WAX CRAYON COMPRISING ZRO ₂

This application claims benefit from the European Patent Application No. 21306898.4, titled: “WAX CRAYON COMPRISING ZRO2”, filed on 22 December 2021, its content being incorporated herein by reference.

Technical Field

The present invention relates to the field of writing instruments. More specifically, the present invention relates to writing instruments comprising ZrO2.

Background

The present invention relates to writing instruments, such as wax crayons, chalks or colored pencils.

Writing instruments such as pencils, wax crayons or chalks comprise or consist of a solid pigment core, also referred to as a lead. The writing instruments comprising a lead are used to create markings by rubbing the lead against a substrate, such as a piece of paper, to form a deposit on the substrate.

The leads comprise a structural component mixed with one or more colorants, such as pigments or dyes. For example, a wax crayon may comprise wax as a structural component, wherein the wax is mixed with a blue pigment to produce a blue wax crayon.

However, the resulting shade of the lead and the markings produces by the lead may be considered too dark. For example, mixing a wax with a blue pigment may result in a dark blue color of the lead and its marking. To obtain a lead of a lighter shade, the wax may be mixed with a white colorant. Typically, the white pigment TiCh is used to lighten the shade of leads, due to its strong whitening effect. For example, a wax may be mixed with a blue pigment and additionally TiCh to obtain a light blue wax crayon, which may provide a light blue deposit, in particular when deposited on a white paper. However, recently concerns have emerged that TiCh dust may possibly be carcinogenic to humans. During the production of leads comprising TiCh, in particular during the mixing of the structural component with the TiCh, TiCh may be generated, which may be harmful to manufacturing personnel.

The present disclosure aims to address the aforementioned issues in optimizing the writing instrument’s lead composition.

Summary

In a first aspect, the present disclosure relates to a writing instrument comprising a lead, wherein the lead may comprise at least about 0.5 wt.-% ZrCh, relative to the total weight of the lead, in particular wherein the lead may comprise less than about 0.5 wt.-%, more specifically less than about 0.2 wt.-% and in particular substantially no or no TiCh.

In some embodiments, the lead may comprise between about 1 wt.-% to about 25 wt.-%, more specifically between about 2 wt.-% to about 20 wt.-%, even more specifically between about 5 wt.-% to about 20 wt.-%, and in particular between about 11 wt.-% to about 15 wt.-% ZrCh, relative to the total weight of the lead.

In some embodiments, an external surface of the lead may have an L*-value of at least 40 and wherein the lead comprises between about 11.0 wt.-% to about 20 wt.-%, more specifically between about 11 wt.-% to about 18 wt.-% and in particular between about 12 wt.-% to about 15 wt.-% ZrCh, relative to the total weight of the lead.

In some embodiments, the external surface of the lead may have an L*-value of less than 40 and wherein the lead comprises between about 0.5 wt.-% to about 10.9 wt.-%, more specifically between about 1 wt.-% to about 9 wt.-% and in particular between about 2 wt.-% to about 8 wt.- % ZrCh, relative to the total weight of the lead.

In some embodiments, the lead may comprise the ZrCh in the form of particles.

In some embodiments, the ZrCh particles may have a Dso between about 0.1 pm to about 17 pm, more specifically between about 0.2 pm to about 10 pm and even more specifically between about 0.3 pm to about 7 pm, in particular between about 0.3 pm to about 5 pm, and in particular between about 0.4 pm to about 2 pm.

In some embodiments, the ZrCh particles may have a D90 between about 0.5 pm to about 50 pm, more specifically between about 0.5 pm to about 15 pm, in particular 1 pm to about 3 pm.

In some embodiments, the ZrCh particles may have a BET-value between about 0.5 m ² /g to about 22 m ² /g, more specifically between about 2.5 m ² /g to about 20 m ² /g, in particular between about 4 m ² /g to about 20 m ² /g, and in particular about 4 m ² /g to about 18 m ² /g, measured according to DIN ISO 9277:2014-01.

In some embodiments, the lead may have a coefficient of friction between about 0.414 to about 0.5, more specifically between about 0.420 to about 0.48 and in particular between about 0.43 to about 0.46.

In some embodiments, the writing instrument may comprise a casing and the lead is may comprised within the casing.

In some embodiments, the lead may have a diameter of between about 2.0 mm to about 4.5 mm, more specifically between about 2.3 mm to about 4.2 mm and in particular between about 2.8 mm to about 4.0 mm.

In some embodiments, the lead may have a diameter between about 5 mm to about 35 mm, more specifically between about 6 mm to about 20 mm and in particular 7 mm to about 12 mm.

In some embodiments, the lead may comprise about 0.005 wt.-% to about 3.45 wt.-% of one or more metal oxides or transition metal oxide from the second, third, fourth and/or thirteenth group of the periodic table, relative to the total weight of the lead.

In some embodiments, the lead may comprise about 1.0 wt.-% to about 14.6 wt.-% of one or more metal oxides or transition metal oxides from the second, third, fourth and/or thirteenth group of the periodic table, relative to the total weight of the ZrCh. In some embodiments, the lead may comprise Y2O3, HfCh, MgO, CaO and/or Ce20s, in particular HfCh and/or Y2O3, and in particular Y2O3.

In some embodiments, the lead may be devoid, or substantially devoid of MgO and/or CaO.

