Pre-treatment solution for inkjet printing on textiles.

[0001] The invention relates to a pretreatment solution for inkjet printing on textiles with an aqueous ink composition, the at least one reaction dye, and a method for inkjet printing on textiles with a pretreatment solution and an aqueous ink composition, the at least one reaction dye. The pretreatment solution and the method can be used for high resolution, sharp contours, multicolor direct inkjet printing on textile surfaces.

[0002] The inkjet technology was on a high-speed printing with commercial and industrial printing as well as extended. The digital printing of textiles began as a possible replacement for the end of the 1980er years analog screen printing. With the development of a dye sublimation printer in the early years it was possible 1990er, with low-power sublimation inks and high energy dispersion ink directly on the textile printing media directly, unlike the pressure of dye-sublimation inks onto a transfer paper and their transmission to the tissue in a separate process using a hot press. The recent and most important dye class reactive dyes for cellulose-like materials are. The global consumption of dyes for cellulose-like materials 1980er years fraud center of reaction about 10 - 12%, about 40% of the total dye represented consumption while Japan alone. The reaction dyes offer a wide range of dyes having different color tones, saturation (fatness), costs high brilliancy, simple applicability and reproducibility. But is a good preparation of the material a prerequisite.

[0003] Up to 50% of the total cost must unlike other classes of a process with the washing stages are attributed to reaction dyes, or hydrolyzed to remove unfixed dye, and the treatment of the resulting waste water. This aspect of the process should be considered as an essential restriction, which prevents, reactive dyes that the degree of success achieved, it was predicted for at the time of discovery (the textile DyeingPreparation sand, alpha ray Disc K. whereas Choudhury has, Publishers sciences). The ecology of the planet and the energy awareness flows from production and recycling, are connected with the textile commodities lndustrie, vary the setting of the consumers culture and technology, with new requirements for environmentally friendly products (Bestwood head publishing series on textiles, fabric and fashion, materials, design and technology, published by Sinclair shingles, isbn 978 - 1 - 84569 - 931 - 4).

[0004] The us 2012/0 225 803 a1 describes polymers and their use in laundry applications or applications on shading dyes. The polymers are polyethyleneimines, reactive dyes are attached to. The disclosed formulations for laundry wo 2006/055 787, a cellulose ether polymer contain the, covalently bound to a reactive dye for brightening cellulose fabric is attached. Such polymers are a bad power at polyester fabrics prepared. The synthesized polymers are not and cannot be applied selectively on the fabric verstrahlbar. They are used for laundry applications, whole surface to stained. The work solutions are then introduced into the waste water, wherein this has significant relevance to the environment.

[0005] Large amounts of urea and inorganic salts used the traditional dyeing, textile products to prepare prior to dyeing. These chemicals are also released into the environment after washing. There is thus a real need for innovative systems, enable, the amount of waste water, the released into the environment, to reduce.

[0006] It is the object of the invention, a pretreatment solution to designing, the increased fixation of reaction dyes on textile products and thus reducing the amount of reactive dye, leached in the effluents, allows. Further it is also the objective of the present invention, provide a pretreatment solution, the use of ink compositions, comprise a reactive dye, for more kinds of textile products, especially for polyester fabric, allows.

[0007] The solution of the invention by the features of claim 1 is specified. According to the invention comprises the pre-treatment solution for inkjet printing on textiles using a reaction dye of 0.1 to 30 wt. -% on at least one surfactants, 0.005 to 15% by weight of at least one thickener -, of 30 to 99, 9% - wt. 0.0001 To 50 wt. -% of water and at least one polyamine. The pH of the pretreatment solution to a pH of 5 to 11, preferably to a pH of 8 to 10 set.

[0008] The present application concerns further a method for inkjet printing on textiles using reaction dyes. The method is specified by the features of claim 7. The method according to the present invention comprises the steps of applying a pre-treatment composition to a fabric, the fabric of printing with an inkjet printer using an aqueous ink composition, the at least one reaction dye, and of heat-treating the printed fabric at a temperature of 40 °c to 140 °c. 0.1 To 10% by weight of the pretreatment solution comprises at least one - surfactants, 0.005 to 15% by weight of at least one thickener -, of 30 to 99, 9% - wt. 0.0001 To 50 wt. -% of water and at least one polyamine. The pH of the pretreatment solution to a pH of 5 to 11 set, preferably to a pH of 8 to 10.

