|Title of Invention
MIXTURE AND METHOD FOR IMPRINTING TEXTILES
|The invention relates to a method for imprinting textiles and to a corresponding mixture which comprises: at least one pigment, at least one dispersant based on oxy alkylated linear or branched alkanes, fatty acids or fatty alcohols and/or alkyl sulfates or alkyl sulfonates and/or poly electrolytes and/ or alkylated and/or arylated glycosides, at least one water-soluble or water-dilutable binder having a molecular weight of more than 2000 g/mol and at least two polymerizable groups per binder molecule, which are linked to the binder molecule via at least one rethane group or urea group, water.
THE PATENT ACT 1970 (39 of 1970)
The Patents Rules, 2003 COMPLETE SPECIFICATION
(See Section 10, and rule 13)
1. TITLE OF INVENTION
MIXTURE AND METHOD FOR IMPRINTING TEXTILES
ITCF INSTITUT FUER TEXTILCHEMIE UND CHEMIEFASERN
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed : -
The invention relates to a mixture and a method for imprinting textiles.
Currently used methods for imprinting textiles include the inkjet printing and the screen printing methods.
The inkjet printing process is widely used as a result of the rapid development of computer technology and, in the private sector, is primarily used for producing colored pictures on paper. This new technology has also moved into the industrial sector for textile imprinting and is currently used advantageously for designing patterns and producing small yardages. The inkjet printing systems presently available in the market place deliver printing resolutions ranging from 180dpi to 720 dpi and work with 4 to 16 basic colors from the assortment of reactive, acid, dispersion, or pigment coloring agents. Above all, the pigment printing is of extreme and central importance because it can be used universally on different substrates. Depending on the print resolution, a printing speed of up to 150m2/h is possible at the present time, which is sufficient for the pattern design and production of small batch sizes because of the extremely short set-up times.
Even though the inkjet printing permits an extremely flexible production of high-quality colored textiles,, conventional fixation methods represent a limiting factor that keeps this technology from gaining ground. Standard fixation units, for example steamer units and dry fixation units, cannot be adapted optionally to this innovative printing technique because of their size, thus negating at least in part the advantages achieved with the inkjet printing. The fact that fixation occurs offline, in a separate operational step, is a particular disadvantage. The fixation units of known systems using inkjet printers for the imprinting of textiles take the form of steamers, which are positioned downstream, immediately following the inkjet printers, and which more or less permit a thermal online fixation of the printing patterns with the aid of hot air or saturated steam. These types of systems have the disadvantage that in order to finish the print patterns on the textiles, the textiles must be rewashed in a last operational step to remove pretreatment chemicals and non-fixated coloring agent components. This post-treatment is carried out in a manner known per se with the aid of washing units and dryers. So far, the production of inkjet printing patterns has not yet been realized with an online method, which represents a limiting factor for the flexible production of individual printing patterns using the inkjet method. It is therefore the object to provide a fixation unit with small dimensions and extremely flexible use, which can be realized using strong UV light sources. However, this requires the development and the use of suitable UV hardenable printing inks.
The inks used for the inkjet printing method must meet a plurality of specific requirements, wherein the viscosity and surface tension among other things play a crucial role in the formulation of the printing ink. Inks which can be used in inkjet printers have a water-like ink viscosity of less than 6mPas and a surface tension of 20 to 50mN/m. To prevent the ink from drying inside the nozzles, hygroscopic additives such as ethylene glycol, urea, or glycerin must furthermore be added to the ink. In addition, the electrolyte content (salts) of the ink must be kept to the lowest
possible level to prevent possible corrosion on the printing head. To avoid nozzle obstructions (nozzle diameter Several UV hardenable systems for the inkjet and screen printing methods have already been introduced in the market place, which for the most part are present as 100% systems and must be adapted to the required viscosity level by adding low-viscous, mostly toxic reactive diluting agents. The expression 100% system is understood to refer to systems, which harden completely during the fixation process, meaning at 100%, after they are applied to the textiles. In the market place, systems of this type are not acceptable for textile applications because of the skin-sensitizing effect and the toxic potential of the monomers in the form of residual monomers with incomplete reaction in the hardened printing pattern. Added to this is the fact that the use of such 100% systems results in an unacceptable stiffening of the imprinted textile patterns and is therefore also not acceptable in the market place.
