the following water-soluble solvents in consideration of preventing water evaporation and drying, and metal pigment dispersion stability. Specifically, polyhydric alcohol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polyethylene glycol, and glycerin, and alcohol-based solvents such as methanol, ethanol, 1-propanol, 2-propanol, isopropanol, isobutanol, t-butanol, propargyl alcohol, allyl alcohol, 3-methyl-1-butyn-3-ol, ethylene glycol monomethyl ether acetate, and other higher alcohols are listed. Among them, polyhydric alcohols are preferable as dispersion aids for metal pigments because they are easy to suppress the precipitation of metal pigments, and when the pen tip dries, the ink contains hard metal powders such as aluminum powder, stainless steel powder, and titanium oxide powder, which easily affect the writing performance during drying up, and therefore polyhydric alcohols are easy to improve. From a more specific perspective, it is preferable to contain at least a polyhydric alcohol having a divalent or trivalent hydroxyl group. A polyhydric alcohol solvent is a compound in which two or more hydroxyl groups are bonded to different carbon atoms of an aliphatic or alicyclic compound. These may be used alone or in combination of two or more types.

The content of the solvent is preferably 1 to 40% by mass of the total ink composition, taking into consideration the solubility of the polyamide resin and metal pigment, drying up properties, bleeding, etc., and more preferably 3 to 30% by mass, and more preferably 5 to 25% by mass.

(water)
The water is not particularly limited, and for example, tap water, ion-exchanged water, ultrafiltered water, distilled water, or the like can be used.

The pH value of the aqueous ink composition for writing instruments of the present invention is preferably 6.0 to 10.0, taking into consideration the dispersibility of metal pigments by polyamide resins. This is because if the pH value approaches the acidic side of less than 6, or approaches the strongly alkaline side of more than 10, it will affect the dispersibility of metal pigments and the metal pigments will be easily corroded, which will affect the metallic luster. Taking this into consideration, a pH value of 7.0 to 9.0 is more preferable. In particular, when aluminum powder is used, a pH value of 7.0 to 9.0 is more preferable, taking into consideration the corrosion of aluminum. The pH value is measured at 20°C using a pH meter HM-30R manufactured by DKK-TOA Corporation.

Examples of pH adjusters include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, N-methylethanolamine, N-methyldiethanolamine, and diisopropanolamine; ammonia; alkaline inorganic salts such as sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, and potassium hydrogen phosphate; and organic acids such as lactic acid, acetic acid, and citric acid. Among these, it is preferable to use alkanolamines, which are more weakly basic, in consideration of the stability of the ink over time.

In addition, taking into consideration the ink stability over time, the content of the pH adjuster is preferably 0.1 to 10 mass % of the total ink composition, and more preferably 0.3 to 5 mass %.

When using a metallic pigment as in the present invention, it is preferable for the composition to contain a chelating agent, since this makes it easier to suppress the precipitation of metal salts and the like by sequestering the metal present in the aqueous ink composition for writing instruments.
Furthermore, the water-based ink composition for writing instruments may be contained in a glass ink reservoir such as a glass bottle. Glass bottles are easy to mold, inexpensive and readily available, and can easily provide a desired strength. However, when inexpensive and versatile soda-lime glass is used, there is a high possibility that an alkali component in the glass will elute into the water-based ink composition for writing instruments if the ink composition is stored therein for a long period of time, and this eluted alkali component may react with a component of the water-based ink composition for writing instruments to form a precipitate.
For this reason, it is effective to further use a chelating agent in the aqueous ink composition for a writing instrument of the present invention, and even when the composition is contained in a glass ink reservoir, the chelating agent can supplement the eluted alkaline components and prevent the alkaline components from reacting with the components in the aqueous ink composition for a writing instrument to produce water-insoluble precipitates, thereby preventing the ink flow path from being blocked by the produced precipitates, causing handwriting to fade or making it impossible to write.

Examples of the chelating agent include aminocarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), glycol ether diaminetetraacetic acid (GEDTA), nitrilotriacetic acid (NTA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), and alkali metal salts, ammonium salts, or amine salts thereof.
Considering that the alkaline components can be sufficiently supplemented and that the physical properties of the aqueous ink composition for writing instruments before and after the incorporation of the chelating agent are not likely to be significantly affected, it is preferable to use aminocarboxylic acids among the above chelating agents, and in particular, it is preferable to use ethylenediaminetetraacetic acid (EDTA) and its salts.