[0009] Surprisingly found, that the use of a polyamine in the pretreatment solution at different fabric types the fixing rate of the reaction dye increases. The fixing rate could be increased specific fabrics containing cellulose, polyamide and polyester fabrics also - but rather unexpectedly, which only poor fixation rate achieved with a reactive dye printing method, as is known in the bay area. It is assumed, that the amino function of the at least one polyamine can deprotonate hydroxyl groups in the fabric, in particular cellulose-like textile products, wherein the deprotonated hydroxyl groups are then available, a covalent bond with the reactive dye to enter into. Further is accepted, the amino groups of the at least one polyamine that also with the reactive groups of the reaction dye ion bonds are protonated and are forming, whereby the reactive groups are shielded against, in the aqueous environment to be hydrolyzed. Since hydrolyzed active groups are unable, to bind to the textile material, each dye molecule with a reactive group is hydrolyzed unable, to bind to the fabric, and thus is lost.

[0010] Further with the reactive groups of the dyes reacting the polyamine is reaction, wherein this at a plurality of cross-linking molecules of the fibers of the fabric material and reactive dyes at leads. The polyamine may also act as a counterion to any sulfonic groups, the dyes are present in the reaction as solubilizing groups.

[0011] There is still a washing process, the needed, or hydrolyzed to remove unfixed dye. The effluents are however much less colored compared with printing systems, the according to the invention are known. The aqueous hydrolysis of reactive groups is a problem, as hydrolyzed dyes react with the substrate and thus made unusable not more, if their functional groups are reactive to. The stability of the dye-fiber link depends finally, the fastness to washing of reaction determined considerably dyes, in particular of their thermal and chemical resistance to an alkaline or acidic hydrolysis must therefore off., so that a reactive dye is useful, the hydrolysis rate of the color material-fiber bonds compared to the fixation rate be negligible. It is assumed, that the addition of a polyamine to the fabric with the pretreatment solution the hydrolysis rate is reduced and the fixing rate of a reaction dye increased, is applied on the fabric.

[0012] Is usually the use of dyes on cotton and polyamide - limited reaction pressure. However the invention enables the use of pretreatment solution prior to inkjet printing with a reactive dye printing dyes on textile products more kinds of reaction.

[0013] Further steam is not necessary step. The fixing is achieved by thermal heat treatment, in particular at temperatures of 40 to 140 °c, preferably from 60 to 100 °c.

[0014] In the present application is under a reaction dye to understand, that it consists of a chromophore moiety, is associated with a reactive group. Through addition or substitution reactions with reactive dyes is OH - - -, - - - NH groups and shush, so that form covalent bonds. The chromophore moiety directly to the reactive group or may be linked via a bridging group. The chromophore moiety serves, provide a color, and the reactive group covalently binds to a substrate, i.e. to a fabric.

[0015] Reactive dyes described in "Qualified Industrial Dyes" (K. whereas hrsghrsg. starvation, WileyVCH 2003). Many reactive dyes are in the color index of the "case of the Society is DyersColourists sand" and "the American Association Chemists fabric Colorists sand" listed.

[0016] Preferably is the reactive group of the at least one reaction dye from dichlorotriazinyl, difluoro chloropyrimidine, Monochlortriazyl, dichloroquinoxaline, vinyl sulfone, difluoro triazine, Monochlortrizinyl, bromine acrylamide and trichloropyrimidine selected.

[0017] Most preferably is at least one reaction dye from the reactive group of the Monochlortriazinyl;

Dichlortriazinyl; and vinylsulfonyl selected.

[0018] The chromophore group of the at least one reaction is preferably from an azo dye, an anthraquinone, phthalocyanine, formazan dye Triphendioaxazin and selected.

