Printing of mixed fibres, woven and non-woven or knitted fabrics

Abstract

The present invention relates to a composition for printing mixed fibres, yarns, woven or nonwoven or knitted fabrics comprising or consisting of at least acrylic, aramid and optionally wool, a process for producing said composition, the use of said composition, a process for printing said mixed fibres, yarns, woven or nonwoven or knitted fabrics and the use thereof for producing printed mixed fibres, yarns, woven or nonwoven or knitted fabrics and articles such as clothing.

Description

[Technical field]

[0001] FIELD OF THEINVENTION The present invention relates to a composition for printing mixed fibres, yarns, woven or nonwoven or knitted fabrics comprising or consisting of at least acrylic, aramid and optionally wool, a process for producing said composition, the use of said composition, a process for printing said mixed fibres, yarns, woven or nonwoven or knitted fabrics and its use for producing printed mixed fibres, yarns, woven or nonwoven or knitted fabrics and articles therefor, such as garments. [Background technology]

[0002] 2. Background of the Invention Modern functional textiles are often mixtures of different fibers made from different materials. Depending on the demands of the functional textile, the respective blends of fibers are used. For example, underwear should be soft to the touch, fit well during wear and be able to absorb moisture. Therefore, underwear is often made from blends of cotton (good moisture absorption) and elastane (improved softness to the touch and better fit due to its elasticity). To obtain a colored underwear of a homogeneous shade, the respective dye or dye composition must be carefully selected, since not all fibers (or textile materials) can be colored with all dyes.

[0003] There are four main "groups" of dyes: acid dyes, reactive dyes, cationic dyes and disperse dyes. The challenge is to use a dye or dye composition (e.g., a combination of reactive and acid dyes) that will color all materials in the mixed fiber while providing excellent lightfastness, color shade, etc.

[0004] One of the particularly difficult fibers to color is the fiber made from aramid, especially para-aramid. The fiber made from para-aramid already has a typical golden color, which is often not suitable for the desired application. For example, the body armor used by the police or the military is made from para-aramid fabric. Cationic dyes are the only dyes suitable for coloring para-aramid fibers or fabrics. However, cationic dyes have the disadvantage of low light fastness. Moreover, if a mixed fiber of, for example, para-aramid and other fibers is to be colored uniformly, the cationic dye must be used together with other colorants (for example, selected from acid dyes, reactive dyes or pigments) in the same colorant composition. Summary of the Invention

[0005] Object of the invention It is therefore an object of the present invention to provide a composition capable of coloring mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics comprising acrylic, aramid, especially para-aramid, and, optionally, wool, while simultaneously improving the light fastness of the colored mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics.

[0006] Summary of the Invention This objective is achieved by the following:

[0007] Item 1: An aqueous composition for printing mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics comprising or consisting of acrylic and aramid, said composition comprising: a) at least one cationic dye, b) a dispersion containing at least one pigment, c) at least one leveling agent, d) at least one solvent, e) at least one binder.

[0008] Item 2: 2. The aqueous composition according to claim 1, wherein the composition further comprises at least one reactive dye or at least one acid dye.

[0009] Item 3: 3. The aqueous composition according to at least one of items 1 or 2, wherein the at least one leveling agent is selected from fatty acids, ethylene urea, aliphatic alcohols or sulfates thereof, aliphatic amines or sulfated aliphatic amines, alkylaryls or sulfonates thereof, aliphatic alcohol ethylene oxides, phosphates, aliphatic polyglycol ethers, triazine derivatives or mixtures thereof.

[0010] Item 4: 4. The aqueous composition according to at least one of items 1 to 3, wherein the composition further comprises at least one stabilizer selected from an acrylate polymer, an acrylamide copolymer, an alkylphenol polyglycol ether or a mixture thereof.

[0011] Item 5: 5. The aqueous composition according to at least one of items 1 to 4, wherein the composition further comprises an additive selected from the group comprising a thickener, an acid donor or a mixture thereof.

[0012] Item 6: 6. The aqueous composition according to at least one of items 1 to 5, wherein the composition comprises, based on 100% by weight of the entire composition, 0.01 to 7% by weight of at least one cationic dye, 0.01 to 3% by weight of at least one dispersion containing at least one pigment, 4 to 12% by weight of at least one solvent, 4 to 12% by weight of at least one leveling agent, 0.5 to 12% by weight of at least one binder, 0 to 4% by weight of at least one stabilizer, 0 to 7% by weight of at least one reactive dye or 0 to 7% by weight of at least one acid dye, 0 to 8% by weight of at least one thickener, 0 to 5% by weight of an acid donor, and the remainder to 100% by weight is water.

[0013] Item 7: 7. The aqueous composition according to at least one of items 1 to 6, wherein the composition comprises, based on 100% by weight of the composition, 0.1 to 5% by weight of at least one cationic dye, 0.01 to 5% by weight of at least one reactive dye or 0.01 to 5% by weight of at least one acid dye, 1 to 10% by weight of at least one binder, 0.01 to 2.5% by weight of at least one dispersion containing at least one pigment, 5 to 11% by weight of at least one solvent, 5 to 11% by weight of at least one leveling agent, 0.1 to 4% by weight of at least one stabilizer, 1 to 5% by weight of at least one thickener, 1 to 3% by weight of at least one acid donor, and the remainder to 100% by weight is water.

[0014] Item 8: A method for producing the aqueous composition according to at least one of items 1 to 7, comprising the following steps: step A: mixing and homogenizing all components of the composition according to at least one of items 1 to 7, except for at least one dispersion containing at least one cationic dye and at least one pigment; step B: adding at least one dispersion containing at least one cationic dye and at least one pigment to the mixture obtained in step A; and step C: mixing and homogenizing the mixture obtained in step B.

[0015] Item 9: 9. Use of an aqueous composition according to at least one of items 1 to 7, or use of an aqueous composition produced according to the process according to item 8, for printing mixed fibres, yarns, woven, nonwoven or knitted fabrics comprising or consisting of acrylic and aramid.

[0016] Item 10: 10. Use according to item 9 for printing mixed fibres, yarns, woven, nonwoven or knitted fabrics which further comprise wool or consist of acrylic, aramid and wool.

[0017] Item 11: A process for printing mixed fibres, yarns, woven, nonwoven or knitted fabrics comprising or consisting of acrylic and aramid and, optionally, wool, comprising the steps of: The method comprises the steps of: step 1: printing a mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric using the aqueous composition according to at least one of items 1 to 7, or printing a mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric using the aqueous composition produced according to item 8; step 2: drying the printed mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric obtained in step 1 at a temperature of 100°C to 200°C; step 3: subjecting the printed mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric obtained in step 2 to a steam process by applying saturated steam at a temperature of at least 90°C to 110°C for at least 10 minutes to 50 minutes, thereby obtaining a printed mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric according to items 1 to 7. 5. A method according to claim 4, comprising the steps of: fixing at least one cationic dye present in the aqueous composition according to claim 1 or produced according to claim 8 on the mixed fibre, yarn, woven fabric, nonwoven fabric or knitted fabric; step 4: subjecting the printed mixed fibre, yarn, woven fabric, nonwoven fabric or knitted fabric obtained in step 3 to a curing step at a temperature of at least 130°C to 200°C for at least 1 minute to 7 minutes; step 5: subjecting the printed mixed fibre, yarn, woven fabric, nonwoven fabric or knitted fabric obtained in step 4 to a washing step; step 6: subjecting the printed mixed fibre, yarn, woven fabric, nonwoven fabric or knitted fabric obtained in step 5 to a final drying step at a temperature of at least 100°C to 200°C.

