WO2020229183A1

WO2020229183A1 - Solid ink composition and water-based ink composition comprising the same

Info

Publication number: WO2020229183A1
Application number: PCT/EP2020/061883
Authority: WO
Inventors: Damien CONCEDIEU
Original assignee: BIC SA
Current assignee: BIC SA
Priority date: 2019-05-16
Filing date: 2020-04-29
Publication date: 2020-11-19
Anticipated expiration: 2021-11-16

Abstract

The present invention relates to a solid ink composition comprising a specific polyethylene glycol and at least one coloring agent selected from the group consisting of dyes and/or pigments, as well as a method for preparing such a solid ink composition. The invention also concerns a water-based ink composition comprising a solid ink composition according to the invention and a solvent, preferably water. The invention also relates to a rechargeable coloring or marking instrument, in particular a felt-pen, a highlighter, a roller pen, a marker, comprising a solid ink composition or a water-based ink composition according to the invention. Finally, the invention aims at a method for recharging a rechargeable coloring or marking instrument according to the invention.

Description

SOLID INK COMPOSITION AND WATER-BASED INK

COMPOSITION COMPRISING THE SAME

The present invention relates to a solid ink composition comprising a specific polyethylene glycol and at least one coloring agent selected from the group consisting of dyes and/or pigments, as well as a method for preparing such a solid ink composition. The invention also concerns a water-based ink composition comprising a solid ink composition according to the invention and a solvent, preferably water. The invention also relates to a rechargeable coloring or marking instrument, in particular a felt-pen, a highlighter, a roller pen, a marker, comprising a solid ink composition or a water-based ink composition according to the invention. Finally, the invention aims at a method for recharging a rechargeable coloring or marking instrument according to the invention,

The present invention provides a rechargeable coloring or marking instrument which can be refilled with a specific solid ink composition and water when said instrument is empty. The consumer is therefore able to produce himself the final ink of its coloring or marking instrument, by simply adding a solid ink in the coloring or marking instrument and diluting it with water, avoiding the complete replacement of the coloring or marking instrument. The resulting coloring or marking ink presents the same specifications as conventional non-refillable coloring or marking inks. Furthermore, the solid ink of the invention present the advantages of being simple to manufacture, convenient in transportation, and half cheaper than bottle inks.

EP1458819 describes a process for preparing a solid pigment composition for pigment ink by dissolving polyvinyl alcohol in water, and dispersing pigments in the resulting solution, to provide water-insoluble resins (polyvinyl acetal). The goal of this process is to prepare a mixture of resin and pigments which is an intermediate product dispersible in water, not to obtain a solid ink composition. CN 1197094 discloses solid ink made up of triphenyl methane sodium sulfonate through pulverization, sieving and tableting. The corresponding ink is obtained by dissolving the solid ink in water. Said ink needs heating to dissolve the ink, and presents the disadvantage of being of short life.

The inventors have now surprisingly found that the use of a specific polyethylene glycol, solid at room temperature, in a solid ink composition helps improving the stability of the resulting solid ink composition, without altering the coloring or marking properties of the resulting ink. For this purpose, the solid ink of the invention simply needs water, and even only tap water. The solid ink composition of the invention is advantageously soluble in cold water with a very short dissolution time (less than 30 minutes).

The present invention thus concerns a solid ink composition comprising polyethylene glycol solid at room temperature (20°C), and at least one coloring agent selected from the group consisting of dyes and/or pigments, wherein the polyethylene glycol has a number average molecular weight Mn ranging from 800 to 7,800 g.mol ¹.

For the purposes of the present invention, the term "ink" is intended to mean a "writing ink" which is intended to be used in a writing instrument, and in particular in a pen. A writing ink should not be confused with a "printing ink" which is used in printing machines and which does not have the same technical constraints, and thus the same specifications. Indeed, a writing ink must not contain solid particles of which the size is greater than the channels of the writing instrument, in order to avoid blocking them, which would inevitably lead to writing being irreversibly stopped.

In the sense of the invention, a "solid ink" means that the ink is solid at room temperature (20°C), and preferably that said "solid ink" presents at room temperature (20°C) a melting point higher than 45°C, measured by Differential Scanning Calorimetry (DSC). The polyethylene glycol of the invention having a number average molecular weight Mn ranging from 800 to 7,800 g.mol ¹ is solid at room temperature (20°C), preferably is solid at a temperature of up to 35°C, and more preferably is solid at a temperature of up to 40°C. The polyethylene glycol of the invention having a number average molecular weight Mn ranging from 800 to 7,800 g.mol ¹ may be solid at a temperature of up to 70°C.