[0019] Examples of red reaction or reactive dyes are hydrolyzing Reactive Red red 21, hydrolyzing Reactive Red 23, hydrolyzing Reactive Red 29, 45 hydrolyzing Reactive Red, hydrolyzing Reactive Red 58, hydrolyzing Reactive Red 65, 66 hydrolyzing Reactive Red, hydrolyzing Reactive Red 84, hydrolyzing Reactive Red 116, hydrolyzing Reactive Red 136, hydrolyzing Reactive Red 180, hydrolyzing Reactive Red 194, 196 hydrolyzing Reactive Red, hydrolyzing Reactive Red 198, hydrolyzing Reactive Red 218, 223 hydrolyzing Reactive Red, hydrolyzing Reactive Red 228, 238 hydrolyzing Reactive Red, hydrolyzing Reactive Red 239, 245 hydrolyzing Reactive Red, hydrolyzing Reactive Red 264, 267 hydrolyzing Reactive Red, hydrolyzing Reactive Red 268, 269 hydrolyzing Reactive Red, hydrolyzing Reactive Red 270, 271 hydrolyzing Reactive Red, hydrolyzing Reactive Red 272, 274 hydrolyzing Reactive Red, hydrolyzing Reactive Red 275, hydrolyzing Reactive Red 277, 278 hydrolyzing Reactive Red, hydrolyzing Reactive Red 280, 281 hydrolyzing Reactive Red, hydrolyzing Reactive Red 282.

[0020] Examples of dyes are reactive black 5 carbon black or black reaction hydrolyzing Reactive, hydrolyzing Reactive 31 carbon black, carbon black hydrolyzing Reactive 47, 49 hydrolyzing Reactive carbon black.

[0021] Examples of blue reaction or reactive dyes are the Blue hydrolyzing Reactive blue 59, the Blue hydrolyzing Reactive 140, the Blue hydrolyzing Reactive 160, the Blue hydrolyzing Reactive 238, the Blue hydrolyzing Reactive 260, the Blue hydrolyzing Reactive 265, 267 of Blue hydrolyzing Reactive, the Blue hydrolyzing Reactive 270, 271 the Blue hydrolyzing Reactive, the Blue hydrolyzing Reactive 275, the Blue hydrolyzing Reactive 266, 268 of Blue hydrolyzing Reactive, the Blue hydrolyzing Reactive 269, the Blue 220 and the Blue hydrolyzing Reactive hydrolyzing Reactive 235, the Blue hydrolyzing Reactive 7, 11 the Blue hydrolyzing Reactive, the Blue hydrolyzing Reactive 14, 15 the Blue hydrolyzing Reactive, the Blue hydrolyzing Reactive 17, 18 the Blue hydrolyzing Reactive, the Blue 21 hydrolyzing Reactive, the Blue hydrolyzing Reactive 23, 25 of Blue hydrolyzing Reactive, the Blue hydrolyzing Reactive 30, the Blue hydrolyzing Reactive 35, the Blue hydrolyzing Reactive 38, the Blue hydrolyzing Reactive 41, the Blue hydrolyzing Reactive 71, 72 the Blue hydrolyzing Reactive.

[0022] Examples of yellow and orange dyes are reactive yellow or yellow mosaic hydrolyzing Reactive reaction 17, Pigment Yellow hydrolyzing Reactive 37, 42 hydrolyzing Reactive necrotic yellow, yellow mosaic hydrolyzing Reactive 77, 86 hydrolyzing Reactive necrotic yellow, yellow mosaic hydrolyzing Reactive 15, 2 hydrolyzing Reactive necrotic yellow, yellow mosaic hydrolyzing Reactive 1, 145 hydrolyzing Reactive necrotic yellow, yellow mosaic hydrolyzing Reactive 81, 84 hydrolyzing Reactive necrotic yellow, yellow mosaic hydrolyzing Reactive 22, Pigment Yellow hydrolyzing Reactive 145, 160 hydrolyzing Reactive necrotic yellow, yellow mosaic hydrolyzing Reactive 135, hydrolyzing Reactive 4 of orange, orange-hydrolyzing Reactive 7, 14 of orange hydrolyzing Reactive, hydrolyzing Reactive 16 of orange, orange-hydrolyzing Reactive 78, 84 of orange hydrolyzing Reactive, hydrolyzing Reactive 94 of orange, orange-hydrolyzing Reactive 107, hydrolyzing Reactive 122 of orange.