[0018] Item 12: 1. A printed mixed fiber, yarn, woven, nonwoven or knitted fabric comprising or consisting of acrylic and aramid, and optionally wool, said mixed fiber, yarn, woven, nonwoven or knitted fabric containing as colorants at least one cationic dye and at least one pigment derived from the aqueous composition according to at least one of items 1 to 7 or the aqueous composition produced by the process according to item 8.

[0019] Item 13: 13. The printed mixed fibre, yarn, woven, nonwoven or knitted fabric according to item 12, which comprises 30-50% by weight of acrylic, 30-50% by weight of aramid and 0-25% by weight of wool, based on 100% by weight of the mixed fibre, yarn, woven or knitted fabric.

[0020] Item 14: 1. A printed mixed fiber, yarn, woven, nonwoven or knitted fabric comprising or consisting of acrylic, aramid and optionally wool, said mixed fiber, yarn, woven, nonwoven or knitted fabric being printed by the method according to item 11 or printed with an aqueous composition according to at least one of items 1 to 7 or printed with an aqueous composition produced according to item 8.

[0021] Item 15: 15. The printed mixed fibre, yarn, woven, non-woven or knitted fabric according to at least one of items 12 to 14, used for producing protective fabrics for military and police uniforms and equipment such as backpacks, camping tents and belongings. [Brief description of the drawings]

[0022] [Figure 1a] FIG. 1a shows a fabric printed with a composition comprising a cationic dye without the inclusion of a dispersion containing at least one pigment. [Figure 1b] FIG. 1b shows a fabric printed with a composition according to the present invention comprising a cationic dye and a dispersion containing at least one pigment, as described herein. [Figure 2a] FIG. 2a illustrates the technical effect of the leveling agent. [Figure 2b] FIG. 2b illustrates the technical effect of the leveling agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Detailed Description of the Invention The object of the present invention is solved by an aqueous composition comprising at least one cationic dye, at least one dispersion containing at least one pigment, at least one leveling agent, at least one binder and at least one solvent.

[0024] The aqueous composition according to the invention has the advantage that it can be used for uniform printing of mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics, which contain or consist of acrylic, aramid, especially para-aramid, and optionally wool.Furthermore, the aqueous composition according to the invention has the advantage that it provides good light fastness and print quality.The aqueous composition according to the invention is preferably designed as a printing paste.

[0025] The term "fabric" is used within the context of this application as a general term for "fibers," "mixed fibers," "yarns," "knits," "nonwovens," and "wovens."

[0026] The term "mixed fibres" as used within the context of the present application means that at least two fibres are combined into one mixed fibre by commonly known spinning processes, at least two fibres being made of different materials, at least one fibre being made of or consisting of acrylic (such fibres are known for example under the trade name "Pyrotex" available from PyroTex, Hamburg) and the second fibre being made of or consisting of aramid, preferably para-aramid. Thus, as used within the context of the present application, the term mixed fibres refers to a combination of at least two fibres, one of which is made of acrylic and the second fibre is made of aramid, preferably para-aramid.

[0027] The term mixed fibers further encompasses embodiments in which the mixed fibers comprise or consist of at least three or more fibers, the three or more fibers being made of different materials, for example a first fiber is made of acrylic, a second fiber is made of aramid, preferably para-aramid, a third fiber is made of or consists of a material different from acrylic and aramid, and a fourth fiber is made of or consists of acrylic, aramid, and a material different from the material of the third fiber. In a preferred embodiment, the mixed fibers comprise or consist of three different fibers, the first fiber is made of acrylic, the second fiber is made of aramid, preferably para-aramid, and the third fiber is made of a material different from acrylic and aramid. Particularly suitable as a material for the third fiber is wool. Such mixed fibers are also available, for example, from Pyrotex, Hamburg. The advantages of a mixed fiber comprising or consisting of three fibers made of wool, aramid, acrylic fibers, especially Pyrotex, are high flame retardancy, improved antiviral rate, and at the same time provide a very comfortable wearing experience.

[0028] As used within the context of this application, the term "woven fabric" refers to a two-dimensional or three-dimensional fabric made from yarns by a weaving process. The yarns used to make the woven fabric consist of mixed fibers as defined above. As used within the context of this application, the term "yarn" refers to an agglomeration of mixed fibers achieved by a spinning process. This means that the yarn can contain two or more of the mixed fibers defined above, depending on the desired yarn properties, such as strength or thickness.

[0029] As used within the context of this application, the term "nonwoven" refers to a two-dimensional or three-dimensional fabric made from yarns bonded together by chemical, mechanical, thermal or solvent treatment, i.e. by a method other than the weaving method. The yarns used to make the nonwoven consist of mixed fibers as defined above. As used within the context of this application, the term "yarn" refers to an agglomeration of mixed fibers achieved by a spinning process. This means that the yarn can contain two or more of the mixed fibers defined above, depending on the desired yarn properties, such as strength or thickness.

[0030] As used within the context of this application, the term "knitted fabric" refers to a two- or three-dimensional fabric made from yarns by a knitting process, as defined above.

[0031] As used within the context of this application, the term "printing" refers to a method of applying color to fabrics, especially fibers, yarns, woven fabrics, nonwoven fabrics and knitted fabrics. In the prior art, this method is also called "textile printing". The color is usually applied as a dye or pigment. According to the present invention, at least one cationic dye is used to impart color to the fabric, especially mixed fibers, yarns, woven fabrics, nonwoven fabrics and knitted fabrics. Optionally, additional dyes, such as reactive dyes and / or acid dyes, can also be used in combination with the at least one cationic dye. During the printing process or during a finishing process (such as a curing process), the applied dye is fixed to the fabric, especially mixed fibers, yarns, woven fabrics, nonwoven fabrics and knitted fabrics, such that the dye cannot be washed off or otherwise removed from the fabric, especially mixed fibers, yarns, woven fabrics, nonwoven fabrics and knitted fabrics. There are many art-known printing methods for printing fabrics, especially mixed fibers, yarns, woven fabrics, nonwoven fabrics and knitted fabrics, such as block printing, perotine printing, roller, cylinder or machine printing, stencil printing, screen or flat printing, digital textile printing, flexotextile printing. The aqueous composition according to the present invention is suitable for use in any known method for printing fabrics, especially for printing mixed fibers, yarns, woven fabrics, nonwoven fabrics and knitted fabrics. The printing process or the printed fabric is particularly characterized in that a distinct pattern or design is applied to the fabric, especially mixed fibers, yarns, woven fabrics, nonwoven fabrics and knitted fabrics. Thus, the term "printed" as used within the context of the present application refers to fabrics, in particular mixed fibres, yarns, woven fabrics, nonwoven fabrics and knitted fabrics, which have been subjected to a printing process as defined above by colouring the fabrics, in particular mixed fibres, yarns, woven fabrics, nonwoven fabrics and knitted fabrics, by using an aqueous composition according to the present invention.

[0032] The term "wool" as used within the context of this application refers to natural fibers of animal origin. Typically, wool is obtained from sheep and other animals such as rabbits (angora), goats (cashmere and mohair), musk oxen (qiviut), and camels. Wool is made from a specific type of fiber structural protein called keratin (also known as sclerotin), which contains disulfide bridges. Wool has several desirable properties: excellent fire resistance, low density that allows lightweight fabrics to be produced, excellent insulating properties, excellent light fastness when colored, and excellent water absorption, but at the same time, wool can easily release absorbed water, giving it a dry feel, antistatic properties, and self-cleaning properties (i.e., odors are released after ventilation). Wool fibers can be colored with acid dyes, reactive dyes, or pigments.

