Compositions for coloring substrates and uses thereof - Patents.com

Abstract

The present invention relates to a composition for coloring a substrate, the composition comprising 10 to 70 wt. % of water; 0.025 to 12.5 wt. % of a colorant; and 0.1 to 10 wt. % of a tetrahydric alcohol, each of which is based on the total weight of the composition, wherein the tetrahydric alcohol has at least one carbon atom; and to use of the composition for coloring a substrate to produce a film on the substrate.

Description

[Technical Field]

[0001] The present invention relates to a composition for coloring a substrate.

[0002] The present invention also relates to the use of the composition for coloring a substrate to produce a film on the substrate.

[0003] Background of the Invention Aqueous writing fluids, such as inks, are known from the prior art and generally contain water as a solvent and pigments or water-soluble dyes as colorants, and generally contain further additives, such as surfactants, emulsifiers, preservatives or humectants.

[0004] Pigmented inks (paints) have been known for many years, especially for artistic purposes (drawing, sketching, etc.). These are often formulated with plastic dispersions as binders and / or wetting agents.

[0005] The "cap-off time (COT)" of a writing fluid refers to the period of time during which the writing fluid will not dry out and harden when stored in a writing instrument or applicator with the writing tip open or uncapped. In practical use of a writing fluid, it is advantageous for the writing instrument or other applicator to be able to remain bare for a relatively long period of time, preferably several hours or days, without the writing fluid drying out and hardening.

[0006] The aqueous writing fluids known from the prior art can be divided into three groups:

[0007] a) Inks that are intended to have a very good COT. These contain a high content of so-called drying retardants or humectants to prevent the writing tip from starting to dry out or drying out completely (fineliner, fiber painter). Due to the high proportion of drying retardants or humectants, such inks can only contain a small amount of binder. As a result, the writing tip generally has a very long drying time and is not very durable. Such writing fluids are generally only suitable for absorbent substrates, such as paper.

[0008] b) Inks intended to dry quickly and permanently on non-absorbent substrates. Unfortunately, these inks usually have a completely unsatisfactory COT.

[0009] c) Inks that offer a compromise between a) & b), i.e. have good COT and satisfactory resistance, but are only effective on absorbent substrates.

[0010] EP 3613814, for example, describes a writing, marking and / or drawing liquid containing an aqueous pigment formulation, a binder, a base and a dispersing wetting agent, the dispersing wetting agent being an aqueous solution of a modified polymer having pigment-affinic groups.

[0011] Pigment liner inks known from the prior art contain 20% by weight of urea plus 15% of a humectant to achieve a COT of 18 hours. The addition of urea ensures a satisfactory rapid drying time at the end of writing, even on moderately absorbent substrates, and also provides a practical resistance to drying after a relatively long time, during which the urea crystallizes.

[0012] On the other hand, on unsuitable, poorly absorbent paper types, or even sheet-coated substrates (e.g., photographic prints, laminated papers, etc.), the inks dry unsatisfactorily or become resistant to drying even after hours or days. As a result, the inks smear or transfer to the touch. Furthermore, a high urea content impairs the waterfastness of the inks, and when the ink is stored for a relatively long period of time (especially at high temperatures according to the T50 storage test), the urea decomposes in the alkaline range to produce CO2 and ammonia, which tends to further increase the pH. As a result, the ink gradually becomes unstable.

[0013] For about 20 years, so-called "dry-safe" technology has offered a solution to this problem: alcohol-based inks (Lumocolor permanent, whiteboard markers) that not only offer good COT and short drying times, but also very good resistance. In this case, a special wax additive, which dissolves moderately in the ink, prevents it from drying out. During this process, the saturated wax precipitates from the tip if the nib is left "bare," forming an extremely thin barrier film that prevents further solvent loss and therefore drying out. However, this film is mechanically very unstable; it breaks even with the slightest contact of the tip with the substrate, allowing the ink to flow immediately. No corresponding solution exists for water-based writing fluids.

[0014] Problem to be solved by the invention The object of the present invention is therefore to provide an aqueous writing liquid which overcomes the drawbacks of the prior art, in particular an aqueous writing liquid which has an excellent cap-off time (COT) and nevertheless has a very short drying time and has good durability even on all kinds of substrates, in particular on non-absorbent surfaces, and preferably a corresponding aqueous writing liquid which has a reduced proportion of urea or does not contain urea at all.

[0015] Disclosure of the Invention This problem is solved according to the subject matter of the independent claims. Preferred embodiments emerge from the dependent claims and the following description.

[0016] The problem is particularly solved by a composition for coloring a substrate, which comprises Each based on the total weight of the composition - 10-70% by weight of water; 0.1 to 50% by weight of a colorant; and - 1 to 6% by weight of tetrahydric alcohol Including, The tetrahydric alcohol has at least 5 carbon atoms. This is solved by the composition.

[0017] This problem is further solved by the use of a composition according to the invention for coloring a substrate, for producing a film on an absorbent substrate.

[0018] Composition for coloring a substrate The compositions according to the invention are suitable for, and preferably proposed for, coloring substrates.

[0019] Coloring The colouring advantageously comprises or consists of writing, drawing, painting, printing, spraying or a combination of two or more thereof.

[0020] Base material The substrate is preferably an absorbent substrate, such as an absorbent writing medium, more preferably drawing paper or paper, particularly preferably watercolor paper, or a non-absorbent substrate, such as a synthetic or plastic substrate, particularly preferably a synthetic or plastic sheet, or a mixed-media substrate, i.e., one made of, for example, absorbent and non-absorbent material, or canvas. Likewise, any further suitable substrate, such as wood, stone, eggshell, etc., may be proposed.

[0021] water The composition for coloring a substrate according to the present invention contains water in an amount of 10 to 70% by weight based on the total weight of the composition. It is preferable to use deionized water or demineralized water as the water. This makes it possible to avoid the inclusion of unwanted impurities, such as hardness components such as calcium and magnesium.

[0022] It may be proposed that the composition contains water as the main solvent, advantageously in an amount of at least 90% by volume, based on the total amount of solvents in the composition. It is particularly preferred that the composition contains water as the only solvent.

[0023] The composition preferably contains water in an amount of at least 15% by weight, especially preferably at least 20% by weight, most preferably at least 25% by weight, each based on the total weight of the composition.