According to a preferred embodiment, the polyethylene glycol has a number average molecular weight Mn ranging from 3,000 to 7,500 g.mol , and more preferably from 3,400 to 7,000 g.mol ¹.

Advantageously, the polyethylene glycol is present in the solid ink of the invention in a content ranging from 40 to 98% by weight, preferably from 45 to 95% by weight, and more preferably from 50 to 90% by weight, relative to the total weight of the solid ink composition, As mentioned above, the solid ink composition of the invention comprises a coloring agent selected from the group consisting of dyes and/or pigments.

Dyes are intensely colored or fluorescent organic substances only, which impart color to a substrate by selective absorption of light. They are soluble and/or go through an application process which, at least temporarily, destroys any crystal structure by absorption, solution, and mechanical retention, or by ionic or covalent chemical bonds.

On the contrary, pigments are colored, black, white or fluorescent particulate organic or inorganic solids which usually are insoluble in, and essentially physically and chemically unaffected by, the vehicle or substrate in which they are incorporated. They alter appearance by selective absorption and/or by scattering of light. Pigments are usually dispersed in vehicles or substrates for application. Pigments retain a crystal or particulate structure throughout the coloration process.

Both pigments and dyes are used to color different materials, but the way in which they do it is very, and is due to solubility - the tendency to dissolve in a liquid, especially water. How the colorant actually attaches itself to the material also differs greatly between pigments and dyes. While dyes chemically bind with the material, pigments are painted onto the surface, so they physically bind.

According to a preferred embodiment, the coloring agent present in the solid ink composition consists of at least one dye. In this case, the ink is a dye-based ink.

The dyes usable in the ink of the invention may be any dyes well- known by the skilled person, such as black, blue, red, green, violet, pink, turquoise, etc. dyes. In particular, the dyes usable in the ink according to the present invention are alcohol-soluble dyes, oil-soluble dyes, direct dyes, acid dyes, basic dyes, metallized dyes and various salt-forming type dyes, more particularly the dyes are chosen in the group consisting of azoic dyes, triaryl methane dyes, phtalocyanine derivatives dyes, xanthene dyes, and mixtures thereof.

Azoic dyes contain an azoic skeleton having the formula below:

Triaryl methane dyes contain a tryaryl methane skeleton having the formula below:

Phtalocyanine derivatives dyes contain a phtalocyanine skeleton having the formula below: Xanthene dyes contain a xanthene skeleton having the formula below:

Examples of a dye usable in the solid ink composition of the invention are as follow: Direct Blue 199, Acid Blue 9, Acid Red 52, Acid Yellow 23, Food Yellow 3, Solvent Green 7, Acid Orange 7, Reactive Red 141, Reactive Red 24:1, Acid Red 18, Acid Red 51, Acid Red 27, Acid Black 172.

The coloring agent of the invention can also be a pigment.

Examples of pigments according to the invention include organic, inorganic and processed pigments. Thus, the pigment may for example be an inorganic pigment such as a carbon black, ultramarine and titanium dioxide pigment, an organic pigment such as an azo-based pigment, phthalocyanine-based pigment, indigo pigment, thioindigo pigment, thren pigment, quinacridone-based pigment, anthraquinone-based pigment, thron-based pigment, diketopyrrolopyrrole-based pigment, dioxazine- based pigment, perylene-based pigment, peri none-based pigment and isoindolinone-based pigment, a metal pigment such as an aluminum powder or aluminum powder whose surface is treated with a colored resin, a metal gloss pigment obtained by forming a metal vapor deposition film such as that of aluminum on a transparent or colored transparent film, a metal pigment having a thickness of 0.01 to 0.1 pm obtained by peeling a metal vapor deposition film such as that of aluminum formed on a substrate such as a film, a colloidal particle having a mean particle size of 5 to 30 nm selected from gold, silver, platinum and copper, a fluorescent pigment, light-storing pigment, pearl pigment obtained by coating the surface of a core which is a naturally occurring mica, synthetic mica, glass flake, alumina and transparent film with a metal oxide such as titanium oxide, and the like.

Advantageously, the coloring agent is present in the solid ink of the invention in a content ranging from 2 and 50% by weight, preferably from 10 to 40% by weight, and more preferably from 15 to 30% by weight, relative to the total weight of the solid ink composition.