The option of lowering the viscosity to improve the printability by adding organic solvents with correspondingly low viscosity must be ruled out from the start for ecological reasons and is not acceptable for the inkjet printing on textiles, particularly textile material used for clothing. The use of water-dilutable systems is in principle conceivable for the textile finishing process. However, the water-dilutable UV hardenable printing inks for inkjet applications, described so far in the relevant literature, contain biologically non-degradable alkylphenol ethoxylates (APEO) as dispersing agents for the pigments, which will be banned in the near future because of their toxicity to fish and their toxic decomposition products. Also used in such formulations are dispersing agents on the basis of condensates from formaldehyde and aryl sulfonic acids, as well as naphthalene sulfonic acid formaldehyde condensates, which also decompose slowly biologically and furthermore have the problem that the skin-sensitizing formaldehyde forms again. Examples of these systems are described in the following German Patent Applications: 197 39 620 Al, 197 53 831 Al, 197 27 766 Al and 197 27 767 Al. Owing to the above-described disadvantages, neither the 100% systems nor the water-dilutable UV hardenable systems have found their way into practical operations involving textile materials.
It is the object of the present invention to make possible an environment-friendly, highly efficient imprinting of textiles while ensuring a high quality and functionality of these textiles.
This object is solved with the features disclosed in claims 1 and 36.
Advantageous embodiments and useful modifications of the invention are described in the dependent claims.
One essential advantage of the mixture according to the invention, as disclosed in claim 1, is that this mixture is completely free of alkyl phenol ethoxylates (APEO), as well as formaldehyde condensates, and is therefore extremely friendly to the environment.
A further critical advantage is that the textiles imprinted with the mixtures according to the invention are soft to the touch and have good fastness values, especially good light fastness and fastness to rubbing and washing, without requiring further post-treatment steps.
One essential advantage of the method according to the invention is that the printing and fixation can be realized with an online method, meaning the fixation occurs immediately after the printing operation and without intermediate steps. The fixation of the mixture imprinted on the textiles can be realized efficiently and energy-saving by irradiating and simultaneously supplying heat to the textiles.
According to a first embodiment, electron beams can be used for the hardening of the mixtures applied to the textiles during the imprinting.
With this embodiment, a mixture having the components as disclosed in claim 1 is sufficient since a polymerization of the binding agent is achieved by using the electron beams, without further admixtures, thereby resulting in agglutination of the pigments in the mixture and the textile fibers.
Alternatively or in addition thereto, the mixture can be hardened by exposing it to UV radiation, wherein the component E must be added to the mixture, as disclosed in claims 3 and 4.
Alternatively or in addition, the mixture can also be hardened by using infrared (IR) radiation, wherein this requires the admixture of radical primers as disclosed in claims 6 and 7.
According to one advantageous embodiment of the invention, the textiles to be imprinted can be pre-treated by impregnating them with chemicals. An improvement in the contour quality during the printing can be achieved through pre-impregnation with cationic compounds and/or thickening agents. Improvements in the fastness are achieved through pre-impregnation of the textiles with binding agents and photo-initiators and/or with adhesion promoters.
According to one advantageous embodiment, the mixture according to the invention contains color pigments for generating preferably multi-colored printing patterns.
However, the invention is not limited to generating printing patterns of this type. Rather, the mixtures can contain different pigments for achieving defined functionalities for the textiles.
In particular, the pigments can be embodied as white pigments, wherein these can be composed in particular of Ti02, barium sulfate and/or zinc oxide and can be used for producing white inks.
Optically brightening pigments can furthermore be used for producing inks of a lighter color. Suitable for this are optical brightening agents on the basis of stilbenes, cumarin derivatives, diphenylpyrazolines, bisbenzazoles.
Transparent mixtures can also be produced using nanoscale particles as pigments. Transparent mixtures of this type can be used, for example, for providing the textiles with safety codes, which are not visible to the human eye and can be made visible only with the aid of UV or IR radiation. Safety codes of this type make it possible to distinguish original goods from plagiarized goods.
According to a different variant, the mixtures according to the invention can contain conductive particles that make it possible to achieve specific conductivity characteristics or electromagnetic screening effects for the textiles imprinted therewith. Alternatively or additionally, the mixtures can also contain magnetic particles.