[0033] As used within the context of this application, the term "aramid" refers to synthetic fibers made from aromatic polyamides, which are obtained by the reaction of aryl-containing dicarboxylic acids with aryl-containing diamine compounds. Aramid fibers are fibers with high melting points, heat resistance and strength. Commonly known aramid fibers are, for example, Kevlar, Nomex or Twaron. Essentially, there are two different "classes" of aramids: meta-aramids and para-aramids. The difference between meta-aramids and para-aramids is the substitution of the aromatic ring. If the amide bond between the two aryl moieties is in the para position to each other, the aramid is a para-aramid (Kevlar, Twaron, etc.), and if the amide bond between the two aryl moieties is in the meta position to each other, the aramid is a meta-aramid (Nomex, etc.). Para-aramids have a characteristic golden color. Aramid fibers can only be colored with cationic dyes.

[0034] As used within the context of this application, the term "acrylic" refers to synthetic fibers made by polymerizing acrylonitrile monomer, optionally together with one or more comonomers, such as vinyl acetate or methyl acrylate. Typically, acrylonitrile is present in acrylic fibers in an amount of 85% by weight. As used within the context of this application, "modacrylic" is a modified acrylic fiber characterized in that the amount of acrylonitrile present in the fiber is at most 85 wt%, with the remainder made from other comonomers (and thus also encompassed by "acrylic" within the context of this application). Furthermore, acrylic and modacrylic fibers can be further modified by chemical and / or physical means to further improve properties such as flame retardancy. Acrylic fibers are self-extinguishing and difficult to ignite, making them flame retardant. Furthermore, acrylic fibers and fabrics made therefrom are wool-like, i.e., soft, warm, dimensionally stable, and have good stretch. Furthermore, acrylic fibers have low thermal conductivity. One particularly advantageous acrylic fiber is sold under the trade name Pyrotex (PyroTex, Hamburg). Acrylic fabrics, especially blended fibers, yarns, wovens, nonwovens and knits, can be dyed with cationic, acid and reactive dyes.

[0035] As used within the context of this application, the term "cationic dye", also known in the prior art as a basic dye, is a synthetic dye that acts as a base. Cationic dyes, when solubilized in water, form colored cationic salts (i.e., cationic groups are formed within the dye structure). These cationic groups react with anionic groups on the surface of the substrate to be colored. Cationic dyes produce bright shades with high coloring strength. Cationic dyes are the only dyes that can color (e.g., by printing) aramid, especially para-aramid based fabrics, especially blended fibers, yarns, wovens, nonwovens and knits. The main disadvantage of cationic dyes is their poor light fastness. Suitable cationic dyes are represented by the formula: [ka] In the above formula, R represents -OCH3 or -CH3, and X represents Cl. - , CH3OSO3 - , [ka] In the above formula, R 1 represents any one of the following formulae (IIa), (IIb) and (IIc), and * represents a bond to the azo bond of the azo compound (II). [ka] In the above formula, R 2 represents methyl or ethyl, R 3 represents methyl, ethyl, -CH2CH2OH, -CH2C6H5, and X represents Cl - , CH3OSO3 - Represents. Further suitable cationic dyes include those having the following Color Index Numbers (CI Numbers): CI Basic Yellow 24 (CAS: 52435-14-0), CI Basic Yellow 28 (CAS: 54060-92-3), CI Basic Yellow 29 (CAS: 39279-59-9), CI Basic Yellow 13 (CAS: 12217-50-4), CI Basic Yellow 82 (CAS: 12227-67-7), CI Basic Orange 22 (CAS: 4657-00-5), CI Basic Red 4 It is known as CI Basic Red 6 (CAS: 12221-69-1), CI Basic Red 14 (CAS: 12217-48-0), CI Basic Red 29 (CAS: 42373-04-6), CI Basic Blue 3 (CAS: 33203-82-6), CI Basic Blue 41 (CAS: 12270-13-2), CI Basic Blue 54 (CAS: 15000-59-6), CI Basic Blue 141 (CAS: 63641-90-7), CI Basic Brown 4 (CAS: 5421-66-9). The at least one cationic dye is preferably present in an amount of at least 0.01% by weight, or at least 0.1% by weight, or at least 0.5% by weight, or at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight and up to 7% by weight, or up to 6% by weight, or up to 5% by weight, or up to 4% by weight, or from at least 0.01% to up to 7% by weight, or from at least 0.1% to up to 5% by weight, or from at least 0.5% to up to 4% by weight, based on 100% by weight of the total aqueous composition according to the present invention.

[0036] When used within the context of this application, the term "reactive dyes" is also known as "fiber-reactive azo dyes". Reactive dyes are well known in the art. Reactive dyes are characterized in that the dye chromophore contains one or more substituents that can react with substrates such as mixed fibers, yarns, woven, nonwoven and knitted fabrics, including or consisting of aramid or acrylic, etc. Reactive dyes are a class of organic dyes that contain at least one substituent that reacts with the substrate and thus forms a covalent bond between the dye molecule and the substrate to be colored. For example, WO2007 / 039573A2 relates to azo-reactive dyes and mixtures of fiber-reactive azo dyes, their preparation methods and their use for dyeing and printing hydroxyl- and carboxamide-containing materials. Furthermore, WO2004 / 088031 also discloses azo-reactive dyes and mixtures of fiber-reactive dyes, their preparation and their use. WO2015 / 149940 relates to compounds obtained by coupling two aminoaryl compounds in diazotized form to 3-aminophenylurea. These compounds are used as azo reactive dyes in dyeing and printing processes. Suitable reactive dyes are represented by the following formula: [ka] In the above formula, R 1 represents H, methyl, or ethyl, and R 2 Ha-SO3 - X + R 3 is H, methyl or -SO3 - X + represents X + is H + , Li + , Na + , K + , NR4 + and R represents one or more of H, C1-C6 branched or unbranched alkyl residues, or a mixture of one or more of these cations. [ka] In the above formula, R 1represents H, methyl, or ethyl, and R 2 Ha-SO3 - X + R 3 is H, methyl or -SO3 - X + represents X + is H + , Li + , Na + , K + , NR4 + and R represents one or more of H, C1-C6 branched or unbranched alkyl residues, or a mixture of one or more of these cations. [ka] In the above formula, R 1 and R 4 are each independently H, methyl, or ethyl; R 2 Ha-SO3 - X + R 3 is H, methyl or -SO3 - X + represents X + is H + , Li + , Na + , K + , NR4 + and R represents one or more of H, C1-C6 branched or unbranched alkyl residues, or a mixture of one or more of these cations. [ka] In the above formula, R 1 represents -NHCONH2, -NHCOCH3, and R 2 is H, phenyl, or one or two -SO3-X - represents a phenyl substituted with a group, + is H + , Li + , Na + , K + , NR4 +and R represents one or more of H, C1-C6 branched or unbranched alkyl residues, or a mixture of one or more of these cations. Alternatively, the -SO3H group shown in formulas (III)-(VI) above can be -SO3X - X may be a group; + Li + , Na + , K + , NR4 + wherein R represents one or more of H, C1-C6 branched or unbranched alkyl residues, or a mixture of one or more of these cations. Suitable reactive dyes are known under the following Color Index Numbers (CI Numbers): CI Reactive Red 24, CI Reactive Blue 49, CI Reactive Orange 12. At least one reactive dye is optionally present in the aqueous composition according to the invention in addition to at least one cationic dye. However, the presence of at least one reactive dye in the aqueous composition according to the invention is not essential. The at least one reactive dye may be absent in the aqueous composition according to the present invention or may be present in an amount of at least 0.01% by weight, or at least 0.1% by weight, or at least 0.5% by weight, or at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight, and up to 7% by weight, or up to 6% by weight, or up to 5% by weight, or up to 4% by weight, or from 0% to 7% by weight, or from at least 0.01% to 5% by weight, or from at least 0.1% to 4% by weight, based on 100% by weight of the total aqueous composition according to the present invention.