[0024] Preferably, the composition contains water in an amount of at most 65 wt.%, further preferably at most 60 wt.%, even more preferably at most 55 wt.%, even more preferably at most 50 wt.%, and most preferably at most 45 wt.%, for example at most 40 wt.%, each based on the total weight of the composition.

[0025] The composition preferably contains water in an amount of 15 to 65% by weight, more preferably 20 to 40% by weight, most preferably 25 to 35% by weight, for example about 30% by weight, each based on the total weight of the composition.

[0026] With the specified preferred amount of water in the composition, it was possible to achieve optimized coloring on the one hand and practicality on the other hand.

[0027] Further solvents It may be proposed that water is the only solvent in the composition according to the invention for coloring a substrate. Alternatively, it may be proposed that the composition according to the invention for coloring a substrate comprises a further solvent in addition to water.

[0028] It may be proposed that the composition for coloring a substrate contains a further solvent in an amount of at least 1% by weight, particularly preferably at least 5% by weight, most preferably at least 10% by weight, each based on the total weight of the composition.

[0029] Preferably, the composition for coloring a substrate contains a further solvent in an amount of at most 40 wt.-%, further preferably at most 35 wt.-%, even more preferably at most 30 wt.-%, more preferably at most 20 wt.-%, and most preferably at most 15 wt.-%, each based on the total weight of the composition.

[0030] The composition for coloring a substrate preferably contains a further solvent in an amount of 1 to 40% by weight, further preferably 5 to 20% by weight, most preferably 10 to 15% by weight, each based on the total weight of the composition.

[0031] Preferably, the further solvent is a water-soluble organic solvent, more preferably an alcohol, even more preferably a polyhydric alcohol, most preferably glycerin or a glycol, such as 1,2-propanediol.

[0032] By adding further solvents to the compositions according to the invention, an improved dissolution behavior of substances that are sparingly soluble in water, such as pigments or other colorants, can be achieved.

[0033] Additionally, the effectiveness of tetrahydric alcohols as cap-off additives can be synergistically enhanced. Finally, the addition of suitable solvents can favorably affect film formation and therefore end-of-write durability.

[0034] coloring agent The composition according to the present invention for coloring a substrate contains the colorant in an amount of 0.025 to 12.5% ​​by weight, based on the total weight of the composition.

[0035] The colorant is preferably a dye, a pigment, or a mixture of two or more thereof.

[0036] As dyes, in particular water-soluble dyes can be used, advantageously food dyes and / or water-soluble dyes based on acidic and / or basic dyes.

[0037] Dyes mentioned below: Food colours from the following group: E 110, CI 15985, Food Yellow No. 3; E 104, CI 47005, Food Yellow No. 13; E 102, CI 19140, Food Yellow No. 4; E 124, CI 16255, Food Red No. 7; E 127, CI 45430, Food Red No. 14; E 133, CI 42090, Food Blue No. 2; E 131, CI 42051, Food Blue No. 3 and / or Acid dyes from the following groups: Acid Yellow 23, CI 1910; Acid Red 18, CI 16255; Acid Red 51, CI 45430; Acid Orange 4, CI 16230; Acid Blue 93; Acid Blue 9, CI 42090; Acid Blue 104, CI 42735; Acid Violet 49, CI 42640 has proven to be particularly suitable.

[0038] Basic dyes, advantageously from the group of the xanthene, coumarin and rhodamine dyes, such as Basic Violet 11, Basic Yellow 40, Basic Blue 3, Basic Blue 7, Basic Red 1, Basic Green 1.

[0039] As pigments, advantageously organic pigments can be used, further preferably quinacridone, phthalocyanine, metal complex, dioxazine, isoindoline, isoindolinone, benzimidazolone, anthraquinone, arylide, perinone, perylene, naphthol, diketopyrrolopyrrole or azo pigments, particularly preferably Magenta Red PR122 or other quinacridones and / or inorganic pigments such as titanium dioxide, iron oxide, ultramarine or carbon black.

[0040] The colorants specified as preferred allow particularly vivid, intense, and stable coloring to be achieved. The composition preferably contains the colorant in an amount of at least 0.05% by weight, particularly preferably at least 0.075% by weight, each based on the total weight of the composition.

[0041] Preferably, the composition contains a colorant (or colorant blend) in an amount of at most 11.25 wt.-%, further preferably at most 10 wt.-%, even more preferably at most 8.75 wt.-%, more preferably at most 7.5 wt.-%, and most preferably at most 6.25 wt.-%, for example at most 5 wt.-%, each based on the total weight of the composition.

[0042] It may be proposed that the pigments are present and used as components of pigment preparations.

[0043] The composition preferably contains the colorant in an amount of 0.025 to 10 wt %, more preferably 0.05 to 7.5 wt %, and most preferably 0.075 to 5 wt %, each based on the total weight of the composition.

[0044] When the colorant is a dye, the composition preferably contains the colorant in an amount of 0.025 to 3 wt %, more preferably 0.05 to 2 wt %, and most preferably about 0.1 to 1 wt %, each based on the total weight of the composition.

[0045] When the colorant is a pigment, the composition preferably comprises the colorant in an amount of 0.25 to 10 wt. %, more preferably 1.25 to 7.5 wt. %, most preferably 2.5 to 5 wt. %, for example about 4.8 wt. %, each based on the total weight of the composition.

[0046] For pastel shades, the pigment content can be reduced to 0.025% by weight.

[0047] The amount of colorant specified as preferred allows optimum coloration to be achieved.

[0048] tetrahydric alcohol The composition according to the invention for coloring a substrate contains 0.1 to 10% by weight of a tetrahydric alcohol, based on the total weight of the composition.

[0049] The tetrahydric alcohol has at least 5 carbon atoms, advantageously up to 22 carbon atoms, further preferably 5 to 18 carbon atoms, even more preferably 5 to 15 carbon atoms, also preferably 5 to 12 carbon atoms, most preferably 5 to 12 carbon atoms.

[0050] The tetrahydric alcohol is advantageously contained in an amount of at least 1% by weight, further preferably at least 2% by weight, even more preferably at least 3% by weight and most preferably at least 4% by weight, based on the total weight of the composition.