In some embodiments, the lead may comprise less than 0.05% of SiO2, more specifically less than 0.04% of SiO2, and even more specifically less than 0.03% of SiO2, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 90 wt.-% of one or more waxes, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 50 wt.-% to about 95 wt.-%, more specifically, between about 60 wt.-% to about 90 wt.-% and in particular between about 70 wt.-% to about 85 wt.-% of one or more waxes, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 45 wt.-%, more specifically, between about 15 wt.-% to about 40 wt.-% and in particular between about 20 wt.-% to about 30 wt.-% of one or more waxes, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 45 wt.-%, more specifically, between about 15 wt.-% to about 35 wt.-% and in particular between about 18.5 wt.-% to about 27 wt.-% of a polymer, more specifically a thermoplast, even more specifically an olefine and in particular polyethylene or polypropylene, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 1 wt.-% to about 20 wt.-%, more specifically, between about 3 wt.-% to about 17 wt.-% and in particular between about 5 wt.-% to about 15 wt.-% of a fatty acid or salt thereof, relative to the total weight of the lead. In some embodiments, the fatty acid or salt may comprise a monovalent linear or branched saturated or unsaturated carboxylic acid salt having between about 8 to about 24 carbon atoms, more specifically a monovalent linear saturated carboxylic acid salt having between about 16 to about 20 carbon atoms, and in particular stearic acid, calcium stearate, zinc stearate or mixtures thereof.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise a filler, in particular a hydrous aluminum phyllosilicate and/or an alkali and/or earth alkali carbonate.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 50 wt.-%, more specifically, between about 17 wt.-% to about 40 wt.-% and in particular between about 23.5 wt.-% to about 32 wt.-% of the filler, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.-% to about 25 wt.-% and in particular between about 15 wt.- % to about 20 wt.-% of a hydrous aluminum phyllosilicate, more specifically a layered hydrous aluminum phyllosilicate and in particular kaolinite, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 5 wt.-% to about 20 wt.-%, more specifically, between about 7 wt.-% to about 15 wt.-% and in particular between about 8.5 wt.- % to about 12 wt.-% of an alkali and/or earth alkali carbonate, more specifically an earth alkali carbonate and in particular calcium carbonate, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 0.5 wt.-% to about 5 wt.-%, more specifically between about 1 wt.-% to about 3.5 wt.-% and in particular between about 1.5 wt.- % to about 2.5 wt.-% of a plasticizer, more specifically of a phthalic acid ester and in particular of C7-C9 alkyl benzyl phthalate, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 0.05 wt.-% to about 10 wt.-%, more specifically between about 0.05 wt.-% to about 7 wt.-% and in particular between about 0.1 wt.-% to about 5 wt.-% of one or more colorants, relative to the total weight of the lead. In some embodiments, the lead may comprise between about 0.05 wt.-% to about 10 wt.-%, more specifically between about 0.05 wt.-% to about 7 wt.-% and in particular between about 0.1 wt.-% to about 5 wt.-% of one or more pigments, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 5 wt.-% to about 80 wt.-%, more specifically, between about 5 wt.-% to about 60 wt.-%, more specifically, between about 10 wt.-% to about 55 wt.-% and in particular between about 15 wt.-% to about 50 wt.-% of a hydrous aluminum phyllosilicate, more specifically a layered hydrous aluminum phyllosilicate and in particular kaolinite, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.-% to about 25 wt.-% and in particular between about 13 wt.- % to about 17 wt.-% of one or more colorants, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.-% to about 25 wt.-% and in particular between about 13 wt.- % to about 17 wt.-% of one or more pigments, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 3 wt.-% to about 50 wt.-%, more specifically, between about 10 wt.-% to about 50 wt.-%, more specifically, between about 15 wt.-% to about 45 wt.-% and in particular between about 20 wt.-% to about 40 wt.-% of a binder, more specifically a polymeric binder, and in particular styrenic polymers such as polystyrene and/or acrylonitrile butadiene styrene, relative to the total weight of the lead.

In some embodiments, the lead may comprise between about 0.5 wt.-% to about 10 wt.-%, more specifically between about 2 wt.-% to about 8 wt.-% and in particular between about 3.5 wt.-% to about 6.5 wt.-% of a plasticizer, more specifically of a benzoate ester.

In some embodiments, the lead may comprise ZnS and/or ZnO. Detailed Description

Hereinafter, a detailed description will be given of the present disclosure. The terms or words used in the description and the aspects of the present disclosure are not to be construed limitedly as only having common-language or dictionary meanings and should, unless specifically defined otherwise in the following description, be interpreted as having their ordinary technical meaning as established in the relevant technical field. The detailed description will refer to specific embodiments to better illustrate the present disclosure, however, it should be understood that the presented disclosure is not limited to these specific embodiments.

Writing instruments such as pencils, wax crayons or chalks comprise or consist of a solid pigment core, also referred to as a lead. The writing instruments comprising a lead are used to create markings by rubbing the lead against a substrate, such as a piece of paper. To adjust the lightness of a lead and its deposit, TiCh is typically used as an effective whitening pigment.

However, recently concerns have emerged that TiCh dust may possible be carcinogenic to humans. During the production of leads comprising TiCh, in particular during the mixing of the structural component with the TiCh, TiCh dust may be generated, which may be harmful to manufacturing personnel. Further, in some jurisdictions TiCh in powder form has been banned to be used above certain concentration due to concern about a carcinogenic risk by inhalation. For example, the EU has placed a limit on the use of TiCh powder at 1 wt.-% or the product must be labelled as comprising possible carcinogens, even if the TiCh cannot become airborne from the product. As a result, an alternative for TiCh to adjust the lightness of leads is required.