[0037] As used within the context of this application, the term "acid dye" refers to dyes that contain more acidic groups (e.g., sulfonic groups (-SO3 2- ) or carboxyl group (-CO3 2- )) refers to dyes containing the acid group. Acid dyes are usually applied under acidic conditions due to their acidic group. Suitable acid dyes are represented by the formula: [ka] In the above formula, R1 Ha-SO3X - , -NO2, R 2 H, -SO3-X + R 3 represents H, -OCH3, and X + is H + , Li + , Na + , K + , NR4 + and R represents one or more of H, C1-C6 branched or unbranched alkyl residues, or a mixture of one or more of these cations. [ka] In the above formula, R 1 represents H or -NO2. [ka] In the above formula, R 1 is H, alkyl (in particular methyl, ethyl, branched or unbranched propyl or branched or unbranched butyl), -OR 2 In the formula, R 2 represents -CH3, -CH2CH3, -CH2CH2OCH3. Alternatively, the -SO3H group shown in the above formulas (VII) to (IX) represents -SO3X - X may be a group; + Li + , Na + , K + , NR4 +R represents a cation selected from the group consisting of: R represents H, one or more C1-C6 branched or unbranched alkyl residues, or a mixture of one or more of these cations. Suitable acid dyes are known by the Color Index Numbers (CI Numbers): CI Acid Brown 289, CI Acid Brown 282, CI Acid Brown 283, CI Acid Brown 298, CI Acid Black 194, CI Acid Black 216, CI Acid Black 177, CI Acid Black 132, CI Acid Black 194. At least one acid dye is optionally present in the aqueous composition according to the invention in addition to the at least one cationic dye. However, the presence of at least one acid dye in the aqueous composition according to the invention is not mandatory. The at least one acid dye may be absent in the aqueous composition according to the present invention or may be present in an amount of at least 0.01% by weight, or at least 0.1% by weight, or at least 0.5% by weight, or at least 1% by weight, or at least 1.5% by weight, or at least 2% by weight and up to 7% by weight, or up to 6% by weight, or up to 5% by weight, or up to 4% by weight, or from 0% to 7% by weight, or from at least 0.01% to 5% by weight, or from at least 0.5% to 4% by weight, based on 100% by weight of the total aqueous composition according to the present invention.

[0038] In the aqueous composition according to the invention, at least one cationic dye and at least one pigment preparation are present in order to provide a composition which can be used to color, preferably print, mixed fibers, yarns, wovens, nonwovens or knitted fabrics, including aramids, especially para-aramids (which can only be colored, especially printed, using cationic dyes, and not especially printed, using reactive or acid dyes) and acrylics, especially pyrotex (which can be colored, especially printed, with cationic, acid and reactive dyes), in which high light fastness is achieved despite the use of at least one cationic dye.

[0039] As mentioned above, cationic dyes have a rather poor light fastness. Therefore, in the aqueous composition according to the invention, a dispersion containing at least one pigment is used. The advantage of this dispersion containing at least one pigment is that the light fastness of the cationic dye is improved without adversely affecting other properties of the cationic dye, such as the light shade of the cationic dye. This technical effect is shown in Figures 1a and 1b. Figure 1a shows a fabric printed with a composition containing a cationic dye without containing a dispersion containing at least one pigment (see the left "column" under the heading "unexposed" in Figure 1a). From Figure 1a, it can be clearly derived that the fabric is decolorized (light fastness rating 1.5) when exposed to light (see the right "column" under the heading "exposed" in Figure 1a). Figure 1b shows a fabric printed with a composition according to the invention, comprising a cationic dye and a dispersion containing at least one pigment, as described herein. The "left" column of FIG. 1b shows the fabric before exposure (under the heading "unexposed"). The right "column" of FIG. 1b shows the fabric after exposure (under the heading "exposed"). As can be clearly derived from the photographs, the fabric colored with an aqueous composition according to the invention, comprising at least one cationic dye and at least one dispersion containing at least one pigment, as described herein, is only slightly decolorized after exposure to light while maintaining a bright shade, achieving the required lightfastness rating (4.0). The ISO 105 / A02 lightfastness rating according to the grey scale for assessing the change in shade is used. The lightfastness rating is determined according to the numbers on the grey scale corresponding to the difference in colour between the print before and after the test (AATCC TM 16.3: 2014 option 3 for 40 hours). Furthermore, the dispersion containing at least one pigment can provide a treated fabric, especially a mixed fiber, yarn, woven, nonwoven or knitted fabric, with infrared reflection, i.e. the ability to reflect IR light. As used within the context of this application, the term "dispersion containing at least one pigment" refers to a liquid medium in which pigment particles are finely and uniformly dispersed.As used within the context of this application, the term "pigment" refers to a colorant that is essentially insoluble in the liquid medium in which it is uniformly dispersed. Pigments can be of natural or synthetic origin and can be either organic or inorganic. Commonly known pigments are, for example, TiO2 (white pigment), carbon black (black pigment), azo pigments such as Pigment Red 146, Pigment Yellow 83, phthalo pigments such as Pigment Blue 15:3, Pigment Green 7, Pigment Violet 23, Indigo (blue pigment), etc. Further suitable pigments are represented by the formula: [ka] In the above formula, R=H, Cl. Also suitable pigments include Color Index Numbers (CI Numbers): CI Pigment Yellow 83 (CAS: 5567-15-7), CI Pigment Yellow 139 (CAS: 36888-99-0), CI Pigment Yellow 42 (CAS: 51274-00-1), CI Pigment Red 146 (CAS: 5280-68-2), CI Pigment Red 122 (CAS: 980-26 ... Pigment Red 101 (CAS: 1309-37-1), CI Pigment Blue 28 (CAS: 68186-86-7), CI Pigment Blue 15:3 (CAS: 147-14-8), CI Pigment Green 7 (CAS: 1328-53-6), CI Pigment Green 17 (CAS: 1308-38-9), CI Pigment Black 7 (CAS: 1333-86-4). The liquid medium in which the at least one pigment is finely and uniformly ground and dispersed can be selected from water, polyglycols or mixtures thereof. The dispersion can be designed as a liquid, a semi-paste or a paste. In general, the concentration of the at least one pigment in the dispersion is at least 0.5% by weight and up to a maximum of 7% by weight, based on the total weight of the dispersion. A dispersion suitable for use in the aqueous composition according to the invention can contain one pigment. A dispersion suitable for use in the aqueous composition according to the invention can also contain two or more pigments. Dispersions containing at least one pigment that can be used in the aqueous composition according to the invention are generally known under the trade name Printofix (by Archroma), in particular Printofix T or TF. The particular advantage of Printofix T and Printofix TF is that they are aqueous pigment dispersions with an excellent environmental profile with excellent dispersion stability allowing easy preparation of printing pastes and very good performance during the printing process.The dispersion containing at least one pigment is present in an amount of at least 0.01% by weight, or at least 0.1% by weight, or at least 0.5% by weight, or at least 1% by weight, and up to 3% by weight, or up to 2.5% by weight, or up to 2% by weight, or at least 0.01% to up to 3% by weight, or from 0.01% to 2.5% by weight, or from 0.05% to 2% by weight, or from 0.1% to 1% by weight, or from 0.1 to 0.5% by weight, based on 100% by weight of the total aqueous composition according to the present invention.