The mixtures according to a different variant of the invention can contain heat-reflecting or heat-absorbing particles, which make it possible to achieve a cooling effect or a heating effect for the textiles imprinted therewith.
The mixture according to the invention contains alkyl sulfates or alkyl sulfonates as components of the dispersing agent. In particular, these act as plasticizers and represent an essential characteristic of the mixture according to the invention, especially for achieving a soft feel for the imprinted textiles.
The mixture according to the invention can furthermore contain plasticizers on the basis of silicones, and/or on the basis of fatty acid poly glycol esters, and/or alkoxylated fatty alcohols, and/or alkyl amine poly glycol ether, and/or fatty acid amide poly glycol ether, and/or fatty alcohol sulfates, and/or alkyl carboxylates, wherein cationic plasticizers on the basis of quaternary ammonium compounds can also be used.
The mixtures according to the invention preferably can be embodied as ink preparations, wherein preferred embodiments are described in claims 24-31. In that case, the textile materials are preferably imprinted using an inkjet printing method.
The characteristics of the ink preparations, particularly their viscosities, can be adapted to the requirements of these inkjet printing methods.
The mixtures according to the invention can furthermore be embodied as paste preparations, wherein preferred embodiments are described in claims 31 - 33. In that case, the textiles are advantageously imprinted with a screen printing method.
The invention is explained in further detail in the following with the aid of specific embodiments and examples.
The APEO free pigment dispersions are preferably produced through grinding in a pearl grinder of the pigments (component A) with water and the dispersing agents (component B) on the basis of suitable oxalkylated linear or branched alkanes, fatty acids or fatty alcohols, and/or alkyl sulfates/sulfonates, and/or polyelectrolytes, and/or alkylated, and/or arylated glycosides. The pigments (component A) are understood to be fine-particle inorganic or organic pigments or mixtures thereof. Examples for pigments of this type are Pigment Red 122, Pigment Black 7, Pigment Blue 15:3, Pigment Yellow 17, and Pigment Yellow 83, which are particularly suitable for the formulation of CMYK [cyan, magenta, yellow, and key (Black)] inks. Other inorganic or organic color pigments and non color-providing pigments can generally also be used for the ink formulation. The share of dispersing agent relative to the pigment is in the range of 10-300%, depending on the pigment and dispersing agent that is used. Following the grinding in the pearl grinder, the pigment dispersions are diluted with water to the necessary concentrations for use, ranging from 0.1 to 10%, thereby resulting in sedimentation-stable and low-viscous (viscosity is Radically hardenable urethane acrylates, hardenable with at least two reactive, polymerizable groupings for each molecule, are used as binding agents (component C) for the radiation hardenable pigment inks according to the invention. Especially preferred are hydrophilic modified urethane acrylates or urethane methacrylates, but also the corresponding analog urea compounds (urea acrylates or urea methacrylates with a molecular weight of > 2000g/mol), which can be produced easily in a two-stage synthesis. In the first synthesis stage, a diol and/or a polyol molecule (diamine and/or polyamine), which in turn can be alkoxylated multiple times (e.g. ethoxylated, propoxylated, or mixed alkoxylated) and/or which can support functional groups, is allowed to react with at least 2 mol of a diisocyanate (especially preferred is a diisocyanate with graduated reactivity such as isophorondiisocyanate (IPDI) but also hexamethylene diisocyanate or mixtures of diisocyanates) in the presence of a catalyst to form a water-soluble diisocyanate and/or polyisocyanate. In a second synthesis step, the non-reacting isocyanate groups in the resulting water-soluble diisocyanate and/or the polyisocyanate are allowed to react in the presence of a catalyst with hydroxyalkylacrylates or hydroxy alkylmethacrylates to form urethaneacrylate and/ or urethanemethacrylate (urea acrylate, urea methacrylate), resulting in at least two reactive polymerizable groupings for each molecule. The obtained urethaneacrylate and/or the urethane
methacrylate (urea acrylate, urea methacrylate) is water soluble and can be adjusted to the desired application concentration for the inkjet ink by adding water. The UV hardenable inkjet inks can be produced by using such water-dilutable urethane acrylates and/or urethane methacrylates (and the analog urea acrylates and/or urea methacrylates) containing several polymerizable groups. Following the hardening, these inks form a cross linked polymer film that glues together the pigment and the fiber and, with the standard application amounts of up to 20ml ink/qm, results in a particularly high fastness to rubbing with simultaneously soft feel. It must be considered an additional advantage of this binding agent that it can be used equally well in a watery diluted form, especially in concentrations of up 20%, for the printing with piezo inkjet printers as well as bubble jet printers, thus making it possible to have a sufficiently high binder concentration on the imprinted substrate for meeting the fastness requirements. One advantage of these binding agents is that they can also be used without the admixture of pigments for the printing.