However, exchanging TiCh for other white colorants, in particular pigments, is not straightforward since white colorants cannot be used interchangeably. Alternative white colorants may not be equally effective in improving the lightness of the lead and/or the lead’s deposit. Further, alternative white colorants may lead to other discoloration, in particular a yellowish tinge, of the lead and/or the lead’s deposit. To make matters worse, TiCh is an almost ideal white colorant since it is effective in providing leads, in which the lead’ s color is perceived very similar to the formed deposit. This may make it easier for users to choose between different colors and predicting how the markings will look. Alternative white colorants can result in leads, where the perceived color of the lead varies strongly from the lead’s deposit. Surprisingly, it has been found that zirconium dioxide, ZrCh, may be an effective white pigment to increase the lightness of leads, in particular in comparatively low amounts. Further, ZrCh may not lead to a significant other discoloration. Additionally, ZrCh may allow producing leads, wherein the perceived color of the lead does not strongly vary from the color perceived from the lead’s deposit on e.g. paper.

Accordingly, in a first aspect, the present disclosure relates to a writing instrument comprising a lead, wherein the lead may comprise at least about 0.5 wt.-% ZrCh, relative to the total weight of the lead, in particular wherein the lead may comprise less than about 0.5 wt.-%, more specifically less than about 0.2 wt.-% and in particular substantially no or no TiCh.

In some embodiments, the lead may comprise between about 1 wt.-% to about 25 wt.-%, more specifically between about 2 wt.-% to about 20 wt.-%, even more specifically between about 5 wt.-% to about 20 wt.-%, and in particular between about 11 wt.-% to about 15 wt.-% ZrCh, relative to the total weight of the lead. A higher proportion of ZrCh may result in a lighter lead.

The lightness and the color of the lead in general may be defined as per the CIELAB or CIELCh color space. The CIELAB color space, also referred to as L*a*b*, is a color space defined by the International Commission on Illumination. The color space is designed to approximate human vision. The CIELAB color space defines color in term of three coordinates L*, a* and b*. L* represents the lightness of the color. An L* = 0 yields black and an L* = 100 indicates diffuse white. Specular white may attain L* values above 100. a* defines a color’s position between red and green. A negative a* value indicates green and positive values indicate red. b* defines a color’s position between blue and yellow. A negative b* value indicates blue and positive values indicate yellow.

The CIELCh color space is based on the CIELAB color space. In the CIELCh color space the lightness L* remains unchanged. However, the a* and b* are converted into the polar coordinates C*, for chroma/relative saturation, and h° for hue angle/angle of the hue in the CIELAB color wheel. The term “chroma” within this disclosure is well-known in the art and attributed its common meaning in this technical field. In some embodiments, the term “chroma” may refer to colorfulness of an area judged as a proportion of the brightness of a similarly illuminated area that appears white or highly transmitting. The C* may be derived from a* and b* by formula I:

C* = 7« ² + b ² (I)

The h° may be derived from a* and b* by formula II: h = atan

Further, based on the L*, a* and b* value a color-difference AEQ ₀ can be calculated based on ISO/CIE 11664-6:2014 - Colorimetry Part 6: CIEDE2000 Colour-difference formula. The ISO/CIE 11664-6:2014 - Colorimetry Part 6: CIEDE2000 Colour-difference formula, in particular the Colour-difference formula, are incorporated herein by reference.

A protocol for measuring the L*, a* and b* value is provided in the experimental section.

In some embodiments, an external surface of the lead may have an L*-value of at least 40 and wherein the lead comprises between about 11.0 wt.-% to about 20 wt.-%, more specifically between about 11 wt.-% to about 18 wt.-% and in particular between about 12 wt.-% to about 15 wt.-% ZrCh, relative to the total weight of the lead.

In some embodiments, the external surface of the lead may have an L*-value of less than 40 and wherein the lead comprises between about 0.5 wt.-% to about 10.9 wt.-%, more specifically between about 1 wt.-% to about 9 wt.-% and in particular between about 2 wt.-% to about 8 wt.- % ZrCh, relative to the total weight of the lead.

In some embodiments, the lead may comprise the ZrCh in the form of particles.

In some embodiments, the ZrCh particles may have a Dso between about 0.1 pm to about 17 pm, more specifically between about 0.2 pm to about 10 pm and even more specifically between about 0.3 pm to about 7 pm, in particular between about 0.3 pm to about 5 pm, in particular between about 0.4 pm to about 5 pm, and in particular between about 0.4 pm to about 2 pm . Dso is a measure for the particle size. Of a given sample, 50% of the particles have a particle size above the D50 and 50% have a particle size below D50. It has been surprisingly found that the particle size may influence the color of the lead. In particular, ZrCh of a smaller particle size may lead to an increased L*-value of the lead compared to ZrCh of a greater particle size. Hence, ZrCh of a smaller particle size may produce leads of lighter colors compared to ZrCh of greater particle size or ZrCh of a smaller particle size may be used in smaller amounts compared to ZrCh of greater particle size. Often leads are significantly darker compared to their deposit, in particular as the lightness of the deposit may be aided by the white color of the paper the deposit is formed upon. However, it may be preferable to produce leads of lighter colors as these more closely resemble the color of the final deposit. Further, the color of leads with a low L* may be harder to distinguish from other colors compared to leads with a higher L*. For example, two wax crayons may both produce a blue deposit of the same color, but a first wax crayon appears darker than a second wax crayon. It may be difficult for a user to distinguishing the first darker wax crayon from for example a black wax crayon.