[0040] The aqueous composition according to the invention further comprises at least one leveling agent. The leveling agent has the advantage of increasing the color yield and color strength on all fibers, for example aramid fibers, and for example acrylic fibers (such as Pyrotex fibers). By using the leveling agent, the color yield and color strength on the fiber can be increased by at least 15%, or at least 17%, or at least 20%, or at least 25%, or at least 30%, or at least 35% compared to a composition without a leveling agent. The leveling agent also has the advantage of improving the print quality. The technical effect of the leveling agent is shown in Figures 2a and 2b: Figure 2a shows a composition identical to the composition according to the invention, except that there is no leveling agent in the composition. The relative color strength (K / S) of the printed fabric was measured by the light reflectance technique using the Kubelka-Munk equation. The reflectance (R) of the printed fabric was measured with a Konica Minolta MF-3700d (Japan). As can be seen in the top photo of Figure 2a, the color of the fabric is not uniform and lacks color depth and light shades (color density = 100%). The bottom photo of Figure 2a shows that the printing process caused the design to bleed at the borders and reduce sharpness. The printed lines are interrupted. In contrast, the fabric shown in Figure 2b was printed with a composition according to the present invention, i.e. a composition containing a leveling agent. As can be seen from the top photo of Figure 2b, the color on the fabric is uniform, with a satisfactory color depth and lighter shades. This is due to the improved color yield and color density (123%) provided by the leveling agent. The bottom photo of Figure 2b shows a clear and sharp design without bleed at the borders. Also, the lines are printed evenly and very sharp. This is due to the ability of leveling agents to improve print quality. As used within the context of this application, the term "leveling agent" refers to a compound that can slow down the uptake of dye by the fiber. Leveling agents contain chemical groups that have an attractive force towards the dye.Since there is also an attractive force between the dye and the fiber, the attractive force of the leveling agent balances the attractive force of the fiber towards the dye, thereby slowing down the absorption of the dye by the fiber during the printing process, thus obtaining the above-mentioned demonstrated advantages. There are anionic, cationic and non-ionic leveling agents known in the prior art. The at least one leveling agent present in the aqueous composition according to the invention is preferably selected from fatty acids, ethylene urea, fatty alcohols or sulfates thereof, fatty amines or sulfated fatty amines, alkylaryls or sulfonates thereof, fatty alcohol ethylene oxide, alkyl phosphates, aliphatic polyglycol ethers, acrylic copolymers, triazine derivatives or mixtures thereof. Suitable leveling agents are known under the trade names Solidokol VN (nonionic, polyglycol ether), Primasol NF (anionic, alkyl phosphate), Printogen Additive CT (anionic triazine derivative) (all by Archroma), Lyoprint AP (Huntsman). The at least one leveling agent is present in the composition according to the invention in an amount of at least 4% by weight, or at least 4.5% by weight, or at least 5% by weight, or at least 6% by weight, or at least 7% by weight, and up to 12% by weight, or up to 11% by weight, or up to 10% by weight, or from at least 4% to up to 12% by weight, or from at least 5% to up to 11% by weight, or from at least 6% to up to 10% by weight, based on 100% by weight of the total aqueous composition according to the invention.

[0041] The composition according to the invention is preferably applied as a printing paste to mixed fibres, yarns, wovens, nonwovens, knitted fabrics. A certain amount of solvent is therefore necessary to be able to dissolve the dye and provide a homogeneous printing paste in which all the necessary compounds are uniformly distributed. As used within the context of the present application, the term "solvent" refers to a liquid capable of dissolving at least cationic dyes, and possibly reactive dyes or acid dyes, so that the dyes are uniformly distributed in the printing paste and can therefore be uniformly printed on the mixed fibres, yarns, wovens, nonwovens or knitted fabrics. Commonly known solvents are aromatic alcohols or aliphatic alcohols with aromatic groups, or cyclic heteroaliphatic derivatives. Suitable examples of solvents are benzyl alcohol, aromatic-substituted propanols, aromatic-substituted ethanols, aromatic-substituted butanols, pyrrolidone derivatives. Suitable solvents are known, for example, under the trade name Printogen Enhancer PAW (carboxamide derivatives mixture, by Archroma). This solvent has the advantage of being biodegradable (e.g., compared to benzyl alcohol). Therefore, less wastewater treatment is required. The solvent is present in the aqueous composition according to the invention in an amount of at least 4% by weight, or at least 4.5% by weight, or at least 5% by weight, or at least 6% by weight, or at least 7% by weight, and in an amount of up to 12% by weight, or up to 11% by weight, or up to 10% by weight, or from at least 4% to up to 12% by weight, or from at least 5% to up to 11% by weight, or from at least 6% to up to 10% by weight, based on 100% by weight of the total aqueous composition according to the invention.

[0042] The term "stabilizer" as used within the context of this application refers to a compound capable of improving the ionic stability of the composition according to the invention. In the aqueous composition according to the invention, at least one cationic dye is present, which has a cationic charge. Furthermore, a dispersion containing at least one pigment is present in the composition according to the invention. Such pigment dispersions are anionic. The attraction between the cationic dye and the pigment dispersion may adversely affect the stability of the composition according to the invention. To improve the stability of the aqueous composition according to the invention (e.g. to ensure a certain storage stability), at least one stabilizer can be added to the aqueous composition according to the invention. The at least one stabilizer can be selected from acrylate polymers, acrylamide copolymers, alkylphenol polyglycol ethers or derivatives thereof, or mixtures thereof. Suitable stabilizers are known under the trade names Decol SN (aqueous solution of acrylic acid and maleic anhydride copolymer as sodium salt, according to Archroma), Solidokol DPR or Lyogen SMK. When the at least one stabilizer is present in the aqueous composition according to the invention, it is present in an amount of at least 0.1%, or at least 0.5%, or at least 1%, up to 4%, or up to 3.5%, or up to 3%, by weight, or the at least one stabilizer is present in the aqueous composition according to the invention in an amount of 0% to 4%, or 0.1% to 4%, or 0.5% to 2%, by weight, based on 100% by weight of the total aqueous composition according to the invention.

[0043] The composition according to the invention further comprises at least one binder. The at least one binder has the advantage of forming a film on the substrate to which it is applied. In this case, the binder forms a film on the fabric, in particular on the mixed fibers, yarns, woven, nonwoven or knitted fabric. By film formation, the at least one pigment present in the composition according to the invention is fixed on the fabric, in particular on the mixed fibers, yarns, woven, nonwoven or knitted fabric. Thus, under the term "binder" as used within the context of the present application, it should be understood that it is a composition capable of forming a film on the substrate to which it is applied, thereby fixing the pigment on the substrate. The binder present in the composition of the invention is designed as an aqueous dispersion comprising a liquid medium and polymer particles dispersed therein. The liquid medium comprises or consists of water, one or more surfactants or mixtures thereof. Preferably, the liquid medium does not comprise an organic solvent. This has the advantage that the binder has a low flammability. The polymer particles dispersed in the liquid medium have an average particle size of 120 to 300 nm. The polymer particles serve to form a film. The liquid medium is a reaction medium for forming the polymer particles and acts as a stabilizer for the polymer particles dispersed therein during transportation and storage. The polymer particles dispersed in the liquid medium are produced by emulsion polymerization. The monomers constituting the polymer particles are dispersed in the liquid medium and polymerization is initiated by free radical polymerization. Suitable monomers are unsaturated monomers selected from the group comprising vinyl chloride, dichloroethane, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, acrylic acid esters, vinyl esters, diolefins such as styrene, butadiene, or mixtures thereof. The binder comprises a large amount of polymer particles, in particular at least 35% by weight, or at least 40% by weight, or at least 45% by weight, or up to 50% by weight, based on the total weight of the binder, with the remainder up to 100% by weight being made up of the liquid medium, which is water, a surfactant, or a mixture thereof. As mentioned above, when used in the composition according to the invention, the binder is designed as a dispersion as defined above and is therefore present in the composition according to the invention as a dispersion comprising or consisting of polymer particles dispersed in the liquid medium.The film formation on the substrate to which the binder (or in this case the composition according to the invention) is applied occurs once the substrate (in this case mixed fibers, yarns, woven, nonwoven or knitted fabric) is subjected to a heating step, in particular a drying step. The liquid medium is then removed, for example by evaporation, and the previously dispersed polymer particles coalesce and flow together, thereby forming a three-dimensional network, i.e. a film in which the pigment is trapped. Since the film is a three-dimensional network, the fixation of said film onto the substrate, in particular mixed fibers, yarns, woven, nonwoven or knitted fabric, is achieved. As a result, it is another advantage of the binder to ensure that the trapped pigment is firmly fixed against abrasion and cleaning. Suitable polymers are, for example, poly(butyl acrylate), copolymers of butyl(acrylate), ethyl(acrylate) and styrene, polyvinyl acrylate, acrylonitrile or mixtures thereof. Suitable binders are known under the trade names Helizarin One (acrylic vinyl copolymer aqueous dispersion, by Archroma), Cresacryl, Unicryl or Tubifast. The at least one binder is present in the composition according to the invention in an amount of at least 0.5% by weight, or at least 1% by weight, or at least 2% by weight, or at least 3% by weight, at least 4% by weight and up to 12% by weight, or up to 10% by weight, or up to 8% by weight, or up to 7% by weight, or from at least 0.5% to 12% by weight, or from at least 1% to 10% by weight, or from at least 2% to 8% by weight, based on the total weight of the aqueous composition according to the invention.