The UV hardenable ink formulations furthermore contain a photo initiator (component E), in a concentration for use of up to 14%, relative to the binding agent. Particularly suitable as photo initiators are mixtures of watery formulations (dispersions and water-soluble photo initiators) of various generally known photo initiator structures and their derivatives (e.g. a hydroxy ketones, benzyl ketones, monomer and polymer hydroxy ketones, a amino ketones, bis-acyl diphenyl phosphinoxides (e.g. 2,4,6-trimethylbenzoyldiphenylphosphinoxide), benophenones, acetophenon, 2-phenylacetophenones, isopropyl thioxanthon, bi-functional photo initiators on the basis of ketosulfones and others), which can absorb UV radiation with a specific wavelength and, as a result of the absorbed energy, can form radicals that start the polymerization of the polymer binding agent. Furthermore added can be nitrogen-containing co-initiators (e.g. ethyl-4-dimethylaminobenzoate), as well as synergetic acting tertiary amines and alkoxylated acrylat monomers.
Further components of the UV hardenable pigment inks according to the invention can include watery dispersions of a thermally activated radical starter (component F), such as dibenzoylperoxide, Na peroxide sulfate and more. IR radiation can thus also be used for the hardening. De-gassed water (component D) can be used as diluting medium. The radiation hardenable inkjet inks according to the invention can furthermore include admixtures for improving the running characteristics and the fastnesses of the ink in the form of the component G, wherein multivalent alcohols and/or polyalkylene alcohols are preferably used for this. The ink can also contain additional admixtures in the form of the component H, for example defoamers, plasticizers, preserving agents, and thickening agents.
The UV hardenable, watery pigment inks according to the invention in particular have the following preferred compositions:
Pigment share (A):
Dispersing agent (B): Binding agent (C):
Photo initiator (E): Radical starter (F): Hygroscopic additives (G): Additives (H):
De-gassed water (D):
up to 10% (standard concentration for standard
up to 6% (for standard CMYK 2% pigment share)
up to 10% water-soluble UV hardenable binding
up to 1.4% active photo initiator
up to 1%
up to 5%
up to 0.5% surfactant, plasticizer, defoamer,
The printing inks are produced by mixing together the required amounts for use of the components A - C, as well as E, F and the components G and H in a suitable device (e.g. a beaker with stirring mechanism) and stirring this mixture for 10 minutes. Following this, the mixture is diluted to the required application concentration by adding de-gassed water and by stirring it intensively for 15 minutes. Prior to the use, the printing inks produced in this way are filtered with the following multi-stage filtering method:
No. Filter pore size Typical filtration period for 100ml ink
1 40mm 30s
2 20mm 2min
3 11mm 2min
4 6mm 3min
5 2.5mm 8min
6 8mm 30s
7 5mm 30s
8 3mm 30s
9 0.8mm 2min
The filtered inks are ready for printing and can be used either in the bubble jet printer or the piezo inkjet printer. The above-described inks can be used for directly imprinting textiles with an inkjet printer and the ink can be fixated online, using a downstream connected UV fixation unit, without intermediate drying and at an operating temperature of >70°C. The UV fixation unit is preferably embodied as UV scanner, with periodic scanning by the UV radiation source or the UV rays emitted by this source.
Printing samples were prepared with a Mimaki JV2-130 inkjet printer, which operates based on the drop-on-demand (DOD) method with piezo technology. The printing was realized with a print resolution of 720dpi and 8 pass and a printing speed of 5qm/h, resulting in an average ink application of approximately 18.7ml/m2 for the completely imprinted surface, wherein the nozzle diameter is 20mm. Additional printing samples were prepared with an EN-CAD TX1500 (bubble jet printer), at a printing speed of 6qm/min and a print resolution of 360dpi at 4 pass.