The content of the chelating agent is preferably 0.01 to 1% by mass based on the total amount of the ink composition. If it is 1% by mass or less, it will not adversely affect the performance and physical properties of the ink composition, such as discoloration of the ink. If it is 0.01% by mass or more, it can supplement the alkaline components eluted from a glass ink container such as a glass bottle, and suppress the occurrence of precipitation.
Furthermore, the addition of an appropriate amount of the chelating agent tends to further improve the resistance to leakage from the pen tip. Therefore, in consideration of suppressing the occurrence of precipitates and further improving the resistance to leakage from the pen tip, the amount is more preferably 0.01 to 0.5% by mass.

When a metallic pigment is used as in the present invention, it is preferable to contain a phosphate ester surfactant. This is because, when a metallic pigment is used, the ink composition contains a phosphate ester surfactant, which sequesters the metal present in the ink composition, making it easier to suppress precipitation of metal salts and the like.
Furthermore, when used in a ballpoint pen, the phosphate group adsorbs to metal, thereby improving lubricity, suppressing wear of the ball seat, and tending to improve the writing feel. Furthermore, taking lubricity into consideration, it is preferable to use a phosphate ester surfactant, and it is preferable to use a phosphate ester surfactant having an alkyl group.
Examples of the types of phosphate ester surfactants having an alkyl group include styrenated phenols, nonylphenols, lauryl alcohols, tridecyl alcohols, octylphenols, octyl alcohols, etc. Among these, it is preferable to use a phosphate ester surfactant that does not have a phenyl skeleton, since the surfactants having a phenyl skeleton tend to affect lubricity due to steric hindrance and, further, tend to affect the ink stability over time due to compatibility with the metal powder.

Examples of phosphate ester surfactants include polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether phosphate monoesters, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether phosphate diesters, polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether phosphate triesters, alkyl phosphate esters, alkyl ether phosphate esters, or derivatives thereof. These phosphate ester surfactants may be used alone or in combination of two or more.

The content of the phosphate ester surfactant is preferably 0.1 to 5% by mass based on the total amount of the ink composition. This is because if it exceeds 5% by mass, the ink stability over time tends to be affected, so from further consideration, 0.1 to 3% by mass is more preferable.

When using metal pigments as in the present invention, the ink contains hard metal powders such as aluminum powder, stainless steel powder, and titanium oxide powder, which can easily affect the writing performance when the ink dries up, so it is preferable to use a moisturizer.Specific examples include urea, sorbitol, and N,N,N-trialkylamino acids such as trimethylglycine, triethylglycine, and tripropylglycine, but urea is preferable because it is easier to obtain a moisture absorption effect.In addition, if the ink is left for a long period of time, the pH value tends to shift to the acidic side due to carbon dioxide in the air, but by containing urea as in the present invention, the pH value is prevented from becoming less than 7 even over a long period of time, so it can be used more effectively when setting the pH value.

In the present invention, a colorant other than the metal pigment may be used in combination. Inorganic, organic, and processed pigments may be used, and specific examples include carbon black, aniline black, ultramarine, yellow lead, iron oxide, phthalocyanine, azo, quinacridone, quinophthalone, threne, triphenylmethane, perinone, perylene, dioxazine, pearl pigment, fluorescent pigment, and phosphorescent pigment. In addition, a microencapsulated pigment may be used in which a colored body formed by dispersing a pigment in a medium is encapsulated or solid-dissolved in a shell made of a resin wall-forming material by a known microencapsulation method or the like as a colored resin particle body. A dye may also be used in combination as a colorant. As for the dye, direct dyes, acid dyes, basic dyes, metal-containing dyes, and various salt-forming dyes can be used. Furthermore, colored resin particles in which a pigment is covered with a transparent or semitransparent resin, and colored resin particles or colorless resin particles colored with a pigment or dye can also be used. These pigments and dyes may be used alone or in combination of two or more. The content of the metallic pigment is preferably 0.01% by mass to 20% by mass based on the total amount of the ink composition.
In addition, when a metal pigment is used as in the present invention, it is preferable to contain a black colorant, since the inclusion of a black colorant increases the visibility of handwriting on white paper, which makes it easier to improve the color tone. The content of the black colorant is preferably 0.001 to 1 mass %, and more preferably 0.01 to 0.5 mass %, based on the total amount of the ink composition, taking the color tone into consideration.