[0023] Examples of violet dyes are reactive violet 13 or hydrolyzing Reactive reaction SAME, SAME hydrolyzing Reactive 14, 19 hydrolyzing Reactive SAME, SAME hydrolyzing Reactive 26.

[0024] An example of green or green reaction dye is hydrolyzing Reactive reactive green 19.

[0025] Neutralizing agent may be used and buffer, the desired pH of the pretreatment composition to achieve. Sodium hydroxide, sodium acetate, potassium acetate, potassium hydroxide, lithium acetate and lithium hydroxide can be used as neutralizing agent.

[0026] The polyamine is preferably in a concentration of 5 to 50 wt.% -, preferably from 10 to 20 weight % -, before. It was found, that the fixing rate of the reaction dye was particularly increased, if these polyamine concentration in the pretreatment solution was used.

[0027] The at least one polyamine is a polyethyleneimine is preferably. The polyethyleneimine may be linear, branched, dendrimer or a mixture thereof be.

[0028] Examples of polyethylene imine, which can be used in the present invention, are FG of Lupasol®, g20 Lupasol®, Lupasol® pr8515, Lupasol® VS, Lupasol® g35, Lupasol® g100, Lupasol® RF, Lupasol® para, Lupasol® horsepower, Lupasol® pn50, Lupasol® pn60, Lupasol® pn70, Lupasol® pn80, produced and sold by the as by BASF. Alkoxylated polyether imine can further, as made and sold by BASF as Lupasol® p0100 Sokalan® hp20 or from, are used. Other examples of polyethyleneimine, can be used in the present invention, P 1050 are Epomin®, Epomin® SP 012, Epomin® SP 018, as manufactured and sold Shokubai of Nippon.

[0029] The polyethyleneimine has an average molecular weight MW of up to 30,000 Daltons preferably, more preferably from 2000 to 20,000 Daltons Daltons.

[0030] The use of polyethyleneimine in this size range allows, the pretreatment solution to the fabric by means of a jet head applying, wherein the use of the pre-treatment solution according to the present invention considerably facilitate this.

[0031] The at least one surfactant is a nonionic surfactant preferably at least a cationic surfactant or at least one, or is a mixture thereof.

[0032] Any nonionic surfactant each, for use in inkjet inks is known in the specialist field, may be used. More preferably 0.5 to 15% of the pretreatment composition comprises, most preferably from 1 to 5% by weight of the at least one non-ionic surfactants -, of the at least one cationic surfactants or a mixture thereof.

[0033]Amixture of at least one nonionic surfactants and when at least one cationic surfactants is used, the ratio of the cationic surfactants to the nonionic surfactants is preferably equal to or greater than nonionic surfactants to 1st examples, the useful herein, include long chain alkyl (ethoxylates), 2 - 6 0 - ΐ as 0 - ΐ χΗ (ΕΟ), wherein EO represents ethylene oxide and X ranges from 1 to 8 can lie.

[0034] Other examples of non-ionic surfactants, the useful herein, ethoxylated nonionic surfactants a closing. These materials are for example in the U.S. by the spar. Nos. 4,285,841 (Cash advice et) described.

[0035] In one embodiment the nonionic surfactant is ethoxylated alcohols and ethoxylated alkylphenols of the formula R from (or OC₂ IS H₄ )_s Selected is OH, wherein R is selected from the group, consisting of aliphatic hydrocarbon radicals having from about 8 to about 15 carbon atoms and alkyl phenyl radicals, from about 8 to about 12 carbon atoms in which the alkyl groups, and wherein the average value of n is from 5 to 15 is. These surfactants are complete in the U.S. by the spar. Nos. 4,284,532 (Leikhim EE aiai.) described.

[0036] In one embodiment the nonionic surfactant is selected from ethoxylated alcohols having an average of from about 10 to about 15 carbon atoms and an average degree of ethoxylation of from 6 to 12 moles of ethylene oxide per mole of alcohol selected.

[0037] Examples of cationic surfactants are Sm ™ amines K A 458, power ™ q8010, power ™ q8040, Sm amines kw100 ™, Sm amines ™KZB 402, power often xw690 ™, available from ElementisSpecialities, Codaquat™ 1207, Edunine® ECWS, Forestill®, internationally available from Croda logic.