It has been further surprisingly found, that for leads comprising ZrCh particles of a smaller particle size the color difference quantified as AEoo may be smaller between the lead and the deposit created by the lead. A smaller color difference AEoo may make it easier for a user to determine the color of a deposit a lead will produce by looking at the lead. Wax crayons are commonly supplied without a casing and may not even comprise a wrapping or the wrapping may be removed. As a result, the only way to distinguish wax crayons from one another and/or to determine which color the deposit may create, may be by looking at the surface of the wax crayon.

In some embodiments, the ZrCh particles may have a D90 between about 0.5 pm to about 50 pm, more specifically between about 0.5 pm to about 15 pm, in particular 1 pm to about 3 pm. D90 is a measure for the particle size. Of a given sample, 10% of the particles have a particle size above the D90 and 90% have a particle size below D90.

The D50 and D90 may be measured for example according to ISO 13320:2020.

In some embodiments, the ZrO2 particles may have a BET-value between about 0.5 m ² /g to about 22 m ² /g, more specifically between about 2.5 m ² /g to about 20 m ² /g, in particular about 4 m ² /g to about 20 m ² /g, and in particular about 4 m ² /g to about 18 m ² /g, measured according to DIN ISO 9277:2014-01. The BET-value is a measure for the specific surface area of a material, for example for ZrO2 particles. It has been surprisingly found, that leads comprising ZrCh particles of an increased BET -value the hue h* may be similar between the lead and an otherwise equal lead comprising TiCh in the amount of weight. Hence, it may be easier for suppliers to adjust their lead compositions by exchanging TiCh with the same amount of ZrCh particles.

In some embodiments, the lead may have a coefficient of friction between about 0.414 to about 0.5, more specifically between about 0.420 to about 0.48 and in particular between about 0.43 to about 0.46. An increased coefficient of friction may result in a greater deposit per area when marking a substrate. A greater deposit per area may increase the visibility and/or color intensity of the made marking. The coefficient of friction may be measured as described in the Experimental Section.

In some embodiments, the writing instrument may be a wax crayon.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may have a diameter between about 5 mm to about 35 mm, more specifically between about 6 mm to about 20 mm and in particular 7 mm to about 12 mm.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 90 wt.-% of one or more waxes, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 50 wt.-% to about 95 wt.-%, more specifically, between about 60 wt.-% to about 90 wt.-% and in particular between about 70 wt.-% to about 85 wt.-% of one or more waxes, relative to the total weight of the lead.

In some further alternative embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 45 wt.-%, more specifically, between about 15 wt.-% to about 40 wt.-% and in particular between about 20 wt.-% to about 30 wt.-% of one or more waxes, relative to the total weight of the lead.

The term “wax,” in the present disclosure is intended to be used as is well-established in the field of writing instruments and is, in particular, meant to refer to a lipophilic (fatty) compound that is solid at e.g. room temperature (e.g. about 25 °C) with a reversible solid/liquid change of state. The method of measuring the melting point of the wax is not particularly limited and may be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 3 by the company Mettler Toledo.

Amongst the aforementioned waxes, the present disclosure relates to waxes having a melting point of at least about 40°C and a solubility water at about 25°C of less than about 1000 mg/L. These properties may help in providing a relatively water-insoluble solid base matrix for the writing instrument, in particular for a wax crayon, for the dispersion of the pigment therein. In some embodiments, the one or more waxes may have a melting point of at least about 35°C, more specifically at least about 50°C and in particular at least about 75°C. In some embodiments, the wax may have a melting point range of between about 35°C and about 200°C, more specifically between about 55°C and about 180°C, and in particular between about 75°C and about 150°C.

In some embodiments, the wax may have a solubility in water at about 25°C of less than about 100 mg/L, more specifically a solubility of less than about 10 mg/L, and in particular a solubility of less than about 1 mg/L. In some embodiments, the wax may be substantially insoluble or insoluble in water at about 25 °C. The method of determining the solubility of the wax is not particularly limited and may be performed by any suitable means, for instance using a USP Dissolution Apparatus 2 (paddle type).