Preservatives may also be used, and examples of rust inhibitors include benzotriazole and its derivatives, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, sodium thiosulfate, saponin, and dialkylthiourea.

Preservatives may also be used, and examples of preservatives include phenol, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, sodium 2-pyridinethiol-1-oxide, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and 2-n-octyl-4-isothiazolin-3-one.

A pigment dispersant may be used to improve the dispersibility of the metal pigment and suppress metal precipitation or aggregation. Examples of pigment dispersants include acidic resins, basic resins, nonionic surfactants, and anionic surfactants, but considering the long-term pigment dispersion stability, it is preferable to use acidic resins. Examples of acidic resins include acidic resins having a carboxyl group, a phenyl group, or a sulfonic acid group, and specific examples include acrylic resins, styrene-acrylic resins, styrene-maleic acid resins, phenolic resins, and polyvinyl-sulfonic acid resins. Among the above acidic resins, acidic resins having a carboxyl group are preferred.

If the content of the pigment dispersant is less than 0.1% by mass of the total ink composition, it is difficult to obtain the desired pigment dispersion effect, and if it is 5.0% by mass or more, the ink stability over time is likely to deteriorate, so the content is preferably 0.1 to 5.0% by mass. More preferably, it is 1.0 to 4.0% by mass.

When using metal pigments as in the present invention, the shape of the metal powder in the metal pigment may be scaly, angular, or plate-like, and since air bubbles trapped during ink production tend to be difficult to remove, it is preferable to use an air bubble absorber. Examples of air bubble absorbers include hydroxylamines, ascorbic acids, erythorbic acids, and polyphenols. These air bubble absorbers are compounds that exhibit reducing properties, and absorb oxygen in the ink to achieve air bubble absorption. Examples of hydroxylamines, ascorbic acids, erythorbic acids, and polyphenols include hydroxylamines, hydroxylamine derivatives, polyphenols, polyphenol derivatives, ascorbic acid, ascorbic acid derivatives, erythorbic acid, erythorbic acid derivatives, and salts thereof.

As for the air bubble absorbent, some ascorbic acids are highly acidic (pH value = 2) and react with the components in the ink, affecting the ink stability over time and likely affecting the dispersibility of the metal powder used in the present invention. Furthermore, ascorbic acids and polyphenols tend to affect the color tone, it is preferable to use hydroxylamines and erythorbic acids. In addition, hydroxylamines may produce an amine odor, so it is preferable to use erythorbic acids.

The content of the bubble absorber is preferably 0.01 to 5% by mass of the total ink composition. This is because if it is less than 0.01% by mass, it is difficult to sufficiently absorb the oxygen in the ink, and if it exceeds 5% by mass, it is likely to affect the ink stability over time. From further consideration, 0.1 to 3% by mass is preferable, and 0.1 to 1% by mass is most preferable.

When making an ink composition for a ballpoint pen, a shear thinning agent may be used in consideration of improving the dispersibility of the metal pigment. Examples of shear thinning agents include polyacrylic acid, xanthan gum, welan gum, succinoglycan, guar gum, locust bean gum, λ-carrageenan, cellulose derivatives, oxidized cellulose, diutan gum, etc., and the inclusion of these agents forms a three-dimensional network structure in the ink, making it easier to stabilize the dispersion of the metal pigment. These shear thinning agents may be used alone or in combination of two or more.