[0051] The tetrahydric alcohol is advantageously contained in an amount of at most 9% by weight, further preferably at most 8% by weight, even more preferably at most 7% by weight and most preferably at most 6% by weight, based on the total weight of the composition.

[0052] The tetrahydric alcohol is advantageously contained in an amount of 1 to 9% by weight, further preferably 2 to 8% by weight, even more preferably 3 to 7% by weight, most preferably 4 to 6% by weight, for example about 5% by weight, based on the total weight of the composition.

[0053] Alcohol refers to an organic compound that has one or more functional hydroxyl groups (-OH). Polyhydric alcohols have multiple hydroxyl groups. Tetrahydric alcohols have four hydroxyl groups.

[0054] The tetrahydric alcohols contained in the compositions according to the invention for coloring substrates have, in addition to the four hydroxyl groups, an organic moiety having at least 5 carbon atoms, which may be a hydrocarbylene group, in particular a C5-C 22 , advantageously C5~C 18 , more preferably C5 to C 15, and more preferably C5 to C 12 , most preferably C5 to C 10 Hydrocarbylene or heterohydrocarbylene groups, especially C5-C 21 , advantageously C5~C 18 , more preferably C5 to C 15 , and more preferably C5 to C 12 , most preferably C5 to C 10 It may be a heterohydrocarbylene group.

[0055] According to the IUPAC definition, hydrocarbyl refers to a monovalent group resulting from the removal of one hydrogen atom H from a hydrocarbon molecule. Accordingly, according to the present application, a hydrocarbylene group results from the removal of at least one hydrogen atom H, in particular four hydrogen atoms, from a hydrocarbon molecule.

[0056] Heterohydrocarbylene groups according to the present disclosure are hydrocarbylene groups in which at least one of the carbon atoms has been replaced with a heteroatom, in particular a heteroatom selected from the group consisting of O, N, S and P.

[0057] The hydrocarbylene group may be an alkylene group, an arylene group, an alkene group, an alkyne group, an alkylarylene group, an arylalkylene group, etc. The hydrocarbylene group may be an alkylene group.

[0058] The hydrocarbylene group is particularly preferably C5-C 22 Alkyl groups, preferably C5-C 18 Alkyl groups, more preferably C5 to C 15 Alkyl groups, more preferably C5 to C 12 Alkyl groups, most preferably C5-C 10 It may be an alkyl group.

[0059] It is especially preferred that the hydrocarbylene group is a tert-pentylene group.

[0060] A heterohydrocarbylene group can contain, between two or more hydrocarbylene groups, one or more ether groups, thioether groups, amine groups, particularly secondary amine groups, alkylphosphine groups, etc. A heterohydrocarbylene group can contain an ether group between two hydrocarbylene groups.

[0061] The heterohydrocarbylene group is a C5-C 22 Heteroalkyl groups, preferably C5-C 18 Heteroalkyl groups, more preferably C5 to C 15 Heteroalkyl groups, more preferably C5-C 12 Heteroalkyl groups, most preferably C5-C 10 It may be a heteroalkyl group. In this context, a heteroalkyl group is an alkyl group in which one or more carbon atoms have been replaced by one or more heteroatoms (e.g., O, S, N, or P).

[0062] Advantageously, the heterohydrocarbylene group is a C5-C 22 Heteroalkyl groups, preferably C5-C 18 Heteroalkyl groups, more preferably C5 to C 15 Heteroalkyl groups, more preferably C5-C 12 Heteroalkyl groups, most preferably C5-C 10 A heteroalkyl group is one that contains an ether linkage, that is, formally, one of the carbon atoms of the alkyl group is replaced with an oxygen atom.

[0063] The tetrahydric alcohol preferably has a molecular weight of 100 to 1,000 g / mol, more preferably 100 to 750 g / mol, even more preferably 100 to 500 g / mol, even more preferably 100 to 300 g / mol, and most preferably 130 to 230 g / mol, for example, 136 to 223 g / mol.

[0064] The tetrahydric alcohol preferably has a solubility in deionized water at 20° C. of 10 to 100 g / L, advantageously 15 to 80 g / L, most preferably 21 to 70 g / L.

[0065] The tetrahydric alcohol is preferably symmetrical, particularly one that acts to prevent the tetrahydric alcohol from having dipolar properties. The tetrahydric alcohol is preferably symmetrical with respect to the four hydroxyl groups of the tetrahydric alcohol. The tetrahydric alcohol preferably has a plane of symmetry. The tetrahydric alcohol preferably has a plane of symmetry, with two of the four hydroxyl groups of the tetrahydric alcohol being located on one side of the mirrored plane and the remaining two hydroxyl groups being located on the other side of the mirrored plane.

[0066] Advantageously, the tetrahydric alcohol is of the following formula (1): [ka] [Wherein R is C1 to C 18 a hydrocarbylene group or a C1-C group having 1 to 3 heteroatoms independently selected from O, N, S, and P; 17 a heterohydrocarbylene group.

[0067] Advantageously, R in formula (1) is C1 to C 12 Hydrocarbylene group or C1-C having 1-2 heteroatoms independently selected from O and S 11 It is a heterohydrocarbylene group. Even more preferably, R in formula (1) is a C1-C8 hydrocarbylene group, or a C1-C8 heterohydrocarbylene group having one heteroatom independently selected from O and S. Even more preferably, R in formula (1) is a C1-C6 hydrocarbylene group, or a C1-C6 heterohydrocarbylene group having O (oxygen) as the only heteroatom.

[0068] Advantageously, R in formula (1) is C1 to C 12 or a C1-C alkylene group having 1-2 heteroatoms independently selected from O and S. 11It is a heteroalkylene group. Even more preferably, R in formula (1) is a C1-C8 alkylene group, or a C1-C8 heteroalkylene group having one heteroatom independently selected from O and S. Even more preferably, R in formula (1) is a C1-C6 alkylene group, or a C1-C6 heteroalkylene group having O (oxygen) as the only heteroatom.

[0069] Tetrahydric alcohols are represented by the formulas (2) and (3) [ka] Most preferably, the tetrahydric alcohol is selected from the following:

[0070] The tetrahydric alcohol acts as a cap-off additive in the composition according to the invention for coloring a substrate. The cap-off additive improves the "cap-off time," which is understood to mean the time during which a writing instrument or writing system can be stored naked, i.e., uncapped, or left unused without drying out and hardening.