In some embodiments, the one or more waxes may comprise one or more apolar waxes. Examples of such apolar waxes include paraffin waxes, microcrystalline waxes, ozokerine and Fisher-Tropsch waxes. Apolar waxes may be hydrocarbon-based and may be substantially free or free of polar groups.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 45 wt.-%, more specifically, between about 15 wt.-% to about 35 wt.-% and in particular between about 18.5 wt.-% to about 27 wt.-% of a polymer, more specifically a thermoplast even more specifically an olefine and in particular polyethylene or polypropylene, relative to the total weight of the lead. The polymer may increase the leads resistance to breaking. The addition of the polymer may increase the leads modulus of elasticity and/or hardness. In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 1 wt.-% to about 20 wt.-%, more specifically, between about 3 wt.-% to about 17 wt.-% and in particular between about 5 wt.-% to about 15 wt.-% of a fatty acid or salt thereof, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the fatty acid or salt may comprise a monovalent linear or branched saturated or unsaturated carboxylic acid salt having between about 8 to about 24 carbon atoms, more specifically a monovalent linear saturated carboxylic acid salt having between about 16 to about 20 carbon atoms, and in particular stearic acid, calcium stearate, zinc stearate or mixtures thereof. The fatty acid and/or fatty acid salts may improve the smoothness of writing and/or drawing, in particular by improving the glide. Moreover, the fatty acid and/or fatty acid salt may increase the laydown and thereby the quality of the deposit. Fatty acids may migrate to the surface of the lead, which may lead to the formation of a fatty film, which may be unpleasant to the user. Fatty acid salts may be in some instances advantageous as they have a reduced tendency to migrate to the surface of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise a filler, in particular a hydrous aluminum phyllosilicate and/or an alkali and/or earth alkali carbonate.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 10 wt.-% to about 50 wt.-%, more specifically, between about 17 wt.-% to about 40 wt.-% and in particular between about 23.5 wt.-% to about 32 wt.-% of the filler, relative to the total weight of the lead. Some fillers, in particular kaolinite, may comprise a layered structure. As a result, filler, such as kaolinite, may improve the laydown of a lead by providing surfaces where along shearing action may occur. Additionally, the fillers may decrease the price of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.-% to about 25 wt.-% and in particular between about 15 wt.-% to about 20 wt.-% of the hydrous aluminum phyllosilicate, more specifically a layered hydrous aluminum phyllosilicate and in particular kaolinite, relative to the total weight of the lead. In some embodiments, the hydrous aluminum phyllosilicate may be at least partly or fully substituted in mica and/or talc. In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 5 wt.-% to about 20 wt.-%, more specifically, between about 7 wt.-% to about 15 wt.-% and in particular between about 8.5 wt.-% to about 12 wt.-% of the alkali and/or earth alkali carbonate, more specifically an earth alkali carbonate and in particular calcium carbonate, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 0.5 wt.-% to about 5 wt.-%, more specifically between about 1 wt.-% to about 3.5 wt.-% and in particular between about 1.5 wt.-% to about 2.5 wt.-% of a plasticizer, more specifically of a phthalic acid ester and in particular of C7-C9 alkyl benzyl phthalate, relative to the total weight of the lead. The plasticizer may soften the lead and thereby increase the laydown of the lead, which in turn may improve the visibility and/or intensity of the deposit.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 2 wt.-% to about 20 wt.-%, more specifically between about 4 wt.-% to about 15 wt.-% and in particular between about 7 wt.-% to about 11 wt.-% of a processing aid, more specifically a lubricant and in particular tetrastearate pentaerythritol. The processing aid may improve manufacturing efficiency of the lead. In particular, as the ZrCh has been shown to lead to a higher coefficient of friction, the manufacturing may be improved by adding processing aids, more specifically a lubricant and in particular tetrastearate pentaerythritol.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 0.05 wt.-% to about 10 wt.-%, more specifically between about 0.05 wt.-% to about 7 wt.-% and in particular between about 0.1 wt.-% to about 5 wt.-% of one or more colorants, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a wax crayon, the lead may comprise between about 0.05 wt.-% to about 10 wt.-%, more specifically between about 0.05 wt.-% to about 7 wt.-% and in particular between about 0.1 wt.-% to about 5 wt.-% of one or more pigments, relative to the total weight of the lead. The one or more colorant and/or pigments may adjust the color of the lead. For example, the addition of a blue pigment may lead to a blue lead. The term “pigment” and “colorant” used within this disclosure are well known in the art. Within this disclosure the proportions attributed to “pigments” and “colorants” shall not apply to ZrCh or TiCh.

In some embodiments, in particular wherein the writing instrument is a pencil, the writing instrument may comprise a casing and the lead may be comprised within the casing.

In some embodiments, in particular wherein the writing instrument is a pencil, the lead may have a diameter of between about 2.0 mm to about 4.5 mm, more specifically between about 2.3 mm to about 4.2 mm and in particular between about 2.8 mm to about 4.0 mm.

In some embodiments, in particular wherein the writing instrument is a pencil, the lead may comprise between about 5 wt.-% to about 80 wt.-%, more specifically, between about 5 wt.-% to about 60 wt.-%, more specifically, between about 10 wt.-% to about 55 wt.-% and in particular between about 15 wt.-% to about 50 wt.-% of a hydrous aluminum phyllosilicate, more specifically a layered hydrous aluminum phyllosilicate and in particular kaolinite, relative to the total weight of the lead. In some embodiments, the hydrous aluminum phyllosilicate may be at least partly or fully substituted in mica and/or talc.

In some embodiments, in particular wherein the writing instrument is a pencil, the lead may comprise between about 1 wt.-% to about 20 wt.-%, more specifically, between about 3 wt.-% to about 17 wt.-% and in particular between about 5 wt.-% to about 15 wt.-% of a fatty acid or salt thereof, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a pencil, the fatty acid or salt may comprise a monovalent linear or branched saturated or unsaturated carboxylic acid salt having between about 8 to about 24 carbon atoms, more specifically a monovalent linear saturated carboxylic acid salt having between about 16 to about 20 carbon atoms, and in particular stearic acid, calcium stearate, zinc stearate or mixtures thereof.

