Composition for dyeing a substrate and use thereof

Abstract

The present invention relates to a composition for dyeing a substrate comprising, based on the total weight of the composition: 10 to 70% by weight of water; 0.025 to 12.5 wt% of a colorant; and 0.1 to 10 wt% of a tetrahydric alcohol wherein the tetrahydric alcohol has at least 5 carbon atoms; the invention also relates to the use of the composition for dyeing a substrate for producing a film on a substrate.

Description

Technical Field

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

[0002] The present invention also relates to the use of the composition for dyeing a substrate for producing a film on a substrate. Background Art

[0003] Aqueous writing fluids (such as inks) are known in the prior art and generally contain water as a solvent and pigments or water-soluble dyes as colorants. They generally also contain other additives, such as surfactants, emulsifiers, preservatives or humectants.

[0004] Pigment-based inks (dyes) have been known for many years, in particular for artistic applications (painting, drawing, etc.). Such inks are usually formulated with plastic dispersions as binders and / or with wetting agents.

[0005] The "cap-off time" (COT) of a writing fluid is the period of time that the writing fluid can remain open without drying out when stored in a writing or application device with the writing tip unsealed or the cap removed. For practical applications of writing fluids, it is advantageous if the writing or other application device can remain open for extended periods of time, preferably hours or days, without the writing fluid drying out.

[0006] Water-based writing fluids known in the prior art can be divided into the following three categories:

[0007] a) Inks designed to have an excellent COT. These inks contain a high proportion of so-called drying retardants or humectants to prevent the writing tip from drying out or drying out (fineliners, fiber brushes). Due to the high proportion of drying retardants or humectants, these inks can only contain small amounts of binder. Consequently, these writing fluids typically have very long drying times and poor stability. These writing fluids are generally only suitable for absorbent substrates, such as paper.

[0008] b) Inks that are intended to dry quickly and permanently on non-absorbent substrates. Unfortunately, the COT of such inks is often completely unsatisfactory.

[0009] c) is a compromise between inks a) and b), i.e., it has a good COT and satisfactory stability, but is only suitable for absorbent substrates.

[0010] For example, EP 3613814 B1 describes a writing, marking and / or drawing fluid comprising an aqueous pigment preparation, a binder, a base and a dispersing wetting agent, wherein an aqueous solution of a modified polymer having pigment-affinic groups is present as the dispersing wetting agent.

[0011] Pigmented liner inks known in the prior art contain 20% by mass of urea and an additional 15% of a humectant to achieve a COT of 18 hours. The addition of urea results in a satisfactory fast drying time even on moderately absorbent substrates and usable stability even after longer drying times. During this process, the urea crystallizes.

[0012] On the other hand, on less absorbent paper, or even on coated substrates (e.g., photographic prints, laminated paper), the coating does not dry or stabilize satisfactorily even after hours or days. Consequently, the coating can smudge or stain upon contact. Furthermore, high urea content impairs the water resistance of the coating, and upon prolonged storage of the ink (particularly at elevated temperatures according to the T50 storage test), urea tends to decompose in the alkaline range, generating carbon dioxide and ammonia, which further increases the pH. Consequently, the ink becomes increasingly unstable.

[0013] Alcohol-based inks (such as Lumocolor permanent whiteboard markers) have offered a solution to this problem for about two decades using so-called "anti-drying" technology, combining an excellent COT with a short drying time and excellent stability. Here, a special wax additive, moderately dissolved in the ink, prevents drying out. When the pen is "open," the wax, dissolved to saturation, settles at the tip and forms a very thin barrier film, preventing further solvent loss and thus drying out. However, this film has such poor mechanical stability that it breaks at the slightest contact between the tip and the substrate, instantly ensuring ink flow. There is no corresponding solution for water-based writing fluids.

[0014] Purpose of the Invention

[0015] The object of the present invention was therefore to provide an aqueous writing fluid which overcomes the disadvantages of the prior art, in particular to provide an aqueous writing fluid having an excellent capping time (COT), which nevertheless has a very short drying time and excellent stability on all types of substrates, in particular also on non-absorbent surfaces; preferably to provide a corresponding aqueous writing fluid which has a reduced proportion of urea or is even urea-free. Summary of the Invention

[0016] This object is achieved according to the subject matter of the independent claims. Preferred embodiments emerge from the dependent claims and the following description.

[0017] This object is achieved in particular by a composition for dyeing substrates comprising:

[0018] - 10 to 70% by weight of water;

[0019] - 0.1 to 50% by weight of a colorant; and

[0020] - 1 to 6% by weight of tetraols,

[0021] in

[0022] The tetraol has at least 5 carbon atoms.

[0023] The object is also achieved by the use of the composition according to the invention for dyeing substrates for producing films on absorbent substrates.

[0024] Composition for dyeing a substrate

[0025] The composition according to the invention is suitable and preferably intended for dyeing substrates.

[0026] dyeing

[0027] The coloring comprises writing, drawing, painting, printing, spraying or a combination of two or more thereof, or preferably consists of writing, drawing, painting, printing, spraying or a combination of two or more thereof.

[0028] substrate

[0029] The substrate is preferably an absorbent substrate, such as an absorbent writing substrate, more preferably drawing board or paper, particularly preferably watercolor paper; or a non-absorbent substrate, such as a synthetic substrate or plastic substrate, particularly preferably a synthetic film or plastic film; or a mixed media substrate, i.e., a substrate made of absorbent and non-absorbent materials; or canvas. Any other suitable substrate may also be provided, such as wood, stone, eggshell, etc.

[0030] water

[0031] The composition for dyeing 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. Preferably, deionized or demineralized water is used as the water. This avoids the introduction of undesirable impurities, such as hardening agents such as calcium or magnesium.

[0032] It can be provided that the composition comprises water as the main solvent, preferably in an amount of at least 90% by volume, based on the total solvent content of the composition. Particularly preferably, the composition comprises water as the only solvent.

[0033] Preferably, the composition comprises water in an amount of at least 15% by weight, based on the total weight of the composition, particularly preferably at least 20% by weight, most preferably at least 25% by weight.