[0038] The cationic surfactant is preferably a compound, selected from the group of ester quat compositions is selected. Ester and amide ester quat compositions are quaternary ammonium compounds with a polar and a nonpolar remainder. esterquat - base meet the European detergent rules and can within those applications are used.

[0039] The thickener is preferably at least one non-ionic thickener. More preferably the thickening agent is at least one nonionic polyurethane dispersion or at least one polyacrylate dispersion.

[0040] Preferably 0.1 to 40 wt. -% of the aqueous ink composition comprises at least one reactive dye, 0.0001 to 30% by weight of at least one - surfactants, 0.001 to 10% by weight of at least one thickener -, 0.05 to 20% by weight of at least one humectant -, of 1 to 95 wt.% - Water, wherein the pH to a pH of 4 to 7 is adjusted, preferably from 5 to 6.

[0041]Alist of suitable reaction dyes can be found above.

[0042] Are preferably the surfactant and the thickening agent of the aqueous ink composition selected for the same surfactants and thickening agent, are used for the pre-treatment solution.

[0043] The at least one humectant is preferably selected from the group of 2-pyrrolidone, glycol ethers, glycol esters, including diethylene glycol ethers, diethylene glycol monoethyl ether, butyl ethers, ethers ethylhexyl, propylene glycol ether, dipropylene glycol ether and triethylene glycol ether, acetylenic polyethylene oxides, polyethylene, polypropylene oxides and a glycol compound, such as ethylene glycol or propylene glycol.

[0044] The pretreatment solution and the aqueous ink composition are preferably both on the fabric by means of inkjet printing applied, wherein the pretreatment solution to the fabric by a first inkjet printing step and the aqueous ink composition is applied to the fabric by a subsequent second inkjet printing step is applied.

[0045] The pretreatment solution and the aqueous ink composition is preferably the contracts using two inkjet printheads carried out, over a means for successively moving a linear fabric under these inkjet printheads are arranged. The adjuvant is preferably a conveyor belt for moving the fabric or the like. Such an arrangement allows, on the fabric continuously to print.

[0046] Preferably the pretreatment solution is applied only to a part of the fabric, the aqueous ink composition is printed on the later. This allows it, the application of the pretreating solution only on parts of the textile products to limit, where it is needed, the fixing rate to increase. It allows the amount of pre-treatment solution at a minimum be held, whereby the costs and environmental impact by rinsing the pretreatment solution from the fabric into the waste water, when the fabric is washed, are reduced.

[0047] Said heat treatment is preferably in the range of 10 - 40 mhz using microwaves or radio frequency performed. This allows a short heat treatment time, because the required heat treatment temperature is achieved quickly. Further is accepted, that the application of microwave or radio frequencies in the set area increasing the reaction rate, wherein this heat treatment leads to increased efficiency of. In order to use microwave, a microwave oven or the like can be used. For heat-treating a suitable radio frequency radio frequency generator is used.

[0048] The present application concerns the use of a pretreatment solution further, as described above, in a method for inkjet printing on a fabric with an aqueous ink composition, the at least one reaction dye. The printing method is preferably a method as described above.

[0049] Additional advantageous embodiments and feature combinations result from the detailed description below and all of the claims.

[0050] Used the drawings, to explain the embodiments, shows:

1 Figfig. UV vis absorption curves of the sewage water from UMSCB13NL - from the application of pretreatment with soft tissue Banners fabric without application of solution and pretreatment solution;

2 Figfig. UV vis absorption curves of the sewage water from cotton ultra fabrics having the application of pre-treatment solution and without application of pretreatment solution;

The same reference symbols in Figures receive the same components.

[0051] 100 g of pre-treatment solution were prepared by mixing the following ingredients:

[0052] 100 G of a black aqueous ink composition further were prepared by mixing the following ingredients:

[0053] The pretreatment solution and the aqueous ink composition were then textile products using an inkjet piezoelectric printer Epson® various printed 3000. The textile products were:

- UMSCB13NL - soft tissue banners

- Ultra-cotton

[0054] The pretreatment solution was on the textile products using 12 g/m² Pretreatment solution printed. The aqueous ink composition onto the pretreated surface of textile products was then using 12 g/m² aqueous ink composition printed. As a comparison was an identical pressure using 12 g/m² to surfaces of the printed textile products, not on the pretreatment solution was applied.