According to a preferred embodiment, the solid ink composition of the invention is anhydrous, which means that it contains less than 2.5%by weight of water (moisture %) in its composition.

The solid ink composition of the invention may also comprises at least one additive selected from the group consisting of antimicrobial agents (biocides), dispersing agents, antifoam agents, wetting agents, pH regulators (such as sodium hydroxide, triethanolamine or 2-(2- aminoethoxyethanol), and mixtures thereof.

Advantageously, the solid ink composition of the invention comprises at least one antimicrobial agent selected from the group consisting of methyl paraben, isothiazolinone, l,2-benzisothiazolin-3-one, 2-methyl-4-isothiaolin-3-one, and mixtures thereof, and preferably methyl paraben. The antimicrobial agent is preferably present in a content ranging from 0.05 to 3% by weight, and more preferably from 0.1 to 1.5% by weight, relative to the total weight of the solid ink composition.

The solid ink composition of the invention is advantageously in the form of tablet, cachet, or powder, and preferably in the form of tablet or cachet.

The present invention also concerns a method for preparing a solid ink composition according to the invention, comprising the steps of:

(i) melting polyethylene glycol at a temperature ranging from 40 to 90°C, (ii) adding at least one coloring agent and optional additives, under stirring, at a temperature ranging from 40 to 90°C, preferably from 45 to 80°C, and more preferably from 65 to 75°C,

(iii) drying the melted ink composition at room temperature (20°C), preferably for at least one hour, and more preferably for at least two hours, and

(iv) shaping the solid ink composition in the form of tablet or cachet, or grinding it in the form of powder.

The components polyethylene glycol, coloring agent and additives, implemented in the method of the invention, are as defined above for the solid ink composition of the invention.

In the method of the invention, step (i) is advantageously carried out at a temperature ranging from 45 to 80°C, and more preferably from 65 to 75°C.

In the method of the invention, step (ii) is advantageously carried out at a temperature ranging from 45 to 80°C, and more preferably from 65 to 75°C.

In the method of the invention, step (iii) of drying the melted ink composition is advantageously realized by pouring the melted composition between two aluminum foils.

Another subject-matter of the invention concerns a water-based ink composition comprising a solid ink composition as defined according to the invention and a solvent.

The solvent of the water-based ink composition is advantageously water, and more advantageously selected in the group consisting of demineralized water and tap water.

In the water-based ink composition of the invention, the solid ink composition may represent from 2 to 40% by weight, preferably from 5 to 25% by weight, and more preferably from 7 to 22% by weight, relative to the total weight of the water-based ink composition. In the water-based ink composition of the invention, the solvent may represent from 60 to 98% by weight, preferably from 75 to 95% by weight, and more preferably from 78 to 90% by weight, relative to the total weight of the water-based ink composition.

The water-based ink composition of the invention advantageously present a viscosity ranging from 1 to 10 mPa.s, and more advantageously from 2 to 6 mPa.s, when measured at room temperature (20°C) at a speed of 60 rpm, with a BROOKFIELD viscosimeter such as a Brookfield viscosimeter DV-I or DV-II using spindle UL.

The water-based ink composition of the invention advantageously present a pH ranging from 2 to 10, and more advantageously from 4 to 8, when measured at room temperature (20°C) with a pH-meter SEVEN EASY from METTLER TOLEDO.

The invention also concerns the use of a solid ink composition according to the invention, or of a water-based ink composition according to the invention, as a free ink or in a coloring instrument selected from the group consisting of felt-pens, highlighters, roller pens, markers, and preferably felt-pens.

The term "free ink instrument" or "writing instrument having a free ink reservoir" is a writing instrument in which the ink is free to flow in the reservoir. In other words, the ink flows instantaneously from one side of the reservoir to the other, for example under the influence of gravity. This "free ink" will be understood as being capable of moving when the writing instrument is manipulated or when the writing instrument is moved.

Another subject-matter of the invention relates to a rechargeable coloring or marking instrument, in particular a felt-pen, a highlighter, a roller pen, a marker, and preferably a felt-pen, comprising a solid ink composition according to the invention or a water-based ink composition according to the invention.

The rechargeable coloring or marking instrument of the invention may comprise: - an axial barrel comprising a solid ink composition as defined according to the invention, or a water-based ink composition as defined according to the invention, and

- a pen body which delivers the water-based ink composition stored in the axial barrel.