[0044] The composition according to the invention is an aqueous composition, so that the remainder to 100% by weight is water.

[0045] Furthermore, the composition according to the invention may comprise one or more additives selected from the group comprising a thickener, an acid donor or a mixture thereof. The thickener may be present in the aqueous composition according to the invention in an amount of 0 to 8% by weight, or 1 to 5% by weight, based on the total weight of the aqueous composition according to the invention. The acid donor may be present in the aqueous composition according to the invention in an amount of 0 to 5% by weight, or 1 to 3% by weight, based on the total weight of the aqueous composition according to the invention.

[0046] In one embodiment, the aqueous composition according to the invention comprises at least 0.01% to at most 7% by weight of at least one cationic dye, at least 0.01% to at most 3% by weight of at least one dispersion containing at least one pigment, at least 4% to at most 12% by weight of at least one solvent, at least 4% to at most 12% by weight of at least one leveling agent, and 0.5-12% by weight of at least one binder, based on 100% by weight of the total aqueous composition according to the invention. The remainder to 100% by weight is water, since the composition according to the invention is an aqueous composition.

[0047] The aqueous composition according to the invention may also comprise, based on 100% by weight of the total aqueous composition according to the invention, 0.01-5% by weight, or 0.1-4% by weight, of at least one cationic dye, 0% by weight to a maximum of 7% by weight, or at least 0.01% by weight to a maximum of 5% by weight, of at least one reactive dye and / or at least one acid dye, at least 0.01% by weight to a maximum of 2.5% by weight, or at least 0.05% by weight to a maximum of 2% by weight, of at least one dispersion containing at least one pigment, at least 5% by weight to a maximum of 11% by weight, or at least 6% by weight to a maximum of 10% by weight, of at least one leveling agent, at least 1% by weight to a maximum of 10% by weight, or 2% by weight to a maximum of 8% by weight, of at least one binder, and 0.1-4% by weight, or 0.5-2% by weight, of at least one stabilizer. The remainder to 100% by weight is water, since the composition according to the invention is an aqueous composition.

[0048] The present invention further relates to a method for producing the aqueous composition according to the invention. The method according to the invention comprises or consists of the following steps: step A, step B and step C.

[0049] Step A: In step A, all the components of the composition according to the invention are mixed and homogenized, except for the dye, in particular at least one cationic dye, and at least one dispersion containing at least one pigment. Step A results in a paste, also called "raw paste" in the following. The mixing and homogenization can be carried out in equipment conventionally used for mixing and homogenizing the components of pastes, in particular print pastes or raw pastes. A preferred equipment for step A is a supershear mixing blade. The mixing and homogenization of the components can be carried out at any suitable steering speed and for any suitable time, for example 5 to 15 minutes, with a steering speed of 200 rpm to 4000 rpm.

[0050] Step B: At least one cationic dye and at least one dispersion containing at least one pigment and optionally at least one reactive or acid dye are added to the mixture obtained in step A. The addition of the dye and the dispersion can be carried out simultaneously or one after the other. It is also possible to mix the dye and the dispersion before adding them to the mixture obtained in step A. It is also possible to carry out step B immediately after step A. It is also possible for the mixture obtained in step A to be stored for a certain period of time before being subjected to step B. It is also possible to add further components other than the dye and the dispersion to the mixture obtained in step A in step B. It is also possible to premix the further components with one or more dyes and dispersions before adding them to the mixture obtained in step A.

[0051] Step C: The mixture obtained in step B is mixed and homogenized. The mixing and homogenization can be carried out in equipment conventionally used for mixing and homogenizing the components of pastes, especially printing pastes or stock pastes. A preferred equipment for step C is a high-speed mixer. Step C can be carried out immediately after step B. It is also possible to store the mixture obtained in step B for a certain period of time before subjecting it to step C. Once step C is completed, the aqueous composition according to the invention is ready for use, i.e. ready to be applied to fibers, yarns, woven, nonwoven or knitted fabrics. Preferably, the composition according to the invention is designed as a printing paste after step C is completed.

[0052] Furthermore, it is possible to carry out additional steps before step A, after step C or between steps A, B and / or C. Possible steps are for example heating steps, cooling steps, sieving steps.

[0053] The present invention further relates to the use of an aqueous composition according to the invention or of an aqueous composition produced according to the process according to the invention for colouring, in particular printing, fabrics, in particular mixed fibres, yarns, wovens, nonwovens or knitted fabrics, wherein said fabrics, in particular mixed fibres, yarns, wovens, nonwovens or knitted fabrics, comprise or consist of aramid, in particular para-aramid, and acrylic, in particular Pyrotex, and optionally wool.

[0054] The present invention also relates to a method for dyeing, in particular printing, mixed fibres, yarns, woven, nonwoven or knitted fabrics, which comprise or consist of aramid, in particular para-aramid and acrylic, in particular Pyrotex, and optionally wool, said method comprising the following steps: steps 1 to 6:

[0055] Step 1: Using the aqueous composition according to the invention or using the aqueous composition produced according to the method according to the invention to print mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics. In this step, the composition is preferably designed as a printing paste. Printing is carried out by conventional methods as described above. Preferably, printing is carried out using a rotary or flat printing machine.

[0056] Step 2: Drying the printed mixed fibre, yarn, woven, nonwoven or knitted fabric obtained in step 1. The drying step is carried out at a temperature of at least 100°C, or at least 110°C, or at least 120°C, or at least 125°C, or at least 130°C, or at least 135°C. The temperature should be at most 200°C, or at most 190°C, or at most 180°C, or at most 170°C, or at most 160°C, or at most 155°C, or at most 150°C, or at most 145°C, or at most 140°C. Step 2 can be carried out immediately after step 1. The printed mixed fibre, yarn, woven, nonwoven or knitted fabric obtained in step 1 can also be stored for a certain period of time before being subjected to step 2.

[0057] Step 3: The at least one cationic dye present in the composition according to the invention or produced according to the method according to the invention is fixed on the mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric obtained in step 2 by subjecting the printed mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric obtained in step 2 to a steam process by applying saturated steam at a temperature of at least 90°C, at least 95°C, at least 100°C, and up to 105°C, or up to 110°C. Steam is applied for at least 10 minutes, or at least 15 minutes, or at least 20 minutes, or at least 30 minutes, but not more than 50 minutes, or not more than 45 minutes, or not more than 40 minutes. Step 3 can be carried out immediately after step 2. Also, if at least one acid dye and / or at least one reactive dye are present in the composition according to the invention, the fixation of these one or more dyes occurs in this step 3. It is also possible to store the printed mixed fiber, yarn, woven fabric, nonwoven fabric or knitted fabric of step 2 for a certain period of time before subjecting it to step 3.