The ink application is approximately 15ml/m2 and the nozzle diameter is 45mm. The printing involved a pattern consisting of differently fine lines and color surfaces, as well as a full-surface printing (90cm width), which makes it possible to assess the quality of the contour, as well as the color depth and the print penetration.
The fixation of the printing patterns occurs continuously online during the printing operation, with the aid of a UV scanner by the company IST-METZ GmbH (Nurtingen), connected downstream of the inkjet printer, and using 5 dual radiation passes (5 pass). The UV scanner was adjusted such that the total average time for irradiating the textile material was at maximum 10s lag. An Hg-UV lamp with a capacity of 200 W/cm, arranged at a distance to the textile material of approx. 5cm, was used for the fixation. Owing to the IR radiation emitted by the UV scanner, the textile material is heated during the fixation to temperatures above 70°C, which positively supports the fixation of the binding agent according to the invention. When using a cold light UV fixation device, the textile material would have to be heated to above 70°C with a separate unit to achieve the necessary fastness values.
The textiles, imprinted with the inks according to the invention, and fixated using the method according to the invention, deliver color-depth printing patterns with high fastness values. In addition, the textiles imprinted with this method have excellent dry fastness, wet fastness, and light fastness values and, in particular, also have a soft feel. A further advantage of the invention is the fact that high fastness values can be achieved when optionally imprinting polypropylene and fiber mixtures.
APEO free pigment dispersions by the company Minerva/Italy are used for the ink formulation. These are products stemming from the Innoprint project, namely Pigment Blue 153-16, Pigment Red 122-01, as well as Pigment Yellow83-02 and Pigment Black 07-01, which are present as 10% watery dispersion in the starting batch, at a share of 20% relative to the finished ink. The binding agent used for the starting batch is a urethane acrylate-based water-diluted system called Ebecryl 2001 by the company UCB/Belgium, which is added at a share of 10% relative to the finished ink. Watery dispersed photo initiators (Esacure DP250) by the company Lamberti/ Italy, with a share of 0.3% relative to the finished ink, represent a different main component that is added and subsequently stirred in for 10 minutes. The mixture is then diluted with 69.7% de-gassed water, intensively stirred in for 15 minutes, to obtain the required application concentration. The printing inks produced in this way are then filtered by using the following multi-stage methods, with an applied vacuum of approximately l00mbar.
No. Filter pore size Typical filtration period for 100ml ink
1 40mm 30s
2 20mm 2min
3 11mm 2min
4 6mm 3min
5 2.5mm 8min
6 8mm 30s
7 5mm 30s
8 3mm 30s
9 0.8mm 2min
The filtered inks are ready for printing and have an ink viscosity of less than 5mPas, as well as a surface tension in the range of 20 to 50mN/m. These inks can be printed directly onto the textiles with bubble jet printers (Encad) as well as piezo inkjet printers (Mimaki).
The printing results listed in the following were achieved with a Mimaki JV2-130 inkjet printer, which operates based on the DOD method and using piezo technology. The printing was carried out with a print resolution of 720dpi and 8 pass and a printing speed of 5qm/h, resulting in an average ink application of approximately 18.7 ml/m2 for the completely imprinted surface, wherein the nozzle diameter was 20mm. The online fixation of the printing patterns occurred continuously during the printing operation, with the aid of a UV scanner by the company IST-METZ GmbH (Nurtingen), connected downstream of the inkjet printer, and 5 dual radiation passes (5 pass). The UV scanner was adjusted for a total average irradiation period of the textile material at maximum 10s lag. An Hg-UV lamp with a capacity of 200 W/cm and positioned at a distance of approx. 5cm to the textile material was used for the fixation. As a result of the IR radiation emitted by the UV scanner that is used, the textile material heats up during the fixation to temperatures above 70°C, thus positively supporting the fixation of the binding agent according to the invention. During the fixation process, the following temperatures were measured in dependence on the number of illuminations and a scanner speed of 300 mm/s:
1. Illumination 37°C
2. Illumination 43°C
3. Illumination 49°C
4. Illumination 70°C
5. Illumination 77°C
6.-10. Illumination 88°C
Pre-treated textile materials of 100% cotton were imprinted. Also imprinted as comparison materials were textiles of polyester and viscose.