[0034] Preferably, the composition comprises water in an amount of at most 65 wt%, more preferably at most 60 wt%, further preferably at most 55 wt%, more preferably at most 50 wt%, most preferably at most 45 wt%, e.g. at most 40 wt%, based on the total weight of the composition.

[0035] Preferably, the composition comprises water in an amount of 15 to 65 wt%, more preferably 20 to 40 wt%, most preferably 25 to 35 wt%, for example about 30 wt%, based on the total weight of the composition.

[0036] By means of these preferred water contents in the composition, it is possible, on the one hand, to achieve optimized dyeing and, on the other hand, to achieve optimized usability.

[0037] Additional solvents

[0038] It can be provided that in the composition according to the invention for dyeing substrates, water is the only solvent. Alternatively, it can be provided that the composition according to the invention for dyeing substrates comprises a further solvent in addition to water.

[0039] It can be provided that the composition for dyeing substrates comprises 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, based on the total weight of the composition.

[0040] Preferably, the composition for dyeing a substrate comprises an additional solvent in an amount of at most 40% by weight, more preferably at most 35% by weight, further preferably at most 30% by weight, more preferably at most 20% by weight, most preferably at most 15% by weight, based on the total weight of the composition.

[0041] Preferably, the composition for dyeing a substrate comprises the additional solvent in an amount of 1 to 40 wt%, more preferably 5 to 20 wt%, most preferably 10 to 15 wt%, based on the total weight of the composition.

[0042] Preferably, the additional solvent is a water-soluble organic solvent, further preferably an alcohol, more preferably a polyol, most preferably glycerol or a glycol, such as 1,2-propylene glycol.

[0043] By adding additional solvents to the compositions according to the invention, the dissolution behavior of poorly water-soluble substances, such as pigments or other colorants, can be improved. Furthermore, the effectiveness of the tetraol as a decapping agent can be synergistically enhanced. Finally, the addition of suitable solvents can have a positive influence on film formation and, therefore, on the stability of the coating.

[0044] Colorants

[0045] The composition for dyeing a substrate according to the invention comprises from 0.025 to 12.5% ​​by weight of colorant, based on the total weight of the composition.

[0046] Preferably, the colorant is a dye, a pigment or a mixture of two or more thereof.

[0047] In particular, water-soluble dyes, preferably water-soluble dyes based on food dyes and / or acid dyes and / or basic dyes, can be used as the dyes.

[0048] The dyes listed below have proven to be particularly suitable:

[0049] Food dyes are selected from: E110, CI15985, Food Yellow 3; E104, CI47005, Food Yellow 13; E102, CI19140, Food Yellow 4; E124, CI16255, Food Red 7; E127, CI45430, Food Red 14; E133, CI42090, Food Blue 2; E131, CI42051, Food Blue 3; and / or

[0050] The acid dye is selected from: Acid Yellow 23, CI1910; Acid Red 18, CI16255; Acid Red 51, CI45430; Acid Orange 4, CI16230; Acid Blue 93; Acid Blue 9, CI42090; Acid Blue 104, CI42735; Acid Violet 49, CI42640.

[0051] The basic dye is preferably selected from the group consisting of xanthene dyes, coumarin dyes and rhodamine dyes, such as Basic Violet 11, Basic Yellow 40, Basic Blue 3, Basic Blue 7, Basic Red 1 and Basic Green 1.

[0052] Organic pigments, further preferably quinacridones, phthalocyanines, metal complexes, dioxazines, isoindolines, isoindolinones, benzimidazolones, anthraquinones, arylidenes, perylenes, perylenes, naphthols, diketopyrrolopyrroles or azo pigments, particularly preferably fuchsin PR122 or other quinacridone pigments; and / or inorganic pigments such as titanium dioxide, iron oxide, ultramarine or carbon black can be preferably used as pigments.

[0053] Particularly bright, intense and stable colorings can be achieved by means of the above-mentioned preferred colorants. Preferably, the composition comprises the colorant in an amount of at least 0.05% by weight, particularly preferably at least 0.075% by weight, based on the total weight of the composition.

[0054] Preferably, the composition comprises a colorant (or colorant preparation) in an amount of at most 11.25 wt%, more preferably at most 10 wt%, further preferably at most 8.75 wt%, more preferably at most 7.5 wt%, most preferably at most 6.25 wt%, for example at most 5 wt%, based on the total weight of the composition.

[0055] It may be provided that the pigment is present and used as a component of a pigment preparation.

[0056] Preferably, the composition comprises the colorant in an amount of 0.025 to 10 wt%, more preferably 0.05 to 7.5 wt%, most preferably 0.075 to 5 wt%, based on the total weight of the composition.

[0057] If the colorant is a dye, preferably the composition comprises the colorant in an amount of from 0.025 to 3 wt%, more preferably from 0.05 to 2 wt%, most preferably from about 0.1 to 1 wt%, based on the total weight of the composition.

[0058] If the colourant is a pigment, preferably the composition comprises the colourant in an amount of from 0.25 to 10 wt%, more preferably from 1.25 to 7.5 wt%, most preferably from 2.5 to 5 wt%, for example about 4.8 wt%, based on the total weight of the composition.

[0059] In pastel shades, the pigment content can be reduced to 0.025% by weight.

[0060] By means of the preferred colorant amounts mentioned above, optimal dyeing can be achieved.

[0061] Tetraol

[0062] The composition for dyeing a substrate according to the invention comprises from 0.1 to 10% by weight of tetraol, based on the total weight of the composition.

[0063] The tetraol has at least 5 carbon atoms, preferably up to 22 carbon atoms, more preferably 5 to 18 carbon atoms, more preferably 5 to 15 carbon atoms, still more preferably 5 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms.

[0064] Preferably, the content of the tetraol is at least 1 wt%, more preferably at least 2 wt%, further preferably at least 3 wt%, most preferably at least 4 wt%, based on the total weight of the composition.

[0065] Preferably, the tetraol is present in an amount of at most 9 wt%, more preferably at most 8 wt%, further preferably at most 7 wt%, most preferably at most 6 wt%, based on the total weight of the composition.

[0066] Preferably, the content of the tetraol is 1 to 9 wt%, more preferably 2 to 8 wt%, further preferably 3 to 7 wt%, most preferably 4 to 6 wt%, for example about 5 wt%, based on the total weight of the composition.

