WO2020229183A1 - Composition d'encre solide et composition d'encre à base d'eau la comprenant - Google Patents

Composition d'encre solide et composition d'encre à base d'eau la comprenant Download PDF

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Publication number
WO2020229183A1
WO2020229183A1 PCT/EP2020/061883 EP2020061883W WO2020229183A1 WO 2020229183 A1 WO2020229183 A1 WO 2020229183A1 EP 2020061883 W EP2020061883 W EP 2020061883W WO 2020229183 A1 WO2020229183 A1 WO 2020229183A1
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WO
WIPO (PCT)
Prior art keywords
ink composition
water
composition according
solid ink
coloring
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Application number
PCT/EP2020/061883
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English (en)
Inventor
Damien CONCEDIEU
Original Assignee
Societe Bic
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Societe Bic filed Critical Societe Bic
Publication of WO2020229183A1 publication Critical patent/WO2020229183A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/18—Writing inks specially adapted for ball-point writing instruments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks

Definitions

  • 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.
  • 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.
  • 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.
  • 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
  • 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 .
  • 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.
  • 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.
  • 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 .
  • 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,
  • 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.
  • 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.
  • the coloring agent present in the solid ink composition consists of at least one dye.
  • 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.
  • 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.
  • pigments according to the invention include organic, inorganic and processed pigments.
  • 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
  • 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.
  • 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.
  • antimicrobial agents biocides
  • dispersing agents such as sodium hydroxide, triethanolamine or 2-(2- aminoethoxyethanol)
  • antifoam agents such as sodium hydroxide, triethanolamine or 2-(2- aminoethoxyethanol
  • 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:
  • polyethylene glycol, coloring agent and additives are as defined above for the solid ink composition 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.
  • step (ii) is advantageously carried out at a temperature ranging from 45 to 80°C, and more preferably from 65 to 75°C.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the invention also concerns a method for recharging a rechargeable coloring or marking instrument according to the invention, comprising the steps of:
  • step O' 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
  • the invention concerns a method for recharging a rechargeable coloring or marking instrument according to the invention, comprising the steps of:
  • 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
  • the solid ink composition of the invention was prepared according to the following protocol:
  • PEG 4000 Pluriol E 4000, BASF
  • a DISPERMAT TANK 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.
  • 1.90g of methyl paraben Ueno Methyl Paraben NF, Ueno
  • 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.
  • HI Humidity of a blank sample (empty vial)
  • H2 Humidity of the solid ink composition.
  • the moisture % measured for the solid ink composition of Example 1 was of 1.59%.
  • the melting point measured for the solid ink composition of Example 1 was of 59.5°C.
  • 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.
  • 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,
  • 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).
  • DE color difference
  • the color obtained by dissolution of solid ink with demineralized water is the reference.
  • the solid ink is dissolved in tap water and its color is measured with the Spectrolocolori meter Konica Minolta.
  • 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.
  • the comparative ink composition was prepared according to the following protocol:
  • 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 formulation was very liquid and it was difficult to flow correctly the ink composition between aluminium foils.
  • 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.
  • 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
  • the comparative ink composition was prepared according to the following protocol:
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une composition d'encre solide comprenant un polyéthylène glycol spécifique et au moins un agent colorant choisi dans le groupe constitué de teintures et/ou de pigments, ainsi qu'un procédé de préparation d'une telle composition d'encre solide. L'invention concerne également une composition d'encre à base d'eau comprenant une composition d'encre solide selon l'invention et un solvant, de préférence de l'eau. L'invention concerne également un instrument de coloration ou de marquage rechargeable, en particulier un feutre, un surligneur, un stylo à bille, un marqueur, comprenant une composition d'encre solide ou une composition d'encre à base d'eau selon l'invention. Enfin, l'invention concerne un procédé de recharge d'un instrument de coloration ou de marquage rechargeable selon l'invention.
PCT/EP2020/061883 2019-05-16 2020-04-29 Composition d'encre solide et composition d'encre à base d'eau la comprenant WO2020229183A1 (fr)

Applications Claiming Priority (2)

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EP19305626 2019-05-16
EP19305626.4 2019-05-16

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WO2020229183A1 true WO2020229183A1 (fr) 2020-11-19

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3932999A1 (fr) * 2020-06-30 2022-01-05 Société BIC Outil d'écriture rechargeable pour une composition d'encre à base d'eau
EP3932998A1 (fr) * 2020-06-30 2022-01-05 Société BIC Outil d'écriture portable à temps cap-off amélioré
EP4141076A3 (fr) * 2021-08-24 2023-04-05 Mitsubishi Pencil Company, Limited Tablette colorante et composition d'encre à base d'eau pour instrument d'écriture l'utilisant

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1197094A (zh) 1997-04-20 1998-10-28 杨立群 固体墨水
EP1458819A1 (fr) 2002-07-26 2004-09-22 Orient Chemical Industries, Ltd. Composition de pigment solide destinee a une encre pigmentaire, encre pigmentaire comprenant cette derniere et procede de preparation de la composition et de l'encre pigmentaire
US20100166934A1 (en) * 2006-05-15 2010-07-01 Sun Chemical Corporation Edible inks
KR101064393B1 (ko) * 2011-07-15 2011-09-14 김선목 투명 고체형 형광마카잉크 조성물 및 그의 제조방법
US20140168314A1 (en) * 2012-05-09 2014-06-19 Canon Kabushiki Kaisha Aqueous ink, ink cartridge, and ink jet recording method
US20140363642A1 (en) * 2012-02-02 2014-12-11 Nippon Kayaku Kabushiki Kaisha Aqueous coloring agent dispersion for inkjet, ink composition, inkjet recording method, and colored body
CN104893419A (zh) * 2015-07-06 2015-09-09 重庆大学 一种实用的水性白板笔墨水及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1197094A (zh) 1997-04-20 1998-10-28 杨立群 固体墨水
EP1458819A1 (fr) 2002-07-26 2004-09-22 Orient Chemical Industries, Ltd. Composition de pigment solide destinee a une encre pigmentaire, encre pigmentaire comprenant cette derniere et procede de preparation de la composition et de l'encre pigmentaire
US20100166934A1 (en) * 2006-05-15 2010-07-01 Sun Chemical Corporation Edible inks
KR101064393B1 (ko) * 2011-07-15 2011-09-14 김선목 투명 고체형 형광마카잉크 조성물 및 그의 제조방법
US20140363642A1 (en) * 2012-02-02 2014-12-11 Nippon Kayaku Kabushiki Kaisha Aqueous coloring agent dispersion for inkjet, ink composition, inkjet recording method, and colored body
US20140168314A1 (en) * 2012-05-09 2014-06-19 Canon Kabushiki Kaisha Aqueous ink, ink cartridge, and ink jet recording method
CN104893419A (zh) * 2015-07-06 2015-09-09 重庆大学 一种实用的水性白板笔墨水及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3932999A1 (fr) * 2020-06-30 2022-01-05 Société BIC Outil d'écriture rechargeable pour une composition d'encre à base d'eau
EP3932998A1 (fr) * 2020-06-30 2022-01-05 Société BIC Outil d'écriture portable à temps cap-off amélioré
WO2022002819A1 (fr) * 2020-06-30 2022-01-06 Societe Bic Outil d'écriture portatif ayant un temps de fermeture amélioré
EP4141076A3 (fr) * 2021-08-24 2023-04-05 Mitsubishi Pencil Company, Limited Tablette colorante et composition d'encre à base d'eau pour instrument d'écriture l'utilisant

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