The following characteristics of the printing patterns were detected:
Table 1: Color depth in cotton
Ink color depth K/S in cotton for the ink ace. to example 1 color depth K/S in cottonfor the standard ink(BASF EVO P 100)
Cyan 2 4
Magenta 2.8 3.06
Yellow 3.3 2.4
Black (key) 5.8 6.4
Table 2: Fastness values for wet and dry shown with the Example 1
Ink (example 1) Cotton Polyester Viscose
dry wet dry wet dry wet
Cyan 4-5 3 5 4 4 3-4
Magenta 4-5 3 5 4 4 2-3
Yellow 4-5 3 5 3 4 2
Black 3-4 2 5 3 3 2
(Scale ranging from 5 = good to 1 = poor)
Table 3: Fastness values for wet and dry for the comparison ink (BASF)
Ink(BASF EVO P100) Cotton Polyester Viscose
dry wet dry wet dry wet
Cyan 4 3 4 1 4 2
Magenta 4 3 4 1 4 3
Yellow 5 4 4 1 5 3
Black 2 2 4-5 3 4-5 2
Table 4: Washing fastness (DIN EN ISO 105-C06) for example 1 of cotton
Color change Bleeding into cotton Bleeding into viscose
Cyan 5 5 5
Magenta 5 5 5
Yellow 5 5 5
Table 5: Light fastness values for cotton, used in example 1 (600 h Xenotest)
Cyan Magenta Yellow Black
7 6-7 6-7 7
Table 6: Comparison of the flexural strengths for cotton
Example 1 BASF EVO P100
warp weft warp weft
Cyan 4.93 2.03 6.85 3.32
Magenta 6.29 2.65 5.5 2.84
Yellow 5.19 1.97 6.14 2.75
Black 4.86 2.29 5.28 2.34
The results showed that print-ready, UV hardenable inks can be produced for the inkjet printing on textiles, for which the quality level is in the range of or exceeds conventional, thermally hardenable pigment inks. The inks can be used in a continuous operation and can be fixated online. The achievable color depths must be considered sufficient. The rubbing fastnesses for the dry and wet state must be considered extremely good with a rating of 3-4 and above, wherein these value in part considerably exceed the corresponding values for the standard ink used (BASF EVO P100, thermal fixation for 3 minutes at 160°C). A further improvement in the fastness values can be achieved through hardening of the imprinted substrate in an oxygen-reduced atmosphere (inert gas) (Table 7). Excellent washing fastness values with maximum ratings of 5 are furthermore obtained. Also emphasized should be the softness when handling the finished printing patterns (flexural strength values are lower than for comparison patterns) as well as the excellent light fastness values, which reach fastness ratings of 6-7 and above for all colors.
The print-ready inks according to Example 1 were used for printing patterns on cotton, in the same way as for the Example 1, wherein the UV lamp housing that is open toward the printing side was flushed with an inert gas during the irradiation. Nitrogen gas was selected as inert gas, which generates an oxygen-reduced atmosphere in the illuminated field with a flow of 250 1/min (oxygen content Table 7: Wet and dry fastness values for the fixation under the effect of inert gas on cotton
Inert gas Cyan Magenta Yellow
dry wet dry wet dry wet
without 4-5 3-4 4-5 3 4-5 3
nitrogen 4-5 4 4-5 3-4 4-5 3-4
An electrically conductive UV hardenable paste can be produced when using graphite. For this, a starting batch is prepared with 20g graphite powder together with 5g of the dispersing agent Brij78 (eicosaethyleneglycol octadecylether) and 50ml
water and the mixture is then ground for 30min in a pearl mill. Stirred into this dispersion are 2g of a urethane acrylate-based water-dilutable binding agent called Ebecryl 2001 by the company UCB/Belgium, along with 0.2g of the watery dispersed photo initiator Esacure DP250 by the company Lamberti/ Italy and the resulting mixture is stirred for 5 minutes. Following this, 1.5g of the thickening agent Prisulon SNP113 S (company CHT/Germany) is added along with water to form lOOg paste, and the mixture is stirred for 30 minutes to complete the printing paste. A comparison paste without binding agent and photo initiator is produced in the same way.