[0067] Alcohols are understood to be organic compounds having one or more hydroxyl (—OH) functional groups. Polyols have multiple hydroxyl groups. Tetraols have four hydroxyl groups.

[0068] In addition to the four hydroxyl groups, the tetraol contained in the composition for dyeing a substrate according to the invention also has an organic part containing at least 5 carbon atoms. This organic part can be an alkylene group, in particular a C5 to C 22 Hydrocarbylene, preferably C5 to C 18 Hydrocarbylene, more preferably C5 to C 15 Alkylenes, more preferably C5 to C 12 Hydrocarbylene, most preferably C5 to C 10 or heteroalkylene, especially C5 to C 21 Heteroalkylene, preferably C5 to C 18 Heteroalkylene, more preferably C5 to C 15 Heteroalkylene, further preferably C5 to C 12 Heteroalkylene, most preferably C5 to C 10 Heteroalkylene.

[0069] According to the IUPAC definition, a hydrocarbyl group is a monovalent group derived from a hydrocarbon molecule by removing one hydrogen atom H. Accordingly, according to the present application, a hydrocarbylene group is a group derived from a hydrocarbon molecule by removing at least one hydrogen atom H, in particular four hydrogen atoms.

[0070] A heteroalkylene group according to the present disclosure refers to an alkylene group in which at least one carbon atom is replaced by a heteroatom, in particular a heteroatom selected from O, N, S and P.

[0071] The hydrocarbylene group may be an alkylene group, an arylene group, an alkenylene group, an alkynylene group, an alkylarylene group, an arylalkylene group, etc. The hydrocarbylene group may be an alkylene group.

[0072] The alkylene group may be particularly C5 to C 22 Alkyl, preferably C5 to C 18 Alkyl, more preferably C5 to C 15 Alkyl, more preferably C5 to C 12 Alkyl, most preferably C5 to C 10 alkyl.

[0073] Particularly preferably, the hydrocarbylene group is a tert-pentenyl group.

[0074] The heteroalkylene group may contain one or more ether groups, sulfide groups, amine groups (particularly secondary amine groups), alkylphosphine groups, etc. between two or more alkylene groups. The heteroalkylene group may contain an ether group between two alkylene groups.

[0075] The heteroalkylene group may be C5 to C 22 Heteroalkyl, preferably C5 to C 18 Heteroalkyl, more preferably C5 to C 15 Heteroalkyl, further preferably C5 to C 12 Heteroalkyl, most preferably C5 to C 10 Heteroalkyl. Herein, heteroalkyl refers to an alkyl group in which one or more carbon atoms are replaced by one or more heteroatoms (such as O, S, N or P).

[0076] Preferably, the heteroalkylene group is a C5 to C 22 Heteroalkyl, preferably C5 to C 18 Heteroalkyl, more preferably C5 to C 15 Heteroalkyl, further preferably C5 to C 12 Heteroalkyl, most preferably C5 to C 10 Heteroalkyl groups are groups in which one carbon atom of a formal alkyl group is replaced by an oxygen atom in an ether linkage.

[0077] Preferably, the molecular weight of the tetraol is 100 to 1000 g / mol, more preferably 100 to 750 g / mol, further preferably 100 to 500 g / mol, further preferably 100 to 300 g / mol, most preferably 130 to 230 g / mol, for example 136 to 223 g / mol.

[0078] Preferably, the solubility of the tetraol in deionized water at 20° C. is 10 to 100 g / L, preferably 15 to 80 g / L, most preferably 21 to 70 g / L.

[0079] Preferably, the tetraol is symmetrical, in particular having a symmetry such that the tetraol does not have a dipolar property. Preferably, the tetraol is symmetrical with respect to the four hydroxyl groups of the tetraol. Preferably, the tetraol has a symmetry plane. Preferably, the tetraol has a symmetry plane in which two of the four hydroxyl groups of the tetraol are arranged on one side of the mirror plane and the remaining two hydroxyl groups of the tetraol are arranged on the other side of the mirror plane.

[0080] Preferably, the tetraol has the following formula (1):

[0081]

[0082] Where R is C1 to C 18 alkylene or C1 to C2 alkylene having 1 to 3 heteroatoms independently selected from O, N, S and P17 Heteroalkylene.

[0083] Preferably, R in formula (1) is C1 to C 12 alkylene or C1 to C2 alkylene having 1 to 2 heteroatoms independently selected from O and S 11 Further preferably, R in formula (1) is a C1 to C8 alkylene group or a C1 to C8 heteroalkylene group having one heteroatom independently selected from O and S. More preferably, R in formula (1) is a C1 to C6 alkylene group or a C1 to C6 heteroalkylene group having a single O (oxygen) heteroatom.

[0084] Preferably, R in formula (1) is C1 to C 12 Alkylene or C1 to C2 having 1 to 2 heteroatoms independently selected from O and S 11 Further preferably, R in formula (1) is C1 to C8 alkylene or C1 to C8 heteroalkylene having one heteroatom independently selected from O and S. More preferably, R in formula (1) is C1 to C6 alkylene or C1 to C6 heteroalkylene having a single O (oxygen) heteroatom.

[0085] Most preferably, the tetraol is selected from the tetraols of formula (2) and formula (3):

[0086]

[0087] The tetraol is used as a decapping agent in the composition for dyeing a substrate according to the invention. The decapping agent improves the "decapping time". The "decapping time" is understood to mean the time during which a writing device or writing system can remain open (i.e., unclosed), stored, or not in use without drying out in the process.

[0088] binder

[0089] It may be provided that the composition for dyeing a substrate further comprises 0.1 to 50% by weight of a binder.

[0090] Preferably, the composition comprises a total binder content of at least 5 wt %, particularly preferably at least 10 wt %, further preferably at least 20 wt %, more preferably 25 wt %, most preferably at least 28 wt %, based on the total weight of the composition.

[0091] Preferably, the composition comprises a total content of binder of at most 45% by weight, particularly preferably at most 40% by weight, for example about 38% by weight, based on the total weight of the composition.