[0058] Step 4: The printed mixed fiber, yarn, woven, nonwoven or knitted fabric obtained in step 3 is subjected to a curing step to fix the at least one pigment (from at least one dispersion). The curing step is carried out at a temperature of at least 130°C, at least 140°C or at least 145°C. The temperature should be at most 200°C, at most 190°C, at most 180°C, at most 170°C, at most 160°C, at most 155°C, or at most 150°C for at least 1 minute, or at least 2 minutes, or at least 3 minutes, or at least 4 minutes, but not more than 5 minutes, or not more than 6 minutes, or not more than 7 minutes. Step 4 can be carried out immediately after step 3. It is also possible to store the printed mixed fiber, yarn, woven, nonwoven or knitted fabric of step 3 for a certain time before subjecting it to step 4.

[0059] Step 5: The printed mixed fiber, yarn, woven, nonwoven or knitted fabric obtained in step 4 is subjected to a washing step. The washing step may include one or more of the following steps: cold rinsing, warm rinsing, and / or hot water washing. Step 5 may be performed immediately after step 4. It is also possible to store the printed mixed fiber, yarn, woven, nonwoven or knitted fabric of step 4 for a certain time before subjecting it to step 5.

[0060] Step 6: The printed blended fibre, yarn, woven, non-woven or knitted fabric obtained in step 5 is subjected to a final drying step at a temperature of at least 100°C up to 200°C.

[0061] Furthermore, it is possible to carry out additional steps before step 1, after step 6, or between steps 1 and 6. Possible steps are, for example, a heating step, a cooling step, a sieving step, a mixing step.

[0062] The invention further relates to a colored, especially printed, mixed fiber, yarn, woven, nonwoven or knitted fabric comprising or consisting of acrylic, especially Pyrotex and aramid, especially para-aramid. Preferably, wool is also present in the mixed fiber, yarn, woven, nonwoven or knitted fabric. The printed mixed fiber, yarn, woven, nonwoven or knitted fabric according to the invention contains as colorants at least one cationic dye and at least one pigment derived from the aqueous composition according to the invention or from the aqueous composition produced according to the process according to the invention. The printed mixed fiber, yarn, woven, nonwoven or knitted fabric according to the invention preferably comprises 30-50% by weight of acrylic, especially Pyrotex, 30-50% by weight of aramid, especially para-aramid, and 0-25% by weight of wool, based on 100% by weight of the mixed fiber, yarn, woven, nonwoven or knitted fabric.

[0063] The present invention further relates to colored, especially printed, mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics which comprise or consist of aramid, especially para-aramid and acrylic, especially Pyrotex, and also optionally wool, wherein the mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics are printed according to the method according to the invention or are printed with an aqueous composition according to the invention or are printed with an aqueous composition prepared according to the invention.

[0064] The invention further relates to the coloured, in particular printed, mixed fibres, yarns, woven, nonwoven or knitted fabrics according to the invention, which are used to manufacture protective fabrics for military and police uniforms and equipment such as backpacks, camping tents or belongings. EXAMPLES

[0065] example The present invention will now be described in more detail with reference to the following non-limiting examples.

[0066] Fabric: Fabric made from a blend of Pyrotex, para-aramid and wool fibers was used throughout the following examples (from Pyrotex Industries, Hamburg, Germany). The fabric was washed by boiling for 30 minutes in a solution containing 1 g / l non-ionic detergent (Kieralon OLB, Archroma) and 1 g / l sodium carbonate in a liquor ratio of 50:1, then rinsed thoroughly and dried at room temperature.

[0067] Dyes and Chemicals: The cationic dyes used were: Basic Yellow 24 and 82, Basic Red 14 and 29, Basic Blue 3 and 54. The pigmented dispersions used were Printofix (Archroma) with Pigment Yellow 83 and 139, Pigment Red 101 and 146, Pigment Blue 15:3 and 28, Pigment Black 7. The binder used was Helizarin One (Archroma). As solvent, Printogen Enhancer PAW (Archroma) was used. As leveling agent, Printogen Additive CT (Archroma) was used. Furthermore, the stabilizer (Lyogen SMK from Archroma), acid donor (ammonium tartrate), urea and thickener (medium viscosity guar gum (Polygal AC-CH)) were of laboratory reagent grade and were applied without further purification.

[0068] Raw paste: 10 liters of water was added to a mixing vessel and mixed with 3 kg of ammonium tartrate under stirring. 50 kg of thickener paste (92 liters of water and 8 kg of thickener) was added to a mixing vessel and finalized into a raw paste by mixing with 10 kg of water, 10 kg of urea, 8 kg of Printogen Additive CT, 4 kg of Printogen Enhancer PAW, 2 kg of Lyogen SMK, 2 kg of binder, 4.5 kg of ammonium tartrate solution (30% w / v) under stirring. The mixture was stirred for an additional 15 minutes. The raw paste was completed to 100 kg with water, followed by stirring for an additional 15 minutes and cooling to room temperature.

[0069] Printing paste: For each desired shade, the dye was then solubilized and mixed with the pigment as follows: The cationic dye was placed in a mixing vessel and then solubilized with boiling water and acetic acid in the weight percent of the cationic dye. The raw paste was added to the mixture, followed by the pigment dispersion to 100 weight percent. As can be derived from the table below, the following compositions (printing pastes) according to the invention were prepared (% w / w): [Table 1]

[0070] Comparative Example 1: A printing paste "Dark Green" was prepared according to Example 1 (table above) with the only difference that the raw paste did not contain a leveling agent (Printogen Additive CT).

[0071] Comparative Example 2: A printing paste "Olive Green" was prepared according to Example 2 (table above) with the only difference that the raw paste did not contain a leveling agent (Printogen Additive CT).

[0072] Comparative Example 3: A printing paste "brown" was prepared according to Example 3 (table above) with the only difference that the raw paste did not contain a leveling agent (Printogen Additive CT). A fabric printed with this printing paste according to Comparative Example 3 is shown in Figure 2a.

[0073] Comparative Example 4: A printing paste "Dark Green" was prepared according to Example 1 (table above) with the only difference that the raw paste contained neither a levelling agent (Printogen Additive CT) nor a dispersion containing at least one pigment (Printofix).

[0074] Comparative Example 5: The printing paste "Olive Green" was prepared according to Example 2 (table above) with the only difference that the raw paste contained neither a leveling agent (Printogen Additive CT) nor a dispersion containing at least one pigment (Printofix).

[0075] Comparative Example 6: A printing paste "brown" was prepared according to Example 3 (table above) with the only difference that the raw paste contained neither a leveling agent (Printogen Additive CT) nor a dispersion containing at least one pigment (Printofix).

[0076] Printing applications using the compositions according to the invention (method of printing on fabrics according to the invention): The above-mentioned printing pastes of Examples 1-3 according to the invention and Comparative Examples 1-6 were applied to fabrics by conventional flat screen printing (J. Zimmer, GmbH; Austria-Mini MDF / 796). Fixation of the prints was carried out by drying at 100° C. for 1 min, followed by steaming at 102° C. for 40 min and then curing at 160° C. for 3 min. The made prints were subsequently rinsed with cold water, washed with 2 g / l cationic detergent (Lyogen WD liq) at 40° C. and 60° C. for 10 min, rinsed thoroughly and air dried. High-quality prints according to the invention having high wet fastness and light fastness properties (Print Example 1, printed with the print paste according to Example 1, Print Example 2, printed with the print paste according to Example 2, Print Example 3, printed with the print paste according to Example 3) were obtained according to this printing method according to the invention.