Finally, the invention also concerns a method for recharging a rechargeable coloring or marking instrument according to the invention, comprising the steps of:

O') adding a solvent, and preferably water, to a solid ink composition according to the invention,

0 inserting the water-based ink composition obtained in step O') in the pen body of a rechargeable coloring or marking instrument, in particular in order to obtain a liquid composition, and

OO shaking the rechargeable coloring or marking instrument before using it for coloring or marking a substrate, such as paper or cardboard.

Alternatively, the invention concerns a method for recharging a rechargeable coloring or marking instrument according to the invention, comprising the steps of:

(i") inserting a solid ink composition according to the invention in the pen body of a rechargeable coloring or marking instrument,

(ii") adding a solvent, and preferably water, to the solid ink composition, in particular in order to obtain a liquid composition, and

(iii") shaking the rechargeable coloring or marking instrument before using it for coloring or marking a substrate, such as paper or cardboard.

In addition to the foregoing, the invention also comprises other provisions which will emerge from the additional description which follows, which relates to the preparation of solid ink compositions according to the invention and comparative examples. Examples:

Example 1: Preparation of a solid ink composition according to the invention and of the corresponding water-based ink composition

A solid ink according to the present invention and the corresponding water-based ink composition, obtained after addition of water, having the compositions presented in Table 1 below, were prepared.

Table 1

The solid ink composition of the invention was prepared according to the following protocol:

150.77g of PEG 4000 (Pluriol E 4000, BASF) was put in a DISPERMAT TANK at a temperature of 70°C, under slow stirring at 150 rpm. When PEG 4000 was totally melted, 1.90g of methyl paraben (Ueno Methyl Paraben NF, Ueno) was added, and the mixture was left under slow stirring at 500 rpm during 10 minutes. 64.36g of Food Blue 2 was then added. The stirring was increased at 2,000 rpm in order to have a "doughnut effect" (i.e. when a hole opens up around the stirring blade) for 15 minutes. 33.18g of Acid Red 52 (Rhodamine Sanolin B 02, Clariant) was added, while maintaining the stirring in order to keep the "doughnut effect" for 30 minutes.

The resulting melted ink composition was then poured between two aluminium foils at room temperature (20°C), and left for 2 hours, in order to obtain a solid ink composition.

The characteristics of the solid ink composition were as follows:

Measurement of the moisture % of the solid ink composition:

Equipment: Coulometer Metrohm 831 KF

Method:

1. Check that the top of the electrode of measurement dips in Hydranal Coulomat E solution (Riedel-de-Haen)

2. Weight 10 mg of solid ink composition

3. Calculate the % difference between two measurements at 105°C as:

(H1-H2)/H1*100,

wherein:

HI: Humidity of a blank sample (empty vial), and

H2: Humidity of the solid ink composition.

The moisture % measured for the solid ink composition of Example 1 was of 1.59%.

Measurement of the melting point of the solid ink composition:

Equipment: Differential Scanning Calorimetry (DSC)

Method:

1. Equilibrate at 40°C

2. Mark end of cycle

3. Ramp: l°C/min to 70°C

4. Isothermal for 2 minutes 5. Ramp: l°C/min to 0°C

6. Isothermal for 2 minutes

7. End of method

The melting point measured for the solid ink composition of Example 1 was of 59.5°C.

Measurement of the dissolution time of the solid ink composition in demineralized water and tap water:

Method:

1. Weight the quantity of solid ink composition

2. Add a specific quantity of water

3. Put on a chronometer, shake for 30 seconds and stop the shaking

4. At each minute, shake 10 seconds and verify if the solid ink composition is dissolved in water. Stop the shaking when the solid ink composition is totally dissolved

5. Stop the chronometer, and note the dissolution time

The dissolution time of the solid ink composition was: Table 2

The dissolution time of the solid ink composition was equivalent with demineralized water and tap water. A water-based ink composition of the invention was then prepared by dissolving 0.67g of the solid ink composition previously prepared in 4.33g of demineralized water contained in a test tube, and shaken by the operator to reproduce the consumer action.

The characteristics of the water-based ink composition of the invention were as follows:

- Viscosity: 3.6 mPa.s at 20°C with a shear rate of 60 rpm, measured with a BROOKFIELD viscosimeter DV-II with spindle UL,

- Surface tension: 50.3 mN.m ¹ at 20°C, measured with a tensiometer K100 from KRLISS, and

- pH = 5 at 20°C, measured with Inlab Science PRO-ISM with pH-meter SEVENEASY from METTLER TOLEDO. The water-based ink composition of the invention was then introduced in a felt-pen Visacolor™ system. The water-based ink composition of the invention appeared homogeneous, with no leakage and no sedimentation. The water-based ink composition of the invention did not show any colorimetry difference with respect to the conventional water-based ink composition Visacolor™.