[0092] Preferably, the composition contains a total binder content of 5 to 45 wt %, particularly preferably 10 to 40 wt %, further preferably 20 to 40 wt %, most preferably about 25 to 38 wt %, for example about 28 to 38 wt %, based on the total weight of the composition.

[0093] A corresponding amount of binder in the composition helps the tetraol to dissolve and function.

[0094] The binder can be used in the composition as a solid and / or aqueous binder preparation, ie can be used in these forms for preparing the composition. In this context, an aqueous binder preparation is particularly a binder solution or a binder dispersion.

[0095] Preferably, a binder dispersion is used to prepare the composition according to the invention. In this case, the binder content in the composition is expressed with reference to the total weight of the binder dispersion (including solvent, etc.). By using the corresponding binder dispersion to prepare the composition according to the invention, advantageous mixing in the composition can be achieved.

[0096] It may be provided that the binder is a synthetic polymer binder, preferably a polyacrylate, a polyurethane, a polyester, a sulfopolyester, a maleate resin or a copolymer of two or more thereof, or a wax (eg beeswax).

[0097] The binder may be Acronal 12DE (acrylonitrile-acrylate copolymer dispersion, BASF), Neocryl XK166N (acrylic acid-styrene copolymer dispersion, Covestro), NeoRez R-3972 (polyurethane dispersion, Covestro), Eastek 1000 (sulfopolyester colloid solution, Eastman), or Neocryl XK-39 (alkali-soluble polyacrylate dispersion, Covestro).

[0098] Preferably, the binder is an acrylic acid-styrene copolymer, a sulfopolyester, or a mixture thereof, preferably a mixture of an acrylic acid-styrene copolymer and a sulfopolyester. Further preferably, the binder is a mixture of an acrylic acid-styrene copolymer and a sulfopolyester in a weight ratio of 10:1 to 1:2, more preferably 5:1 to 1:1.5, more preferably 3:1 to 1:1, for example, about 2:1.

[0099] For example, the binder may be a mixture of Neocryl XK166N (acrylic acid-styrene copolymer dispersion, Covestro) and Eastek 1000 (sulfopolyester colloid solution, Eastman) in a weight ratio of 2:1.

[0100] Alternatively, it can be provided that the acid number of the binder is preferably at most 250 mg KOH / g dry matter, more preferably at most 220 mg KOH / g dry matter, further preferably at most 200 mg KOH / g dry matter, further preferably at most 180 mg KOH / g dry matter, even more preferably at most 170 mg KOH / g dry matter, most preferably at most 160 mg KOH / g dry matter, for example about 130 mg KOH / g or 160 mg KOH / g dry matter.

[0101] The acid value of the binder may preferably be 50 to 250 mg KOH / g dry matter, more preferably 60 to 220 mg KOH / g dry matter, further 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, further preferably 100 to 160 mg KOH / g dry matter, 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 or 160 mg KOH / g dry matter. By using a binder having a corresponding acid value, an advantageous effect can be achieved in terms of redissolubility with the aid of an alkaline composition for watercoloring.

[0102] The binder may preferably be a polymer binder. The binder may preferably be a polymer resin. It may be provided that the binder has carboxyl groups and / or nitrile groups and / or sulfonyl groups, preferably carboxyl groups. This allows for particularly good dyeability, especially when using basic dyes. It is preferably provided that the binder is a polymer resin containing carboxyl-containing monomer units. Particularly preferably, the binder comprises or consists of a polyacrylate resin.

[0103] It can be provided that the pH value of the binder dispersion is at most 7, preferably less than 7, more preferably 1 to 5, further preferably 1.5 to 3, and most preferably 1.9 to 2.5. It can be provided that the binder dispersion is a white or translucent dispersion of binder particles with low viscosity in the acidic or neutral pH range (i.e. pH≦7), wherein these binder particles gradually dissolve at higher pH values ​​until a clear, transparent and highly viscous solution is formed.

[0104] Provision can be made for the binder dispersion to have a solids content of 30 to 60% by weight, preferably 40 to 50% by weight, particularly preferably 43 to 47% by weight, most preferably 44 to 46% by weight, based on the total weight of the binder dispersion.

[0105] The binder may be an alkali-soluble acrylate dispersion. The binder may be an alkali-soluble polyacrylate dispersion. The binder may be an acidic acrylate dispersion. The binder may be an acidic polyacrylate dispersion. The binder may be an ASE thickener. Commercially available examples of corresponding binders include 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 use of corresponding alkali-soluble polyacrylate dispersions achieves the most significant effect of the present invention, namely, particularly easy-to-adjust water resistance.

[0106] It may be provided that the binder, in particular the binder dispersion, comprises binder particles. It may be provided that the binder particles have an average particle size of at least 50 nm, preferably at least 100 nm. The particle size can be determined by dynamic light scattering according to the ASTM E3247-20 standard in force on the priority date. A correspondingly larger binder particle size can ensure that the composition does not penetrate too deeply into the absorbent substrate, thereby improving the watercolor properties, i.e., the subsequent coatability of the ink on the substrate.

[0107] Preservatives / Biocides

[0108] The composition may also contain 0.01 to 0.5% by weight of a preservative and / or biocide, based on the total weight of the composition. Preferred preservatives include, for example, mixtures of tert-butyl hydroperoxide and ethylene glycol monophenyl ether, particularly preferably mixtures of 12 to 60% by weight of tert-butyl hydroperoxide and 3 to 50% by weight of ethylene glycol monophenyl ether; or mixtures of 1,6-dihydroxy-2,5-dioxane and tetramethylolacetylene diurea. Such preservatives are particularly suitable for aqueous solutions and emulsions. Preferred biocides include, for example, mixtures of 2-bromo-2-nitropropane-1,3-diol and 2-octyl-2H-isothiazol-3-one; or, for particularly effective protection against contamination, mixtures of BIT (1,2-benzisothiazolin-3-one), MIT (2-methyl-4-isothiazolin-3-one), and OIT (2-octyl-2H-isothiazol-3-one). Another preferred biocide is a mixture of CIT / MIT in a weight ratio of 3:1. Another preferred biocide is 2-bromo-2-nitropropane-1,3-diol. Another preferred biocide is 2-octyl-2H-isothiazol-3-one. Another preferred biocide is phenoxyethanol.