The ink viscosity is preferably 1000 (mPa·s) or less at a shear rate of 1.92 (sec ⁻¹ ) (at rest) in a 20° C. environment. This is because maintaining a large ink discharge volume improves the color tone (metallic glossiness) of handwriting and also prevents good writing properties, color tone (metallic glossiness) of handwriting, and handwriting smearing, so 350 (mPa·s) or less is preferable, and from a more specific perspective, 300 (mPa·s) or less is preferable. Furthermore, from a consideration of preventing the settling of colorants (pigments), resin particles, etc., 50 (mPa·s) or more is preferable, 100 (mPa·s) or more is preferable, and 150 (mPa·s) or more is even more preferable.
The ink viscosity is set to 100 (mPa·s) or less at a shear rate of 38.4 (sec ^-1 ) in a 20°C environment, but since the ink discharge amount is kept large, the color tone (metallic glossiness) of the handwriting can be improved and handwriting smearing can be suppressed, so 70 (mPa·s) or less is preferable, and more preferably 60 (mPa·s) or less is preferable, and from the viewpoint of suppressing handwriting smearing and improving writing properties and the color tone (metallic glossiness) of the handwriting, 30 (mPa·s) or less is preferable. Also, from the viewpoint of suppressing the sedimentation of the metal pigment, 5 (mPa·s) or more is preferable, 10 (mPa·s) or more is preferable, and furthermore 15 (mPa·s) or more is more preferable. As described above, when the ink viscosity is set to a low viscosity, the metal pigment is likely to sediment, so it is preferable to use a polyamide resin as in the present invention, since a remarkable effect is easily obtained.
Furthermore, in order to suppress smearing of handwriting and to facilitate good writing properties, the ink viscosity is preferably 20 (mPa·s) or less, and more preferably 10 (mPa·s) or less, in an environment of 20°C and at a shear rate of 384 (sec ^-1 ) (during writing).
Furthermore, in order to maintain the ink ejection volume, improve the color tone (metallic luster) of the handwriting, and suppress blurring of the handwriting while also suppressing sedimentation of the metal pigment, it is preferable that the viscosity gradient during flow of the ink composition be at least a certain level, in other words, that the viscosity ratio of the ink composition at high shear and low shear be at least a certain level.
Therefore, the viscosity ratio of the ink composition under high shear (when writing) to low shear (when at rest) (viscosity at a shear rate of 1.92 sec ^-1 /viscosity at a shear rate of 384 sec ^-1 ) is preferably 10 or more, more preferably 20 or more, and even more preferably 25 or more, and the viscosity ratio (viscosity at a shear rate of 1.92 sec ^-1 /viscosity at a shear rate of 384 sec ^-1 ) is preferably 50 or less, more preferably 40 or less.

(Writing implements)
The aqueous ink composition for writing instruments of the present invention can be used in writing instruments such as marking pens and ballpoint pens with pen cores such as fiber tips, felt tips, and plastic tips, or ballpoint pen tips, and fountain pens with metal tips. Even if the ink viscosity is low as in the present invention, sedimentation of metal pigments can be suppressed, so that the aqueous ink composition for writing instruments of the present invention is effective for use as an ink composition for marking pens or fountain pens, and is particularly effective for use as an ink composition for fountain pens.

The ink composition for writing instruments of the present invention can also be used in those that are directly filled with the ink composition, or those that have an ink reservoir that can be filled with the ink composition.

The aqueous ink composition for writing instruments of the present invention can be suitably used in writing instruments equipped with an ink reservoir (ink cartridge) that can be freely attached and detached to the main body of the writing instrument, or an ink reservoir (ink inhaler) that has the function of directly sucking ink into the ink reservoir from an ink container such as an ink bottle.
Since the ink reservoir as described above may be provided inside the barrel of a writing instrument, the inner diameter of the ink reservoir is likely to be restricted. Therefore, the ink composition is unlikely to flow inside the ink reservoir, and special consideration must be given to the ink mobility inside the ink reservoir. The ink composition of the present invention can suppress the decrease in wettability of the ink reservoir when the ink moves, and has excellent ink mobility inside the ink reservoir, so it can be suitably used in a writing instrument equipped with the ink reservoir as described above.
In particular, when the material of the ink reservoir is made of a resin material, the ink reservoir tends to have poor wettability with the ink composition, and it is necessary to take into consideration the ink mobility within the ink reservoir in particular. The ink composition of the present invention can suppress the decrease in wettability when the ink moves with respect to the resin material, and therefore can be suitably used in a writing instrument having a resin ink reservoir.