Color Analysis:

The color obtained by dissolution of solid ink with demineralized water and tap water is evaluated by measuring the color difference (DE) of the ink by using a spectro-colori meter (Spectrocolori meter Konica Minolta - Illuminated with a CIE D65 light source and measured 10° observer angle).

The color obtained by dissolution of solid ink with demineralized water is the reference.

Method: 1. The solid ink is dissolved in demineralized water and its color is measured with the Spectrocolori meter Konica Minolta.

2. The solid ink is dissolved in tap water and its color is measured with the Spectrolocolori meter Konica Minolta.

3. Measurement of DE (difference between the solid ink dissolved in demineralized water and the solid ink dissolved in tap water)

If the color difference DE is less than 3, the difference of colors for the observer is not visible to the naked eye.

The color difference measured for the solid ink composition of the invention is: DE = 0.65. Therefore, the use of demineralized water or tap water does not affect the color of the ink.

Example 2: Preparation of a comparative ink composition and of the corresponding water-based ink composition

A comparative ink composition, having the formula presented in Table 3 below, was prepared.

Table 3

The comparative ink composition was prepared according to the following protocol:

260.60g of PEG 600 was put in a DISPERMAT TANK at a temperature of 70°C, under slow stirring at 300 rpm. When PEG 600 was totally melted, 1.70g of methyl paraben (Ueno Methyl Paraben NF, Ueno) was added, and the mixture was left under slow stirring at 300 rpm during 5 minutes. 59.00g of Food Blue 2 was then added. The stirring was increased at 1,400 rpm in order to have a "doughnut effect" (i.e. when a hole opens up around the stirring blade) for 15 minutes. 30.40g of Acid Red 52 (Rhodamine Sanolin B 02, Clariant) was added, while maintaining the stirring in order to keep the "doughnut effect" for 30 minutes.

At the end of the process, the formulation was very liquid and it was difficult to flow correctly the ink composition between aluminium foils.

After two hours at room temperature (20°C) between aluminium foils, the ink composition was still not solid and the aluminium foils stuck to the formulation.

The ink composition was then put at -20°C for one hour in order to obtain a solid ink composition. However, it was impossible to remove the aluminium foils from the ink composition.

The ink composition was thus put for another 10 minutes at room temperature (20°C) (after the one hour at -20°C). The interface between the aluminium foils and the ink composition was melted, but the ink composition remained very sticky and it was impossible to remove the aluminium foils from the ink composition.

In conclusion, it was impossible to formulate a solid ink composition solid at room temperature (20°C) with a PEG 600. Furthermore, the ink composition with PEG 600 showed a poor stability at room temperature (20°C), and cannot be stored at temperatures higher than 45°C because of its melting point (no storage in the sun).

Example 3: Preparation of a comparative ink composition and of the corresponding water-based ink composition A comparative ink composition, having the formula presented in Table 4 below, was prepared. Table 4

97.28g of PEG 8000 was put in a DISPERMAT TANK at a temperature of 70°C, under slow stirring at 300 rpm. When PEG 9000 was totally melted, 1.95g of methyl paraben (Ueno Methyl Paraben NF, Ueno) was added, and the mixture was left under slow stirring at 300 rpm during 5 minutes. 66.54g of Food Blue 2 was then added. The stirring was increased at 1,400 rpm in order to have a "doughnut effect" (i.e. when a hole opens up around the stirring blade) for 15 minutes. 34.24g of Acid Red 52 (Rhodamine Sanolin B 02, Clariant) was added, while maintaining the stirring in order to keep the "doughnut effect" for 30 minutes.

Flowever, it was impossible to obtain a solid ink composition because there were more powder raw materials than liquid raw materials at 70°C. Furthermore, the ink composition with PEG 8000 showed a high viscosity at room temperature (20°C), and cannot be implemented in a coloring or marking instrument.

Claims

1. A solid ink composition at room temperature (20°C) comprising polyethylene glycol and at least one coloring agent selected from the group consisting of dyes and/or pigments, said polyethylene glycol being solid at room temperature (20°C) and having a number average molecular weight Mn ranging from 800 to 7,800 g.mol ¹.