[0109] Preferably, the composition comprises a total content of preservatives and / or biocides of at least 0.05 wt%, more preferably at least 0.2 wt%, further preferably at least 0.15 wt%, most preferably at least 0.1 wt%, based on the total weight of the composition.

[0110] Preferably, the composition comprises a total content of preservatives and / or biocides of at most 0.4 wt.-%, particularly preferably at most 0.3 wt.-%, further preferably at most 0.25 wt.-%, most preferably at most 0.2 wt.-%, based on the total weight of the composition.

[0111] Preferably, the composition comprises a total content of preservatives and / or biocides of 0.025 to 0.4 wt. %, particularly preferably 0.05 to 0.3 wt. %, further preferably 0.75 to 0.2 wt. %, most preferably about 0.1 wt. %, based on the total weight of the composition.

[0112] moisturizer

[0113] It may be provided that the composition further comprises 0.01 to 20% by weight of a moisturizing agent, based on the total weight of the composition. The moisturizing agent is preferably an organic polyol and / or polyethylene glycol and / or a sugar alcohol and / or a polar organic compound that is liquid at room temperature and pressure, particularly preferably selected from diethylene glycol, propylene glycol, 1,2-propylene glycol, glycerol, trimethylolpropane, di-trimethylolpropane, neopentyl glycol, erythritol, dimethyl sulfoxide, pyrrolidone (especially 2-pyrrolidone or N-methyl-2-pyrrolidone (NMP)) and mixtures thereof, and particularly preferably 1,2-propylene glycol.

[0114] A preferred combination is: on the one hand, an organic polyol and / or polyethylene glycol and / or a polar organic compound that is liquid at room temperature and normal pressure as a humectant; on the other hand, pentaerythritol and / or bis(trimethylolpropane). A preferred combination is: on the one hand, an organic polyol and / or polyethylene glycol as a humectant; on the other hand, pentaerythritol and / or bis(trimethylolpropane). Further, a preferred combination is: on the one hand, an organic polyol as a humectant; on the other hand, pentaerythritol and / or bis(trimethylolpropane). In particular, a preferred combination is 1,2-propylene glycol as a humectant and pentaerythritol and / or bis(trimethylolpropane) as a tetrahydric alcohol. Particularly preferred is a combination of 1,2-propylene glycol as a humectant and pentaerythritol as a tetrahydric alcohol.

[0115] Preferably, the composition comprises the moisturizer in an amount of at least 1 wt %, particularly preferably at least 5 wt %, further preferably at least 7.5 wt %, most preferably at least 10 wt %, based on the total weight of the composition.

[0116] Preferably, the composition comprises the moisturizer in an amount of at most 17.5 wt %, particularly preferably at most 15 wt %, further preferably at most 13.5 wt %, based on the total weight of the composition.

[0117] Preferably, the composition contains the moisturizer in an amount of 1 to 17.5 wt %, particularly preferably 5 to 15 wt %, further preferably 7.5 to 14.5 wt %, and most preferably about 10 to 13.5 wt %, based on the total weight of the composition.

[0118] The corresponding humectants in appropriate concentrations improve the COT and writing performance after a short time interval. Furthermore, they have a positive effect on film formation and, therefore, on the stability of the marking. In particular, corresponding synergistic effects can be observed in interaction with tetraols.

[0119] Surfactants / surfactants

[0120] It may be provided that the composition further comprises from 0.01 to 7% by weight, based on the total weight of the composition, of surfactants and / or surface-active substances.

[0121] The surfactant may be an emulsifier, dispersant, stabilizer or substrate wetting agent, preferably a silicone surfactant, fatty alcohol ether sulfate (especially sodium C12-14 fatty alcohol ether sulfate (30EO)), fatty alcohol ether phosphate, fatty alcohol phosphate ester, sulfosuccinate or the like.

[0122] The surfactant is preferably a nonionic surfactant, anionic surfactant or amphoteric surfactant.

[0123] Stabilizers in the sense of the present disclosure are in particular surface-active substances which stabilize colloidal particle systems against reagglomeration or agglomeration by adsorption at the particle interfaces by means of steric, electrostatic or electrosteric interactions, thereby preventing sedimentation, syneresis, particle size increase and viscosity increase.

[0124] In the context of the present disclosure, nonionic surfactants can be classified according to the following system. This is the system described by Atlas Chemie, the "HLB system" (Hydrophilic-Lipophilic Balance). In the HLB system, each emulsifier is assigned a numerical value, called the HLB value. The HLB value indicates the hydrophilic-lipophilic balance.

[0125] All emulsifiers contain both hydrophilic and lipophilic groups. Lipophilic emulsifiers have low HLB values, below 9.0, while hydrophilic emulsifiers have high HLB values, above 11.0. Emulsifiers with low HLB values ​​tend to be oil-soluble, while emulsifiers with high HLB values ​​are water-soluble. For example, water-soluble emulsifiers are used when the end product can be diluted with water. O / W emulsifiers have HLB values ​​between 8 and 18. Hydrophilic emulsifiers with high HLB values ​​promote the formation of O / W emulsions.

[0126] In the compositions according to the invention, the nonionic dissolution aid used may preferably be a commercially available emulsifier, which is available, for example, as a viscous solution and is prepared by reacting ethylene oxide with hydrogenated castor oil. It may, for example, consist of 90% by weight of hydrogenated castor oil, 5% by weight of 1,2-propylene glycol, and 5% by weight of water. Components of this type of emulsifier may also include fatty acid glycerol polyglycol esters and fatty acid polyglycol esters. These represent the hydrophobic portion of the product. The hydrophilic portion may consist of polyethylene glycol and glycerol ethoxylate.

[0127] Possible emulsifiers that come into consideration are preferably nonionic emulsifiers selected from the group consisting of alcohol fatty acid esters, ethylene fatty acid esters, polyethylene glycol fatty acid esters, glycerol or poly fatty acid esters, sorbitol fatty acid esters, pentaerythritol fatty acid esters, glyceride fatty acid esters, sucrose fatty acid esters, alcohol polyglycol ethers, fatty acid polyglycol ethers, fatty acid ester polyglycol ethers, fatty amine polyglycol ethers, fatty acid alkanolamide polyglycol ethers, oil and fat polyglycol ethers, polypropylene glycol polyglycol ethers, lanolin polyglycol ethers, alcohol polypropylene glycol ethers, fatty acid polypropylene glycol ethers, fatty amine polypropylene glycol ethers, lanolin polypropylene glycol ethers.