In addition, it is desirable for the ink reservoir to be made of a semi-transparent or transparent material that allows the remaining amount of ink to be seen. Examples of such materials include thermoplastic resins such as polyethylene, polypropylene, polymethylpentene, polyethylene terephthalate, polycyclohexane terephthalate, polycarbonate, and nylon.
In addition, since the ink reservoir stores the ink composition for a long period of time, it is preferable to use a crystalline resin that has excellent chemical resistance, and therefore it is more preferable to use a crystalline olefin resin such as polyethylene, polypropylene, or polymethylpentene.

In addition, writing instruments that can use the aqueous ink composition for writing instruments of the present invention may be cap-type instruments with a cap that covers the writing tip, or may be retractable types that allow the writing tip to be stored inside the barrel, such as knock-type, rotating-type, and sliding-type instruments.

There is no particular limitation on the ink supply mechanism of the writing instrument in which the aqueous ink composition for writing instruments of the present invention can be used, and examples include (mechanism 1) a mechanism that has an ink guide core made of a fiber bundle or the like as an ink flow regulator and supplies the ink composition to the pen tip through this, (mechanism 2) a mechanism that has a comb-shaped ink retaining member as an ink flow regulator and supplies the ink composition to the pen tip, (mechanism 3) a mechanism that has an ink flow regulator using a valve mechanism and supplies the ink composition to the writing tip, and (mechanism 4) a mechanism that supplies the ink composition directly to the pen tip without an ink flow regulator.

In the case of ballpoint pens, the ball material is not particularly limited, but examples include cemented carbide balls whose main component is tungsten carbide, silicon carbide, alumina, zirconia, silicon nitride, etc. Considering the lack of metal corrosion and the writing feel, it is preferable to use a silicon carbide ball. The size of the ball is determined by the purpose of the writing instrument and the width of the line required when writing, but is generally selected from the range of 0.1 to 2.0 mm.

The amount of movement of the ball in the ballpoint pen tip along the vertical axis is preferably 15 to 50 μm, because a large amount of ink can be ejected to improve the color tone (metallic luster) of the handwriting. If it is less than 15 μm, the amount of ink consumed is likely to be small and the metallic luster of the handwriting is likely to be poor, and if it exceeds 50 μm, the handwriting drying speed and ink leakage prevention are likely to be poor. If the color tone (metallic luster) of the handwriting is taken into consideration, it is preferable to set it to 30 to 50 μm.

<Water-based ink products>
The water-based ink product according to the present invention may contain the water-based ink composition for a writing instrument according to the present invention in an ink reservoir made of glass.
In particular, when the water-based ink composition for a writing instrument contains a chelating agent, even when the composition is contained in a glass ink reservoir, the chelating agent supplements the eluted alkaline components, prevents the alkaline components from reacting with the components in the water-based ink composition for a writing instrument to form water-insoluble precipitates, and is effective and preferred because it is easy to prevent the ink flow path from being blocked by the precipitates, causing handwriting to fade or making writing impossible. In particular, when the water-based ink composition for a writing instrument is combined with a glass ink reservoir using soda-lime glass, a particularly high effect is easily exhibited, which is preferred.

The glass ink container that contains the ink composition for writing instruments can be made of a single glass product, such as a glass bottle, or the ink container can be coated (decorated) with resin, wood, lacquer, or other materials.

(Method of producing water-based ink composition)
The water-based ink composition for writing instruments of the present invention can be produced by any conventionally known method. Specifically, the ink components are mixed in the required amounts and mixed with various stirrers such as a propeller stirrer, a homodisper, or a homomixer, or various dispersers such as a bead mill, to produce the composition.

