PEELABLE WRITING INK COMPOSITION WITH COLOR-CHANGING FOR WRITING POROUS SUBSTRATES

Abstract

The present disclosure concerns a writing ink composition comprising: (a) at least one film-forming elastomeric polymer wherein the film-forming elastomeric polymer (a) is an homopolymer or copolymer of polyurethane, (b) at least one polyether-modified polysiloxane, (c) at least one dye, (d) at least one pigment, and (e) water.

The disclosure also concerns a method for preparing such a writing ink composition. A writing instrument comprising such a writing ink composition, and a method for writing on a writing porous substrate, are also part of the disclosure. Finally, the disclosure aims at a writing porous substrate coated with a writing ink composition according to the disclosure.

Claims

1. A writing ink composition comprising: (a) at least one film-forming elastomeric polymer wherein the film-forming elastomeric polymer (a) is an homopolymer or copolymer of polyurethane, (b) at least one polyether-modified polysiloxane, (c) at least one dye, (d) at least one pigment, and (e) water wherein the total content of the at least one dye (c) ranges from 0.1 to 10% by weight, relative to the total weight of the writing ink composition and the total amount of the pigment (d) ranges from 0.1 to 10% by weight, relative to the total weight of the writing ink composition.

2. The writing ink composition according to claim 1, wherein the homopolymer or copolymer of polyurethane (a) is selected from the group consisting of amphoteric polyurethanes, anionic polyurethanes, cationic polyurethanes, non-ionic polyurethanes, polyester-polyurethanes, polyether-polyurethanes and mixtures thereof.

3.-15. (cancelled)

16. The writing ink composition according to claim 1, wherein the homopolymer or copolymer of polyurethane (a) is an anionic polyurethane homopolymer.

17. The writing ink composition according to claim 1, wherein the homopolymer or copolymer of polyurethane (a) is in the form of an aqueous dispersion.

18. The writing ink composition according to claim 1, wherein the total solid content of the polyurethane (a) ranges from 8 to 25%, by weight relative to the total weight of the writing ink composition.

19. The writing ink composition according to claim 1, wherein the at least one polyether-modified polysiloxane (b) is non-ionic.

20. The writing ink composition according to claim 1, wherein the at least one polyether-modified polysiloxane (b) is a polyether-modified polydimethylsiloxane.

21. The writing ink composition according to claim 1, wherein the at least one polyether-modified polysiloxane (b) is a Bis-PEG 15-Methyl Ether Dimethicone.

22. The writing ink composition according to claim 1, wherein the total amount of the at least one polyether-modified polysiloxane (b) ranges from 0.5 to 5% by weight relative to the total weight of the writing ink composition.

23. The writing ink composition according to claim 1, wherein the at least one dye (c) is selected from the group consisting of direct dyes, acid dyes, food dyes, and mixtures thereof.

24. The writing ink composition according to claim 1, wherein the at least one pigment (d) is in the form of a pigment dispersion.

25. The writing ink composition according to claim 1, wherein the total amount of the pigment (d) ranges from 0.5 to 7% by weight, relative to the total weight of the writing ink composition.

26. The writing ink composition according to claim 1, wherein the total content of the at least one dye (c) ranges from 0.2 to 8%, relative to the total weight of the writing ink composition.

27. The writing ink composition according to claim 1, wherein the total amount of water (e) ranges from 10 to 80% by weight, relative to the total weight of the writing ink composition.

28. The writing ink composition according to claim 1, wherein the composition further comprises at least one additive.

29. The writing ink composition according to claim 1, wherein the writing ink composition is a peelable writing ink.

30. The writing ink composition according to claim 1, wherein the writing ink composition is a peelable color-changing writing ink.

31. A writing instrument containing a writing ink composition according to claim 1, wherein the writing instrument is a pen.

32. The writing instrument according to claim 31, wherein the writing instrument comprises an eraser.

33. A method for writing on a writing porous substrate, comprising a step of applying a writing ink composition according to claim 1, to a writing porous substrate.

Description

EXAMPLES

Example 1: Preparation of a Writing Ink Composition According to the Invention

[0089] A writing ink composition according to the present invention comprising the ink ingredients of Table 1 was prepared.