In some embodiments, in particular wherein the writing instrument is a pencil, the lead may comprise between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.- % to about 25 wt.-% and in particular between about 13 wt.-% to about 17 wt.-% of one or more colorants, relative to the total weight of the lead. In some embodiments, in particular wherein the writing instrument is a pencil, the lead may comprise between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.- % to about 25 wt.-% and in particular between about 13 wt.-% to about 17 wt.-% of one or more pigments, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a pencil, the lead may comprise between about 3 wt.-% to about 50 wt.-%, more specifically, between about 10 wt.- % to about 50 wt.-%, more specifically, between about 15 wt.-% to about 45 wt.-% and in particular between about 20 wt.-% to about 40 wt.-% of a binder, more specifically a polymeric binder, and in particular styrenic polymers such as polystyrene and/or acrylonitrile butadiene styrene, relative to the total weight of the lead.

In some embodiments, in particular wherein the writing instrument is a pencil, the lead may comprise between about 0.5 wt.-% to about 10 wt.-%, more specifically between about 2 wt.- % to about 8 wt.-% and in particular between about 3.5 wt.-% to about 6.5 wt.-% of a plasticizer, more specifically of a benzoate ester.

In some embodiments, the writing instrument may be a chalk.

In some embodiments, the lead may comprise about 0.005 wt.-% to about 3.45 wt.-% of one or more metal oxides or transition metal oxide from the second, third, fourth and/or thirteenth group of the periodic table, relative to the total weight of the lead.

In some embodiments, the lead may comprise about 1.0 wt.-% to about 14.6 wt.-% of one or more metal oxides or transition metal oxides from the second, third, fourth and/or thirteenth group of the periodic table, relative to the total weight of the ZrCh.

In some embodiments, the lead may comprise Y2O3, HfCh, MgO, CaO and/or Ce2Os, in particular HfCh and/or Y2O3, and in particular Y2O3. The aforementioned metal oxides and/or transition metal oxides may be used to increase the mechanic properties of the ZrCh. For writing instruments, in particular chalks or pencils, this may be useful as the ZrCh may not only constitute the pigment, but also a structural component. As a result, the mechanical stability of the lead may be increased. The ZrCh may be stabilized prior to the addition of the pigment to the lead or the process may occur during manufacturing of the lead, for example during the calcination.

In some embodiments, the lead may be devoid, or substantially devoid of MgO and/or CaO.

In some embodiments, the lead may comprise less than 0.05% of SiCh, more specifically less than 0.04% of SiCh, and even more specifically less than 0.03% of SiCh, relative to the total weight of the lead.

In some embodiments, the lead may comprise ZnO and/or ZnS. ZnO and ZnS may further increase the colorimetric properties of the lead, in particular the L* -value.

Experimental Section

Experiments to determine the influence of different ZrCh compositions on the colorimetric values and coefficient of friction of leads were performed. The results were also compared to a TiCh composition. Wax crayon compositions were used for the tests. The compositions are provided in Table 2.

The following steps were performed to manufacture the test specimen with a composition according to Table 2:

1) Mix all components.

2) Set a thermostatic bath (For example, AMETEK Brookfield TC-202) to a temperature of 150 °C and add a mixing vessel into the thermostatic bath.

3) Add the mixture to the mixing vessel in the thermostatic bath.

4) Stir the mixture of neutral base and colorant at 2000 rpm with a butterfly tool attached to the DISPERMAT CV3 Plus by VMA-Getzmann GmbH for 2 hours.

5) Remove butterfly tool and fill molten mixture into a cubic mold of the dimensions: 25 mm x 100 mm x 10 mm.

6) Let mixture cool and subsequently remove the finished specimen from the mold. Table 1 shows the properties of different types of ZrO ₂ and TiCh used to manufacture the Test specimen according to Table 2.

Table 1 - Properties of ZrCh powders.

Table 2 - Compositions of Test Specimen for Tests Colorimetry of deposits - Test Setup:

All colorimetric measurements on deposits have been performed on deposits created on a white paper AURORA ISO-12757.

To create the deposit a Writing apparatus HST 10 by the company HUTT Maschinenbau from Germany was used under the conditions described in Table 3. Further, to measure the colorimetric data in the CIE L*a*b* color space, e.g. L*, a* and b*a KONICA MINOLTA CM- 3610 A spectrophotometer was used. The following setting were applied for the KONICA MINOLTA CM-3610 A spectrophotometer: illuminant: D65, angle: 10°, specular components: included.

Table 3 - Parameters for producing the deposits for colorimetry.

The test for the deposit’s colorimetric measurement was carried out by the following protocol:

1. Place the writing article in the appropriate supports;

2. Produce a deposit according to the parameters specified in Table 3;

3. Measure the colorimetric data of the deposit with the KONICA MINOLTA CM-3610 A spectrophotometer with an opening of measurement at 25.4mm. Colorimetry of deposits - Test Setup:

All colorimetric measurements done on a surface of a crayon were performed using a KONICA MINOLTA CM-3610 A spectrophotometer with an opening of measurement at 4mm. For colorimetric measurements of the surface of a crayon, the crayon’s surface is placed in direct contact with the lens of the spectrophotometer.

Friction Tests Setup:

All coefficient of friction measurements have been performed on a white paper AURORA ISO- 12757. A TriboLab UMT by the company Bruker Corporation with a sensor DFH-5.0 was used to measure the coefficient of friction.