[0128] Preferably, the composition comprises a total content of surfactants and / or surface-active substances of at least 0.1 wt.-%, based on the total weight of the composition, particularly preferably at least 0.5 wt.-%, further preferably at least 1 wt.-%, most preferably at least 1.5 wt.-%.

[0129] Preferably, the composition comprises a total content of surfactants and / or surface-active substances of at most 5 wt.-%, based on the total weight of the composition, particularly preferably at most 4 wt.-%, further preferably at most 3 wt.-%, most preferably at most 2 wt.-%.

[0130] Preferably, the composition comprises a total content of surfactants and / or surface-active substances of 0.1 to 5% by weight, preferably 0.5 to 4% by weight, further particularly preferably 1 to 3% by weight, most preferably 1.5 to 2% by weight, for example about 1.5% by weight, based on the total weight of the composition.

[0131] By using corresponding amounts of corresponding surfactants and / or surface-active substances, the ink stability and the wetting of the substrate to be dyed can be improved.

[0132] Oligomers / polymers with surface active groups / pigment-affinity groups

[0133] It can be provided that the composition further comprises a compound having surface-active groups and / or pigment-affinity groups, preferably an oligomer having surface-active groups and / or pigment-affinity groups and / or a polymer having surface-active groups and / or pigment-affinity groups, in an amount of 0.01 to 5% by weight, based on the total weight of the composition.

[0134] In the sense of the present disclosure, a pigment-affinic group refers to an anchoring group which is selected according to the type of pigment, for example whether the pigment is organic or inorganic.

[0135] In the sense of the present disclosure, surface-active groups are groups which have an affinity for surfaces and interfaces, such as surfaces and interfaces of glass, metal, plastic, air, binder particles (mineral or organic) or pigments (mineral or organic).

[0136] In particular, for use with inorganic or mineral pigments (TiO2, iron oxide, etc.), compounds having anionic or cationic surface-active groups and / or pigment-affinity groups, in particular compounds having amino groups, phosphate groups, quaternary ammonium groups, sulfonate groups, carboxylate groups, etc., can be provided.

[0137] Unmodified organic pigments are generally nonpolar and lack a surface charge. Nonionic dispersants with hydrophilic and hydrophobic molecular segments are often used, with the nonpolar segments adhering to the pigment surface via van der Waals interactions (see HLB value). The corresponding nonpolar segments are considered pigment-affinity groups. Examples of hydrophobic, surface-active and / or pigment-affinity groups include nonylphenol, isotridecyl, isotriphenylethylene, C13, siloxane, and phenolic resin groups.

[0138] These compounds having surface active and / or pigment-affinity groups are added to pigmented writing fluids to stabilize them against agglomeration, sedimentation, syneresis, viscosity drift, tinting strength fluctuations, hue changes, and other aging effects, or to improve the compatibility between the binder and the colorant.

[0139] Preferably, the composition contains compounds having surface-active groups and / or pigment-affinity groups in an amount of at least 0.1% by weight, particularly preferably at least 0.5% by weight, further preferably at least 0.75% by weight, and most preferably at least 1% by weight, based on the total weight of the composition.

[0140] Preferably, the composition contains compounds having surface-active groups and / or pigment-affinic groups in an amount of at most 5% by weight, based on the total weight of the composition, particularly preferably at most 2.5% by weight, further preferably at most 1.5% by weight, most preferably at most 1% by weight.

[0141] Preferably, the total content of compounds having surface-active groups and / or pigment-affinity groups contained in the composition is 0.1 to 5 wt. %, particularly preferably 0.5 to 2.5 wt. %, further preferably 0.75 to 1.5 wt. %, and most preferably about 1 wt. %, based on the total weight of the composition.

[0142] Other components

[0143] In addition, co-binders (such as acid-free acrylate polymers, etc.) and co-film formers (Texanol, butyl glycol, butyl diglycol, etc.) can be added to further optimize the film properties and other application performance of the ink.

[0144] Likewise, waxes may be added to improve scratch resistance.

[0145] It may be provided that the composition contains no urea. In this context, "free" means that no urea has been actively added to the composition and that it is at most present only as an impurity in amounts that cannot be avoided by conventional purification methods. DETAILED DESCRIPTION

[0146] In one embodiment, the present invention relates to a composition for dyeing a substrate comprising, based on the total weight of the composition:

[0147] - 20 to 40% by weight of water;

[0148] - 1 to 6% by weight of tetraol;

[0149] - 0.1 to 0.5% by weight of biocide;

[0150] - 5 to 15% by weight of moisturizer;

[0151] - 1 to 3% by weight of surfactants and / or surface-active substances;

[0152] - 1 to 12.5% ​​by weight of a colorant; and

[0153] - 25 to 45% by weight of a binder;

[0154] in

[0155] The tetraol has at least 5 carbon atoms.

[0156] In one embodiment, the present invention relates to a composition for dyeing a substrate comprising, based on the total weight of the composition:

[0157] - 20 to 40% by weight of water;

[0158] - 1 to 6% by weight of tetraol;

[0159] - 0.1 to 0.5% by weight of biocide;

[0160] - 5 to 15% by weight of moisturizer;

[0161] - 1 to 3% by weight of surfactants and / or surface-active substances;

[0162] - 1 to 12.5% ​​by weight of a colorant; and

[0163] - 25 to 45% by weight of a binder;

[0164] in

[0165] The tetraol has the following formula (1):

[0166]

[0167] wherein R is a C1 to C18 alkylene group or a C1 to C17 heteroalkylene group having 1 to 3 heteroatoms independently selected from O, N, S, and P.