A flat screen printing machine by the company Zimmer was used for printing on cotton, wherein this machine has a printing speed of 5m/min. The fixation of the printing pattern occurred under the same conditions as described for Example 1. The rubbing fastness is evaluated by subjecting the printed patterns to 100 abrasive strokes at the crock meter while the electrical resistance is measured at a distance of lcm to the measuring electrodes. The following measuring values were obtained:
Table 8: Influence of the binding agent on the fastness to rubbing and the electrical resistance when printing on cotton (Example 3)
Ink (Example 3) Resistance of fixated patterns Resistance of fixated patterns after 100 abrasion strokes at the crock meter
electrically conductive ink with binding agent 2.3 kW 5.0kW
electrically conductive ink without binding agent 0.8 kW >40MW
Electrical resistance measurements show that the use of a UV hardenable binding agent in electrically conductive pastes leads to a noticeable improvement in the fastness to rubbing.
1. A mixture used for the imprinting of textiles, comprising:
A) at least one pigment;
B) at least one dispersing agent on the basis of oxalkylated linear or branched alkanes, fatty acids or fatty alcohols, and/or alkyl sulfates or alkyl sulfonates, and/or poly electrolytes, and/or alkylated, and/ or arylated glycosides;
C) at least one water-soluble or water-dilutable, radiation-hardenable binding agent with a molecular weight above 2000g/mol and at least two polymerizable groups for each binding agent molecule, which are cross-linked to the binding agent molecule by at least one urethane group or urea group;
2. The mixture according to claim 1, characterized in that the binding agent is hardened by subjecting it to electron beams.
3. The mixture according to claim 2, characterized in that the mixture comprises the following additional component
E) at least one water-soluble or water-dispersed photo initiator.
4. The mixture according to claim 3, characterized in that a hydroxyketones, benzyl ketones, monomer and polymer hydroxyketones, a aminoketones, bis-acyl-diphenylphosphinoxides, benzophenones, acetophenon, 2-phenylacetophenones, or isopropyl thioxanthone can be used for the photo initiators, wherein co-initiators, in particular nitrogen-containing co-initiators, tertiary amines and/or alkoxylated acrylat monomers can also be added to the photo initiators.
5. The mixture according to one of the claims 3 or 4, characterized in that the binding agent can be hardened with UV radiation.
6. The mixture according to one of the claims 1 to 5, characterized in that it comprises the following additional component:
F) at least one thermally activated radical starter.
7. The mixture according to claim 6, characterized in that the radical starter is dibenzoylperoxide or sodiumperoxidedisulfate.
8. The mixture according to one of the claims 6 or 7, characterized in that the binding agent can be hardened with IR (infrared) radiation.
9. The mixture according to one of the claims 1 to 8, characterized in that the polymerizable groups of the binding agent are acrylat or methacrylat.
10. The mixture according to one of the claims 1 to 9, characterized in that the pigments are organic or inorganic color pigments.
11. The mixture according to one of the claims 1 to 10, characterized in that white pigments are provided for the pigments.
12. The mixture according to claim 11, characterized in that the white pigments are composed of Ti02, barium sulfate and/or zinc oxide.
13. The mixture according to one of the claims 1 to 12, characterized in that electrically conductive particles are provided for the pigments.
14. The mixture according to claim 13, characterized in that the electrically conductive particles are composed of graphite, soot, tin antimony oxide or are metallic particles.
15. The mixture according to one of the claims 1 to 14, characterized in that the pigments take the form of magnetic particles.
16. The mixture according to claim 15, characterized in that the magnetic particles are composed of iron or Fe304.
17. The mixture according to one of the claims 1 to 15, characterized in that the pigments provided are heat-reflecting particles.
18. The mixture according to claim 17, characterized in that the heat-reflecting particles are composed of Ti02 or are metal oxide-coated mica.
19. The mixture according to one of the claims 1 to 18, characterized in that the pigments are heat-absorbing particles.
20. The mixture according to claim 19, characterized in that the heat-absorbing particles are composed of Sb-doped Sn02 or soot.
21. The mixture according to one of the claims 1 to 20, characterized in that it has optically transparent characteristics as a result of the use of nano-scale particles for the pigments.
22. The mixture according to one of the claims 1 to 21, characterized in that it comprises optically brightening pigments.