Table 4 - Parameters for measuring the coefficient of friction.

Results of the Tests

Table 5 Results of Colorimetry Tests The results Table 5 shows that a smaller particle size may lead to an increased L*-value. Further, the results show that a smaller particle size may lead to a lower AE00 value. Additionally, the results in Table 5 show, that a higher BET -value may result in a lead with a hue h° closer to that of TiCh.

Results of the Friction Tests

Table 6 Results of Friction Tests

The results Table 6 shows that a smaller particle size and increased BET-value may lead to an increased Coefficient of Friction. The coefficient of friction of ZrCh may surpass that of TiCh compositions. In particular, ZrCh of smaller particle sizes may lead to a higher coefficient of friction compared to TiCh, which in turn may increase the laydown of the writing instrument.

The present disclosure furthermore relates to the following aspects.

Aspects

1. A writing instrument comprising a lead, wherein the lead comprises at least about 0.5 wt.- % ZrCh, relative to the total weight of the lead, in particular wherein the lead comprises less than about 0.5 wt.-%, more specifically less than about 0.2 wt.-% and in particular substantially no or no TiCh.

2. The writing instrument according to aspect 1, wherein the lead comprises between about

1 wt.-% to about 25 wt.-%, more specifically between about 2 wt.-% to about 20 wt.-%, even more specifically between about 5 wt.-% to about 20 wt.-%, and in particular between about 11 wt.-% to about 15 wt.-% ZrCh, relative to the total weight of the lead.

3. The writing instrument according to any one of aspects 1 or 2, wherein an external surface of the lead has an L*-value of at least 40 and wherein the lead comprises between about 11.0 wt.-% to about 20 wt.-%, more specifically between about 11 wt.-% to about 18 wt.- % and in particular between about 12 wt.-% to about 15 wt.-% ZrCh, relative to the total weight of the lead.

4. The writing instrument according to any one of aspects 1 or 2, wherein the external surface of the lead has an L*-value of less than 40 and wherein the lead comprises between about 0.5 wt.-% to about 10.9 wt.-%, more specifically between about 1 wt.-% to about 9 wt.-% and in particular between about 2 wt.-% to about 8 wt.-% ZrCh, relative to the total weight of the lead.

5. The writing instrument according to any preceding aspect, wherein the lead comprises the ZrCh in the form of particles.

6. The writing instrument according to aspect 5, wherein the ZrCh particles have a Dso between about 0.1 pm to about 17 pm, more specifically between about 0.2 pm to about 10 pm and even more specifically between about 0.3 pm to about 7 pm, in particular between about 0.3 pm to about 5 pm, and in particular between about 0.4 pm to about

2 pm. 7. The writing instrument according to aspect 5 or 6, wherein the ZrCh particles have a D90 between about 0.5 pm to about 50 pm, more specifically between about 0.5 pm to about 15 pm, in particular 1 pm to about 3 pm.

8. The writing instrument according to any preceding aspect, the wherein ZrCh particles have a BET-value between about 0.5 m ² /g to about 22 m ² /g, more specifically between about 2.5 m ² /g to about 20 m ² /g, in particular about 4 m ² /g to about 20 m ² /g and in particular about 4 m ² /g to about 18 m ² /g, measured according to DIN ISO 9277:2014-01.

9. The writing instrument according to any preceding aspect, wherein the lead has a coefficient of friction between about 0.414 to about 0.5, more specifically between about 0.420 to about 0.48 and in particular between about 0.43 to about 0.46.

10. The writing instrument according to any preceding aspect, wherein the writing instrument comprises a casing and the lead is comprised within the casing.

11. The writing instrument according to any preceding aspect, wherein the lead has a diameter of between about 2.0 mm to about 4.5 mm, more specifically between about 2.3 mm to about 4.2 mm and in particular between about 2.8 mm to about 4.0 mm.

12. The writing instrument according to any preceding aspect, wherein the lead has a diameter between about 5 mm to about 35 mm, more specifically between about 6 mm to about 20 mm and in particular 7 mm to about 12 mm.

13. The writing instrument according to any preceding aspect, wherein the lead comprises about 0.005 wt.-% to about 3.45 wt.-% of one or more metal oxides or transition metal oxide from the second, third, fourth and/or thirteenth group of the periodic table, relative to the total weight of the lead.

14. The writing instrument according to any preceding aspect, wherein the lead comprises about 1.0 wt.-% to about 14.6 wt.-% of one or more metal oxides or transition metal oxides from the second, third, fourth and/or thirteenth group of the periodic table, relative to the total weight of the ZrCh. 15. The writing instrument according to any preceding aspect, wherein the lead comprises Y2O3, HfCh, MgO, CaO and/or Ce20s, in particular HfCh and/or Y2O3, and in particular Y2O3.

16. The writing instrument according to any preceding aspect, wherein the lead is devoid, or substantially devoid of MgO and/or CaO.

17. The writing instrument according to any preceding aspect, wherein the lead comprises less than 0.05% of SiO2, more specifically less than 0.04% of SiO2, and even more specifically less than 0.03% of SiO2, relative to the total weight of the lead.

18. The writing instrument according to any preceding aspect, wherein the lead comprises between about 10 wt.-% to about 90 wt.-% of one or more waxes, relative to the total weight of the lead.