[0168] In one embodiment, the present invention relates to a composition for dyeing a substrate comprising, based on the total weight of the composition:

[0169] - 20 to 40% by weight of water;

[0170] - 1 to 6% by weight of tetraol;

[0171] - 0.1 to 0.5% by weight of biocide;

[0172] - 5 to 15% by weight of moisturizer;

[0173] - 1 to 3% by weight of surfactants and / or surface-active substances;

[0174] - 1 to 12.5% ​​by weight of a colorant; and

[0175] - 25 to 45% by weight of a binder;

[0176] in

[0177] The tetrahydric alcohol is selected from the tetrahydric alcohols of the following formula (2) and formula (3):

[0178]

[0179] Preparation of compositions for dyeing substrates

[0180] The composition for dyeing substrates can be prepared by mixing methods known in the art, for example by adding the individual components of the composition for dyeing substrates to a mixing kettle. In this case, the individual components are continuously mixed with one another thoroughly by means of suitable stirring means in order to distribute them sufficiently evenly.

[0181] Provision can be made to heat the components of the composition according to the invention for dyeing substrates for a sufficiently long time (preferably 30 to 60 minutes), preferably to 50 to 60° C., to obtain a particularly homogeneous composition (for example in the form of a dispersion).

[0182] After cooling, the soluble components of the composition remain permanently dissolved. Without being bound by this assumption, it can be assumed that the tetraol attaches or adsorbs to the particle interfaces (pigment and polymer particles) present in the composition (or to dissolved polymer molecules).

[0183] Use of a composition for dyeing a substrate

[0184] The invention also relates to the use of the composition according to the invention for dyeing substrates for producing a film on a substrate.

[0185] The use according to the present invention may particularly include providing a substrate, preferably an absorbent substrate, such as an absorbent writing substrate, more preferably drawing board or paper, particularly preferably watercolor paper; or a non-absorbent substrate, such as a synthetic substrate or plastic substrate, particularly preferably a synthetic or plastic film; or a mixed media substrate, i.e., a combination of absorbent and non-absorbent materials, for example; or a canvas. Any other suitable substrate may also be provided, such as wood, stone, eggshell, etc.

[0186] Provision may be made for the composition according to the invention for dyeing substrates to then be applied to the substrate.

[0187] In this case, the composition can be applied to at least a surface of the base material. In this case, the composition is applied to at least a part of the corresponding surface. The application can include writing, painting, painting, printing, spraying or a combination of two or more thereof. The application can be carried out by a paintbrush, a pen (particularly a watercolor pen), a print head, a fountain pen or other conventional application devices (such as a spray gun) or a combination of two or more thereof.

[0188] After application, the applied composition can be dried on the substrate (or partially dried in the substrate if some of the composition has penetrated the substrate). The drying can be carried out at room temperature (23° C.) and standard atmospheric pressure. Drying can be supported by supplying heat, passing a gas flow (air stream) through the composition to be dried, applying a vacuum, etc.

[0189] Effects of the present invention

[0190] The compositions according to the invention for dyeing substrates surprisingly have an excellent cover-off time (COT) combined with very short drying times and excellent stability on various types of substrates, in particular also on non-absorbent surfaces.

[0191] In particular, it has surprisingly been found that the addition of certain tetraols can lead to very good COT, wherein other application properties are not impaired and can even be significantly improved. Two substances, di-trimethylolpropane (Di-TMP) and pentaerythritol (pentaerythritol), can produce particularly pronounced effects and have proven to be particularly advantageous.

[0192] Furthermore, surprisingly, the compositions according to the invention for dyeing substrates can be formulated urea-free, in particular using only substances which, in contrast to urea, are hydrolytically stable, do not readily decompose and have no effect on the long-term pH of the composition.

[0193] Compared to writing fluids known in the prior art, the composition for dyeing a substrate according to the present invention can also significantly reduce the overall humectant content. At the same time, the composition according to the present invention can significantly increase the binder content. This provides new flexibility and new possibilities for formulating writing fluids.

[0194] General Definition

[0195] Unless expressly stated otherwise, features stated in the singular (a) also include the plural form. For example, if it is stated that a composition according to the invention comprises a dye, this also includes the case where the composition comprises a mixture of a plurality of dyes.

[0196] Unless expressly stated otherwise, terms such as “comprising”, “including” and the like also include the meaning of “essentially comprising”, “essentially consisting of” or “consisting of…”

[0197] The sum of the individual contents stated for the composition according to the invention for dyeing substrates is 100% by weight, thus giving the total content of the composition.

[0198] Unless expressly stated otherwise, the term "composition" as used herein refers to "a composition for dyeing a substrate according to the present invention".

[0199] Working Example

[0200] Recipe Example 1

[0201] 30.0 g water

[0202] 0.10 g Acticide MBT1 (biocide)

[0203] 10.0 g 1,2-propylene glycol (humectant)

[0204] 5.0 g pentaerythritol (tetrahydric alcohol)

[0205] 1.50 g sodium C12-14 fatty alcohol ether sulfate (30EO) (surfactant)

[0206] 24.0 g Neocryl XK-166N (first binder)

[0207] 12.0 g Eastek 1100 (second binder)

[0208] 2.50 g texanol (film former)

[0209] 16.0 g of fuchsin preparation (30% PR122)

[0210] The components were mixed, heated to 60°C for 30 minutes, and then cooled to room temperature.

[0211]

[0212] Recipe Example 2

[0213] Formulation Example 2 was prepared as in Formulation Example 1, with the only difference being that bis(trimethylolpropane) was used as the tetraol instead of pentaerythritol.

[0214]

[0215] Recipe Example 3

[0216] Formulation Example 3 was prepared as in Formulation Example 1, with the only difference being that urea was used as the humectant instead of 1,2-propylene glycol.

[0217] Recipe Example 4

[0218] 36.9 grams water

[0219] 0.10 g Acticide MBT1 (biocide)

[0220] 10.0 g 1,2-propylene glycol (humectant)

[0221] 5.0 g pentaerythritol (tetrahydric alcohol)

[0222] 1.50 g sodium C12-14 fatty alcohol ether sulfate (30EO) (surfactant)

[0223] 28.0 g Neocryl XK-39 (acidic and alkali-soluble binder)

[0224] 0.7 g triethanolamine (pH adjuster, base)

[0225] 20.0 g carbon black preparation (34% pigment)

[0226] Comparison Formula 1

[0227] Comparative Formulation 1 was prepared as in Formulation Example 1, with the only difference being that the tetrahydric alcohol used was erythritol instead of pentaerythritol.