23. The mixture according to claim 22, characterized in that the pigments are optically brightening agents on the basis of stilbenes, cumarin derivatives, diphenylpyrazolines, or bisbenzazoles.
24. The mixture according to one of the claims 1 to 23, characterized in that the mixture is an ink preparation.
25. The mixture according to claim 24, characterized in that the ink preparation is
composed of the following shares, relative to the weight:
0.1 to 10 weight % of the component A
0.1 to 30 weight % of the component B
0.1 to 15 weight % of the component C
0.1 to 5 weight % of the component E
0 to 5 weight % of the component F
at least 50 weight % of the component D.
26. The mixture according to one of the claims 24 or 25, characterized in that the ink preparation comprises as additional component G a multivalent alcohol and/or a polyalkyleneglycol with a higher boiling point than water for improving the running characteristics.
27. The mixture according to one of the claims 24 to 26, characterized in that the ink preparation comprises as additional component H an additive in the form of a surfactant, a plasticizer, a defoamer and/or a preserving agent.
28. The mixture according to claim 27, characterized by the use of plasticizers on the basis of silicones, and/or fatty acid polyglykolesters, and/ or alkoxylated fatty alcohols, and/or alkylaminepolyglycolether, and/or fatty acid amidepolyglycolether, and/or fatty alcohol sulfates, and/or alkylcarboxylates, and/or cationic plasticizers on the basis of quaternary ammonium compounds.
29. The mixture according to one of the claims 26 to 28, characterized in that the ink preparation comprises 0.1 to 10 weight % of the components G and/or H.
30. The mixture according to one of the claims 24 to 29, characterized in that the ink preparation has an ink viscosity of less than 10mPas and a surface tension in the range of 20 to 50mN/m.
31. The mixture according to one of the claims 24 to 30, characterized in that the pigment has a particle size of less than 0.8mm.
32. The mixture according to one of the claims 1 to 23, characterized in that the mixture is a paste preparation.
33. The mixture according to claim 32, characterized in that the paste preparation also comprises a thickening agent in addition to the components for the ink preparation.
34. The mixture according to claim 33, characterized in that the thickening agent is a polyacrylic acid-based and/or polyvinyl alcohol-based agent or is composed of guar gum, starch, carboxy methyl cellulose, alginate, or mixtures thereof.
35. The mixture according to claim 34, characterized in that the paste preparation has a paste viscosity exceeding 10mPas.
36. A method for imprinting textiles with the aid of a continuous processing operation, said method comprising the process of imprinting textiles with a mixture as defined in one of the claims 1 to 35 and fixating the imprinted patterns immediately thereafter with the aid of radiation, at a temperature that exceeds 70°C and falls below 140°C.
37. The method according to claim 36, characterized in that the fixation occurs with the aid of electron beams, UV rays and/or infrared radiation.
38. The method according to one of the claims 36 or 37, characterized in that the mixture in the form of an ink is used for the printing with an inkjet printer.
39. The method according to one of the claims 37 or 38, characterized in that a screen printing technique is used for the printing with the mixture present in the form of a paste.
40. The method according to one of the claims 36 to 39, characterized in that the textiles are irradiated in an oxygen-reduced atmosphere.
41. The method according to one of the claims 36 to 40, characterized in that the textiles to be imprinted are pre-treated with impregnating chemicals.
Dated this 16th day of July, 2007
The invention relates to a method for imprinting textiles and to a corresponding mixture which comprises: at least one pigment, at least one dispersant based on oxy alkylated linear or branched alkanes, fatty acids or fatty alcohols and/or alkyl sulfates or alkyl sulfonates and/or poly electrolytes and/ or alkylated and/or arylated glycosides, at least one water-soluble or water-dilutable binder having a molecular weight of more than 2000 g/mol and at least two polymerizable groups per binder molecule, which are linked to the binder molecule via at least one rethane group or urea group, water.
The Controller of Patents,
The Patent Office,
|Indian Patent Application Number
|PG Journal Number
|Date of Filing
|Name of Patentee
|ITCF INSTITUT FUER TEXTILCHEMIE UND CHEMIEFASERN
|KOERSCHTALSTRASSE 26, 73770 DENKENDORF
|PCT International Classification Number
|PCT International Application Number
|PCT International Filing date