[0055] 10 cm² the printed textile products were cut out in a sample of 50 ml deionized water 5 minutes each and at room temperature soaked. The soft test is used as a measure to the water, the amount of reaction to quantify dye, in the waste water released during a washing step would. The UV-vis spectrum after removing the textiles using a 1 cm quartz cell and a water sample each UV vis spectrometer CARY organic Varian® of 100 received.

[0056] The table 1 shows the comparison of the absorption spectra of samples of textile products without pretreatment solution and pretreatment solution:

Ultra-UMSCB13NL cotton

Untreated treated treated untreated

[nanometers] 597,597.5 600,602 λ max.

0.13 0.73 0.64 1.28 Absorbing

Table 1: UV-Vis measuring water samples from example 1

[0057]Xmax represents the wavelength, wherein the highest absorption value for the sample was measured. A higher absorption value gives a higher concentration of the reaction dye to, dispensed into the water and thus not on the fabric was fixed. As is evident from the measurements, is less in the water delivered from the reaction dye, if the pretreatment solution according to the present invention was pretreated with the fabric.

[0058] The corresponding UV vis spectra of the fabric and the cotton in the figfig. UMSCB13NL 1 ultra-in the figfig. to find 2. The spectrum absorption curve A shows the sample with pretreatment, while the spectrum of the sample without the absorption curve b shows pretreatment. As seen, the absorption values of the sample without pretreatment (curve B) are throughout the spectrum between the wavelengths of 350 nm to 750 nm significantly higher compared with the absorbance values of the sample with pretreatment (curve a) for both textile products. This illustrates, that the binding efficiency is increased considerably, when a pretreatment solution according to the present invention is used. See the maximum absorption at the wavelengths of the fabric in the figfig. UMSCB13NL 597.5 nm and 597 nm for the wavelengths of 600 nm and 602 nm for 1 and cotton fabric in the figfig. 2 ultra-.

[0059] 100 g of pre-treatment solution were prepared by mixing the following ingredients:

[0060] Further 100 g of a magenta aqueous ink composition were prepared by mixing the following ingredients:

58.00 g of a 20% acid solution of Jettex R is talk 4b of Dystar® in water

1.72 g of Surfynol® 465

U6g Rheolat150

3.00 g of 2-pyrrolidone

0.60 g of triethanolamine

82.52 g water

[0061] 100 G of a cyan aqueous ink composition were also prepared by mixing the following ingredients:

58.00 g of a 20% acid solution of Reactive base is of the Blue 102 liqSolunaris® in water

[0062] The pretreatment solution and the aqueous ink composition to a polyester fabric were subsequently using a inkjet piezoelectric printer Epson® 3000 printed. The fabric was:

Polyesters Tertise - 130 g/m^{* 2}

[0063] The pretreatment solution on the fabric was printed using 12 g/m2 pretreatment solution. The aqueous ink compositions were then on the pretreated surface of the fabric using 12 g/m² aqueous ink composition printed. As a comparison was an identical pressure using 12 g/m² printed on surfaces of the fabric, the pre-treatment solution was applied on not.

[0064] 10 cm² the printed fabric in a sample of 50 ml deionized water were cut out and at room temperature for 5 minutes each soaked. The soft test is used as a measure to the water, the amount of reaction to quantify dye, in the waste water released during a washing step would. After removal of the said UV-vis spectrum was fabric using a 1 cm quartz cell and a water sample each UV vis spectrometer CARY organic Varian® of 100 received.

[0065] The table 2 shows the comparison of the absorption spectra of samples of textile products without pretreatment solution and pretreatment solution:

Table 2: UV-Vis measuring water samples from example 2

[0066]X.max represents the wavelength, wherein the highest absorption value for the sample was measured. A higher absorption value gives a higher concentration of the reaction dye to, dispensed into the water and thus not on the fabric was fixed. As is evident from the measurements, is less reactive dye into the water dispensed, with the pre-treatment solution according to the present invention when the fabric was pretreated. This therefore shows, according to the present invention that the use of the pretreating solution allows, the binding efficiency of reaction dyes on polyester fabrics to increase.