[0071] Binder Furthermore, it can be proposed that the composition for coloring the substrate comprises 0.1 to 50% by weight of a binder.

[0072] The composition preferably contains binders in a total amount of at least 5 wt. %, particularly preferably at least 10 wt. %, even more preferably at least 20 wt. %, even more preferably 25 wt. %, and most preferably at least 28 wt. %, each based on the total weight of the composition.

[0073] The composition preferably contains binders in a total amount of at most 45% by weight, particularly preferably at most 40% by weight, for example about 38% by weight, each based on the total weight of the composition.

[0074] The composition preferably contains a binder in a total amount of 5 to 45 wt %, particularly preferably 10 to 40 wt %, even more preferably 20 to 40 wt %, and most preferably about 25 to 38 wt %, for example about 28 to 38 wt %, each based on the total weight of the composition.

[0075] A reasonable amount of binder in the composition promotes the solubility and efficacy of the tetrahydric alcohol.

[0076] The binder can be used in the composition as a solid and / or as an aqueous binder preparation, i.e., can be used in these forms for the preparation of the composition. Aqueous binder preparations in this context are in particular binder solutions or binder dispersions.

[0077] It is preferred to use binder dispersion in the preparation of the composition according to the present invention.In this case, the amount of binder in the composition is indicated based on the total weight of binder dispersion (including solvent, etc.).By using a corresponding binder dispersion in the preparation of the composition according to the present invention, it is possible to achieve favorable mixing in the composition.

[0078] The binder may be proposed to be a synthetic polymeric binder, advantageously a polyacrylate, polyurethane, polyester, sulfopolyester, maleate resin, or a copolymer of two or more thereof, or a wax, for example beeswax.

[0079] For example, the binder can be Acronal 12DE (a dispersion of an acrylonitrile-acrylic acid ester copolymer, BASF), Neocryl XK166N (a dispersion of an acrylic styrene copolymer, Covestro), NeoRez R-3972 (a polyurethane dispersion, Covestro), Eastek 1000 (a colloidal solution of a sulfopolyester, Eastman), or Neocryl XK-39 (an alkali-soluble polyacrylate dispersion, Covestro).

[0080] Preferably, the binder is an acrylic-styrene copolymer, a sulfopolyester, or a mixture thereof, advantageously a mixture of an acrylic-styrene copolymer and a sulfopolyester. More preferably, the binder is a mixture of an acrylic-styrene copolymer and a sulfopolyester in a weight ratio of 10:1 to 1:2, further preferably 5:1 to 1:1.5, even more preferably 3:1 to 1:1, for example about 2:1.

[0081] For example, the binder can be a 2:1 weight ratio mixture of Neocryl XK166N (a dispersion of an acrylic styrene copolymer, Covestro) and Eastek 1000 (a colloidal solution of sulfopolyester, Eastman).

[0082] Alternatively, it can be proposed that the binder advantageously has an acid number of at most 250 mg KOH / g dry substance, still also preferably at most 220 mg KOH / g dry substance, even more preferably at most 200 mg KOH / g dry substance, more preferably at most 180 mg KOH / g dry substance, even more preferably at most 170 mg KOH / g dry substance, most preferably at most 160 mg KOH / g dry substance, for example about 130 mg KOH / g or 160 mg KOH / g dry substance.

[0083] The binder advantageously has an acid value of 50 to 250 mg KOH / g dry matter, preferably 60 to 220 mg KOH / g dry matter, more preferably 70 to 220 mg KOH / g dry matter, more preferably 80 to 180 mg KOH / g dry matter, even more preferably 100 to 170 mg KOH / g dry matter, even more preferably 100 to 160 mg KOH / g dry matter, and most preferably 110 to 160 mg KOH / g dry matter, for example about 110 to 130 mg KOH / g dry matter, for example about 130 mg KOH / g dry matter or about 160 mg KOH / g dry matter. Using binders with corresponding acid values, advantageous effects can be achieved with regard to resolubility in basic compositions for watercolor painting.

[0084] The binder can advantageously be a polymer binder. The binder can advantageously be a polymer resin. It can be proposed that the binder has carboxyl and / or nitrile and / or sulfonyl groups, preferably carboxyl groups. This allows particularly good coloring properties to be achieved, especially with basic dyes. It is advantageously proposed that the binder is a polymer resin containing carboxyl-containing monomer units. It is particularly preferred that the binder comprises or is a polyacrylate resin.

[0085] The binder dispersion may be proposed to have a pH value of at most 7, advantageously less than 7, further preferably between 1 and 5, even more preferably between 1.5 and 3, most preferably between 1.9 and 2.5. The binder dispersion may be proposed to be a low-viscosity, white or translucent binder particle dispersion in the acidic or neutral pH range (pH≦7), which binder particles gradually dissolve at higher pH values ​​until a clear, transparent and highly viscous solution is formed.

[0086] It may be proposed that the binder dispersion has a solids content of 30 to 60% by weight, advantageously 40 to 50% by weight, particularly preferably 43 to 47% by weight, most preferably 44 to 46% by weight, each based on the total weight of the binder dispersion.

[0087] The binder can be an alkali-soluble acrylate dispersion. The binder can be an alkali-soluble polyacrylate dispersion. The binder can be an acidic acrylate dispersion. The binder can be an acidic polyacrylate dispersion. The binder can be an ASE thickener. Exemplary corresponding binders available commercially are, for example, Joncryl 142, 661, 662, 667 (BASF), Texicryl 13-812, 13-825 (Scott Bader), NeoCryl BT-9, BT-21, BT-24, BT-100, BT-107, BT-207 (DSM), NeoCryl XK-39 (DSM), GLASCOL LE510, LE520, etc. (BASF) or Lucidene 198 (Brenntag). The most remarkable effect according to the invention, namely, above all, easily adjustable water resistance, was achieved using the corresponding alkali-soluble polyacrylate dispersions.

[0088] It is proposed that the binder, particularly the binder dispersion, contains binder particles. It is proposed that the binder particles have an average particle size of at least 50 nm, preferably at least 100 nm. The particle size can be measured by dynamic light scattering in accordance with the version of ASTM E 3247-20 effective as of the priority date. The binder particles have a correspondingly large diameter, which can prevent the composition from penetrating too deeply into the absorbent substrate, thereby improving the watercolor colorability, i.e., the subsequent application of the ink on the substrate.