[0077] Measurement method

[0078] Color Intensity: The relative color density (K / S) of the printed fabrics was measured by light reflection technique using the Kubelka-Munk equation. The reflectance (R) of the printed fabrics was measured with a Konica Minolta MF-3700d (Japan).

[0079] Leveling characteristics: The leveling properties of the printed fabrics under the selected printing conditions were evaluated on a Konica Minolta MF-3700d by measuring the color difference within each sample at five separate points and determining the average color difference (dE) between these points. dE indicates the delta variation between two shades and is a measure of the leveling properties (the closer the dE value is to 0, the better the leveling properties). The shades obtained were as shown in the following table. In the table, L * is the brightness, a * are the red / green coordinates of the CIE LAB color system, b * is the yellow / blue coordinate. [Table 2]

[0080] The results in the above table show that the fabrics printed with the compositions according to the present invention (i.e. the printing pastes "Dark Green", "Olive Green" and "Brown" according to Examples 1 to 3) show very good leveling properties as well as at least 21% increased color strength compared to the respective comparative examples.

[0081] Light fastness: It is determined according to AATCC TM 16.3:2014 option 3. This test method provides general principles and procedures for determining the light fastness of textile materials. The test options described are applicable to all kinds of textile materials and to colorants, finishes and treatments applied to textile materials. The test options included are: 1) Xenon-Arc Lamp, Alternating Light and Dark, 2) Xenon-Arc Lamp, Continuous Light, Black Standard Option, 3) Xenon-Arc Lamp, Continuous Light, Black Panel Option. These tests were performed on an Atlas Xenon-Arc Weatherometer Model Ci3000+ at a temperature of 40°C for 40 hours. The results are summarized in the table below. [Table 3]

[0082] In the above table, L * indicates the brightness, and a * is the red / green coordinate in the CIE LAB color system, and b * is the yellow / blue coordinate. To evaluate the shade change in ISO 105 / A02, a lightfastness rating according to a grey scale is used. The lightfastness rating is determined according to the number on the grey scale which corresponds to the colour difference between the print before and after the test. After 40 hours in AATCC TM 16.3: 2014 option 3, the print application according to the invention showed a higher degree of lightfastness (the higher the number, the better the lightfastness).

Claims

1. An aqueous composition for printing mixed fibers, yarns, woven fabrics, nonwoven fabrics, or knitted fabrics containing or consisting of acrylic and aramid, wherein the composition is a) at least one cationic dye, b) At least one dispersion containing at least one pigment, c) At least one leveling agent in an amount of 4 to 12% by mass, wherein the leveling agent is selected from fatty acids, ethylene urea, aliphatic alcohols or their sulfates, aliphatic amines or sulfated aliphatic amines, alkylaryls or their sulfonates, aliphatic alcohol ethylene oxide, phosphates, aliphatic polyglycol ethers, triazine derivatives, or mixtures thereof. d) 4 to 12% by mass of at least one solvent, wherein the solvent is selected from aromatic alcohols, aliphatic alcohols having aromatic groups, or cyclic heteroaliphatic derivatives, and e) 0.5 to 12% by mass of at least one binder, wherein the binder is selected from poly(butyl acrylate), butyl(acrylate), ethyl(acrylate) and styrene copolymer, polyvinyl acrylate, or mixtures thereof. Includes, The aforementioned mass% is based on 100% by mass of the entire aqueous composition. Aqueous composition.

2. The aqueous composition according to claim 1, wherein the composition further comprises at least one reactive dye or at least one acidic dye.

3. The aqueous composition according to claim 1 or 2, wherein the composition further comprises at least one stabilizer selected from acrylate polymers, acrylamide copolymers, alkylphenol polyglycol ethers, or mixtures thereof.

4. The aqueous composition according to at least one of claims 1 to 3, wherein the composition further comprises an additive selected from the group comprising a thickener, an acid donor, or a mixture thereof.

5. The composition is based on 100% by mass of the entire composition, 0.01 to 7% by mass of at least one cationic dye, A dispersion containing at least one pigment in an amount of 0.01 to 3% by mass, 0 to 4% by mass of at least one stabilizer, 0 to 7% by mass of at least one reactive dye, or 0 to 7% by mass of at least one acidic dye, 0 to 8% by mass of at least one thickening agent, It contains 0-5% by mass of an acid donor, and, The remainder up to 100% by mass is water. The aqueous composition according to at least one of claims 1 to 4.

6. The composition is based on 100% by mass of the entire composition, 0.1 to 5% by mass of at least one cationic dye, 0.01 to 5% by mass of at least one reactive dye, or 0.01 to 5% by mass of at least one acidic dye, 1 to 10% by mass of at least one binder, A dispersion containing at least one pigment in an amount of 0.01 to 2.5% by mass, 5 to 11% by mass of at least one solvent, 5 to 11% by mass of at least one leveling agent, 0.1 to 4% by mass of at least one stabilizer, 1 to 5% by mass of at least one thickening agent, It contains 1 to 3% by mass of at least one acid donor, The remainder up to 100% by mass is water. The aqueous composition according to at least one of claims 1 to 5.

7. The following steps: Step A: Mix and homogenize all components of the composition except for at least one dispersion containing at least one cationic dye and at least one pigment. Step B: Add to the mixture obtained in Step A at least one dispersion containing at least one cationic dye and at least one pigment. Step C: Mixing and homogenizing the mixture obtained in Step B. A method for producing an aqueous composition according to at least one of claims 1 to 6, including

8. Use of at least one of claims 1 to 6, or use of an aqueous composition prepared according to the method of claim 7, for printing mixed fibers, yarns, woven fabrics, nonwoven fabrics, or knitted fabrics containing or consisting of acrylic and aramid.

9. The use according to claim 8, further comprising wool, or for printing a mixed fiber, yarn, woven fabric, nonwoven fabric, or knitted fabric comprising acrylic, aramid, and wool.

10. A method for printing mixed fibers, yarns, woven fabrics, nonwoven fabrics or knitted fabrics containing or comprising acrylic and aramid, and optionally wool, The following steps: Step 1: Print a mixed fiber, yarn, woven fabric, nonwoven fabric, or knitted fabric using an aqueous composition according to at least one of claims 1 to 6, or print a mixed fiber, yarn, woven fabric, nonwoven fabric, or knitted fabric using an aqueous composition produced according to claim 7. Step 2: Dry the printed mixed fibers, yarn, woven fabric, nonwoven fabric, or knitted fabric obtained in Step 1 at a temperature of 100°C to 200°C. Step 3: The printed mixed fibers, yarn, woven fabric, nonwoven fabric, or knitted fabric obtained in Step 2 is subjected to a steam process by applying saturated steam at a temperature of at least 90°C to 110°C for at least 10 to 50 minutes, thereby fixing at least one cationic dye present in at least one of the aqueous compositions described in claims 1 to 6, or present in the aqueous composition produced according to claim 7, onto the mixed fibers, yarn, woven fabric, nonwoven fabric, or knitted fabric. Step 4: The printed mixed fibers, yarn, woven fabric, nonwoven fabric, or knitted fabric obtained in Step 3 is subjected to a curing process at a temperature of at least 130°C to 200°C for at least 1 to 7 minutes. Step 5: The printed mixed fibers, yarn, woven fabric, nonwoven fabric, or knitted fabric obtained in Step 4 is subjected to a washing process. Step 6: The printed mixed fibers, yarn, woven fabric, nonwoven fabric, or knitted fabric obtained in Step 5 is subjected to a final drying step at a temperature of at least 100°C to 200°C. including, method.

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