The present invention will now be described with reference to examples.
(Water-based ink composition for writing instruments)
Example 1
Metal pigment (containing 65% aluminum powder, 3% octylphosphonic acid, leafing type, mass ratio of alkylphosphonic acid to mass of metal powder: 0.05 times (alkylphosphonic acid metal powder)) 2.0 parts by mass Dye (Direct Black 154) 0.01 parts by mass Water 80.5 parts by mass Polyhydric alcohol (diethylene glycol) 7.0 parts by mass Polyamide resin (containing 22.5% active ingredient, propylene glycol monomethyl ether (SP value 10.2), acid value: 24 mg KOH/g), amine neutralized) 8.0 parts by mass pH adjuster (triethanolamine) 1.0 parts by mass Aminocarboxylic acid (ethylenediaminetetraacetic acid) 0.5 parts by mass Phosphate ester surfactant 1.0 parts by mass

First, for the metal pigment, metal powder was surface-treated with alkylphosphonic acid (octylphosphonic acid), and imidazoline and propylene glycol monomethyl ether (SP value 10.2) were mixed to prepare a paste-like metal pigment.
Furthermore, a base ink was prepared by heating and stirring a dye, water, a polyhydric alcohol, a polyamide resin, a pH adjuster, an aminocarboxylic acid, and a phosphate ester surfactant, and the base ink was mixed with the metallic pigment prepared earlier, and the mixture was heated and stirred to prepare an aqueous ink composition for a writing instrument.

The ink viscosities of Examples 1 to 3, Examples 12 to 14, and Comparative Example 1 were measured using a TA Instruments AR-G2 rheometer (cone plate 40 mm, angle 2°) at a shear rate of 1.92 ^sec (rotation speed 0.5 rpm), a shear rate of 38.4 ^sec (rotation speed 10 rpm), and a shear rate of 384 ^sec (rotation speed 100 rpm) in an environment of 20°C.
The ink viscosity was measured at a shear rate of 1.92 sec ^-1 (rotation speed of 0.5 rpm) in an environment of 20°C, and the results were as follows: Example 1: 577 (mPa·s), Example 2: 372 (mPa·s), Example 3: 162 (mPa·s), Example 12: 100 (mPa·s), Example 13: 180 (mPa·s), Example 14: 267 (mPa·s), and Comparative Example 1: 3.2 (mPa·s).
Furthermore, when the ink viscosity was measured at a shear rate of 38.4 sec ^-1 (rotation speed of 10 rpm) in an environment of 20°C, the following were obtained: Example 1: 57 (mPa·s), Example 2: 38 (mPa·s), Example 3: 16 (mPa·s), Example 12: 9.7 (mPa·s), Example 13: 17 (mPa·s), Example 14: 26 (mPa·s), and Comparative Example 1: 3.0 (mPa·s).
Furthermore, when the ink viscosity was measured at a shear rate of 384 sec ^-1 (rotation speed of 100 rpm) in an environment of 20°C, the following were obtained: Example 1: 15 (mPa·s), Example 2: 11 (mPa·s), Example 3: 10 (mPa·s), Example 12: 5.1 (mPa·s), Example 13: 6.4 (mPa·s), Example 14: 7.8 (mPa·s), and Comparative Example 1: 2.4 (mPa·s).
The viscosity ratios of the ink compositions (viscosity at a shear rate of 1.92 sec ^-1 /viscosity at a shear rate of 384 sec ^-1 ) were as follows: Example 1: 38.5, Example 2: 33.8, Example 3: 16.2, Example 12: 19.8, Example 13: 26.9, Example 14: 34.2, and Comparative Example 1: 1.3.
The pH values of Examples 1 and 2 were measured at 20° C. using a pH meter HM-30R manufactured by DKK-TOA Corporation, and were found to be 8.1, 7.8, and 7.9, respectively.

Examples 2 to 16
Except for changing the ink formulation as shown in the table, the aqueous ink compositions for writing instruments of Examples 2 to 16 were obtained in the same manner as in Example 1. The ink formulations and evaluation results are shown in the table.

Comparative Examples 1 to 4
Except for changing the ink formulation as shown in the table, the water-based ink compositions for writing instruments of Comparative Examples 1 to 4 were obtained in the same manner as in Example 1. The ink formulations and evaluation results are shown in the table.

<Preparation of test writing implements>
The aqueous ink compositions for writing implements of Examples 1 to 16 and Comparative Examples 1 to 4 were poured into an ink aspirator made of crystalline olefin resin (polymethylpentene) (an ink aspirator with a resin movable body movable in the forward and backward directions disposed therein) with the ink aspirator opening facing upward, so that the movable body was completely immersed in the ink composition. The ink aspirator was attached to a retractable knock-type writing implement (Pilot Corporation, fountain pen, FCN-1MR-BM) having a fountain pen-shaped nib and a comb-shaped ink retaining member disposed as an ink flow rate regulator, and the following tests and evaluations were carried out using the writing implement, and the evaluations for the color tone test and writing property test were carried out using JIS P3201 writing paper A as the writing test paper.