[0089] Preservatives / Biocides Furthermore, it may be proposed that the composition contain 0.01 to 0.5% by weight of a preservative and / or biocide, based on the total weight of the composition. Preferred preservatives are, for example, mixtures of tert-butyl hydroperoxide and monophenyl glycol ether, particularly preferably mixtures of 12 to 60% by weight of tert-butyl hydroperoxide and 3 to 50% by weight of monophenyl glycol ether, or mixtures of 1,6-dihydroxy-2,5-dioxahexane and tetramethylolacetylenediurea. Such preservatives are particularly suitable for aqueous solutions and emulsions. Preferred biocides are, for example, mixtures of 2-bromo-2-nitropropane-1,3-diol and 2-octyl-2H-isothiazol-3-one, or mixtures of BIT (1,2-benzisothiazolin-3-one), MIT (2-methyl-4-isothiazolin-3-one), and OIT (2-octyl-2H-isothiazol-3-one), which mixtures are particularly effective in preventing fouling. A further preferred biocide is a mixture of CIT / MIT in a weight ratio of 3:1. A further preferred biocide is 2-bromo-2-nitropropane-1,3-diol. A further preferred biocide is 2-octyl-2H-isothiazol-3-one. A further preferred biocide is phenoxyethanol.

[0090] Preferably, the composition contains preservatives and / or biocides in a total amount of at least 0.05% by weight, particularly preferably at least 0.2% by weight, even more preferably at least 0.15% by weight, and most preferably at least 0.1% by weight, each based on the total weight of the composition.

[0091] Preferably, the composition contains preservatives and / or biocides in a total amount of at most 0.4% by weight, particularly preferably at most 0.3% by weight, even more preferably at most 0.25% by weight, and most preferably at most 0.2% by weight, each based on the total weight of the composition.

[0092] The composition preferably contains preservatives and / or biocides in a total amount of 0.025 to 0.4 wt. %, particularly preferably 0.05 to 0.3 wt. %, even more preferably 0.75 to 0.2 wt. %, and most preferably about 0.1 wt. %, each based on the total weight of the composition.

[0093] moisturizer Furthermore, it may be proposed that the composition contains 0.01 to 20 wt. % of a humectant, based on the total weight of the composition. Preferably, the humectant is an organic polyol and / or polyglycol and / or sugar alcohol and / or polar organic compound that is liquid at room temperature and normal pressure, particularly preferably selected from the group consisting of diethylene glycol, propylene glycol, 1,2-propanediol, glycerin, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, erythritol, dimethyl sulfoxide, pyrrolidone, in particular 2-pyrrolidone or N-methyl-2-pyrrolidone (NMP), and mixtures thereof, particularly preferably 1,2-propanediol.

[0094] A combination of an organic polyol and / or polyglycol and / or polar organic compound that is liquid at room temperature and normal pressure as a humectant, on the one hand, and pentaerythritol and / or di(trimethylolpropane) on the other hand, is preferred. A combination of an organic polyol and / or polyglycol as a humectant, on the other hand, and pentaerythritol and / or di(trimethylolpropane) on the other hand, is also preferred. A combination of an organic polyol as a humectant, on the other hand, and pentaerythritol and / or di(trimethylolpropane) on the other hand, is also preferred. In particular, a combination of 1,2-propanediol as a humectant and pentaerythritol and / or di(trimethylolpropane) as a tetrahydric alcohol is preferred. A combination of 1,2-propanediol as a humectant and pentaerythritol as a tetrahydric alcohol is particularly preferred.

[0095] The composition preferably contains a moisturizer in an amount of at least 1 wt. %, particularly preferably at least 5 wt. %, even more preferably at least 7.5 wt. %, and most preferably at least 10 wt. %, each based on the total weight of the composition.

[0096] The composition preferably contains a moisturizer in an amount of at most 17.5 wt. %, particularly preferably at most 15 wt. %, and even more preferably at most 13.5 wt. %, each based on the total weight of the composition.

[0097] The composition preferably contains the moisturizer in an amount of 1 to 17.5 wt. %, particularly preferably 5 to 15 wt. %, even more preferably 7.5 to 14.5 wt. %, and most preferably about 10 to 13.5 wt. %, each based on the total weight of the composition.

[0098] The use of suitable humectants in suitable concentrations improves the COT and writing behavior after short time intervals. In addition, they have a positive effect on film formation and therefore on the durability of the writing end. In particular, a corresponding synergistic effect can be observed in combination with tetrahydric alcohols.

[0099] Surfactants / surface-active substances Furthermore, it may be proposed that the composition comprises from 0.01 to 7% by weight of surfactants and / or surface-active substances, based on the total weight of the composition.

[0100] The surfactant may be an emulsifier, dispersant, stabilizer or substrate wetting agent, preferably a silicone surfactant, a fatty alcohol ether sulfate, in particular C 12 ~C 14 The fatty alcohol ether sulfate-sodium salt (30EO), fatty alcohol ether phosphate, fatty alcohol phosphate, sulfosuccinate, etc. may be used.

[0101] The surfactant is advantageously a nonionic surfactant, an anionic surfactant or an amphoteric surfactant.

[0102] Stabilizers in the sense of the present disclosure are in particular surface-active substances which, by adsorption to the particle interface, stabilize colloidal particle systems against reagglomeration or coagulation by steric, electrostatic or electrosteric interactions, thus preventing sedimentation, syneresis, particle size and viscosity increase.

[0103] Nonionic surfactants within the meaning of the present disclosure can be classified according to the following system: the "HLB system" (hydrophilic-lipophilic balance) developed by Atlas Chemie. In the HLB system, each emulsifier is assigned a numerical value called the HLB value. The HLB value indicates the hydrophilic-lipophilic balance.

[0104] All emulsifiers contain both hydrophilic and lipophilic groups. Lipophilic emulsifiers have a low HLB value below 9.0, while hydrophilic emulsifiers have a high HLB value above 11.0. Emulsifiers with low HLB values ​​tend to be oil-soluble, while emulsifiers with high HLB values ​​tend to be water-soluble. For example, if the final product can be diluted with water, a water-soluble emulsifier is used. O / W emulsifiers have an HLB value between 8 and 18. Hydrophilic emulsifiers with high HLB values ​​promote the formation of O / W emulsions.