TABLE-US-00001 TABLE 1 Composition 1 according to the invention Trade name Chemical name (% by weight) Water 45.90% Esacote Anionic dispersion of 40% (ie 14% of SW3 ® polyurethane (dry extract: polyurethane) 35 wt. % and about 65% of water Belsil ® INCI name: Bis-PEG-15-    2% DMC6038 Methyl Ether Dimethicone Glycerin Glycerin  7.5% APE FREE Pigment dispersion  3.50% BL 15:3 Disp (water-based dispersion (ie 1.47% of BPD 0015 comprising about pigment) 42 wt. % pigment) Sanolin ® Acid Red 52  0.60% Rhodamine B02 Acticide PHE Phenoxyethanol  0.50% Total   100%

[0090] For a preparation of 1 kg, 459 g of water was introduced at room temperature in a dissolver DISPERMAT® LC75 (dissolver disc Ø 60 mm), and 6 g of Sanolin® Rhodamine B02 (Clariant) were added under agitation (stirring speed: 500 rpm). Then, 400 g of Esacote SW3® (Lamberti) were added at the same stirring speed. The % of polyurethane in Esacote SW3® (Lamberti) represents 35 wt. % (dry extract), and thus the % of polyurethane in the final ink composition is of 14% by weight. After 5 minutes, 75 g of glycerin were introduced. After 5 minutes under the same stirring speed, 20 g of Belsil® DMC6038 (Wacker) were added. After 5 minutes under the same stirring speed, 35 g of a blue pigmented dispersion APE FREE BL 15:3 Disp BPD 0015 (SunChemical) were added. The mixture was stirred for 5 minutes more. Then, 5 g of Acticide PHE were added, and the mixture was stirred for 5 minutes more to obtain the final writing ink com position.

[0091] The viscosity of the writing ink composition was measured at 20° C. with a Shell Cup #1 marketed by NORCROSS® Corporation, according to the following procedure: [0092] 1. Dip the Shell Cup in the writing ink composition until the cup is completely filled with ink composition. [0093] 2. Take the Shell Cup out of the fluid and start the timer simultaneously. [0094] 3. Stop the timer as soon as the fluid does not flow out any more. The time displayed on timer is reported as the Shell Cup viscosity at 20° C. of the fluid. [0095] 4. Clean and dry the Shell Cup. [0096] 5. Repeat steps 1 to 5 with the same fluid two times. [0097] 6. Report the average viscosity of the three measures. [0098] 7. Store the Shell Cup at 20° C.

[0099] The viscosity of the writing ink composition of example 1 measured according to this procedure was: 5.9 mPa.Math.s.

Example 2: Preparation of a Comparative Writing Ink Composition 2

[0100] A comparative writing ink composition comprising the ink ingredients of Table 2 was prepared.

TABLE-US-00002 TABLE 2 Comparative ink composition 2 Trade name Chemical name (% by weight) Water 38.40% Europrene ® Anionic dispersion of 45% (ie 18.45 Latice 084 styrene butadiene % of SBR) copolymer (SBR) (dry extract: 41 wt. %) Belsil ® INCI name: Bis-PEG-15-    2% DMC6038 Methyl Ether Dimethicone Glycerin Glycerine   10% APE FREE Pigment dispersion  3.50% BL 15:3 Disp (water-based dispersion (ie 1.47% of BPD 0015 comprising about pigment) 42 wt. % pigment) Sanolin ® Acid Red 52  0.60% Rhodamine B02 Acticide PHE Phenoxyethanol  0.50% Total   100%

[0101] For a preparation of 1 kg, 384 g of water were introduced at room temperature in a dissolver DISPERMAT® LC75 (dissolver disc Ø 60 mm), and 6 g of Sanolin® Rhodamine B02 (Clariant) were added under agitation (stirring speed: 500 rpm). Then, 450 g of Europrene Latice 084® (Versalis) were added at the same stirring speed. The % of SBR in Europrene Latice 084® (Versalis) represents 41 wt. % (dry extract), and thus the % of SBR in the final ink composition is of 18.45% by weight. After 5 minutes, 100 g of glycerin were introduced. After 5 minutes under the same stirring speed, 20 g of Belsil® DMC6038 (Wacker) were added. After 5 minutes under the same stirring speed, 35 g of a blue pigmented dispersion APE FREE BL 15:3 Disp BPD 0015 (SunChemical) were added. The mixture was stirred for 5 minutes more. Then, 5 g of Acticide PHE were added, and the mixture was stirred for 5 minutes more in order to obtain the final writing ink composition.

[0102] The viscosity of the writing ink composition measured at 20° C. with a Shell Cup #1 marketed by NORCROSS® Corporation was 4.6 mPa.Math.s.

Example 3: Preparation of a Comparative Writing Ink Composition 3

[0103] A comparative writing ink composition comprising the ink ingredients of Table 3 was prepared.