Metal pigment sedimentation test: Each water-based ink composition for writing instruments was placed in a tightly closed glass test tube having a diameter of 15 mm, and after leaving it at room temperature for 7 days, the sedimentation of the metal pigment was visually observed.
There is almost no supernatant liquid (sedimentation of metal pigments) and the result is good... ◎
Some supernatant liquid (sedimentation of metal pigment) was found, but it was at a level that did not pose a problem for practical use...○
Metal pigments have settled so much that it is problematic... ×

Color tone test: The color tone after handwriting was visually observed.
The color tone (metallic luster) of the writing is very good and there is no shading...◎
Good color tone (metallic luster) of handwriting...○
The color tone (metallic luster) of the writing is slightly inferior... △
The color tone (metallic luster) of the writing is poor and it is of little practical use... ×

Writability test: The handwritten mark was visually observed.
There are no smudges in the writing...
Some smudges in the writing...
The handwriting is smudged and of little practical use... ×

As can be seen from the results in the table, in Examples 1 to 16, good or problem-free performance was obtained in the color tone test, metal pigment sedimentation test, and writing test. As in Examples 1 to 16, the water-based ink composition for writing instruments containing a chelating agent was stored in a glass ink storage unit (water-based ink product: glass bottle) made of soda-lime glass, and the ink was observed under a microscope after three months at room temperature, and good performance was obtained with no practical problems.

The results in the table show that in Comparative Examples 1 to 3, since no polyamide resin was used, there was severe sedimentation of the metal pigment, resulting in poor writing results in some cases.

As can be seen from the results in the table, in Comparative Example 4, the ink viscosity exceeded 100 (mPa·s) at a shear rate of 38.4 (sec ⁻¹ ), so the ink ejection amount was small, the color tone (metallic gloss) of the handwriting was poor, and smudged handwriting occurred.

The aqueous ink composition for writing instruments of the present invention can be used as an aqueous ink composition for various writing instruments such as fountain pens, ballpoint pens, brush pens, calligraphy pens, marking pens, and plate pens. More specifically, the aqueous ink composition for writing instruments can be widely used as a writing instrument filled with the aqueous ink composition for writing instruments, such as a cap type or a retractable type.

Claims (7)

A water-based ink composition for a writing instrument comprising water, a solvent, a metal pigment, and a polyamide resin,
a mass ratio of the polyamide-based resin to the total mass of the metallic pigment (polyamide-based resin/metallic pigment) is 0.1 to 3 times;
The ink viscosity of the aqueous ink composition for a writing instrument is 100 (mPa·s) or less at a shear rate of 38.4 (sec ⁻¹ ) in a 20° C. environment ;
the ink viscosity is 100 (mPa·s) or more and 1000 (mPa·s) or less at a shear rate of 1.92 (sec ⁻¹ ), and the ink viscosity is 20 (mPa·s) or less at a shear rate of 384 (sec ⁻¹ );
and an ink viscosity ratio (viscosity at a shear rate of 1.92 sec ⁻¹ / viscosity at a shear rate of 384 sec ⁻¹ ) of 20 or more and 50 or less . The aqueous ink composition for writing instruments according to claim 1, characterized in that the acid value of the polyamide resin is 50 (mgKOH/g) or less. 3. The water-based ink composition for a writing instrument according to claim 1, further comprising a black colorant. 4. The water-based ink composition for a writing instrument according to claim 1, further comprising a chelating agent. 5. The water-based ink composition for writing instruments according to claim 1, wherein the content of the polyamide resin is 0.01 to 5% by mass based on the total amount of the ink composition. 6. The water-based ink composition for a writing instrument according to claim 1, wherein the solvent has a solubility parameter of 8 to 12. A writing instrument, comprising an ink reservoir tube directly filled with the water-based ink composition for a writing instrument according to any one of claims 1 to 6 .