[0105] In the composition of the present invention, the nonionic solubilizer is preferably a commercially available emulsifier, which is available as a viscous solution and is produced by reacting ethylene oxide with hydrogenated castor oil, and may consist of, for example, 90% by weight of hydrogenated castor oil, 5% by weight of 1,2-propylene glycol, and 5% by weight of water. The components of this type of emulsifier can also be fatty acid glycerin polyethylene glycol esters and fatty acid polyethylene glycol esters. These form the hydrophobic portion of the product. The hydrophilic portion can consist of polyethylene glycol and glycerin ethoxylate.

[0106] Among all possible emulsifiers, nonionic emulsifiers from the following groups may preferably be considered: alcohol fatty acid esters, ethylene fatty acid esters, polyethylene glycol fatty acid esters, glycerol or polyfatty acid esters, sorbitol fatty acid esters, pentaerythritol fatty acid esters, fatty acid esters of glycerol esters, sucrose fatty acid esters, alcohol polyglycol ethers, fatty acid polyglycol ethers, fatty acid ester polyglycol ethers, fatty amine polyglycol ethers, polyglycol ethers of fatty acid alkanolamides, polyglycol ethers of fats and oils, polypropylene glycol polyglycol ethers, lanolin polyglycol ethers, alcohol polypropylene glycol ethers, fatty acid polypropylene glycol ethers, polypropylene glycol ethers of fatty amines, lanolin polyglycol ethers.

[0107] The composition preferably contains surfactants and / or surface-active substances in a total amount of at least 0.1 wt. %, particularly preferably at least 0.5 wt. %, even more preferably at least 1 wt. %, and most preferably at least 1.5 wt. %, each based on the total weight of the composition.

[0108] Preferably, the composition contains surfactants and / or surface-active substances in a total amount of at most 5% by weight, particularly preferably at most 4% by weight, even more preferably at most 3% by weight, and most preferably at most 2% by weight, each based on the total weight of the composition.

[0109] The composition preferably contains surfactants and / or surface-active substances in a total amount of 0.1 to 5 wt. %, preferably 0.5 to 4 wt. %, more preferably 1 to 3 wt. %, most preferably 1.5 to 2 wt. %, for example about 1.5 wt. %, each based on the total weight of the composition.

[0110] By adding appropriate surfactants and / or surface-active substances in appropriate amounts, improvements in ink stability and wetting of the substrate to be pigmented can be achieved.

[0111] Oligomers / polymers with surface-active / pigment-affinity groups Furthermore, it may be proposed that the composition comprises a compound having surface-active and / or pigment-affinitive groups, advantageously an oligomer having surface-active and / or pigment-affinitive groups and / or a polymer having surface-active and / or pigment-affinitive groups, in an amount of 0.01 to 5% by weight, based on the total weight of the composition.

[0112] Pigment-affinitive groups in the sense of the present disclosure are anchoring groups that are selected depending on the type of pigment, for example whether it is organic or inorganic.

[0113] Surface active groups in the sense of the present disclosure are groups that have an affinity for surfaces and interfaces of glass, metal, plastic, air, binder particles (mineral or organic) or pigments (mineral or organic).

[0114] In particular, when used in combination with inorganic or mineral pigments (TiO2, iron oxides, etc.), compounds having anionic or cationic surface-active and / or pigment-affinity groups may be proposed, in particular amino groups, phosphate groups, quaternary ammonium groups, sulfonate groups, carboxylate groups, etc.

[0115] Unmodified organic pigments are often non-polar and have no surface charge. Non-ionic dispersants with hydrophilic and hydrophobic molecular moieties are often used, with the non-polar moieties attaching to the pigment surface via van der Waals interactions (see HLB values). The corresponding non-polar moieties are considered pigment-affinity groups. Exemplary hydrophobic surface-active groups and / or pigment-affinity groups are, for example, nonylphenol, isotridecyl, isotristyrene, C 13 -, siloxane, novolac groups.

[0116] The addition of such compounds having surface-active and / or pigment-affinity groups to pigment writing fluids has the effect of stabilizing the effects of aggregation, sedimentation, syneresis, viscosity drift, changes in color strength, changes in color tone and further deterioration, or improving the compatibility between binders and colorants.

[0117] The composition preferably contains a compound having a surface-active group and / or a pigment-affinity group in a total amount of at least 0.1 wt %, particularly preferably at least 0.5 wt %, even more preferably at least 0.75 wt %, and most preferably at least 1 wt %, each based on the total weight of the composition.

[0118] The composition preferably contains at most 5% by weight of compounds having surface-active groups and / or pigment-affinitive groups, particularly preferably at most 2.5% by weight, even more preferably at most 1.5% by weight, and most preferably at most 1% by weight, each based on the total weight of the composition.

[0119] The composition preferably contains a compound having a surface active group and / or a pigment-affinity group in a total amount of 0.1 to 5 wt %, particularly preferably 0.5 to 2.5 wt %, even more preferably 0.75 to 1.5 wt %, and most preferably about 1 wt %, based on the total weight of the composition.

[0120] Further ingredients Furthermore, to further optimize the film properties and other use characteristics of the ink, the addition of co-binders (such as, for example, acrylate polymers without acid values) and co-film formers (such as Texanol, butyl glycol, butyl diglycol, etc.) may be suggested.

[0121] Likewise, to improve scratch resistance, the addition of waxes may be suggested.

[0122] The composition may be proposed to be urea-free. In this context, "free" means that urea has not been actively added to the composition and is present, at most, only as an impurity in amounts that cannot be prevented by conventional purification methods.

[0123] Embodiment In one embodiment, the present invention provides a composition for coloring a substrate, comprising: Each based on the total weight of the composition - 20-40% by weight of water; - 1-6% by weight of tetrahydric alcohol; - 0.1-0.5% by weight of biocides; - 5-15% by weight of humectant; - 1 to 3% by weight of surfactants and / or surface-active substances; 1 to 12.5% ​​by weight of a colorant; and - 25-45% by weight of binder; Including, The tetrahydric alcohol has at least 5 carbon atoms. It relates to a composition.