[0228]

[0229] Comparison Formula 2

[0230] Comparative Formulation 2 was prepared as in Formulation Example 1, with the only difference being that the hexavalent alcohol (water solubility => 2.4 g / l) dipentaerythritol was used instead of pentaerythritol.

[0231]

[0232] Compare Recipe 3

[0233] Comparative Formulation 3 was prepared as in Formulation Example 1, with the only difference being that ε-caprolactam was used instead of pentaerythritol.

[0234]

[0235] Comparison Formula 4

[0236] Comparative Formulation 4 was prepared as in Formulation Example 1, with the only difference being that the hexavalent alcohol sorbitol was used instead of pentaerythritol.

[0237]

[0238] Compare Recipe 5

[0239] Comparative Formulation 5 was prepared as in Formulation Example 1, with the only difference being that ε-caprolactone was used instead of pentaerythritol.

[0240]

[0241] Compare Formula 6

[0242] Comparative Formulation 6 was prepared as in Formulation Example 1, except that the diol neopentyl alcohol was used instead of pentaerythritol.

[0243]

[0244]

[0245] Compare Recipe 7

[0246] Comparative Formulation 7 was prepared as in Formulation Example 1, except that the triol 1,1,1-trimethylolpropane (TMP) was used instead of pentaerythritol.

[0247]

[0248] Compare Recipe 8

[0249] Comparative Formulation 8 was prepared as in Formulation Example 1, except that the pentavalent alcohol xylitol was used instead of pentaerythritol.

[0250]

[0251] Working Example

[0252] Example 1

[0253] The composition prepared in Formulation Example 1 was dispensed into test pens (fiber pens with capillary reservoirs). These pens were then fitted with extruded POM plastic nibs (0.5 mm) and placed horizontally overnight.

[0254] Subsequently, a decapping test was carried out under standard climatic conditions (23° C., 50% relative humidity). For this purpose, three pens were used per formulation and the composition of the formulation example was applied with these pens to standard paper (Xerox 80 g) as substrate.

[0255] The cap of the test pen was removed at the start time and the test pen was used for writing after time intervals of 10 minutes, 30 minutes, 60 minutes and 10 hours.

[0256] If the pen writes again spontaneously and forms an evenly covered line, it is considered to have passed the decapping test very well and is marked as "+++". If the pen writes again satisfactorily after writing for a few millimeters, it is considered to have passed the test and is marked as "+". If the pen no longer writes or only writes after a longer "tap", it is considered to have failed the test and is marked as "-".

[0257] Examples 2 to 4

[0258] Examples 2 to 4 were carried out as in Example 1, with the only difference being that the compositions of Formulation Example 2 to Formulation Example 4 were used instead of the composition of Formulation Example 1.

[0259] Comparative Examples 1 to 8

[0260] Comparative Examples 1 to 8 were carried out as in Example 1, except that the compositions of Comparative Formulations 1 to 8 were used instead of the composition of Formulation Example 1.

[0261] The results of Examples 1 to 4 and the experimental example are shown in Table 1.

[0262] Table 1:

[0263] Uncapping time 10 minutes 30 minutes 60 minutes 10 hours Example 1 +++ +++ +++ +++ Example 2 +++ ++ + +++ Example 3 +++ ++ + +++ Example 4 +++ ++ + +++ Comparative Example 1 / - / - -- --- Comparative Example 2 / - - -- --- Comparative Example 3 / - - -- --- Comparative Example 4 / - - -- --- Comparative Example 5 / - - -- --- Comparative Example 6 / + - -- --- Comparative Example 7 / + - -- --- Comparative Example 8 / - - -- ---

[0264] +++The pen writes again spontaneously and evenly. =>See instructions on previous page

[0265] ++The pen writes again almost spontaneously and evenly. =>See instructions on previous page

[0266] + The pen writes evenly again after a short interruption.

[0267] -The pen can only be written again after writing for several centimeters

[0268] --The pen no longer writes even after being tapped for a long time

[0269] ---The pen cannot be used, even after a long time of recovery after putting the protective case back on.

[0270] In addition, the drying time and water resistance of the compositions were tested. The experimental conditions and results are summarized in Table 2.

[0271] Table 2:

[0272]

[0273] The features of the invention disclosed in the preceding description and in the claims may be essential, alone or in any combination, for the realization of the invention in its various embodiments.

Claims

1. A composition for dyeing a substrate, comprising, 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 tetraols, in The tetraol has at least 5 carbon atoms.

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

3. The composition for dyeing a substrate according to claim 1 or 2, wherein The substrate is an absorbent writing substrate, preferably a drawing board or paper, or a non-absorbent substrate, preferably a synthetic film or plastic film, or a mixed media substrate, or a canvas.

4. A composition for dyeing a substrate according to any one of the preceding claims, wherein The colorant is a dye, a pigment, or a mixture of two or more thereof.

5. A composition for dyeing a substrate according to any one of the preceding claims, wherein The tetraol has the following formula (1): Where R is C1 to C 18 alkylene or C1 to C2 alkylene having 1 to 3 heteroatoms independently selected from O, N, S and P 17 Heteroalkylene.

6. A composition for dyeing a substrate according to any one of the preceding claims, wherein The tetrahydric alcohol is selected from the tetrahydric alcohols of the following formula (2) and formula (3):

7. A composition for dyeing a substrate according to any one of the preceding claims, wherein The composition further comprises 0.1 to 50 wt % of a binder, based on the total weight of the composition.

8. A composition for dyeing a substrate according to any one of the preceding claims, wherein The composition further comprises 0.01 to 0.5 wt % of a preservative and / or biocide, based on the total weight of the composition.

9. A composition for dyeing a substrate according to any one of the preceding claims, wherein The composition further comprises 0.01 to 20 weight percent of a humectant, based on the total weight of the composition.

10. A composition for dyeing a substrate according to any one of the preceding claims, wherein The composition further comprises 0.01 to 7 weight percent of a surfactant, based on the total weight of the composition.

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

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