TABLE-US-00003 TABLE 3 Comparative ink composition 3 Trade name Chemical name (% by weight) Water 45.90% Esacote Anionic dispersion 40% (ie 14% of SW3 ® of polyurethane polyurethane) (dry extract: 35 wt. %) PAT ® Polyoxyethylene sorbitan    2% 662(Wurtz) monolaurate Glycerin Glycerine  7.5% APE FREE Pigment dispersion  3.5% BL 15:3 Disp (water-based dispersion (ie 1.47% of BPD 0015 comprising about pigment) 42 wt. % pigment) Sanolin ® Acid Red 52  0.6% Rhodamine B02 Acticide PHE Phenoxyethanol  0.5% Total   100%

[0104] For a preparation of 1 kg, 459 g of water was introduced at room temperature in a dissolver DISPERMAT® LC75 (dissolver disc Ø 60 mm), and 6 g of Sanolin® Rhodamine B02 (Clariant) were added under agitation (stirring speed: 500 rpm). Then, 400 g of Esacote SW3® (Lamberti) were added at the same stirring speed. The % of polyurethane in Esacote SW3® (Lamberti) represents 35 wt. % (dry extract), and thus the % of polyurethane in the final ink composition is of 14% by weight. After 5 minutes, 75 g of glycerin were introduced. After 5 minutes under the same stirring speed, 20 g of PAT® 662(Wurtz) were added. After 5 minutes under the same stirring speed, 35 g of a blue pigmented dispersion APE FRE BL 15:3 Disp BPD 0015 (SunChemical) were added. The mixture was stirred for 5 minutes more. Then, 5 g of Acticide PHE were added, and the mixture was stirred for 5 minutes more to obtain the final writing ink com position.

[0105] The viscosity of the writing ink composition measured at 20° C. with a Shell Cup #1 marketed by NORCROSS® Corporation was 5.7 mPa.Math.s.

Example 4: Peelability Performances Of The Prepared Writing Ink Compositions 1-3

Erasability Performance: Measurement of Peelability

[0106] The peelability (erasing efficiency of the first color) is the ability of the eraser to peel correctly the written mark of first color applied on a writing porous substrate (calligraph notebook: Calligraphe LIGNE 7000 (70g/m2, 210×297 mm, 80 pages, by Clairefontaine), evaluated by visual assessment according to the following method at 23° C. and 50% relative humidity. The erasability performance is part of the color-changing performances of the writing ink com position.

[0107] The color of the obtained written mark made on the writing porous substrate is called “color 1” and corresponds to the initial (first) color of the written mark (here color 1: blue). The written mark was then peeled (or rubbed) with an eraser, i.e. polyether based polyurethane (PTU), just after writing (around 10 seconds after writing), to peel the initial color of the written mark and allow it to change from initial color 1 (here color 1: blue) into a second color 2 (here color 2: pink). Hence, the initial color 1 (here color 1: blue) was removed by peeling with the eraser.

[0108] The method is as follows:

[0109] Loops were drawn with a pen on the writing porous substrate, and then peeled in one time back and forth.

[0110] The scoring (i.e. the peeling efficiency of color 1) is defined as follows:

[0111] 10: Erasability by peeling of the first color 1 is very efficient (no remaining written mark of the initial color 1)—The color of the writing ink composition after applying on the writing porous substrate and after peeling corresponds to color 2.

[0112] 5: The color of the writing ink composition after applying on the porous substrate and after peeling is not efficient (remaining written marks of the initial color 1 into the color 2).

[0113] 0: Erasability by peeling of the first color 1 is not efficient—The color of the writing ink composition after applying on the writing porous substrate and after peeling is not efficient (significant residual written marks of the initial (first) color 1 into the color 2).

[0114] The results are indicated in Table 4 below.

TABLE-US-00004 TABLE 4 Comparison of the color-changing performances of the writing ink composition 1 of the invention (example 1) with the comparative writing ink compositions 2 and 3 (Comparative examples 2 and 3) Color-changing of the initial color after peeling-Peeling Writing ink efficiency compositions of color 1 writing ink 10 composition 1 (invention) Comparative  5 writing ink composition 2 Comparative  0 writing ink composition 3

[0115] As shown in Table 4, the written marks of the writing ink composition 1 according to the invention (example 1) exhibit good results in terms of efficiency of the erasing by peeling (the initial color of the written mark was efficiently removed).

[0116] The written mark made, with the comparative writing ink compositions 2 and 3 of examples 2 and 3 cannot be peeled efficiently, in particular when compared with the written mark made with the writing composition of example 1 according to the invention, which can be peeled efficiently and easily. In particular, it should be also noted that even if the comparative composition 2 comprises more film-forming elastomeric polymer than composition 1 according to the invention, it can be less efficiently peeled than composition 1.