[0124] In one embodiment, the present invention provides a composition for coloring a substrate, comprising: Each based on the total weight of the composition - 20-40% by weight of water; - 1-6% by weight of tetrahydric alcohol; - 0.1-0.5% by weight of biocides; - 5-15% by weight of humectant; - 1 to 3% by weight of surfactants and / or surface-active substances; 1 to 12.5% ​​by weight of a colorant; and - 25-45% by weight of binder; Including, Tetrahydric alcohols are represented by the following formula (1): [ka] [Wherein R is C1 to C 18a hydrocarbylene group or a C1-C group having 1 to 3 heteroatoms independently selected from O, N, S, and P; 17 a heterohydrocarbylene group; It relates to a composition.

[0125] In one embodiment, the present invention provides a composition for coloring a substrate, comprising: Each based on the total weight of the composition - 20-40% by weight of water; - 1-6% by weight of tetrahydric alcohol; - 0.1-0.5% by weight of biocides; - 5-15% by weight of humectant; - 1 to 3% by weight of surfactants and / or surface-active substances; 1 to 12.5% ​​by weight of a colorant; and - 25-45% by weight of binder; Including, Tetrahydric alcohols are represented by formula (2) and formula (3) [ka] tetrahydric alcohols selected from the group consisting of It relates to a composition.

[0126] Preparation of a composition for coloring a substrate The composition for coloring a substrate can be prepared by mixing methods known from the prior art, for example in a mixing vessel in which the components of the composition for coloring a substrate are added, and in this case the components are vigorously mixed with one another using a suitable stirring tool in order to disperse them sufficiently homogeneously.

[0127] It may be proposed to heat the components of the composition according to the invention for coloring the substrate for a sufficient time, advantageously between 30 and 60 minutes, advantageously to a temperature of 50 to 60°C, in order to obtain a particularly homogeneous composition, for example in the form of a dispersion.

[0128] After cooling, the soluble components of the composition remain dissolved. Without being bound by this assumption, it can be assumed that the tetrahydric alcohol adheres or adsorbs to particle interfaces (pigment & polymer particles) present in the composition (or adheres to dissolved polymer molecules).

[0129] Use of the composition for coloring a substrate Furthermore, the present invention relates to a composition according to the invention for coloring a substrate, for producing a film on the substrate.

[0130] The use according to the invention can in particular be on substrates, advantageously absorbent substrates, such as absorbent writing media, more preferably drawing paper or paper, particularly preferably watercolor paper, or non-absorbent substrates, such as synthetic or plastic substrates, particularly preferably synthetic or plastic sheets, or mixed-media substrates, i.e., those made of, for example, absorbent and non-absorbent materials, or canvas. Likewise, any further suitable substrates, such as wood, stone, eggshells, etc., may be proposed.

[0131] It may then be proposed to apply to the substrate a composition according to the invention for colouring the substrate.

[0132] In this case, the composition can be applied to at least one surface of the substrate. In this case, the composition is applied to at least a portion of the corresponding surface. The application can include writing, drawing, painting, printing, spraying, or a combination of two or more thereof. The application can be carried out using a paintbrush, a pen, especially a watercolor pen, a printhead, a fountain pen holder, or other conventional application tools (e.g., an airbrush), or a combination of two or more thereof.

[0133] After application, the applied composition can be allowed to dry on the substrate (or partially within the substrate if part of the composition has penetrated the substrate). Drying can be carried out at room temperature (23°C) under atmospheric pressure. Drying can be assisted by the application of heat, by passing a gas stream (air stream) through the composition to be dried, by applying a vacuum, etc.

[0134] Effect of the invention The compositions according to the invention for coloring substrates surprisingly have excellent cap-off times (COT) and at the same time very short drying times as well as good durability on various types of substrates, especially on non-absorbent surfaces.

[0135] In particular, it was surprisingly found that the addition of a specific tetrahydric alcohol significantly improved the COT and did not impair other usage properties, but rather significantly improved them. Di-TMP (ditrimethylolpropane) and pentaerythritol, which produced particularly remarkable effects, were found to be particularly preferable.

[0136] Furthermore, surprisingly, the compositions according to the invention for coloring substrates can be formulated without urea, using only substances which, in particular - in contrast to urea - are hydrolytically stable, do not tend to decompose and do not affect the long-term pH value of the composition.

[0137] Likewise, the compositions according to the invention for coloring substrates allow a significant overall reduction in the humectant content compared to writing fluids known from the prior art. At the same time, the compositions according to the invention allow a significant increase in the binder content. This allows new latitude and freedom in the formulation of writing fluids.

[0138] General definition Unless specifically stated otherwise, features described in the singular also include the plural, for example, if a composition according to the invention is described as containing a dye, the composition also includes instances in which it contains a mixture of dyes.

[0139] Unless specifically stated otherwise, the terms "comprise", "contain", and the like include the meanings "essentially comprise", "essentially contain" or "consist of".

[0140] All amounts listed for compositions according to the invention for coloring a substrate add up to a total of 100% by weight and therefore the total amount of the composition.

[0141] Unless otherwise specified, the term "composition" as used herein means "a composition according to the present invention for coloring a substrate."

[0142] Example Formulation example 1 30.0g water Acticide MBT1 (biocide) 0.10g 1,2-propanediol (moisturizer) 10.0g Pentaerythritol (tetrahydric alcohol) 5.0g C 12 ~C 14 Fatty alcohol ether sulfate sodium salt (30EO) (surfactant) 1.50g Neocry XK-166N (first binder) 24.0g Eastek 1100 (second binder) 12.0g TEXANOL (film-forming agent) 2.50g Magenta Red Preparation (30% PR122) 16.0g

[0143] The corresponding components were mixed and heated to 60° C. for 30 minutes, followed by cooling to room temperature.

[0144] [ka]

[0145] Formulation example 2 Formulation Example 2 was prepared in the same manner as Formulation Example 1, except that di(trimethylolpropane) was used as the tetrahydric alcohol instead of pentaerythritol.

[0146] [ka]

[0147] Formulation example 3 Formulation Example 3 was prepared in the same manner as Formulation Example 1, with the only difference being that urea was used as the moisturizing agent instead of 1,2-propanediol.