2. A solid ink composition according to claim 1, wherein the polyethylene glycol has a number average molecular weight Mn ranging from 3,000 to 7,500 g.mol ¹, and more preferably from 3,400 to 7,000 g.mol ¹.

3. A solid ink composition according to claim 1 or claim 2, wherein the polyethylene glycol is solid at a temperature of up to 35°C.

4. A solid ink composition according to any one of claims 1 to 3, wherein the coloring agent consists of at least one dye.

5. A solid ink composition according to claim 4, wherein the dye is selected from the group consisting of azoic dyes, triarylmethane dyes, phtalocyanine derivatives dyes, xanthene dyes, and mixtures thereof.

6. A solid ink composition according to any one of claims 1 to 5, wherein the polyethylene glycol is present in a content ranging from 40 to 98% by weight, preferably from 45 to 95% by weight, and more preferably from 50 to 90% by weight, relative to the total weight of the solid ink composition.

7. A solid ink composition according to any one of claims 1 to 6, wherein the coloring agent is present in a content ranging from 2 and 50% by weight, preferably from 10 to 40% by weight, and more preferably from 15 to 30% by weight, relative to the total weight of the solid ink composition.

8. A solid ink composition according to any one of claims 1 to 7, wherein it is anhydrous.

9. A solid ink composition according to any one of claims 1 to 8, wherein it comprises at least one additive selected from the group consisting of antimicrobial agents, dispersing agents, antifoam agents, wetting agents, pH regulators, and mixtures thereof.

10. A solid ink composition according to claim 9, wherein it comprises at least one antimicrobial agent selected from the group consisting of methyl paraben, isothiazolinone, l,2-benzisothiazolin-3-one, 2-methyl-4-isothiaolin-3-one, and mixtures thereof.

11. A solid ink composition according to any one of claims 1 to 10, wherein it is in the form of tablet, cachet or powder, and preferably in the form of tablet or cachet.

12. A method for preparing a solid ink composition according to any one of claims 1 to 11, comprising the steps of:

(i) melting polyethylene glycol at a temperature ranging from 40 to 90°C,

(ii) adding at least one coloring agent and optional additives, under stirring, at a temperature ranging from 40 to 90°C,

(iii) drying the melted ink composition at room temperature (20°C), preferably for at least one hour, and

13. A water-based ink composition comprising a solid ink composition according to any one of claims 1 to 11 and a solvent.

14. A water-based ink composition according to claim 13, wherein the solvent is water, preferably selected in the group consisting of demineralized water and tap water.

15. A water-based ink composition according to claim 13 or claim 14, wherein the solid ink composition represents from 2 to 40% by weight, preferably from 5 to 25% by weight, and more preferably from 7 to 22% by weight, relative to the total weight of the water-based ink composition.

16. A water-based ink composition according to any one of claims 13 to 15, wherein the solvent represents from 60 to 98% by weight, preferably from 75 to 95% by weight, and more preferably from 78 to 90% by weight, relative to the total weight of the water-based ink composition.

17. Use of a solid ink composition according to any one of claims

1 to 11, or of a water-based ink composition according to any one of claims 13 to 16, as a free ink or in a coloring instrument selected from the group consisting of felt-pens, highlighters, roller pens, markers, and preferably felt-pens.

18. A rechargeable coloring or marking instrument, in particular a felt-pen, a highlighter, a roller pen, a marker, and preferably a felt-pen, comprising a solid ink composition according to any one of claims 1 to 11, or a water-based ink composition according to any one of claims 13 to 16.

19. A rechargeable coloring or marking instrument according to claim 18 comprising: - an axial barrel comprising a solid ink composition according to any one of claims 1 to 11, or a water-based ink composition according to any one of claims 13 to 16, and

20. A method for recharging a rechargeable coloring or marking instrument according to claim 18 or claim 19, comprising the steps of:

O') adding a solvent, and preferably water, to a solid ink composition according to any one of claims 1 to 11,

0 inserting the water-based ink composition obtained in step O') in the pen body of a rechargeable coloring or marking instrument, and

21. A method for recharging a rechargeable coloring or marking instrument according to claim 18 or claim 19, comprising the steps of:

0") inserting a solid ink composition according to any one of claims 1 to 11 in the pen body of a rechargeable coloring or marking instrument,

(ii") adding a solvent, and preferably water, to the solid ink composition according to any one of claims 1 to 11, and