19. The writing instrument according to any preceding aspect, wherein the lead comprises between about 50 wt.-% to about 95 wt.-%, more specifically, between about 60 wt.-% to about 90 wt.-% and in particular between about 70 wt.-% to about 85 wt.-% of the one or more waxes, relative to the total weight of the lead. 0. The writing instrument according to any preceding aspect, wherein the lead comprises between about 10 wt.-% to about 45 wt.-%, more specifically, between about 15 wt.-% to about 40 wt.-% and in particular between about 20 wt.-% to about 30 wt.-% of the one or more waxes, relative to the total weight of the lead. 1. The writing instrument according to any preceding aspect, wherein the lead comprises between about 10 wt.-% to about 45 wt.-%, more specifically, between about 15 wt.-% to about 35 wt.-% and in particular between about 18.5 wt.-% to about 27 wt.-% of a polymer, more specifically a thermoplast even more specifically an olefine and in particular polyethylene or polypropylene, relative to the total weight of the lead. 2. The writing instrument according to any preceding aspect, wherein the lead comprises between about 1 wt.-% to about 20 wt.-%, more specifically, between about 3 wt.-% to about 17 wt.-% and in particular between about 5 wt.-% to about 15 wt.-% of a fatty acid or salt thereof, relative to the total weight of the lead.

23. The writing instrument according to any preceding aspect, wherein the lead comprises a fatty acid salt, wherein the fatty acid or salt comprises a monovalent linear or branched saturated or unsaturated carboxylic acid salt having between about 8 to about 24 carbon atoms, more specifically a monovalent linear saturated carboxylic acid salt having between about 16 to about 20 carbon atoms, and in particular stearic acid, calcium stearate, zinc stearate or mixtures thereof.

24. The writing instrument according to any preceding aspect, wherein the lead comprises a filler, in particular a hydrous aluminum phyllosilicate and/or an alkali and/or earth alkali carbonate.

25. The writing instrument according to aspect 24, wherein the lead comprises between about 10 wt.-% to about 50 wt.-%, more specifically, between about 17 wt.-% to about 40 wt.-% and in particular between about 23.5 wt.-% to about 32 wt.-% of the filler, relative to the total weight of the lead.

26. The writing instrument according to aspect 24 or 25, wherein the lead comprises between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.-% to about 25 wt.-% and in particular between about 15 wt.-% to about 20 wt.-% of a hydrous aluminum phyllosilicate, more specifically a layered hydrous aluminum phyllosilicate and in particular kaolinite, relative to the total weight of the lead.

27. The writing instrument according to any one of aspect 24 to 26, wherein the lead comprises between about 5 wt.-% to about 20 wt.-%, more specifically, between about 7 wt.-% to about 15 wt.-% and in particular between about 8.5 wt.-% to about 12 wt.-% of an alkali and/or earth alkali carbonate, more specifically an earth alkali carbonate and in particular calcium carbonate, relative to the total weight of the lead.

28. The writing instrument according to any preceding aspect, wherein the lead comprises between about 2 wt.-% to about 20 wt.-%, more specifically between about 4 wt.-% to about 15 wt.-% and in particular between about 7 wt.-% to about 11 wt.-% of a processing aid, more specifically a lubricant and in particular tetrastearate pentaerythritol.

29. The writing instrument according to any preceding aspect, wherein the lead comprises between about 0.5 wt.-% to about 5 wt.-%, more specifically between about 1 wt.-% to about 3.5 wt.-% and in particular between about 1.5 wt.-% to about 2.5 wt.-% of a plasticizer, more specifically of a phthalic acid ester and in particular of C7-C9 alkyl benzyl phthalate, relative to the total weight of the lead.

30. The writing instrument according to any preceding aspect, wherein the lead comprises between about 0.05 wt.-% to about 10 wt.-%, more specifically between about 0.05 wt.-% to about 7 wt.-% and in particular between about 0.1 wt.-% to about 5 wt.-% of one or more pigments, relative to the total weight of the lead.

31. The writing instrument according to any one of aspects 24 or 28 to 30 when dependent on aspect 22, wherein the lead comprises between about 5 wt.-% to about 80 wt.-%, more specifically, between about 10 wt.-% to about 60 wt.-%, more specifically, between about 15 wt.-% to about 55 wt.-% and in particular between about 15 wt.-% to about 50 wt.-% of a hydrous aluminum phyllosilicate, more specifically a layered hydrous aluminum phyllosilicate and in particular kaolinite, relative to the total weight of the lead.

32. The writing instrument according to any one of aspect 1 to 29 or 31, wherein the lead comprises between about 5 wt.-% to about 30 wt.-%, more specifically, between about 10 wt.-% to about 25 wt.-% and in particular between about 13 wt.-% to about 17 wt.-% of a pigment, relative to the total weight of the lead.

33. The writing instrument according to any preceding aspect, wherein the lead comprises between about 3 wt.-% to about 50 wt.-%, more specifically, between about 10 wt.-% to about 50 wt.-%, more specifically, between about 15 wt.-% to about 45 wt.-% and in particular between about 20 wt.-% to about 40 wt.-% of a binder, more specifically a polymeric binder, and in particular styrenic polymers such as polystyrene and/or acrylonitrile butadiene styrene, relative to the total weight of the lead. 34. The writing instrument according to any preceding aspect, wherein the lead comprises ZnS or ZnO.