[0148] Formulation example 4 36.9g water Acticide MBT1 (biocide) 0.10g 1,2-propanediol (moisturizer) 10.0g Pentaerythritol (tetrahydric alcohol) 5.0g C 12 ~C 14 Fatty alcohol ether sulfate sodium salt (30EO) (surfactant) 1.50g Neocryl XK-39 (acid- and alkali-soluble binder) 28.0g Triethanolamine (pH adjuster, base) 0.7g 20.0 g of carbon black preparation (pigment 34%)

[0149] Comparison formulation 1 Comparative Formulation 1 was prepared in the same manner as Formulation Example 1, with the only difference being that erythritol, a tetrahydric alcohol, was used instead of pentaerythritol.

[0150] [ka]

[0151] Comparison formulation 2 Comparative Blend 2 was produced in the same manner as Blend Example 1, with the only difference being that dipentaerythritol, a hexahydric alcohol (water solubility: 2.4 g / l), was used instead of pentaerythritol.

[0152] [ka]

[0153] Comparison formulation 3 Comparative Blend 3 was prepared in the same manner as Blend 1, with the only difference being that ε-caprolactam was used instead of pentaerythritol.

[0154] [ka]

[0155] Comparison formulation 4 Comparative Formulation 4 was prepared in the same manner as Formulation Example 1, with the only difference being that sorbitol, a hexahydric alcohol, was used instead of pentaerythritol.

[0156] [ka]

[0157] Comparison formulation 5 Comparative Formulation 5 was prepared in the same manner as Formulation Example 1, with the only difference being that ε-caprolactone was used instead of pentaerythritol.

[0158] [ka]

[0159] Comparison formulation 6 Comparative Formulation 6 was prepared in the same manner as Formulation Example 1, with the only difference being that neopentyl alcohol, a dihydric alcohol, was used instead of pentaerythritol.

[0160] [ka]

[0161] Comparison formulation 7 Comparative Formulation 7 was prepared in the same manner as Formulation Example 1, with the only difference being that the trihydric alcohol 1,1,1-trimethylolpropane (TMP) was used instead of pentaerythritol.

[0162] [ka]

[0163] Comparison formulation 8 Comparative Formulation 8 was prepared in the same manner as Formulation Example 1, with the only difference being that xylitol, a pentahydric alcohol, was used instead of pentaerythritol.

[0164] [ka]

[0165] Example Example 1 The composition prepared in Formulation Example 1 was filled into a test pen (fiber pen with a capillary reservoir). Subsequently, an extruded POM plastic tip (0.5 mm) was attached to the test pen, and the test pen was stored horizontally overnight.

[0166] A cap-off test was then carried out under standard climatic conditions (23°C, 50% relative humidity) using three pens for each formulation, with which the formulation example compositions were applied to plain paper (Xerox 80g) as substrate.

[0167] The cover of the test pen was removed at the start and the test pen was used for writing after time intervals of 10 minutes, 30 minutes, 60 minutes and 10 hours.

[0168] The cap-off test is when the pen starts writing naturally again and produces a line with even coverage. Very good and is marked as passed "+++". If the pen writes without any problems again after a few millimeters, the test is still marked as passed "+". If the pen can no longer write, or can only write after a relatively long "scribble", the test is marked as failed "-".

[0169] Examples 2 to 4 Examples 2 to 4 were carried out in the same manner as Example 1, except that the composition of Blending Example 1 was replaced with the compositions of Blending Examples 2 to 4, respectively.

[0170] Comparative Examples 1 to 8 Comparative Examples 1 to 8 were carried out in the same manner as Example 1, except that the composition of Formulation Example 1 was replaced with the compositions of Comparative Formulations 1 to 8, respectively.

[0171] The results of Examples 1 to 4 and Experimental Examples are shown in Table 1.

[0172] [Table 1]

[0173] Additionally, the compositions were tested for their drying time and water resistance. The test conditions and results are summarized in Table 2.

[0174] [Table 2]

[0175] The features of the invention disclosed in the above description and in the claims may be important, both alone and in any combination, for realizing various embodiments of the invention.

Claims

1. 1. A composition for coloring a substrate, comprising: Each based on the total weight of the composition: 10 to 70% by weight of water; - 0.025 to 12.5% ​​by weight of a colorant; and - 0.1 to 10% by weight of a tetrahydric alcohol Including, The tetrahydric alcohol has at least 5 carbon atoms. composition.

2. 10. The composition for coloring a substrate according to claim 1, wherein the coloring is by writing, drawing, painting, printing, spraying, or a combination of two or more thereof.

3. 3. A composition for coloring a substrate according to claim 1 or 2, wherein the substrate is an absorbent writing medium, preferably drawing paper or paper, or a non-absorbent substrate, preferably a synthetic or plastic sheet, a mixed-media substrate, or a canvas.

4. 4. The composition for coloring a substrate according to claim 1, wherein the colorant is a dye, a pigment, or a mixture of two or more thereof.

5. The tetrahydric alcohol is represented by the following formula (1): 【Chemistry 1】 wherein R is C １ ~C １８ a hydrocarbylene group or a C having 1 to 3 heteroatoms independently selected from O, N, S and P １ ~C １７ 5. The composition for coloring a substrate according to claim 1, wherein the aryl group is a heterohydrocarbylene group.

6. The tetrahydric alcohol is represented by the formula (2) and the formula (3): 【Chemistry 2】 6. A composition for coloring a substrate according to claim 1, wherein the tetrahydric alcohol is selected from the group consisting of:

7. The composition for coloring a substrate according to any one of claims 1 to 6, further comprising 0.1 to 50 wt % of a binder, based on the total weight of the composition.

8. 8. The composition for coloring a substrate according to any one of claims 1 to 7, further comprising 0.01 to 0.5 wt. % of a preservative and / or biocide, based on the total weight of the composition.

9. 9. The composition for coloring a substrate according to any one of claims 1 to 8, further comprising 0.01 to 20% by weight of a humectant, based on the total weight of the composition.

10. 10. The composition for coloring a substrate according to any one of claims 1 to 9, further comprising 0.01 to 7 wt. % of a surfactant, based on the total weight of the composition.

11. 11. Use of a composition for coloring a substrate according to any one of claims 1 to 10 for producing a film on a substrate.

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